Made available in DSpace on 2014-10-09T12:36:26Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:27Z (GMT). No. of bitstreams: 1 03872.pdf: 3194792 bytes, checksum: c608bc82f2dd8dcd16cb89209d801adc (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:48:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:03Z (GMT). No. of bitstreams: 1 09313.pdf: 17480162 bytes, checksum: 68e2e858c1f33e3137e90b76bd5cbc99 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:32:54Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:46Z (GMT). No. of bitstreams: 0 / Três métodos de obtenção de pó de U3O8 de alta densidade foram estudados: trituração de pastilhas sInterizadas de U3O8; sinterização de grânulos de U3O8 calcinado; e sinterização de grânulos de diuranato de amônio (DUA). Testes foram conduzidos variando-se a temperatura e o tempo de calcinação do DUA, bem como o tempo de sinterização, resultando em dez lotes de U3O8. Os processos foram comparados em termos de características dos pós obtidos, rendimento granulométríco e número de etapas. O teor de impurezas, a área de superfície específica, a estequiometria, a morfologia, a densidade, a distribuição de porosidade e a identificação de fases foram considerados como parametros de caracterização dos pós. As principais conclusões mostraram que o segundo método (no qual o DUA foi calcinado a 600°C por 3h) forneceu os melhores resultados. Além disso, o terceiro método também produziu bons resultados, porém com dificuldades de manuseio do DUA. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:37:17Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:07Z (GMT). No. of bitstreams: 1 02044.pdf: 6648951 bytes, checksum: 98f65fdf18484fade28803cf88a3e67d (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Nutrient pollution from industrial activity is an environmental problem that persists in water bodies near urban settings, and has been a primary contributor to eutrophication, bacterial contamination, and harmful algal blooms. Biogenic iron oxides offer a potential solution to the treatment of lakes and rivers containing high concentrations of phosphate, the limiting nutrient in aquatic systems. Soluble ferrous iron can act as an electron donor for iron-oxidizing bacteria, which thrive in low-oxygen environments. This results in the formation of insoluble ferric iron minerals, ideal adsorbents for negatively charged phosphate. Conversely, iron-reducing bacteria reduce ferric iron to form ferrous iron, resulting in the formation of secondary minerals depending on the chemistry of the particular environment. This project investigates the chemical conditions at which biogenic iron oxides have the maximum adsorptive capacity, especially with respect to organic carbon content. A simplified model of natural biogenic iron oxides was synthesized by co-precipitating the mineral ferrihydrite (a common iron oxide) with the polysaccharide alginate, an analogue to bacterial exopolysaccharides. At the levels of carbon investigated, organic matter was not found to affect the adsorptive capacity of iron oxides at the C/Fe ratios analyzed. Similarly, organic matter did not appear to significantly influence the rate of reduction of ferrihydrite by the iron-reducing bacterium Shewanella putrefaciens CN32. Presence of organics did however influence rates of reduction and the mineralogy of the post-reduction precipitates. Phosphate adsorbed to iron oxides prior to microbial reduction greatly increased both the rate and the extent of ferric iron reduced, and also had an impact on the secondary minerals that formed (vivianite, green rust). An improved understanding of these conditions could contribute to a more efficient process by which iron-oxidizing bacteria are used for large-scale industrial water treatment.

Increase in carbon dioxide emissions due to economic activity induce global warming. The strong increase in energy demand, mainly based on oil and coal, induces a rapid increase in CO2 in the atmosphere. Within Canada, the amount of human-produced carbon dioxide is considerable because a large portion of energy is supplied by burning of fossil fuels. The Reverse Water Gas Shift (RWGS) reaction is a promising catalytic process for the utilization and subsequent activation of carbon dioxide to carbon monoxide, which can be further converted into fuels such as gasoline. The current thesis studies the development of nano-catalytic systems for the RWGS reaction. Mono- and bi-metallic nanoparticles based on Cu, Fe, Ru and Pt were prepared using a polyol synthesis method. The catalytic performance of three different types of metal oxides (ionically conductive, mixed ionic-electronic conductive and non-conductive) was investigated for the RWGS reaction. Conductive metal oxides including samarium-doped ceria (SDC), ceria (CeO2), yttria-stabilized zirconia (YSZ) and iron III oxide (Fe2O3) were further used as the catalyst supports and the nanoparticles of Cu, Fe, CuxFe1-x (x = 50 and 95 at.%), Ru, Pt, Ru50Pt50 and RuxFe1-x (x = 80 and 90 at.%) were subsequently deposited on them. A stoichiometric mixture of H2 and CO2, i.e. H2/CO2 = 1, was used under atmospheric pressure in the temperature range of 300 - 600°C in order to evaluate the catalyst performance in terms of activity, stability and selectivity. Nanoparticles deposited on ceria-based supports (CeO2 and SDC) showed superior catalytic performance compared to other metal oxides. Among all the catalyst tested, 5 wt.% Ru50Pt50/CeO2 showed the highest CO yield and satisfactory stability for RWGS reaction. The second best catalytic systems were based on Ru90Fe10/CeO2 and Ru80Fe20/CeO2, which are more attractive from the practical point of view.

No description available.

No description available.

An investigation was conducted on the interaction between nickel metal and single crystals of magnesium oxide. The nickel was cleaned with purified hydrogen gas at 800°C and melted under vacuum (5 x 10⁻⁵ mm. Hg) in contact with the magnesium oxide. The interface was examined metallographic-ally. The formation of compounds at the interface was examined by X-ray diffraction techniques. The magnesium oxide was plastically deformed by thermal stresses which occurred on cooling. Slip occurred on four slip planes only. The slip sources were present in the surface at a depth not exceeding ten microns. They were in the form of dislocation half-loops introduced in the surface during cleavage. The introduction of these half-loops was due to the formation of cleavage steps. Rows of dislocation half-loops were due to the multiplication of a half-loop on a slip plane oriented in the direction of propagation of the cleavage crack. Bond formation consisted of the formation of a magnesium-nickel compound (Mg₂Ni). The bond strength exceeded the stress for brittle fracture of magnesium oxide. Attack of the magnesium oxide occurred preferentially at the perimeter of the interface. This led to groove-formation, which resulted in a large hysteresis of wetting. The diffusion of nickel into magnesium oxide seemed to take place mainly by diffusion along dislocations. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Les travaux menés dans le cadre de cette thèse ont porté sur l’ingénierie de la croissance épitaxiale (par épitaxie par jets moléculaires, MBE) et des propriétés d’oxydes fonctionnels pérovskites ABO3. Ces matériaux suscitent un intérêt fort, du fait notamment de leur grande flexibilité chimique et structurale donnant accès à de nombreuses propriétés physiques : ferroélectricité, piézoélectricité, supraconductivité à hautes températures, thermoélectricité, etc…. Dans ce contexte, l’objectif de cette thèse était d’utiliser la souplesse et le contrôle ultime de la croissance offerts par l’MBE pour exploiter au mieux cette flexibilité chimique et structurale et démontrer le potentiel des couches minces, des superréseaux et des phases de Ruddlesden-Popper basés sur le SrTiO3 et le LaSrTiO3 pour des applications en photonique. Nous avons en particulier démontré que de telles structures, si elles sont contrôlées, ouvrent des perspectives importantes pour la plasmonique, pour la réalisation de métamatériaux optiques aux performances inégalées, et pour la fabrication de couches minces fortement anisotropes. Plus spécifiquement, les principaux résultats de cette thèse sont (i) la mise en évidence des excellentes propriétés plasmoniques dans l’infrarouge des couches minces conductrices de LaxSr1-xTiO3 (SrTiO3 dopé au La), et leur forte accordabilité obtenue en contrôlant la concentration en La, (ii) la démonstration d’une nouvelle classe de métamatériaux hyperboliques dans l’infrarouge constitués de superréseaux LaxSr1-xTiO3/SrTiO3, dont l’hyperbolicité peut être largement accordée, et dont les performances surpassent celles des meilleurs métamatériaux hyperboliques basés sur du ZnO dopé au Ga ou à l’Al, et (iii) l’exploration de la croissance et de l’anisotropie optique potentiellement très forte des phases homologues de Ruddlesden-Popper à base de SrTiO3 (Srn+1TinO3n+1). Ces résultats originaux ouvrent des perspectives intéressantes pour l’utilisation de couches minces et de superréseaux structurés jusqu’à l’échelle de la monocouche à base d’oxydes pérovksites pour des applications à la photonique. / The work conducted during this thesis focused on the epitaxial growth (by molecular beam epitaxy, MBE) and the optical properties engineering of perovskite functional oxides ABO3. These materials arouse strong interest, in particular thanks to their strong chemical and structural flexibility giving access to many physical properties: ferroelectricity, piezoelectricity, high temperature superconductivity, thermoelectricity, etc.... In this context, the objective of this thesis was to use the flexibility and ultimate growth control offered by the MBE to exploit this strong chemical and structural flexibility and to demonstrate the potential of thin layers, superlattices and Ruddlesden-Popper phases based on SrTiO3 and LaSrTiO3 for photonics applications. In particular, we have demonstrated that such structures, if they are controlled, open important prospects for plasmonics, for the production of optical metamaterials with unrivalled performances, and for the production of highly anisotropic thin films. More specifically, the main results of this thesis are (i) the demonstration of the excellent infrared plasmonic properties of the LaxSr1-xTiO3 conductive thin films (La-doped SrTiO3), and their strong tunability obtained by controlling the La concentration, (ii) the demonstration of a new class of hyperbolic metamaterials in the infrared consisting of LaxSr1-xTiO3 / SrTiO3 superlattices, whose hyperbolicity can be broadly adjusted, and whose performances surpass those of the best hyperbolic metamaterials based on Ga or Al doped ZnO, and (iii) the exploration of the growth and potentially very strong optical anisotropy of Ruddlesden-Popper homologous phases based on SrTiO3 (Srn+1TinO3n+1). These original results open interesting perspectives for the use of thin layers and structured superlattices up to the monolayer scale based on perovskite oxides for photonics applications.