Peculiarities of structural transformations in zirconia nanocrystals

The transitions of metastable tetragonal phase as well as high-temperature tetragonal phase into the low-temperature monoclinic phase upon heating and cooling were thoroughly studied in zirconia nanoparticles. High-temperature X-ray diffraction, thermal analysis and Raman spectroscopy were used to provide the systematic approach to the investigation of zirconia nanoparticles thermal behavior. A phase transformation sequence in the ZrO₂–H₂O system was determined, and the mechanisms of tetragonal-to-monoclinic transition upon heating and cooling were suggested. Here, the phenomenon was found and described, which was determined as “self-powdering” of nanoparticles occurring during structural transition. This phenomenon was observed by in situ investigation of the evolution of crystalline nanoparticles from amorphous zirconium hydroxide during thermal treatment in air. The tetragonal-to-monoclinic phase transition, induced by cooling from the temperature of equilibrium of tetragonal zirconia (i.e., above 1170 °C), is accompanied by a significant crystallite size decrease (with corresponding 3–4 times decrease of crystallite volume). The experimental results facilitate applications of zirconia nanoparticles to obtain high-performance nanopowders for nanoceramics.