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。     

Preparation and Characterization of Porous Titania by Modified Sol-Gel Method

Mesoporous titania, especially anatase, is attractive due to its potential applications. A novel method to control pore structure of titania, surfactant- or polymer modification, is proposed. The wet gels and gel films, prepared from Ti(O-nC₄H₉)₄ were dried at 90°C and annealed at 500°C after immersion in surfactant or polymer solutions, and mesoporous anatase was obtained. The pore size, pore volume and specific surface area of the surfactant-modified bulk gels, estimated from N₂ absorption-desorption curves, are more than twice larger than those of the gels without modification. The pore size of the surfactant-modified gel films, observed by SEM, are similar to that of the bulk gels. The pore size obviously depended on the size of micelles. The pore size of the gels modified with hydrophilic polymers hardly increased, but the pore volume and the specific surface area increased.     

Preparation and Characterization of Molybdenum Oxide Thin Films by Sol-Gel Process

This paper presents a new sol-gel process to prepare molybdenum oxide thin films. A molybdenum acetylacetonate sol was prepared by employing the system CH₃COCH₂COCH₃/MoO₃/C₆H₅CH₃/HOCH₂CH₂OCH₃. A molybdenum acetylacetonate gel was prepared by addition of aqueous NH₃. Thermal gravimetry (TG) and differential thermal analyses (DTA) of the gel suggested that crystallization of MoO₃ occurs in a 140 K temperature range around 508°C. MoO₃ films were prepared on fused silica, Si (111) and Al₂O₃ (012) substrates by annealing spin coating films of the sol in oxygen environment at 508°C. X-ray diffraction (XRD) showed that all films crystallize in -MoO₃ structure, and crystallites on fused silica substrate are arbitrarily oriented while those on Si (111) and Al₂O₃(012) substrates oriented in the (010) direction. SEM investigations showed that MoO₃ grains of all films are randomly distributed, with a longitudinal dimension of about 1–5 m and the film thickness is about 1 m.     

Preparation and Characteristics of Porous Silica Films by a Modified Base-Catalyzed Sol-Gel Process Containing PVA: II. Film Preparation

Porous SiO₂ films were successfully deposited on silicon substrates by a modified base-catalyzed Sol-Gel process (MBCP) containing polyvinyl alcohol (PVA). The process conditions, such as the gelation time, the synthesis temperature, the stabilizing agent of the precursor solution and the spin coating speed, the heat-treatment, the annealing temperature of the film on the microstructure and porosity of porous SiO₂ films were systematically investigated by SEM, XRD and ellipsometry techniques. This study provides a novel preparation technique for the porous SiO₂ film. Using this process, the resultant film can reach a thickness of 3.6 m for one layer, a porosity of 25–50%, a low thermal conductivity of 0.11 W/m·K. This film will be used as a low dielectric layer, an thermal-insulating layer and a low refractive index layer.     

Titania-Doped Silica Fibers Prepared by Electrospinning and Sol-Gel Process

Titania-doped silica fibers were prepared by electrospinning of the sol of silica containing titania. The electrospun fibers had ribbon type morphology. The fibers had significant quantities of hydroxyl groups of Si—OH and Ti—OH. The fibers did not have crystalline structure. Diameters of the fibers were reduced by solvent evaporation and calcination. The hydroxyl groups on the fibers disappeared by calcination. The hydroxyl groups, M—OH (MSi, Ti) were changed to M—O—M by intermolecular and intramolecular condensation reactions.     

Synthesis and Characterization of Lead Sulfide Nanoparticles in Zirconia-Silica-Urethane Thin Films Prepared by the Sol-Gel Process

PbS nanocrystals (NCs) ranging between 4–8 nm were incorporated into Zirconium-Silica-Urethane (ZSUR) matrix obtained by the sol-gel method. The sizes of the particles were controlled by temperature treatment and by concentration of PbS in ZSUR matrix. The sizes of PbS NCs were determined by TEM measurements. The quantum size effect could also be extracted from optical absorption and photoluminescence spectra. The new matrix allows incorporation of up to 40% PbS forming a characteristic structure of dendrite by reacting lead acetate with ammonium thiocyanate in sol-gel matrix. The sol precursors of the matrix for Zirconium-Silica-Urethane contained zirconium oxide (ZrO₂) matrix solution, tetramethoxysilane (TMOS), 3-glycid oxypropyl trimethoxysilane (GLYMO) and polyethylene urethane silane (PEUS) synthesized separately. The ZrO₂ matrix solution was obtained from zirconium n-tetrapropoxide in propanol and acetic acid was used as a chelating agent to stabilize the zirconium oxide precursor.     

表面活性剂辅助酸催化溶胶-凝胶法制备高强度超亲水二氧化硅减反增透纳米粒子涂层

以正硅酸乙酯(TEOS)、十六烷基三甲基溴化氨(CTAB)、盐酸(HCl)、乙醇和水为原料,通过溶胶-凝胶法提拉涂膜,再经700 ℃快速淬火200 s,制备了二氧化硅（SiO2）纳米粒子涂层。 研究了CTAB浓度、提拉速度、停留时间和提拉涂膜次数对透射率的影响,结果表明,当CTAB质量分数为2.5%,提拉速度为100 mm/min,停留时间为60 s,提拉涂膜1次得到的SiO2纳米粒子涂层透射率最高,可达95.9%。 该涂层具备超亲水性并能耐受6H铅笔刮痕测试。 实验还表明,在SiO2溶胶液中加入CTAB,通过其与TEOS部分水解生成的物种的相互作用,可以改善酸性催化条件下形成的SiO2溶胶的微观结构,从而提高了涂层的透射率和亲水性。     

SiO2纳米粒子对溶胶凝胶涂层性能的影响

在高强钢表面制备了防护性溶胶凝胶涂层,并研究了不同浓度二氧化硅纳米粒子的加入对于涂层形貌、耐蚀性和硬度的影响。采用扫描电子显微镜(SEM)和电子能谱(EDS)观察了涂层的微观结构和成分;采用显微硬度计测试了涂层的硬度;采用电化学方法研究了二氧化硅纳米粒子的浓度对于涂层耐蚀性能的影响;采用傅里叶红外光谱研究涂层的化学结构,进而探讨了二氧化硅纳米粒子对于涂层的强化机理。结果显示涂层加入二氧化硅纳米粒子的最佳浓度为500 mg.L-1,此条件下的涂层表面均匀致密,有较高的硬度并且在3.5%NaCl溶液中体现出较好的耐蚀作用。纳米粒子在溶胶中反应形成活性羟基基团并与硅烷发生反应生成空间网状结构,从而强化涂层。     

Polyaniline/Silica Hybrid Composite Gels Prepared by the Sol-Gel Process

The preparation of polyaniline/silica hybrid gel was studied by chemical polymerization of aniline with sodium dodecyl sulfate (SDS) during the sol-gel processing. As a typical procedure, aqueous solutions of SDS, aniline, HCl, and tetramethoxysilane (TMOS) were mixed. Then ammonium peroxodisulfate (APS) in an acidic aqueous solution was added as initiator oxidant into the sol-gel systems at different sol-gel stages: (A) just after mixing (sol), (B) after gelation (wet gel), and (C) after 7 d (dried gel). As for the condition (A), several green areas and several tens of dark green spots with absorption peaks at 343, 422, and 802 nm were seen in the xerogel, indicating that emeraldine salt type polyaniline is aggregated in the silica xerogel. Polymerization of aniline little occurred in the dried gel (C), possibly because APS could not soak the silica pores and/or aniline could not polymerize in the gel. The xerogel from (B) showed a homogeneously green color with peaks at 339, 425, and 769 nm, showing that emeraldine salt type polyaniline can be uniformly dispersed in sol-gel silica.     

Synthesis and Characterization of Gelatin-Siloxane Hybrids Derived through Sol-Gel Procedure

A new type of inorganic-organic hybrid materials incorporating gelatin and 3-(glycidoxypropyl) trimethoxysilane (GPSM) was prepared through sol-gel processing. A solid-state ²⁹Si NMR analysis indicated that all the methoxy silane groups of GPSM were polymerized to yield —Si—O—Si— bridging bonds. An amino acid analysis confirmed grafting reactions of GPSM against gelatin chains. The increasing GPSM/gelatin ratio stimulated gel formation, phase separation, and the density of GPSM-crosslinking of the gelatin chains as well as it changed the micro- and macro- structures and the viscoelastic properties of the final products.     

Preparation and Characterization of BaTiO3 Long Fibers by Sol-Gel Process Using Catechol-Complexed Alkoxide

BaTiO₃ ceramic fibers were prepared by the sol-gel method in which catechol-complexed titanium isopropoxide and barium acetate hydrate were used as starting materials. The green fibers of ca. 30 cm in length were obtained from the precursor sols. The BaTiO₃ ceramic fibers with the average length of ca. 20 cm were of the order of 3 to 10 m in diameter and elliptical shapes in cross section. The green fibers and those sintered at different temperatures were characterized by TGA/DSC, XRD, IR, SEM and TEM techniques.     

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。     

溶胶-凝胶法合成杂化材料中的增容剂的应用

讨论了溶胶 -凝胶法合成有机 /无机杂化聚合物材料中的增容剂的应用 ,并详细介绍了三类增容剂的结构、增容机理和性能。     

Preparation of Optical Cores of Silica Optical Fibers by the Sol-Gel Method

Preforms for drawing silica optical fibers have been fabricated by using the MCVD method for the preparation of the optical claddings and the sol-gel method for the preparation of the optical cores consisting of TiO₂−SiO₂ or RE³⁺−Al₂O₃−P₂O₅−SiO₂ (RE=Er, Yb) glasses. A novel method has been developed for depositing thin gel layers on the inner silica tube wall, under rotation of the tube inclined at a small angle to the horizontal. The gel layers have been deposited from sols prepared by mixing Si(OC₂H₅)₄, POCl₃, Ti(n-OC₄H₉)₄, AlCl₃, ErCl₃, YbCl₃ H₂O, C₂H₅OH and HCl. The gel layers deposited using these sols on the inner tube wall were heat-treated in a flow of CCl₄ or POCl₃ with O₂ at temperatures of from 800° to 1400°C. After collapsing the composite tube into a preform, an optical fiber has been drawn. The refractive-index profiles of the preforms and the attenuation spectra of the drawn fibers are shown, as well as some results on the lasing characteristics of Yb³⁺ sensitized, Er³⁺ doped fibers.     

Preparation and Optical Properties of Sb2S3 Microcrystallite Doped Silica Glasses by the Sol-Gel Process

The sol-gel process has been applied to the preparation of nano-size Sb2S3 crystallite doped silica glasses and thin films. Silica glasses containing 1–1.5 wt% Sb2S3 are prepared by hydrolysis of complex solution of Si(OC2H5)4, SbCl3 and SC(NH2)2, and subsequent heat treatment. The nano-size crystallite in the matrix is observed by means of TEM. The transmission spectra of the films show that the transmission valley shifts toward longer wavelengths with increasing heat treatment time and temperature. Second harmonic generation (SHG) has been observed in the glasses illuminated with intense 1.06 m and frequency-doubled laser beams from mode-locked Nd:YAG laser.     

表面改性纳米SiO2复合聚合物电解质的制备及性能

通过化学方法将具有增塑效果的环状碳酸酯基团引入纳米SiO2表面,并用FTIR与TGA对改性纳米SiO2进行了表征.将改性纳米SiO2添加到以聚氧化乙烯(PEO)为基体的聚合物电解质中,制备了复合聚合物电解质.通过DSC和交流阻抗等方法对该聚合物电解质膜的热力学和电化学性能进行了研究.结果表明,掺杂改性纳米SiO2的聚合物电解质具有更高的离子电导率,室温最高离子电导率可达到1.84×10-5 S/cm;具有较高的锂离子迁移数,最高可达到0.49,且具有更好的界面稳定性.     

Synthesis and Characterization of Silver Sulfide Nanoparticles Containing Sol-Gel Derived HPC-Silica Film for Ion-Selective Electrode Application

Silver sulfide nanoparticles dispersed in sol-gel derived hydroxypropyl cellulose (HPC)-silica films have been successfully synthesized using H₂S gas diffusion method. This is the first attempt to produce silver sulfide nanoparticles using this technique. Ag₂S nanoparticles are generated through reaction of H₂S gas with AgNO₃ precursor dissolved in the HPC-silica matrix. Transmission electron microscope (TEM) and atomic force microscope (AFM) analysis reveal nanoparticles size distribution from 2.5 nm to 56 nm for H₂S gas exposed sample. The surface chemistry of Ag₂S nanoparticles and sol-gel derived HPC-silica matrix is confirmed by X-ray photoelectron spectroscopy (XPS). The negative shifts in the core-level XPS Ag (3d) binding energy of Ag₂S nanoparticles are attributed to Ag : S surface atomic ratio exhibited by these nanoparticles with varying processing conditions. Following processing and characterization, suitability of the present method to produce silver sulfide ion-selective electrode is demonstrated by depositing Ag₂S nanoparticles on a graphite rod. The high reponse function of the electrode is due to the presence of nanoparticles.     

Preparation and Characterization of TiO2 Thin Films by Sol-Gel Method

Titanium dioxide (TiO₂) thin films have been deposited on silicon and glass substrates by the sol-gel process using titanium iso-propoxide [Ti(O-i-C₃H₇)₄]. The bond configuration of the TiO₂ thin films was analyzed by using FTIR in the wavenumber range from 400 to 4000 cm^–1. The spectral transmittance of as-deposited TiO₂ films deposited on fused silica glass was measured in the wavelength range from 200 to 900 nm. X-ray diffraction measurements were performed to determine the crystallinity of the TiO₂ films. As-deposited films were amorphous. As the film was annealed at higher temperature, the structure was transformed from amorphous to the anatase crystalline state. The chemical composition of the deposited film was investigated using X-ray photoelectron spectroscopy (XPS). The films are essentially stoichiometric with carbon as the dominant impurity on the surface. Raman spectra show the characteristic of TiO₂ anatase phase. The electrical properties of the TiO₂ films were measured using capacitance-voltage (C-V) and current-voltage techniques. From C-V measurements, the dielectric constants were calculated to be approximately 26 for the as-deposited films and 75–82 for films annealed at 700°C in different atmosphere. For the as-deposited samples, the breakdown voltage was 2.7 MV/cm, and for an electric field of 1 MV/cm, the leakage current was 5 × 10^–5 A/cm² and the resistivity was 2.2 × 10¹⁰ -cm.     

Structural Study of Silica Xerogel Composites Containing Pd Aggregates

Composites containing Pd aggregates dispersed in amorphous silica are of interest from both a fundamental and applied point of view because of their attractive catalytic properties. The silica powders added with palladium, prepared by the sol-gel method, were studied using X-ray diffraction, and IR- and UV-Vis-spectrophotometry. Silica xerogel samples were prepared using a ethanol/H₂O/TEOS molar ratio of 4:11.6:1 and loaded with sodium tetrachloropalladate. The silica xerogel microstructure of the powders was studied as a function of annealing temperature. Attention was paid to the evolution of the glass matrix as well as the palladium aggregates in the SiO₂ matrix. We found in our samples partial crystallization of the glass matrix in form of quartz and cristobalite phases with palladium oxide and metallic palladium phase at 1000^∘C. The Rietveld refinement method was used in order to determine the percentage of the phase contents.     

溶胶—凝胶法制备有机—无机纳米复合材料

溶胶－凝胶法以其温和的反应条件，尤其是低的反应温度成为有机－无机纳米复合材料制备的最有效的方法．本文根据合成路线的不同，分５个方面对用溶胶－凝胶法制备复合材料进行概要介绍．