Amorphous Alumina Nanoparticles: Structure, Surface Energy, and Thermodynamic Phase Stability

To provide a complete picture of the energy landscape of Al2O3 at the nanoscale, we directed this study toward understanding the energetics of amorphous alumina (a-Al2O3). a-Al2O3 nanoparticles were obtained by condensation from gas phase generated through laser evaporation of alpha-Al2O3 targets in pure oxygen at25 Pa. As-deposited nanopowders were heat-treated at different temperatures up to 600 degrees C to provide powders with surface areas of 670-340 m(2)/g. The structure of the samples was characterized by powder X-ray diffraction, transmission electron microscopy, and solid-state nuclear magnetic resonance spectroscopy. The results indicate that the microstructure consists of aggregated 3-5 nm nanoparticles that remain amorphous to temperatures as high as 600 degrees C. The structure consists of a network of AlO4, AlO5, and AlO6 polyhedra, with AlO5 being the most abundant species. The presence of water molecules on the surfaces was confirmed by mass spectrometry of the gases evolved on heating the samples under vacuum. A combination of BET surface-area measurements, water adsorption calorimetry, and high-temperature oxide melt solution calorimetry was employed for thermodynamic analysis. By linear fit of the measured excess enthalpy of the nanoparticles as a function of surface area, the surface energy of a-Al2O3 was determined to be 0.97 +/- 0.04 J/m(2). We conclude that the lower surface energy of a-Al2O3 compared with crystalline polymorphs gamma- and alpha-Al2O3 makes this phase the most energetically stable phase at surface areas greater than 370 m(2)/g.