First-principles lattice dynamics and thermodynamic properties of α-, θ-, κ- and γ-Al2O3 and solid state temperature-pressure phase diagram

Abstract

γ-Al2O3 is a commonly observed high temperature alumina phase during Al-based alloy oxidation. Due to the partially ordered, defective nature of the spinel structure arising from the partial occupancy in the Al sites, first-principles prediction of the thermodynamic properties of γ-Al2O3 has been challenging. In this work, employing the first-principles quasiharmonic approach, we obtain the finite temperature thermodynamic properties of γ-Al2O3, including entropy, chemical potential, heat capacity, thermal expansion coefficient, and elastic constants and the results are compared with those calculated for the other three alumina phases, i.e., α-Al2O3, θ-Al2O3, and κ-Al2O3. The calculated lattice constants and the predicted relative phase stability under 0 K and 0 GPa, α>κ>θ>γ, are consistent with experimental values and existing calculations, respectively. Based on the results, we constructed the temperature-pressure phase diagram covering the four Al2O3 phases (α, κ, θ, γ), which could provide for experimentally synthesizing the different alumina phases.