Espectroscopia vibracional e de impedância de A1-xA’xTaWO6.nH2O (A=H, Li, A’ = Ag,H)

• Ano de defesa: 2009
• Autor(a) principal: Reis Júnior, Daniel Valim dos
• Tipo de documento: Tese
• Tipo de acesso: Acesso aberto
• Idioma: por
• Palavras-chave em Português: Condutores elétricos; Pirocloro; Trirrutilo; Pirochlores; Trirrutile; Impedance Spectroscopy
• Link de acesso: http://www.repositorio.ufc.br/handle/riufc/11925

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 “easy-path”, 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.