Oxygen exchange at gas/oxide interfaces: how the apparent activation energy of the surface exchange coefficient depends on the kinetic regime

In the dedicated literature the oxygen surface exchange coefficient KO and the equilibrium oxygen exchange rate [Fraktur R]0O are considered to be directly proportional to each other regardless of the experimental circumstances. Recent experimental observations, however, contradict the consequences of this assumption. Most surprising is the finding that the apparent activation energy of KO depends dramatically on the kinetic regime in which it has been determined, i.e. surface exchange controlled vs. mixed or diffusion controlled. This work demonstrates how the diffusion boundary condition at the gas/solid interface inevitably entails a correlation between the oxygen surface exchange coefficient KO and the oxygen self-diffusion coefficient DO in the bulk (“on top” of the correlation between KO and [Fraktur R]0O for the pure surface exchange regime). The model can thus quantitatively explain the range of apparent activation energies measured in the different regimes: in the surface exchange regime the apparent activation energy only contains the contribution of the equilibrium exchange rate, whereas in the mixed or in the diffusion controlled regime the contribution of the oxygen self-diffusivity has also to be taken into account, which may yield significantly higher apparent activation energies and simultaneously quantifies the correlation KO ∝ DO1/2 observed for a large number of oxides in the mixed or diffusion controlled regime, respectively

Nitrogen diffusion in nitrogen-doped yttria stabilised zirconia

Nitrogen self-diffusion was measured in single crystalline nitrogen-doped yttria-stabilised zirconia (YZrON) containing 10 mol% yttrium oxide. Samples containing two different nitrogen contents (5 and 6 mol% N on the anion sublattice) were investigated as a function of temperature (650–1000 K) using implanted 15N as a stable tracer. For a given temperature, the nitrogen diffusivity was nearly independent of the nitrogen content in the nitrogen-doped yttria-stabilised zirconia, which can be only partially understood using defect chemistry. The activation enthalpy of nitrogen diffusion was between 2 and 2.5 eV with a preexponential factor of the order of 100 cm2 s−1, which corresponds to a migration entropy of 5 kB. The surface exchange reaction between nitrogen and the oxonitride surface was investigated at 1073 K using 200 mbar gaseous 15N2 and was found to be slow but considerable. Decreasing the oxygen content in the gas phase can enhance the nitrogen incorporation into the oxonitrides.Instituto de Física La Plat

Lanthanide transport in stabilized zirconias : Interrelation between ionic radius and diffusion coefficient

The diffusion of all stable lanthanides in calcia stabilized zirconia (CSZ) and in yttria stabilized zirconia (YSZ) was measured. Lanthanide migration enthalpies were calculated using the Mott-littleton approach. The results suggest that the bulk diffusion coefficient depends on the ionic radius of the lanthanide tracer. It was also found that the experimental activation enthalpies are about 6eV for CSZ and between 4 and 5 eV for YSZ and almost constant for all lanthanides.Instituto de Física La Plat