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Doctoral Thesis
DOI
https://doi.org/10.11606/T.43.2010.tde-29062010-093911
Document
Author
Full name
Luiz Tomaz Filho
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2010
Supervisor
Committee
Watanabe, Shigueo (President)
Itri, Rosangela
Pontuschka, Walter Maigon
Sabioni, Antônio Claret Soares
Teles, Lara Kuhl
Title in Portuguese
Estudo de propriedades de luminescência, de ressonância paramagnética eletrônica e de centros de cor da pumpelita e de sua correlação com defeitos pontuais.
Keywords in Portuguese
Ressonância paramagnética de spin (EPR)
Silicatos (pumpelita)
Termoluminescência
Abstract in Portuguese
Cristais naturais de pumpelita Ca8Al8(Mg,Fe,Mn,Al)[(SiO4)4/(Si2O7)4/(OH)8(H2O, OH)4]), provenientes da mina de Brejui, município de Currais Novos, Rio Grande do Norte, foram investigados através das técnicas de termoluminescência (TL), absorção óptica (AO) e ressonância paramagnética eletrônica (EPR) com o intuito de entender os efeitos da radiação ionizante e de recozimento em altas temperaturas sobre estes cristais. As curvas TL obtidas apresentaram cinco picos, 90, 145, 220, 315 e 390 oC, após terem sido irradiadas para uma taxa de quecimento de 4 °C/s. A decomposição espectral da luz TL foi obtida para todos os picos e presentou uma emissão centrada em 575 nm e largura à meia altura de 75 nm e outras duas emissões menores em 470 nm e 660 nm indicando que o processo TL pode possuir mais de um centro de recombinação, independentemente das temperaturas dos picos. Em um segundo momento, foi investigado o efeito de diferentes tratamentos térmicos pré-irradiação (500, 600, 700, 800 e 900 °C) nas propriedades TL dos cristais. Somente a intensidade das emissões mostrou ser dependente da temperatura destes tratamentos térmicos, a posição dos quatro picos não foi alterada. Os picos em 220 e 390 °C apresentaram grande sensibilidade ao tratamento térmico. Uma análise termogravimétrica mostrou que entre 650 e 800 °C houve grande perda de massa envolvida num processo endotérmico, sugerindo uma provável mudança de estado. O espectro de ressonância paramagnética eletrônica mostra um sinal muito intenso que se estende de 1000 a 6000 Gauss e seis linhas típicas hiperfinas de Mn2+ entre 3000 e 4000 Gauss. O sinal EPR gigante é devido à interação dipolo (magnético) dipolo magnético) de Fe3+. Os espectros de AO de amostras recozidas em 600 °C, 700 °C e 900 °C mostram num resultado muito interessante, a banda em torno de 1060 nm, que, é devida a Fe2+ muda pouco com o tratamento térmico até 800 °C, mas, entre 800 °C e 900 °C a banda decresce. Nessa região de temperatura, ocorre a reação: Fe2+ temperaturae + Fe3+ Fe2+ perde um elétron e se torna Fe3+. Este processo é, também, responsável pelo aumento muito grande da intensidade EPR na região de g = 2,0, em amostras que sofreram recozimentos em temperaturas acima de 850 °C, Nestas temperaturas, a coloração da pumpelita é também afetada. Todos os picos TL sofrem fotoesvaziamento (bleaching), quando a amostra irradiada é exposta a luz UV.
Title in English
Study of luminescence, electron paramagnetic resonance and color conters in pumpellyte and their correlation with point defeets
Keywords in English
Electron Spin Resonance (ESR)
Silicates (pumpellyte)
Thermoluminescence
Abstract in English
Natural mineral of pumpellyite, one of the members of epidote group has been investigated. With chemical formula (Ca8Al8(Mg,Fe,Mn,Al)[(SiO4)4/(Si2O7)4/(OH)8(H2O, OH)4]), the sample here studied was collected from Brejui Mine, Currais Novos County, state of Rio Grande do Norte. The work was aimed to investigate its thermoluminescence (TL), color centers and electron paramagnetic properties. Annealing at high temperatures, heavy irradiation and UV irradiation techniques have been used. The physical properties of interest are due to the elements composing crystal structure such as Si, Al, Mg, Fe and Mn, however among about twenty elements that can be considered impurities; only Na, K and Cr participate. The TL glow curve obtained from 600 °C for one hour pre-annealed and then - irradiated sample has shown 90, 145, 220, 275 and 390 °C peaks. A heating rate of 4 °C has been used for TL read out. The lowest 90 °C peak is very unstable, however, it is by far the most sensitive one to the irradiation; at 50 Gy -dose its peak height is almost 100 times larger. Among others, the 315 °C peak grows faster. Heat treatments before irradiation increase the sensitivity of TL peaks slowly from 500 to 800 °C, but such increase becomes very large above 800 °C. For example the 390 °C peak sensitivity increases by a factor 100 on going from 500 C to 900 °C annealing. The spectral analysis of the emitted TL light has shown that there are 470, 575 and 600 nm bands indicating that there are at least three recombination centers. The 575 nm is by far the dominating one. The UV light bleaching has shown that all the TL peaks decay fast up to 10 minutes exposure and a residual TL is left after long time exposure. The optical absorption spectrum is characterized by four absorption bands in the visible region, one strong and broad band around 1060 nm and several in near IR region. The 1060 nm band is due to Fe2+ which around 850 900 °C annealing decreases indicating that Fe2+ liberates electrons leaving Fe3+. The EPR spectrum is dominated by Fe3+ spin spin interaction. Mn2+ six hyperfine lines superpose Fe line around g = 2,0. Under 850 900 °C heating, that broad Fe3+ lines becomes stronger and broader due to Fe2+ changing to Fe3+. The EPR intensity of 800 °C annealed sample and then irradiated to 1 kGy - dose increases with microwave power, but start saturation around 30 to 40 mW power.
 
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Publishing Date
2010-06-29
 
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