ABSTRACT
The mechanism of oxygen exchange between the gas phase and Ba0.5Sr0.5Co0.8Fe0.2O3-δ oxide was evaluated by considering the inhomogeneity of the oxide surface. The applicability of existing models for the analysis of the oxygen exchange mechanism was considered. A new model with a dissociation step was suggested. The rate-determining steps of the oxygen exchange process were revealed under different experimental conditions. The change in the rate-determining step occurred at 600-650 °C. The probable cause was considered taking into account the parameter of nonequivalency of adsorption centers. A relationship between the oxygen isotope redistribution rates and the rates of the elementary steps in a "gas phase-solid oxide" system was revealed.
ABSTRACT
Oxygen surface exchange kinetics and diffusion have been studied by the isotope exchange method with gas phase equilibration using a static circulation experimental rig in the temperature range of 600-800 °C and oxygen pressure range of 0.13-2.5 kPa. A novel model which takes into account distributions of the dissociative adsorption and incorporation rates has been developed. The rates of the elementary stages have been calculated. The rate-determining stages for a La2NiO(4±Î´) polycrystalline specimen have been discussed. The diffusion activation energies calculated using the gas phase equilibration method (1.4 eV) differ significantly from those calculated using isotope exchange depth profiling (0.5-0.8 eV), which was attributed to the influence of different oxygen diffusion pathways.
ABSTRACT
Oxygen nonstoichiometry of GdBaCo2O6-δ was studied by means of the thermogravimetric technique in the temperature range 600-1000 °C. The defect structure model based on the simple cubic perovskite GdCoO3-δ was shown to be valid for GdBaCo2O6-δ up to temperatures as low as 600 °C. Two independent methods, namely dc-polarization with the YSZ microelectrode and (18)O-isotope exchange with gas phase analysis, were used to determine the oxygen self-diffusion coefficient in the double perovskite GdBaCo2O6-δ. All measurements were carried out using ceramic samples identically prepared from the same single phase powder of GdBaCo2O6-δ. The experimental data on oxygen nonstoichiometry of GdBaCo2O6-δ allowed a precise calculation of the oxygen interphase exchange rate and the oxygen tracer diffusion coefficient on the basis of the isotope exchange measurements. The values of the oxygen self-diffusion coefficient measured by the dc-polarization technique were found to be in very good agreement with the ones of the oxygen tracer diffusion coefficient.
