136 resultados para Nonisothermal kinetics


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The influence of additions of 2, 4, 6, 8, 10 and 12 wt.% Ag in the isothermal aging kinetics of the Cu-8 wt.% Al alloy was studied using microhardness measurements, differential scanning calorimetry, optical and scanning electron microscopy and X-ray diffractometry. The results indicate that the presence of silver is responsible for the shift of the equilibrium concentration to higher Al contents, allowing the formation of the gamma(1) phase (Al4Cu9) in this alloy. For Ag additions up to 6% the dominant kinetic process is Ag precipitation and for additions from 8 to 12% Ag the nucleation of the perlitic phase dominates. (C) 2003 Elsevier B.V. B.V. All rights reserved.

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The kinetics of Ag-rich precipitates formation in the Cu-2 wt.% Al alloy with additions of 2, 4, 6, 8, 10 and 12 wt.% Ag was studied using microhardness changes with temperature and time, differential scanning calorimetry (DSC), differential thermal analysis (DTA), scanning electron microscopy (SEM), optical microscopy (OM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). The results indicated that an increase in the Ag content decreases the activation energy for Ag-rich precipitates formation, and that it is possible to estimate the values of the diffusion and nucleation activation energies for the Ag precipitates. (C) 2004 Elsevier B.V. All rights reserved.

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The non-occurrence of the beta' -> (alpha+ gamma(1)) decomposition reaction in the Cu-9 wt.% Al-6 wt.% Ag alloy, on ageing between 200 and 450 degrees C, is discussed considering the influence of Ag on point defects redistribution and energy difference between martensite and the ordered parent phase. (c) 2005 Elsevier B.V All rights reserved.

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The influence of 4 wt.%Ag addition on the isothermal decomposition kinetics of the beta' phase in the Cu-9wt.%Al alloy was studied by microhardness measurements, optical and scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, and X-ray diffractometry. The results showed that the presence of Ag decreases the beta' --> (alpha + gamma(1)) decomposition reaction rate in the Cu-9%Al-4%Ag alloy, an effect that may be associated to the gamma(1) phase which catalyses the Ag precipitation, making it faster than the decomposition reaction, and thus, stabilizing the martensitic phase. (C) 2003 Elsevier B.V. All rights reserved.

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The influence of the disordered (Cu)-alpha phase in the isothermal aging kinetics of the Cu-19 at.%Al alloy was studied using microhardness measurements, optical and scanning electron microscopy and X-ray diffractometry. The results indicate that the beta'-->(alpha+gamma (1)) decomposition reaction rate increases with the increase of the temperature in the range between 150 and 500 degreesC and at 600 degreesC the reaction is delayed by the alpha phase precipitation. The value obtained for the activation energy indicates an interface diffusion controlled reaction. (C) 2001 Elsevier B.V. B.V. All rights reserved.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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The recycling of soft drink bottles poly(ethylene terephthalate) (PET) has been used as an additive in varnish containing alkyd resin. The PET, called to recycled PET (PET-R), was added to the varnish in increasing amounts. Samples of varnish containing PET-R (VPET-R) were used as a film onto slides and its thermal properties were evaluated using thermogravimetry (TG). Throughout the visual analysis and thermal behavior of VPET-R it is possible to identify that the maximum amount of PET-R added to the varnish without changing in the film properties was 2%.The kinetic parameters, such as activation energy (E) and the pre-exponential factor (A) were calculated by the isoconversional Flynn-Wall-Ozawa method for the samples containing 0.5 to 2.0% PET-R. A decrease in the values of E was verified for lower amounts of PET-R for the thermal decomposition reaction. A kinetic compensation effect (KCE) represented by the lnA=-13.42+0.23E equation was observed for all samples. The most suitable kinetic model to describe this decomposition process is the autocatalytic Sestak-Berggren, being the model applied to heterogeneous systems.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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A criação de jacaré do Pantanal (Caiman crocodilus yacare) em cativeiro tem sido estimulada, e entre as técnicas de processamento de sua carne, a salga é um processo de conservação relativamente simples e de baixo custo. O objetivo deste trabalho foi estudar a cinética de difusão de cloreto de sódio em carne de jacaré do Pantanal criado em cativeiro, durante a salga úmida. Foram utilizados volumes limitados de salmoura e os experimentos foram realizados com relações salmoura/músculo de 3, 4 e 5, com concentrações de salmoura de 15%, 20% e 25% em peso e temperaturas de 10, 15 e 20ºC. A solução analítica da segunda lei de Fick, considerando difusão unidimensional em uma placa infinita em contato com uma solução bem agitada de volume limitado, foi utilizada para calcular os coeficientes de difusão efetivos de sal e estimar o conteúdo de cloreto de sódio nos filés. Obteve-se boa concordância entre o modelo analítico considerado e os dados experimentais. As difusividades do sal nos filés ocorreram na faixa de 0,47x10-10 a 9,62x10-10 m²/s.

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Colloidal suspensions of tin oxide nanocrystals were synthesized at room temperature by the hydrolysis reaction of tin chloride (II), in an ethanolic solution. The coarsening kinetics of such nanocrystals was studied by submitting the as-prepared suspensions to hydrothermal treatments at temperatures of 100, 150 and 200 degrees C for periods between 60 and 12,000 min. Transmission electron microscopy (TEM) was used to characterize the samples (i.e. distribution of nanocrystal size, average particle radius and morphology). The results show that the usual Ostwald ripening coarsening mechanism does not fit well the experimental data, which is an indicative that this process is not significant for SnO2 nanocrystals, in the studied experimental conditions. The morphology evolution of the nanocrystals upon hydrothermal treatment indicates that growth by oriented attachment (OA) should be significant. A kinetic model that describes OA growth is successfully applied to fit the data. (c) 2006 Elsevier B.V. All rights reserved.

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Kinetics of short-range ordering (SRO) in Ag with 21, 23 and 28 at% Zn is investigated by residual resistometry during isochronal and isothermal heat treatment for different states of post-deformation defect annealing after cold-rolling to about 30 and 60% thickness reduction. Resistivity changes due to pure ordering can be separated from the as-measured total resistivity change which includes defect annealing. Although the initial state of SRO of the as-rolled material can be estimated to be comparably low, for as-rolled and partially annealed states by appropriate thermal treatment evolution of SRO is achieved which corresponds quite well to that of recrystallized samples. It is observed, however, that quenched-in surplus vacancies contribute considerably to the ordering process for the recrystallized state and that this contribution is still increased by the grain growth during the final stage of annealing. It therefore turns out that SRO-kinetics under equilibrium vacancy conditions can be better observed in a state of post-deformation annealing, for which deformation induced point defects are annealed-out, but a relatively high dislocation density is still present to act as a vacancy sink. Copyright (C) 1996 Acta Metallurgica Inc.

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The crystal nucleation rates of a metastable phase (chi) on the surface of a near stoichiometric cordierite glass were determined for temperatures between 839 and 910 degrees C (T-g similar to 800 degrees C). The surface nucleation kinetics of that phase on our glass, as well as on a stoichiometric glass (2 MgO-2Al(2)O(3)-5SiO(2)) studied by other authors, were analysed in terms of the classical nucleation theory; for the first time. It was shown that the effective interfacial energy for surface nucleation is substantially lower than that for homogeneous volume nucleation in silicate glasses, vindicating the assumption of heterogeneous nucleation on free glass surfaces. The average wetting angle between the nucleating crystals and the active solid particles was estimated to be around 46 degrees C. The pre-exponential constant was several orders of magnitude higher than the theoretical values as found for volume homogeneous nucleation in oxide glasses.

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An understanding of isoniazid (INH) drug resistance mechanism in Mycobacterium tuberculosis should provide significant insight for the development of newer anti-tubercular agents able to control INH-resistant tuberculosis (TB). The inhA-encoded 2-trans enoyl-acyl carrier protein reductase enzyme (InhA) has been shown through biochemical and genetic studies to be the primary target for INH. In agreement with these results, mutations in the inhA structural gene have been found in INH-resistant clinical isolates of M. tuberculosis, the causative agent of TB. In addition, the InhA mutants were shown to have higher dissociation constant values for NADH and lower values for the apparent first-order rate constant for INH inactivation as compared to wild-type InhA. Here, in trying to identify structural changes between wild-type and INH-resistant InhA enzymes, we have solved the crystal structures of wild-type and of S94A, I47T and I21V InhA proteins in complex with NADH to resolutions of, respectively, 2.3 angstrom, 2.2 angstrom, 2.0 angstrom, and 1.9 angstrom. The more prominent structural differences are located in, and appear to indirectly affect, the dinucleotide binding loop structure. Moreover, studies on pre-steady-state kinetics of NADH binding have been carried out. The results showed that the limiting rate constant values for NADH dissociation from the InhA-NADH binary complexes (k(off)) were eleven, five, and tenfold higher for, respectively, I21V, I47T and S94A INH-resistant mutants of InhA as compared to INH-sensitive wildtype InhA. Accordingly, these results are proposed to be able to account for the reduction in affinity for NADH for the INH-resistant InhA enzymes. (c) 2006 Elsevier Ltd. All rights reserved.