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Valence variations in titanium-based perovskite oxides by high-pressure and high-temperature method

Published online by Cambridge University Press:  31 January 2011

Liping Li ,
Guangshe Li ,
Jipeng Miao ,
Wenhui Su  and
Hiroshi Inomata
Liping Li
Affiliation:
Department of Physics, Jilin University, Changchun 130023, People's Republic of China
Guangshe Li*
Affiliation:
Research Center of Supercritical Fluid Technology, Department of Chemical Engineering, Tohoku University, Sendai 980–8579, Japan
Jipeng Miao
Affiliation:
Department of Physics, Jilin University, Changchun 130023, People's Republic of China
Wenhui Su
Affiliation:
Department of Physics, Jilin University, Changchun 130023, People's Republic of China
Hiroshi Inomata
Affiliation:
Research Center of Supercritical Fluid Technology, Department of Chemical Engineering, Tohoku University, Sendai 980–8579, Japan
*
a)Address all correspondence to this author. e-mail: [email protected]
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Abstract

Typical titanium-based perovskite oxides Eu1−xBaxTiO3 (x = 0.6−0.8), Eu1−xKxTiO3 (x = 0.2,0.32), and La0.7 (Na,K)0.3TiO3 were synthesized by high pressure and temperature using RE2O3 (RE = La,Eu), TiO2, alkaline, or alkaline earth carbonates as the starting materials. X-ray diffraction data analysis showed that there was a structural transformation in Eu1−xBaxTiO3 by varying Ba content [i.e., from cubic (x = 0.6,0.7) to tetragonal (x = 0.8)], and that samples Eu1−xKxTiO3 and La0.7(Na,K)0.3TiO3 crystallized in the cubic perovskite structure. 151Eu Mössbauer spectroscopy and electron paramagnetic resonance measurements revealed mixed valence of Eu2+/Eu3+ in samples Eu1−xBaxTiO3 and Eu1−xKxTiO3, while Ti ions were present in pure Ti4+ state. Cubic Eu1−xKxTiO3 was metastable, which decomposed into a mixture of perovskite and pyrochlore phases at high temperatures as accompanied by an oxidation process from Eu2+ to Eu3+. For samples La0.7 (Na,K)0.3TiO3, Ti3+ signals were clearly observed. The reduction mechanisms for Eu ions at A site and Ti ions at B site in the perovskite oxides are discussed in terms of the chemical nature of the framework ions and substitution ions under high pressure and temperature.

Type
Articles
Information
Journal of Materials Research , Volume 16 , Issue 2 , February 2001 , pp. 417 - 424
Copyright
Copyright © Materials Research Society 2001

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