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Thesis (Ph. D.)--School of Chemistry and Biochemistry, Georgia Institute of Technology, 2004. Directed by Z. John Zhang. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Z. John Zhang; Committee Member: Angus Wilkinson; Committee Member: C P Wong; Committee Member: E. Kent Barefield; Committee Member: Mostafa El-Sayed. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (B.S.)--University of Missouri, School of Mines and Metallurgy, 1937. / The entire thesis text is included in file. Typescript. Title from title screen of thesis/dissertation PDF file (viewed July 21, 2010) Includes bibliographical references (p. 53-54) and index (leaves 51-53).

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Magnesium aluminate spinel inclusions are a concern in the steelmaking industry since these particles affect the processing and the properties of steel. During the refining of low carbon aluminum killed steel in the ladle furnace; the initial alumina inclusions shift their composition towards higher contents of MgO and eventually they become magnesium aluminate spinel inclusions. This research developed a kinetic model for the transformation of alumina inclusions to spinel in liquid steel. The aspects of simultaneous deoxidation and of solid state cation counterdiffusion were addressed in the model. Coupling the model for spinel inclusions to a kinetic model for the slag-steel reactions in the ladle furnace allowed verifying the modeled concentrations in the inclusions with the plant data measurements of ArcelorMittal Dofasco operations. Good agreement between the experimental and calculated Mg contents in the inclusions was obtained for most of the industrial heats analyzed. Finally, a sensitivity analysis of the coupled kinetic model was performed to compare the effect of the different processing conditions and mass transfer rates on the amount of Mg and spinel in the inclusions. Several results from this work indicate that the rate limiting step on the formation of magnesium aluminate spinel inclusions is the supply rate of dissolved [Mg] from the slag-steel reaction; the supply of [Mg] is in turn controlled by the changes at the slag-steel interface. / Thesis / Master of Applied Science (MASc)

Ceramic materials are in general characterized by high hardness, high modulus of elasticity, excellent abrasion resistance, etc. These properties make ceramics among others useful in optically transparent applications. An ideal form of optically transparent ceramic material is monocrystalline. However, the monocrystalline fabrication is expensive and/or time consuming. From this point of view polycrystalline ceramics is preferred. But the polycrystalline transparent ceramics fabrication is fraught with complications such as porosity, inappropriate grain size and insufficient purity. These circumstances could be solved by using sintering additives. This master’s thesis compiles literature research summarizing modern technologies of advanced ceramics sintering and ceramic polycrystalline microstructure dependence on its optical properties. The experimental part of this thesis focuses on the fabrication parameters of polycrystalline advanced ceramics based on Al2O3MgO and evaluation of their optical properties. Polycrystalline magnesium-aluminate spinel with sintering additive contents 0; 0.3 and 0.6 weight % LiOH was fabricated by optimalisation of Spark Plasma Sintering cycle. Fully dense ceramic samples of polycrystalline magnesium-aluminate spinel with favourable optical properties in visible spectrum radiation were achieved. Real In-line Transmission RIT and Total Forward Transmittance TFT were analysed. RIT exceeded 84 % at wavelength of 633 nm and TFT exceeded 83 % at wavelength above 860 nm. The decisive factors in terms of the optical properties of ceramics sintered with sintering additives were the amount of time-spending at high temperatures and the purity of ceramic powders.

The high temperature oxidation of ferritic stainless steel interconnects results in chromium poisoning of the solid oxide fuel cell (SOFC) electrodes, which is a limiting factor for their utilisation as SOFC interconnects. Chromium-rich spinel materials were studied as electrode supports that would be situated at the interface between interconnect and electrode, in order to reduce the effect of chromium poisoning of the electrodes. The main goal of this thesis was to find chromium-rich spinel materials with good electrical conductivity (σ ≥ 0.1 S∙cm⁻¹) in air and reducing atmosphere, chemically and mechanically stable in SOFC testing conditions. The structure and properties of newly formulated chromium-rich spinels, such as Mn₁₊ₓCr₂₋ₓO₄ (x = 0, 0.5), MnFeₓCr₂₋ₓO₄ (x = 0.1, 1), MgMnCrO₄, MnLiₓCr₂₋ₓO₄ (x = 0.1) and MgMₓCr₂₋ₓO₄, (M = Li, Mg, Ti, Fe, Cu, Ga) were studied aiming at their application as electrode support material for solid oxide fuel cells. Cation distributions were determined by Rietveld refinement from X-ray diffraction (XRD), within the limits of XRD precision and correlated with electrical properties determined experimentally. The chemical stability in reducing conditions was studied and the reduction effects upon materials were evaluated by XRD phase analysis and microstructure analysis. It was found that MnMₓCr₂₋ₓO₄ materials have a limited stability to reduction, only MnCr₂O₄ proved to have good stability when reduced, with negative influence for its p-type semiconductor conductivity. Even though MnFeCrO₄ had limited stability to reduction, in reducing conditions the conductivity changed from p-type to n-type semiconductor. A similar behaviour to reduction was observed for MgFeCrO₄. Also the mechanical and chemical compatibility of some spinels with YSZ was studied in terms of thermal expansion coefficient (TEC/K⁻¹), sintering step and possible chemical reactions. Lithium titanate spinels, starting with LiCrTiO₄, were investigated in terms of structure, properties and spinel - ramsdellite phase transition temperature also with the purpose of new material development. For these materials positive results were obtained in conductivity and chemical stability in reducing conditions. The performance of MnFeCrO₄ and MgFeCrO₄ as electrode support materials was investigated when used alone or impregnated with (La₀.₇₅Sr₀.₂₅)₀.₉₇Cr₀.₅Mn₀.₅O₃, La₀.₈Sr₀.₂FeO₃, Ce₀.₉Gd₀.₁O₂, CeO₂ or Pd. Composite anodes for SOFC were prepared by aqueous infiltration of nitrate salts into porous MnFeCrO₄ and MgFeCrO₄ scaffolds and studied by electrochemical impedance spectroscopy (EIS) in symmetrical cell configuration. The performance of the composite anodes was evaluated in humidified 5%H₂/Ar in order to understand their stability and performance at 850 °C or lower temperature with respect to the porous substrates. It was found that all the impregnated phases adhere very well to the spinel and considerably enhance performance and stability to a level required for SOFC applications. An interesting next step in this work would be to apply such spinel materials on steel interconnects, integrate them into testing SOFC devices and evaluate their effect upon chromium poisoning of the electrodes.

Na última década, para atender à demanda de aço requerida pelo aquecimento da economia mundial, aliado ao aumento da produtividade dos altos fornos, as usinas siderúrgicas vêm enfrentando problemas de disponibilidade de equipamentos, principalmente para escoar a produção do gusa dos Altos Fornos para a Aciaria realizada por Carros Torpedo. Estudos sobre mecanismos de corrosão em refratários utilizados em carro torpedo mostraram que a presença de espinélio, MgAl2O4, melhora a resistência à erosão e à penetração de escória, em refratários de alta alumina. Considerando que a corrosão em refratários é governada pela área de interface com o metal/escória, a diminuição da porosidade dos refratários contribui para a diminuição desta área. Portanto, para que a resistência à corrosão do revestimento refratário seja melhorada, é necessário que os caminhos que conduzem à penetração do banho (gusa/escória), sejam preenchidos ao máximo, sem comprometer a microestrutura diante de possíveis variações volumétricas, resultantes de expansão térmica diferencial. O objetivo desse trabalho é avaliar o comportamento ao desgaste por corrosão gusa/escória em refratários formados a base de Al2O3/SiC/C/MgAl2O4 incorporados com espinélio de alumínio magnésio na porosidade aberta do material refratário. Para análise da formação e estabilidade química do espinélio, a partir das soluções mistas de nitratos de magnésio e alumínio foram utilizadas análises termogravimétrica, (TG), análise térmica diferencial, (DTA), difratometria de raios X, (DRX). Após as impregnações dos corpos de prova e ensaios de corrosão e escorificação, realizados em Forno Tamman foram utilizadas as técnicas de microscopia eletrônica de varredura (MEV), porosimetria de mercúrio, difratometria de raios X, DRX, para avaliar os mecanismos de desgaste do refratário. / In the last decade to get the demand of steel required for the global economy warming, coupled with the increasing blast furnaces productivity, steel mills have had problems of equipment availability, mainly to transfer hot metal productionl from blast furnaces to Steelmaking by Torpedo Cars. Studies of corrosion mechanisms in refractory materials used in torpedo cars showed that the presence of spinel, MgAl2O4, improves the erosion resistance and slag penetration in high-alumina based refractories. Considering that the refractories corrosion is controlled by the interface with the hot metal or slag, the decrease of refractories porosity contributes to the reduction in this surface area. Therefore, the refractory lining corrosion resistance improved when the pathways lead to penetration of the bath (hot metal/slag) are filled up to the maximum, without jeopardizing the microstructure, avoiding volumetric changes by differential thermal expansion. The goal of this study is to evaluate the corrosion wear behavior by hot metal/slag of Al2O3/C/SiC/MgAl2O4 based materials incorporated with aluminum magnesium spinel into open porosity of this refractory materials. Thermal analysis (TG/DTA) and X-ray diffraction (XRD) were simultaneously study used the formation and chemical stability of spinel obtained from mixed solutions of b using magnesium and aluminum nitrates. After impregnation and corrosion tests Tammann furnace materials samples were characterized by scanning electron microscopy (SEM), mercury porosimetry, X-ray diffraction (XRD) to evaluate the wear mechanisms of refractory.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE / Vita. / Includes bibliographical references. / by Normand Denis Corbin. / M.S.