Abstract
AbstractPhase equilibrium studies of the Bi–Zn–Nb–O system show that pyrochlore does not form at chemical compositions predicted by the traditional formula for this crystal structure, A2B2O6O', where A denotes large (8‐coordinated, e.g. Bi3+) and B small (6‐coordinated, e.g. Zn2+, Nb5+) cation sites. Instead, pyrochlore forms only at compositions with excess B cations which, surprisingly, occupy the large A‐cation sites. Reports of similar behavior in other pyrochlores suggest a previously unrecognized inherent structural feature (displacive disorder) which allows the formation of a large family of cubic pyrochlores with small B cations occupying up to ca. 25 % of the large A‐cation sites. Many pyrochlores can now be synthesized by deliberately combining large and small metal ions on the A sites. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
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