The Calcia–Zirconia Phase Diagram Revisited: Stability of the Ordered Phases φ1 and φ2

Abstract
Single crystals of CaO‐stabilized ZrO2 containing between 15.3 and 18.9 mol% CaO were heat‐treated for 5000 h at 1200°C to study the stability of the ordered defect‐fluorite phase, CaZr4O91). Subsequent TEM analysis of the equiaxed φ1 domains in samples richer than approximately 18 mol% in CaO showed a random distribution of φ1 variants, with no preferred interfacial habit planes. A critical review of the literature, combined with the new data, supports the Stubican‐Hellmann‐Hannon version of the phase diagram in the region 15 to 26 mol% CaO and 1000° to 1400°C and strongly suggests that φ1 is a stable phase in the ZrO2‐CaO systems.

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