溶胶-凝胶法制备有机/无机杂化材料工艺及其应用

介绍了溶胶–凝胶法制备有机/无机杂化材料的原理和基本过程,杂化材料的制备方法及对材料性能的影响,概述了杂化材料在结构材料、光学材料及其它材料中的应用研究。     

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.     

Preparation of Silica-Based Inorganic-Organic Hybrid Membrane via the Sol-Gel Route

Silica-based inorganic-organic hybrid membranes have been prepared on porous -Al₂O₃ substrate (pore size, 2 m) using tetraethoxysilane (TEOS) and phenyltrimethoxysilane (PTMOS) as precursors. The effects of sol synthesis conditions on the processing and performance of deposited hybrid layers were observed. The thickness of the hybrid layers after three deposition cycles is about 2 m, estimated from their cross-section SEM micrographs. The gas permselectivity of the hybrid membrane was characterized by O₂/N₂, CO₂/N₂, and CO₂/O₂ mixing gases, which was mainly governed by the surface diffusion at lower pressures and Knudson diffusion at higher pressures. The introduction of phenyl groups can not only improve the selectivity of O₂/N₂ and CO₂/N₂, but also densify the membrane network.     

Hybrid Organic-Inorganic Sol-Gel Materials Based on Epoxy-Amine Systems

Understanding the synthesis-structure-properties relationship of hybrid organic-inorganic materials is an important and fundamental task to develop a new generation of highly performing systems for the new needs of nanotechnologies. This issue is, also, important to improve the properties of hybrids when used in applications where nanoscale control is not a fundamental request. In this article, a short overview of epoxy amine sol-gel hybrids is reported. The synthesis of these materials has a large flexibility to allow the fabrication of a wide group of hybrids with different structures and properties, whose applications are ranging from non-linear optics to adhesive and protective coatings.     

Synthesis of New Hybrid Organic-Inorganic Alumina Gels by the Sol-Gel Method

New hybrid organic-inorganic alumina gels have been prepared by reacting aluminum sec-butoxide and propane-1,2-diol, in CCl₄ as solvent. This reaction occurred without water addition and without the use of any catalyst, leading to the formation of transparent and monolithic gels. IR,²⁷Al and¹³CNMR show that an interchange reaction between OBu ^s alkoxide groups and diol groups occurred, leading to the hybrid gels. Samples heat treated at different temperatures under argon are weakly porous and have a small specific surface area. XRD indicates the presence of pure α-alumina at 1450°C.     

有机-无机杂化硅胶基质整体柱的制备及其电色谱性能

采用溶胶-凝胶法,以四乙氧基硅烷和苯基三乙氧基硅烷作为反应单体,通过酸碱两步催化在毛细管中进行原位缩聚反应,制备了新型有机-无机杂化硅胶基质毛细管整体柱,制备过程简单。整体柱基质中均匀分布的苯基基团可直接用于反相毛细管电色谱的分离,因而不需要对基质再进行衍生化。优化了整体柱的制备条件,采用扫描电镜和压汞法对整体柱的微观结构和孔径分布进行了表征。分别考察了溶胶-凝胶初始反应液中水的用量对柱床结构的影响和两种单体的配比对材料孔径分布的影响。研究了稠环芳烃类化合物在整体柱上的保留行为,用所制备的整体柱分离了7种苯酚类化合物,平均柱效达100000塔板/m。     

Titan Based Hybrid Organic-Inorganic Gels Comprising Carbohydrate Moiety

Abstract

A series of titanium based gels comprising carbohydrate moieties was synthesized. The sugars used include a specific hydrazide group as complex forming agent. Additionally, this group forms stable hydrates which allow further slow water release. As a result, the compounds used in this study form transparent and stable gels with titanium alkoxide without addition of external water. Interpretation of the IR-spectra reveals that some compounds form monodentate ligands and other bidentate ligands. Further Tian-Calvet calorimetric measurements confirmed our IR-based conclusions. This strategy of synthesis gives a new opportunity to obtain hybrid materials by addition of natural chelating ligands to slow down the hydrolysis/condensation reactions that occur during the sol-gel process. Therefore, carbohydrate moieties have been incorporated in the gels obtained and different type of Ti coordination was proposed based on the IR spectroscopy studies. SEM investigations show the influence of the ligand on the morphology of the xerogel.

GRAPHICAL ABSTRACT      

溶胶-凝胶工艺制备发光薄膜研究进展

本文综述了通过深胶－凝胶工艺制备发光薄膜的基本过程、薄膜的表征方法、发光薄膜的当前发展及应用情况。依据组成特点,对溶胶－凝胶法制备的发光薄膜乾地了分类阐述,并预言了今后该法制备发光薄膜的发展趋势。     

Synthesis and Characterisation of Aluminium-Zirconium Based Organic-Inorganic Materials via Sol-Gel Route

Monolithic and transparent hybrid Al-Zr gels were obtained by the reaction of homogeneous mixtures of metal alkoxides: (Al(OBu^s)₃ + Zr(OPr)₄) with Butan-1,3-diol at room temperature, without solvent, catalyst, or water. The products have been characterized by IR spectroscopy, DTA and TGA. The results show that the diol has reacted with the mixture of alkoxides leading to the monolithic transparent gels in which both organic-inorganic (–Al–O–R–O–Zr–) and inorganic (–Al–O–Zr–O–) bridges are formed.Xerogels obtained after the drying of gels were pyrolysed at different temperatures in air. The structure and morphology of the obtained materials were studied by X-ray powder diffraction (XRD) and the Brunauer-Emmett-Teller (BET) method. At 1200°C, the materials were composed of Al₂O₃, t-ZrO₂ and m-ZrO₂.     

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。     

Structural Analysis and Properties of Organic-Inorganic Hybrid Ionic Conductor Prepared by Sol-Gel Process

Organic-inorganic hybrid lithium ion conductors were prepared by the sol-gel process. The hybrid ion conductor will be used as the electrolyte for Li based high-energy density batteries. The hybrid ion conductor was prepared from a mixture of tetramethyl orthosilicate (TMOS), polyethylene glycol 200 (PEG₂₀₀), lithium perchlorate (LiClO₄) and water. A wet gel was prepared at room temperature. The gels dried at 80°C under vacuum did not contain water. The dried hybrid ion conductor gel had homogeneity and high transparency. Ionic conductivity of the hybrid sample was measured by the complex impedance method and it increased with increasing PEG₂₀₀ content. The dried hybrid gel that contained no LiClO₄ did not show ion conduction. Conductivity on the order of 10^–5 S·cm^–1 at room temperature was obtained. Structural characterization was done by Fourier Transform Infrared Spectra (FTIR) and NMR measurement of ¹³C and ¹H, and the thermal stability and glass transition properties were studied by DSC. Glass transition temperature decreased with increasing PEG₂₀₀ content and increased with increasing [Li]/[O] ratio (the oxygen considered is from the polyethylene glycol). Existence of the Si–O–(C₂H₄O) _n –bond and the C–OH bond in the framework of the organic and inorganic phases was confirmed. TMOS and PEG₂₀₀ were hydrolyzed and condensed. The organic and inorganic phases were chemically bonded and the microstructure of the hybrid matrix was shaped as comb. The comb shape leads to high ionic conduction.     

烷氧基硅烷溶胶-凝胶反应机理

利用烷氧基硅烷作为前驱体之一,进行溶胶-凝胶(sol-gel)反应制备无机氧化物和有机－无机杂化材料,近几十年来一直是一个研究热点。对烷氧基硅烷的sol-gel反应过程,特别是起始的水解和初步缩合过程已有较多的研究。本文综述了烷氧基硅烷的sol-gel反应机理研究的进展,并对未来发展提出了看法。     

Vanadium-Based Organic-Inorganic Hybrid Materials Prepared by a Sol-Gel Method

Synthesis and characterization of hybrid organic-inorganic nanocomposites based on reaction of vanadium i-propoxide with an organically functionalized poly(ethylene glycol) having di-carbonyl groups is reported. The bulk gels were characterized by thermal analyses (DSC, TGA and TMA) and FT-IR spectroscopy. The results revealed that the gels consist of vanadium-oxygen-vanadium groupings which are cross-linked with the functionalized polymer through the di-carbonyl groups. Gels doped with lithium salt show significant electrical conductivity.     

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.     

Nanostructured Silica-Based Organic-Inorganic Hybrid Materials-Evidence for Self-Organization of a Xerogel Prepared by Sol-Gel Polymerization

A hydrolytic polycondensation reaction of a rigid, rodlike nonmesomorphous precursor leads to an isotropic sol and then an anisotropic birefringent xerogel (see scheme). Optical and X-ray structural analyses demonstrate a short-range order and the possibility of a crystalline order.     

Ethylene Glycol-Citric Acid-Silica Hybrid Organic-Inorganic Materials Obtained by the Sol-Gel Method

The combination of inorganic polymeric networks with organic molecules leads to hybrid materials. Tetraethoxysilane (TEOS) was used as the precursor for the inorganic component, covalently bonded to ethylene glycol (EG) and citric acid (CA) molecules, whose esterification provides the in situ water for hydrolysis of TEOS. Ethanol was added in various amounts to the TEOS-EG-CA mixtures in order to induce different molecular separations among the reacting molecules, thus modifying the molecular weight distributions of the resulting materials. Characterization of these hybrid materials was performed by several techniques, with consistent results among them. The materials obtained are thermoplastic systems which can be used as coatings, or as bulk materials. In particular, their rheological and thermal properties suggest their possible use as components of drilling fluids in the tertiary recovery of petroleum.     

Atomic Force Microscopy Study of TiO2 Films Obtained by the Sol-Gel Method

Atomic Force Microscopy (AFM) was used to study the influence of thermal treatments on the structural and textural properties of the sol-gel TiO2 films obtained from Ti(OC3H7i)4. X-ray diffraction (XRD), ellipsometric and porosity measurements have also been made.The TiO2 sol-gel films were homogeneous, transparent and amorphous. Heat treatments in the 400–600°C range indicate that the films have a strong tendency to crystallization. The high initial homogeneity of the TiO2 films was preserved during the crystallization process. AFM shows that the thermally treated films exhibit uniform, monodispersed crystals.     

Ferroelectric Properties of Modified Lead Titanate Thin Films Obtained by a Sol-Gel Method

Calcium substituted lead titanate thin films have been prepared by a sol-gel method, deposited by spin-coating, and thermally treated so as to obtain a perovskite structure. Two types of thermal treatments were given, differing in the heating rate, which in conventional treatments was of some 10°C/min, and in rapid treatments >500°C/min. With rapid heating, materials are obtained in which greater polarizations are commuted and bias fields are smaller. This, together with the fact that additional (undesired) phases are not observed by X-ray diffractometry when rapid treatments are used, shows that these are to be preferred over conventional treatments.     

Sol-Gel Processing of Organic-Inorganic Nanocomposite Protective Coatings

Organic-inorganic nanocomposite protective coatings are prepared on aluminum substrates by the spinning technique with the concept of incorporating homogeneously nanosized particles (of AlOOH, Al2O3, ZrO2, SiC) into molecular organic-inorganic hybrid matrices. The hybrid matrices are prepared from epoxysilane and bisphenol A with imidazol as catalyst. The AlOOH particles are derived from aluminum isoprooxide and introduced into the hybrid sols directly, and Al2O3, ZrO2, SiC particles are first surface-modified with Si–OH from hydrolyzed TEOS. The coatings are dense, smooth and flexible and inhibit corrosion.     

Thermal Evolution of Hybrid Organic-Inorganic Gels Derived from Reaction of 1,4 Butanediol with Tetraethoxysilane

Transparent monolithic discs of organic-inorganic hybrid gels have been prepared by hydrolysis-condensation reactions of tetraethyl orthosilicate with 1,4 butanediol. The gels and glasses have been characterized by infrared spectroscopy and ²⁹Si MAS NMR. The characterization of the gels by infrared spectroscopy showed the incorporation of carbonaceous groups in the polymeric structure and Si–C bonding in the glasses. Pyrolysis of the gels has been studied using thermal analysis. It showed that the pyrolysis of the gels occurs in two temperature domains. The first is below 400°C due to condensation reactions and second is in the temperature range 450–550°C due to decomposition of carbonaceous groups and crosslinking. Pyrolysis of the gels at 1000°C resulted in X-ray amorphous, hard black glasses similar to oxycarbide glasses obtained by pyrolysis of siloxanes. On further heat treatment to 1400–1600°C, development of cristobalite structure and crystalline silicon carbide is observed in the otherwise amorphous black mass. The pyrolysed materials have been found to exhibit good resistance towards oxidation at 1000°C.