Ab initio study of the effect of Si on the phase stability and electronic structure of γ- and α-Al2O3

Using density functional theory, the effect of Si on the stability and electronic structure of γ- and α-Al2O3 has been investigated. The concentration range from 0 to 5 at.% is probed and the additive is positioned at different substitutional sites in the γ-phase. The calculations for (Al,Si)2O3 predict a trend towards spontaneous decomposition into α-/γ-Al2O3 and SiO2. Therefore, the formation of the metastable γ-(Al,Si)2O3 phase can only be expected during non-equilibrium processing where the decomposition is kinetically hindered. The Si-induced changes in stability of this metastable solid solution may be understood based on the electronic structure. As the Si concentration is increased, stiff silicon–oxygen bonds are formed giving rise to the observed stabilization of the γ-phase.