Thermodynamics and Calculation of the Liquidus-Solidus Gap in Homogeneous, Monotonic Alloy Systems

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Abstract
A general expression for the thermodynamic relationship between liquidus and solidus equilibrium compositions is derived for systems which are nonideal but homogeneous and monotonic. For a number of typical systems, the nonideal term in this expression is found to be very small, thus indicating that the ideal form of the general expression can be used to calculate one of the boundaries of the two-phase field when the other one and the enthalpies of fusion of the pure components are known. For many of the systems examined (InAs–GaAs, InSb–InAs, InSb–GaSb, GaSb–AlSb, InSb–AlSb, CdTe–ZnTe, CdTe–CdSe, HgTe–CdTe, GeTe–MnTe, PbBr2–PbCl2), the solidus curves calculated by this method are in good to excellent agreement with the published experimental values; for the Ag–Au, InAs–InP, SnTe–PbTe, and PbTe–PbSe systems they confirm the results of the more recent and more dependable investigations; for the Cu–Ni, Ge–Si and HgTe–HgSe systems however, they suggest the need for a critical reevaluation of the presently available data. In the absence of pertinent experimental data, calculated solidus and liquidus curves, respectively, are also presented for the ZnTe–ZnSe and HgTe–ZnTe systems.

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