Point Defects and Cation Tracer Diffusion in (CrxFe1-x)3-δO4 Spinels

1994 ◽  
Vol 369 ◽  
Author(s):  
J. TÖpfer ◽  
R. Dieckmann
Keyword(s):  
Point Defect ◽  
Tracer Diffusion ◽  
Oxygen Activity ◽  
Spinel Solid Solution ◽  
Low Oxygen ◽  
Cation Diffusion ◽  
Cationic Composition ◽  
Deviation From Stoichiometry ◽  
Tracer Diffusion Coefficients ◽  
Defect Species

AbstractThe cation diffusion in the spinel solid solution (CrxFe1-x)3-δO4 (0 ≤ x ≤ 0.5) was experimentally investigated at 1200 °C as a function of oxygen activity, aO2 (= PO2/P°with P° = 1 bar) and cationic composition, x. Cation tracer diffusion coefficients, DMe' of Me = Co, Cr, Fe and Mn, were determined using the radioactiveisotopes Co-60, Cr-51, Fe-59 and Mn-54. For each cationic composition V-shaped log DMe vs. log aO2 plots were obtained. The observed oxygen activity dependences indicate that the cation diffusion is determined by different point defect species prevailing at high and low oxygen activities, respectively. The observed oxygen activity dependences, in comparison with considerations based on point defect thermodynamics, suggest that cations diffuse via cation vacancies at high aO2' while at low aO2 cation interstitials prevail in the cation diffusion. In addition, new experimental data for tihe deviation from stoichiometry ≤in (CrxFe1-x)3-≤O4 are presented and discussed.

Non-Stoichiometry and Cation Tracer Diffusion Studies in the Magnetite-UlvÖSpinel Solution, (Fe,Ti)3-δO4

1994 ◽  
Vol 369 ◽  
Author(s):  
Sanjeev Aggarwal ◽  
Rudiger Dieckmann
Keyword(s):  
Diffusion Coefficients ◽  
Tracer Diffusion ◽  
Oxygen Activity ◽  
Spinel Solid Solution ◽  
Low Oxygen ◽  
Cation Diffusion ◽  
Deviation From Stoichiometry ◽  
Diffusion Studies ◽  
Tracer Diffusion Coefficients ◽  
Point Defect Structure

AbstractCation diffusion in the spinel solid solution (Fe1-xTix)3-δO4 (0≤ x ≤ 0.3) was investigated at 1200 ºC as a function of oxygen activity, aO2 and cationic composition, x. At different cationic compositions, cation tracer diffusion coefficients, D*Me of Me = Fe and Ti were measured as a function of oxygen activity. Plots of log DMe vs. loga0 show V-shaped curves, indicating that different types of point defects prevail at high anc low oxygen activities. Thermogravimetric experiments were conducted, using a high resolution microbalance, to determine the deviation from stoichiometry in (Fe1-xTix)3-δO4 at 1200 °C. δversus log aO2 curves are S-shaped. An analysis of the oxygen activity dependences of thecation diffusion coefficients and the deviation from stoichiometry with regardto the point defect structure suggests that at high oxygen activities cation vacancies are the predominant defects governing the deviation from stoichiometry and the diffusion ofcations. At low oxygen activities, and at small values of x, cation interstitials determine the deviation from stoichiometry, while they dominate for 0 ≤ x ≤ 0.3 inthe cation diffusion.

scholarly journals Is Reduced Strontium Titanate a Semiconductor or a Metal?

Crystals ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 744
Author(s):  
Christian Rodenbücher ◽  
Christo Guguschev ◽  
Carsten Korte ◽  
Sebastian Bette ◽  
Kristof Szot
Keyword(s):  
Point Defect ◽  
Decisive Role ◽  
Thermal Reduction ◽  
Defect Chemistry ◽  
Oxygen Activity ◽  
Metallic State ◽  
Metallic Behavior ◽  
Reducing Conditions ◽  
History Play ◽  
Semiconducting Behavior

In recent decades, the behavior of SrTiO3 upon annealing in reducing conditions has been under intense academic scrutiny. Classically, its conductivity can be described using point defect chemistry and predicting n-type or p-type semiconducting behavior depending on oxygen activity. In contrast, many examples of metallic behavior induced by thermal reduction have recently appeared in the literature, challenging this established understanding. In this study, we aim to resolve this contradiction by demonstrating that an initially insulating, as-received SrTiO3 single crystal can indeed be reduced to a metallic state, and is even stable against room temperature reoxidation. However, once the sample has been oxidized at a high temperature, subsequent reduction can no longer be used to induce metallic behavior, but semiconducting behavior in agreement with the predictions of point defect chemistry is observed. Our results indicate that the dislocation-rich surface layer plays a decisive role and that its local chemical composition can be changed depending on annealing conditions. This reveals that the prediction of the macroscopic electronic properties of SrTiO3 is a highly complex task, and not only the current temperature and oxygen activity but also the redox history play an important role.

Dependence of Diffusion Paths on Thermodynamic Factors in Ternary Systems

2008 ◽  
Vol 277 ◽  
pp. 119-124 ◽  
Author(s):  
Ü. Ugaste ◽  
J. Priimets ◽  
Tony Laas
Keyword(s):  
Approximate Equation ◽  
Ternary Systems ◽  
Diffusion Path ◽  
Tracer Diffusion ◽  
Diffusion Paths ◽  
Slope Function ◽  
Experimental Values ◽  
The Impact ◽  
Tracer Diffusion Coefficients ◽  
Thermodynamic Factors

The impact of thermodynamic factors on deviation from linearity of diffusion path in the ternary system Cu-Fe-Ni is analyzed. For that the slope function of the diffusion path for the diffusion couples 65Ni30Cu5Fe –29.5Ni16.5Cu54Fe, 49.5Ni50.5Fe – 51Ni49Cu and 84Cu16Ni – 50Ni50Fe, annealed at 1000°C for 196h, were calculated by an approximate equation using only thermodynamic data. Results of the calculation were compared with the values of the slope function obtained directly from experimental data. It is shown that despite of the fact that the tracer diffusion coefficients of the components in the system Cu-Fe-Ni are not equal the coincidence between the calculated and experimental values of the slope function is remarkable. This allows us to conclude that at least in this case the deviation of the diffusion path from linearity depends mainly on the thermodynamic properties of the system.

Self-diffusion of Ag+ and Na+ in molten Ca(NO3)2-KNO3

1972 ◽  
Vol 25 (8) ◽  
pp. 1613 ◽  
Author(s):  
BJ Welch ◽  
CA Angell
Keyword(s):  
Electrical Conductance ◽  
Ionic Species ◽  
Tracer Diffusion ◽  
Dilute Solution ◽  
Self Diffusion ◽  
Capillary Method ◽  
Arrhenius Temperature Dependence ◽  
Radio Tracer ◽  
Tracer Diffusion Coefficients ◽  
Arrhenius Temperature

In order to explore the behaviour of diffusing ionic species in a molten salt in which non-Arrhenius behaviour of other transport properties is established, the diffusivities in dilute solution of Ag+ and Na+ in 38.1 mol% Ca(NO3)2+ 61.9 mol% KNO3 have been measured. For both ions limited radio-tracer diffusion coefficients, determined using a diffusion-out-of-capillary method, are reported. D(Ag+) has also been measured by chronopotentiometry, by which means the range and reliability of the measurements were considerably extended. Chronopotentiometric and tracer data agree within expected errors of measurement. Both ionic diffusivities show a non-Arrhenius temperature dependence which is indistinguishable in magnitude from that of the electrical conductance of the solvent melt.

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