Abstract The oxygen-uranium (O-U) system has various oxides, such as UO2, U4O9, U3O8, and UO3. Uranium dioxide is the most important one because it is used as nuclear fuel in nuclear power plants. UO2 can have a wide stoichiometric variation due to excess or deficiency of oxygen in its crystal lattice, which can cause significant modifications of its proprieties. O/U relation determination by gravimetry cannot differentiate a stoichiometric deviation from contents of other uranium oxides in UO2. The presence of other oxides in the manufacturing of UO2 powder or sintered pellets is a critical factor. Fourier Transform Infrared Spectroscopy (FTIR) was used to identify U3O8 in samples of UO2 powder. UO2 can be identified by bands at 340 cm-1 and 470 cm-1, and U3O8 and UO3 by bands at 735 cm-1, 910 cm-1, respectively. The methodology for sample preparation for FTIR spectra acquisition is presented, as well as the calibration for quantitative measurement of U3O8 in UO2. The content of U3O8 in partially calcined samples of UO2 powder was measured by FTIR with good agreement with X-rays diffractometry (XRD).

Mulita com composição 1,4 Al2O3.SiO2 foi sintetizada a partir de α-alumina comercial (Alfa Cesar Company) e de sílica obtida da calcinação da casca de arroz. Essa sílica possui alta área superficial, alta pureza e pequeno diâmetro médio de partícula. Pós de sílica e de alumina foram misturados na proporção estequiométrica 3Al2O3-2SiO2 correspondente a 71,8 % em peso de Al2O3 e 26,2 % em peso de SiO2, homogeneizados em moinho de disco orbital de alumina antes e após a calcinação a 1100ºC, durante 4 h, ao ar. Em seguida, os pós foram prensados uniaxialmente sob uma pressão de 1200 MPa. Os corpos verdes foram sinterizados a 1650ºC, por 4 h, ao ar. As densidades dos corpos sinterizados foram determinadas pelo método hidrostático. As caracterizações química e estrutural foram realizadas por ICP, DRX e MAS RMN de 29Si, respectivamente, e a análise microestrutural por MEV. Os resultados obtidos mostram que é possível sintetizar cerâmica mulita de alta pureza, com pouca fase vítrea, a partir da α-alumina e sílica, obtida da casca de arroz purificada e calcinada.

Mullite, composed of 1,4Al2O3.SiO2 was synthesized using commercial α-alumina (Alpha Cesar Company) and silica obtained from the calcinations of rice husk. This silica exhibits a high specific surface area, high purity and small average particle diameter. Silica (26.2 wt.%) and α-alumina powders (71.8 wt. %) were mixed and homogenized using an alumina orbital disc mill before and after the calcinations at 1100ºC for 4 h in an air atmosphere. Then, the powders were pressed uniaxially at a pressure of 1200 MPa. The green compacts were sintered at 1650ºC, for 4 h, in air. The density of compacted sintering samples was determined using the hydrostatic method. The chemical and structural properties were observed using ICP (Inductively Coupled Plasma), XRD (X-ray diffraction) and 29Si MAS (Magic Angle Spinning) NMR (Nuclear Magnetic Resonance) and the microstructural characterization performed using SEM (Scanning Electron Micrography). The results show that it is possible to synthesize mullite ceramic of high-purity and with little glassy phase from the α-alumina and silica obtained from the rice husk that is purified and calcinated.

In order to clarify the influence of Bi-doping on oxygen diffusion in ZnO, the bulk and grain boundary oxygen diffusion coefficients were measured in Bi2O3-doped ZnO polycrystals by means of the gas-solid exchange method using the isotope 18O as the oxygen tracer. The experiments were performed on ZnO sintered samples containing 0.1, 0.3 and 0.5 mol% Bi2O3. The diffusion annealings were performed at 942, 1000 and 1092 °C, 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 in the oxygen diffusion in the Bi2O3-doped ZnO, when compared to the oxygen diffusion in the undoped ZnO polycrystal under the same experimental conditions, both in bulk and in grain-boundaries. Moreover, it was observed that the higher the Bi2O3 concentration, the higher the oxygen diffusion. These results suggest that the incorporation of Bi2O3 increases the interstitial oxygen concentration which agrees with an interstitial diffusion mechanism both in bulk and in grain-boundaries.

Variantes do Processo Sol-Gel foram utilizadas com sucesso para obter microesferas de (Th,U)O2 com os requisitos exigidos para seu uso em reatores HTGR. O Processo Hidrólise foi empregado para obtenção de microesferas de UO2 e o Processo de Gelação Externa foi empregado para obtenção de microesferas de (Th,U)O2 com teores de urânio de até 25%. O Processo Hidrólise ainda necessita de otimização das condições de síntese.

Sol-Gel processes were successfully used to obtain (Th,U)O2 microspheres with the properties required for its use in HTGR reactors. The Hydrolysis Process was used to obtain UO2 microspheres, and the External Gelation Process was used to obtain (Th,0-25%U)O2 microspheres. Optimization of synthesis conditions is still required for the Hydrolysis Process.

Oxygen diffusion coefficients in pure and doped ZnO polycrystals were determined by means of the gas-solid isotope exchange method using the isotope 18O as oxygen tracer. The diffusion experiments were performed from 900 to 1000 °C, under an oxygen pressure of 10(5) Pa. After the diffusion annealings, the 18O diffusion profiles were determined by secondary ion mass spectrometry. The results of the experiments show that oxygen diffusion in Li-doped ZnO is similar to the oxygen diffusion in pure ZnO, while in Al-doped ZnO the oxygen diffusion is enhanced in relation to that observed in pure ZnO, in the same experimental conditions. Based on these results is proposed an interstitial mechanism for oxygen diffusion in ZnO. Moreover, it was found that oxygen grain-boundary diffusion is ca. 3 to 4 orders of magnitude greater than oxygen volume diffusion in pure and doped ZnO, which means that the grain-boundary is a fast path for oxygen diffusion in ZnO.

Zinc self-diffusion coefficients were measured in polycrystalline ZnO of high density (>99% of the theoretical density) and of high purity (> 99.999%). The diffusion experiments were performed from 1006 to 1377 °C, in oxygen atmosphere, for times between 16 and 574 h. The diffusion profiles were established by means of Residual Activity Method using the 65Zn radioactive isotope as zinc tracer. In our experimental conditions, the zinc volume diffusion coefficients can be described by the following Arrhenius relationship: D(cm²/s) = 1.57×10-3 exp[(-2.66 ± 0.26) eV/kT]. In the same experimental conditions, the grain-boundary diffusion coefficients are approximately 4 orders of magnitude greater than the volume diffusion coefficients, and can be described by the Arrhenius relation: D'delta (cm³/s) = 1.59×10-6 exp[(-2.44 ± 0.45) eV/kT], where D' is the grain-boundary diffusion coefficient and delta is the grain boundary width.