Stress and Cracks in Gel-Derived Ceramic Coatings and Thick Film Formation

Residual stress was evaluated by measuring the substrate curvature for alkoxide-derived silica and titania films deposited on silica glass substrates. The residual stress was tensile, increasing with increasing heat-treatment temperature. The stress in fired films was affected greatly by water/alkoxide ratio and chelating agents in starting solutions. Secondly, in situ observation was made on cracking of gel films subjected to heat-treatment. Silica and titania gel films deposited on silicon wafers were cracked in the heating-up stage at temperatures of 100°–400°C, depending on the film thickness and heating rate. Larger thickness and lower heating rates were found to lower the cracking onset temperature. Finally, organic polymers with amide groups were demonstrated to increase the uncracking critical thickness. The polymers include polyvinylpyrrolidone and polyvinylacetamide, allowing single layer ceramic coating films over 1 m in thickness to be formed without cracking.     

Structural and Photoluminescence Behaviors of Nano-Structure Thin Film and Bulk Silica Gel Derived Glasses

Nano-structure bulk and thin film silica gel derived glasses were prepared by sol-gel technique. Both samples were derived from the same precursor and subjected to the same heat-treatment regime. Structural information about prepared samples are obtained by analyzing the XRD patterns and TEM micrographs. The bulk samples phase changes from amorphous to -crystoballite at higher temperature (1300°C) than that in the thin film (500°C). The crystallite size depends to a large extent on the heat-treatment temperature. Bulk sample heat treated at 1400°C was as small as 10.4 nm. Thin film samples show higher response to heat-treatment temperature than the bulk samples, where the film is denser, has smaller pores and seems more homogeneous at lower temperature than bulk sample as revealed by SEM. The observed Raman spectra for bulk and thin film samples are in accordance with that of the -crystoballite. The Raman peak intensity is higher for thin film than bulk samples. The photoluminescence PL measurements for bulk samples show a broad intense peak at 532 nm combined with three weak peaks at longer wavelength 587, 635 and 666 nm. The PL peak intensity shows a reasonable decrease with increasing the heat-treatment temperature while the peak position shifted slightly to a lower wavelength. While the thin film samples show a unique peak at wavelength = 523 nm. The appearance of PL bands are interpreted on the light of non-bridged oxygen hole center as well as the structure defects.     

Surface Energy Changes of Heat Treated TEOS Derived Silica Xerogels

The surface energy of monolithic silica xerogels was examined by measuring the interaction of organic probes with xerogels heated at temperatures close to the gel-to-glass transition temperature. Values of the dispersive component of the surface energy, , between 60 and 80 mJ m^-2 have been observed using n-alkanes for silica xerogels heated at 700, 800 and 900°C. At 1000°C, decreases to 8.37 mJ · m^-2. Also the differential heat of adsorption, variation of standard free energy and entropy of adsorption decrease when the silica xerogel is heated at 1000°C, showing a lower interaction potential of the organic probes with the silica surface. For the silica xerogels heated between 700 and 900°C, the acid character varies in accordance with the variation of the chemical nature of the silica. Upon heating at 1000°C, both acid and base characters are very close in accordance with a neutral surface. Within the experimental conditions used in this work, the surface of the obtained monolithic silica xerogels behaves as a glass surface when the treating temperature is 1000°C.     

Preparation and Characterization of Forsterite (Mg2SiO4) Xerogels

Mg2SiO4 gels were prepared from alkoxide precursors, and the formation of the forsterite crystal phase was studied after heat treatments up to 1200°C. Prehydrolyzed TEOS in solution with 2-methoxyethanol was mixed with Mg(OEt)2, and the solution was hydrolyzed using excess water. The resultant gels were dried at 100°C to form xerogels which were subsequently powdered. These powders were characterized using thermal analysis (DTA and TGA), surface area analysis (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM).DTA and XRD indicated that forsterite crystallized at 770°C, and by 1000°C the powders were predominantly crystalline. BET gave powder surface areas between 400 and 550 m2 g–1. TEM revealed angular particles with sizes between 0.2 and 2 m. The low temperature of crystallization of forsterite indicates a high degree of intimate mixing between the precursor alkoxides, although XRD indicated some degree of inhomogeneity.     

Effect of aging temperature of alkaline aluminosilicate and silicate gels on the kinetics of crystallization of zeolite ZSM-5 and silicalite-1

The temperature dependences of nucleation of zeolite ZSM-5 and silicalite-I pass through extrema in the range from 110 °C to 120 °C. Despite having the same crystalline structures, zeolite ZSM-5 has a maximum and silicalite-1 has a minimum of nucleation in the temperature range mentioned. A method for preparation of single crystals of silicalite-1 up to 150 m in size has been developed. The comparison of the curves of the temperature dependences of nucleation for zeolites Na-X, Na-A, and ZSM-5 shows that the positions of the maxima on these curves are determined by the type of the crystal structure of zeolite.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1091–1095, May, 1996.     

Precursor-Support Interactions in Silica-Supported Manganese Oxide Catalysts

Summary. Catalyst materials investigated in this study were obtained by calcination of impregnated silica with Mn(CH₃COO)₂·4H₂O and MnC₂O₄·2H₂O, so as to yield 10wt% Mn/SiO₂. The precursor compounds as well as pure and impregnated silica support were calcined at 600 and 1000°C in a static air atmosphere for 5h. Structural characteristics of the catalysts thus obtained were investigated by DTA, TG, XRD, IR and DRS. N₂ adsorption at –195°C was used for the assessment of surface texture of the test materials. Results of structural characterisation of catalysts obtained by calcination of manganese acetate-impregnated silica at 1000°C indicated the presence of strong silica-precursor interactions. Species of manganese silicates were detectable. Moreover, the decomposition of manganese acetate enhanced the transformation of amorphous silica into well crystallised -quartz. In contrast, Mn₂O₃, Mn₃O₄, and minor proportions of MnO were detected in the catalysts derived from the manganese oxalate-impregnated silica. This has been ascribed to much weaker precursor/support interactions in the oxalate-impregnated silica than the acetate-impregnated one.     

Physico-Chemical and Catalytic Study of the Co/SiO2 Catalysts

This paper is focused on the physico-chemical and catalytic properties of Co/SiO₂ catalysts. Silica-supported cobalt catalysts were prepared by sol-gel and impregnation methods and characterized by BET measurements, temperature programmed reduction (TPR_H2), X-ray diffraction (XRD), and thermogravimetry-mass spectroscopy (TG-DTA-MS). The sol-gel method of preparation leads to metal/support catalyst precursor with a homogenous distribution of metal ions into bulk silica network or on its surface. After drying the catalysts were calcined at 500, 700, and 900°C. The reducibility of the supported metal oxide phases in hydrogen was determined by TPR measurements. The influence of high temperature—atmosphere treatment on the phase composition of Co/SiO₂ catalysts was investigated by XRD and TG-DTA-MS methods. At least five crystallographic cobalt phases may exist on silica: metallic Co, CoO, Co₃O₄, and two different forms of Co₂SiO₄ cobalt silicate. Those catalysts in which cobalt was chemically bonded with silica show worse reducibility as a result of strongly bonded Co-O-Si species formed during high-temperature oxidation. The TPR measurements show that a gradual increase in the oxidation temperature (500–900°C) leads to a decrease in low-temperature hydrogen reduction effects (<600°C). The decrease of cobalt oxide reduction degree is caused by cobalt silicate formation during the oxidation at high temperature (T 1000°C). The catalysts were tested by the reforming of methane by carbon dioxide and methanation of CO₂ reactions.     

Sol-Gel Synthesis and Microstructural Characterization of Silicon Oxycarbide Glass Sheets with High Fracture Strength and High Modulus

A synthesis route to silicon oxycarbide glass sheets (thickness 40 to 1000 m and area up to 20 × 35 cm2) has been developed for the first time starting from a methyl modified sol containing nano-particulate SiO2 and having a solid content of 70 wt%. The gel sheets obtained by casting and drying of this sol were sintered in N2 atmosphere at temperatures between 900–1650°C. Only by the incorporation of colloidal silica (0.10–0.35 mole per mole alkoxide) to the sol could crack-free, large area glass sheets be obtained. Fracture strength (three point bending) was found to attain a maximum (200–300 MPa) for the sheets sintered at 1000°C. Young's modulus attained a peak value between 120 and 130 GPa for the sheets sintered at 1200°C. HR-TEM studies showed an amorphous and homogeneous matrix up to a sintering temperature of 1200°C, whereas at 1450°C and 1650°C, crystallites of SiC and lamellar graphite were formed. It is concluded that addition of colloidal silica to the sol does not lead to inhomogeneities after sintering and therefore does not decrease the strength and elastic modulus.     

The Iron Behaviour in Aluminosilicate Gel-Derived Materials

Electron spin resonance (ESR) measurements have been carried out on a 10Fe₂O₃ · 10Al₂O₃ · 80SiO₂ gel heat-treated at different temperatures in air and under reducing conditions. ESR spectra were obtained at 300, 50 and 5 K. The effective g value (g = h/H), linewidth (H_pp) and ESR amplitude (A) depend on heat-treatment temperature of the gel-derived samples. ESR spectra exhibit different magnetic characteristics as a function of heat-treatment temperature and atmosphere. X-ray diffraction (XRD), scanning electron microscopy (SEM) and a.c. susceptibility (_a.c.) analyses were used to better understand the ESR results. The results show that in the samples heat-treated in air, up to 700°C, Fe³⁺ ions are incorporated in the glass network in tetrahedral and/or octahedral co-ordinations. In the samples heat-treated between 250 and 700°C was not detected, by ESR, the presence of iron oxide aggregates. However, the formation of hematite particles was observed by XRD and SEM. The presence of iron oxide aggregates was detected (by ESR) in the samples heat-treated at temperatures higher than 700°C. These aggregates are formed, at 1200 and 1300°C, by hematite and magnetite particles as proved by XRD. The ESR spectra and a.c. susceptibility, of the samples heat-treated at 250°C (under reducing conditions), show a behaviour characteristic of small magnetite particles presence. The sample heat-treated at 500°C (under reducing conditios) contains magnetite particles (XRD). In the ESR spectra of the sample heat-treated at 1000°C, under reducing conditions, was not detected any resonance signal.     

Study of the binary CaCO3-SiO2 system by quantatitative DTA

Solid-state reactions in the CaCO₃-SiO₂ system with different mass ratios (CaCO₃:SiO₂=from 10.2 to 110) were studied by means of thermogravimetry, quantitative DTA and high-temperature X-ray diffraction up to 1500 °C.It was found that not CaCO₃, but CaO reacted with SiO₂. The rate of decarboxylation increased and the temperature of formation of silicate phases decreased significantly with increasing silica content. Only mono- and dicalcium silicates could be detected as solid-state reaction products. Above 1400 °C, an intensive melting process took place; the amount of silica had no clear effect on its temperature range.Quantitative DTA and X-ray diffraction data proved that, below 1000 °C, not only the decarboxylation process, but also silicate formation must be taken into consideration.     

Microstructural and Dielectric Characterization of Sol-Gel Derived Silicon Oxycarbide Glass Sheets

Thin (50—1000 m) silicon oxycarbide glass sheets were synthesized by the pyrolysis of gel sheets obtained from a methyl-modified silica sol containing colloidal silica under inert atmosphere between 900 and 1450°C. The microstructure of these glass sheets was investigated with the help of high resolution scanning and transmission electron microscopy (HR-SEM and HR-TEM), X-ray diffraction and Raman spectroscopy and their dielectric properties were determined. The surface morphology as observed with HR-SEM did not exhibit a notable temperature dependence. HR-TEM studies showed that the glass sheets sintered up to 1200°C are amorphous, whereas those sintered at 1450°C contain uniformly dispersed crystallites of SiC and graphite. X-ray diffraction studies were found in agreement with the HR-TEM results. Raman spectroscopy showed that free carbon is present as an amorphous phase till a temperature of 1000°C, whereas at temperatures 1200°C, the presence of graphitic carbon was observed. Silicon oxycarbide glass sheets heat treated at temperatures up to 1200°C, showed a dielectric constant between 4.1 ± 0.11 and 4.6 ± 0.15 in the frequency range from 75 kHz to 5 MHz, with corresponding losses between 0.0008 and 0.1100. Such silicon oxycarbide glass sheets sintered at 1200°C could find an application as substrates for electronic packaging.     

Preparation of TiO2 coating films containing Pd fine particles by sol-gel method

TiO₂ coating films of 0.3–0.4 m in thickness that contain fine Pd particles have been prepared by sol-gel method using Ti(OC₃H ₇ ⁱ )₄ and PdCl₂ as starting materials in an attempt to obtain optical materials that show surface plasma resonance in the visible range. A temperature higher than 900°C was required for formation of Pd metal particles when the heat-treatment was conducted in air. Heat-treatment of pre-heated amorphous films in air at 800°C resulted in precipitation of PdO particles, the size of which could be varied by changing the time of heat-treatment, and subsequent heat-treatment in H₂/Ar gas converted the PdO particles into Pd metal particles. Heat-treatment of pre-heated amorphous films in H₂/Ar gas also resulted in precipitation of Pd metal particles. The size of the Pd metal particles precipitated in the films was 6 to 90 nm, depending on the conditions of heat-treatment. The resultant TiO₂ films containing Pd metal particles were brownish grey in color and showed optical absorption in the visible range over 400 nm, which is attributed to surface plasma resonance of Pd metal particles.     

Silicalite-1 growth from clear solution: Effect of alcohol identity and content on growth kinetics

In situ small-angle X-ray scattering (SAXS) is used to investigate the influence of alcohol identity and content on silicalite-1 growth from clear solutions at 368 K. Several tetraalkyl orthosilicates (Si(OR)4, R = Me, Pr, and Bu) are used to synthesize silicalite-1 from clear solution mixtures comparable to those previously investigated (i.e. 1:0.36:20 TEOS:TPAOH:H2O (TEOS = tetraethyl orthosilicate; TPAOH = tetrapropylammonium hydroxide), 368 K). All TPAOH-organosiloxane mixtures studied form silica nanoparticles after aging at room temperature for 24 h. Full-profile fitting analysis of the SAXS data indicates the particles are ellipsoidal and is inconsistent with the presence of "nanoslabs" or "nanoblocks". Synthesis using TEOS as the silica source have an induction period of approximately 7.5 h and a growth rate of 1.90 +/- 0.10 nm/h at 368 K. Changing the silica source to tetramethyl orthosilicate (TMOS) does not change the induction period; however the particle growth rate is decreased to 1.65 +/- 0.09 nm/h at 368 K. Variable-temperature SAXS measurements for syntheses with TEOS and TMOS show the activation energy for silicalite-1 growth is 60.0 +/- 2.9 and 73.9 +/- 2.8 kJ/mol, respectively, indicating the alcohol identity does influence the growth rate. By mixing tetrapropyl orthosilicate (TPOS) with TEOS (1.6:1.0 molar ratio) as the silica source, the precursor solution shows a shorter induction period (6.0 h) and a faster particle growth rate (2.16 +/- 0.06 nm/h). The alcohol identity effect is more pronounced when other organocations (e.g. alkyltripropylammonium cations) are used to make silicalite-1 at 368 K. Removing ethanol from the precursor solution decreases the induction period to approximately 4.5 h and increases the particle growth rate to 2.99 +/- 0.13 nm/h. Mixtures with 2 equiv of ethanol have an induction period and particle growth rate of 6.0 h and 2.04 +/- 0.03 nm/h, respectively. The results demonstrate the alcohol identity and content influence silicalite-1 growth kinetics. One possible explanation is varying the alcohol identity and content changes the strength of the hydrophobic hydration of the structure-directing agent and the water-alcohol interaction, resulting in less efficient interchange between clathrated water molecules and solvated silicate species.     

High Temperature Behavior of a Gel-Derived SiOC Glass: Elasticity and Viscosity

The high temperature behavior of a sol-gel derived silicon oxycarbide glass containing 12 at.% carbon has been characterized by means of creep and in-situ ultrasonic echography measurements. Temperature induced changes include structural relaxation and densification from 1000 to 1200°C, and crystallization to form a fine and homogeneous -SiC/glass-matrix nanocomposite with 2.5 nm large crystals above 1200°C. Young's modulus measurements clearly reveal a consolidation of the material upon annealing below 1200°C. Crystallization is almost complete after few hours at 1300°C and results in a significant increase in Young's modulus. The viscosity of the oxycarbide glass is much higher than that of fused silica, with two orders of magnitude difference at 1200°C, and the glass transition temperature ranges from 1320 to 1370°C.     

Preparation and properties of polybenzoxazole-silica nanocomposites via sol-gel process

A novel organic/inorganic hybrid material has been prepared through the sol-gel process. A high temperature polymer, polybenzoxazole (PBO), was chosen as the organic phase due to its inherent low dielectric constant and low water absorption. The inorganic phase was generated via sol-gel reaction from a silica precursor, phenyltriethoxysilane (PTEOS). Due to the hydroxyl groups in the PBO precursor backbone and the water release during the cyclization of the precursor, the sol-gel reaction proceeded without the addition of water and any catalyst. After curing at 350 °C, we obtained the PBO/silica nanocomposites. From TEM and SEM photographs, the silica particles dispersed in the PBO matrix were nano-sized. With an addition of 100 wt% of PTEOS, the T_g of PBO was increased 35 °C. The dielectric constant of the hybrid materials increased with the increasing amount of PTEOS.     

Effect of the Measurement Temperature on the Dispersive Component of the Surface Free Energy of a Heat Treated SiO2 Xerogel

The surface free energy of a monolithic silica xerogel treated at 1000°C has been measured by inverse gas chromatography in the temperature range 25–150°C using n-alkanes. Values of the dispersive component, _S ^D, vary from 49.07 mJ·m^–2 at 25°C to 17.20 mJ·m^–2 at 150°C. The _S ^D value obtained at 25°C is lower than that found for amorphous and crystalline silicas but higher than that found for glass fibres meaning that the heat treatment at 1000°C changes drastically the structure of the silica xerogel showing a surface similar to a glass. However, the higher value of _S ^D in comparison to glass fibres can be attributed to the mesoporous structure present in the silica xerogel. In the temperature range of 60–90°C there exists an abrupt change of the _S ^D values as well as in the dispersive component of the surface enthalpy, h _S ^D. Such abrupt change can be attributed to an entropic contribution of the surface free energy.     

Low-Density Forsterite (Mg2SiO4) Powders Prepared from Modified Alkoxides

2MgO-SiO₂ low-density powders have been prepared from alkoxide precursors modified with acetic anhydride. The resultant solutions did not gel, but formed precipitates. These consisted of an organic magnesium compound and amorphous silica. Tapping densities comparable with those of forsterite aerogels were obtained, with the density increasing as the precursor solution concentration increased. Crystalline forsterite formed around 790°C. Higher initial solution concentrations led to greater amounts of MgO in the powders after heating to 1000°C. Transmission electron microscopy showed primary particles between 20 and 30 nm which formed loose fractal agglomerates. By altering the preparation conditions, powders with morphologies more like aerogels than xerogels could be produced.     

The Effect of Precursor Chemistry on the Crystallisation and Densification of Sol-Gel Derived Mullite Gels and Powders

Stoichiometric and silica-rich mullite gels and powders were prepared using four different sol-gel methods. Thermal analysis, X-ray powder diffraction and dilatometry techniques were used to investigate the thermal decomposition, crystallisation and sintering of these mullite precursor gels. The method of preparation, by controlled hydrolysis of various mixtures of tetraethylorthosilicate, aluminium sec-butoxide and aluminium nitrate, affected the texture of the gels, producing single-phase or diphasic samples.The crystallisation sequence of the gels depended on the composition and method of preparation. Single phase mullite crystallised from homogeneous gels at 980°C, while diphasic gels initially formed of a mixture of -Al₂O₃ spinel and mullite, or simple -Al₂O₃ spinel, which subsequently transformed to mullite at 1260°C.Dilatometry and density measurement were used to investigate the sintering of compacts formed by pressing powders prepared from gels precalcined at 500°C. Varying the heating rates from 2 to 10°C min^-1 had little effect on the densification to 1500°C. However, the densification rate was sensitive to the degree of crystallinity and the amount and type of phases present at the sintering temperature. The presence of -Al₂O₃ spinel in the structure initially promoted densification, but the sintering rate was reduced considerably after mullite crystallised. Diphasic materials, especially those with an excess amount of silica in the original gel, sintered to higher densities due to the presence of excess silica promoting densification by viscous phase sintering.     

Preparation of Transparent, Partially-Crystallized BaTiO3 Monolithic Xerogels by Sol-Gel Processing

Transparent, partially-crystallized nanostructured barium titanate (BaTiO3) monolithic xerogels (dried at 90°C) have been successfully synthesized via hydrolysis of Ba, Ti alkoxide precursor solutions in a concentration range of 1.0 mol/l with addition of water with a molar ratio of H2O/Ba 6.3. Transparent monolithic xerogels obtained from a precursor solution of 1.0 mol/l remained transparent even after firing at 500°C in oxygen, although the degree of their transparency was considerably decreased. Firing at temperatures above 500°C yielded translucent ceramics of BaTiO3, and ultimately, firing above 600°C resulted in normal opaque ceramic bodies. Those obtained from a more concentrated precursor solution of 1.2 mol/l were, on the other hand, still transparent after firing at 600°C in oxygen, and turned opaque at 700°C. The results demonstrate that the materials retained their transparency even after pyrolysis of organic compounds involving exothermic oxidation at temperatures in the range of 200 to 400°C. The densification behavior of transparent BaTiO3 monolithic xerogels obtained was found to be excellent; for example, those derived from a 1.0 mol/l precursor solution could be sintered to form monolithic BaTiO3 ceramics with a relative sintered density of about 94% and an average grain size of 1 m by firing at 1100°C for 2 h in oxygen.     

Effect of Prefiring Condition on the In-Plane Orientation of Epitaxial Oxide Films in Coating-Pyrolysis Process

Epitaxial -Fe₂O₃ films were obtained by using iron 2-ethylhexanoate as a starting material. A coating solution was spun on -Al₂O₃ single-crystal substrates, and prefiring and final heat-treatment at various temperatures in air or low oxygen partial pressure were carried out. The degree of in-plane orientation was estimated in terms of full width at half maximum of X-ray diffraction (XRD) -scans. The results of TG-DTA, IR, and XRD suggested that the optimum prefiring condition for obtaining highly epitaxial films is in the range 200–300°C which corresponds to removal of most of the organic component from the precursor, prior to crystallite formation of metal oxide. When the films were prefired at higher temperatures, different atmospheres in prefiring and final heat-treatment lowered the in-plane orientation of the films.