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High-pressure perovskites on the join CaTiO3-FeTiO3

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Abstract

An exploratory high-pressure study of the join CaTiO3-FeTiO3 has uncovered two intermediate perovskites with the compositions CaFe3Ti4O12 and CaFeTi2O6. These perovskites have ordering of Ca2+ and Fe2+ on the A sites. Both of these perovskites are unusual in that the A sites containing Fe2+ are either square planar or tetrahedral, due to the particular tilt geometries of the octahedral frameworks.

For CaFe3Ti4O12, the structure has been refined from a powder using the Rietveld technique. This compound is a cubic double perovskite (SG Im \(\bar 3\), a = 7.4672 Å), isostructural with NaMn7O12. Fe2+ is in a square-planar A site (similar to Mn3+ in NaMn7O12) with Fe-O = 2.042(3) Å, with distant second neighbors in a rectangle at Fe-O = 2.780(6) Å. Calcium is in a distorted icosahedron with Ca-O =2.635(5) Å.

CaFeTi2O6 crystallizes in a unique tetragonal double perovskite structure (SG P42/nmc, a = 7.5157(2), c = 7.5548(2)), with A-site iron in square-planar (Fe-O = 2.097(2) Å) and tetrahedral (Fe-O = 2.084(2) Å) coordination, again with distant second neighbor oxygens near 2.8 Å.

Rietveld refinement was also performed for the previously known perovskite-related form of FeTiO3 recovered from high pressure (lithium niobate type). This compound is trigonal R3c, with a = 5.1233(1) and c = 13.7602(2).

The ordered perovskites appear to be stable at 1215 GPa and CaFe3Ti4O12 is found as low as 5 GPa. Thus these perovskites may be important to upper mantle mineralogy, particularly in kimberlites. These compounds are the first known quenchable perovskites with large amounts of A-site ferrous iron, and add greatly to the known occurrences of ferrous iron in perovskites.

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Author notes

  1. K. Leinenweber

    Present address: Department of Chemistry, Arizona State University, 85287-1604, Tempe, AZ, USA

Authors and Affiliations

  1. Center for High Pressure Research, Department of Earth and Space Sciences, University at Stony Brook, 11794-2100, Stony Brook, New York, USA

    K. Leinenweber & J. B. Parise

  2. Center for High Pressure Research, Department of Geological and Geophysical Sciences, Princeton University, 08544, Princeton, NJ, USA

    J. Linton & A. Navrotsky

  3. Center for High Pressure Research, Geophysical Laboratory, Carnegie Institution of Washington, 20015, Washington, D.C., USA

    Y. Fei

Authors
  1. K. Leinenweber
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  2. J. Linton
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  3. A. Navrotsky
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  4. Y. Fei
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  5. J. B. Parise
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Leinenweber, K., Linton, J., Navrotsky, A. et al. High-pressure perovskites on the join CaTiO3-FeTiO3 . Phys Chem Minerals 22, 251–258 (1995). https://doi.org/10.1007/BF00202258

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  • DOI: https://doi.org/10.1007/BF00202258

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