Study of gold-based alloy phase diagrams

This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University.The partial constitutions of the Au-Ge-X and Au-Pb-X ternary alloys have been investigated, where X is a metallic element, selected from the sub-groups period 1m and rrm of the periodic table (In, Ga, Zn, or Cd), which forms one or more stable compounds with gold, but which forms no stable compound with Ge and Pb. The Smith Thermal Analysis Method, supplemented by metallographic and X-ray techniques, was used to determine the constitutions of the ternary systems. Eutectiferous, pseudobinary systems were found between Ge and the stable congruent intermediate compounds, AuIn, Auln2' AuGa, AuGa2' AuZn and AuCd. The solubility of Ge in the AuX compounds was not determined directly. However, it was 1.3 at.% Ge for Zn and Cd containing alloys and less than 1.0 at. % Ge for In and Ga containing alloys at the eutectic temperatures, which is in accordance with the Hume-Rothery rule. Ternary eutectic points were also determined in the Auln-AuIn2-Ge, Auln2-In-Ge and AuGa-AuGa2-Ge partial ternary systems. No evidence of liquid immiscibility was found in any of these ternary systems. The experimental results obtained were in good agreement with computed features of the diagrams. However, pseudobinary systems were not found between Pb and the stable congruent melting intermediate compounds, AuGa, AuGa2, AuZn and AuCd (the AuIn-Pb and AuIn2-Pb sections had already been investigated). The evidence of an extensive liquid immiscibility was found in each of these systems. The miscibility in the liquid state was found to decrease progressively down group IV when the elements of this group react with AuX compounds, which can be attributed to the progressive increase of the atomic size and decrease in electronegativities and solubility parameters of the elements, down this group. Two rules were derived to relate the liquid immiscibility/miscibility of ternary systems. One of the rules based upon the atomic sizes and melting points of the constituent elements showed a fair agreement with many systems. However, the other rule based upon the solubility parameter and electronegativities of the constituent elements showed good agreement with immiscible systems, but gave a poor predictability for miscible systems. The lower temperature equilibria of the Au-rich portion of the Au-Sn binary phase diagram are not well defined. So, long term heat treatment of samples at appropriate temperatures and compositions was carried out. Optical microscopy and SEMIEDAX techniques were employed and hence the low temperature equilibria of the Au-Sn binary system have been amended.This study is partly funded by the Ministry of Science and Technology, Government of Pakistan for the S & T scholarship award and Punjab University, Lahore