Site Disorder as a Predictor for Compositionally Complex 5RE₂Zr₂O₇ Ceramic Phase Stability

Abstract

Phase formation and stability of five component compositionally complex rare earth zirconates (5RE2Zr2O7) were investigated by X‐ray diffraction and electron microprobe analysis. Zirconates with different rare earth compositions (LaNdSmEuDy, LaNdSmEuYb, LaNdEuErYb, LaNdDyErYb, SmEuDyYHo, LaYHoErYb, and DyYHoErYb) were synthesized at 1700°C and 2000°C by the solid‐state method to investigate the effect of A‐site site disorder (δA) on phase stability. Increased site disorder results from mixed cation occupancy with localized crystallographic strain and bond disorder. Compositions LaNdSmEuDy (δA = 4.6) and LaNdSmEuYb (δA = 6.0) produced a single pyrochlore phase and compositions SmDyYHoErYb (δA = 2.8), LaYHoErYb (δA = 6.2), and DyYHoErYb (δA = 1.7) produced a single fluorite phase. High δA compositions LaNdEuErYb (δA = 6.9) and LaNdDyErYb (δA = 7.2) produced a pyrochlore and fluorite phase mixture at 1700°C. Single phase was obtained for the latter composition at 2000°C. Of the single phase compositions calcined at 1700°C, LaNdSmEuYb and LaYHoErYb (both with largest δA) showed decomposition to mixed fluorite and pyrochlore phases during lower temperature anneals, indicating entropic stabilization. Comparison with prior work shows a temperature dependence of the critical δA for phase stability, and compositions near it are expected to be entropy stabilized.