Surface Energies and Thermodynamic Phase Stability in Nanocrystalline Aluminas

Corundum, α-Al 2 O 3 , is the thermodynamically stable phase of coarsely crystalline aluminum oxide, but syntheses of nanocrystalline Al 2 O 3 usually result in γ-Al 2 O 3 . Adsorption microcalorimetry, thermogravimetric analyses, and Brunauer-Emmett-Teller adsorption experiments, coupled with recently reported high-temperature solution calorimetry data, prove that γ-Al 2 O 3 has a lower surface energy than α-Al 2 O 3 and becomes energetically stable at surface areas greater than 125 square meters per gram and thermodynamically stable at even smaller surface areas (for example, 75 square meters per gram at 800 kelvin). The results are in agreement with recent molecular dynamics simulations and provide conclusive experimental evidence that differences in surface energy can favor the formation of a particular polymorph.