Modeling the Equilibrium Vacancy Concentration in Multi-Principal Element Alloys from First-Principles

Abstract: Multi-principal element alloys (MPEAs), also known as high-entropy alloys, have garnered significant interest across many applications due to their exceptional properties. Equilibrium vacancy concentrations in MPEAs influence diffusion and microstructural stability in these alloys. However, computing vacancy concentrations from ab-initio methods is computationally challenging due to the vast compositional space of MPEAs and the complexity of the local environment around each vacancy. In this work, we present an efficient approach to connect electronic structure calculations to equilibrium vacancy concentrations in MPEAs through embedded cluster expansions (eCE) and rigorous statistical mechanics methods. Using first-principles calculations and Monte Carlo simulations informed by eCE, we assess the variation in vacancy formation with alloy composition and temperature. Our method is demonstrated on a nine-component MPEA comprised of elements in groups 4, 5, and 6 of the periodic table. Correlations between alloy chemistry, short-range order, and equilibrium vacancy concentrations in alloys containing up to 9 different elements are analyzed. The vacancy concentration of refractory alloys increases with the addition of group 4 elements or elements whose mixing is energetically unfavorable. The insights into vacancy behavior and the efficient computational framework presented in this study serve as a guide for the design of complex concentrated alloys with controlled vacancy concentrations.