有机硅烷共缩合制备抗紫外超疏水减反射涂层

doi:10.16085/j.issn.1000-6613.2019-0057

摘要/Abstract

摘要：

具有超疏水自洁功能的减反射涂层对太阳能光热组件在室外长期使用上有重要的意义，可以减少减反射涂层的清洗成本，延长减反射涂层的使用寿命。利用含有甲基和乙基等疏水基团的有机硅氧烷制备具有一定孔隙率的涂层，有望实现减反射和超疏水双重性能。本研究采用四甲氧基硅烷（TMOS）和甲基三乙氧基硅烷（MTES）共缩合，并利用甲氧基三甲基硅烷（MMS）进行羟基封端，制备了可以稳定两个月以上的均一溶胶。通过控制MTES和TMOS的水解工艺条件，采用浸渍提拉法制备了在400～800nm可见光波段平均透光率为97.06%、最高透光率为98.27%、水接触角为165°的超疏水减反射涂层，提出了MTES/TMOS/MMS溶胶的共缩合反应机理。涂层经过紫外耐久测试1080h后，涂层仍具有良好的减反射性能、疏水性和抗刻划强度，表现出良好的紫外耐久性。

关键词: 二氧化硅, 纳米材料, 膜, 超疏水, 抗紫外, 甲基三乙氧基硅烷, 减反射

Abstract:

Antireflective coatings with super-hydrophobic characteristic have advantages in application for optical devices and solar thermal components,which can reduce the cleaning cost of the anti-reflection film and prolong the service life of the anti-reflection film. Organosilanes containing hydrophobic groups such as methyl groups are used to prepare coatings with a certain porosity expected to enhance both antireflective and the hydrophobic durability of coatings. In this study, tetramethoxysilane (TMOS) and methyltriethoxysilane (MTES) were used to prepare the sol by co-polycondensation, methoxytrimethylsilane (MMS) was used as hydroxyl end-capping to terminate the condensation reaction during the gum phase and prepare a sol that was stable for more than 120 days. Under the optimum conditions, a super-hydrophobic antireflective coating was prepared by immersion pulling method with an average transmittance of 97.06% at 400―800nm, the highest transmittance of 98.27% and a water contact angle of 165°. And the reaction mechanism of the MTES/TMOS/MMS sol was deduced. After UV aging test for 1080 hours, the coating still had good anti-reflection properties, hydrophobicity and anti scratching strength, and exhibited good UV durability.

Key words: silica, nanomaterials, film, superhydrophobic, anti-ultraviolet, MTES, anti-reflection

中图分类号:

TQ12

李怡雯,郝丽琴,王红宁,陈若愚. 有机硅烷共缩合制备抗紫外超疏水减反射涂层[J]. 化工进展, 2019, 38(08): 3829-3837.

Yiwen LI,Liqin HAO,Hongning WANG,Ruoyu CHEN. Preparation of anti-ultraviolet superhydrophobic anti-reflective coatings by co-condensation of organosilanes[J]. Chemical Industry and Engineering Progress, 2019, 38(08): 3829-3837.

图/表 7

图1 不同比例的MTES/TMOS/MMS涂层的性质

图2 不同体积比例的MTES/TMOS/MMS溶胶粒子的高分辨透射电镜图

图3 MTES/TMOS不同体积比的样品N2吸附-解吸等温线、BJH孔径分布及MTES，TMOS，MTES/TMOS和MTES/TMOS/MMS的FTIR谱图

表1 不同比例的样品BET测试结果、孔隙率和折射率推测结果

MTES∶TMOS	测量的BET数据		估算数据		550nm处折射率测量值
MTES∶TMOS	孔体积/cm³·g^-1	孔直径/nm	孔隙率/%	折射率	550nm处折射率测量值
95.5∶7.5	0.43	3.8	50	1.24	1.23
100∶0	0.01	—	—	1.44	1.45
0∶100	0.71	4.2	62	1.19	1.15

图4 MTES/TMOS/MMS体系的反应机理

图5 MTES/TMOS/MMS涂层的SEM图像和不同体积比下MTES∶TMOS∶MMS涂层的AFM图像

图6 紫外耐久测试前后MTES/TMOS/MMS涂层的水接触角变化趋势、透光率变化趋势、SEM、红外谱图及抗刻化性对比图

参考文献 27

1	KIM Y S , KUSAKABE K , MOROOKA S , et al . Preparation of microporous silica membranes for gas separation[J]. Korean J. Chem. Eng., 2001, 18: 106-112.
2	ZHANGL, QIAO A , ZHENG M , et al . Rapid and substrate-independent layer-by-layer fabrication of antireflection and antifogging-integrated coatings[J]. J. Mater. Chem., 2010, 20: 6125-6130.
3	荚桂玉, 李怡雯, 王红宁, 等 . 具有梯度渐变折射率的超疏水减反膜的制备及其性能[J]. 无机材料学报, 2018, 33(9): 92-97.
	JIA Guiyu , LI Yiwen , WANG Hongning , et al . Preparation and properties of superhydrophobic anti-reflection films with gradient refractive index[J]. Journal of Inorganic Materials, 2018, 33(9): 92-97.
4	PRENE P , PRIOTTON J , BEAURAIN L , et al . Preparation of a sol-gel broadband antireflective and scratch-resistant coating for amplifier blast shields of the french laser LIL[J]. J.Sol-Gel Sci. Technol., 2000, 19: 533-537.
5	KAMEGAWA T , SHIMIZU Y , YAMASHIDA H . Superhydrophobic surfaces with photocatalytic self-cleaning properties by nanocomposite coating of TiO₂ and polytetrafluoroethylene[J]. Advanced Materials, 2012, 24(27): 3697.
6	LIU M , RODE A , FU L , et al . Reply to comment on water droplet motion control on superhydrophobic surfaces: exploiting the wenzel-to-cassie transition [J]. Langmuir, 2011, 27(22): 13962-13963.
7	CAI S , ZHANG Y , ZHANG H , et al . Sol-gel preparation of hydrophobic silica antireflective coatings with low refractive index by base/acid two-step catalysis [J]. ACS Applied Materials & Interfaces, 2014, 6(14): 11470.
8	YUAN Y , CHEN Y , CHEN L , et al . Preparation, durability and thermostability of hydrophobic antireflective coatings for solar glass covers[J]. Solar Energy, 2015, 118: 222-231.
9	SHIRTCLIFFE N J , MCHALE G , ATHERTON S , et al . An introduction to superhydrophilicity[J]. Advances in Colloid & Interface Science, 2010, 161(1-2): 124.
10	BUDUNOGLU H , YILDIRIM A , GULER M O , et al . Highly transparent, flexible, and thermally stable superhydrophobic ORMOSIL aerogel thin films[J]. ACS Applied Materials & Interfaces, 2011, 3(2): 539.
11	PETCU C , PURCAR V , IANCHIS R , et al . Synthesis and characterization of polymer-silica hybrid latexes and sol-gel-derived films[J]. Applied Surface Science, 2016, 389: 666-672.
12	YUAN Y , YAN G H , HUANG S H , et al . Preparation of hydrophobic SiO₂/PMHS sol and ORMOSIL antireflective films for solar glass cover[J]. Solar Energy, 2016, 130: 1-9.
13	BERGER F M . The pharmacological properties of 2-methyl, 2-n-amyl-4-hydroxy-methyl-1,3-dioxolane (Glyketal), a new blocking agent of interneurons[J]. Journal of Pharmacology and Experimental Therapeutics, 1949, 96(3): 213-223.
14	卫晓利, 张发兴 . 硅改性高固含量水性聚氨酯分散体的制备及性能研究[J]. 聚氨酯工业, 2014, 29(5): 22-25.
	WEI Xiaoli , ZHANG Faxing . Preparation and properties of silicon modified high solid content waterborne polyurethane dispersion[J]. Polyurethane Industry, 2014, 29(5): 22-25.
15	FAUSTINI M , NICOLE L , BOISSIERE C , et al . Hydrophobic, antireflective, self-cleaning, and antifogging sol-gel coatings: an example of multifunctional nanostructured materials for photovoltaic cells[J]. Chemistry of Materials, 2010, 22(15): 4406-4413.
16	KANAMORI K , AIZAWA M , NAKANISHI K , et al . New transparent methylsilsesquioxane aerogels and xerogels with improved mechanical properties[J]. Advanced Materials, 2007, 19(12): 1589-1593
17	NARAYAN K , RAMAN, MARK T , et al . Template-based approaches to the preparation of amorphous, nanoporous silicas[J]. Chemistry of Materials, 1996, 8(8): 1682-1701.
18	ZHANG Y , ZHAO C , WANG P , et al . A convenient sol-gel approach to the preparation of nano-porous silica coatings with very low refractive indices[J]. Chemical Communications, 2014, 50(89): 13813.
19	BERNSMEIER D , POLTE J , ORTEL E , et al . Antireflective coatings with adjustable refractive index and porosity synthesized by micelle-templated deposition of MgF₂ sol particles[J]. ACS Applied Materials & Interfaces, 2014, 6(22): 19559-19565.
20	WEN X F , WANG K , PI P H , et al . Organic-inorganic hybrid superhydrophobic surfaces using methyltriethoxysilane and tetraethoxysilane sol-gel derived materials in emulsion[J]. Applied Surface Science, 2011, 258(3): 991-998.
21	SHEN Y C , CHANG W H , CHEN W C , et al . Non-fluorinated superamphiphobic surfaces through sol-gel processing of methyltriethoxysilane and tetraethoxysilane[J]. Materials Chemistry and Physics, 2009, 114(1): 63-68.
22	XU Y , WU D , SUN Y H , et al . Comparative study on hydrophobic anti-reflective films from three kinds of methyl-modified silica sols[J]. Journal of Non-Crystalline Solids, 2005, 351(3): 258-266.
23	CASSIE A B D , BAXTER S . Wettability of porous surfaces[J]. Transactions of Faraday Society, 1944, 40: 546-551.
24	ISIMJAN T , WANG T , ROHANI S . A novel method to prepare superhydrophobic, UV resistance and anti-corrosion steel surface[J]. The Chemical Engineering Journal, 2012, 210(6): 182-187.
25	LIU Juan , LU X , XIN Z , et al . Preparation and surface properties of transparent UV-resistant “petal effect” superhydrophobic surface based on polybenzoxazine[J]. Applied Surface Science, 2015, 353: 1137-1142.
26	Yonghao XIU , HESS D W , WONG C P . UV-resistant and superhydrophobic self-cleaning surfaces using sol-gel processes[J]. Journal of Adhesion Science and Technology, 2008, 22(15): 1907-1917.
27	XU L , HE J . A novel precursor-derived one-step growth approach to fabrication of highly antireflective, mechanically robust and self-healing nanoporous silica thin films[J]. Journal of Materials Chemistry C, 2013, 1(31): 4655-4662.

[1]	张祚群, 高扬, 白超杰, 薛立新. 二次界面聚合同步反扩散原位生长ZIF-8纳米粒子制备聚酰胺混合基质反渗透（RO）膜[J]. 化工进展, 2023, 42(S1): 364-373.
[2]	王尚彬, 欧红香, 薛洪来, 曹海珍, 王钧奇, 毕海普. 黄原胶和纳米二氧化硅对无氟泡沫性能的影响[J]. 化工进展, 2023, 42(9): 4856-4862.
[3]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[4]	李雪佳, 李鹏, 李志霞, 晋墩尚, 郭强, 宋旭锋, 宋芃, 彭跃莲. 亲水和疏水改性膜的抗结垢和润湿能力的对比[J]. 化工进展, 2023, 42(8): 4458-4464.
[5]	王报英, 王皝莹, 闫军营, 汪耀明, 徐铜文. 聚合物包覆膜在金属分离回收中的研究进展[J]. 化工进展, 2023, 42(8): 3990-4004.
[6]	王鑫, 王兵兵, 杨威, 徐志明. 金属表面PDA/PTFE超疏水涂层抑垢与耐腐蚀性能[J]. 化工进展, 2023, 42(8): 4315-4321.
[7]	吴亚, 赵丹, 方荣苗, 李婧瑶, 常娜娜, 杜春保, 王文珍, 史俊. 用于复杂原油乳液的高效破乳剂开发及应用研究进展[J]. 化工进展, 2023, 42(8): 4398-4413.
[8]	尹新宇, 皮丕辉, 文秀芳, 钱宇. 特殊浸润性材料在防治油气管道中水合物成核与聚集的应用[J]. 化工进展, 2023, 42(8): 4076-4092.
[9]	潘宜昌, 周荣飞, 邢卫红. 高效分离同碳数烃的先进微孔膜：现状与挑战[J]. 化工进展, 2023, 42(8): 3926-3942.
[10]	徐杰, 夏隆博, 罗平, 邹栋, 仲兆祥. 面向膜蒸馏过程的全疏膜制备及其应用进展[J]. 化工进展, 2023, 42(8): 3943-3955.
[11]	陆诗建, 刘苗苗, 杨菲, 张俊杰, 陈思铭, 刘玲, 康国俊, 李清方. 改良型CO₂湿壁塔内气液两相流动规律及传质特性[J]. 化工进展, 2023, 42(7): 3457-3467.
[12]	冯江涵, 宋钫. 阴离子交换膜电解池的研究进展[J]. 化工进展, 2023, 42(7): 3501-3509.
[13]	陈香李, 李倩倩, 张甜, 李彪, 李康康. 自愈合油水分离膜的研究进展[J]. 化工进展, 2023, 42(7): 3600-3610.
[14]	徐沛瑶, 陈标奇, KANKALA Ranjith Kumar, 王士斌, 陈爱政. 纳米材料用于铁死亡联合治疗的研究进展[J]. 化工进展, 2023, 42(7): 3684-3694.
[15]	刘战剑, 付雨欣, 任丽娜, 张曦光, 袁中涛, 杨楠, 汪怀远. 超疏水涂层在防腐阻垢领域研究进展[J]. 化工进展, 2023, 42(6): 2999-3011.