Structure and Electron Spin Resonance of Annealed Sol-Gel Glasses Containing Ag

In this work, SiO₂ samples with silver, prepared using the sol-gel method, were analyzed after being thermally treated in air in the range of 100 to 800°C. The sol-gel starting solutions were prepared by mixing tetra-ethyl-orthosilicate (TEOS), water and ethanol. Samples with 4 different H₂O/TEOS molar ratios (3.3, 5, 7.5 and 11.7 respectively) and with different nominal Ag concentrations were prepared (1, 2 and 4%vol. of Ag). It was found that upon annealing, different silver spices were formed, such as Ag₂ ⁺, Ag⁺, Ag°, and metallic silver aggregates. The identification of these spices was carried out by means of X-ray diffraction, Electron Paramagnetic Resonance (EPR), optical emission and optical absorption. It was also found that the specific type of silver spices observed depends on the structure of the SiO₂ matrix and on the annealing temperatures. It was found that samples prepared from precursor solutions with a low H₂O/TEOS ratio have a more open structure, and therefore silver diffuses faster and forms agglomerates at lower temperatures. Samples prepared from solutions with larger H₂O/TEOS ratios have a more dense structure, which allows the formation of atomic or molecular spices in addition to silver particles. A systematic study of this system was carried out using EPR on samples prepared from solutions having different H₂O/TEOS molar ratios, various Ag concentrations and subjected to different thermal treatments.     

FT-IR and Porosity Study of Si-B-C-O Materials Obtained from TEOS-TEB-PDMS Derived Gel Precursors

Mixed vitreous oxycarbide glasses containing silicon and boron were prepared by pyrolysis of hybrid precursors in N₂ at 1100°C. Four different precursors were synthesized through the sol-gel process using TEOS, TEB and PDMS. Poly-condensation between the Si(OH) groups, from the hydrolysed TEOS, and the PDMS was observed by FT-IR spectroscopy. Boron seems not to incorporate into the network until pyrolysis of the precursors that form the oxycarbides. The oxycarbides were porous made of spherical interconnected particles. The porosity and mean pore size of the glasses increased with increasing TEB content.     

具有光催化性能的TiO_2-SiO_2/TiO_2两层增透膜的设计与制备

采用膜层设计理论设计了以TiO2为内层膜,TiO2-SiO2复合膜为外层膜的两层增透膜,以钛酸丁酯(TBOT)和正硅酸乙酯(TEOS)作为前驱体,采用溶胶-凝胶法制备了TiO2溶胶以及SiO2溶胶,将两种溶胶按比例混合得到了TiO2-SiO2复合溶胶,在高硼硅玻璃上镀膜测试。透过率测试结果表明,在波长为550 nm处的透过率最高能达到99.4%。在光催化实验中,采用罗丹明B模拟有机污染物,考察了TiO2对光催化反应的影响。结果表明,在TiO2存在的情况下,罗丹明B的降解速度大大提高,光催化效率显著增加。     

具有光催化性能的TiO2-SiO2/TiO2两层增透膜的设计与制备

采用膜层设计理论设计了以TiO₂为内层膜,TiO₂-SiO₂复合膜为外层膜的两层增透膜,以钛酸丁酯（TBOT）和正硅酸乙酯（TEOS）作为前驱体,采用溶胶-凝胶法制备了TiO₂溶胶以及SiO₂溶胶,将两种溶胶按比例混合得到了TiO₂-SiO₂复合溶胶,在高硼硅玻璃上镀膜测试。透过率测试结果表明,在波长为550nm处的透过率最高能达到99.4%。在光催化实验中,采用罗丹明B模拟有机污染物,考察了TiO₂对光催化反应的影响。结果表明,在TiO₂存在的情况下,罗丹明B的降解速度大大提高,光催化效率显著增加。     

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。     

Composite of SiO2 and Hydrogel Having Microphase Separated Structure: Physical Properties Dependence on pH

Abstract

Organic-inorganic composite gel was prepared by using PEG-modified urethane acrylate (PMUA) gel and tetraethoxysilane (TEOS). PMUA gel was prepared by the phase-inversion emulsion polymerization of PMUA emulsion. The gelation of PMUA emulsion using this method enables PMUA gel to swell with H₂O, TEOS, and ethanol. Hydrolysis and condensation reaction rates of the sol-gel process are strongly influenced by the pH controlled by catalysts such as HCl and NH₄OH. Additionally, the morphology on the cross section of composite and the amount of silica ingredient incorporated into the composite gel were dependent on solvent, the molar ratio of H₂O to TEOS, as well as the pH value.

As the silica content increased, due to hydrogen bonds interacting between PMUA gel and SiO₂, particles, the tensile strength of composites considerably increased, whereas the elongation at break decreased. The incorporation of silica ingredient in PMUA gel/silica composites was verified with FTIR/ATR and SEM. The amount of the silica component in the composite was indirectly investigated by using TGA thermal analysis.     

POLYVINYLACETATE-SiO2 GELS OBTAINED IN HOMOGENEOUS MEDIA

Polyvinylacetate-SiO₂ gels have been obtained by radical polymerization of vinyl acetate (VAc) in the presence of tetraethoxysilane (TEOS). The reaction system was: VAc:TEOS:EtOH:H₂O:S (nonylphenol ethoxylated with 25 moles ethylene oxide) in different ratios. The reaction was performed at 65°C. The initiator of radical polymerization was benzoyl peroxide and a crosslinking agent of sol-gel process bis maleate of diethylene glycol. Traces of acetic acid, maleic acid or acrylic acid catalyze the polymerization of TEOS. The presence of the surfactant (S) ensures the homogeneity of the initial system. The conditions of obtaining homogeneous gels have been selected. Ternary diagrams containing TEOS:EtOH:H₂O or (VAc+TEOS):EtOH:H₂O:S were used in order to establish the domains of homogeneous compositions in the systems. Refractometric and conductometric measurements have shown that the mentioned systems are microemulsions. X-ray diffraction, surface area measurements, DTA/TGA method, as well as IR spectrometry have been used in the characterization of the gels obtained.     

Preparation and microstructure of sol-gel derived silver-doped silica

Silver-doped silica was prepared by hydrolysis and condensation of tetraethyl orthosilicate (TEOS, Si(OC₂H₅)₄) in the presence of a silver nitrate (AgNO₃) solution by two different synthesis methods. In the first synthesis route, sol-gel mixtures were prepared using an acid catalyst. In the second synthesis route, silver-doped silica gels were formed by two-step acid/base catalysis. For the same concentration of silver dopant [AgNO₃]/[TEOS] = 0.015 acid-catalyzed sol-gel formed a microporous silica with an average pore size of <25 Å whereas the two-step catalyzed silica had an average pore size of 250 Å and exhibited a mesoporous structure when fully dried. The differences in the pore size affected the silver particle formation mechanism and post-calcination silver particle size. After calcination at 800 °C for 2 h the acid-catalyzed silica contained metallic silver particles size with an average particle size of 24 ± 2 nm whereas two-step catalyzed silica with the same concentration of [AgNO₃]/[TEOS] = 0.015 contained silver nanoparticles with an average size of approximately 32 ± 2 nm. Mechanisms for silver particle formation and for silica matrix crystallization with respect to the processing route and calcination temperature are discussed.     

Heat of Reaction of the Hydrolysis-Polymerization Process of Tetraethyl Orthosilicate in Acidic Condition

Heat of reaction of the hydrolysis-polymerization process of tetraethyl orthosilicate with water in acidic condition was investigated to clarify the thermodynamic driving force of sol-gel reactions. Heat of reaction was measured using an isoperibol calorimeter by mixing a dilute tetraethyl orthosilicate (TEOS) ethanolic solution with another solution of water, ethanol, and hydrochloric acid. The temperature change of the reaction cell had been measured more than 24 hours after mixing under the quasi-isothermal condition. Large exothermic reaction (12.9 kJ·mol^–1 for 1 mole of TEOS) due to the hydrolysis of TEOS was observed. A slow exothermic reaction followed it, and after that, the sol-gel reaction was changed to a small endothermic one.     

SiO2-Iron Oxide Composites Obtained by Sol-Gel Method

Composite SiO₂-iron oxide materials were prepared by three experimental procedures. In the first case (1), the iron oxides were precipitated during the sol-gel process. In the second case (2), the SiO₂ matrix was initially obtained, and the iron oxides were formed by thermal treatment after impregnation of a soluble Fe²⁺ salt in the previously processed matrix. In the third method (3), ferrite powders, prepared by wet chemical method, were embedded into a SiO₂ based sol-gel matrix. Two type of precursors (tetraethoxysilane (TEOS) or methyltriethoxysilane (MTEOS) were used as SiO₂ sources. Various properties versus both type of precursor and on the method of preparation were noticed. Materials with high porosity and nano-sized iron oxide content could be prepared using the mentioned above methods.     

A Spectroscopic Study of the Effects of Various Solvents and Sol-Gel Hosts on the Chemical and Photochemical Properties of Thionin and Nile Blue A

Tetraethyl orthosilicate (TEOS)-based gels were doped with two optically active organic indicators, thionin and nile blue A. Before trapping in a sol-gel host, thionin and nile blue A were both evaluated for solvent and protonation effects on their spectral properties. Only extreme pH values provided by HCl, NaOH, and NH₄OH produced new absorption and/or fluorescence bands. Introduction of nile blue A into alkaline environments (0.1N NaOH, NH₄OH) results in the appearance of a broad absorption band centered near 520 nm whereas highly acidic environments (1N HCl) show a reduction of the 635 nm absorption peak accompanied by an absorption band located near 460 nm. A marked decrease is observed in the optical density of thionin in 1N HCl solution which results in a reduction in the fluorescence intensity. The absorption and fluorescence spectra also reveal a decrease in a pH 11 solution of NH₄OH as compared to neutral conditions. Both dyes formed dimers when the sol-gel host, initially synthesized with TEOS, was organically modified with methyltrimethoxysilane (MTMS). However, thionin dimers were present in all silica-based sol-gel compositions, as evidenced by the absorption and fluorescence spectra. Substitution of MTMS for some of the TEOS in the gel matrix resulted in blue shifts in the absorption and fluorescence spectra of nile blue A. The absorption peak shifted 50 nm to 596 nm whereas the fluorescence shifted around 40 nm to 635 nm. These blue shifts resulted from the reduced polarity of the silica-based xerogel. Thionin also exhibited shifts in its absorption and fluorescence spectra with organic modification by MTMS. The absorption shifted approximately 3 nm to 595 nm while the fluorescence maximum decreased 7 nm to 630 nm. The blue shifts in the spectra of thionin with additions of MTMS were attributed to surface sites that altered the molecular structure of the adsorbed thionin molecules.     

Coating and water permeation properties of SiO2 thin films prepared by the sol-gel method on nylon-6 substrates

Nylon-6 substrates were coated with SiO₂ thin films by the sol-gel method and their water permeability coefficient was evaluated. Methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) were used as starting materials. The addition of MTES to TEOS has enabled the formation of crack-free thin films on the substrates. The thin films strongly adhered to the substrates. The water permeability coefficients of nylon-6 substrates coated with these thin films decreased with the increase in the ratio of TEOS to the total alkoxides. The pretreatment of the nylon-6 substrates with -aminopropyltriethoxysilane was found to be effective to suppress the water permeability. The water permeability was suppressed by about 40% under the optimal condition.     

Immobilization of Bromocresol Purple in Inorganic-Organic Sol-Gel Thin Film with Presence of Anionic and Non-ionic Surfactants

Sol-gel materials known as organically modified silicates (ORMOSILs) offer interesting features such as chemical and mechanical stability. In this paper VTES (vinyltriethoxysilane) and TEOS (tetraalkoxysilane) are mixed in 3:1 ratio. Sol-gel solution was prepared by hydrolysis process of precursors by using ethanol as solvent. After a while a pH-sensitive indicator bromocresol purple (BCP) and surfactant were incorporate into the sol-gel mixture. The percentage of sodium dodecyl sulfate (SDS) and polyethylene glycol (PEG) which act as surfactant were varied to observe the effect of improving host material's nanostructure as well as the interaction between BCP and sol-gel matrices. The absorption peak of the BCP dye changed significantly in the presence of surfactant compared to pure VTES: TEOS mixture (control) in the range of 400 to 450 nm. The presence of BCP dye in the sol-gel mixture can be determined via FTIR spectrum with a =C–H stretch in aromatics observed at 3100-3000 cm^-1 which represented the aromatic of the BCP structure. The addition of BCP and surfactant had influenced the FTIR spectra of VTES: TEOS sol-gel materials. Addition of an anionic surfactant to the sol-gel mixtures was found to increase the BCP dye and the sol-gel matrices interaction, thus reducing the dye's tendency to leach. This work shows that sol-gel derived matrices yield dyes with sufficient rigid environment and addition of the surfactant helps to improve the interaction of filler matrices. The anionic SDS shows better leaching resistant compared to non-ionic PEG surfactant. Results of this study offer an attractive possibility to optimize the doped sol gel matrices to be used as sensing material in aqueous condition.     

Use of the sol-gel technique to prepare capillary columns coated with a macrocyclic dioxopolyamine for open-tubular capillary electrochromatography

Summary Columns for open-tubular (OT) capillary electrochromatography (CEC), coated with 1,4,7,10-tetraazacyclotridecane-11,13-dione (dioxo[13]aneN₄) by use of the sol-gel technique, have been investigated for the first time. Dioxol[13]aneN₄ was reacted with 3-(2-cyclooxypropoxy)propyltrimethoxysilane and the product was then mixed with tetraethoxysilane (TEOS) and water to form a glass matrix as a network in which the stationary phase (dioxo[13]aneN₄) was incorporated. In comparison with OTCEC columns prepared by the sol-gel process with TEOS only, the sol-gel-derived macrocyclic dioxopolyamine columns enabled better separations of a mixture of isomeric nitrophenols and benzenediols, a mixture of isomeric aminophenols and diaminobenzenes, and a mixture of four biogenic monoamine neurotransmitters. High efficiencies (60 000—340 000 plates m⁻¹) were achieved for isomeric benzenediols, aminophenols, nitrophenols, and diaminobenzenes. Migration time and theoretical plate number reproducibility was satisfactory;RSD was <2% for one column and <8.5% from column to column.     

Methyltriethoxysilane-derived sol-gel coatings doped with silver metal particles

Silica sol-gel films were prepared by dipping, starting from an acid catalyzed solution of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS). Silver metal nanoparticles were produced in the silica layer by introducing in the sol-gel precursor solution AgNO₃ or AgClO₄·H₂O. The silver ions were thermally reduced in air at 800°C, giving an intense yellow coating film. The silver metal particles were observed by transmission electron microscopy and X-ray diffraction. The diameter of the silver particles was found to be about 10 nm. Absorption measurements in the UV-Vis were used to evaluate the volume fraction of silver colloids embedded in the silica layer.     

Preparation and Spectroscopy of Aluminosilicate Films Deposited on Graphite Surfaces via an Anhydrous Sol-Gel Route

Anhydrous aluminosilicate sols with Al : Si molar ratio ranging from 1 : 10 to 1 : 5 were prepared by a two-step anhydrous sol-gel process, in which tetraethoxysilane (TEOS) is pre-hydrolysed by formic acid, followed by addition of aluminium ethoxide. Unlike the case of aqueous sol-gel routes, where the Si–O–Al network homogeneity is greatly restricted by precipitation of Al(OH)₃, this anhydrous route yields clear, homogeneous sols. The sol formation and densification processes were investigated by infrared spectroscopy and X-ray powder diffraction (XRD) techniques, and the existence of Al–O–Si linkages was confirmed. To demonstrate an application of the anhydrous sol-gel process, aluminosilicate films were deposited onto graphite surfaces by dip coating and densified at 800°C under nitrogen, and their protective effect was evaluated.     

Preparation of Saccharide-Silica Composites by a Sol-Gel Method and the Application for Optical Resolution of Metal Chelate Compounds

A novel organic-inorganic composite was prepared by a sol-gel process using hydrolysis and condensation of tetraethoxysilane (TEOS) reacted with a saccharide. During the process, ethoxy groups of the TEOS were replaced with hydroxyl groups of the saccharide and, consequently, saccharide molecules were combined with silica through their hydroxyl groups. Samples obtained under different reaction conditions were used for optical resolution of a metal chelate compound. The resolution ability of the composites was affected by the amount of water added for hydrolysis and of the saccharide. In particular, the amount of water drastically influenced the optical resolution performance. Composites obtained at the lower H2O/TEOS ratio gave the metal chelate compound a higher optical rotation. Three types of composites with the same composition were prepared by kneading, impregnation and by the sol-gel method, and were compared. The sol-gel composite showed the best optical resolution ability. It was concluded that the optical resolution ability was closely related to dispersibility of saccharide in the silica matrix.     

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。     

Preparation of nonwoven polyimide/silica hybrid nanofiberous fabrics by combining electrospinning and controlled in situ sol-gel techniques

A controlled in situ sol-gel synthesis combined with the electrospinning technique and postspun imidization was applied in the fabrication of polyimide/silica hybrid nonwoven nanofiberous fabrics with excellent thermal and mechanical performance. The nanofiberous fabrics were prepared by electrospinning of the solution of tetraethoxysilane (TEOS) and polyamic acid (PAA). The different silica contents in the fabrics were achieved by varying the amount of TEOS while fitting the solid content of PAA. The final polyimide/silica fabrics was obtained after imidization of PAA and gelation of silica phase simultaneously accomplished through a step-wise heating process. Some specific IR techniques and other characterizations indicated the successful incorporation of the silicon dioxide (SiO₂) into the PI matrix and the relatively even distribution of the SiO₂ in the fabrics. An increase of 133 °C in the decomposition temperature and 4-fold enhancement of the ultimate tensile strength were achieved for the hybrids with a 6.58 wt.% of SiO₂ content, compared to the pure PI fabric. The excellent performance could be attributed to the good compatibility between the polyimide and silica, and good adhesion among the fibers, which resulted from the controlled TEOS hydrolysis and the simultaneous imidization and gelation process.     

Influence of Sol-Gel Synthesis Parameters on the Microstructure of Particulate Silica Xerogels

The influence of key sol-gel synthesis parameters on the pore structure of microporous silica xerogels was investigated. The silica xerogels were prepared using an acid-catalyzed aqueous sol-gel process, with tetraethoxysilane (TEOS) as the silicon-containing precursor. At high H2O : TEOS ratios, sols synthesized at pH 2–3 yielded minimum values of mean micropore diameter and micropore volume. Analysis of the resulting Type I nitrogen adsorption isotherms and the equilibrium adsorption of N(C4F9)3 indicated micropore diameters for these xerogels of less than approximately 10 Å.Xerogel micropore volumes corresponding to sols prepared at pH 3 and an H2O : TEOS ratio of r = 83 were consistent with nearly close packing of silica spheres in the xerogel. Xerogel microstructure was only weakly dependent upon H2O : TEOS ratio during sol synthesis for r > 10. Xerogel micropore volume increased rapidly with sol aging time during an initial induction period of particle formation. However, the xerogel microstructure changed only slowly with time after this initial period, suggesting potential processing advantages for the particulate sol-gel route to porous silica materials.Surface adsorption properties of the silica xerogels were investigated at ambient temperature using N2, SF6, and CO2. CO2 adsorbed most strongly, SF6 also showed measurable adsorption, and N2 adsorption was nearly zero. These results were consistent with the surface transport of CO2, and to a lesser extent SF6, observed in gas permeation studies performed through thin membrane films cast from similarly prepared silica sols.