PVP改性氧化硅溶胶的微结构和流变性

以正硅酸乙酯为前驱体,聚乙烯吡咯烷酮（PVP）为聚合物改性添加剂,在碱性条件下制备氧化硅溶胶,通过小角X射线散射测量了改性溶胶的微结构参数,辅以动态光散射观测溶胶颗粒生长,研究了聚合物量、碱催化剂量和水量对溶胶颗粒度、分形特征以及流变性的影响规律.由于PVP链中强极性的分子内酰胺基团和氧化硅颗粒表面的羟基形成氢键,致使溶胶颗粒被聚合物链包裹,严重阻碍了溶胶颗粒的生长,使凝胶时间延长,流变性发生变化,同时对溶胶颗粒的微结构产生影响.     

小角X射线散射技术在高分子表征中的应用

小角X射线散射(SAXS)技术是表征高分子材料微观结构的一种重要手段.当X射线穿过材料时,在材料不均一的电子云密度分布作用下,发生散射并形成特定的散射图案,使得我们可以根据特定的模型来反推材料的微观结构,并计算相关结构参数.SAXS特有的对微观结构的统计平均及无损探测使其成为了一种不可或缺的高分子材料微观结构分析手段....     

NaCl、KCl、Na_2CO_3、K_2CO_3等电解质溶液对含水卵磷脂液晶结构影响的SAXS研究

关于电解质溶液对卵磷脂液晶结构的影响前人有过报导。例如Chapman和G. Shiply等在研究碱金属氯化物对卵磷脂液晶结构的影响时指出:随着Li~ 到Cs~ 离子半径增加,脂双层的厚度也发生相应变化。Plainer等也指出KCI,NaCl溶液使磷脂层厚度发生变化。关于磷脂蛋白复合膜与Na~ ,K~ 、Ca~(2 )离子的作用也有一些报导。本文报导用小角X射线散射(SAXS)方法研究几种电解质溶液对卵磷脂形成液晶结构的影响。     

单分散SiO2体系制备中TEOS水解动力学研究

采用一种与他人不同的萃取－冷冻分离－气相色谱法,跟踪形成单分散二氧化硅体系条件下正硅酯乙酯（TEOS）的水解过程,考察了温度（25～45℃）、氨浓度（0．5～0．2mol•L－1）、水浓度（6．0～15．0mol•L－1）等实验条件范围内,以上实验参数对TEOS水解速度的影响;并回归得到目前适用于在乙醇介质中氨催化下,形成单分散二氧化硅微粒常用实验条件范围内,唯一的较完整的水解动力学方程式．     

NaCl、KCl、Na2CO3、K2CO3等电解质溶液对含水卵磷脂液晶结构影响的SAXS研究

This paper describs the structural character of liquid-crystal of 5%H_2O-egg yolk phospholipid (PC) containing in avarious salt's solution, the layer distance was determined by means of SAXS method. Experimental results show that the layer distance of liquid crystal phase is increased in the 5%H_2O-PC system as the amount of solution of NaCl or KCl is increased. But on the addition of Na_2CO_3 or K_2CO_3 solution into the 5%H_2O-PC system the layer distance of liquid-crystal phase is held constant. It is considered that Na_2CO_3 or K_2CO_3, might be hydrolyzed producing OH~- ions, so that the latter could stablize the interfacial potential between water and egg yolk phospholipid. Absence of this behavior for solution of NaCl or KCl might be due to NaCl and KCl are salts which formed by strong acids and strong bases.     

疏水增透SiO2膜的制备及其性能研究

以正硅酸乙酯(TEOS)和二甲基二乙氧基硅烷(DDS)为前驱体,在碱催化体系中通过选择合适的原料配比以及对体系溶胶 凝胶过程的控制使DDS和TEOS的水解产物发生共缩聚反应,进而制备出改性的SiO2溶胶,并采用旋转镀膜法(spin coating)直接获得了同时具有良好疏水和增透性能的SiO2光学膜,克服了增透膜防潮性能差的缺点.同时采用透射电子显微镜（TEM）、粒度分布（SDP）等手段研究了不同条件下溶胶的性质及其对膜层性能的影响,并与未经改性的SiO2增透膜进行了比较,结果表明改性后的膜层不仅疏水性大大增加,且在相同镀膜条件下,膜层的厚度随着老化时间的延长增加较小,故其透过率曲线在300～800 nm范围内不易出现多个增透峰.     

氨水诱导硅核自组装制备介孔SiO2

在无模板剂的条件下,通过控制氨水用量,利用正硅酸乙酯水解制备了粒径约20 nm的SiO2初级粒子;随后用过量氨水诱导SiO2初级粒子交联生长,得到孔径在10~50 nm、孔容达2.05 cm3.g-1的介孔SiO2;考察了介孔SiO2的吸附性能.结果表明,所制备的介孔SiO2具有优良的吸附性能.     

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.     

PbF2·SiO2基玻璃陶瓷的溶胶-凝胶制备及结构转变研究

采用溶胶-凝胶法制备了PbF2·SiO2纳米晶玻璃陶瓷块体;利用TG-DSC和IR技术分析了干凝胶在热处理过程中有机基团的分解及内部原子键合方式的演变;结合XRD和TEM研究了凝胶玻璃中PbF2纳米晶粒的长大过程,并分析了Er3+掺杂的影响.结果表明,采用此方法制备的PbF2.SiO2纳米晶粒玻璃陶瓷具有较好的成形性,晶化温度在320℃左右;经480℃热处理,镶嵌在玻璃基体中的PbF2晶粒尺度约为10-25nm,材料透明性良好.在PbF2·SiO2系统中掺入少量的Er3+,将提高PbF2的晶化温度,降低玻璃陶瓷的显微硬度;掺杂可能对PbF2晶粒表面原子的活性起抑制作用,阻碍晶粒的表面迁移,使晶粒的生长速度明显降低.     

PU/纳米SiO2溶胶杂化材料的前端聚合研究

前端聚合(FP)是通过在单体前端区域引发增长聚合将单体合成为聚合物的一种不同于传统的反应模式．它是一种通过局部反应区域在聚合物单体中的移动而将聚合物单体转变为聚合物的一种反应模式,主要运用在放热反应中,在反应初始阶段进行短时间的加热,然后停止加热,借助放热反应的热自催化完成单体的聚合。根据反应机理的不同,     

培养真核微生物矿化生成纳米SiO2构筑体及其表征

细胞模板;生物矿化;纳米结构SiO2;TEOS;Na2SiO3     

Multi-fractal imaging and structural investigation of silica hydrogels and aerogels

In this work, we report on the preparation of TEOS gels by means of the sol–gel method employing different TEOS/ethanol/water ratios at room temperature. Small-angle X-ray scattering (SAXS) measurements provide the first-generation structural parameters, which indicate that particle size and fractal dimension are synthesis and depth dependent. These results are supported by the second- and third-generation aggregates observed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The fiber-like first-generation clusters aggregate as spherical second-generation particles which, in turn, in the third generation rearrange into complex structures.     

培养真核微生物矿化生成纳米SiO2构筑体及其表征

硅在生物体沉积是自然界的普遍现象,SiO2是其存在的基本形式。本文选择真核间型酒香酵母、近似内孢霉酵母、黑根霉菌三种菌,利用生物矿化手段,采用正硅酸乙酯（TEOS）、Na2SiO3两种硅源进行生物纳米SiO2沉积实验,实验结果采用SEM、TEM、EDX、ED等表征手段进行了深入细致的研究,结果表明①间型酒香酵母沉积颗粒状SiO2纳米粒子;②近似内孢霉酵母沉积壳鞘状的SiO2纳米结构;③黑根霉菌沉积管状的SiO2纳米结构;④真核微生物能够利用TEOS,也可以利用Na2SiO3。说明真核微生物矿化与模板组成、表面张力、空间结构及硅营养等因素有关系,为利用真核生物矿化材料提供大量依据。     

酵母细胞为模板矿化合成SiO2纳米结构材料的研究

根据无机盐可以在生物细胞膜上沉积形成纳米结构材料的现象和生物矿化理论, 在人工培养条件下, 成功地以低等真核生物细胞-酵母菌为模板, 以正硅酸乙酯(TEOS)作为硅源, 矿化合成了一种壳鞘状的SiO2纳米结构材料, 厚度达150 nm左右, 并采用TEM、SEM、EDX、FT-IR、TGA等表征手段对实验结果进行了深入细致的研究, 获得了大量的实验数据, 为利用生物细胞模板合成介观尺寸有序SiO2纳米材料作出了有益的尝试.     

生物矿化合成纳米管状SiO2

生物体利用生物矿化作用,在有机分子模板上,通过蛋白和多糖生物分子的诱导及有机-无机界面分子识别自组装合成物貌形态可控的固态SiO₂结构。本文以真核生物细胞根霉菌为模板,以正硅酸乙酯(TEOS)作为硅源进行了生物矿化实验,并采用TEM、SEM、FTIR、XPS EDX、TGA等手段对实验结果进行了表征。结果表明,TEOS/培养基浓度为80 mg·L^-1时,矿化合成了一种厚度为5 nm的管状SiO₂纳米结构材料。     

Near-Infrared Spectroscopic Study for the Sol-Gel Reaction Using Alkoxysilanes

Near-Infrared spectroscopic studies on varying water contents in the sol-gel system using methyltriethoxysilane and tetraethoxysilane were performed. Water and silanol were clearly distinguished from alcoholic OH groups in the spectra. The change of water and silanol contents in acetone or 2-butanone was larger than those in alcoholic solvents. ¹H nuclear magnetic resonance spectroscopic measurement showed that hydrolysis and condensation reaction in methanol is faster than those in 2-butanone.     

利用聚合物乳液合成聚甲基丙烯酸甲酯/二氧化硅纳米杂化材料

通过正硅酸乙酯分别在聚甲基丙烯酸甲酯乳液和四氢呋喃溶液中的溶胶－凝胶反应制备出不同的聚甲基丙烯酸甲酯／二氧化硅复合材料。利用扫描电镜、透镜电镜、差热分析和热失重对试样进行了分析。结果表明,利用聚合物乳液可以获得纳米分散的聚甲基丙烯酸甲酯／二氧化硅复合材料,并且在某种程度上其分散尺度小于利用聚合物溶液获得的复合材料。同时,利用聚合物乳液来制备聚甲基丙烯酸甲酯／二氧化硅杂化材料更有利于凝胶过程中二氧化硅网络的形成。     

Silica-Polymers for Processing Gas Separation Membranes: High Temperature Growth of Fractal Structure

A study is performed to investigate the structure and shape of silicate molecules, grown from TEOS (tetra-ethyl-ortho-silicate) at 65°C, as building bricks for the preparation of gas separation membranes. The study is mainly carried out with in situ Small Angle X-ray Scattering (SAXS). The structure of the resulting silicate polymers could be interpreted in terms of fractals with a fractal dimension Df and a radius of gyration Rg.During the first minutes of reaction of TEOS with water in the presence of protons as catalysts fast hydrolysis take place with a heat effect of about 15–30 kJ/mol. Condensation (growth) of hydrolyzed species follows according to a diffusion-limited cluster-cluster aggregation (DLCCA). Growth is faster with higher amount of water and acid but a plateau-value is reached for both Rg and Df on a 60-hour timescale when a moderate amount of water or protons are present. These plateau-values are 15 nm and 1.8 for Rg and Df, respectively.The values of Rg and Df have large effects on gas separation performance of the resulting membranes made from these sols. With relatively small deviations in the values of Rg and Df a 2-decade difference in the permeation of helium through the membrane was observed.     

Structural models for homogeneous organic-inorganic hybrid materials: Simulations of small-angle X-ray scattering profiles

Two morphological models have been proposed to describe small-angle x-ray scattering from organic-inorganic composite (OIC) materials. The first model invokes the idea of a liquid-like arrangement among noninterpenetrating fractal clusters, and the second employs an empirical correlation function that would be expected for a bicontinuous two-phase (B2P) picture with the inorganic portion exhibiting fractal characteristics. Simulated scattering profiles have been generated for direct comparison with experimental data. The samples studied were a triethoxysilane-endcapped bisphenol A epoxide resin (EAS) reacted in the presence of tetraethoxysilane (TEOS) under slightly basic conditions, and a random trimethoxysilane-functionalized copolymer of poly(methyl methacrylate) (MMA-TMS) with added tetramethoxysilane (TMOS), reacted in an acidic medium. Each morphology model qualitatively simulates the broad scattering maximum and limiting high-angle slope commonly seen in SAXS profiles. It is concluded that the inorganic phase in the EAS hybrid exhibits particle-like characteristics at length scales less than approximately 250 Å, and the organic and inorganic components are bicontinuous at larger distances. The MMATMS composite is better described by bicontinuous organic and inorganic phases with a periodic fluctuation of about 40 Å. The scattering maximum arises either from the mean separation of particles or a dominant wavelength in a concentration fluctuation, similar to that observed for spinodal decomposition. In either case, the SAXS peak position is related to the distance between junction points of the crosslinked organic polymer. © 1995 John Wiley & Sons, Inc.