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Thermodynamic analysis and crystal-chemical modeling of the defect structure of calcium iron garnets

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Abstract

This paper presents detailed analysis of the phase equilibria and thermodynamic stability of CaO, Fe2O3, Gd2O3, Nd2O3, Pr2O3, ZrO2, NiO, and ThO2, and detect formation during high-temperature synthesis of gadolinium (yttrium) calcium and zirconium calcium iron garnets doped with praseodymium, neodymium, nickel, cerium, thorium, and other oxides. The origin of point defects in each garnet is discussed. Crystal-chemical modeling indicates that all calcium-containing garnets are nonstoichiometric, but differ in the origin of non-stoichiometry, δ. The values of δ are shown to correlate with the activation energy for oxygen-ion conduction determined by emf measurements on solid electrolytes. The mechanisms of formation of different garnets from binary oxides are compared.

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References

  1. Strübel, G. and Zimmer, S. H., Lexikon der Mineralogie, Stuttgart: Enke, 1982.

    Google Scholar 

  2. Landolt, H and Börnstein, R, Numerical Data and Functional Relationships in Science and Technology. New Series Group III: Crystal and Solid State Physics, vol. 9: Magnetic and Other Properties of Oxides and Related Compounds, part a: Garnets and Perovskites, Hellwege, K.-H., Ed., Berlin: Springer, 1978.

    Google Scholar 

  3. Balbashov, A.M., Lisovskii, F.V., Raev, V.K., et al., Elementy i ustroistva na tsilindricheskikh magnitnykh domenakh (Bubble Components and Devices), Evtikhiev, N.N. and Naumov, B.N., Eds., Moscow: Radio i Svyaz’, 1987.

    Google Scholar 

  4. Vonsovskii, S.V., Magnetizm (Magnetism), Moscow: Nauka, 1971.

    Google Scholar 

  5. Kaminskii, A.A., Crystalline Lasers: Physical Processes and Operating Schemes, Boca Ration: CRC, 1996.

    Google Scholar 

  6. Comini, E., Toncelli, A., Tonelli, M., et al., Optical Spectroscopy and Fluorescence Dynamic of Er3+ in Ca3Sc2Ge3O12 Crystal, J. Opt. Soc. Am., 1997, vol. 14, no. 8, pp. 1938–1944.

    CAS  Google Scholar 

  7. Vorobiov, Yu.P., Men’, A.N., and Fetisov, V.B., Raschet i prognozirovanie svoistv oksidov (Calculating and Predicting Properties of Oxides), Moscow: Nauka, 1983.

    Google Scholar 

  8. Vorobiov, Yu.P. and Carban, O.V., Defects in Oxide Crystals, Zh. Neorg. Khim., 2002, vol. 47, no. 5, pp. 738–747.

    Google Scholar 

  9. Vorobiov, Yu.P., Structural, Magnetic, and Thermal Properties of Garnets, Kristallografiya, 1989, vol. 34, no. 6, pp. 1461–1469.

    Google Scholar 

  10. Vorobiov, Yu.P., A Method for Evaluating Nonstoichiometry of Epitaxial Garnet-Structure Oxide Films, Metallofiz. Noveishie Tekhnol., 2004, vol. 26, no. 1, pp. 27–34.

    Google Scholar 

  11. Vorobiov, Yu.P. and Carban, O.V., Defect Structure of Rare-Earth Gallium Germanium Garnets, Neorg. Mater., 2000, vol. 30, no. 7, pp. 862–867 [Inorg. Mater. (Engl. Transl.), vol. 30, no. 7, pp. 718–725].

    Google Scholar 

  12. Ronniger, G., Garnet Structure Vanadates: Isomorphism, Synthesis, and Crystal Growth, Cand. Sci. (Eng.) Dissertation, Moscow: Moscow State Univ., 1971.

    Google Scholar 

  13. Krasnenko, T.I., Zolotukhina, L.V., Zabolotskaya, E.V., et al., Defect Structure and Electrical and Magnetic Properties of Calcium Manganese Vanadium Garnets, Neorg. Mater., 1999, vol. 35, no. 11, pp. 1377–1381 [Inorg. Mater. (Engl. Transl.), vol. 35, no. 11, pp. 1179–1182].

    Google Scholar 

  14. Vorobiov, Yu.P., Diffusionless Electron Exchange in Garnet-Structure Oxide Crystals, Izv. Akad. Nauk SSSR. Neorg. Mater., 1991, vol. 27, no. 5, pp. 1041–1045.

    Google Scholar 

  15. Vorobiov, Yu.P. and Carban, O.V., A New Empirical Formula for the Calculation of an Elementary Cell Parameter of Synthetic Oxides-Garnets, J. Solid State Chem., 1997, vol. 134, no. 1/2, pp. 338–343.

    Article  CAS  Google Scholar 

  16. Kulikov, I.S., Termodinamika oksidov (Thermodynamics of Oxides), Moscow: Metallurgiya, 1986.

    Google Scholar 

  17. Kazenas, E.K. and Tsvetkov, Yu.V., Isparenie oksidov (Vaporization of Oxides), Moscow: Nauka, 1997.

    Google Scholar 

  18. Kazenas, E.K., Termodinamika ispareniya dvoinykh oksidov (Thermodynamics of Vaporization of Double Oxides), Moscow: Nauka, 2004.

    Google Scholar 

  19. Tret’yakov, Yu.D., Termodinamika ferritov (Thermodynamics of Ferrites), Leningrad: Khimiya, 1967.

    Google Scholar 

  20. Fetisov, V.B., Dvinina, M.A., Vorobiov, Yu.P., et al., 1270-K Phase Equilibria in the Y-Fe-O System, Izv. Akad. Nauk SSSR. Neorg. Mater., 1983, vol. 19, no. 11, pp. 1871–1874.

    CAS  Google Scholar 

  21. Kharton, V.V., Shaula, A.L., Naumovich, E.N., et al., Ionic Transport in Gd3Fe5O12 and Y3Fe5O12-Based Garnets, J. Electrochem. Soc., 2003, vol. 150, no. 7, pp. J33–J42.

    Article  CAS  Google Scholar 

  22. Vorobiov, Yu.P., Dragoshanskaya, T.I., Matskevich, S.L., and Men’, A.N., Nonstoichiometry of Y3Fe5O12, Gd3Fe5O12, and Y1.5Gd1.5Fe5O12 between 800 and 1400°C, Izv. Akad. Nauk SSSR, Neorg. Mater., 1980, vol. 16, no. 6, pp. 1083–1087.

    Google Scholar 

  23. Vorobiov, Yu.P., Goncharov, O.Yu., and Carban, O.V., Structure Field and Formula for Calculating the Lattice Parameter of Synthetic Garnets, Zh. Neorg. Khim., 1988, vol. 43, no. 4, pp. 644–652.

    Google Scholar 

  24. Urusov, V.S., Rusakov, V.S., Kabalov, Yu.K., and Yudintsev, S.V., Tetragonal Distortion of (Ca3 − x Ax)(Zr2 − y Fey)Fe3O12 (A = Ce, Th, Gd) Garnets Studied by Mössbauer Spectroscopy and Rietveld Analysis, Dokl. Akad. Nauk. 2004, vol. 399, no. 5, pp. 609–616.

    Google Scholar 

  25. Neiman, A.Ya., Tkachenko, E.V., and Zhukovskii, V.M., The Nature of Defect Formation in Me3A5O12 Garnets, Dokl. Akad. Nauk SSSR, 1978, vol. 240, no. 4, pp. 876–879.

    CAS  Google Scholar 

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Original Russian Text © Yu.P. Vorobiov, 2006, published in Neorganicheskie Materialy, 2006, Vol. 42, No. 10, pp. 1248–1256.

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Vorobiov, Y.P. Thermodynamic analysis and crystal-chemical modeling of the defect structure of calcium iron garnets. Inorg Mater 42, 1138–1146 (2006). https://doi.org/10.1134/S0020168506100165

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  • DOI: https://doi.org/10.1134/S0020168506100165

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