Papers by Author: Antônio Claret Soares Sabioni

Abstract: Mullite whiskers were obtained by thermal decomposition of powders of natural topaz, pure and doped with 3 and 5% in weight of La₂O₃ and Y₂O₃, at the temperatures of 1300 and 1400^°C, for 1h, in air. Pure and doped mullite whiskers showed a molar ratio Al₂O₃: SiO₂ close to 2:1, rich in alumina. The aspect ratio (AR) of whiskers varies with dopant concentrations and temperatures. The ARs for pure whiskers were 28 and 31.5, at the temperatures of 1300 and 1400°C, respectively, showing no glassy phase. For the doped whiskers, there were observed a reduction in the ARs, ranging from 14.13 to 16.10 (3 and 5% La₂O₃) and from 6.32 to 7.35 (3 and 5% Y₂O₃), for the temperatures of 1300 and 1400°C, respectively. The Y₂O₃ was not entirely incorporated, and part of it formed Y₂Si₂O₇ and Y₂O_3-δ, with δ = 0.33 according to quantitative X-ray diffraction analysis (XRD analysis) with the presence of small amount of vitreous phase.

Abstract: Oxygen ion diffusion coefficient was measured, for the first time, in oxide films grown by the high temperature oxidation of the AISI 304 austenitic stainless steel. The steel samples were polished and then oxidized in synthetic air in order to grow the chromia oxide (Cr₂O₃) film. The oxygen diffusion experiments in the oxide films were performed by using the¹⁸O isotope as oxygen tracer. The isotope diffusion studies were performed from 750 to 900^o C, in Ar +21%¹⁸O₂ atmosphere and the oxygen ion diffusion profiles were established by secondary ion mass spectrometry (SIMS) analysis. From the¹⁸O diffusion profiles, the bulk, effective and grain boundary diffusivities were determined. Using Wagner´s theory, it is shown that, under the used experimental conditions, the oxygen ion diffusion is large enough to assure the growth rate of the chrome oxide films formed by the oxidation of the AISI 304 stainless steel.

Abstract: In order to investigate the role of oxygen diffusion in the oxidation process of the AISI 439 ferritic stainless steel, oxygen ion diffusion coefficients were determined, for the first time, in oxide films formed by the oxidation of this steel. Steel samples were firstly oxidized from 750^o C to 900^o C, in synthetic air, in order to grow oxide films mainly made up of chrome oxide; the oxygen diffusion experiments were then performed using the stable isotope ¹⁸O as oxygen tracer. The introduction of the ¹⁸O in the oxide film was performed by means of the gas-solid isotopic exchange method, in the temperature range of 750-900^o C, in Ar+21%¹⁸O₂ atmosphere. The ¹⁸O diffusion profiles were established by secondary ion mass spectrometry (SIMS). Parabolic oxidation constants calculated by means of Wagner´s theory, using the oxygen ion diffusion coefficient determined by our experimental process, are greater than oxidation constants previously determined in oxidation experiments from 850 to 950º C, in air, which indicates that the oxygen ion diffusion is large enough to assure the growth rate of the oxide film formed by the oxidation of the AISI 439 steel in these temperatures.

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: 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: This work deals with the study of zinc self-diffusion in ZnO polycrystal of high density and of high purity. The diffusion experiments were performed using the 65Zn radioactive isotope as zinc tracer. A thin film of the tracer was deposited on the polished surface of the samples, and then the diffusion annealings were performed from 1006 to 1377oC, in oxygen atmosphere. After the diffusion treatment, the 65Zn diffusion profiles were established by means of the Residual Activity Method. From the zinc diffusion profiles were deduced the volume diffusion coefficient and the product dDgb for the grain-boundary diffusion, where d is the grain-boundary width and Dgb is the grain-boundary diffusion coefficient. The results obtained for the volume diffusion coefficient show good agreement with the most recent results obtained in ZnO single crystals using stable tracer and depth profiling by secondary ion mass spectrometry, while for the grain-boundary diffusion there is no data published by other authors for comparison with our results. The zinc grain-boundary diffusion coefficients are ca. 4 orders of magnitude greater than the volume diffusion coefficients, in the same experimental conditions, which means that grain-boundary is a fast path for zinc diffusion in polycrystalline ZnO.

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.