Chemistry, Ames Laboratory
Journal or Book Title
Journal of the American Chemical Society
Synthetic explorations in the CaAu5−CaAu4Bi−BiAu2 system at 400 °C reveal five separate solid solution regions that show three distinct substitution patterns in the CaAu5 parent: (I) CaAu4(Au1−mBim) with 0 ≤ m ≤ 0.15(1), (II) 0.33(1) ≤ m ≤ 0.64(1), (III) 0.85(4) ≤ m ≤ 0.90(2); (IV) (Ca1−rAur)Au4(Bi1−sAus) with 0 ≤ r ≤ 0.39(1) and 0 ≤ s ≤ 0.12(2); (V) (Ca1−p−qAupBiq)Au4Bi with 0.09(2) ≤ p ≤ 0.13(1) and 0.31(2) ≤ q ≤ 0.72(4). Single crystal X-ray studies establish that all of these phase regions have common cubic symmetry F4̅3m and that their structures (MgCu4Sn-type, an ordered derivative of MgCu2) all feature three-dimensional networks of Au4 tetrahedra, in which the truncated tetrahedra are centered and capped by Ca/Au, Au/Bi, or Ca/Au/Bi mixtures to give 16-atom Friauf polyhedra. TB-LMTO-ASA and -COHP calculations also reveal that direct interactions between Ca−Au and Ca−Bi pairs of atoms are relatively weak and that the Bi−Au interactions in the unstable ideal CaAu4Bi are antibonding in character at EF but that their bonding is optimized at ±1 e. Compositions between the five nonstoichiometric phases appear to undergo spinodal decompositions. The last phenomenon has been confirmed by HRTEM, STEM-HAADF, EPMA, and XRD studies of the nominal composition CaAu4.25Bi0.75. Its DTA analyses suggest that the phases resulting from spinodal decomposition have nearly the same melting point (∼807 °C), as expected, and that they are interconvertible through peritectic reactions at ∼717 °C.
American Chemical Society
Lin, Qisheng and Corbett, John D., "Multiple Nonstoichiometric Phases with Discrete Composition Ranges in the CaAu5-CaAu4Bi-BiAu2 System. A Case Study of the Chemistry of Spinodal Decomposition" (2010). Chemistry Publications. 968.