80 resultados para Structural evolution


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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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The structural evolution during sintering of compacted SnO2 sol-gel powder was investigated using nitrogen adsorption isotherm analysis. Results show that for sintering temperatures up to 400°C the samples have a fractal pore size distribution. As the sintering temperature increases, a structural rearragement occurs, allowing an increase of the efficiency of particle packing and the reduction of fractality. Above 400°C, the pore size growth associated with grain coalescence is the main structural change observed as the sintering temperature increases. © 1995.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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A strong greenish-light photoluminescence (PL) emission was measured at room temperature for disordered and ordered powders of CaMoO4 prepared by the polymeric precursor method. The structural evolution from disordered to ordered powders was accompanied by XRD. Raman spectroscopy, and TEM imagery. High-level quantum mechanical calculations in the density functional framework were used to interpret the formation of the structural defects of disorder powders in terms of band diagram and density of states. Complex cluster vacancies [MoO3 center dot V-O(z)] and [CaO7 center dot V-O(z)] (where V-O(z) = V-O(X), V-O(center dot), V-O(center dot center dot)) were suggested to be responsible to the appearance of new states shallow and deeply inserted in the band gap. These defects give rise to the PL in disordered powders. The natural PL emission of ordered CaMoO4 was attributed to an intrinsic slight distortion of the [MoO4] tetrahedral in the short range.

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Samples of the V(2)O(5)/TiO(2) system were prepared by the sol-gel method and calcined at different temperatures. Surface species of vanadium, their dispersion, as well as the structural evolution of the system were analysed by XRD, Raman, EPR, and XPS techniques. The results of XRD showed the evolution of TiO(2) from anatase phase to rutile. phase. The Raman spectra for calcination temperatures up to 500 degreesC showed a good dispersion of vanadium over titania in the form of monomeric vanadyl groups (V(4+)) and polymeric vanadates (V(5+)). At least three families of V4+ ions were identified by EPR investigations. Two kinds of isolated V(4+) species are placed in sites of octahedral symmetry, substituting Ti(4+) in the rutile phase. The third is formed by pairs of V(4+) species on the surface of titania. Above 500 degreesC part of superficial V(4+) is inserted into the,matrix of titania and part is oxidized to V(5+). The XPS results showed that the V/Ti ratio rises with increasing calcination temperature, indicating a smaller dispersion of vanadium.

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The structural evolution in silica sols prepared from tetraethoxysilane (TEOS) sonohydrolysis was studied 'in situ' using small-angle x-ray scattering (SAXS). The structure of the gelling system can be reasonably well described by a correlation function given by gamma(r) similar to (1/R(2))(1/r) exp(- r/xi), where xi is the structure correlation length and R is a chain persistence length, as an analogy to the Ornstein-Zernike theory in describing critical phenomenon. This approach is also expected for the scattering from some linear and branched molecules as polydisperse coils of linear chains and random f-functional branched polycondensates. The characteristic length. grows following an approximate power law with time t as xi similar to t(1) (with the exponent quite close to 1) while R remains undetermined but with a constant value, except at the beginning of the process in which the growth of. is slower and R increases by only about 15% with respect to the value of the initial sol. The structural evolution with time is compatible with an aggregation process by a phase separation by coarsening. The mechanism of growth seems to be faster than those typically observed for pure diffusion controlled cluster-cluster aggregation. This suggests that physical forces (hydrothermal forces) could be actuating together with diffusion in the gelling process of this system. The data apparently do not support a spinodal decomposition mechanism, at least when starting from the initial stable acid sol studied here.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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There are many advantages to using a microwave as a source of heat in hydrothermal reactions. Because it is a quick and homogeneous way to crystallize ceramic powders, it was used in this work for the production of antiferroelectric sodium mobate (NaNbO3) in a cubic-like form and its intermediary phase, disodium diniobate hydrate (Na2Nb2O6 center dot H2O), with a fiber morphology. The syntheses were carried out by treating niobic acid (Nb2O5 center dot nH(2)O) with NaOH. By changing the reaction time and the concentration of the reactants, particles with different structures and different morphologies could be obtained. The structural evolution of the products of this reaction was elucidated on the basis of the arrangement of the NbO6 octahedral units. Conclusive results were obtained with morphological and structural characterizations through XRD, TEM, MEV, and NMR and Raman spectroscopy. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Glasses having the composition (100 - x)As2P2S8-xGa(2)S(3) with x ranging from 0 to 50% were investigated to determine the compositional effect on properties and local structure. The glass transition temperature (T-g) and the stability parameter against crystallization (T-x - T-g) increased with the addition of Ga2S3. The structure of these glasses was probed by Raman scattering, Fourier transform infrared (FT-IR) and P-31 nuclear magnetic resonance. on the basis of the observed vibrations and the strength of the P-31-P-31 homonuclear magnetic dipolar coupling, two scenarios can be proposed for the structural evolution induced by the addition of Ga2S3. For x <= 20% we may have the formation of GaS4E- groups (E = nonbonding electron), and for x >= 30% we have depolymerization of the As2P2S8 units and the formation of a network of GaPS4 units with each PS4/2 unit (Q(4)) species carrying a single positive formal charge.

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The nanostructural characteristics of acid-catalyzed sonogels are studied along the aging process at 60 degreesC in saturated conditions and after the CO, supercritical extraction (aerogel). The structural evolution was studied by means of small-angle X-ray scattering (SAXS) and UV-Visible absorption techniques. The sonogel exhibits a mass fractal structure in a length scale between zeta - 1/q(0) similar to 5.3 and a(1) similar to 1/q(m) similar to 0.22 nm, as the length scale probed by SAXS. The apparent mass fractal dimension lightly increases from 2.0 for fresh gel until 2.2 for 14 days aging in wet conditions. The UV absorption also increases with the aging time in wet conditions. Both observations are consistent with the syneresis process accompanying the polycondensation progress during aging in saturated conditions. For long aging times, the wet sonogels show a light transition from a mass to a surface fractal. in a very small interval of the length scale, developing an extremely rough surface with fractal dimension D-S similar to 2.9, the fractal characteristics of the sonogels practically do not change with the alcohol exchange. With the CO2 supercritical extraction (aerogel). The interval in the length scale in which the surface fractal is defined increases, while the surface fractal dimension diminishes to D-S similar to 2.5. The mass fractal characteristics are less apparent in the aerogels. (C) 2001 Elsevier B.V. B.V. All rights reserved.