溶胶凝胶法制备超疏水二氧化硅涂膜及其表面润湿行为

采用溶胶-凝胶法以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为前驱体制备超疏水SiO2涂层。红外光谱(FTIR)和热重分析(TGA)表征合成SiO2的化学组成,通过透射电镜(TEM)和扫描电镜(TEM)观察制备SiO2的结构形貌,扫描电镜(SEM)和原子力显微镜(AFM)观察SiO2涂膜的表面形貌,通过测试水接触角(WCA)讨论SiO2涂层的表面微观结构与其表面疏水性能的关系。结果表明以TEOS和MTES为共前驱体可以制备得到表面带-CH3基团的SiO2溶胶,SiO2溶胶在老化过程中纳米SiO2粒子由于自组装作用形成草莓状微米-纳米双微观结构,这种结构赋予SiO2涂膜表面不同等级的粗糙度,使得水滴与涂膜表面接触时能够形成高的空气捕捉率和较小的粗糙度因子,与SiO2表面疏水性的-CH3基团共同作用形成类荷叶超疏水结构。     

具有双亲特性的水相哑铃型SiO2纳米粒子的制备

以纳米SiO2水溶胶为原料,3?氨丙基三乙氧基硅烷(APTES)和3?氯丙基三乙氧基硅烷(CPTES)为改性剂,在水基环境下分别对SiO2纳米粒子进行改性,得到了具有亲水特性的APTES改性SiO2粒子和具有亲油特性的CPTES改性SiO2粒子水溶胶。2种粒子按不同比例混合,利用接枝在SiO2粒子表面氨基和氯丙基的取代反应,使得2种具有亲水/亲油特性的改性SiO2纳米粒子偶联,制备了粒径为40~50 nm的哑铃型SiO2纳米粒子。并通过透射电镜(TEM)、傅里叶变换红外光谱(FT?IR)、X射线光电子能谱(XPS)以及动态光散射(DLS)等方法对其进行了系统表征。结果表明,2种粒子成功偶联形成了具有哑铃型结构的水相SiO2纳米粒子,该粒子两面具有不同的亲水性,粒径近似等于APTES改性SiO2粒子和CPTES改性SiO2粒子的粒径之和。     

酸和碱催化制备二氧化硅溶胶及其稳定性

以正硅酸乙酯(TEOS)为原料,氨水和盐酸为催化剂,制备了SiO2溶胶;研究了pH值对溶胶的稳定性以及SiO2粒子生长方式的影响.结果表明,在酸性条件下,随着pH值的增加,凝胶时间呈现先变长后变短的趋势;而在碱性条件下,凝胶时间随pH的增大快速增加.透射电镜(TEM)和动态光散射(DLS)分析结果表明,溶胶中的SiO2粒子处于纳米量级,且两种催化条件下粒子的粒径分布存在明显差异.     

磁性SiO2/PSt中空复合微球的细乳液法制备及表征

采用双原位细乳液聚合工艺,将疏水改性的磁性纳米粒子(MNP)加入到细乳液反应体系的油相中,利用增长的聚合物和单体TEOS之间的相分离原理,实现了聚合物的生成和TEOS的水解缩合同步进行,一步获得了磁性SiO2/PSt中空复合微球.通过红外光谱(FTIR)、透射电镜(TEM)、热重差热分析(TGA/DSC)和振动磁强计(VSM)对中空复合微球进行了表征.结果表明,制备的SiO2/PSt中空复合微球的尺寸范围为300～600 nm,当加入磁性纳米粒子后,得到的磁性SiO2/PSt中空微球保持了原来的中空结构,中空复合微球内腔的大小可以通过改变单体TEOS的加入量来控制.SiO2/PSt中空微球对磁性纳米粒子的包封率达到了86%.磁性SiO2/PSt中空复合微球具有超顺磁性,饱和磁强度值为14.7 emu/g.     

原位制备PEI/SiO2复合材料及其改性环氧树脂的研究

在N,N-二甲基乙酰胺/四氢呋喃(DMAc/THF)混合溶剂中,在正硅酸乙酯(TEOS)存在条件下,通过溶胶-凝胶法原位制备了聚醚酰亚胺(PEI)/SiO2复合材料.在该复合材料中,当SiO2含量低于20 wt％时,透射电镜(TEM)和扫描电镜(SEM)的观察表明,SiO2纳米粒子可以均匀分散,粒径可在80～300 n...     

SNAP溶胶组成对镁合金涂层耐蚀性的影响

本文利用纳米自组装颗粒工艺(SNAP)在AZ31B镁合金表面制备了防腐涂层。通过透射电镜(TEM)和扫描电镜(SEM)观察及电化学阻抗谱(EIS)、电导率测试等,对SNAP溶胶的纳米粒子形态和电导率,以及SNAP涂层的表面形貌和耐蚀性进行了测试,研究了不同含量的有机硅烷前躯体3-缩水甘油醚丙基三甲氧基硅烷(GPTMS)和正硅酸乙酯基硅烷(TEOS)、溶剂水、助溶剂无水乙醇、交联剂三乙烯四胺(TETA)等对镁合金SNAP涂层耐蚀性的影响。研究结果表明,随着溶胶中TEOS和TETA含量的增大,镁合金涂层耐蚀性呈先增大后减小的趋势;随着溶胶中水含量的增大,镁合金涂层耐蚀性提高;溶胶中无水乙醇的含量较低时,对镁合金涂层耐蚀性的影响较小。     

单分散空心SiO2纳米微球的合成与表征

聚乙烯吡咯烷酮(PVP)功能化的聚苯乙烯(PS)粒子在SiO2包覆的同时被乙醇/氨水介质溶解, 得到了单分散空心SiO2纳米微球. 该空心SiO2纳米微球的尺寸和形态可以通过PVP, NH4OH和正硅酸乙酯(TEOS)的用量来调节. PVP用量增加导致PS粒子变小, 从而得到较小的空心SiO2纳米微球; NH4OH用量增加, 空心SiO2纳米微球表面变得粗糙; TEOS用量增加, 空心SiO2纳米微球的壳层厚度增加. 包覆(溶解)温度是控制空心SiO2纳米微球形成的最有效手段. 在70 ℃的包覆(溶解)温度下可以获得全部空心的SiO2纳米微球.     

SiO2@P（MMA/BA/3FMA）复合纳米粒子的制备及膜性能

通过溶胶-凝胶法与半连续种子乳液聚合法相结合,以正硅酸乙酯(TEOS)制备的纳米SiO2为核,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和甲基丙烯酸三氟乙酯(3FMA)的共聚物P(MMA/BA/3FMA)为壳,合成了SiO2@P(MMA/BA/3FMA)核-壳结构纳米复合粒子.为防止纳米SiO2的团聚,提高其与共聚物的结合力,用乙烯基三甲氧基硅烷(VTMS)对纳米SiO2进行改性.通过红外光谱、透射电子显微镜、动态激光散射粒度仪、静态接触角测试仪、X射线光电子能谱分析和热重分析等表征了乳液结构及膜性能.结果表明,获得的复合纳米粒子呈现粒径分布为40～50 nm的核-壳结构球型颗粒.由于含氟官能团的迁移使得氟元素在膜-空气界面富集,有效降低了膜的表面自由能.当3FMA质量分数达到25%时,膜表面自由能达到最低值(23.13 mN/m).随着3FMA含量的增加,共聚物初始热分解温度由350℃提高到390℃.     

二氧化硅纳米粒子薄膜的制备及光学性能

以二氧化硅胶体和聚二烯丙基二甲基氯化铵(PDDA)为原料,利用静电自组装技术制备了PDDA/SiO2复合薄膜. TEM图象显示,薄膜中的SiO2纳米粒子为密堆积,薄膜均匀、致密;电子衍射实验结果显示,所组装的薄膜为非晶态膜.载玻片表面组装SiO2纳米粒子薄膜后,透射率随薄膜双层数增加呈现周期变化.薄膜具有增透作用,载玻片双面组装薄膜后在一定波长范围内的透射率可提高5％以上. PDDA/SiO2复合薄膜的光学性质主要由SiO2纳米粒子决定,每一双层的平均物理厚度小于SiO2纳米粒子的粒径,薄膜中存在层间穿插现象,逐层组装的复合薄膜具有单层光学薄膜的特性.     

酚醛/SiO2双体系凝胶网络结构杂化气凝胶的制备与性能

通过Sol-Gel反应过程控制,调节酚醛树脂(PR)溶液和SiO2溶胶液的凝胶时间,共凝胶反应制备PR和SiO2凝胶网络互穿的PR/SiO2杂化气凝胶.考察了杂化气凝胶表观密度、收缩率、孔结构、微观形貌、热稳定性和力学性能随SiO2气凝胶含量的基本变化规律.研究结果表明：伴随SiO2气凝胶含量的增加,PR/SiO2杂化气凝胶表观密度正比增加;同纯PR有机气凝胶相比,杂化气凝胶孔结构得到明显改善,当[TEOS] = 1.50 mol/L时,平均孔径减小了一半,降至0.25 μm,比表面积由24.60 m2/g增至44 m2/g左右;微观形貌照片显示有机气凝胶网络骨架中的大孔逐渐被SiO2溶胶粒子填充,变成更细小疏松的孔结构形貌,孔径分布明显变宽,SiO2气凝胶在PR凝胶骨架中纳米尺度内均匀分散;无机SiO2气凝胶的引入能有效提高有机气凝胶骨架结构的强度和热稳定性,纳米分散SiO2溶胶粒子的热阻隔效应抑制了PR有机骨架的热分解速率,当[TEOS] = 1.00 mol/L时,杂化气凝胶的Tmax由539 °C提高到602 °C,热分解温度区间明显展宽.     

碱/酸两步催化法制备耐候性SiO2增透膜的研究

以正硅酸乙酯(TEOS)为先驱体,采用碱/酸两步催化溶胶-凝胶法制备出一种兼具碱催化增透膜的高透过率和酸催化增透膜的良好耐摩擦性能的优点的SiO2增透膜。对酸碱催化SiO2相对比例及酸催化时水含量的系统研究表明,当酸催化SiO2的含量为50%时,增透膜综合性能最好,即具有高透过率和高耐摩擦性;当nH2O/nHCl=1∶0.0010时,增透膜的透过率最高。碱/酸两步催化法制备的增透膜与水的接触角仅为11.3°,本文进一步用六甲基二硅氧烷(HMDS)对增透膜表面进行了修饰,修饰后增透膜的接触角提高至52.5°,增透膜的疏水性及环境稳定性得到较大的提高。     

耐环境性SiO2/SiO2-TiO2 增透膜的设计与制备

根据膜层设计理论设计出以K9玻璃为基体的耐环境性的双层增透膜, 这种增透膜在特定波长处具有超高的透过率. 以盐酸为催化剂, 分别以正硅酸乙酯和钛酸丁酯为前驱体制备了SiO2和TiO2溶胶, 将SiO2和TiO2溶胶按一定比例混合得到SiO2-TiO2复合溶胶. 通过改变复合溶胶中SiO2的含量调节复合膜的折射率, 通过改变提拉速度控制薄膜的厚度. 实验结果表明, 双层增透膜在550 nm处的透过率达到99.9%. 增透膜经较强机械摩擦后峰值透过率基本保持不变, 表明该增透膜具有优良的耐摩擦性. 进一步采用六甲基二硅氮烷对增透膜表面进行修饰, 修饰后增透膜的接触角增大至98.3°, 增透膜的疏水性及环境稳定性得到较大提高.     

Effect of microstructure and surface roughness on the wettability of superhydrophobic sol–gel nanocomposite coatings

Sol–gel nanocomposite coatings were fabricated by spraying precursor mixtures containing hydrophobically modified silica (HMS) nanoparticles dispersed in sol–gel matrices prepared with acid-catalyzed tetraethoxysilane (TEOS), and methyltriethoxysilane (MTEOS). The hydrophobicity of the coatings increased with increase in the concentration of HMS nanoparticles. Superhydrophobic coatings with water contact angle (WCA) of 166° and roll-off angle <2° were obtained by optimizing the sol–gel processing parameters and the concentration of silica nanoparticles in the coating. FESEM studies have shown that surface has a micro-nano binary structure composed of microscale bumps and craters with protrusions of nanospheres. The properties of composite coatings fabricated by spin coating and spray coating methods were compared. It was found that the microstructure and the wettability were also dependent on the method of application of the coating.     

甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜的发光性能

采用溶胶-凝胶(Sol-Gel)法, 以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为先驱物, 盐酸为催化剂, 用二步水解法制备了Ti3+/SiO2薄膜和甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜. 采用红外光谱仪、X射线衍射仪、椭偏仪、荧光光谱仪等对膜层性质进行了分析. 结果表明, 掺杂Ti3+的SiO2薄膜分别在250 nm附近有一弱的激发峰, 294 nm附近有一强的激发峰, 在393 nm附近出现一强的发射峰. IR光谱发现, MTES修饰的Ti3+/SiO2复合薄膜的Si—OH的吸收峰强度比Ti3+/SiO2薄膜的略减小, Si—O—Si的吸收峰明显增强, 表明复合薄膜硅氧网络结构更规则, 有利于Ti3+的均匀分散. Ti3+/SiO2薄膜与复合薄膜的孔隙率分别为13.64%和6.66%, 表明MTES的加入使薄膜更致密. 在空气中陈放30 d后, Ti3+/SiO2薄膜已经检测不到荧光发射峰, 而MTES修饰的Ti3+/SiO2复合薄膜荧光强度只下降了18%. 在氮气中陈放30 d后, 普通薄膜与复合薄膜的荧光强度均仅下降了10%. 表明Ti3+的荧光猝灭的主要原因是由于Ti3+被氧化造成的. 溶胶中加入MTES后, 薄膜表面结构得到改善, 有效地防止了Ti3+的氧化, 荧光强度更稳定.     

Fabrication of highly transparent superhydrophobic coatings from hollow silica nanoparticles

We herein report a simple and effective method to fabricate excellent transparent superhydrophobic coatings. 3-Aminopropytriethoxysilane (APTS)-modified hollow silica nanoparticle sols were dip-coated on slide glasses, followed by thermal annealing and chemical vapor deposition with 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (POTS). The largest water contact angle (WCA) of coating reached as high as 156° with a sliding angle (SA) of ≤2° and a maximum transmittance of 83.7%. The highest transmittance of coated slide glass reached as high as 92% with a WCA of 146° and an SA of ≤6°. A coating simultaneously showing both good transparency (90.2%) and superhydrophobicity (WCA: 150°, SA: 4°) was achieved through regulating the concentration of APTS and the withdrawing speed of dip-coating. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) were used to observe the morphology and structure of nanoparticles and coating surfaces. Optical properties were characterized by a UV-visible spectrophotometer. Surface wettability was studied by a contact angle/interface system. The effects of APTS concentration and the withdrawing speed of dip-coating were also discussed on the basis of experimental observations.     

Preparation and characterization of mesoporous silica thin films from polyethoxysiloxanes

Tetraethoxysilane (TEOS) and polyethoxysiloxanes (PEOSs; prepared by the acid‐catalyzed hydrolytic polycondensation of TEOS) were subjected to the sol–gel process in the presence of cetyltrimethylammonium bromide (CTAB), respectively. The PEOSs with M_w 700–26,000, as prepared by sol–gel coating of TEOS and PEOS under various conditions, were used. Uniform and crack‐free thin films of thickness 276–613 nm were prepared by spin‐coating of a PEOS solution containing CTAB. When the coating films were sintered at 400 °C, the combustion of ethoxy groups and CTAB took place to provide porous silica thin films. The structure of the thin films was found to be dependent on the molecular weight of PEOS and the molar ratio of CTAB/Si: lamellar or hexagonal phase was observed for M_w less than 15,000 and for CTAB/Si molar ratios greater than 0.10. Honeycomb structures were observed for M_w less than 5000 and for CTAB/Si molar ratios of 0.15. The honeycomb structure was also observed by atomic force microscopy and transmission electron microscope. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2542–2550, 2006     

Layer-by-layer fabrication of broad-band superhydrophobic antireflection coatings in near-infrared region

Broad-band superhydrophobic antireflective (AR) coatings in near infrared (NIR) region were readily fabricated on silicon or quartz substrates by a layer-by-layer (LbL) assembly technique. First, a porous poly(diallyldimethylammonium chloride) (PDDA)/SiO2 nanoparticle multilayer coating with AR property was prepared by LbL deposition of PDDA and 200 nm SiO2 nanoparticles. PDDA was then alternately assembled with sodium silicate on the PDDA/SiO2 nanoparticle coating to prepare a two-level hierarchical surface. Superhydrophobic AR coating with a water contact angle of 154 degrees was finally obtained after chemical vapor deposition of a layer of fluoroalkylsilane on the hierarchical surface. Quartz substrate with the as-fabricated superhydrophobic AR coating has a maximal transmittance above 98% of incidence light in the NIR region, which is increased by five percent compared with bare quartz substrate. Simultaneously, the superhydrophobic property endows the AR coating with water-repellent ability. Such superhydrophobic AR coatings can effectively avoid the disturbance of water vapor on their AR property and are expected to be applicable under humid environments.     

Hybrid silica coatings on polycarbonate: enhanced properties

Hybrid silica coatings based on 3- glycidoxypropyltriethoxysilane (GPTES), tetraethylorthosilicate (TEOS) and colloidal silica were deposited on polycarbonate (PC) by the sol–gel method, in order to obtain a material with enhanced properties with respect to raw PC (mainly scratch resistance, hydrophobicity and density), and consequently reach increased durability. The necessity of performing a N₂-plasma treatment on PC (before coating deposition) was highlighted in order to obtain a good adherence between the coating and the substrate: XPS measurements showed that after treatment, nitrogenous radicals had formed on the PC surface and were able to link covalently with the sol during its deposition. Adherence was also higher when young sols (<8-day-old) were used. Different alkoxysilanes/colloidal silica ratios were tested to optimize the coating resistance: crack resistance of the coatings was found to be greater when the ratio was high. Scratch resistance of raw PC was enhanced as soon as PC was coated, irrespective of the alkoxysilanes/colloidal silica ratio or the sol ageing time. The density of the coatings was assessed by environmental ellipsometric porosimetry and found to be very high. Water contact angle measurements showed that the hydrophobicity of the coatings was inferior to raw PC. The addition in the sol of a small wt% of octyltriethoxysilane (OTES), 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FTES) and silicone surface additive (BYK-306) allowed a significant increase in hydrophobicity of the samples.     

SiO2 溶胶及其静电自组装薄膜的制备

Silica sols were prepared by hydrolysis of Si（OC2H5）4（TEOS）using HCl,NH3·H2O,HCl/NH3·H2O as catalyzers,and the different granularities of SiO2 sols which catalyzed by HCl first and then NH3·H2O have the same terminal pH value were prepared. The silica colloidal particles were investigated with Transmission Electron Microscope（TEM）. The results showed sol catalyzed by HCl possesses very little particle,catalyzed by NH3·H2O has particle configuration,catalyzed by HCl/NH3·H2O possesses consecutive configuration. Poly（diallyldimethylammonium chloride）（PDDA）and SiO2 nanoparticulate complex thin films were prepared by electrostatic self-assembly multiplayer（ESAM）method. After assembling films,thin films surface conformation was observed with Electron Microscope and their transmittance was tested with 721 Spectrophotometer. The results showed that the silica sol catalyzed with HCl is not good for the fabrication of ESAM films and the silica sol catalyzed with HCl first and then NH3·H2O or by NH3·H2O only are very suitable for ESAM film fabrication. TEM data indicate that the microstructure of PDDA/ SiO2 prepared from silica sol catalyzed with HCl first and then NH3·H2O is consecutive and that the microstructure of PDDA/ SiO2 prepared from silica sol catalyzed by NH3·H2O only is particulate-parking like. The dependence of the transmittance of assembled films on the bilayer number of the films and the anti-scratching properties of the films were investigated. The results show that PDDA/ SiO2 films prepared from silica sol catalyzed by NH3·H2O only possess higher transmittance but lower anti-scratching properties. The effect of granularity of sols on optical performances of the thin films was studied,results showed the less the granularity of sol,the better the optical performances. For the sake of improving the light transmittance of films,we can reduce the granularity of sol,but it may play down its mechanical damage resist intensity.     

不同厚度三倍频SiO2增透膜的设计、制备与改性

本文通过光学计算设计了具有不同厚度的三倍频增透膜。以氨水为催化剂、正硅酸乙酯(TEOS)为前驱体,通过溶胶-凝胶(Sol-Gel)技术制得SiO2溶胶;采用浸渍提拉法镀膜得到符合设计要求的三倍频增透膜。研究结果表明,增透膜的耐磨擦性能随着膜层厚度的增大而增大,本文制得的厚度达到200 nm以上的三倍频增透膜耐磨擦性能显著优于传统的1/4波长三倍频增透膜。此外,本文以甲基含氢硅油为膜表面修饰剂,提出一种全新的超快的表面疏水性改性的方法。经该方法处理后,增透膜由亲水膜转变为疏水膜,对水的接触角从23.4°增大至95°,增透膜的耐环境性显著提高。