Cu-Au, Ag-Au, Cu-Ag and Ni-Au intermetallics: First-principles study of phase diagrams and structures

TL;DR

This study uses first-principles calculations and cluster expansion to analyze phase stability, structures, and thermodynamics of noble metal alloys, improving accuracy over previous models and providing insights into stable phases and entropies.

Contribution

It offers a more accurate first-principles analysis of noble metal alloy phase diagrams, including stable structures and thermodynamic properties, with improved treatment of atomic relaxations.

Findings

Correctly reproduces tendencies of alloy phase formation and separation.

Identifies most stable low-temperature phases and transition temperatures.

Finds large vibrational entropies in size-mismatched systems.

Abstract

The classic metallurgical systems -- noble metal alloys -- that have formed the benchmark for various alloy theories, are revisited. First-principles fully relaxed general potential LAPW total energies of a few ordered structures are used as input to a mixed-space cluster expansion calculation to study the phase stability, thermodynamic properties and bond lengths in Cu-Au, Ag-Au, Cu-Ag and Ni-Au alloys. (i) Our theoretical calculations correctly reproduce the tendencies of Ag-Au and Cu-Au to form compounds and Ni-Au and Cu-Ag to phase separate at T=0 K. (ii) Of all possible structures, Cu/sub 3/Au (L1/sub 2/) and CuAu (L1/sub 0/) are found to be the most stable low-temperature phases of Cu/sub 1-x/Au/sub x/ with transition temperatures of 530 K and 660 K, respectively, compared to the experimental values 663 K and 670 K. The significant improvement over previous first-principles studies is attributed to the more accurate treatment of atomic relaxations in the present work. (iii) LAPW formation enthalpies demonstrate that L1/sub 2/, the commonly assumed stable phase of CuAu/sub 3/, is not the ground state for Au-rich alloys, but rather that ordered <100> superlattices are stabilized. (iv) We extract the non-configurational (e.g., vibrational) entropies of formation and obtain large values for the size mismatched systems: 0.48 k/sub B//atom in Ni/sub 0.5/Au/sub 0.5/ (T=1100 K), 0.37 k/sub B//atom in Cu/sub 0.14/Ag/sub 0.86/ (T=1052 K), and 0.16 k/sub B//atom in Cu/sub 0.5/Au/sub 0.5/ (T=800 K). (v) Using 8 atom/cell special quasirandom structures we study the bond lengths in disordered Cu-Au and Ni-Au alloys and obtain good qualitative agreement with recent EXAFS measurements.