Size effect on thermal stability of nanocrystalline anatase TiO2

Thermal stability of nanocrystalline anatase TiO2 against coarsening and anatase-rutile phase transformation was studied using both a pyroprobe heater and a conventional furnace. The pyroprobe heater, because of the programmable control and the ultra-fast heating rate (up to 20 000 degrees C s(-1)), for the first time, allows us to access the very early stage of the sintering and phase-transformation processes. Our short time (0-30 s) heat treatments reveal that rapid grain growth takes place first in anatase nanoparticles (NPs) upon the initial heating due to the lower activation energy compared with that for the anatase-rutile phase transformation. Meanwhile, rutile-like structural elements develop at the interface between anatase NPs during the fast grain growth period, which evolve into rutile nuclei with time, followed by nuclei growth, to convert nanocrystalline anatase into rutile rapidly in the temperature range where the phase transformation does not occur in coarse anatase TiO2. Overall, both grain growth and phase transformation in smaller anatase NPs happen at lower temperatures and faster than in bigger ones. The coupled sintering-phase-transformation mechanism can be exploited to design thermally stable nanocrystalline anatase TiO2 by reducing the sintering kinetics, for example, via minority additives.