Papers - Thermodynamic Properties of Magnesium-Tin Alloys by an Improved Isopiestic Method

Activities of magnesium in liquid Mg-Sn alloys have been determined between 5 and 90 at. pct Sn and 990" and 1290°K by an improved isopiestic method wherein tin specimens, heated in a temperature gradient and contained in crucibles of special geometry, were equilibrated with magnesium vapor in a closed titanium system. The crucibles were designed so that the equilibrium compositions of the specimens were satisfactorily preserved on termination of the experimental runs by quenching. The activity values are in excellent agreement with those predicated on the phase diagram and allowed a delineation of the solidus curve of the compound Mg2Sn near its melting point. EQUATIONS have been recently derived relating the chemical potentials of the components to the liquidus and enthalpy data for binary systems exhibiting one congruently melting compound.' The liquidus curve of the Mg-Sn system between the eutectics was carefully redetermined and the thermodynamic properties thus calculated were in reasonably good agreement with values derived from electromotive-force measurements of an,' but differed greatly from the iso-piestically determined values of Ashtakala and Pid-geon.3 The present study was initiated: a) to resolve the discrepancies; b) to develop a method for measuring activities in systems having volatile (and possibly highly reactive) components; and c) to use the method in a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVb systems, i.e., Mg-Pb, Mg-Sn, Mg-Ge, and Mg-Si. This paper describes the results for the Mg-Sn system. An isopiestic technique, originally developed by Herasymenko 4 and adapted for alloys having a component of high reactivity and low volatility,5-8 was modified in this study by using crucibles designed to preserve the equilibrium composition of highly volatile liquid specimens on quenching from high temperatures. Tin specimens, contained in tightly covered graphite crucibles and heated in a temperature gradient, were equilibrated with magnesium vapor of fixed pressure from a magnesium reservoir kept at constant temperature in a previously evacuated and sealed titanium tube. During equilibration magne-