Precise Determination of the Chemical Diffusion Coefficient of Calcium‐Doped Lanthanum Chromites by Means of Electrical Conductivity Relaxation

Chemical relaxation experiments were conducted on sintered samples of calcium‐doped lanthanum chromites by abruptly changing the oxygen partial pressure in the atmosphere and following the time change of conductivity. The re‐equilibration kinetics was analyzed by fitting the relaxation data to the solutions of Fick's second law for appropriate boundary conditions. The diffusion equation ignoring the effect of surface reaction failed to describe the transient behavior especially for the initial stage, while that taking the surface effect into account gave a satisfactory interpretation of the overall relaxation process and allowed a precise determination of the two kinetic parameters: oxygen chemical diffusion coefficient and surface reaction rate constant. The chemical diffusion coefficients increased with a decrease of the oxygen partial pressure due to the corresponding change in the concentration of the moving species. The activation energy was similar to that of oxygen vacancy diffusion coefficients in other monocrystalline perovskites, suggesting that the measured diffusion coefficients were attributable to lattice diffusion. The surface reaction rate constant increased with a decrease of the oxygen partial pressure similarly to the reported oxygen nonstoichiometry, which implies that the presence of oxygen vacancies plays an important role in the surface reaction kinetics.