Low Temperature Oxygen Transport in Nonstoichiometric CeO2

  • S. P. Ray
  • A. S. Nowick
Part of the Materials Science Research book series (MSR, volume 9)


The dioxides of the f luorite structure are known to have oxygen-ion nobilities which are much greater than the cation mobilities, due to the relative ease of incorporation of oxygen vacancies [1–3]. The oxides of Ce, Pr and Tb are of special interest, since they show gross nonstoichiometric behavior ranging between the sesquioxide R2O3 (where R = Ce, Pr or Tb) and the dioxide RO2. In each of these systems the nonstoichiometric defects are believed to be oxygen vacancies. At a high enough temperature, the vacancies exist essentially at random in an otherwise perfectly ordered fluorite lattice. However, at a lower temperature (T < 500°C), a series of intermediate phases are found to occur, in which the vacancies are ordered and the symmetry of the crystal is lowered. A homologous series of the general formula Rn°2n-2 iias been proposed for these structures, mainly through studies on PrOy, where a number of such phases are observed [4–6].


Oxygen Vacancy Initial Slope Cerium Oxide Chemical Diffusion Fluorite Structure 


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  1. 1.
    A.B. Auskern and J. Belle, J. Nucl. Mat. 3, 311 (1961).CrossRefGoogle Scholar
  2. 2.
    C. B. Alcock in “Electromotive Force Measurements in High Temperature Systems” (C.B. Alcock, ed.) p. 109, Institution of Mining and Met., London, (1968).Google Scholar
  3. 3.
    M.F. Berard, “Diffusion in Ceramic Systems: A Selected Bibliography” Ames laboratory Report #I5448 (1962).Google Scholar
  4. 4.
    J.O. Sawyer, B.G. Hyde and L. Eyring, Bull. Soc. Chim. France, 1190 (1965).Google Scholar
  5. 5.
    D.A. Burnham and L. Eyring, J. Phys. Chen. 72, 4415 (1968).CrossRefGoogle Scholar
  6. 6.
    B.G. Hyde, D.J.M. Bevan and L. Eyring, Phil. Trans. Royal Soc. A 259, 583 (1966).CrossRefGoogle Scholar
  7. 7.
    D.J.M. Bevan and J. Kordis, J. Inorg. Nucl. Chen. 26, 1509 (1964).CrossRefGoogle Scholar
  8. 8.
    Y. Ban and A.S. Nowick, in “Proceedings of 5th Materials Research Symposium”, NBS special Publ. 364, p. 353 (1972).Google Scholar
  9. 9.
    J. Crank, “Mathematics of Diffusion”, p. 1ll, Oxford University Press (1967).Google Scholar
  10. 10.
    L. Eyring, in “Heterogeneous Kinetics at Elevated Temperatures” (G.R. Belton and W.L. Worrell, eds.) Plenum Press, New York, (1970).Google Scholar
  11. 11.
    B.G. Hyde, E.E. Garver, U.E. Kuntz and L. Eyring, J. Phys. Chan. 69, 1667 (1955).CrossRefGoogle Scholar
  12. 12.
    B.C.H. Steele and J.M. Floyd, Proc. British Ceram. Soc., No. 19, 55 (1971).Google Scholar
  13. 13.
    B.C.H. Steele, in “Fast Ion Transport in Solids” (W. Van Gool, ed.) p. 103, North Holland, Amsterdam, (1973).Google Scholar
  14. 14.
    P. E. Childs and J. B. Wagner, Jr. in “Heterogeneous Kinetics at Elevated Temperatures” (G.R. Belton and W.L. Worrell, eds.) p. 269, Plenum Press, New York, (1970).Google Scholar
  15. 15.
    L.S. Darken, Trans. AIME, 175, 184 (1948).Google Scholar
  16. 16.
    B.C.H. Steele and C.C. Rlccardi, in “Proc. 7th Intl. Symp. on Reactivity of Solids”, Chapnan and Hall, London, (1974).Google Scholar
  17. 17.
    B.G. Hyde and L. Eyring in “Proceedings of the 4th Conference on Rare Earth Research, 1964” (L. Eyring, ed.) p. 623, Gordon and Breach, New York, (1965).Google Scholar

Copyright information

© Plenum Press, New York 1975

Authors and Affiliations

  • S. P. Ray
    • 1
  • A. S. Nowick
    • 1
  1. 1.Henry Krumb School of MinesColumbia UniversityNew YorkUSA

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