Oxygen ionic conduction in brownmillerite CaAl0.5Fe0.5O2.5+δ

Abstract

The oxygen permeability of CaAl0.5Fe0.5O2.5+δ brownmillerite membranes at 1123-1273 K was found to be limited by the bulk ionic conduction, with an activation energy of 170 kJ/mol. The ion transference numbers in air are in the range 2 × 10-3 to 5 × 10-3. The analysis of structural parameters showed that the ionic transport in the CaAl0.5Fe0.5O2.5+δ lattice is essentially along the c axis. The largest ion-migration channels are found in the perovskite-type layers formed by iron-oxygen octahedra, though diffusion in tetrahedral layers of the brownmillerite structure is also possible. Heating up to 700-800 K in air leads to losses of hyperstoichiometric oxygen, accompanied with a drastic expansion and, probably, partial disordering of the CaAl0.5Fe0.5O2.5+δ lattice. The average thermal expansion coefficients of CaAl0.5Fe0.5O2.5+δ ceramics in air are 16.7 × 10-6 and 12.6 × 10-6 K-1 at 370-850 and 930-1300 K, respectively.