Small-angle X-ray scattering and X-ray absorption near-edge structure study of iron-doped siloxane-polyoxyethylene nanocomposites

The local and medium-range structures of siloxane-POE hybrids doped with Fe(III) ions and prepared by the sol-gel process were investigated by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) and small-angle X-ray scattering (SAXS), respectively. The experimental results show that the structure of these composites depends on the doping level. EXAFS data reveal that, for low doping levels ([O]/[Fe] > 40, oxygens being of the ether-type of the POE chains), Fe(III) ions are surrounded essentially by a shell of chlorine atoms, suggesting the formation of FeCl4- anions. At high doping levels ([O]/[Fe] < 20), Fe(III) ions interacts mainly with oxygen atoms and form FeOx species. The relative proportion of FeOx species increases with iron concentration, this result being consistent with the results of SAXS measurements showing that increasing iron doping induces the formation of iron-rich nanodomains embedded in the polymer matrix.

A dissolution and reaction modeling for hydrolysis of TEOS in heterogeneous TEOS-water-HCl mixtures under ultrasound stimulation

A simplified dissolution and reaction modeling was employed to study the hydrolysis of heterogeneous tetraethoxysilane (TEOS)-water-HCl mixtures under ultrasound stimulation. The nominal pH was changed from 0.8 to 2.0. The acid specific hydrolysis rate constant was determined as k = 6.1 mol(-1) 1 min(-1) [H+](-1) at 39 degreesC, in good agreement with the literature. Along the heterogeneous step of the reaction, the ultrasound maintains an additional quantity of water under a virtual state of dissolution besides the water dissolved due to the homogenizing effect of the alcohol produced in the reaction. The forced virtually dissolved water is probably represented by water at the TEOS-water interface during the heterogeneous step of the reaction. The mean radius of the heterogeneity represented by water dispersed in TEOS phase, while hydrolysis has not started yet, was evaluated as about 290 A. The HCl concentration accordingly increases the hydrolysis rate constant but its fundamental role on the immiscibility gap of the TEOS-water-ethanol system has not been unequivocally established. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Electrode surface modifications improve cathode hydrogen production and anode capacity in Ni-MH batteries

This paper reports results from electrochemical evaluations of electrodes used as cathodes for a hydrogen evolution reaction and anodes in Ni-MH batteries that had been surface-modified by micro-encapsulation, co-deposition and sol-gel methods. The surface modifications produced actual improvements in the corresponding electrochemical reactions by enhancing the performance and/or the mechanical stability of the electrode material. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Decay of photo-excited conductivity of Er-doped SnO2 thin films

Er-doped SnO2 thin films, obtained by sol-gel-dip-coating technique, were submitted to excitation with the 4th harmonic of a Nd:YAG laser (266 nm), at low temperature, and a conductivity decay is observed when the illumination is removed. This decay is modeled by considering a thermally activated cross section of an Er-related trapping center. Besides, grain boundary scattering is considered as dominant for electronic mobility. X-ray diffraction data show a characteristic profile of nanoscopic crystallite material (grain average size approximate to 5 nm) in agreement with this model. Temperature dependent and concentration dependent decays are measured and the capture barrier is evaluated from the model, yielding 100 meV for SnO2:0.1% Er and 148 meV for SnO2:4% Er.

Silica-PEG hybrid ormolytes: structure and properties

The effect of lithium salt doping on the structure and ionic conduction properties of silica-polyethyleneglycol composites is reported. These materials, so called ormolytes (organically modified electrolytes), were obtained by the sol-gel process. They have chemical stability due to the covalent bonds between the inorganic (silica) and organic (polymer) phase. The structure of these hybrid materials was investigated by small-angle X-ray scattering (SAXS) as a function of lithium concentration [O]/[Li] (O being the oxygens of the ether type). The spectra have a well-defined peak attributed to the existence of a liquid-like spatial correlation of silica clusters. The ionic conductivity was studied by AC impedance spectroscopy and is maximum for [O]/[Li] = 15. This result is consistent with SAXS and thermo-mechanical analysis measurements and is due to the formation of cross-linking between the polymer chains for the larger lithium concentrations. These materials are solid, transparent, flexible and have an ionic conductivity up to 10(-4) S/cm. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Microstructure and corrosion resistance of inorganic-organic (ZrO2-PMMA) hybrid coating on stainless steel

Zirconia-polymethylmetacrylate hybrids prepared by a sol-gel method were deposited by dip-coating on stainless steel to improve the resistance against wet corrosion. The effect of the concentration of polymethylmetacrylate and the number of coating applications on the microstructure and corrosion performance of coated samples was investigated. The microstructural properties of samples was analyzed by scanning electron and atomic force microscopy, adhesion tests and profilemeter measurements. The electrochemical corrosion was evaluated through potentiodynamic polarization curves at room temperature. Results show that the sample prepared with 17 vol.% of polymethylmethacrylate has a maximum corrosion resistance, smaller roughness, are hermetic and adherent to the substrate. This film increases the life time of the stainless steel by a factor 30. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Crystallographic and magnetic structure of polycrystalline Zn7-xNixSb2O12 spinels

The crystallographic and magnetic structure of sintered, polycrystalline samples of zinc-antimony spinel, Zn7-xNixSb2O12, have been investigated. The samples were prepared by the modified polymeric precursors method. The magnetic contributions of the Ni2+ ions distributed in three non-equivalent crystallographic sites were investigated, revealing the occurrence of different magnetic regimes. A hysteresis response in the magnetic susceptibility indicates a spin-glasslike behavior at low temperatures. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Gelation of siloxane-poly(oxypropylene) composites

The viscoelastic properties of siloxane-poly(oxypropylene) (PPO) nanocomposites prepared by the sol-gel process has been analyzed during gelation by dynamic rheological measurements. The changes of storage and loss moduli, complex viscosity and phase angle has been measured as a function of time showing the newtonian viscosity of the sol in the initial step of gelation, and its progressive transformation to a viscoelastic gel. The rheologic properties have been correlated to mass fractal, nearly linear growth models and percolation theory. This study, completed by quasi-elastic light scattering and Si-29 solid state nuclear magnetic resonance measurements, shows that the mechanisms of gelation of siloxane-PPO hybrids depend on the molecular weight of the polymer and on the pH of the hybrid sol. For hybrids prepared in acid medium, a polymerization involving silicon reactive species located at the extremity of the polymer chains and presenting a functionality f = 2 occurs, forming a fractal structure during the first stage of sol-gel transition. For samples prepared under neutral pH, the fractal growth is only observed for hybrids containing short polymer chains (M-w similar to 130 gmol(-1)). The fractal dimensionality determined from the change in the rheological properties, indicates that the fractal growth mechanism changes from reaction-limited to diffusion-limited aggregation when the molecular weight of the PPO increases from 130 to 4000 gmol(-1) and as catalyst conditions change from acidic to neutral. Near the gel point, these hybrid gels have the typical scaling behavior expected from percolation theory. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Structure of luminescent mono and di-urethanesil nanocomposites doped with Eu3+ ions

A structure modeling of two families of sol-gel derived Eu3+-doped organic/inorganic hybrids based on the results of small-angle X-ray scattering experiments is reported. The materials are composed of poly(oxyethylene) chains grafted at one or both ends to siloxane groups and are called mono- and di-urethanesils, respectively. A theoretical function corresponding to a two-level hierarchical structure model fits well the experimental Scattering curves. The first level corresponds to small siloxane clusters embedded in a polymeric matrix. The secondary level is associated to the existence of siloxane cluster rich domains surrounded by a cluster-depleted polymeric matrix. Results show that increasing europium doping favors the growth of the secondary domains. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Optical characteristics of Er3+-Yb3+ doped SnO2 xerogels

Er3+ doped SnO2 xerogels have been obtained from aqueous colloidal suspensions. Emission and excitation spectra were obtained and allowed the identification of two main families of sites for Er3+. In the first one Er3+ substitutes for Sn4+ in the SnO2 cassiterite structure. In the second Er3+ are found adsorbed at the SnO2 particle surface. For the first family of sites the technological important infrared Er3+ emission about 1.5 mum is efficiently excited through absorption at the SnO2 conduction band at 3.8 eV. on the other hand the emission due to adsorbed ions appears inhomogeneously broadened by the statistical distribution of sites available for Er3+ ions at the surface of the particles. Moreover it is not excited by the host. The emission of this second family of sites could be also excited by an energy transfer mechanism involving Yb3+ ions also adsorbed a posteriori at particles surface. Results are compared with spectra obtained for Eu3+ doped samples. (C) 2002 Elsevier B.V. B.V. All rights reserved.

A CALORIMETRIC STUDY OF THE ULTRASOUND-STIMULATED HYDROLYSIS OF SOLVENTLESS TEOS-WATER MIXTURES

The kinetics of ultrasound-stimulated and HCl-catalyzed hydrolysis of solventless TEOS-water mixtures was studied as a function of temperature ranging from 10 degrees C up to 65 degrees C by means of flux calorimetry measurements. A specially designed device was utilized for this purpose. The exothermic peak arising few minutes after sonication began has been attributed mainly to the hydrolysis reaction. The overall hydrolysis process, which was measured through the irradiation time up to the hydrolysis peak, was found to be thermally activated, with an apparent activation energy Delta E = 36.4 kJ/mol. The alcohol produced at the early hydrolysis due to sonication seems to further enhance the reaction, via a parallel autocatalytic path, which is controlled by a faster pseudo second order rate constant (k'). Our modeling yielded k' = 6.3 x 10(-2) M(-1) min(-1) at 20 degrees C, which is in a reasonable agreement with the literature, and an activation energy Delta E = 40.4 kJ/mol for the specific process of hydrolysis in presence of alcohol.

Effect of salt nature on structure and ionic conductivity of sodium-doped siloxane-PPO ormolytes

Siloxane-polyoxypropylene (PPO) hybrids obtained by the sol-gel process and containing short polymer chain have been doped with different sodium salts NaX (X = ClO4, BF4 or I). The effect of the counter-ion (X) on the chemical environment of the sodium ions and on the ionic conductivity of these hybrids was investigated by Na-23 NMR, small angle X-ray scattering (SAXS), complex impedance, Raman spectroscopy and differential scanning calorimetry (DSC). Results reveal that the different sodium salts have essentially the same effect on the nanoscopic structure of the hybrids. The formation of immobile Na+ cations involved in NaCl-like species could be minimized by using a low amount of HCl as hydrolytic catalyst. The differences in the ionic conductivity of hybrids doped with different sodium salts were correlated with the proportion of Na ions solvated by ether-type oxygen of the polymeric chains and by the carboxyl oxygen located in the urea groups of the PPO chain extremities. (c) 2005 Elsevier Ltd. All rights reserved.

Influence of pH and precipitation temperature on the structural characteristics of aluminium hydroxides prepared form nitrate aqueous solutions

Aluminium Hydroxides were precipitated from Aluminium Nitrate and Ammonium Hydroxide, at the temperatures 64 degrees C (hot) and 25 degrees C (cold), under the pH conditions 5, 7 and 9. The samples were characterized by X-Ray Diffraction (XRD) and Differential Thermal Analysis (DTA). The hydroxide precipitated at pH 9 and 64 degrees C is built up by pseudoboehmite and a minor share of others apparently amorphous hydroxides. The crystallinity of the hot yielded pseudoboehmite diminishes with the pH. The crystallite size was evaluated as about 40 Angstrom for the best crystallized sample. The cold precipitated product is apparently composed by amorphous or very poorly crystallized hydroxides. Upon heating, the cold precipitated hydroxides, and the low pH and hot precipitated hydroxide, release their structural water before the occurrence, about 430 degrees C, of the transition of the pseudoboehmite to gamma-alumina, and exhibit a shifting (towards low temperature side) and a broadening in the peak of the transition to alpha-alumina, which occurs at 1200 degrees C in the pseudoboehmite pattern. The yielded pseudo-boehmite peptized by HNO3, addition and gelified by evaporation in a critical concentration approximately 0.17 gcm(-3).

Rare earth doped synthetic opals and inverse opals

Monodisperse spheres of silica and latex were obtained by a surfactant free styrene polimerization and the Stober method respectively. Controlling settling either by centrifugation or by dip-coating colloidal crystals could be obtained. Silica inverse opals were prepared by using the latex colloidal crystals as templates and TEOS/ethanol solution. Eu3+ containing silica spheres were obtained dispersing silica spheres in Eu(NO3)(3) isopropanol solutions. Emission spectra suggest the formation of an amorphous Eu3+ containing phase well adhered at the spheres surface. The utilization of solutions of trifluoroacetates salts of Pb2+ and Eu3+ was observed to destroy the silica spherical pattern when samples are treated at 1000degreesC. In that case nanocrystals of PbF2 and amorphous silica were obtained after heat treatment.

Strontium titanate films prepared by spray pyrolysis

Strontium titanate thin films were prepared by spray pyrolysis technique. Deposition parameters, such as solution concentration, time and temperature of deposition, and flow rate of carrier gas were optimized to obtain dense films without cracks. Films with different thicknesses were prepared through the control of deposition time. Prepared thin films were homogeneous, well crystallized, with uniform grain size. (C) 2003 Elsevier Ltd. All rights reserved.