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Effect of the sintering temperature on the properties of nanocrystalline Ca1−xSmxMnO3 (0 ≤ x ≤ 0.4) powders

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Resumo:Nanocrystalline Ca1−xSmxMnO3 (0 ≤ x ≤ 0.4) manganites were prepared by a soft chemical method (Pechini method) followed by auto-combustion and sintering in air at 1073 or 1473 K. Single-phase powders with general composition Ca1−xSmxMnO3 were obtained after 18 h annealing. The particle and grain sizes of the substituted Sm-manganites did not exhibit variation with samarium content, but increase with increasing the sintering temperature. All manganites show two active IR vibrational modes near 400 and 600 cm−1 characteristic of the BO6 octahedron vibrations. For the samples sintered at Ts = 1473 K, the partial substitution of calcium by samarium in the CaMnO3 phase induces a marked decrease in the electrical resistivity, in the temperature range of 300–900 K, and at the same time a metal-to-insulator transition occurs; for Ts = 1073 K all the samples present semiconductor behaviour. With the increase of the annealing temperature the grain size increases and a metal–semiconductor transition appears. The results can be ascribed to the Mn4+/Mn3+ ratio and particle grain size. The effects of particle size on the electrical properties can be attributed to the domain status, changes in the Mn–O–Mn bond angle and Mn–O bond length.
Autores principais:Lopes, M E
Outros Autores:Melo Jorge, M. E.; Sério, S.; Nunes, M. R.; Matos, I.
Assunto:Nanocrystalline manganites Samarium substituted Citrate gel method Rietveld analysis Electrical properties
Ano:2012
País:Portugal
Tipo de documento:artigo
Tipo de acesso:acesso restrito
Instituição associada:Universidade de Évora
Idioma:português
Origem:Repositório Científico da Universidade de Évora
Descrição
Resumo:Nanocrystalline Ca1−xSmxMnO3 (0 ≤ x ≤ 0.4) manganites were prepared by a soft chemical method (Pechini method) followed by auto-combustion and sintering in air at 1073 or 1473 K. Single-phase powders with general composition Ca1−xSmxMnO3 were obtained after 18 h annealing. The particle and grain sizes of the substituted Sm-manganites did not exhibit variation with samarium content, but increase with increasing the sintering temperature. All manganites show two active IR vibrational modes near 400 and 600 cm−1 characteristic of the BO6 octahedron vibrations. For the samples sintered at Ts = 1473 K, the partial substitution of calcium by samarium in the CaMnO3 phase induces a marked decrease in the electrical resistivity, in the temperature range of 300–900 K, and at the same time a metal-to-insulator transition occurs; for Ts = 1073 K all the samples present semiconductor behaviour. With the increase of the annealing temperature the grain size increases and a metal–semiconductor transition appears. The results can be ascribed to the Mn4+/Mn3+ ratio and particle grain size. The effects of particle size on the electrical properties can be attributed to the domain status, changes in the Mn–O–Mn bond angle and Mn–O bond length.