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Nonstoichiometry in Inorganic Fluorides. IV: The Initial Stage of Anionic Nonstoichiometry in RF3 (R = Y, La, Ln)

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Abstract

The anionic nonstoichiometry in inorganic fluorides is at result of substitution of F1– for O2– in the anionic sublattice. All families of fluorides exhibit the initial stage of anionic nonstoichiometry (ISAN), which was previously studied for trifluorides of rare-earth elements (REEs), RF3. Partial substitution of F1– for O2– in RF3 occurs in reactions with H2O vapor upon heating (pyrohydrolysis), exchange reactions of RF3 and R2O3 in melts, hydrothermal solutions, solid phase, and during mechanochemical synthesis. The ISAN is based on the formation of RF3 – 2xOx oxofluorides, the type and structure of which depend on the crystalline RF3 forms. Congruently melting tys-RF3 – 2xOx compounds are formed based on the tysonite forms tys-RF3 (R = La–Gd, the LaF3 type). Berthollide phases ~tys-RF3 – 2xOx, which are isostructural to the above-mentioned phases and melts incongruently above the corresponding RF3 compounds, are formed with R = Tb–Ho. The effect of stabilization of tys-RF3 – 2xOx when moving up the temperature scale (+ΔTfus) changes nonmonotonically along the REE series, exhibiting a maximum of ~100°C in the range of Gd–Tb. There are no F1– → O2– substitutions in the β-RF3 forms (R = Er–Lu, Y) of the β-YF3 type. The α-RF3 – 2xOx phases of the α-YF3 (α-UO3) type melt incongruently and decompose at high temperatures. The ISAN products in RF3 may serve as sources of new congruently melting fluorine–oxygen materials.

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ACKNOWLEDGMENTS

I am grateful to N.I. Sorokin and D.N. Karimov for fruitful discussions and to E.A. Krivandina and Z.I. Zhmurova for supplying crystals for study.

Funding

This work was supported by the Ministry of Science and Higher Education of the Russian Federation within a State assignment for the Federal Scientific Research Centre “Crystallography and Photonics” of the Russian Academy of Sciences.

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  1. Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics”, Russian Academy of Sciences, 119333, Moscow, Russia

    B. P. Sobolev

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Correspondence to B. P. Sobolev.

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Translated by Yu. Sin’kov

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Sobolev, B.P. Nonstoichiometry in Inorganic Fluorides. IV: The Initial Stage of Anionic Nonstoichiometry in RF3 (R = Y, La, Ln). Crystallogr. Rep. 66, 349–360 (2021). https://doi.org/10.1134/S1063774521030238

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