Properties of optical absorption (OA), of electron paramagnetic resonance (EPR), and of thermoluminescence (TL) of grossular-Calculation of the crystal field.

Granada é um grupo de seis silicatos com a mesma estrutura cristalina e fórmulas químicas semelhantes, diferindo um do outro pelos cátions, dos quais o GROSSULAR de fórmula química Ca IND.3Al IND.2Si IND.30 IND.12 é o segundo mineral mais abundante no Brasil, e talvez o mais colorido das granadas. Foram obtidas duas amostras de Araçuaí - Minas Gerais, denominadas GV e GVI que diferem somente no teor de impurezas, as quais foram pulverizadas e peneiradas para realizar medidas de Termoluminescência (TL) e Ressonância Paramagnética Eletrônica (EPR); e cortadas em lâminas e polidas para as medidas de Absorção Ótica(AO). A análise de fluorescência mostrou a presença de 1,37mol% de Fe IND.20 IND.3 na amostra GV e, 6,2mol% na GVI, 1,03mol% de MnO na GV e 0,26mol% na GVI, 0,66mol% de MgO na GV e 0,72mol% na GVI, que participam como defeitos extrínsecos na amostra. A curva de emissão termoluminescente apresentou um pico intenso em alta temperatura em 470ºC para as amostras naturais. Amostras tratadas termicamente em 600ºC/1h. e irradiadas com diferentes doses gama mostraram picos em 145, 235 e 335ºC em GV e em 145, 200, 250, 335 e 445ºC em GVI, mostrando-se mediante a deconvolução da curva TL que GV está formada de seis picos e GVI de sete picos bastante superpostos. Enquanto que em GV os picos de baixa temperatura crescem mais rápido com a irradiação, é o pico em 340ºC que aumenta rapidamente em GVI mantendo sua individualidade, porém em ambos casos os picos TL crescem sublinearmente após 100Gy de doses gama. Outras diferenças consideráveis entre as amostras GV e GVI foram observadas do comportamento com os diferentes tratamentos térmicos, observando-se o aumento da sensibilidade TL somente em GV enquanto que na amostra GVI, não houve a sensibilização, mas, um comportamento bastante caótico. A irradiação ultra-violeta (UV) produz decaimento na intensidade TL, onde em GV a TL residual diminui com a temperatura do pico e em GVI o comportamento é contrário. Estas diferenças não podem ser explicadas baseados somente na diferença do teor de impurezas das amostras e, possivelmente a estrutura cristalina esteja também envolvida. Os íons de ferro e manganês entram na estrutura do grossular, e o cálculo do campo cristalino mostrou que o Fe POT.3+ pode ocupar o sítio tetraédrico e octaédrico substituindo o AI e Si. Os íons Mn POT.2+ e Fe POT.2+ ocupam posições dodecaédricas substituindo o Ca na estrutura. O espectro de EPR. apresentou sinais em g=4,3 , 6,0 relacionados ao ferro e, o sinal em g=2,004 devido à interação de troca e dipolar de ambos íons Fe POT.3+ e Mn POT.2+. O recozimento das amostras em alta temperatura mostrou que os íons de Fe POT.2+ oxidam-se para Fe POT.3+ e os íons de Mn POT.3+ mudam para Mn POT.2+, respectivamente. Não foi encontrada uma correlação entre os defeitos responsáveis pelos espectros de AO e EPR e os centros que participam na termoluminescência.Garnet is a group of six silicates with the same crystal structure but with chemical formula differing by their cations. Grossular of chemical formula Ca3AlzSi3012 is the second most abundant garnet in Brazil and probably the most colorful of the garnets. Two samples of grossular, named GV and GVI were obtained of Araçuai-Minas Gerais difIering by impurities content. These samples were pulverized and sieved for termoluminescence (TL) and electron paramagnetic resonance (EPR) measurements. Polished plates of 2.0mm thickness were prepared for optical absorption (AO) measurements. The X-ray fluorescence has revealed several kinds of impurities, being the most important 1,37mol% of Fe203 in GV e, 6,2mol% in GVI, 1,03mol% of MnO in GV and O,26mol% in GVI, O,66mol% of MgO in GV and 0,72mol% in GVI, which might participate as extrinsic defects in the samples. The TL glow curve of natural samples shows a high temperature peak at 470°C that is greater in GVI than in GV. Samples heat treated at 600°C/1h and irradiated with different gamma dose present peaks at 145, 235 and 335°C in GV and, 145 200, 250, 335 and 445°C in GVI. However, the glow curve deconvolution shows that in fact GV is formed by six peaks and GVI by seven peaks overlapped. While, the low temperature peaks increase with the dose in GV, it is the last peak in GVI (340°C) that increases fast keeping its individuality, however a similar sublinear dependence with the irradiation dose was founded for both samples. Other differences between these samples refer to the behavior with the pre-irradiation anneal temperature, namely increase in the TL sensibilities observed only in GV and a caotic behavior in GVI. The UV irradiation produces decay in TL intensity with exposure time. The residual TL diminishes with the peak temperature in GV, being opposite in GVI. The iron and manganese ions can replace some ions in the grossular structure. The crystal field analysis shows that the Fe3+ ions occupy tetrahedral and octahedral sites replacing AI and Si, similarly Ca can be substituited by Fe2+ and Mn2+ in the dodecahedral position. The EPR spectra show signals in g=4.3, g=6.0 related to the iron and g=2.004 signal is due to the dipolar and exchange interactions between M 712+ and Fé+ ions. The high temperature heat treatment of the samples give rise to the change from Fe2+ to Fe3+ by oxidation and from Mn3+ to Mn2+ . No correlation between the defects responsible for the AO and EPR spectra and the TL centers was found

Properties of optical absorption (OA), of electron paramagnetic resonance (EPR), and of thermoluminescence (TL) of grossular-Calculation of the crystal field.

Granada é um grupo de seis silicatos com a mesma estrutura cristalina e fórmulas químicas semelhantes, diferindo um do outro pelos cátions, dos quais o GROSSULAR de fórmula química Ca IND.3Al IND.2Si IND.30 IND.12 é o segundo mineral mais abundante no Brasil, e talvez o mais colorido das granadas. Foram obtidas duas amostras de Araçuaí - Minas Gerais, denominadas GV e GVI que diferem somente no teor de impurezas, as quais foram pulverizadas e peneiradas para realizar medidas de Termoluminescência (TL) e Ressonância Paramagnética Eletrônica (EPR); e cortadas em lâminas e polidas para as medidas de Absorção Ótica(AO). A análise de fluorescência mostrou a presença de 1,37mol% de Fe IND.20 IND.3 na amostra GV e, 6,2mol% na GVI, 1,03mol% de MnO na GV e 0,26mol% na GVI, 0,66mol% de MgO na GV e 0,72mol% na GVI, que participam como defeitos extrínsecos na amostra. A curva de emissão termoluminescente apresentou um pico intenso em alta temperatura em 470ºC para as amostras naturais. Amostras tratadas termicamente em 600ºC/1h. e irradiadas com diferentes doses gama mostraram picos em 145, 235 e 335ºC em GV e em 145, 200, 250, 335 e 445ºC em GVI, mostrando-se mediante a deconvolução da curva TL que GV está formada de seis picos e GVI de sete picos bastante superpostos. Enquanto que em GV os picos de baixa temperatura crescem mais rápido com a irradiação, é o pico em 340ºC que aumenta rapidamente em GVI mantendo sua individualidade, porém em ambos casos os picos TL crescem sublinearmente após 100Gy de doses gama. Outras diferenças consideráveis entre as amostras GV e GVI foram observadas do comportamento com os diferentes tratamentos térmicos, observando-se o aumento da sensibilidade TL somente em GV enquanto que na amostra GVI, não houve a sensibilização, mas, um comportamento bastante caótico. A irradiação ultra-violeta (UV) produz decaimento na intensidade TL, onde em GV a TL residual diminui com a temperatura do pico e em GVI o comportamento é contrário. Estas diferenças não podem ser explicadas baseados somente na diferença do teor de impurezas das amostras e, possivelmente a estrutura cristalina esteja também envolvida. Os íons de ferro e manganês entram na estrutura do grossular, e o cálculo do campo cristalino mostrou que o Fe POT.3+ pode ocupar o sítio tetraédrico e octaédrico substituindo o AI e Si. Os íons Mn POT.2+ e Fe POT.2+ ocupam posições dodecaédricas substituindo o Ca na estrutura. O espectro de EPR. apresentou sinais em g=4,3 , 6,0 relacionados ao ferro e, o sinal em g=2,004 devido à interação de troca e dipolar de ambos íons Fe POT.3+ e Mn POT.2+. O recozimento das amostras em alta temperatura mostrou que os íons de Fe POT.2+ oxidam-se para Fe POT.3+ e os íons de Mn POT.3+ mudam para Mn POT.2+, respectivamente. Não foi encontrada uma correlação entre os defeitos responsáveis pelos espectros de AO e EPR e os centros que participam na termoluminescência.Garnet is a group of six silicates with the same crystal structure but with chemical formula differing by their cations. Grossular of chemical formula Ca3AlzSi3012 is the second most abundant garnet in Brazil and probably the most colorful of the garnets. Two samples of grossular, named GV and GVI were obtained of Araçuai-Minas Gerais difIering by impurities content. These samples were pulverized and sieved for termoluminescence (TL) and electron paramagnetic resonance (EPR) measurements. Polished plates of 2.0mm thickness were prepared for optical absorption (AO) measurements. The X-ray fluorescence has revealed several kinds of impurities, being the most important 1,37mol% of Fe203 in GV e, 6,2mol% in GVI, 1,03mol% of MnO in GV and O,26mol% in GVI, O,66mol% of MgO in GV and 0,72mol% in GVI, which might participate as extrinsic defects in the samples. The TL glow curve of natural samples shows a high temperature peak at 470°C that is greater in GVI than in GV. Samples heat treated at 600°C/1h and irradiated with different gamma dose present peaks at 145, 235 and 335°C in GV and, 145 200, 250, 335 and 445°C in GVI. However, the glow curve deconvolution shows that in fact GV is formed by six peaks and GVI by seven peaks overlapped. While, the low temperature peaks increase with the dose in GV, it is the last peak in GVI (340°C) that increases fast keeping its individuality, however a similar sublinear dependence with the irradiation dose was founded for both samples. Other differences between these samples refer to the behavior with the pre-irradiation anneal temperature, namely increase in the TL sensibilities observed only in GV and a caotic behavior in GVI. The UV irradiation produces decay in TL intensity with exposure time. The residual TL diminishes with the peak temperature in GV, being opposite in GVI. The iron and manganese ions can replace some ions in the grossular structure. The crystal field analysis shows that the Fe3+ ions occupy tetrahedral and octahedral sites replacing AI and Si, similarly Ca can be substituited by Fe2+ and Mn2+ in the dodecahedral position. The EPR spectra show signals in g=4.3, g=6.0 related to the iron and g=2.004 signal is due to the dipolar and exchange interactions between M 712+ and Fé+ ions. The high temperature heat treatment of the samples give rise to the change from Fe2+ to Fe3+ by oxidation and from Mn3+ to Mn2+ . No correlation between the defects responsible for the AO and EPR spectra and the TL centers was found

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.FAPESPFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)CNPqConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)CAPE

Thermoluminescence and optical absorption studies of natural grossular minerals

The optical absorption spectra of two samples of grossular have been measured at room temperature. An intense charge transfer band (UVCT) of iron extends to the visible and near infrared region. Some peaks associated to Fe3+ ions in tetrahedral and octahedral positions have been identified and their energy levels were computed. Mn2+ and Fe2+ ions are responsible with some bands and probably these ions occupy dodecahedral positions. No change in the intensity of optical absorption spectra were found after gamma dose, but only the 505 nm band decreases with irradiation. The OH spectra, consisting of OH overtones at 2750nm and asymmetric OH bands in the near infrared region were observed in the two samples. The heat treatment produces Fe2+ -> Fe3+ and Mn2+ -> Mn3+ by oxidation. This last was observed in sample II only. The thermally stimulated luminescence of both grossular samples has been investigated. Due to differences in iron and manganese concentration, not only a large difference has been observed in their optical absorption behavior, but also a striking difference in their thermoluminescent behavior. Actually, it is not clear whether other impurities such as Ti, Na and K that are present in quite different concentration in grossular I and II are also contributing to the thermoluminescenct properties of both samples. (C) 2008 Elsevier Ltd. All rights reserved.FAPESPFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)CNPqConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CAPESCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES

Thermo luminescence of natural and synthetic diopside

Diopside, a natural silicate mineral of formula CaMgSi2O6, has been investigated concerning its thermoluminescence (TL) and electron paramagnetic resonance (EPR) properties. Glow curves and TL vs. gamma-dose were obtained irradiating natural samples to additional dose varying from 50 to 10,000Gy. Except for a 410 degrees C peak found in the Al-doped artificial diopside, all the other peaks grow linearly with radiation dose, but saturate beyond -1 kGy. To investigate high-temperature effect before irradiation, measurements of TL intensity in samples annealed at 500-900 degrees C and then irradiated to I kGy gamma-dose were carried out. Also the TL emission spectrum has been obtained. To compare with natural diopside, a synthetic pure polycrystal was produced and further those doped with iron, aluminum and manganese were also produced. (c) 2007 Elsevier B.V. All rights reserved