Abstract
A study of the structure of Fe IV CaTi 0.4Fe 0.6O 3− δ is presented and compared to data on the Fe III counterparts. The powder XRD pattern was dominated by a simple cubic perovskite unit cell; however, some small peaks indicated an orthorhombic distortion. All peaks could be indexed using a space group analogous to the Fe III phase Ca 3TiFe 2O 8. From HRTEM the strong cubic peaks are well explained by the superposition of three equivalent and mutually perpendicular orthorhombic unit cells. TEM analysis further revealed a microdomain structure consisting of disordered intergrowths of CaTiO 3- and Ca 3TiFe 2O 8-like phases. Mössbauer spectra show that ca. 4% of the Fe cations are in the 4+ oxidation state. Results suggest that the Fe 4+ cations are associated with octahedral coordination and hence are associated with the CaTiO 3-like regions, transition regions between the CaTiO 3- and Ca 3TiFe 2O 8 intergrown phases and the domain boundaries. Structural models for the intergrowths are proposed based on HRTEM image simulations.
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