单分散胶体颗粒的有序组装及其应用研究进展

本文综述了近1～2年来课题组在单分散胶体微球有序组装及其应用方面的研究进展.其中包括250～1300 nm宽尺寸范围单分散二氧化硅胶体微球的重力沉降自组织;旨在提高光子晶体折射率反差的TiO2/SiO2复合胶体微球的有序组装;硬模板与催化材料一步复合的二元胶体体系颗粒的有序自组装;一种高效的聚苯乙烯胶体颗粒的批量组装技术;低体积分数聚苯乙烯胶体晶体的制备;以及聚苯乙烯胶粒晶体作为可调谐三维非线性光子晶体在高开关对比的光子晶体光开关方面的应用,和作为制备有序大孔材料硬模板在大分子催化方面的应用等.     

InP-SiO2三维光子晶体的制备

用溶剂蒸发法将单分散SiO2微球组装成三维有序结构的胶体晶体,用金属有机化学气相沉积技术向SiO2胶体晶体中填充高折射率材料InP,获得了InP-SiO2两种介质复合的三维光子晶体,通过扫描电子显微镜、X射线衍射、能谱和紫外-可见光谱仪对InP-SiO2三维光子晶体的形貌、结构和光学性能进行了观察测试。研究结果表明：InP在SiO2微球空隙间具有较高的结晶质量,填充较致密均匀、与相同晶格周期的SiO2光子晶体相比,InP-SiO2光子晶体的反射光谱的峰值波长发生明显的红移。     

改性二氧化硅微球的制备及其光子晶体自组装

为提高SiO2微球的表面电荷密度,通过改进Stober法,引入金属Na,合成SiO2微球,并采用垂直沉积法制备出光子晶体.通过Zeta电位粒度仪、带EDS能谱仪的场发射、扫描电子显微镜(SEM)和紫外-可见-近红外光谱仪对其电学性能、显微形貌和光学性能进行测试分析.Zeta电位测试结果显示改性SiO2微球的Zeta电位平均提高13.44 mV;EDS能谱分析表明微球中含有钠元素;SEM照片表明样品平均粒径为318 nm,平均标准偏差小于5%,所得光子晶体为面心立方密排结构;吸收光谱表明在692 nm处具有光子晶体带隙.     

有序大孔二氧化硅微球的制备研究

采用乳液聚合法合成了单分散改性聚苯乙烯（PS）乳胶粒,利用PS乳胶粒自组装制得胶体晶体（“蛋白石”）微球,通过溶胶-凝胶模板法制备了有序大孔SiO2（“反蛋白石”）微球,通过SEM对改性PS乳胶粒、胶体晶体微球和有序大孔SiO2微球表面形貌进行了表征。结果表明,改性PS乳胶粒呈单分散性,粒径为317 nm;胶体晶体微球表面PS乳胶粒排列有序;有序大孔SiO2微球表面呈有序多孔,其孔呈六边形,孔径分布均一,约为200 nm。     

SiO2光子晶体的垂直沉积制备与光学性能研究

采用改进的St(o)ber法合成了不同粒径的单分散SiO2微球颗粒,用种子液法制备了平均粒径约为550 nm的单分散SiO2微球颗粒,在可见光波段垂直沉积制备了SiO2光子晶体薄膜.采用紫外-可见分光光度计测试了不同反应物浓度配比所得微球制备的光子晶体薄膜的光学性能,并分析了退火对光反射性能的影响.     

单分散SiO2/Ag/SiO2核壳结构微球制备及自组装光子晶体

应用湿化学方法,在SiO2微球表面先后包覆5 nm银层、20 nm SiO2介质膜,制备了直径约300 nm的单分散SiO2/Ag/SiO2核壳结构微球.用提拉技术实现微球的自组装,获得了长程有序的面心立方结构排列的光子晶体,并研究了其光学性能.结果表明:在可见至近红外波段存在非完全光子带隙;SiO2/Ag/SiO2球体自组装成的光子晶体并非完全密堆排列.     

光子晶体及SiO2光子晶体的制备技术

光子晶体是一种具有光子带隙的周期性电介质结构,落在光子带隙中的光将不能传播。由于其独特的调节光子传播状态的功能,成为实现光通讯和光子计算机的基础。SiO2胶体球作为胶体光子晶体的组成基元,具有广阔的应用前景。本文介绍了光子晶体的概念、特征与应用领域,以及SiO2光子晶体的制备技术。     

疏水性光子晶体薄膜的制备及性能研究

以一步乳液聚合法制备单分散的聚(苯乙烯-甲基丙烯酸甲酯-丙烯酸)乳胶微球,通过控制表面活性剂十二烷基苯磺酸钠用量来调控乳胶微球粒径的大小,采用竖直沉积法将乳胶微球组装成光子晶体薄膜,继而用疏水改性剂对光子晶体薄膜表面进行改性。利用扫描电镜、紫外-可见分光光谱仪和接触角测量仪对样品进行了表征。结果表明:合成的乳胶微球的单分散性优异;不同带隙的光子晶体薄膜的颜色可实现全可见光的覆盖;疏水性光子晶体薄膜的疏水性能良好,其接触角在130°以上。     

PDA/SiO2改性聚氨酯制备含结构色复合材料

采用改良St?ber法制得187、245、274 nm 3种粒径的SiO2微球，使用聚多巴胺（PDA）对SiO2微球进行包覆，制备了蓝色、绿色、红色3种不同颜色的非晶光子晶体PDA/SiO2（APCs）；将非晶光子晶体PDA/SiO2引入聚氨酯（PU）制得复合材料PDA/SiO2/PU 。利用FT-IR、CA、SEM、TEM、UV-Vis、DLS及万能试验机对PDA/SiO2及复合材料PDA/SiO2/PU的结构与性能进行表征分析。结果表明：APCs的颜色取决于SiO2微球的粒径；通过调节PDA的包覆量可调整APCs的色彩饱和度；APCs引入PU后可得到呈暗红结构色聚氨酯，其最大拉伸强度可达40.28 MPa，水接触角达113°，使得聚氨酯具有结构生色性和优异的机械性能与疏水性。     

等离子体增强化学气相沉积技术制备锗反蛋白石三维光子晶体

采用溶剂蒸发对流自组装法将单分散二氧化硅(SiO2)微球组装形成三维有序胶体晶体模板,以锗烷(GeH4)为先驱体气用等离子增强化学气相沉积法在350℃填充高折射率材料锗.获得了锗反蛋白石光子晶体.通过扫描电镜、X射线衍射仪对锗反蛋白石的形貌、成分、结构进行了表征.结果表明:锗在SiO2微球空隙内填充均匀,得到的锗为多晶态.锗反蛋白石光子晶体为三维有序多孔结构.等离子体增强化学气相沉积的潜在优势在于可实现材料的低温填充,从而以高分子材料为模板进行复型,得到多种结构的三维光子晶体.     

三维有序二氧化硅胶粒膜在垂直基片上的自组装

A method for preparation of particle crystal film constructed trom monodisperse silica colloidal partices in diameter of about 300 nm is reported. The films were prepared from an ethanol suspension by vertical deposition that relies on capillary forces to assemble colloidal crystal particles on a vertical substrate. The 3D ordered films were characterized by transmission spectra and scanning electric microscope (SEM). The effect of evaporation temperature, particle concentration and sintered temperature on the quality of colloidal particle crystal film was investigated.     

垂直排列法组装胶体晶体的最新进展

光子晶体是一种具有光子带隙的新型功能材料．利用胶体粒子自组装三维光子晶体由于其制备过程比较经济、简单，从而为很多人所关注．目前报道的方法已有多种．其中垂直排列法的简便易行使得其受到了广泛的研究，但另一方面这种方法本身的缺点也限制了它的使用范围．针对这种情况，很多研究机构提出了他们的改进方法．本文简要概述了在这一方面的最新进展，并且在本实验室已能够制备任意单分散、均一尺寸二氧化硅粒子的基础上，采用恒温快速蒸发自组装法得到了高质量的胶体晶体排列．     

垂直沉积法制备SiO_2胶体晶体及其光子带隙特性

采用stober法在乙醇介质中合成S iO2微球,将制得的样品在30℃下用双氧水浸泡处理48 h。扫描电子显微镜(SEM)测定结果表明,样品平均粒径为292 nm,平均标准偏差小于5%。傅里叶红外光谱(FTIR)测定表明,经双氧水浸泡处理后,S iO2微球表面的羟基数目增多。Zeta电位和标准氢氧化钠滴定测试结果显示,经双氧水浸泡处理后,S iO2微球在水溶液中的Zeta电位从-55.72 mV提高到-63.26 mV,表面电荷密度从0.19 uC/cm2提高到0.28 uC/cm2。用垂直沉积法制备出有序性较好的密排结构的S iO2胶体晶体。在SEM下,观察到这种胶体晶体是面心立方(fcc)密排结构,其(111)晶面平行于基底。透射光谱表明,所制备的胶体晶体在(111)方向具有光子晶体的带隙性质。     

Light-controlled ion transport through spiropyran-modified nanoporous silica colloidal films

The transport of positively charged redox active species through spiropyran-modified nanopores in silica colloidal films was controlled using light. The silica colloidal films were comprised of 18 layers of face centered cubic (fcc)-packed 170 nm silica spheres. The surface of the films was first modified with amines, which were then used to attach the spiropyran moiety to the surface. The limiting current of a positively charged redox active species through the spiropyran-modified nanopore decreased after irradiation with UV light at pH 6.6. When the silica colloidal film was subsequently irradiated with visible light the initial limiting current was restored.     

P(St-HEA)胶体晶体薄膜的制备及结构研究

采用两阶段种子乳液聚合法制备了单分散P(St-HEA)微球,通过垂直成膜法制备了P(St-HEA)胶体晶体薄膜。研究了引发剂用量、反应温度及反应时间对单体转化率的影响,通过FTIR、SEM、UV-Vis对所制备的单分散P(St-HEA)微球的组成、粒径、单分散性及其胶体晶体薄膜的结构进行了研究。结果表明,随着HEA用量的增大,P(St-HEA)微球粒径逐渐增大,单分散性逐渐降低。     

Surface structuring of diamond-like carbon films by colloidal lithography with silica sub-micron particles

By combining colloidal lithography and pulsed-DC plasma deposition of diamond-like amorphous carbon films, we have fabricated sub-microstructures that modulate the surface properties of this material. A self-assembled monolayer of silica sub-micron spheres was deposited on monocrystalline silicon, which was patterned either by thermal annealing of the particles or by hole-mask lithography via ion beam etching with argon. The samples showed hemispherical close-packed topographies and micro-pillar networks. The coefficient of friction, measured with a nanotribometer, and the wettability were controlled through this special surface patterning. These structures are suitable for applications requiring protective coatings with large area showing hydrophobic properties.     

大孔二氧化硅膜上纳米碳纤维层结构化催化剂载体的制备

1 INTRODUCTION Fast gas-liquid phase reactions over solid cata- lysts easily cause concentration gradient in reactors and catalysts because of relatively slow diffusion as well as the frequent occurrence of low concentration when gasses are dissolved. Such concentration gradi- ent caused by the limitation of mass transfer influ- ences the reaction rate as well as selectivity. Conven- tional strategies for gas-liquid-solid phase catalytic reactions comprise slurry reactors and trickle bed r…     

高硅含量有机无机杂化乳液的制备和溶胶-凝胶驱使成膜

A novel polymer/SiO2 hybrid emulsion (PAES) was prepared by directly mixing colloidal silica with polyacrylate emulsion (PAE) modified by a saline coupling agent. The sol-gel-derived thin films were obtained by addition of co-solvents into the PAES. The effects of γ-methacryloxypropyltrimethoxysilane (KH-570) content and co-solvent on the properties of PAES films were investigated. Dynamic laser scattering (DLS) data indicate that the average diameter of PAES (96 nm) is slightly larger than that of PAE (89 nm). Transmission electron microscopy (TEM) photo discloses that colloidal silica particles are dispersed uniformly around polyacrylate particles and some of the colloidal silica particles are adsorbed on the surface of PAE particles. The crosslinking degree data and Fourier transform infrared (FT-IR) spectra confirm that the chemical structure of the PAES is changed to form Si-O-Si-polymer crosslinking networks during the film formation. Atomic force microscope (AFM) photos show the solvent induced sol-gel process of colloidal silica and the Si-based polymer distribution on the film surface of the dried PAES. Thermogravimetric analysis (TGA) curves demonstrate that the PAES films display much better thermal stability than PAE.