Evolution of oxygen-ion and proton conductivity in Ca-doped Ln₂Zr₂O₇ (Ln = Sm, Gd), located near pyrochlore-fluorite phase boundary

Sm_2-xCa_xZr₂O_7-x/2 (x = 0, 0.05, 0.1) and Gd_2-xCa_xZr₂O_7-x/2 (x = 0.05, 0.1) mixed oxides in a pyrochlore-fluorite morphotropic phase region were prepared via the mechanical activation of oxide mixtures, followed by annealing at 1600 °C. The structure of the solid solutions was studied by X-ray diffraction and refined by the Rietveld method, water content was determined by thermogravimetry (TG), their bulk and grain-boundary conductivity was determined by impedance spectroscopy in dry and wet air (100-900 °C), and their total conductivity was measured as a function of oxygen partial pressure in the temperature range: 700-950 °C. The Sm_2-xCa_xZr₂O_7-x/2 (x = 0.05, 0.1) pyrochlore solid solutions, lying near the morphotropic phase boundary, have proton conductivity contribution both in the grain bulk and on grain boundaries below 600 °C, and pure oxygen-ion conductivity above 700 °C. The 500 °C proton conductivity contribution of Sm_2-xCa_xZr₂O_7-x/2 (x = 0.05, 0.1) is ~ 1 × 10^-4 S/cm. The fluorite-like Gd_2-xCa_xZr₂O_7-x/2 (x = 0.1) solid solution has oxygen-ion bulk conductivity in entire temperature range studied, whereas proton transport contributes to its grain-boundary conductivity below 700 °C. As a result, of the morphotropic phase transition from pyrochlore Sm_2-xCa_xZr₂O_7-x/2 (x = 0.05, 0.1) to fluorite-like Gd_2-xCa_xZr₂O_7-x/2 (x = 0.05, 0.1), the bulk proton conductivity disappears and oxygen-ion conductivity decreases. The loss of bulk proton conductivity of Gd_2-xCa_xZr₂O_7-x/2 (x = 0.05, 0.1) can be associated with the fluorite structure formation. It is important to note that the degree of Ca substitution in such solid solutions (Ln_2-xCa_x)Zr₂O_7-σ (Ln = Sm, Gd) is low, x < 0.1. In both series, grain-boundary conductivity usually exceeds bulk conductivity. The high grain-boundary proton conductivity of Ln_2-xCa_xZr₂O_7-x/2 (Ln = Sm, Gd; x = 0.1) is attributable to the formation of an intergranular CaZrO₃-based cubic perovskite phase doped with Sm or Gd in Zr sublattice.