γ-alumina transforms to θ-alumina and finally to α-alumina in the sequence of thermal dehydration of boehmite. We report a detailed theoretical investigation of the γ- to θ-alumina transformation based on first-principles density-functional calculations. Although the unit cells of cubic γ-alumina and monoclinic θ-alumina look quite different, we have identified cells for both the polytypes (with the composition ${\mathrm{Al}}_{16}{\mathrm{O}}_{24})$ that look very similar and can be continuously transformed one to another. The transformation may be described by a set of aluminum atom migrations between different interstitials while the oxygen atoms remain fixed. Total-energy calculations along the paths of the atomic migrations have been used to map out possible transformation pathways. The calculated conversion rate accurately predicts the experimentally measured transformation temperature. The deduced orientation relationships between the γ- and θ-alumina forms also agree with experimental observations. The formation of several different interfaces observed in domain boundaries of θ-alumina may correspond to different migration paths of the aluminum atoms in neighboring domains during the γ- to θ-alumina phase transition.

• Received 4 November 2002

DOI:https://doi.org/10.1103/PhysRevB.67.224104