Ground- and excited-state properties of M-center oxygen vacancy aggregates in the bulk and the surface of MgO

Aggregates of oxygen vacancies (F centers) represent a particular form of point defects in ionic crystals. In this study we have considered the combination of two oxygen vacancies, the M center, in the bulk and on the surface of MgO by means of cluster model calculations. Both neutral and charged forms of the defect M and M+ have been taken into account. The ground state of the M center is characterized by the presence of two doubly occupied impurity levels in the gap of the material; in M+ centers the highest level is singly occupied. For the ground-state properties we used a gradient corrected density functional theory approach. The dipole-allowed singlet-to-singlet and doublet-to-doublet electronic transitions have been determined by means of explicitly correlated multireference second-order perturbation theory calculations. These have been compared with optical transitions determined with the time-dependent density functional theory formalism. The results show that bulk M and M+ centers give rise to intense absorptions at about 4.4 and 4.0 eV, respectively. Another less intense transition at 1.3 eV has also been found for the M+ center. On the surface the transitions occur at 1.6 eV (M+) and 2 eV (M). The results are compared with recently reported electron energy loss spectroscopy spectra on MgO thin films.

Temperature-dependent orientational ordering on a spherical surface modeled with a lattice spin model

We study the orientational ordering on the surface of a sphere using Monte Carlo and Brownian dynamics simulations of rods interacting with an anisotropic potential. We restrict the orientations to the local tangent plane of the spherical surface and fix the position of each rod to be at a discrete point on the spherical surface. On the surface of a sphere, orientational ordering cannot be perfectly nematic due to the inevitable presence of defects. We find that the ground state of four +1/2 point defects is stable across a broad range of temperatures. We investigate the transition from disordered to ordered phase by decreasing the temperature and find a very smooth transition. We use fluctuations of the local directors to estimate the Frank elastic constant on the surface of a sphere and compare it to the planar case. We observe subdiffusive behavior in the mean square displacement of the defect cores and estimate their diffusion constants.

TL, EPR and optical absorption in natural grossular crystal

Grossular is one of six members of silicate Garnet group. Two samples GI and GII have been investigated concerning their luminescence thermally stimulated (TL). EPR and optical absorption and the measurements were carried out to find out whether or not same point defects are responsible for all three properties. Although X-rays diffraction analysis has shown that both GI and GII have practically the same crystal structure of a standard grossular crystal, they presented different behavior in many aspects. The TL glow curve shape, TL response to radiation dose, the effect of annealing at high temperatures before irradiation, the dependence of UV bleaching parameters on peak temperature, all of them differ going from GI to GII. The EPR signals around g = 2.0 as well as at g = 4.3 and 6.0 have much larger intensity in GI than in GII. Very high temperature (> 800 degrees C annealing causes large increase in the bulk background absorption in GI, however, only very little in GII. In the cases of EPR and optical absorption, the difference in their behavior can be attributed to Fe3+ ions; however, in the TL case one cannot and the cause was not found as yet. (C) 2008 Elsevier B.V. All rights reserved.

Does the TL supralinearity occur during irradiation in alkali halides?

In the last ten to fifteen years, there has been a predominant belief that the linear-supralinear-sublinear behaviour of the TL response of alkali halides to the radiation dose necessarily occurs in the heating stage for TL reading. It is based on the assumption that coloration in these crystals grows linear-sublinearly with the dose during irradiation. Since both colour centre and TL centre are based on the same point defects the TL response should also grow linear-sublinearly with dose. In 1950, half a dozen authors showed that the coloration of F-centres in KCl takes place in two stages, the second one being responsible for non-linear behaviour. In this paper, we show that indeed in NaCl both F-centre and TL grow linear-supralinear-sublinearly with the dose during irradiation.

Correlation between thermoluminescence sensitivity and crystallization temperatures of quartz: Potential application in geothermometry

The thermoluminescence (TL) characteristics of quartz are highly dependent of its thermal history. Based on the enhancement of quartz luminescence occurred after heating, some authors proposed to use quartz TL to recover thermal events that affected quartz crystals. However, little is know about the influence of the temperature of quartz crystallization on its TL characteristics. In the present study, we evaluate the TL sensitivity and dose response curves of hydrothermal and metamorphic quartz with crystallization temperatures from 209 +/- 15 to 633 +/- 27 degrees C determined through fluid inclusion and mineral chemistry analysis. The studied crystals present a cooling thermal history, which allow the acquiring of their natural TL without influence of heating after crystallization. The TL curves of the studied samples present two main components formed by different peaks overlapped around 110 C and 200-400 degrees C. The TL sensitivity in the 200-400 degrees C region increases linearly with the temperature of quartz crystallization. No relationship was observed between temperatures of quartz crystallization and saturation doses (<100 Gy). The elevated TL sensitivity of the high temperature quartz is attributed to the control exerted by the temperature of crystallization on the substitution of Si(4+) by ions such as Al(3+) and Ti(4+), which produce defects responsible for luminescence phenomena. The linear relationship observed between TL in the 200-400 degrees C region and crystallization temperature has potential use as a quartz geothermometer. The relative abundance of quartz in the earth crust and the easiness to measure TL are advantageous in relation to geothermometry methods based on chemistry of other minerals. (C) 2010 Elsevier Ltd. All rights reserved.

Defeitos pontuais nos compostos intermetálicos ZrNi e Zr/sub 2/Ni estudados por dinâmica molecular

Empregamos a técnica de Dinâmica Molecular para estudar propriedades de defeitos pontuais nos compostos intermetálicos ZrNi e Zr2Ni. Descrevemos as configurações estáveis de defeitos e mecanismos de migração, assim como as energias envolvidas. Os potenciais interatômicos foram derivados do Embedded Atom Model. No intuito de levar em conta a variação de estequiometria causada pela presença de alguns tipos de defeitos em intermetálicos, apresentamos um método numérico que fornece a energia efetiva de formação de defeitos e aplicamos o método ao ZrNi e Zr2Ni. Os resultados mostraram que vacâncias são mais estáveis na sub—rede do Ni, com energia de formação de 0,83 e-0,61 eV em ZrNi e Zr2Ni, respectivamente. Vacâncias de Zr são instáveis em ambos compostos; elas decaem espontaneamente em pares anti—sítio e vacância de Ni. Configurações e energias de formação de intersticiais também foram calculadas e mostraram comportamentos similares. Em ZrNi, a migração de vacâncias ocorre preferencialmente nas direções [025] e [100], com as respectivas energias de migração 0,67 e 0,73 eV, e é um processo essencialmente bidimensional no plano (001). Em Zr,Ni, a migração de vacâncias é unidimensional, ocorrendo na direção [001], com energia de migração de 0,67 eV. Em ambos compostos a presença de defeitos de anti—sítio de Ni diminui a energia de migração da vacância de Ni em até 3 vezes e facilita a movimentação em três dimensões. Mecanismos de anel não são energeticamente eficientes em comparação com saltos diretos. As configurações estáveis de intersticiais em ambos compostos consistem em um átomo de Ni sobre o plano (001) entre dois vizinhos de Zr fora do plano. Intersticiais de Zr são instáveis e tendem a deslocar um átomo de Ni, ocupando seu sítio. Energias de deslocamento foram estudadas através de simulações de irradiação de ambos compostos. Durante o processo de colisão binária, um potencial universal ZBL foi usado para colisões a curta distância. Para distâncias intermediárias usamos um potencial de união arbitrário. Zr mostrou—se mais difícil de ser arrancado de seu sítio do que Ni. Encontramos valores de energia de deslocamento no intervalo de aproximadamente 29 eV até 546 eV. Alguns resultados experimentais são mostrados e apresentam boa concordância com os cálculos.

Impact of oxygen atmosphere on piezoelectric properties of CaBi2Nb2O9 thin films

CaBi2Nb2O9 (CBNO) thin films were deposited on platinum-coated silicon substrates by the polymeric precursor method, and were annealed in air and in an oxygen atmosphere. The structure, surface morphology and electrical properties of CBNO thin films have been investigated. The presence of an oxygen atmosphere during crystallization of the films affected the structure perfection and morphology, as well as ferroelectric and piezoelectric properties. A reduction in P-r and piezoelectric coefficient, an increase of V-c and displacement of the Curie point is evident in the films crystallized in an oxygen atmosphere. The impact of exposure to the oxygen atmosphere on the creation of defects caused by bismuth and oxygen vacancies between layers was also investigated by X-ray photoelectron spectroscopy. (c) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Kinetics of martensite decomposition in the Cu-9Al-6Ag alloy

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.

Short-range order kinetics in alpha-AgZn for various states of post-deformation defect annealing after cold-rolling

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.

Changes of microstructure in alpha AgZn during post-deformation annealing after cold-rolling

The annealing processes of deformation-induced defects after cold-rolling to about 30 and 60% thickness reduction were investigated for Ag-21, 23, 28 at% Zn by means of residual electrical resistivity, microhardness, light microscopy and transmission electron microscopy (TEM) Three annealing stages have been detected and consistently interpreted as annealing-out of mainly point defects and their agglomerates (stage I), formation of dislocation cells and recrystallized strain-free grains (stage II) and grain growth (stage III). Further, it is tried to determine the evolution of defect production (point defects and dislocations) during rolling deformation from measured changes of electrical resistivity and microhardness. Copyright (C) 1996 Acta Metallurgica Inc.

Impedance spectroscopy of SnO2: CoO during sintering

SnO2:m mol% CoO (0.5 less than or equal to m less than or equal to 6.0) ceramic specimens were studied by impedance spectroscopy in the 5 Hz-13 MHz frequency range during heating cold-pressed specimens from room temperature to 1250 degrees C. The electrical resistivity during sintering decreases from 4 to 6 orders of magnitude in the 400-1500 K temperature range depending on the amount of CoO. An increase in electrical resistivity in the 570-670 K range is related to the release of adsorbed water. The results for the 970-1500 K show that the higher the amount of the CoO addition, the lower is the temperature at which SnO2:CoO reaches a minimum electrical resistivity. This suggests that oxygen point defects created by dissolution of cobalt ions in the SnO2 lattice are controlling the densification rate of these ceramics.

Influence of doping on the preferential growth of alpha-MoO3

MoO3 is a lamellar material with applications in different areas, as solid lubricants, catalysis, solar cells, etc. In the present work, MoO3 powders, synthesized by the polymeric precursor method, were doped with nickel or cobalt. The powder precursors were characterized by TG/DTA. After calcination between 500 and 700 degrees C, the samples were characterized by X-ray diffraction, infrared and Raman spectroscopy and scanning electron microscopy. beta-MoO3 was obtained after calcination at low temperatures. With the temperature increase, alpha-MoO3 is observed, with a preferential growth of the (0 2k 0) planes, when the material is doped and calcined at 700 degrees C. Doping with nickel increases five times the preferential growth. As a consequence, plate-like particles are observed. (c) 2007 Elsevier B.V. All rights reserved.

Desenvolvimento de um instrumento portátil para detectar falha em rolamento de motor de indução, pela técnica do envelope, usando um DSP de 16 bits e a transformada de Hilbert

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Implementação de técnicas de processamento de sinais para o monitoramento da condição de mancais de rolamento

Pós-graduação em Engenharia Mecânica - FEG

Influência dos defeitos cristalinos nas propriedades dielétricas e não-ôhmicas do 'CA' 'CU IND.3' 'TI IND.4' 'O IND.12'(CCTO)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)