<p>With a view to design processes based on gas-solid reactiontowards the production of fine-grained novel alloys andintermetallics, studies of the reduction of the mixed oxides ofFe and Mo by hydrogen towards the production of Fe-Mo alloyshave been carried out in the present work. The route offersexcellent potentials toward the bulk production of nano-grainedmaterial of tailored-composition in bulk in a green processpath. As a case study, the reduction of the mixed oxides ofiron and molybdenum were carried out from the viewpoint ofmaterials processing, chemical reaction kinetics, as well asmechanical and structural properties. The reduction kinetics ofthin layer of fine oxide particles of Fe2MoO4 was studied usingthermogravimetric technique. This technique allowed determiningreduction parameters such as temperature of reduction as wellas the activation energies for the chemical reaction as therate-controlling step. The end products were analyzed by X-raydiffraction. The reduction product was found to be reduced topure, homogeneous Fe2Mo. In order to examine the upscaling ofthe process, production of the alloy in larger amounts wascarried out in a laboratory-scale fluidized reactor and theprocess parameters were optimized. It was found that, under theconditions of the experiments, the chemical reaction was therate-controlling step. TEM, SEM and X-ray analyses of thereaction product showed the presence of a monolithicintermetallic with micro- and nanocrystalline structure. Themechanical properties of this alloy were determined.Compositions of microcrystalline Fe-Mo alloys were varied byreducing mixtures of Fe2MoO4 with MoO2 or FeO with differentFe/Mo ratios. The products after the reduction consisted of twophases, viz. intermetallic FexMoy compound and metallic Fe orMo. XRD analyses revealed that the former had microcrystallinestructure while the latter were in crystalline form. This workshows that gas-solid reaction method, together with powdermetallurgy technique is a promising process route towards theproduction of novel metallic alloys such as Fe2Mo intermetallicwith micro- and nanocrystalline grains.</p><p><b>Key words</b>: nanoalloys, intermetallics, iron-molybdenumalloy, hydrogen reduction, thermogravimetry, fluidized bed,mechanical properties, structure</p>

Greater demands are being placed on the separable connector to perform with higher reliability in harsher automotive environments. Corrosion in its various forms is a major mechanism which affects contact reliability and this current work focuses on surface oxidation and the related phenomenon of fretting corrosion, from which hot dipped tin (HDT), a common automotive connector coating, is known to suffer. For an in-depth study of high contact resistance, in both static conditions and when subjected to relative micromovement, an interdisciplinary approach was necessary, drawing on the results of published work carried out in the fields of contact and surface science, corrosion and tribology.

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This thesis focuses on the synthesis, structures, and physical properties of ternary rare-earth antimonides and germanides. These ternary compounds exhibit diverse polyanionic substructures with classical and non-classical Sb–Sb bonding, Ge–Ge bonding, or both. The Zintl-Klemm concept and band structure calculations were applied to understand their structures and bonding. Electrical resistivities and magnetic properties were measured for these compounds. The compounds RE2Ti7Sb12 (RE = La–Nd) and RE2Ti11–xSb14+x (RE = Sm, Gd, Tb, Yb), which were synthesized by arc-melting, adopt different structures depending on the size of the RE atoms. Both consist of a complex arrangement of TiSbn polyhedra, linked to form a 3D framework with large cavities in which the RE atoms reside. Hypervalent Sb–Sb bonds are manifested in disordered Sb fragments in RE2Ti7Sb12, and 1D linear chains, zig-zag chains, and pairs in RE2Ti11–xSb14+x. A series of compounds, RECrGe3 (RE = La–Nd, Sm), was synthesized by the Sn-flux method. They adopt a hexagonal perovskite structure type, in which chains of face-sharing Cr-centred octahedra are linked by triangular Ge3 clusters. These unusual single-bonded Ge3 substructures can be rationalized simply by the Zintl-Klemm concept. Electrical resistivity measurements show metallic behaviour with prominent transitions coincident with ferromagnetic transitions (Tc ranging from 62 to 155 K) found in magnetic measurements. Band structure calculations show the presence of a narrow, partially filled band with high DOS at Ef, in agreement with the observation that LaCrSb3 is an itinerant ferromagnet. With a different number of d-electrons in the M site, the isostructural REVGe3 compounds exhibit antiferromagnetic behaviour. The doped quaternary compounds LaCr1-xVxGe3 and LaCr1-xMnxGe3 exhibit depressed Curie temperatures. The structures of RECrxGe2 compounds (RE = Sm, Gd–Er) are built up by inserting transition-metal atoms into the square pyramidal sites of a hypothetical “REGe2” host structure (ZrSi2-type). The presence of extensive anionic Ge substructures in the form of 1D zigzag chains and 2D square sheets can be explained by the Zintl-Klemm concept. Magnetic measurements indicated antiferromagnetic ordering with low TN ranging from 3 to 17 K. Compounds involving a p-block element as the second component were prepared. In RE12Ge7–xSb21 (RE = La–Pr), a complex 3D polyanionic framework with Ge pairs, five-atom-wide Sb ribbons, and 2D Ge/Sb layers is present. The bonding exemplifies the competition of valence electron transfer from the RE atoms to metalloids with similar electronegativities. Full electron transfer from the RE atoms to the anionic substructure cannot be assumed. Magnetic measurements on Ce12Ge6.5Sb21 indicate antiferromagnetic coupling. The metal-rich compounds RE5TtxSb3–x (Tt = Si, Ge) adopt the orthorhombic beta-Yb5Sb3-type structure with a range of solid solubility between 0.9 and 1.6. They are not electron-precise and do not obey the Zintl-Klemm concept.

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The intermetallic compound TiAl possesses a unique complex of properties that include sufficiently low material density, high values of the strength-to-ductility ratio, high elastic moduli, high oxidation resistance, low creep rate, and improved fatigue characteristics. These properties make TiAl alloys very attractive, particularly for structural applications for aerospace and aeronautic industries, where, at certain temperatures, they might be capable of replacing heavy nickel-based superalloys. However, so far applications of TiAl alloys have been limited by their poor ductility. Many of the recent studies have focused on the source of this limited ductility and on methods to improve this property. It has been found out experimentally that the strength and ductility of $gamma$-TiAl alloys can be affected by many different parameters, including alloy stoichiometry, heat treatment, deformation temperature, impurity content, grain size, and ternary element additions. In this thesis we present the results of our computer simulations of deformation and fracture in TiAl. In contrast to many previous studies our simulations include the interaction of the crack with point defects in the lattice. We use the molecular statics technique with atomic interactions described in terms of the embedded atom method. We simulate the crack propagation along (100), (001), (110) and (111) planes in TiAl. The cleavage along (100) and (001) planes shows purely brittle behavior, whereas the cleavage along (110) and (111) planes is accompanied by extensive dislocation emission. Our studies of the crack interaction with point defects reveal that vacancies and antisites near the crack tip can influence the amount of plastic deformation. Another important observation is that the antisite formation energy near the crack tip is generally lower than in the perfect lattice. This observation suggests the formation of relatively disordered zones near the crack tip at high temperatures, and leads us to a formulation of a new mechanism of a brittle-to-ductile transition in TiAl. / Ph. D.

The United States Air Force is in the process of developing magnetic bearings as well as an aircraft Integrated Power Unit and an Internal Starter/Generator for main propulsion engines. These developments are the driving force behind a new emphasis on high temperature, high strength magnetic materials for power applications. Analytical work, utilizing elasticity theory, in conjunction with design requirements, indicates a need for magnetic materials to have strengths in excess of 80 ksi up to about 1000 degrees F. It is this combination of desired material characteristics that is the motivation for this effort to measure, model, and predict the creep behavior of such advanced magnetic materials. Hiperco® Alloy 50HS, manufactured by Carpenter Technology Corporation, is one of the leading candidates for application and is studied in this effort by subjecting mechanical test specimens to a battery of tensile and creep tests. The tensile tests provide stress versus strain behaviors that clearly indicate: a yield point, a heterogeneous deformation described as LuÌ ders elongation, the Portevin-LeChatelier effect at elevated temperatures, and, most often, a section of homogeneous deformation that concluded with necking and fracture. Creep testing indicated two distinct types of behavior. The first was a traditional response with primary, secondary and tertiary stages, while the second type could be characterized by an abrupt increase in strain rate that acted as a transition from one steady state behavior to another. This second linear region was then followed by the tertiary stage. The relationship between the tensile response and the creep responses is discussed. Analyses of the mechanical behavior includes double linear regression of empirically modeled data, scanning electron microscopy for microstructural investigations, isochronous stress-strain relations, and constant strain rate testing to relate the tensile and creep test parameters. Also, elastic and creep deformation analyses are done, which incorporate material property data and material constants determined along with stress and displacement profiles for a specific Air Force design configuration. / Ph. D.

L’utilisation des combustibles fossiles (énergies non renouvelables) est responsable de l’augmentation de la concentration en gaz à effet de serre dans l’atmosphère. Parmi les solutions de remplacement envisagées, l’hydrogène apparaît comme le vecteur énergétique le plus séduisant. Son stockage dans des intermétalliques permet d’obtenir des capacités massiques et volumiques (e.g. 140 g/L) supérieures à celles obtenues en voie liquide ou sous pression (respectivement 71 et 40 g/L). Nous avons élaboré des composés à base de Mg et de terres rares (e.g. Y, Ce et Gd) dérivant des phases de Laves cubiques AB2. Leurs propriétés physico-chimiques ont été étudiées (hydruration, électrochimie, magnétisme, …). Les conditions de sorption (P et T) se sont révélées particulièrement favorables (i.e. absorption à température ambiante et pression atmosphérique). Par ailleurs, afin d’améliorer la cinétique de sorption du magnésium métallique, les composés précédemment élaborés ont été utilisés comme catalyseurs. Ainsi, GdMgNi4 a été co-broyé avec du magnésium et les vitesses d’absorption et de désorption du composite sont supérieures à celles obtenues pour les composites Mg+Ni ou Mg+V qui sont des références. Une approche théorique (DFT) a permis de modéliser la structure électronique des composés ternaires (i.e. TRMgNi4) et ainsi de prédire ou de confirmer les résultats expérimentaux. Enfin nous avons étudié de nouveaux intermétalliques riches en terre rare (TR4MgNi) dont les capacités d’absorption en hydrogène sont élevées (2H/M). / The use of fossil fuels (non-renewable energy) is responsible for increasing the concentration of greenhouse gases in the atmosphere. Among the considered alternatives, hydrogen is seen as the most attractive energy vector. The storage in intermetallics makes it possible to obtain mass and volume capacities (e.g. 140 g/L) higher than those obtained by liquid form or under pressure (respectively 71 and 40 g/L). We have synthesised Mg and Rare Earth based compounds (RE = Y, Ce and Gd), derived from the cubic Laves phases AB2. Their physical and chemical properties have been studied (hydrogenation, electrochemistry, magnetism, ...). The conditions of sorption (P and T) are particularly favorable (i.e. absorption at room temperature and atmospheric pressure). Besides, to improve the sorption kinetics of metallic magnesium, the compounds developed previously were used as catalysts. Thus, GdMgNi4 was milled with magnesium and the speeds of absorption and desorption of the mixture are found higher than those obtained for the composites Mg+Ni or Mg+V, which are reference systems. A theoretical approach (DFT) was used to model the electronic structure of the ternary compounds (i.e. REMgNi4) and thus to predict or confirm the experimental results. Finally we have studied new intermetallics rich in rare earth (RE4MgNi) whose hydrogen absorption capacities are high (2H/M).

Alloys with good toughness and elevated temperature properties like A201 are expensive and can be more difficult to process. This results in the use of heavier but less expensive alternatives in many applications where toughness is of concern, such as steels. Common alloys such as A356 and E357 are relatively cheap and easy to work with. However, these alloys have considerably lower toughness than premium alloys. This research aims to investigate surface modification treatments that could yield better toughness at a low cost in a common aluminum alloy. The process must show significant improvement in said properties, be cost effective, and easily adaptable in a common foundry. Diffusion of coating material into the substrate was investigated with a variety of coating metals. The diffusion process was facilitated in the solutionizing step for the given substrate aluminum in order to strengthen the sub-surface region of the parts. This research aims to provide a platform for further research into the practical effects of the coating and tempering on impact and toughness properties. These samples were characterized by optical and scanning electron microscopy, EDS, impact testing, and tensile testing.