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Journal of Structural Chemistry

2010 year, number 5

STRUCTURAL FEATUREs of the FORMATION of La1-xCaxFeO3-δ (0 ≤ x ≤ 0.7) HETEROVALENT SOLID SOLUTIONs

A. N. Nadeev, S. V. Tsybulya, E. Y. Gerasimov, N. A. Kulikovskaya, L. A. Isupova
Keywords: perovskite, morphotropic phase transition, nanostructured state, mobile oxygen form
Pages: 927-933

Abstract

A synthesis method with the use of polymer-salt compositions (calcination temperature 800°C) provides the preparation of various solid solutions of a La1-xCaxFeO3-δ series in the 0 ≤ x ≤ 0.7 range, which belong to the perovskite structure type. A morphotropic phase transition occurs from the orthorhombic perovskite modification (0 ≤ x ≤ 0.4) to the cubic one (0.5 ≤ x ≤ 0.7). A growing number of microdistortions in the perovskite structure and the formation of a microblock structure in the morphotropic phase transition region are observed with increasing degree of calcium substitution for lanthanum. Calcination of solid solutions with х = 0.6 and 0.7 at temperatures above 1000°C in the air or under conditions of reduced oxygen partial pressure (laboratory vacuum of 10-3 Torr) results in the formation of a nanostructured state with coherently grown blocks of perovskite and Grenier phase, which is due to irreversible oxygen loss.