The main focus of this thesis is the characterization of defects and microstructure in high-energy ball milled magnesium hydride powder and magnesium-based multilayered composites. Enhancement in kinetics of hydrogen cycling in magnesium can be achieved by applying severe plastic deformation. A literature survey reveals that, due to extreme instability of -MgH2 in transmission electron microscope (TEM), the physical parameters that researchers have studied are limited to particle size and grain size. By utilizing a cryogenic TEM sample holder, we extended the stability time of the hydride phase during TEM characterization. Milling for only 30 minutes resulted in a significant enhancement in desorption kinetics. A subsequent annealing cycle under pressurized hydrogen reverted the kinetics to its initial sluggish state. Cryo-TEM analysis of the milled hydride revealed that mechanical milling induces deformation twinning in the hydride microstructure. Milling did not alter the thermodynamics of desorption. Twins can enhance the kinetics by acting as preferential locations for the heterogeneous nucleation of metallic magnesium. We also looked at the phase transformation characteristics of desorption in MgH2. By using energy-filtered TEM, we investigated the morphology of the phases in a partially desorbed state. Our observations prove that desorption phase transformation in MgH2 is of nucleation and growth type, with a substantial energy barrier for nucleation. This is contrary to the generally assumed core-shell structure in most of the simulation models for this system. We also tested the hydrogen storage cycling behavior of bulk centimeter-scale Mg-Ti and Mg-SS multilayer composites synthesized by accumulative roll-bonding. Addition of either phase (Ti or SS) allows the reversible hydrogen sorption at 350C, whereas identically roll-bonded pure magnesium cannot be absorbed. In the composites the first cycle of absorption (also called activation) kinetics improve with increased number of fold and roll (FR) operations. With increasing FR operations the distribution of the Ti phase is progressively refined, and the shape of the absorption curve no longer remains sigmoidal. Up to a point, increasing the loading amount of the second phase also accelerates the kinetics. Microscopy analysis performed on 1-2 wt.% hydrogen absorbed composites demonstrates that MgH2 formed exclusively on various heterogeneous nucleation sites. During activation, MgH2 nucleation occurred at the Mg-hard phase interfaces. On the subsequent absorption cycles, heterogeneous nucleation primarily occurred in the vicinity of internal free surfaces such as cracks. / Materials Engineering

Previous work has shown that when inorganic compounds are milled with quartz in a high energy ball mill the elements are sequestered into the quartz matrix and cannot be easily recovered by simple extraction methods. In this study lead (II) oxide, copper (II) oxide, magnesium oxide, zinc oxide and sodium hydroxide were milled with quartz sand and the recoveries of the metals investigated in detail. The standard EPA3050B method (acid digestion of sediments, sludge and soils) for extractable metals was compared to exhaustive HF digestion method based on ASTM C146-94a (test methods for chemical analysis of glass sand) and UDC 666.123:543.06 (chemical analysis of soda-lime and borosilicate glass). From these two analyses the total recovery of metals was determined. It was found that the elements extracted by the EPA3050B method decreased in an approximately logarithmic way with milling time. The metals are apparently strongly sequestered into the fractured quartz. Total HF digestion of the insoluble matrix gave good recovery of the “lost” elements. A reliable analytical procedure has been developed and the mechanisms leading to this sequestering are discussed. Particle size analysis and electron microscopy of milled samples support a process of brittle alloy formation as the proposed mechanism whereby the elements are sequestered into the milled quartz.

Thesis (B.S.) Magna Cum Laude--Butler University, 2007. / Includes bibliographical references (leaves 26-27).

Durante o período de operação de um empreendimento mineiro, oportunidades de aumento de capacidade produtiva podem gerar ganhos significativos para uma empresa. Para os casos em que se viabiliza maior capacidade de produção da mina deve-se avaliar a capacidade de processamento da usina de beneficiamento, que assim inclui melhorias de desempenho ou expansão mediante adição de equipamentos. Este trabalho contempla a descrição das etapas de amostragem, caracterização do minério, a modelagem do circuito existente e a simulação para aumento da capacidade do circuito de moagem da usina da Mineração Serra Grande da AngloGold Ashanti, situada no município de Crixás no interior de Goiás. Os cenários simulados foram (1) adição de um terceiro moinho de bolas em série aos moinhos existentes, (2) adição de um terceiro moinho de bolas em paralelo ao circuito existente, (3) adição de um moinho vertical para processamento do produto dos dois moinhos de bolas existentes e (4) adição de uma prensa de rolos após o circuito de britagem. O propósito das quatro simulações foi avaliar a viabilidade técnica dos circuitos selecionados mediante modelagem matemática e simulação de processos, assim como dimensionar os novos equipamentos para tal fim. / During operation of the mining cycle, increases the throughput would generate significant capital savings for a company. For cases that enables higher mine production capacity, it must be evaluated plant capacity and also performance improvements or expansion by adding new equipment. This study includes the description of the sampling methodology, the minerals analysis, modeling of the existing circuit and simulation for a possible expansion, specifically for the grinding circuit at Mineração Serra Grande plant of AngloGold Ashanti group, located in Crixás, Goiás. the studied scenarios were: (1) adding a third ball mill in series with existing two ball mills, (2) adding a third ball mill in parallel with existing mills, (3) adding a vertical mill in series with existing mills and (4) adding high pressure grinding rolls to existing mills. The four simulations intend assess the technical feasibility of the circuits selected by mathematical modeling and simulation of processes and design new equipment for this purpose.

Neste trabalho, investigou-se a elaboração mecânica do composto intermetálico TiFe por moagem de bolas com alta energia. Uma forte aderência do material moído, particularmente nas paredes do recipiente de moagem, foi o principal problema verificado com tempos de moagem superiores a 1 hora (moinho agitador). Tentativas para resolver este problema foram realizadas inicialmente com o emprego de agentes controladores de processo (ACPs), como etanol, ácido esteárico, polietileno de baixa densidade, benzeno e ciclohexano, em diferentes quantidades (1 a 20% em massa) e tempos (1 a 40 h), mantendo-se constantes outros parâmetros de moagem como a razão bola:pó em massa (10:1) e o tamanho das bolas (=7mm). Os rendimentos mais elevados (em termos da massa de pó não aderido) foram obtidos quando se utilizaram grandes quantidades de benzeno e ciclohexano (101 e 103% em massa, respectivamente), porém com a formação de TiC ao invés de TiFe em razão da decomposição do ACP e reação do carbono com as partículas de titânio. As moagens foram realizadas posteriormente sem o emprego de qualquer ACP e também utilizando um moinho planetário. Várias estratégias foram investigadas para se tentar mitigar a aderência incluindo-se: (a) moagem de uma pequena quantidade da mistura de pós de Ti e de Fe, revestindo as paredes do recipiente e as bolas de moagem, antes da moagem da carga principal, (b) moagem pausada com aberturas intermediarias do recipiente em atmosfera ambiente, (c) moagem pausada para rotação e inversão da posição do recipiente de moagem (apenas no moinho agitador), (d) moagem isolada dos pós de Ti e de Fe, antes da moagem da mistura, e (e) moagem do pó de Fe com o Ti hidretado. Os melhores resultados, em termos de diminuição da aderência combinada com a formação majoritária do composto TiFe durante a moagem, foram obtidos quando se adotou o procedimento de inversão/rotação, juntamente com o processo de revestimento preliminar do recipiente e das bolas de moagem (26% em massa). Rendimentos maiores foram obtidos com a utilização do TiH2 no moinho planetário, porém sem a formação majoritária do TiFe durante a moagem. / In this work an investigation on the mechanical alloying of the intermetallic compound TiFe by high-energy ball milling was conducted. Strong adherence of milled material, particularly at the vial walls, was seen to be the main problem at milling times higher than 1 hour (shaker mill), hindering the compound synthesis. Attempts to prevent this problem were accomplished first by adding different process control agents (PCAs), like ethanol, stearic acid, low density polyethylene, benzene and cyclohexane at variable quantities (1 to 20 wt. %) and times (1 to 40 h), keeping constant other milling parameters like ball to powder mass ratio (10:1) and balls size (=7mm). Highest yields (related to the non adhered powder) were attained with larger amounts of benzene and cyclohexane (101 and 103 wt. %, respectively), but with TiC formation during milling instead of TiFe due to the PCA decomposition and the reaction of the carbon with and titanium particles. Milling was conducted further without adding any PCA and also using a planetary ball mill. Several strategies were tried to avoid or minimize the adherence including: (a) milling of a small quantity of the Ti and Fe powder mixture, dirtying the vial walls and the balls surfaces before milling the main charge, (b) stepwise milling with intermediate openings of the vial in air, (c) stepwise milling with the rotation and the inversion of the vial position between the steps (only in the shaker mill), (d) milling Ti and Fe powders (apart from each other) before milling the mixture of them, and (e) milling Fe powder with Ti hydride powder. Best results concerning both yield and major TiFe formation during milling were verified with the rotation/inversion procedure combined with preliminar dirtying of the vial and balls (26 wt.% in the shaker mill). Higher yields could be attained by using TiH2 powder in the planetary mill, but with no major TiFe formation during milling.

This diploma thesis deals with changing properties of the thin layered titanium dioxide dispersion depending on the time of ball-milling. Titanium dioxide is immobilized on glass or conductive glass using the spin-coating method and the prepared thin layers are then characterized by various analytical methods. All of used analytical methods are described in theoretical and experimental sections, these methods include scanning electron microscopy, profilometry, dynamic light scattering, integrating sphere, ellipsometry, BET isotherm, voltammetry and chronoamperometry. At the summary of this diploma thesis is described how the properties of titanium dioxide thin layers change during ball-milling process.

The increasing price of oil, global warming and rapid industrial growth has drawn much attention to renewable energy technologies over the last few decades. The total energy consumption is estimated to increase 1.4% per year globally. About 90% of this energy supply is generated through fossil fuel combustion with a typical efficiency of 30-40%. The remaining 60-70% of the energy is lost to the environment via automotive exhaust or industrial processes. It is highly desired to retrieve wasted heat to improve the overall efficiency of the energy conversion. Developing thermoelectric materials and devices is a potential solution to utilize waste heat as an energy source. Skutterudites are known to be promising thermoelectric materials in the temperature range 600K to 900K. Novel nanoengineering approaches and filling of skutterudites structure can further improve the transport properties of the material. In this work, Cobalt Antimonide (Co4Sb12) based skutterudites were fabricated via mechanical milling and alloying. Rear earth material Ytterbium and Cerium are used as fillers to substitute the cages in the crystal lattice of these materials. Base material is synthesized via thermochemical reduction of the precursors under hydrogen. Further processing of the material is performed with ball milling and Spark Plasma Sintering (SPS). Ball milling parameters were optimized for nanostructuring of Co4Sb12. Grain size was significantly reduced after SPS compaction. Finally, Thermoelectric transport properties of the material is evaluated over the temperature range 300K to 900K for five different composition of the skutterudites materials. Significant reduction in materials thermal conductivity was achieved through nanostructuring.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第20476号 / エネ博第345号 / 新制||エネ||69(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 石原 慶一, 教授 野平 俊之, 准教授 奥村 英之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

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