<p>In a time of global environmental problems due to overuse of fossil fuels, and a subsequent depletion of the supplies, hydrogen is considered as one of the most important renewable future fuels for use in clean energy systems with zero greenhouse-gas emission. Hydrogen storage is the main issue that needs to be solved before the technology can be implemented into key areas such as transport. The high energy density, good stability and reversibility of metal hydrides make them appealing as hydrogen storage materials. In this thesis research on synthesis and hydrogen absorption properties for intermetallic compounds based on scandium and aluminium is reported. The compounds were synthesized by arc melting or induction melting and exposed to hydrogen in a high pressure furnace. Desorption investigations were performed by thermal desorption spectroscopy. The samples were analyzed by x-ray powder diffraction and electron microscopy. ScAlNi, crystallizing in the MgZn2-type structure (space group: P63/mmc; a = 5.1434(1) Å, c = 8.1820(2) Å), was found to absorb hydrogen by two different mechanisms at different temperature regions. At ~120 °C hydrogen was absorbed by solid solution formation with estimated compositions up to ScAlNiH0.5. At ~500 °C hydrogen was absorbed by disproportionation of ScAlNi into ScH2 and AlNi. The reaction was found to be fully reversible due to destabilization effects which lowered the decomposition temperature of ScH2 by ~460 °C.</p>

In a time of global environmental problems due to overuse of fossil fuels, and a subsequent depletion of the supplies, hydrogen is considered as one of the most important renewable future fuels for use in clean energy systems with zero greenhouse-gas emission. Hydrogen storage is the main issue that needs to be solved before the technology can be implemented into key areas such as transport. The high energy density, good stability and reversibility of metal hydrides make them appealing as hydrogen storage materials. In this thesis research on synthesis and hydrogen absorption properties for intermetallic compounds based on scandium and aluminium is reported. The compounds were synthesized by arc melting or induction melting and exposed to hydrogen in a high pressure furnace. Desorption investigations were performed by thermal desorption spectroscopy. The samples were analyzed by x-ray powder diffraction and electron microscopy. ScAlNi, crystallizing in the MgZn2-type structure (space group: P63/mmc; a = 5.1434(1) Å, c = 8.1820(2) Å), was found to absorb hydrogen by two different mechanisms at different temperature regions. At ~120 °C hydrogen was absorbed by solid solution formation with estimated compositions up to ScAlNiH0.5. At ~500 °C hydrogen was absorbed by disproportionation of ScAlNi into ScH2 and AlNi. The reaction was found to be fully reversible due to destabilization effects which lowered the decomposition temperature of ScH2 by ~460 °C.

A polymer-based composite reinforced with a mixture of Ni and Al powders was investigated as an example of a multifunctional structural energetic material. Micron-sized Ni powder, nano/micron-sized Al powders, and Teflon or epoxy were fabricated as bulk materials by pressing or casting. The thermally initiated reaction response of these materials was evaluated using differential thermal analysis coupled with x-ray diffraction. The analyses showed evidence of thermally initiated reactions between Ni and Al powders, as well as between Ni+Al and Teflon. Nano-sized Al powder showed a preference for reaction with Teflon over Ni, while micron-sized Al reacted strongly with Ni regardless of the presence of a binder. Teflon was shown to be very reactive with the Ni+Al/nano Al mixture, whereas epoxy was not reactive with the metallic powders, and also inhibited reaction between Ni and nano Al. The structural/mechanical behavior of these materials was evaluated using elastic and plastic property measurements via static and dynamic compression tests. Dynamic mechanical testing using reverse Taylor anvil-on-rod impact tests combined with velocity interferometry gave qualitative and quantitative information about the transient deformation and failure response of the composites. The material containing 20wt% epoxy and nano-sized Al powder showed the most superior mechanical properties in terms of elastic modulus and static and dynamic compressive strength. The addition of Ni and Al powders to the epoxy matrix increased the strength of the composites, and their tendency toward brittle fracture, as evidenced by Ni particle pullout in SEM analysis. The results illustrate that nano-sized Al particles provide significant enhancement to strength of epoxy composites, but at the expense of reactivity. The nano-Al particles get dissociated from the Ni and Al mixture and swept into the epoxy, generating a nano-Al containing epoxy matrix with embedded Ni particles. The chemical reactivity of the system is thus sacrificed as contacts between Ni and Al powders are minimized. A mixture of nano-sized Ni and Al particles may however provide the best combination of high strength and reactivity.

Metal membranes are useful for hydrogen separation from mixed gas streams. They can exhibit perfect selectivity for hydrogen. However, in order to be commercially viable, in addition to providing high hydrogen fluxes, they must also be resistant to poisoning, possess long operating lifetimes and be cost effective. Many types of metal membranes such as pure metals, disordered alloys and amorphous metals have been studied for this application. In this work, we aim to identify intermetallic stoichiometric compounds of two or more metals that could be used as potential membrane materials for hydrogen separation. In the past, first principle calculations combined with Monte Carlo methods have been developed that can accurately predict H₂ fluxes through metal membranes at different hydrogen pressures and temperatures. Although these models are accurate, they are computationally intensive. In this work, we use these methods and develop screening criteria based on calculated properties that enable us to perform detailed calculations on a diminishing set of materials and rapidly identify the favorable candidates for hydrogen separation. We screened 1059 intermetallics at this high level of theory, which is the largest set of materials studied for this application. We divided the intermetallics into Pd-based and non-Pd based materials using additional screening algorithms to reduce the number of calculations required to identify potential candidate materials. 8 intermetallics were identified that had permeabilities that was comparable or higher to that of pure Pd. MgZn₂ and MnTi were found to have the highest H permeabilities among all the intermetallics studied. In addition to ground state structures, metastable structures were also found to be stabilized in the presence of hydrogen. Our work demonstrates the ability of these computational methods to identify potential novel materials for specific applications from large sets of materials that would not be possible experimentally. In the models for hydrogen permeability developed above, H-induced metal lattice rearrangements were not considered. Experimental evidence suggests that hydrogen heat treated (HHT) Pd-Au alloys undergo lattice rearrangement that results in an ordered structure which has a higher solubility than the non-HHT alloys. Using a combination of cluster expansion methods developed for predicting hydrogen permeability of disordered alloys and Monte Carlo methods, we predicted the extent of H induced lattice rearrangement in Pd₉₆Au₄ and Pd₈₅Au₁₅ alloys. We also predicted the solubility, diffusivity and permeability of these rearranged phases and found that their H permeability is higher than the non-rearranged phases. Our models capture the H-induced lattice rearrangement and provide useful insight of the conditions where this phenomenon is significant. Using the tools developed in this work, similar alloys that have a tendency to undergo lattice rearrangement that results in enhanced H permeability can be identified.

Crystalline open-framework intermetallics have long attracted the attention of chemists, physicists, and materials scientists. The intriguing structures such materials exhibit are often intimately related to the unique physical properties they possess. The present work is focused on the preparation and characterization of open-framework intermetallic materials based on group 14 elements, in particular those crystallizing in clathrate and related structures such as the clathrate-II phases. Materials possessing the clathrate-II crystal structure have received increased attention in recent years, as a result of both the unique properties they exhibit as well as potential for use in technologically important applications such as thermoelectrics, photovoltaics, and optoelectronics. However, in comparison with other clathrate structure types, characterization of clathrate-II materials has in general been far less extensive. Moreover, many conceivable compositions have yet to be realized. The purpose of this work is to expand the current knowledge of the structural, chemical, and physical properties of these materials, while simultaneously exploring new compositions and synthetic routes to clathrate-II phases. One of the unique and promising aspects of clathrate-II materials is the ability to vary the guest concentration, which is shown to have significant implications for the structural and physical properties of NaxSi136 (0< x< 24) materials. It is demonstrated that new compositions can be explored by novel approaches to chemical design. Framework substitution in clathrate-II compounds is explored in an effort to assess possibilities for influencing the physical properties of these materials. A novel zeolite-like framework phase, Na1-xGe3+z, has been discovered, and is shown to be a new low-thermal conductivity crystalline solid, suggesting a new approach to the design of crystalline intermetallic materials with low thermal conductivity. New directions in synthesis of intermetallics are identified, with emphasis on unconventional preparative methods and the opportunities they offer. Processing of reactive precursors by spark plasma sintering is demonstrated as a new preparative tool for crystal growth, identifying the first method for preparation of clathrate-II Na24Si136single-crystals since the discovery of these compounds more than four decades ago.

U-Zr metallic fuels cladded in Fe-alloys are being considered for application in an advanced Sodium-Cooled Fast Reactor (SFR) that can recycle the U-Zr fuels and minimize the long-lived actinide waste. To understand the complex fuel-cladding chemical interaction of the U-Zr metallic fuel with Fe-alloys, a systematic multicomponent diffusion study was carried out using solid-to-solid diffusion couples. The U-10 wt.% Zr vs. pure Fe diffusion couples were assembled and annealed at temperatures, 630, 650 and 680°C for 96 hours. Development of microstructure, phase constituents, and compositions developed during the thermal anneals were examined by scanning electron microscopy, transmission electron microscopy and X-ray energy dispersive spectroscopy. A complex microstructure consisting of several layers that include phases such as U6Fe, UFe2, ZrFe2, α-U, β-U, Zr-precipitates, χ, ε, and λ was observed. Multiphase layers were grouped based on phase constituents and microstructure, and the layer thicknesses were measured to calculate the growth constant and activation energy. The local average compositions through the interaction layer were systematically determined, and employed to construct semi-quantitative diffusion paths on isothermal U-Zr-Fe ternary phase diagrams at respective temperatures. The diffusion paths were examined to qualitatively estimate the diffusional behavior of individual components and their interactions. Furthermore, selected area diffraction analyses were carried out to determine, for the first time, the exact crystal structure and composition of the χ, ε and λ-phases. The χ, ε and λ-phases were identified as Pnma(62) Fe(Zr,U), I4/mcm(140) Fe(Zr,U)2, and I4/mcm(140) U3(Zr,Fe), respectively.

The first part of this dissertation explores the chemistry of an inhibitor complexation with Cu. First, the Cu oxidation state of the complex was +1. Second, identified by differential RAIRS, one source of Cu(I) for the Cu(I)-inhibitor complex could be Cu(I) oxide. The characteristic Cu(I) oxide peak at 650 cm⁻¹ was observed to decrease after CVD coating process was applied. This led to a major hypothesis that in order for the reaction between Cu(I) oxide and the inhibitor to proceed, protons from the inhibitor and oxygen from Cu₂O are stabilized by reacting to form water. The applicability of the passivation nature of Cu(I)-inhibitor films was explored for Cu-Al wire-bonded devices in its ability to protect from Cu-Al peripheral galvanic corrosion and the galvanic corrosion of the Cu-Al intermetallic compounds in their roles for corrosion-induced liftoff. The second part of this work studied the effect of replacing Al bond pad with Cu on the corrosion induced liftoff of wire-bonds when exposed to low ppm levels of chloride contamination. Applying protective coating to the Cu pad surface before wire-bonding was found to suppress the thermally induced oxidation of Cu in air, helping to enable successful Cu-Cu direct wire-bonding. Compared to Cu-Al devices with passivation coating, which has a few wires liftoff with 6 hours, the Cu-Cu bonded devices survived much longer, over 40 days, with almost no liftoff observed. This demonstrates that removing the galvanic contact, the root cause of the corrosion induced failure, is a more robust and permanent solution to the corrosion experienced by these devices.

The development of molybdenum - silicon - boron (Mo-Si-B) composites having a combination of high temperature strength, creep, and oxidation residence has the potential to substantially increase the efficiency of gas turbines. The refractory nature of the αMo, Mo3Si (A15), and Mo5SiB2 (T2) phases results in good strength and creep resistance up to 1300°C. At this temperature, the formation of a borosilicate surface scale from the two intermetallic phases is able to provide oxidation resistance. However, realization of these advantages has been prevented by both a high brittle to ductile transition temperature and difficulty in forming the initial surface borosilicate to provide bulk oxidation resistance. This dissertation addresses two factors pertaining to this material system: 1) improvements to powder processing techniques, and 2) development of compositions for oxidation resistance at 1300°C. The processing of Mo-Si-B composites is strongly tied to their mechanical properties by establishing the αMo matrix, limiting impurity content, and reducing silicon supersaturation. These microstructural aspects control the brittle to ductile transition temperature which has traditionally been too high for implementation of Mo-Si-B composites. The processing here built upon the previously developed powder processing with silicon and boron nitrides which allowed for a low oxygen content and sintering of fine starting powders. Adjustments were made to the firing cycle based upon dew point measurements made during the hydrogen de-oxidation stage. Under a relatively high gas flow rate, 90% of the total water generated occurred during a ramp of 2°C /min between 450 and 800°C followed by a hold of 30 minutes. The oxidation resistance of Mo-Si-B composites was studied for a wide range of compositions. Silicon to boron atomic ratios were varied from 1 to 5 and iron, nickel, cobalt, yttria, and manganese were included as minor additions. In all these compositions, the αMo volume fraction was kept over 50% to ensure the potential toughness of the composite. For the oxidized surface glass, a silica fraction of 80 to 85% was found to be necessary for the borosilicate to have a sufficiently high viscosity and low oxygen permeability for oxidation resistance at 1300°C. For the Mo-Si-B bulk composition this corresponds to a Si/B atomic ration of 2 to 2.5. Higher viscosity compositions failed due to spallation of poorly attached, high silica scales. Lower viscosity compositions failed from continuous oxidation, either through open channels or repetitive MoO3 bubble growth and popping. Additionally, around 1% manganese was necessary for initial spreading of the borosilicate at 1300°C. In conjunction with flowing air to prevent MoO3 accumulation, oxidation weight loss rates below 0.05 mg/cm2-hr were measured. Finally, a theory is proposed here to describe the mechanisms responsible for the development of oxidation resistance. This theory involves three stages associated with: 1) generation of an initial surface borosilicate, 2) thickening of the borosilicate layer, and 3) slow parabolic oxidation controlled by the high silica surface scale.

<p>In this project, nano powder of CoSb₃ thermoelectric material was synthesized using chemical alloying novel co-precipitation method. This method involved co-precipitation of TE precursor compounds in controlled pH aqueous solutions followed by thermo-chemical treatments including calcination and reduction to produce nano-particulates of CoSb₃. The nano powder was consolidated using rapid solid state spark plasma sintering (SPS) and the processing time was of the order of few minutes. On a result very high densities were achieved and grain growth was almost negligible.</p><p>Various batches of the CoSb₃ nano powder were produced to achieve high purity, minimum particle size and compensate Sb evaporation during thermo-chemical reduction. For de-agglomeration, powder was grinded before and after calcination. Samples were characterized at each stage during synthesis using XRD and SEM (with EDX). Thermal gravimetric analysis (TGA) was done before thermochemical treatments to observe weight losses with heating the powder at high temperatures and other physiochemical changes. Thermal diffusivity of the samples was measured at room temperature using Laser Flash Apparatus (LFA) and heat capacity was measured using Differential Scanning Calorimetry (DSC).   Thermal conductivities are calculated using these thermal diffusivities, heat capacities and densities of the sintered pellets. Average grain size is measure using image size J software.</p><p>It was observed that powder purity and size is affected by batch size, reduction conditions like holding temperature and time.  During sintering with SPS; heating and cooling rates, sintering temperature, holding pressure and time were the main variables. Grain size and morphology was analyzed using SEM.</p><p>It was observed that larger the grain size higher will be the thermal diffusivity, which leads to increase in thermal conductivity. Hence, grain size has affected on thermal conductivity and also on TE performance.</p> / QC 20100708

For microelectronics used in the low-temperature applications, the understanding of their reliability and performance has become an important research subject characterised as electronics to serve under the severe or extreme service conditions. Along with the impact from the increased miniaturization of devices, the various properties and the relevant thermo-mechanical response of the interconnection materials to temperature excursion at micro-scale become a critical factor which can affect the reliable performance of microelectronics in various applications. Pure indium as an excellent interconnection material has been used in pixellated detector systems, which are required to be functional at cryogenic temperatures. This thesis presents an extensive investigation into the thermo-mechanical properties of indium joints as a function of microstructure, strain (loading histories-dependent) and temperature (service condition-sensitive), specifically in the areas as follows: (i) the interfacial reactions and evolution between indium and substrate during the reflow process (liquid-solid) and thermal aging (solid-solid) stages by taking low-temperature cycling into account; (ii) determination of the effects of joint thickness and the types of substrate (e.g. Cu or Ni) on the mechanical properties of indium joints, and the stress- and temperature-dependent creep behaviour of indium joints; (iii) the establishment of a constitutive relationship for indium interconnects under a wide range of homologous temperature changes that was subsequently implemented into an FE model to allow the analysis of the evolution of thermally-induced stresses and strains associated with a hybrid pixel detector.