Phase Separation in 12 mol% Ceria-Doped Zirconia Induced by Heat Treatment in H2 and Ar

The phase separation in 12 mol% CeO₂─ZrO₂ ceramic heattreated in a mixture of H₂ and Ar was investigated by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy, and Raman scattering. After heat treatment at temperatures above 1200°C, the tetragonal solid-solution phase separated into Zr₂Ce₂O₇ and the monoclinic phase. Raman scattering measurements also provided supplementary evidence for the phase separation. XPS showed that the valence change from Ce⁴⁺ to Ce³⁺ predominantly occurred, whereas the reduction from Zr⁴⁺ to Zr³⁺ took place above 1200°C. It is concluded, that in the highly reduced sample, where the valence changes from Ce⁴⁺ (Zr⁴⁺) to Ce³⁺ (Zr³⁺), the phase separation is noticeably promoted. Below 1000°C the phase separation was suppressed because of no appreciable valence change to trigger the phase separation, and the single tetragonal phase was retained.