Preparation of nanometer zirconia by hydrothermal method: Influence of temperature and mechanism

Monoclinic (m-ZrO2) and tetragonal zirconia (t-ZrO2) nanoparticles with average grain size of 22.8 nm were synthesized by hydrothermal method using zirconium oxychloride octahydrate (ZrOCl2·8H2O), urea (CO(NH2)2) and deionized water as zirconium source, precipitant, and solvent, respectively. The effects of CO(NH2)2 hydrolysis rate, hydrothermal temperature, and time on the crystal structure, morphology, and grain size were studied. The structure, morphology, grain size, and crystal phase of zirconium oxide (ZrO2) were characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermogravimetry (TG-DTA), and Fourier Transform Infrared spectroscopy (FT-IR). The results show that the formation mechanisms of different crystal forms can be controlled by the average pH value. The hydrolysis rate of CO(NH2)2 was relatively slow at 120 °C, resulting in a slower rate of OH− production. The lower average pH value favors the formation of m-ZrO2 through the dissolution precipitation mechanism. With the increase of crystallization temperature, the hydrolysis rate of CO(NH2)2 is accelerated, and the average pH value of the solution is increased, which is conducive to the structural rearrangement of [Zr(OH)8(H2O)16]8+ precursor to form tetragonal phase. In addition, the number of defect sites is directly proportional to the crystallization temperature. Extension of crystallization time helps the generation of ZrO2 crystals by polycondensation and directional growth.