First principles study of the solubility of Zr in Al

TL;DR

This study uses ab-initio calculations and statistical models to determine the solubility limits of Zr in Al, including stable and metastable phases, providing theoretical insights that complement experimental data.

Contribution

It presents a first-principles approach to accurately predict Zr solubility in Al for both stable and metastable phases, incorporating volume relaxations and vibrational effects.

Findings

Calculated Zr solubility limit is lower than experimental data.

Identified DO23 as the stable structure for Al3Zr.

Compared vibrational free energy models for accuracy.

Abstract

The experimental solubility limit of Zr in Al is well-known. Al3Zr has a stable structure DO23 and a metastable one L12. Consequently there is a metastable solubility limit for which only few experimental data are available. The purpose of this study is to obtain by ab-initio calculations the solubility limit of Zr in Al for the stable as well as the metastable phase diagrams. The formation energies of several ordered compounds AlxZr(1 x), all based on an fcc underlying lattice, were calculated using the FP-LMTO (Full Potential Linear Mu n Tin Orbital) method. Taking into account all the relaxations allowed by the symmetry, we found the DO23 structure to be the stable one for Al3Zr. This set of results was then used with the cluster expansion in order to fit a generalized Ising model through the inverse method of Connolly-Williams. Di erent ways to consider volume relaxations were examined. This allowed us to calculate in the Bragg-Williams approximation the configurational free energy at finite temperature. According to the previous FP-LMTO calculations the free energy due to electronic excitations can be neglected. For the vibrational free energy of ordered structures we compared results obtained from a calculation of the elastic constants used with the Debye model and results obtained from a calculation of the phonon spectrum. All these di erent steps lead to a calculation of the solubility limit of Zr in Al which is found to be lower than the experimental one. The solubility limit in the metastable phase diagram is calculated in the same way and can thus be compared to the stable one.