M.H.R. Lankhorst

Oxygen exchange and diffusion coefficients of strontium-doped lanthanum ferrites by electrical conductivity relaxation

Electrical conductivity relaxation experiments were performed on thin specimens of La1–xSrxFeO3–delta (x = 0.1, 0.4) at oxygen partial pressures pO2 = 10–5 – 1 bar in the temperature range 923 to 1223 K. The transient response of the electrical conductivity after a sudden change of the ambient oxygen partial pressure was analyzed in the frequency domain. The latter procedure allowed diffusion-limited and surface exchange-limited kinetics of re-equilibration to be distinguished. The response of specimens with thicknesses of 350 to 460 µm indicated diffusion-controlled kinetics at pO2 > 0.03 bar. The chemical diffusion coefficients, D-tilde , were found invariant with oxygen pressure. At 1073 K the absolute values were D-tilde = 6.5 × 10–6 cm2 s–1 for x = 0.1 and D-tilde = 1.1 × 10–5 cm2 s–1 for x = 0.4, with activation energies of about 80 kJ/mol. The equilibration process was governed by surface exchange at pO2 O[sub 2] n , where n = 0.65 to 0.85. This pressure dependency was interpreted in terms of a slow surface process involving an oxygen molecule and a surface oxygen vacancy, and causes the observed sharp transition from diffusion- to exchange-controlled kinetics. The activation energy of kO was estimated at 110 to 135 kJ/mol.

Chemical diffusion and oxygen exchange of La0.6Sr0.4Co0.6Fe0.4O3−δ

The transport parameters of La0.6Sr0.4Co0.6Fe0.4O3−δ were determined by electrical conductivity relaxation and high temperature coulometric titration experiments. The experimental response curves were analyzed in the frequency domain. The results obtained by both methods were in good agreement. The chemical diffusion coefficients measured at temperatures of 923–1255 K and oxygen partial pressures of 0.03–1 bar O2, vary between 10−6–5×10−5 cm2 s−1. The experimental activation energies are in the range 95–117 kJ mol−1. At oxygen partial pressures below 0.03 bar O2 the re-equilibration process is completely governed by the rate of oxygen exchange at the interface. The surface exchange coefficients were determined by conductivity relaxation experiments at temperatures of 1000–1285 K and oxygen pressures of 10−4–0.1 bar O2. The activation energy is about 60–70 kJ mol−1. The exchange coefficients are almost proportional to the oxygen pressure. Treatment of the surface in a nitric acid solution for several hours increases the surface exchange rates by factors of 3–5.

Importance of electronic band structure to nonstoichiometric behaviour of La0.8Sr0.2CoO3

The partial energy and entropy involved in the process of oxygen incorporation into the mixed oxygen ion and electronic conducting La0.8Sr0.2CoO3 was measured by oxygen coulometric titration. The partial entropy can be assigned to the configurational entropy of randomly distributed oxygen vacancies. The partial energy decreases linearly with increasing oxygen nonstoichiometry. These observations can be explained assuming that electrons, created during vacancy formation, gradually fill electron states in a wide band resulting in a corresponding increase of the Fermi level.

Determination of Oxygen Nonstoichiometry and Diffusivity in Mixed Conducting Oxides by Oxygen Coulometric Titration. II Oxygen Nonstoichiometry and Defect Model for La0.8Sr0.2CoO3-delta

The oxygen nonstoichiometry of La0.8Sr0.2CoO3-delta has been determined as a function of oxygen partial pressure and temperature using a high-temperature coulometric titration cell. For each measured value of the oxygen chemical potential, the oxygen nonstoichiometry is found to be nearly independent of temperature. The equilibrium partial energy and entropy associated with oxygen incorporation have been determined as a function of oxygen nonstoichiometry and temperature. The results are interpreted in terms of a model in which it is assumed that conduction electrons, created during vacancy formation, gradually fill electron states in a wide electron band. A new relation between vacancy concentration, temperature, and oxygen partial pressure has been formulated which does not have the familiar appearance of a mass action type of equation.

Determination of oxygen nonstoichiometry and diffusivity in mixed conducting oxides by oxygen Coulometric titration

Oxygen coulometric titration has been applied to measure chemical diffusion in La0.8Sr0.2CoO3-δ between 700 and 1000°C. The transient current response to a potentiostatic step has been transformed from the time domain to the frequency domain. The equivalent circuit used to fit the resulting impedance data contains the element that describes the finite-length diffusion of oxygen into the sample specimen. Other elements included are the gas-phase capacitance and the sum of the gas-phase diffusion resistance and that associated with the limited surface exchange kinetics of the sample. The chemical diffusion coefficient of perovskite La0.8Sr0.2CoO3-δ has been determined as a function of temperature and oxygen partial pressure. Its value can be represented by ~D (cm2/s) = 5.91 x exp [(-135 kJ/mol)/RT], and turns out to be practically independent of oxygen partial pressure in the range 10-2 - 0.209 bar.

Scaling universality at the dynamic vortex Mott transition

The cleanest way to observe a dynamic Mott insulator-to-metal transition (DMT) without the interference from disorder and other effects inherent to electronic and atomic systems, is to employ the vortex Mott states formed by superconducting vortices in a regular array of pinning sites. Here, we report the critical behavior of the vortex system as it crosses the DMT line, driven by either current or temperature. We find universal scaling with respect to both, expressed by the same scaling function and characterized by a single critical exponent coinciding with the exponent for the thermodynamic Mott transition. We develop a theory for the DMT based on the parity reflection-time reversal (PT) symmetry breaking formalism and find that the nonequilibrium-induced Mott transition has the same critical behavior as the thermal Mott transition. Our findings demonstrate the existence of physical systems in which the effect of a nonequilibrium drive is to generate an effective temperature and hence the transition belonging in the thermal universality class.