Organic-Inorganic Insulating Coatings Based on Sol-Gel Technology

The approach for improving bending strength of temperature-resistant flexible ceramic electric insulating coatings prepared by sol-gel processing is considered. Starting suspensions, based on both tetraethoxysilane (TEOS)-derived modified sols and highly dispersed fillers such as Cr₂O₃, are used to deposit the coatings on metals and alloys. Some polymers and organic substances are tested as additives for improving flexibility of the ceramic coatings. The results of study of both bending strength and electrical strength of flexible hybrid organic-inorganic insulation formed on a nichrome wire are discussed. The data obtained on the chemical and phase structure of the coatings, which have been heat treated at temperatures from 95 to 1100°C, using DSC as well as X-ray scattering techniques are presented.     

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.     

有机-无机杂化溶胶-凝胶涂层对不锈钢毛细管柱的脱活作用研究

 用甲基三乙氧基硅烷和四乙氧基硅烷水解缩合后形成的有机 无机杂化溶胶 凝胶 (sol gel)涂层对国产气相用不锈钢毛细管柱进行脱活。通过气相法研究了不同老化温度下所得脱活涂层的行为。结果表明这种涂层不但对不锈钢柱内壁活性点有很好的遮盖作用 ,而且本身具有相当的分离能力。在 2 5 0℃下老化的涂层可使碳原子数在 12以下的正构烷烃达到基线分离 ,与未用涂层的不锈钢裸柱相比 ,吸附活性大大降低 ;但随着老化温度的升高 ,涂层在缩聚老化过程中产生不均匀微孔 ,对被分离物的作用力加强。     

Adhesion of Sol-Gel-Derived Organic-Inorganic Hybrid Coatings on Polyester

Inorganic coatings, including metal-oxide coatings, provide polymer surfaces with excellent abrasion and wear resistance, and protection against environmental degradation. However, one drawback associated with the incorporation of such ceramic coatings to polymeric materials is the adhesion characteristic at the ceramic-polymer interface. In this paper, two strategies for adhesion enhancement of ceramic coatings on polymer substrates were proposed: (1) formation of chemical bonds through surface condensation reactions, and (2) development of interlocked ceramic and polymeric networks through diffusion of alkoxide precursors. The current research has focused on the adhesion of sol-gel-derived organic-inorganic hybrid coatings on polyester by forming chemical bonds between the polymer substrate and the hybrid coatings, as well as developing interlocked polymeric and inorganic networks at the interface. Contact angle, wettability tests, and chemicalanalysis were done to verify the effectiveness of the adhesion of organic-inorganic hybrid coatings on polyester substrates. In addition, dry and wet thermal cycling tests were done to analyze the adhesion behavior of the hybrid coatings on polyester, followed by microscopy examination. It was found that although both approaches resulted in excellent adhesion of hybrid coatings on polyester, adhesion with interlocked ceramic and polymeric networks was far better than that with chemical bonds in the presence of water at elevated temperatures.     

Enhancement of the Photochromic Performance of Spirooxazine in Sol-Gel Derived Organic-Inorganic Hybrid Matrices by Additives

Organic-inorganic hybrid materials synthesized via sol-gel processing are excellent solid matrices for photochromic dyes like spirooxazine, and the photochromic performance can be further enhanced by introducing suitable additives. This work describes the effects of additives on the photochromic intensity (ΔA ₀), decolouration rate (k) and photostability of spirooxazine in sol-gel derived organic-inorganic hybrid matrices. They include fluoroalkylsilane (FAS), bisphenolA (BPA) and methyl-imidazole (MI). FAS enhances both ΔA ₀ and photostability, but has little effect onk. The higher the content of BPA, the higher the ΔA ₀ and the higher the photostability, but the lower thek. The effect of MI on ΔA ₀ andk is not so considerable as that of BPA and is a little complicated, while significant improvement in photostability is achieved by the addition of MI at an optimum concentration with the presence of BPA at a higher content.     

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．     

有机-无机纳米复合水凝胶*

本文综述了近年来有机-无机纳米复合水凝胶领域的研究进展。针对无机成分的不同种类及复合形式,本文将目前已见报道的有机-无机纳米复合水凝胶划分为三类,分别为层状硅酸盐纳米插层复合水凝胶、粘土交联纳米复合水凝胶和二氧化硅纳米杂化复合水凝胶。阐述了三类纳米复合水凝胶的发展趋势,特别就它们的合成方法进行了详细归纳与总结。在此基础上,介绍了纳米无机成分对复合水凝胶的性能增强机理,并就三者之间的增强差异进行了说明。     

Photochromism of Peroxotungstic Acid/PVP Nanocomposite Obtained by Sol-Gel Method

Peroxotungstic acid (PTA)/PVP composite film was prepared via sol-gel method. TEM revealed that the composite films consist of peroxotungstic acid nano-grains embedded in amorphous PVP matrix. The samples were observed to exhibit reversible photochromic effect when irradiated with solar light. The iodometric titration and FT-IR spectra indicated the presence of peroxo groups (W–O–O–W) incorporated into PTA structure. EPR measurement revealed the presence of unpaired paramagnetic electrons in PTA/PVP nanocomposite gel. The UV-Vis-Nir transmittance spectra and EPR spectroscopy of sample indicate that the photochromic behaviour is due to the photo-excitation of the unpaired electrons at W–O octahedral sites of peroxotungstic acid.     

Improving Anti-frosting Performance for Super-hydrophobic Nanocomposite Coatings

Super-hydrophobic surfaces with water contact angle (WCA) higher than 150o have attracted great attention these years1, due to their scientific values and potential technological applications as antifouling coatings, non-sticking coatings, and so on. Alth…     

Optical Nonlinearity of Hybrid and Nanocomposite Materials Prepared by the Sol-Gel Method

In this paper the nonlinear refractive index, optical limiting effect, photoinduced and electroinduced second harmonic generation of dye-doped hybrid and nanoparticle-doped composite materials prepared by the sol-gel process have been reported. The origin of these nonlinear optical effects has been discussed.     

High Precision Diamond Machining of Hybrid Sol-Gel Coatings

Flexible and economic production of complex reflective optical elements is achieved by high-precision machining of aluminum and copper with diamond tools. There is also an increasing demand for complex refractive optical elements like micro lens arrays, Fresnel lenses or prismatic surfaces on silicon wafers or metallic surfaces. For the production of these optical elements, hybrid sol-gel coatings based on methacryloxypropyltrimethoxysilane (MATMS) and zirconium (IV) tetra n-propoxide (ZTP) were deposited on aluminum substrates by spin-coating. The influence of the rotational velocity and the chemical sol composition on the coating thickness was determined. The hardness and elastic modulus of these coatings was measured as a function of the chemical composition. The machining characteristics of these coatings were investigated by high precision turning and fly cutting with diamond tools of different geometry. The resulting surface finish obtained was determined as a function of the machining parameters.     

Bioactive and Protective Sol-Gel Coatings on Metals for Orthopaedic Prostheses

The aim of this work has been the preparation and evaluation of sol-gel coatings for clinical applications. Research was focussed in the development of highly corrosion resistant and/or bioactive sol-gel coatings onto AISI 316L stainless steel. Hybrid SiO₂ sol-gel coatings inhibited corrosion and Fe diffusion, although no signal of bioactivity was detected. The inclusion of Ca- and P-alcoxides in the sol composition did not promote bioactivity. Bioactive coatings were obtained from suspensions prepared by adding glass (CaO·SiO₂·P₂O₅) particles to an hybrid organic-inorganic SiO₂ sol. The dissolution of glass particles promoted in vitro induction of apatite along with a slight reduction in the corrosion resistance of coated pieces. By combining an inner SiO₂ hybrid film acting as barrier against corrosion with an outer coating containing bioactive glass particles, a significant improvement in the electrochemical behaviour was observed. This double-layered coating showed in vitro signals of bioactivity, and preliminary in vivo tests gave promising results.     

Sol-Gel Coatings for the Protection of Brass and Bronze

The effectiveness of sol-gel Ormosil coatings as barriers coatings has already been demonstrated, and it is natural to assume that such coatings can play a unique role in art conservation, where object corrosion and decay are often a major issue. The main feature of ormosil coatings that would make them preferable to polymers is their potentially higher stability to ultra-violet radiation, controlled porosity and good adhesion to many different substrates. The permeability to various gases can also be tailored with changes in the chemical structure. In previous work, we have applied the sol-gel process as part of a multiplayer coating in the conservation of the Last Judgment mosaic in Prague. In the present work, we explore the use of sol-gel organic-inorganic hybrid coatings on various copper alloy substrates frequently encountered in art conservation.     

Synthesis and Characterization of Transparent Hydrophobic Sol-Gel Hard Coatings

It is challenging to make a transparent hydrophobic hard coating when soft hydrophobic additives are added into the coating system. Material non-homogeneity due to phase separation, non-durable hydrophobicity and deteriorated transparency are the main issues. In this paper, we describe a chemical formulation, which contains a pre-linked hydrophobic cluster and a silica hard matrix with silica hard fillers so that the hydrophobic property and hardness can be tuned separately and optimized. The transparency of the coating is found to be related to the effective modification of the reactive titanium tetraisopropoxide (TIP) precursor by ethyl acetoacetate (EacAc) and the right ratio between TIP and polydimethylsiloxane (PDMS) (≤0.5). The water contact angle is increased to a maximum of 133° when 50 Vol% of PDMS is added into the silica matrix. The hardness of coating is proportional to silica filler content and curing temperature, and inversely proportional to PDMS Vol%. 30 Vol% silica filler in silica matrix and curing temperature at 300°C result in the best hardness in this study. Hardness at 50 Vol% PDMS dropped to 0.2 GPa from 0.85 GPa of pure silica coating. The Vol% of PDMS and silica filler will be further optimized in our next stage experiments.     

Bonding Strengths of Titania Sol-Gel Derived Coatings on Titanium

Bioactive ceramic coatings have had poor adhesion to substrate. In this study, the bond strength (tensile strength) of titania gel coating to titanium substrate was studied. In the experiments three different pretreatments were used, namely sodium hydroxide corroding, plasma cleaning and titanium nitride coating. Also the effects of heating temperature, heating in vacuum and titanium surface roughness were studied. The sol properties were altered with valeric acid addition. Samples were analysed by SEM-EDX, AES, AFM and tested by bond strength gauge. Those samples in which the titanium surface was precorroded one hour in sodium hydroxide, predeposited by titanium nitride or ground improved the bonding strengths of titania coatings to over 24 MPa. In these samples a fracture occurred at the glue-coating interface.     

PVB掺杂有机无机复合SiO2增透膜的制备和表征

以聚乙烯醇缩丁醛(PVB)为有机掺杂剂,正硅酸乙酯为前驱体,氨水为催化剂,利用溶胶-凝胶法制备出了一种新型的有机无机复合二氧化硅增透膜。采用红外光谱、X射线衍射、粒度分析、紫外分光光度法、椭偏测定、原子力显微镜、静滴接触角测量等对膜层性质进行了表征。结果表明：PVB分子的引入并没有引起增透膜结构的变化。在相同的实验条件下,未经PVB掺杂的SiO₂增透膜在720 nm处的峰值透过率为99.8％,而PVB掺杂后的SiO₂复合膜在840 nm处的峰值透过率在99.9%以上。掺杂膜层变厚,峰值透过率朝长波方向移动。掺杂前后增透膜对水的接触角从29°增加到71°,膜层的疏水性得到明显提高。     

Hybrid Organic-Inorganic Materials by Nonhydrolytic Sol-Gel Processes: Organosilsesquioxane-Metal Oxide Hybrids

Organosilsesquioxane-metal oxide hybrid materials prepared by the Sol-Gel process are mainly heterogeneous. In this paper we report the preparation of methylsilsesquioxane-titanium oxide, and methylsilsesquioxane-aluminium oxide hybrid materials by a nonhydrolytic sol-gel process involving the etherolysis-condensation of a mixture of methyltrichlorosilane and metal chloride. The Si/M ration in the xerogels were very closed to the one of the starting solutions. ²⁹Si MAS NMR study has revealed that the methylsilsesquioxane-titanium oxide xerogel was heterogeneous at the atomic level. The spectrum of the hybrid containing aluminium, has shown beside a peak at –66 ppm corresponding to MeSi(OSi)₃ environment, another peak at –47 ppm which was ascribed to MeSi(OAl)₃ environment. The presence of only these two sites might be due to their stability.     

Optical Properties of Sol-Gel Coatings on Plastic Foils Embossed with Surface-Relief Gratings

A novel technique has been developed to fabricate surface-relief gratings using sol-gel derived porous coating on plastic foil substrates. Organically modified TiO₂ sol was prepared by roll-coating on OPP foil substrates. The plastic films coated with TiO₂ nano-particles were embossed to form surface-relief gratings with micro-structures. The morphology of the porous coatings and the micro-structures were investigated using electron scanning microscopy (SEM). Optical transmission of the films was measured using UV-VIS and IR spectroscopy. The diffraction efficiency of the gratings on the coated plastic foil was examined in terms of fabrication conditions. It was shown that special figures could be seen in the films when the angle of view was changed. The final products of the composite films are transparent and suitable for industry manufacture and applications.     

Sol-Gel Derived Coatings for Outdoor Bronze Conservation

A new conservation treatment for outdoor bronze sculptures based on inorganic-organic copolymers (ORMOCER^®s) was designed which meets the special requirements defined for this field of conservation. Following a systematic research strategy, a great variety of starting compounds (main components: 3-glycidoxypropyltrimethoxysilane or γ-methacryloxypropyltrimethoxysilane), curing conditions, hardeners and additives were considered for modifying the sol-gel materials. The characterization of the lacquers included IR, GPC and viscosity measurements as well as water and epoxy titrations. Screening was carried out by evaluation of the protective effect on bronze substrates. The material properties of the coatings were adjusted to optimize adhesion and resistance against weathering. Particular emphasis was given to curing the sol-gel polymer at ambient temperatures while retaining reversibility even after aging.     

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。