Synthesis of organic-inorganic hybrid sols with nano silica particles and organoalkoxysilanes for transparent and high-thermal-resistance coating films using sol-gel reaction

Organic-inorganic hybrid sols were synthesized from nano silica particles dispersed in water and from organoalkoxysilanes, using the sol-gel reaction. This work focuses on the effects of the three multifunctional organoalkoxysilanes dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane (MTMS), and tetramethoxysilane (TMOS) to form a transparent and high-thermal-resistance coating film. The stability of the hybrid sol was evaluated as a function of the reaction time for 10 d through the variation of the viscosity. The viscosity of the silica/DMDMS and silica/MTMS sol was slightly increased for 10 d. The multifunctional organoalkoxysilanes formed dense silica networks through hydrolysis and condensation reaction, which enhanced the thermal resistance of the coating films. No thermal degradation of the silica/DMDMS sample occurred up to 600 degrees C, and none of the silica/MTMS and silica/TMOS samples occurred either up to 700 degrees C. The organic-inorganic hybrid sols were coated on the glass substrate using a spin-coating procedure. The organic-inorganic hybrid sols formed flat coating films without cracks. The transmittance of the hybrid sol coating films using MTMS and DMDMS was shown to be over 90%. The transmittance of the silica/TMOS sol coating film reacted for 10 d abruptly decreased due to faster gelation. The silica/DMDMS and silica/MTMS hybrid sols formed smooth coating films while the surface roughness of the silica/TMOS coating film markedly increased when the hybrid sol reacted for 10 d. The increase of the surface roughness of the silica/TMOS coating film can be attributed to the degradation of the stability of the hybrid sol and to the loss of transmittance of the coating film. It was confirmed in this study that the use of organic-inorganic hybrid sol can yield transparent and high-thermal-resistance coating films.     

Effect of poly(acrylic acid) on the preparation of thick silica films by electrophoretic sol–gel deposition of re-dispersed silica particles

Thick silica films were prepared by the electrophoretic sol–gel deposition technique in the presence of poly(acrylic acid) (PAA) using monodispersed silica particles; the particles were prepared by the sol–gel method, pre-heat treated and then re-dispersed in the mixture of H2O and ethanol. The weight of deposited silica films was maximized when 0.2 mass % of PAA against the whole amount of sol was added. The particles constructing the thick silica films were packed densely when the amount of added PAA was less than 0.2 mass%. The weight of the film increased with decrease in the content of H2O in the sol when a fixed amount of PAA was added. After the heat treatment of deposited films at 800 °C, crack-free silica films of about 30 m thickness were prepared. © 1998 Chapman & Hall     

Silicon releasing sol-gel TiO2-SiO230/70 films

TiO₂-SiO₂30/70 mol% sol-gel films were prepared on glass slides by a dip-coating method. The sols were prepared by a two-step hydrolysis process, where either the Si- or Ti-sol was prehydrolyzed before mixing the sols together. The acidity of the prehydrolyzed sol was varied. The surface structure and composition of formed films were characterized by contact angle meter, atomic force microscope and X-ray photoelectron spectroscopy. The silicon dissolution was performed in tris(hydroxymethyl)aminomethane buffer. The films were able to release silicon and the surface chemistry of films was dependent on the preparation method. The prehydrolysis of Si-sol and aging of mixed sol increased surface silica concentration of the formed films. The surface morphology was dependent on the preparation method so that through Si-sol prehydrolysis it was possible to make rougher nanosurfaces with needle-like particles.     

Effect of polyvinyl butyral on the microstructure and laser damage threshold of antireflective silica films

Silica antireflective films modified by polyvinyl butyral (PVB) were deposited on fused silica substrates by sol-gel process. The effects of PVB on the microstructure and laser damage threshold (LIDT) of films were investigated. The results of the nano particle analyzer and scanning probe microscope revealed that PVB molecules surrounded silica particles and controlled the particle growth, which resulted in a stable sol with uniformly distributed silica particles. Therefore, the films deposited from these modified sols possessed more uniform microstructures than the films without PVB. The adhesive-resistance test indicated that the strength of the modified silica films increased due to the bond reaction between PVB molecules and silica particles. The introduction of PVB into silica sols had also increased the LIDT of films. The LIDT of films increased from 30.0 J/cm² to 40.1 J/cm² after 1.0 wt.% PVB was added. The increase in LIDT was attributed to the increased strength and uniform microstructures of films as an effect of the PVB modification.     

Direct coating of bioactive sol-gel derived silica on poly(ε-caprolactone) nanofibrous scaffold using co-electrospinning

This study reports a novel way of directly coating a poly(ε-caprolactone) (PCL) nanofibrous scaffold with bioactive sol-gel derived silica by directly co-electrospinning (Co-ES) a PCL solution and silica sol, used as the core and shell materials, respectively. In particular, the silica sols prepared using a sol-gel process at room temperature were heat-treated at 60 °C for various times, ranging from 0 to 9 h, in order to improve their spinability. The surface of the individual PCL nanofibers could be covered completely with a bioactive silica layer using a silica sol heat-treated at 60 °C for more than 6 h, whilst preserving the nanofibrous structure. Fourier-transform infrared spectroscopy (FT-IR) revealed only the characteristic bands associated with the PCL and sol-gel derived silica materials without any noticeable band shift.     

有机硅KH-570改性硅溶胶杂化涂层的制备研究

以硅溶胶、γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)为原料,将低钠型碱性硅溶胶经强酸性阳离子交换树脂离子交换后,得到酸性硅溶胶,将其与KH-570按一定比例共混搅拌,通过KH-570在酸性条件下,水解缩聚,制得有机/无机杂化溶胶。以低碳钢Q235为基材,制备出硅烷偶联剂KH-570(MEMO)改性硅溶胶的杂化涂层。以FT-IR测试方法对其结构进行了表征,采用动电位极化曲线测试涂层的耐蚀性能。以光学显微镜、SEM观察涂层与碳钢裸片在腐蚀前后的表面形貌。研究结果表明:酸性硅溶胶与KH-570的水解缩聚产物通过共缩聚反应在碳钢表面形成带有有机基团的无机交联网络,基本骨架由Si-O-Si组成,经过100℃热处理,即可得致密涂层,涂层均匀、透明,无缺陷。电化学分析表明涂层形成物理屏障,为基体提供了优良的腐蚀保护。杂化涂层显现出良好的耐蚀性能。     

Effect of SiO2 Particle Size on the Reaction between ZrB2 and SiO2 in Air

The heat resistance of ZrB₂-based composites is shown to depend on the dispersion medium in which the slip-cast bodies were prepared: silica sol ensures the best heat resistance. Heat treatment of ZrB₂–SiO₂ materials in air at temperatures of up to 1400°C leads to the formation of a borosilicate glass melt containing crystalline particles of ZrB₂, SiO₂, and reaction products. Chemical analysis of heat-treated samples demonstrates that the SiO₂ particle size has no effect on this process.     

Alumina coating on quartz glass and nickel substrates using aqueous sol derived from AlCl3 · 6H2O

The thick alumina films (0.2–0.5 m) were prepared on quartz glass and nickel substrates by a dipping method using an alumina sol derived from an aqueous AlCl₃ solution. The hardness of this coating was compared to those of similarly coated substrates that had been heat-treated at various temperatures. The hardness of the alumina coating increased with increasing heat-treatment temperature. This sol gave crack-free and well-coated substrates that could be heat-treated to temperatures up to 800°C. This may have been due to the formation of an amorphous mixed oxide interface layer between the alumina films and the substrates. At temperatures higher than 900°C, problems with the coating started to appear because the oxide layer formed into -alumina accompanying evolution of stress in the interface.     

Novel pathways for the preparation of silica antireflective films: Improvement in mechanical property

Silica antireflective films by the base catalyzed sol-gel process show poor mechanical property. In this study, silica antireflective films with good mechanical property have been prepared by the acid catalyzed templating sol-gel process. The single-layer film was deposited from an acid-catalyzed silica sol solution with polymer F127 incorporation. The silica sol was first dip deposited onto substrate to form films on both sides of the substrate and then subjected to thermal treatment at 500 °C. After thermal treatment, the abrasion resistant antireflective film was achieved due to the formation of porous structure in the resultant film as a result of decomposing F127. Optical spectroscopic measurement shows that the coated glass with maximum transmittance of 99.5% has been obtained. Nanoindenter measurement shows that the elastic modulus and hardness of films are 16 GPa and 1.3, respectively, which are much better than those films derived from base-catalyzed silica sols. The high transmittance and good mechanical property make such films potential in both military and civil applications.     

Adhesion of chromium metallization on alumina surfaces prepared by sol-gel techniques

The adhesion of a sputter-deposited Cr metallization layer to alumina films prepared by a solution-gelation method has been investigated using a pull test. Alumina films with a range of thicknesses (1 to 6 m) were prepared by dipping commercially available polycrystalline alumina substrates into hydrolysed aluminium butoxide sols and fired for 1 h at 500, 900, or 1200 C. Monolithic, crack-free films resulted both from pure alumina and Ti-doped alumina sols. The adhesion strength was dependent on the thickness of the alumina films, as well as on the temperature of the heat treatment. Failure occurred in part between the alumina film and the substrate and in part between the alumina film and the chromium layer. For alumina films fired at 500 C, the adhesion strengths of 1 m thick films were greater than those measured for 3 and 6 m thick films because of the formation of greater mechanical bonds between alumina films and the substrate. The adhesion strength of the chromium layers was greatly improved by firing at 1200 C. This increase in adhesion strength was attributed to an increase in the surface roughness of these specimens, which occurred due to crystallization of the sol layer. The adhesion strengths of films doped with Ti was not significantly different from those of the undoped films.     

Preparation of sols from water-alcohol solutions of tetraethyl orthosilicate and SnCl<Subscript>4</Subscript> and the effect of sol composition on the surface morphology of sol-gel films

We describe a process for the preparation of sols from water-alcohol solutions of tetraethyl orthosilicate and SnCl₄. The kinetics of this process have been studied by measuring the electrical conductivity of the sols, and the optical absorption spectra of the sols have been measured. The surface morphology of films prepared from the sols has been examined by scanning electron microscopy. The results are used to assess the influence of preparation conditions, sol composition, and processes underlying sol formation on the surface morphology of the gas-sensing films prepared from the sols.     

Sol gel preparation,structure and thermal stability of crystalline zirconium titanate microspheres

Very pure and crystalline ZrTiO₄ microspheres (15–50 m) were prepared by two sol gel methods using a zirconia sol and two types of titania sols and characterized by scanning electron microscopy, X-ray diffraction and simultaneous differential thermal and thermogravimetric analysis. On gelation of the mixed sols, microspheres of an amorphous material with Zr/Ti ratio of 1.0 were obtained by each route. The amorphous materials obtained by the two routes transformed to fully crystalline ZrTiO₄ at 500 and 600 °C, respectively. The high temperature thermal stabilities of these materials were also studied.     

Organically modified silica sol-mediated capillary electrophoresis

We describe in this paper the use of ormosil (organically modified silica) sols as additives to the run buffer for selectivity manipulations between solutes in capillary electrophoresis. CE systems that contain sol additives in the run buffer can be thought of as pseudocapillary electrochromatography. Three sols based on different types of silanes were studied. Methyltrimethoxysilane (MTMOS)-based sol was found to improve selectivities between various aromatic acids. Aminopropyltrimethoxysilane (APS) sol interacts differently with structural isomers of aromatic acids than does MTMOS. At low pH with APS sol in the run buffer, neutral solutes can be separated, as well. The separation of the neutral solutes seems to be facilitated by the formation of hydrogen bonds between the solutes and the APS sol. APS and N-[3-(trimethoxysilyl)propyl]-ethylenediamine (EDAS) affect the separation of the same compounds differently, thus indicating that even small changes of the functional groups of the sol have pronounced effect on the interactions between the sols and the solutes.     

Preparation of alumina films by the sol-gel method

This review describes our study on preparation of alumina films by a sol-gel process and their several applications that have been investigated since 1986. Alumina films were prepared from alkoxide or inorganic salt. Both as-prepared alumina films were transparent in ultraviolet, visible and near infrared regions. The alumina from inorganic salt (inorganic alumina) was structureless even after annealed at 300–700°C in air, while the alumina from alkoxide (alkoxide alumina) was in pseudo-boehmite at an annealing temperature lower than 400°C and was in - or -type at 400–700°C. Both alumina films became opaque after annealed at temperatures above 1000°C. The inorganic alumina film annealed at 800°C showed a gas permeability that was influenced by physico-chemical properties of penetrant and alumina. Composite films of alumina and poly(vinyl alcohol) (PVA) were hydrophilic but insoluble in water, and removal of PVA from the composite films by annealing at 600°C led to formation of transparent alumina films. Such properties enabled us to use a counter diffusion method for fabricating -Fe₂O₃-doped alumina films. Alumina films doped with organic dyes such as laser dyes, hole-burning dyes and non-linear optical dyes, which were fabricated by gelation of dye-added alumina sol, exhibited laser emission, hole-spectra and second- or third-harmonic generation properties, respectively. Hydrogenation of alkene was catalyzed by Ni nanoparticles doped alumina films that were prepared by gelation of Ni²⁺ solution-added alumina sol and annealing the Ni²⁺-doped alumina gel in hydrogen gas. Nonlinear optical properties were observed for alumina films doped with CdS, Au and Ag nanoparticles, which were fabricated by gelation of Cd²⁺, HAuCl₄ and AgNO₃ solution-added alumina sols and annealing the Cd²⁺-doped alumina gel in H₂S gas and the Ag⁺- and Au³⁺-doped alumina gels in H₂ gas. Rare earth metal ion-doped alumina films, which were prepared by gelation of rare earth metal ion solution-added alumina sol and annealed the ion-doped alumina gel, exhibited not only normal luminescence but also up-conversion emission, energy transfer type luminescence and long lasting luminescence.     

无机溶胶粒子的有机高分子胶囊化研究EI

采用一种水溶性聚合物—羟丙基甲基纤维素(HPMC)处理硅溶胶粒子(SiO_2);并以这样的粒子作核,制得了SiO_2/PMMA复合胶囊化粒子;通过电泳实验对其胶囊化效果进行了表征。     

Titania powder modified sol-gel process for photocatalytic applications

Thick films of TiO₂ were prepared on glass and stainless steel substrates using an alkoxide sol-gel process modified by addition of Degussa P-25 powder. The prepared films were characterized by SEM, EDS, XRD and other methods. The TiO₂ films obtained from the powder modified sol were compared to films obtained from the alkoxide sol-gel without modification. The films obtained from the modified sol-gel were about ten times thicker for a single dip coating/heat treatment cycle than the films obtained from the sol without powder addition. The prepared thick films were smooth and free of macrocracking, fracture or flaking. The grain size of these films was uniform and in the range 100–150 nm and the films were a mixture of anatase and rutile TiO₂. The films obtained from the powder modified sol on the stainless steel substrate were also much harder compared to the films obtained from sols without modification and displayed excellent adhesion to the substrate.     

Combined Langmuir-Blodgett and sol-gel coatings

Optical properties and in-depth structure of double-layer coatings on glass substrates were investigated. One of the layers was prepared by dip coating either from silica or titania sol, the other layer was made from ca. 130 nm Stöber silica particles by the Langmuir-Blodgett (LB) technique. Two different types of combined coatings were prepared: (1) nanoparticulate LB films coated with sol-gel (SG) films and (2) nanoparticulate LB films drawn onto SG films.Scanning electron microscopy and optical methods, i.e. UV-vis spectroscopy and scanning angle reflectometry were applied for analyzing the structure and thickness of coatings. These measurements revealed that the precursor sols could not penetrate into the particulate LB film completely in case of coating type (1). For coating type (2) very little overlap between the SG and LB layers was found resulting in significant improvement of light transmittance of combined coatings compared to single SG films.To show some possible advantages of the combination of these techniques additional studies were carried out. Surface morphology of combined coatings (1) was studied by atomic force microscopy. Surfaces with different roughness were developed depending on the thickness of the sol-gel film (titania: ca. 70 nm; silica: ca. 210 nm). The adhesive peel off test revealed improved mechanical stability of combined coatings (2), in comparison to LB films which makes them good candidates for further applications.     

Influence of physico-structural properties on the photocatalytic activity of sol-gel derived TiO2 thin films

Sol-gel TiO₂ films were deposited from various sols and heat-treated at different temperatures. Fourier transform infrared spectroscopy, ellipsometry, X-ray diffraction, and scanning electron microscopy methods have been used to study physico-structural properties of the films. These properties are discussed with respect to the experimental parameters. It is shown that, depending on sol formulations and annealing temperatures, a large range of crystallite size, crystallization degree, film porosity, and surface morphology can be covered. The photocatalytic properties of the films have been studied in relation to their physico-structural properties through the photodecomposition of malic acid. This study shows that the photocatalytic activity undergoes a complex dependence on the physico-structural properties.     

Structural and optical properties of nitrogen‐iron co‐doped titanium dioxide films prepared via sol‐gel dip‐coating: Effect of urea and iron nitrate concentration in the sol

In this study, nitrogen‐iron co‐doped titanium dioxide films were prepared via sol‐gel dip‐coating method using urea and iron nitrate as nitrogen and iron source, respectively. Nonmetal doping of TiO₂ have some disadvantages such as massive charge carrier recombination and losing the photo‐catalytic capability. Three different nitrogen‐iron co‐doped titanium dioxide sols with different urea and iron nitrate concentration were prepared. The resulting sols were homogeneous and transparent, and no precipitation was observed in any of them. It was observed that the film prepared with middle urea‐iron nitrate concentration sol got opaque in a short time after the dip‐coating process. All prepared films were characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, confocal microscopy and ultraviolet–visible (UV‐Vis) spectroscopy. It was found that the concentration of the urea and iron nitrate in the sol had an effect on the crystal structure, microstructure, surface morphology and optical properties of the resulting films. Samples with middle concentrations had amorphous structure and bigger particle size. It was seen that sample with higher iron amount has lower band‐gap. It is concluded that we can prepare transparent anatase, transparent amorphous and opaque amorphous titanium dioxide films by changing the urea and iron nitrate concentration in the sol.     

Effect of rheology and processing parameters on the EPD coatings of basic sol-gel particulate sol

Homogeneous thick silica coatings were prepared onto metals substrates by Electrophoretic Deposition (EPD) using particulate sol-gel sols. The synthesis of the sols was performed by mixing tetraethoxysilane and methyltriethoxysilane under basic catalysis. The synthesis, storage and processing conditions were optimised, correlating the rheological properties of the sols with EPD performance and reliability. Homogeneous and crack-free coatings are obtained when both, the synthesis and the deposition, are performed under tight conditions avoiding the contact with room humidity. The maximum crack-free thickness of the sintered coatings was 12 m, three times more than those obtained by dipping.