Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (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.

Preparation of ZnO nanoparticles: Structural study of the molecular precursor

The structure of zinc acetate derived precursor currently used in the sol-gel synthesis of ZnO nanoparticles is described. The reaction products obtained before and after reflux of ethanolic zinc acetate solution have been studied by UV-Vis, photoluminescence, FTIR and EXAFS at the Zn K edge. EXAFS results evidence for both precursor solutions a change from the octahedral coordination sphere of oxygen atoms characteristic of the solid zinc acetate dihydrate compound into a four-fold environment. The EXAFS spectra of precursor solutions can be satisfactorily reproduced using the molecular structure reported for Zn4O(Ac)(6) (Ac = COOCH3). UV-Vis and FTIR measurements are also in agreement with the formation of this oligomeric precursor. The structural modification is more pronounced after reflux at 80degreesC, because the increase of the Zn4O(Ac)(6) amount and the formation of nearly 3.0 nm sized ZnO nanoparticle.

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.

Local structure and near-infrared emission features of neodymium-based amine functionalized organic/inorganic hybrids

Nd3+-based organic/inorganic hybrids have potential application in the field of integrated optics. Attractive sol-gel derived di-urea and di-urethane cross-linked poly (oxyethylene) (POE)/siloxane hybrids (di-ureasils and di-urethanesils, respectively) doped with neodymium triflate (Nd(CF3SO3)(3)) were examined by Fourier transform mid-infrared (FT-IR), Raman (FT-Raman), Si-29 magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and photoluminescence spectroscopies, and small-angle X-ray scattering (SAXS). The goals of this work were to determine which cation coordinating site of the host matrix (ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the photoluminescence properties. The main conclusion derived from this study is that the hydrogen-bonded associations formed throughout the materials play a major role in the hybrids nanostructure and photoluminescence properties.

In situ and simultaneous nanostructural and spectroscopic studies of ZnO nanoparticle and Zn-HDS formations from hydrolysis of ethanolic zinc acetate solutions induced by water

The simultaneous formation of nanometer sized zinc oxide (ZnO), and acetate zinc hydroxide double salt (Zn-HDS) is described. These phases, obtained using the sol-gel synthesis route based on zinc acetate salt in alcoholic media, were identified by direct characterization of the reaction products in solution using complementary techniques: nephelometry, in situ Small-Angle X-ray Scattering (SAXS), UV-Vis spectroscopy and Extended X-ray Absorption Fine Structures (EXAFS). In particular, the hydrolytic pathway of ethanolic zinc acetate precursor solutions promoted by addition of water with the molar ratio N = [H2O]/[Zn2+] = 0.05 was investigated in this paper. The aim was to understand the formation mechanism of ZnO colloidal suspension and to reveal the factors responsible for the formation of Zn-HDS in the final precipitates. The growth mechanism of ZnO nanoparticles is based on primary particle (radius approximate to 1.5 nm) rotation inside the primary aggregate (radius < 3.5 nm) giving rise to an epitaxial attachment of particles and then subsequent coalescence. The growth of second ZnO aggregates is not associated with the Otswald ripening, and could be associated with changes in equilibrium between solute species induced by the superficial etching of Zn-HDS particles at the advanced stage of kinetic.

Local and nanoscopic structure of potassium triflate-doped siloxane-polyoxyethylene ormolytes

Siloxane-poly(oxyethylene) hybrids obtained by the sol-gel process and containing short polymer chain have been doped with potassium triflate (KCF3SO3). The local structure of these hybrids was investigated by X-ray absorption spectroscopy near the potassium K-edge. Small angle X-ray scattering was used to determine the structure at the nanometer scale. Results revealed that at low and medium potassium concentration (n = [O][K] >= 8, where n represents the molar ratio of ether-type oxygen atoms per alkaline cation) the cations interact mainly with the polymer chains, while at larger doping level (n < 8) the formation of a polyehter:KCF3SO3 Complex is observed. The nanoscopic structure of the hybrids is also affected by doping. By increasing the doping level, decreasing trends in the electronic density contrast between siloxane nanoparticles and polyether matrix and in the siloxane interparticle distance are observed. At high doping level the small angle X-ray scattering patterns are strongly modified, showing the disappearance of the correlation peak and the formation of a potassium-containing nanophase. (c) 2006 Elsevier B.V. All rights reserved.

Distributed feedback multipeak laser emission in Rhodamine 6G doped organic-inorganic hybrids

Organic-inorganic hybrid materials were prepared from an ureasil precursor (ureapropyltriethoxysilane designated as UPTES) and acrylic acid modified zirconium (IV) n-propoxide. Thin films containing rhodamine 6G (Rh6G) were prepared by spin-coating on glass substrates with different Zr:Si molar ratios (Zr:Si = 75:25, 50:50 and 25:75). Refractive index, thickness, number of propagating modes and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm wavelengths by the prism coupling technique. Distributed feedback (DFB) laser effect was observed and studied as a function of films thickness and refractive index.

A study of the hydrolysis pathway in oxalic acid catalyzed reacting TMOS-water mixtures under ultrasound stimulation

The hydrolysis of TMOS in oxalic acid catalyzed reacting TMOS-water mixtures, under ultrasound stimulation, was studied by fitting a simplified dissolution and reaction modeling for samples, the hydrolysis rate of which had been measured in a previous work. The reaction pathway represented in a ternary diagram shows a heterogeneous step for the reaction which gradually progresses until complete homogenization of the system. Besides the water dissolved due to the homogenizing effect of the alcohol, ultrasound maintains a virtual and additional dissolution of water located at the interface between the TMOS and water during the heterogeneous step of the reaction. The mean radius of the heterogeneity represented by water dispersed in TMOS was evaluated as around 150 Angstrom. The oxalic acid concentration accordingly increases the hydrolysis rate constant but its fundamental role on the solubility of water in TMOS could not unequivocally be established.

Structure of weakly bonded PPG-silica nanocomposites

The structure of silica-polypropyleneglycol (PPG) nanocomposites with weak physical bonds between the organic (PPG) and inorganic (silica) phase, prepared by the sol-gel process, was investigated by small angle X-ray scattering (SAXS). These nanocomposite materials are transparent, flexible, have good chemical stability and exhibit high ionic conductivity when doped with lithium salt. Their structure was studied as a function of silica weight fraction x (0.06 less than or equal to x less than or equal to 0.29) and [O]/[Li] ratio (oxygens being of ether-type). The shape of the experimental SAXS curves agrees with that expected for scattering intensity produced by fractal aggregates sized between 30 and 90 Angstrom. This result suggests that the structure of the studied hybrids consists of silica fractal aggregates embedded in a matrix of PPG. The correlation length of the fractal aggregates decreases and the fractal dimension increases for increasing silica content. The variations in structural parameters for increasing Li+ doping indicate that lithium ions favor the growth of fractal silica aggregates without modifying their internal structure and promote the densification of the oligomeric PPG matrix.