A study of the microstructure of La_{1 − x} Ca _x MnO₃ (x = 0.5, 0.8) solid solutions

Abstract

HREM and XPD methods are used to study the microstructure of La_{1 − x} Ca _x MnO₃ perovskite-like oxides synthesized by pyrolysis of polymer-salt compositions. The XPD data show that the samples studied are single-phase solid solutions. Morphological transitions are observed in series of samples depending on the substitution parameter x. At 0 ≤ x ≤ 0.4 the samples can be characterized by rhombic symmetry (space group Pnmb); at 0.5 ≤ x ≤ 0.8 the symmetry increases to the tetragonal space group I4/mmm; at 0.9 ≤ x ≤ 1 the symmetry lowers to the monoclinic space group P1121. Heating of samples with x = 0.5 and 0.8 up to 1200°C in air does not lead to noticeable changes in the sample structure, which indicates their high thermal stability. When the La_0.2Ca_0.8MnO₃ sample is heated to 1100°C in vacuum nanocrystalline states with particle disintegration into microphases of different structures form because of a partial decomposition of the solid solution. As a result, a system of Mn₃O₄ nanoparticles appears, which is coherently bound with the perovskite phase of a defective structure.