Sol-Gel-Derived Hybrid Coatings for Corrosion Protection

The corrosion resistance of sol-gel-derived, organic-inorganic, silica-based hybrid coatings was studied. Hybrid sols were prepared by copolymerizing tetraethylorthosilicate (TEOS) and 3-methacryloxypropyltrimethoxysilane (MPS) with a two-step acid-catalyst process. Hybrid coatings were dip-coated on 304 and 316 stainless steel substrates and annealed at 300°C for 30 minutes. The adhesion, flexibility, and biocompatibility of the coatings were examined. Hybrid coatings were found to be relatively dense, uniform and defect free. Electrochemical analyses showed that the coatings provided excellent corrosion protection by forming a physical barrier, which effectively separated the anode from the cathode. In addition, further experimental results revealed that the corrosion patterns are strongly dependent on the nature of the stainless steel substrates. Some possible mechanisms for corrosion breakdown associated with each type of substrate are also introduced.     

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.     

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。     

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.     

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.     

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。     

有机-无机杂化骨修复材料

寻找理想的骨修复材料一直是骨科领域的研究热点之一。骨修复材料已由最初单纯取代天然骨组织的惰性材料向具有诱导骨组织再生功能的生物活性材料发展,其中有机-无机杂化材料由于有机和无机组分在分子/纳米水平的复合使其能够最大程度地实现二者的优势互补和协同优化,近年来受到广泛关注。本文着重介绍了有机-无机杂化骨修复材料近些年来的研究进展,并对其发展趋势进行了展望。     

有机-无机杂化氧化硅基介孔材料

有机基团可以通过嫁接或共聚的方法引入到氧化硅基介孔材料的孔表面或材料的骨架中,形成表面结合型和桥键型两大类有机-无机杂化氧化硅基介孔材料.本文综述了有机-无机杂化氧化硅基介孔材料的最新研究进展,介绍了其合成方法、应用及潜在的应用领域,详细总结了目前已报道的有机-无机杂化氧化硅基介孔材料的种类,展望了桥键型有机-无机杂化氧化硅基介孔材料的发展及应用前景.     

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。     

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.     

有机无机杂化太阳能电池中常见无机缓冲层材料的研究进展

有机无机杂化太阳能电池中, 电极缓冲层的选择对光电转换效率有着重要的影响. 理想的负极缓冲层兼具传输电子和阻挡空穴的作用, 而理想的正极缓冲层兼具传输空穴和阻挡电子的作用. 常见的无机电子传输材料主要有TiO₂和ZnO等, 而常见的无机空穴传输材料主要有CuI、CuSCN和NiO等. 本文就这些常见的无机缓冲层材料在有机无机杂化太阳能电池中的应用作一简要回顾, 并对其可能存在的问题进行了分析和评述.     

LC4铝合金表面电泳沉积硅锆有机-无机杂化涂层的制备及性能

采用阴极电泳沉积的方法在LC4铝合金表面制备硅锆有机-无机杂化涂层, 并探讨了电泳沉积条件对涂层形貌、结构以及耐蚀性的影响. 采用纳米粒度仪检测了不同硅锆杂化溶胶的zeta电位; 采用扫描电子显微镜(SEM)和原子力显微镜(AFM)观察了涂层的表面微观形貌和粗糙程度; 采用傅里叶红外光谱(FTIR)研究了涂层的化学结构; 采用电化学方法研究了沉积电压对涂层耐蚀性能的影响, 进而探讨了电泳沉积增强杂化涂层耐蚀性的机理. 结果显示沉积体系的pH为1.6、沉积电压为5 V时为最佳的沉积条件, 所获得的硅锆有机-无机杂化涂层表面均匀致密性最好, 粗糙程度和耐蚀性都得到了明显的改善, 在3.5% NaCl溶液中体现出较好的耐蚀作用.     

Silica/Silicone Nanofilament Hybrid Coatings with Almost Perfect Superhydrophobicity

A facile method for the preparation of silica/silicone nanofilament hybrid coatings with almost perfect superhydrophobicity (contact angle=179.8° and sliding angle=1.3°) is presented. The coatings are obtained by dip‐coating of silica nanoparticles, followed by chemical vapor deposition of silicone nanofilaments. Predominant growth of silicone nanofilaments onto aggregated silica nanoparticles generates a two‐tier structure. The effect of silica nanoparticle size on the growth of silicone nanofilaments, along with their anti‐wetting properties and transparency are investigated in detail. Surface roughness and anti‐wetting properties can be simply regulated by controlling the size of silica nanoparticles.     

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.     

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.     

十三氟辛基修饰的疏水有机-无机杂化二氧化硅膜孔结构、氢气分离及水热稳定性

采用1,2-双(三乙氧基硅基)乙烷(BTESE)和十三氟辛基三乙氧基硅烷(PFOTES)为前驱体,在酸性条件下通过溶胶-凝胶法制备了十三氟辛基修饰的有机-无机杂化SiO2膜材料。利用接触角测量、红外光谱、动态光散射和N2吸附等测试技术分别对膜材料的疏水性、溶胶粒径和孔结构进行表征,并深入研究有支撑膜材料的氢气渗透、分离性能以及长期水热稳定性。结果表明,十三氟辛基修饰后的膜材料由亲水性变成了疏水性,当nPFOTES/nBTESE=0.6时膜材料对水的接触角达到(110.4±0.4)°,膜材料还保持微孔结构,孔径分布在0.5~0.8 nm。氢气在修饰后的膜材料中的输运遵循微孔扩散机理,在300℃时,氢气的渗透率达到8.5×10-7mol·m-2·s-1·Pa-1,H2/CO2,H2/CO和H2/SF6的理想分离系数分别为5.49,5.90和18.36,均高于相应的Knudsen扩散分离因子。在250℃且水蒸气物质的量分数为5%水热环境下陈化250 h,氢气渗透率和H2/CO2的理想分离系数基本保持不变,膜材料具有良好的水热稳定性。     

新型光敏聚酰亚胺/SiO2杂化材料的制备与性能研究

通过溶胶－凝胶法制备了一种新型的光敏聚酰亚胺／二氧化硅杂化材料。研究表明当ＳｉＯ２的含量≤１０ｗｔ％时杂化材料除了保持光敏聚酰亚胺原有的感光性能外其热稳定性能、力学性能以及与基底的粘附性能均有明显地提高,同时材料的热膨胀系数也显著地降低。     

Chemistry of Hybrid Organic-Inorganic. Access to Silica Materials through Chemical Selectivity

Hybrid organic-inorganic materials containing labile organic fragments with various structural features have been prepared. The mild cleavage of Si–C bonds allowed removal of the organic moities. It led to silica which pore structure varied according to the nature of the organic component eliminated.     

Cellular Patterns in Organic-Inorganic Hybrid Film

The formation of cellular patterns, known as Bénard cell, was investigated in organic-inorganic hybrid films under various conditions. The cells were observed in undoped-hybrid films, and its origin was attributed to the convection of TiO₂ nanoparticles formed in the aging process of the sol. These cells showed the particular properties such as the difference between the center and its surrounding: the center showed a lower refractive index than that of the surrounding, a valley at the center with mountain-like surroundings, and a hydrophobic center and hydrophilic surrounding. How the cell patterns were formed depended on the conditions such as the atmospheric humidity and the gravity. It should be also noted that the cells on a silica glass substrate remained after 1000°C heating.     

Structure of Hybrid Silica Gels Incorporated with Hydrophobic Dye Molecules

Hybrid gels incorporated with functional organic molecules are interesting for their physical properties and microstructures as well as their potential applications. Organic-inorganic hybrid silica gels incorporated with hydrophobic organic dye were prepared by hydrolysis of phenyltriethoxysilane (PhTES) and tetraethoxysilane (TEOS) in ethanol solution containing organic dye, pyrene or rhodamine-B (RB). The structure of the gels were investigated by mean of IR absorption spectra and UV-visible absorption/fluorescence spectra. The xerogel prepared from the solution of [PhTES]/[PhTES + TEOS] < 0.3 was stable, and the incorporated dyes hardly dissolved into ethanol. Si-Ph bond increased with increasing PhTES content in the precursor solutions. The UV-visible absorption spectra of the gels incorporated with RB show increase in the amount of dimer with increasing Ph-content. The fluorescence spectra for the gels incorporated with pyrene show that the hydrophobic dye is preferentially incorporated as monomers when the amount of Ph-group in the gels increases in contrast with hydrophilic RB. It is also suggested that the hydrophobic dye is preferentially incorporated into gels as monomers when the gelation rate is low.