【作者】 张亮；

【导师】 杨柏；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2012， 博士

【摘要】 随着科学技术的不断进步，人们对于光学材料的需求越来越大。与此同时，人们对光学材料的功能化也提出了更高的要求，人们不仅希望光学材料具有良好的光学性质，同时也希望材料具有良好的稳定性，易加工性，耐热性。因此，传统的无机材料和有机材料已经很难满足人们对于光学材料功能性的要求。随着纳米技术的发展，纳米复合光学材料由于其兼顾了无机材料的稳定性，有机材料的易加工性和折射率可控等特点而越来越多的受到人们的广泛关注。纳米复合光学材料在电子学，光学，机械等方面表现出强大的应用前景。在本论文中，我们成功地将具有不同折射率的纳米材料引入到有机体系中，得到了一系列功能性的纳米复合光学薄膜。在第一部分中，在不需要进行化学修饰的条件下，我们将低折射率的介孔二氧化硅微球引入二氧化硅溶胶中，得到了具有仿生形貌的复合涂层。涂层具有良好的减反射防雾耐磨性能。经涂层处理后的玻璃基底在可见光区的光透过率可达99%以上，水滴在涂层表面铺展时间为158毫秒，涂层经负重300g钢丝棉摩擦后性质没有变化。在第二部分中，我们将商品化的晶态硅纳米粒子进行了表面修饰，使其可以稳定分散在常用有机溶剂中。接下来，我们将表面修饰后的晶态硅纳米粒子引入到不同的溶胶和聚合物中，得到了一系列具有高透明性，高折射率，高阿贝数的复合光学薄膜。膜层折射率可达1.990，同时膜层在可见光区透过率高于70%。在第三部分中，我们将单层氧化石墨烯经化学修饰使其可以以单层形式稳定分散，并将这种修饰后的单层氧化石墨烯复合进不同的有机体系中，并利用水合肼还原氧化石墨烯制备了一系列石墨烯掺杂的高折射率复合光学薄膜。膜层的折射率可达1.936，同时膜层在可见光区透过率在80%以上。更多还原

【Abstract】 As one important part of modern society, optical materials are widely used inmilitary, traffic and daily life. People pay more attention to special refractive indexmaterials in different kinds of optical materials. Refractive index is an importantcharacterization of materials. Traditional method of preparing special refractive indexmaterials is to process inorganic or organic （polymer） materials. Inorganic materialsshow high stability and excellent optical performances, but the complexity of processrestricts the appliance. Although impact resistance and convenience of process oforganic （polymer） materials are better than inorganic materials, stability and opticalperformances of inorganic materials are slightly worse. So hybrid materials come intobeing because they integrate the advantages of inorganic and organic （polymer）materials.There are many difficulties to prepare high optical performance materials withspecial refractive index. For low refractive index hybrid materials, traditional etchingmethod limits the size of the production and increases the costs first. And secondcommon low refractive index inorganic particles are easy to aggregate in polymer anddecrease the transmittance of the hybrid materials. Finally mechanical stability oftraditional low refractive materials is poor due to porous structures. For high refractive index hybrid materials, on one hand, people try to synthesis high refractive indexpolymer, but most of polymers contain benzene rings or conjugation structures whichmay decrease the transmittance of materials. On the other hand, people attempt tointroduce modified inorganic particles with high weight content to increase therefractive index. However, too much ligand will decrease the refractive index of hybridmaterials and high weight content nanoparticles may increase the possibility ofaggregation between nanoparticles. In summary, it is an important issue to preparehybrid materials with high performance optical materials.In this dissertation, transparent hybrid optical films with special refractive indexwere prepared by incorporating nano-materials into organic sol and polymers byblending method. The work doesn’t broaden the method of preparing nanocomposites,but also have potential application in fabricating optical materials with special refractiveindex.In chapter one, we summarized the development and outlook of low refractiveindex hybrid materials and high refractive index hybrid materials respectively, andillustrated the high refractive index materials in the actual applications.In chapter two, we used simple method to prepare low refractive index, antifoggingand mechanical stable films doped with mesoporous SiO₂nanoparticles. The size ofnanoparticles prepared in neutral buffer solution is130nm. We dispersed themesoporous SiO₂nanoparticles containing surfactants into the ethanol and blended withsilica sol. We obtained the multifunctional optical films by spin-coating the hybrid soland calcinated to remove the surfactants. The preparation method has advantages asfollows: For one thing, mesoporous SiO₂nanoparticles containing surfactants candisperse in ethanol and silica sol without any aggregation. It can avoid complexchemical modification of mesoporous SiO₂nanoparticles first of all. The next it breakthrough the limitations that hybrid materials doped with unmodified mesoporous SiO₂nanoparticles can only be obtained by LBL method. Finally, the process of removing thesurfactants after solidification of the films can prevent organic sol diffusing into the porous structure and decreasing the air ratio. For another, mesoporous SiO₂nanoparticles embed in the silica film and increase the mechanical stability of the hybridfilms. With the increase of the mesoporous SiO₂nanoparticles weight content, therefractive index of the films decrease and the films show more better performances ofantireflective and antifogging. When the weight content of mesoporous SiO₂nanoparticles was6%, the refractive index of the film was1.24, the transmittance of thefilm was about99%, and the spreading time of water droplet was about158ms.Performances of low refractive index, antireflective and antifogging maintained wellafter the films were scratched repeatedly by weight loaded steel wool and filter paper.In chapter three, we prepared high refractive index transparent hybrid films byintroducing modified commercialized crystalline silicon nanoparticles into sol andpolymers. Modified crystalline silicon nanoparticles could disperse in organic solventsand mixed solvent of solvent and monomer. The dispersion of crystalline siliconnanoparticles was improved after modification, and the crystalline structure kept aftermodification. Crystalline silicon nanoparticles could increase the refractive index of thehybrid films effectively in the premise of high transparent. When the weight content ofcrystalline silicon nanoparticles was10%, the refractive index of c-Si/TiO₂hybrid filmwas about1.957. AFM images showed the surfaces of the films were flat and the phaseswere uniform. The transmittance of the film was about80%. We also prepared highrefractive index c-Si/SiO₂and c-Si/PVA hybrid films. Moreover, we modifiedcrystalline silicon nanoparticles with KH-570and made it polymerized with DMAAunder ultraviolet irradiation. When the refractive index was about1.990andtransmittance was about76.5%with nanophase content of25wt%.In chapter four, we synthesized monolayer graphene oxide and modified grapheneoxide to make it stable in organic system. We prepared graphene/TiO₂hybrid films byreducing the hybrid film of graphene oxide and TiO₂with hydrazine hydrate. Therefractive index of the film could be continuously regulated in the range of1.849–1.908by the content of graphene. The transmittance was above75%when the graphene was15wt%. Furthermore we also prepared graphene/polyurethane hybrid films. Therefractive index of the film increased with the weight content increase of graphene, andthe increase is a linear relationship. TEM images showed graphene was monolayer inthe nanocomposites, it is important for transparent hybrid films. The transmittance ofthe films was higher than85%when graphene is25wt%.更多还原