title: Application of the molecular interaction volume model (MIVM) to calcium-based liquid alloys of systems forming high-melting intermetallics.
abstract: The thermodynamic properties of multiple liquid alloys with strong negative deviation from ideality were successfully modeled by the molecular interaction volume model (MIVM). The modeled partial Gibbs free energy of calcium in Ca-Ag, Ca-In, Ca-Pb, Ca-Sn, Ca-Tl, and Ca-Zn at 800 °C was within 1.5 kJ/mol of the existing experimental data. The partial Gibbs free energy of calcium in Ca-Bi liquid alloys at 600 °C was predicted within 1.6 kJ/mol (or 1%) by the MIVM from experimental data at 800 °C. For the first time, the MIVM was applied to a ternary system far from ideality, Ca-Sb-Pb. The partial Gibbs free energy of Ca in six Ca-Pb-Sb alloys was determined by emf measurements in a cell configured as Ca(s)|CaF2(s)|Ca-Sb-Pb, over the temperature range of 500-830 °C. These values were 2% (or 5 kJ/mol) more negative than those predicted by the MIVM using experimental data for the Ca-Pb, Ca-Sb, and Pb-Sb binary alloys. This difference was attributed to the inability of the MIVM to account for interactions between the first nearest neighbors of Ca, Pb and Sb in the ternary Ca-Sb-Pb alloy.
authors.affiliation: Department of Materials Science and Engineering, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139-4307, United States.
authors.forename: Sophie
authors.initials: S
authors.lastname: Poizeau
authors.forename: Donald R
authors.initials: DR
authors.lastname: Sadoway