Papers by Author: Anne Marie Huntz

Abstract: Oxygen diffusion coefficients were measured in polycrystalline ZnO by means of the gas-solid exchange method using the isotope 18O as the oxygen tracer. The diffusion annealings were performed at 892oC and 992oC, in an Ar+18O2 atmosphere under oxygen partial pressures from 0.1 to 1atm. After the diffusion annealings, the 18O diffusion profiles were established by secondary ion mass spectrometry (SIMS). Increasing the oxygen pressure leads to an increase of the oxygen diffusion in ZnO. The bulk diffusion coefficients depends on oxygen pressure according to , at 882oC, or , at 992oC, which indicates that the oxygen bulk diffusion mechanism should preferentially take place by means of interstitial oxygen having a null effective charge. The grain boundary diffusion coefficients show little dependence on oxygen pressure at 882oC, given by , which should correspond to a diffusion mechanism by means of interstitial oxygen, with a double negative charge, but at 992oC this dependence is corresponding to a diffusion mechanism by interstitial oxygen having a null effective charge. The results also show that the grain boundary is a fast path for the oxygen diffusion in polycrystalline ZnO.

Abstract: Oxygen diffusion coefficients were determined in a commercial ZnO-based varistor by means of the gas-solid exchange method using the isotope 18O as the oxygen tracer. The diffusion annealings were performed at 892, 942, 992 and 1092oC, in an Ar + 18O2 atmosphere under an oxygen partial pressure of 0.2 atm. After the diffusion annealings, the 18O diffusion profiles were established by secondary ion mass spectrometry (SIMS). The results show an increase of the oxygen diffusion in the varistor, both in bulk and in grain boundaries, when compared to the oxygen diffusion in undoped ZnO. The increase of the oxygen bulk diffusion in the varistor agrees with an interstitial mechanism for the oxygen diffusion. The results also show that the grain boundary is a fast path for the oxygen diffusion in the varistor. However, the oxygen diffusion in the grain boundaries of the varistor seems to depend on several chemical and microstructural parameters and does not allow a simple explanation.

Abstract: Yttria-stabilized zirconia (YSZ) ceramic is considered as an attractive matrix for nuclear applications, such as inert matrix for the destruction of excess plutonium or good host material for nuclear waste storage. Some actinide elements in high-level radioactive wastes can be simulated by cerium as tetravalent actinide, and gadolinium as trivalent actinide or neutron absorber. The present work is focused on the diffusion study of Ce and Gd in YSZ single crystal and high density polycrystals. A thin film of Ce or Gd was deposited either by spin-coating method or by physical vapour deposition on the surface of polished samples. The diffusion experiments were performed from 1173 to 1673 K under air. The Ce or Gd diffusion profiles were determined by secondary ion mass spectrometry. The experiments led to the determination of effective diffusion coefficient, Deff, bulk and grain boundary diffusion coefficients, DB and DGB. The dependence of these diffusion coefficients on temperature is described by means of Arrhenius equations and the diffusivity is compared with literature.

Abstract: Iron bulk self-diffusion coefficients were measured in Fe2O3 single crystals using an original methodology based on the utilization of 57Fe stable isotope as iron tracer and depth profiling by secondary ion mass spectrometry (SIMS). The iron self-diffusion coefficients measured along c-axis direction, between 900 and 1100o C, in oxygen atmosphere, can be described by the following Arrhenius relationship: D(cm2/s)= 5.2x106 exp [-510 (kJ/mol)/RT], and are similar to reliable data available in the literature, obtained by means of radioactive techniques.

Abstract: Chromia protective layers are used to prevent corrosion by oxidation of many alloys, such as the stainless steels, for instance. To check if chromia is a barrier to the outward diffusion of iron in these alloys, iron diffusion in chromia was studied in both polycrystals and oxide films formed by oxidation of Ni-30Cr alloy in the temperature range 700-1100°C at an oxygen pressure equal to 10-4 atm. An iron film of about 70 nm thick was deposited on the chromia surface, and after the diffusing treatment, the iron depth profiles were established by secondary ion mass spectrometry (SIMS). Using a solution of the Fick’s second law for diffusion from a thick film, effective or bulk diffusion coefficients were determined in a first penetration domain. Then, Le Claire’s and Hart’s models allowed both the bulk diffusion coefficient and the grain boundary diffusion parameter (aDgbd) to be obtained in a second penetration domain. Iron bulk and grain boundary diffusion does not vary significantly according to the nature-microstructure of chromia. The activation energy of grain boundary diffusion is at least equal or even greater than the activation energy of bulk diffusion, probably on account of segregation phenomena. Iron diffusion was compared to cationic self-diffusion and related to the protective character of chromia.