Preparation and Properties of Hybrid Silica Sol/Organsilicon Oligomer Composite Transparent Superhydrophobic Coatings
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摘要: 以气相纳米二氧化硅、正硅酸乙酯（TEOS）和六甲基二硅氮烷（HMDS）为原料，采用溶胶-凝胶法制备杂化硅溶胶，将γ-（2,3-环氧丙氧）丙基三甲氧基硅烷（KH560）和烷基硅氧烷制备的有机硅低聚物与杂化硅溶胶复合得到透明超疏水涂层，研究了气相纳米二氧化硅、HMDS和KH560用量以及烷基硅氧烷种类对复合涂层性能的影响。结果表明：当气相纳米二氧化硅与TEOS的质量比为0.075，HMDS与TEOS的质量比为0.75，烷基硅氧烷为甲基三乙氧基硅烷（MTES），且KH560和MTES的物质的量之比为0.50，有机硅低聚物与杂化硅溶胶质量比为0.100时，制备的涂层接触角可达165°，具有优异的超疏水性能和良好的附着力、坚固性以及高透光率。Abstract: Transparent superhydrophobic coatings have potential applications in optical devices, solar panels, automobile windshields and glass building facade. However, their real-world applications are restricted by low transparency, poor durability, and the complex preparation processes. Hybrid silica sol is commonly prepared by the sol-gel process using fumed silica, tetraethoxysilane (TEOS) and hexamethyl-disilazane (HDMS) as raw materials. In this study, transparent superhydrophobic composite coatings were obtained via incorporating the hybrid silica sol with organosilicon oligomer synthesized from 2,3-epoxypropoxy propyltrimethoxysilicane (KH560) and alkyl siloxane as precursors. The influence of loading of fumed silica and HDMS on the hydrophobic property of the hybrid silica sol coatings was investigated, and the effects of KH560 , organosiloxane diversity and organosilicon oligomer loading on the properties of composite coatings were studied. The optimal performance of hybrid silica sol coatings was obtained with a water contact angel (CA) of 166° and sliding angel (SA) of less than 3° when the mass ratio of nano-fumed silica to TEOS was 0.075, and the mass ratio of HMDS to TEOS was 0.75, respectively. When the molar ratio of KH560 to MTES was up to 0.50, and the mass ratio of organosilicon oligomer to hyrid silica sol was 0.100, the composite coating remained superhydrophobic with water contact angle being 138° even after ultrasonic treatment for 5 min. Scanning electron microscopic showed a continuous porous network with a large amount of micro-nano composite rough structures on the surface of the composite coating. Furthermore, the optical transmittance of the hybrid silica superhydrophobic composite coating reached 85.4% at 550 nm.
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Key words:
- superhydrophobic /
- transparency /
- silica sol /
- organosilicon oligomer /
- composite coating
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图 1 气相纳米二氧化硅与TEOS质量比对杂化硅溶胶涂层疏水性能的影响
Figure 1. Effect of mass ratios of nano-fumed silica to TEOS on hydrophobic properties of hybrid silica sol coatings
图 2 HMDS与TEOS质量比对杂化硅溶胶涂层疏水性能的影响
Figure 2. Effect of mass ratio of HMDS to TEOS on hydrophobic property of hybrid silica sol coatings
图 3 KH560与MTES的物质的量之比对复合涂层性能的影响
Figure 3. Effect of molar ratio of KH560 to MTES on properties of composite coatings
图 4 烷基硅氧烷种类对复合涂层性能的影响
Figure 4. Effect of different alkyl siloxanes on properties of composite coatings
图 5 有机硅低聚物添加量对复合涂层性能的影响
Figure 5. Effect of adding amount of organsilicon oligomer on properties of composite coatings
图 6 气相纳米二氧化硅（a）、杂化硅溶胶（b）、KH560（c）和有机硅低聚物（d）的红外光谱图
Figure 6. FT-IR spectra of nano-fumed silica (a), hybrid silica sol (b), KH560 (c) and organosilicon oligomer (d)
图 7 杂化硅溶胶涂层和复合涂层的SEM图
Figure 7. SEM images of hybrid silica sol coatings and composite coatings
a, b—Hybrid silica sol coating without nano-fumed silica; c, d—m (Nano-fumed silica)∶m (TEOS)=0.075; e, f—m (Organsilicon oligomer)∶m (Hybrid silica sol)=0.100
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