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Structure Analysis of the 6H - Ba[Ti,Fe3+,Fe4+]O3-δ^ Solid Solution



I E. Grey, C Li, L M. Cranswick, Robert S. Roth, Terrell A. Vanderah


The 6H form of BaTiO3 forms an extensive solid solution with barium iron oxide, having the general formula BaTi1-X-yFe3+xFe4+yO3-δ, δ=x/2, where the Feu3+^/Fe4+ ratio depends on reaction temperature and gas atmosphere. Solid solution members having iron predominantly as Fe3+ or as Fe4+ were prepared by quenching from high temperatures in air or slow cooling to 200 degrees Celsius} in oxygen respectively. The structural variations in both series were obtained from Reitveld refinements of powder X-ray diffraction data. For the series with yO, the progressive substitution of Ti4+ by Fe3+ is accompanied by the formation of O[1] oxygen vacancies in the h-BaO3 layers which separate pairs of occupied face-shared octahedra. The maximum vacancy concentration occurs at x=0.67, corresponding to a composition of Ba O2 in the h-stacked layers, and to a change from face-shared octahedra to pairs of edge-shared square pyramids. Solid solution members with x>0.67 were unstable relative to other polymorphs. Further incorporation of iron into the 6H structure at high temperature occurs by substitution of Ti4+ by Fe4+, ie by increasing y. The observed structural variations in the solid solution phases are explained in terms of the Ba and M atom packing and the changes in interatomic interactions between the metal atoms as oxygen is removed from the O[1] site.
Journal of Solid State Chemistry


barium iron titanium oxides, BaTiO3, hexagonal barium titanate, Rietveld refinement, solid solution


Grey, I. , Li, C. , Cranswick, L. , Roth, R. and Vanderah, T. (1998), Structure Analysis of the 6H - Ba[Ti,Fe<sup>3+</sup>,Fe<sup>4+</sup>]O<sub>3</sub>-&#948;^ Solid Solution, Journal of Solid State Chemistry (Accessed February 27, 2024)
Created January 31, 1998, Updated October 12, 2021