Effect of grain boundary segregation and oxygen vacancy annihilation on aging resistance of cobalt oxide-doped 3Y-TZP ceramics for biomedical applications

This study aims to investigate the diffusion stabilization process of nano-Co2O3 during the non-precursor transformation of 3Y-TZP. 3Y-TZP was set as the control group, and the experimental groups were 0.1–0.3 mol% nano-Co2O3-doped 3Y-TZP. The samples were prepared by the ball milling process, isostatic cool pressing, and sintering. All samples were hydrothermally treated at 134°C and 2 bar for different time periods. The resistance to low-temperature degradation of nano-Co2O3-doped 3Y-TZP was analyzed by X-ray diffraction. The microstructure of zirconia ceramic samples was determined by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and electron paramagnetic resonance studies. The addition of nano-Co2O3 into 3Y-TZP resulted in higher hydrothermal aging resistance than 3Y-TZP. The addition of 0.2 mol% nano-Co2O3 dopants resulted in the highest hydrothermal aging resistance among nano-Co2O3-doped 3Y-TZP ceramics. The grain sizes of 3Y-0.2Co are smaller than those in the control group. With the increase of cobaltous oxide doping contents, the segregation of Co3+ ions at the crystal boundary increased. The content of oxygen vacancies on the surface of the sample increased with the increase of the Co2O3 doping content. The oxygen vacancy concentrations of 3Y-0.2Co increased obviously after aging. 3Y-0.1Co, 3Y-0.3Co, and the control showed decreased oxygen vacancy concentrations after aging. Trivalent element doping of 3Y-TZP effectively improved the aging resistance of 3Y-TZP. The addition of 0.2 mol% nano-Co2O3 resulted in the highest hydrothermal aging resistance. Improved aging resistance is attributed to the nano-Co2O3 doping resulting in the 3Y-TZP grain size inhibition, grain boundary segregation of cobalt ions, and oxygen vacancy maintenance. This work is expected to provide an effective reference for the development and application of budget dental materials by regulating grain boundary engineering.