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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Espectroscopia Vibracional e de ImpedÃncia de A1-xAâxTaWO6.nH2O (A=H, Li, Aâ = Ag,H) / Espectroscopia Vibracional e de ImpedÃncia de A1-xAâxTaWO6.nH2O (A=H, Li, Aâ = Ag,H)

Daniel Valim dos Reis JÃnior 27 February 2009 (has links)
FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / Realizamos a caracterizaÃÃo das amostras H1−x AgxTaWO6.H2O pirocloro e Hx Li1−xTaWO6 trirrutilo. TÃcnicas de espectroscopia Raman e transmitÃncia de infravermelho foram usadas com o objetivo de investigar propriedades estruturais do trirrutilo dopado. Os estudos revelaram que as amostras HxLi1−xTaWO6 pertencem ao sistema tetragonal polar P421m (D32d). Os estudos Raman serviram tambÃm para identificar a natureza dos modos Raman ativos dos materiais pirocloro. Dentre os modos Raman que podemos destacar aqueles observados a 340 e 720cm−1 que sÃo originÃrios dos modos infravermelho ativos ν4 e ν3. A presenÃa destes modos indica desordem posicional dos cations Ta e W. AlÃm disso, estudamos a dependÃncia do nÃmero de onda destes modos com relaÃÃo a concentraÃÃo de Ag+, que revelou um decrÃscimo monotÃnico do nÃmero de onda com a concentraÃÃo (que sà foi quebrada para a concentraÃÃo x = 0,5). Estudo de espectroscopia de impedÃncia foi feito para a caracterizaÃÃo elÃtrica dos materiais pirocloros. O experimento consistiu em medidas da dependÃncia da impedÃncia destes sistemas com a temperatura, durante o aquecimento (25 a 110 oC), e resfriamento (110 a 25 oC). O objetivo foi tentar evitar o efeito da umidade no espectro de impedÃncia. No entanto, para amostra com x = 0,20, obtemos uma resposta anÃmala da condutividade durante o resfriamento. Para explicar esse resultado, realizamos caracterizaÃÃo de microestrutura nessa amostra e nas amostras com x = 0,80 e 0,67. O resultado à que a amostra com x = 0,20 à bem caracterizada pelo modelo de âeasy-pathâ por possuir elevada porosidade enquanto nas outras duas devem possuir estrutura de precipitado de fase tipo Suzuki. Estes resultados serviram para explicar porque a anomalia no grÃfico de Arrehnius ocorreu somente na amostra com concentraÃÃo 0,20: diferenÃa de microestrutura. Neste estudo podemos constatar tambÃm que as amostras dopadas tiveram uma dependÃncia das energias de ativaÃÃo com relaÃÃo Ãs taxas de concentraÃÃo. Com exceÃÃo da amostra com taxa de concentraÃÃo 0,20, as energias de ativaÃÃo no resfriamento, encontram-se entre os valores de 0,60 e 0,23 eV de suas contrapartes puras registradas na literatura. / We have performed the characterization of doped pyrochlore (H1−xAgxTaWO6.H2O) and trirutile (Hx Li1−x TaWO6 ) samples. Raman spectroscopy and infrared transmitance thechniques were used to investigate the structural properties of doped trirutile. The studies revealed that HxLi1−xTaWO6 samples belong to the tetragonal polar symmetry P421m(D32d). Raman spectroscopy studies were also used to identify the nature of the Raman active modes of the pyrochlore materials. Among the Raman modes we can highlight the ones observed at 340 and 720 cm−1 which originate from ν4 and ν3 infrared active modes. Their presence in the Raman spectra indicates a positional disorder of the Ta and W cations. Furthermore, we studied the dependence of the frequency of these modes on the Ag+ concentration, wich revealed a monotonic decrease of the wave number with the dopant concentration x (wich was only broken for a concentration x = 0.5). Impedance spectroscopy study was performed to the electric characterization of the pyrochlore materials. The experiment consisted of measuring the dependence of the im- pedance of these system on the temperature, throughout the heating (25 to 110 o C) and the cooling (110 to 25 o C) processes. The goal was to try to avoid the humidity effect in the impedance spectra. However, for the sample with x = 0.20, we observed an anomalous response for the conductivity during the cooling process. To explain these results, we performed a microstructural characterization of the samples with x = 0.80, 0.67 and 0.20. The result is that the sample with x = 0.20 are well characterized by the model of âeasy-pathâ, having high porosity, while the other two should have a Suzuki-type precipitate phase structure. These results explain the anomaly in the Arrehnius plot observed for the x = 0.20 concentration sample as an effect of the different microstructures. In this study we could also verify that the doped samples had a clear dependence of the activaction energies on the dopant concentration. With the exeption of the sample with concentration x = 0.20, the activation energies during the cooling process were observed to be between 0.60 and 0.23 eV, wich are the values of their pure counterparts, as reported in the literature.

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