Papers - An Electromotive-Force Study of the Thermodynamic Properties of the Liquid Al-Ge System and the Germanium-Rich Al-Ge Liquidus

The activities of both components and the partial and integral molar thermodynamic properties of mixing for the liquid Al-Ge system at 1200°K and for the gertnanium-rich Al-Ge liquidus have been determined from data for eighteen alloys of compositions in the range 0.0593 < 0.880 using the reuersible gal-vanic. cell in the temperature interval 9320 to 1258°K. The liqui-dus compositions above 93 2 °K loere also ve determined by observing the discontinuities in the C us T plots for the high-melting alloys. This system shows moderate negative deviation from ideality throughout, the values for y° being 0.212 and 0.189 for aluminum and germanium, respectively, at 1200°K. Pavtial molar Properties of aluminum on the germanium-rich solidus and at infinite dilution in Ge(s) oboue 932°K were estimated from the foregozng measurements and the equlibrium data of previous investzgators. RECENT compilations of data1" have shown an increasing demand for knowledge of the thermodynamic properties of mixing of metallic alloy systems. In the case of binary-liquid systems where one of the components is a semiconductor this information is useful because, primarily, properties of the second (dopant) component on the liquidus, solidus, and at infinite dilution may be determined more accurately than from calculations based on the phase diagram. In this investigation a reversible galvanic cell was used to determine the chemical potential of aluminum in the two-phase region, liquid + [Ge], on the germanium-rich side of the A1-Ge system in the temperature range 932" to 1193°K. In addition, similar measurements for homogeneous liquid A1-Ge alloys for the entire composition range were obtained for the temperature interval 932" to 1258°K. The cell used was: The experimental technique and the treatment of the data were essentially the same as described earlier394 and are elaborated upon only briefly here. Each cell consisted of a liquid aluminum anode and three A1-Ge alloy cathodes of different composition which were held in Morganite alumina crucibles. The alloys were made up from aluminum and germanium weighed to the nearest 0.1 mg to a total weight of 5 to 10 g. Aluminum was a gift of Aluminum Co. of America and had a purity of 99.995+ pct. Germanium of transistor grade was a gift of Bell Telephone Laboratories. The four electrodes were contained in a larger alumina crucible which also held the prepurified fused chloride electrolyte. Contact to the electrodes was made by tantalum wire leads sheathed in alumina. The tantalum leads were centered in the electrodes by suitable positioning of an alumina radiation shield which fitted on the top of the - alulnina crucible. Two chrome l-alumel thermocouples, sheathed in quartz wells, completed the internal cell arrangement. The entire assembly was enclosed in an alumina tube, fitted with a water-cooled copper head so the system could be evacuated and then flushed with purified argon. *