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Dependence on Temperature of the Distribution of Cations in Oxide Spinels

Abstract

THE fact that the cations in the typical spinel A 2 BO 4 can be distributed in the so-called normal manner A 2 VI B IVO4, in the inverse manner (AB)VI A IVO4 or ‘randomly’ with A and B ions statistically distributed over the sites, has long been used to characterize spinel structure phases. Verwey and Heilman1, Gorter2 and Romeign3 have presented many data and lists on the ‘type’ of a particular spinel. Recent crystal field theory has also attempted to explain the position of a cation in oxide spinels4. Certain phases, for example NiAl2O4, have been characterized as partially inverse or even quantitatively as ‘85 per cent inverse’, the cation distribution being (Ni0.15Al0.85)IV (Ni0.85Al1.15)VIO4. There is in addition, of course, possible ordering on the octahedral and tetrahedral sites in phases such as LiAl5O8.

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References

  1. Verwey, E. J. W., and Heilman, E. L., J. Chem. Phys., 15, 174, (1947).

  2. Gorter, E. W., Philips Res. Rep., 9, 295, 321, 403 (1954).

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  3. Romeign, F. C., Philips Res. Rep., 8, 304 (1953).

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  4. Miller, A., J. App. Phys., 30, 24S (Supp.) (1959).

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  5. Stubican, V., and Roy, Rustum, Z. Krist. (in the press).

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DATTA, R., ROY, R. Dependence on Temperature of the Distribution of Cations in Oxide Spinels. Nature 191, 169–170 (1961). https://doi.org/10.1038/191169a0

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