Influence of alkaline-earth metal substitution on structure, electrical conductivity and oxygen transport properties of perovskite-type oxides La

Structural evolution, electrical conductivity, oxygen nonstoichiometry and oxygen transport properties of perovskite-type oxides La0.6A0.4FeO3-δ (A = Ca, Sr, and Ba) were investigated. La0.6Ca0.4FeO3-δ (LCF64) and La0.6Sr0.4FeO3-δ (LSF64) show a phase transformation in air at elevated temperature, i.e., from orthorhombic (Pnma) to rhombohedral (R3[combining macron]c) and from rhombohedral to cubic (Pm3[combining macron]m), respectively, while La0.6Ba0.4FeO3-δ (LBF64) remains cubic over the entire temperature range from room temperature to 1000 °C. The different phase behaviour of the solids is interpreted to reflect the decreased tendency for octahedral tilting with increasing alkaline-earth-metal dopant ion radius. The electrical conductivity of LSF64 is 191 S cm-1 in air at 800 °C, decreasing to a value of 114 S cm-1 at a pO2 of 0.01 atm, and found over this pO2 range roughly twice as high as those of LCF64 and LBF64. Failure to describe the data of electrical conductivity using Holstein's small polaron theory is briefly discussed. Chemical diffusion coefficients and surface exchange coefficients of the materials in the range 650-900 °C were extracted from data of electrical conductivity relaxation. Data of oxygen nonstoichiometry was used to calculate the vacancy diffusion coefficients from the measured chemical diffusion coefficients. The calculated migration enthalpies are found to decrease in the order LCF64 (1.08 ± 0.04 eV) > LSF64 (0.95 ± 0.01 eV) > LBF64 (0.81 ± 0.01 eV). The estimated ionic conductivities of the materials, at 900 °C, are within a factor of 1.4.