<div> <div> <div> <p>Surfaces and interfaces in ionic solids play a pivotal role in defining the trans- port properties and microstructural evolution in many of the existing and emerging material applications, including energy-related systems such as fuel cells, recharge- able batteries, as well as advanced electronics such as those found in semiconducting, ferroelectric, and piezotronic applications. Here, a variational framework has been developed to understand the effects of ionic species and point defects on the structural, electrochemical and chemomechanical stability of grain boundaries in polycrystalline ceramics. The theory predicts the equilibrium and phase transition conditions of charged interfaces, and quantifies the properties induced by the broad region of electrochemical and chemomechanical influence in front of a grain boundary capable of spanning anywhere from a few angstroms to entire grains. As an example application, the microstructural mechanisms leading to the onset of the flash during electric field assisted sintering were predicted, where the experimentally observed cascading charge flow, resulting in the onset of a flash event was rationalized. Also, the model was applied to describe the effects of grain boundary drag by the interfacially accumulated ionic species and charged defects during grain growth under electrical, chemical, mechanical, or structural driving forces. Finally, abnormal grain growth in ionic solids with an emphasis on the structural and electrochemical character of the grain boundaries was demonstrated. Here, two moving grain boundary types, highly mobile and immobile interfaces are identified, resulting in three grain size populations. </p> </div> </div> </div>

This thesis was developed in the frame of a Brazil-France cooperation agreement between the École des Mines d\'Albi-Carmaux and the Polytechnic School of Engineering of the University of Sao Paulo (EPUSP). It aims to contribute to the study of the mechanical behaviour of Ti6Al4V alloys especially in terms of superplastic forming. The general objective of this research is to develop non-conventional forming processes for new titanium alloys applied to aerospace components Therefore, in accordance of the equipment\'s available in the two groups, the work will be conducted either at the Ecole des Mines d\'Albi-Carmaux and either at EPUSP. This thesis aims to answer questions such as what are the implications in relation to the microstructural and mechanical behaviour of these alloys during superplastic and hot forming in order to establish a behaviour law for these alloys based on titanium. This requires a good knowledge of the properties of materials used in the superplastic and hot forming domain to control the parameters governing the phenomenon of superplasticity or high temperature plasticity. For this, a testing strategy and characterization methodology of those new titanium alloys was developed. The tests include high temperature uniaxial tensile tests on several Ti6Al4V alloys showing different initial grain sizes. Special focus was made on the microstructural evolution prior to testing (i.e. during specimen temperature increase and stabilization) and during testing. Testing range was chosen to cover the hot forming and superplastic deformation domain. Grain growth is depending on alloy initial microstructures but also on the duration of the test at testing temperature (static growth) and testing strain rate (dynamic growth). After testing microstructural evolutions of the alloys will be observed by optical micrograph or SEM and results are used to increase behaviour model accuracy. Advanced unified behaviour models where introduced in order to cover the whole strain rate and temperature range: kinematic hardening, strain rate sensitive and grain growth features are included in the model. In order to get validation of the behaviour model, it was introduced in ABAQUSR numerical simulation code and model predictions (especially macroscopic deformation and local grain growth) were compared, for one of the material investigated, to axisymmetric inflation forming tests of sheet metal parts, also known as bulge test. To obtain a simple control cycle, tests performed at IPT/LEL laboratory in San José Dos Campos in Brazil were operated with a constant strain rate. Results show a very good correlation with predictions and allows to conclude on an accuracy of the behaviour models of the titanium alloys in industrial forming conditions. / Esta tese desenvolvida dentro do acordo de cooperação internacional celebrado entre a Escola Politécnica da Universidade de São Paulo (EPUSP) e a École des Mines d\'Albi-Carmaux tem como tema principal a análise da influência da evolução microestrutural sobre o comportamento mecânico de chapa de liga de titânio - Ti-6Al- 4V sob condições superplásticas e trabalho a quente. O objetivo desta pesquisa é contribuir para o desenvolvimento de processos de conformação não convencional de chapas de ligas a base de titânio utilizadas na manufatura de componentes metálicos. Como objetivo específico, estabelecer uma correlação entre comportamento mecânico e a mudança microestrutural a partir de três tipos de ligas com diferentes tamanhos de grão iniciais (0.5, 3.0 e 4.9 ?m). Os testes foram realizados na faixa de temperatura de 700 a 950 °C combinados às taxas de deformação na faixa de 10-1 s-1 - 10-4 s-1. Para a metodologia, estabeleceu-se uma estratégia de ensaios mecânicos capaz de testar as hipóteses sobre o comportamento do material formuladas no início desta pesquisa. Em seguida, os ensaios mecânicos foram divididos em três partes. Na primeira, utilizou-se um simulador termomecânico modelo Gleeble 3800 para os ensaios a quente variando-se a taxa de deformação (??) entre 10-1 s-1 a 10-3 s-1 e temperaturas da ordem de 700 °C a 850 °C. Na segunda parte dos testes, priorizouse taxas de deformação mais lentas (10-2 s-1 - 10-4 s-1) e temperaturas mais elevadas (800 °C - 950 °C) objetivando atingir as deformações superplásticas do material, nesta etapa utilizou-se como equipamento uma máquina de tração modelo MTS 50kN com câmara de aquecimento acoplada. A terceira parte dos ensaios experimentais envolveu a conformação na condição superplástica por pressão hidrostática (Bulge test) realizadas no LEL-IPT de São José dos Campos. A partir da análise dos dados experimentais levantou-se os parâmetros introduzidos no modelo numérico de comportamento mecânico baseado na evolução da microestrutura da chapa testada permitindo a calibração do modelo numérico a partir das equações constituintes e finalmente introduzido no software de elementos finitos (ABAQUS 6.12) e construído a simulação numérica da conformação superplástica por pressão hidrostática. Os principais resultados indicaram uma forte correlação entre microestrutura inicial da conformação superplástica e a quente de onde se pode observar que tanto menor a microestrutura inicial maior será a quantidade do crescimento de grão. Os resultados da conformação superplástica de expansão multiaxial do domo hemisférico foram, então, comparados à simulação numérica permitindo confrontar os dados do modelo numérico do comportamento mecânico com a lei de comportamento estudada, o que possibilitou um melhor entendimento dos mecanismos da conformação plástica em condições de superplasticidade e também de trabalho a aquente do material.

Many technologically important alloys such as Ni base superalloys and Ti-Al base alloys benefit from the precipitation of an ordered β phase from a disordered α matrix. When the crystallographic symmetry of the β phase is a subgroup of that of the disordered α phase, the microstructure may contain multiple orientational variants of the β phase, each with its own (anisotropic, crystallographically equivalent) misfit (lattice parameter mismatch) with the matrix phase. Examples include orthorhombic precipitates in a hexagonal matrix in Ti-Al-Nb alloys, and tetragonal precipitates in a cubic matrix in ZrO2-Y2O3. We have studied two-phase microstructures containing multiple variants of the precipitate phase. In particular, we have used phase field simulations to study the effect of elastic stresses in a two dimensional system containing a disordered matrix and three different orientational variants of the precipitate phase, with a view to elucidate the effect of different levels of anisotropy in misfit. We consider a two dimensional, elastically homogeneous and isotropic model system in which the matrix (α) and precipitate (β) phases have hexagonal and rectangular symmetries, respectively, giving rise to three orientational variants of the β phase. Therefore, our phase field model has composition (c) and three order parameters (η1, η2, η3) as the field variables.Due to the difference in crystallographic symmetry, the precipitate-matrix misfit strain tensor, ε*, can be anisotropic. ε*maybe represented in its principal form as ε *= (ε xx 0 ) 0 εyy where ε xx and ε yy are the principal components of the misfit tensor. We define t= εyy/εxx as the parameter representing anisotropy in the misfit. In this thesis, we report the results of our systematic study of microstructural evolution in systems with different values of t, representing different levels of anisotropy in misfit: •Case A: t=1 (dilatational or isotropic misfit) • Case B: 0 <t<1 (principal misfit components are unequal but have the same sign) • Case C: t=0 (the principal misfit along the y direction is zero) • Case D: -1 <t<0 (principal misfit components have opposite signs and unequal magnitudes) • Case E: t= -1 (principal misfit components are equal, but with opposite signs; pure shear) In Cases D and E, there is an invariant line along which the normal misfit is zero. In Case D, this invariant line is at ±54.72◦, and in Case E, it is at ±45◦, with respect to the x-axis. Our simulations of microstructural evolution in this system are based on numerical integration of the Cahn-Hilliard and Cahn-Allen equations which govern the evolution of composition and order parameter fields, respectively. In each case, we have studied two different situations: isolated particle (single variant) and many interacting particles (multivariant). Dynamical growth shape of an isolated precipitate In systems with an isotropic misfit (Case A), the precipitate shape remains circular at all sizes. In Cases B and C, the precipitate shape is elongated along the y-axis, which is also the direction in which the magnitude of the misfit strain is lower. In all these cases, the symmetry of the particle shape remains unaltered at all sizes. In contrast, in Cases D and E, the particle shape exhibits a symmetry-breaking transition. In Case D, the precipitate elongates initially along the y direction (i.e. the direction of lower absolute misfit), before undergoing a transition in which the mirror symmetry normal to x and yaxes is lost. In Case E, the particle has an initial square-like shape (with its sides normal to the 11directions) before losing its four-fold rotation axis to become rectangle-like with its long axis along one of the the 11directions. The critical precipitate size at which the symmetry-breaking shape transition occurs is obtained using bifurcation diagrams. In both Cases D and E, the critical size for the dynamical growth shapes is larger than those for equilibrium shapes[1].This critical size is larger when the matrix supersaturation is higher or shear modulus is lower. Microstructural Evolution In all the five cases, the elastic stresses have a common effect: they lead to microstructures in which the precipitate volume fraction is lower than that in a system with no misfit. This observation is consistent with the results from the thermodynamics of stressed solids that show that a precipitate-matrix misfit increases the interfacial composition in both the matrix and the precipitate phase. In systems with isotropic misfit (Case A), the microstructure consists of isolated circular domains of the precipitate phase that retain their circular shape during growth and subsequent coarsening. In Cases B and C with anisotropic misfit with t≥0, the three orientational variants of the precipitate phase are elongated along the directions of lower misfit (y-axis and ±120◦to y-axis). At a given size, particles in Case C (in which one of the principal misfits is zero) are more elongated than those in Case B. Systems with a higher shear modulus enhance the effect of misfit stresses, and therefore, lead to thinner and longer precipitates. When the precipitate volume fraction is increased, these elongated precipitates interact with (and impinge against) one another to a greater extent, and acquire a more jagged appearance. For Cases D and E, each orientation domain is associated with an invariant line along which the normal misfit is zero. Thus, in Case D, early stage microstructures show particles elongated along directions of lower absolute misfit (y-axis and ±120°to y-axis). At the later stages, the domains of the precipitate phase tend to orient along the invariant lines; this leads some of the particles to acquire a ‘Z’ shape before they completely re-orient themselves along the invariant line. In Case E, each variant grows as a thin plate elongating along the invariant line. The growth and impingement of these thin plates leads to a microstructure exhibiting complex multi-domain patterns such as stars, wedges, triangles, and checkerboard. These patterns have been compared (and are in good agreement) with experimental observations in Ti-Al-Nb alloys containing the precipitate (O) and matrix (α2)phases[2]. Since in Case E the sum of misfit strains of the three variants is zero, elastic energy considerations point to the possibility of compact, self-accommodating clusters of the three variants, sharing antiphase boundaries (APBs). Thus, if the APB energy is sufficiently low, the microstructure may consist of such compact clusters. Our simulations with such low APB energy do show triangle shaped clusters with six separate particles (two of each variant)in a self-accommodating pattern. (Refer PDF file)

Superplastic forming (SPF) is a near net-shape forming process which offers many advantages over conventional forming operations including low forming pressure due to low flow stress, low die cost, greater design flexibility, and the ability to shape hard metals and form complex shapes. However, low production rate due to slow forming process and limited predictive capabilities due to lack of accurate constitutive models for superplastic deformation, are the main obstacles to the widespread use of SPF. Recent advancements in finite element tools have helped in the analysis of complex superplastic forming operations. These tools can be utilized successfully in order to develop optimized superplastic forming techniques. In this work, an optimum variable strain rate scheme developed using a combined micromacro stability criterion is integrated with ABAQUS for the optimization of superplastic forming process. Finite element simulations of superplastic forming of Ti-6Al-4V sheet into a hemisphere and a box are carried out using two different forming approaches. The first approach is based on a constant strain rate scheme. The second one is based on the optimum variable strain rate scheme. It is shown that the forming time can be significantly reduced without compromising the uniformity of thickness distribution when using the proposed optimum approach. Further analysis is carried out to study the effects of strain rate, microstructural evolution and friction on the formed product. Finally the constitutive equations and stability criterion mentioned above are used to analyze the forming of dental implant superstructure, a modern industrial application of superplastic forming.

This thesis was developed in the frame of a Brazil-France cooperation agreement between the École des Mines d\'Albi-Carmaux and the Polytechnic School of Engineering of the University of Sao Paulo (EPUSP). It aims to contribute to the study of the mechanical behaviour of Ti6Al4V alloys especially in terms of superplastic forming. The general objective of this research is to develop non-conventional forming processes for new titanium alloys applied to aerospace components Therefore, in accordance of the equipment\'s available in the two groups, the work will be conducted either at the Ecole des Mines d\'Albi-Carmaux and either at EPUSP. This thesis aims to answer questions such as what are the implications in relation to the microstructural and mechanical behaviour of these alloys during superplastic and hot forming in order to establish a behaviour law for these alloys based on titanium. This requires a good knowledge of the properties of materials used in the superplastic and hot forming domain to control the parameters governing the phenomenon of superplasticity or high temperature plasticity. For this, a testing strategy and characterization methodology of those new titanium alloys was developed. The tests include high temperature uniaxial tensile tests on several Ti6Al4V alloys showing different initial grain sizes. Special focus was made on the microstructural evolution prior to testing (i.e. during specimen temperature increase and stabilization) and during testing. Testing range was chosen to cover the hot forming and superplastic deformation domain. Grain growth is depending on alloy initial microstructures but also on the duration of the test at testing temperature (static growth) and testing strain rate (dynamic growth). After testing microstructural evolutions of the alloys will be observed by optical micrograph or SEM and results are used to increase behaviour model accuracy. Advanced unified behaviour models where introduced in order to cover the whole strain rate and temperature range: kinematic hardening, strain rate sensitive and grain growth features are included in the model. In order to get validation of the behaviour model, it was introduced in ABAQUSR numerical simulation code and model predictions (especially macroscopic deformation and local grain growth) were compared, for one of the material investigated, to axisymmetric inflation forming tests of sheet metal parts, also known as bulge test. To obtain a simple control cycle, tests performed at IPT/LEL laboratory in San José Dos Campos in Brazil were operated with a constant strain rate. Results show a very good correlation with predictions and allows to conclude on an accuracy of the behaviour models of the titanium alloys in industrial forming conditions. / Esta tese desenvolvida dentro do acordo de cooperação internacional celebrado entre a Escola Politécnica da Universidade de São Paulo (EPUSP) e a École des Mines d\'Albi-Carmaux tem como tema principal a análise da influência da evolução microestrutural sobre o comportamento mecânico de chapa de liga de titânio - Ti-6Al- 4V sob condições superplásticas e trabalho a quente. O objetivo desta pesquisa é contribuir para o desenvolvimento de processos de conformação não convencional de chapas de ligas a base de titânio utilizadas na manufatura de componentes metálicos. Como objetivo específico, estabelecer uma correlação entre comportamento mecânico e a mudança microestrutural a partir de três tipos de ligas com diferentes tamanhos de grão iniciais (0.5, 3.0 e 4.9 ?m). Os testes foram realizados na faixa de temperatura de 700 a 950 °C combinados às taxas de deformação na faixa de 10-1 s-1 - 10-4 s-1. Para a metodologia, estabeleceu-se uma estratégia de ensaios mecânicos capaz de testar as hipóteses sobre o comportamento do material formuladas no início desta pesquisa. Em seguida, os ensaios mecânicos foram divididos em três partes. Na primeira, utilizou-se um simulador termomecânico modelo Gleeble 3800 para os ensaios a quente variando-se a taxa de deformação (??) entre 10-1 s-1 a 10-3 s-1 e temperaturas da ordem de 700 °C a 850 °C. Na segunda parte dos testes, priorizouse taxas de deformação mais lentas (10-2 s-1 - 10-4 s-1) e temperaturas mais elevadas (800 °C - 950 °C) objetivando atingir as deformações superplásticas do material, nesta etapa utilizou-se como equipamento uma máquina de tração modelo MTS 50kN com câmara de aquecimento acoplada. A terceira parte dos ensaios experimentais envolveu a conformação na condição superplástica por pressão hidrostática (Bulge test) realizadas no LEL-IPT de São José dos Campos. A partir da análise dos dados experimentais levantou-se os parâmetros introduzidos no modelo numérico de comportamento mecânico baseado na evolução da microestrutura da chapa testada permitindo a calibração do modelo numérico a partir das equações constituintes e finalmente introduzido no software de elementos finitos (ABAQUS 6.12) e construído a simulação numérica da conformação superplástica por pressão hidrostática. Os principais resultados indicaram uma forte correlação entre microestrutura inicial da conformação superplástica e a quente de onde se pode observar que tanto menor a microestrutura inicial maior será a quantidade do crescimento de grão. Os resultados da conformação superplástica de expansão multiaxial do domo hemisférico foram, então, comparados à simulação numérica permitindo confrontar os dados do modelo numérico do comportamento mecânico com a lei de comportamento estudada, o que possibilitou um melhor entendimento dos mecanismos da conformação plástica em condições de superplasticidade e também de trabalho a aquente do material.

With the rapid development in electronic packaging due to product miniaturisation, the size of solder joints is decreasing considerably, thus the failure of solder interconnects induced by electro-migration (EM) and thermo-migration (TM) became a reliability concern. The incorporation of foreign reinforcement can effectively improve properties of the solder alloys. However, this presents an imperative need for a further investigation to elaborate the underlying fundamentals associated with the reliability of reinforced solders. In this study, the Sn-Ag-Cu (SAC) based solder alloy powders as matrix were incorporated with Fullerene (FNS), TiC and Ni-coated graphene (NG) reinforcements to form composite solders through powder metallurgical method. These composite solders were then characterised in terms of their microstructure, physical property, solderability, followed by a systematic investigation of their performance under isothermal ageing, current stressing and large thermal gradient, respectively. The results showed that three types of reinforcements were successfully incorporated into the solder matrix; with all reinforcements added being embedded in the solder matrix or around the intermetallic compounds (IMC). The average loss of FNS and TiC particles in the solders was approximately 80% after the initial reflow, while this was only 40% for NG particles. It has been observed that β-Sn and Ag3Sn in the SAC solder alloys can be refined by adding appropriate amount of FNS and TiC, which is beneficial to the wettability with a reduced coefficient of thermal expansion (CTE) with the minimal influence on the melting point and electrical resistivity of solder alloys. For the SAC alloys without reinforcements, obvious extrusion of interfacial IMC at the anode was present after 360 hours of current (1.5×104 A/cm2) stressing, while the changes of surface profiles of all reinforced solders were unnoticeable. Under the current stressing regimes, a continuous increase of interfacial IMCs at the anode of the original SAC alloys was observed, but decreased at the cathode with stressing time. For the composite solders, both anode and cathode showed a continuous growth of interfacial IMCs; the growth rates of IMCs at the anode were greater than that at cathode. In addition, NG and TiC were found to be most effective to retard the growth of Cu3Sn IMC under current stressing. A gradient in hardness across the stressed SAC joints was present, where it was harder at anode. However, no such obvious gradient was found in SAC/FNS and SAC/NG solder joints. FNS and NG were proven to be beneficial to prolong the service life of solder joints up to approximately 7.6% and 10.4% improvements, respectively. Thermal stressing made the interfacial IMC in the original SAC joints to grow at the cold end considerably; causing serious damage at the hot end after 600 hours under temperature gradient of 1240K/cm stressing; a large number of IMCs, cracks and voids appeared in the SAC solder joints. However, a uniform increase of IMCs at both sides in the composite solders was observed without apparent damages at the interfaces under the same thermal stressing conditions, indicating an effective reduction of the elemental migration in the reinforced solders. Although there were also some voids and IMCs formed in the composite solder joints after a long-term thermal stressing, the integrity of the composite solder joints was enhanced compared with the SAC alloys. During thermal stressing, the dissolution rate of Cu atom into the SAC solder joints was estimated to be 3.1×10-6 g/h, while the values for SAC/FNS, SAC/NG and SAC/TiC were only 1.22×10-6 g/h, 1.09×10-6 g/h and 1.67×10-6 g/h, respectively.

This dissertation investigates microstructure/property relations in ultrahigh carbon steel (UHCS) with the aim of improving toughness while retaining high hardness. Due to high C contents (ranging from 1 to 2 wt%), UHCS exhibit high strength, hardness, and wear resistance. Despite this, applications for UHCS are currently limited because they typically contain a continuous network of proeutectoid cementite that greatly reduces ductility and toughness. In previous research, thermomechanic processing had seen considerable success in breaking up the network. However, the processing is difficult and has thus far seen very limited industrial application. Chemical modification of the steel composition has also seen some success in network break-up, but is still not well understood. There have been relatively few fundamental studies of microstructure evolution in UHCS; studies in the literature typically focused on lower C steels (up to 1 wt% C) or on cast irons (>2.1 wt% C). Thus, this work was undertaken to gain a better understanding of microstructural changes that occur during heat treatment and/or chemical modification of UHCS with a focus on the distribution of proeutectoid cementite within the microstructure. This dissertation is composed of eight chapters. The first chapter presents an introduction to phases found in UHCS, descriptions of research materials used in each chapter, and the hypotheses and objectives guiding the work. The second chapter describes a study of the microstructure found in a 2C-4Cr UHCS before and after an industrial-scale austenitizating heat treatment that increased hardness and toughness and also produced discrete carbide particles in the matrix. The third chapter establishes and demonstrates a metric for measuring connectivity in carbide networks. The fourth chapter describes a series of heat treatments designed to investigate kinetics of spheroidization and coarsening of carbide particles and denuded zones near cementite network branches in 2C-4Cr UHCS. The fifth chapter describes an additional series of heat treatments comparing coarsening kinetics in 2C-1Cr and 2C-4Cr UHCS. Lowering the Cr content caused clustering of cementite particles near grain boundaries, in contrast to the denuded zones observed in the higher Cr UHCS. The fifth chapter details four in situ confocal laser scanning microscopy heat treatments of 2C-4Cr UHCS. The seventh chapter investigates the effects of a 2wt% Nb addition on 2C-4Cr UHCS. The eighth and final chapter summarizes the findings of all the experiments of the previous chapters and revisits the objectives and conclusions.

The Reduced Enrichment for Research and Test Reactor (RERTR) now known as the Material Minimization and Management Reactor Control program (MMMRC) seeks to replace the use of highly enriched uranium (HEU) fuels used in research and test nuclear reactors around the world. The low enriched uranium (LEU) fuels must have fissionable uranium densities comparable to the HEU fuels. After extensive investigation by various researchers around the world, the U-Mo alloys were selected as a promising candidate. The Mo alloyed with U allows for the stabilization of the face-centered cubic ?-U phase, which demonstrated favorable irradiation behavior. However, deleterious diffusional interaction between the fuel and the cladding, typically Al-base alloy, remain a challenge to overcome for application of U-Mo alloys as the LEU fuel. Zr has been identified as a potential diffusion barrier between monolithic U-10 wt.% Mo (U10Mo) metallic fuel and AA6061 cladding alloys for the development of a LEU fuel system. However, interdiffusion and reaction between the Zr barrier and U10Mo fuel can produce phases such as Mo2Zr, and promote the destabilization of ?-U phase into ?'-U (U2Mo) and ?-U. In order to better understand this phenomenon, this study examined the phases that are present in the U10Mo alloys with varying Zr concentration, 0, 0.5, 1.0, 2.0, 5.0, 10.0, 20.0 wt.% at room temperature after heat treatment at 900°C for 168 hours and 650°C for 3 hours. These two temperatures are relevant to fuel plate fabrication process of homogenization and hot-rolling, respectively. Scanning electron microscopy and X-ray diffraction were employed to identify and quantitatively document the constituent phases and microstructure to elucidate the nature of phase transformations. For U10Mo alloys containing less than 1.0 wt.% Zr, there was no significant formation of Mo2Zr after 900?C homogenization and subsequent heat treatment at 650?C for 3 hours. The ?-U phase also remained stable correspondingly for these alloys containing less than 1.0 wt.% Zr. For U10Mo alloys containing 2 wt.% or more Zr, a significant amount of Mo2Zr formation was observed after 900?C homogenization and subsequent heat treatment at 650?C for 3 hours. For these alloys, destabilization of ?-U into ?'-U (U2Mo), UZr2 and ?-U was observed. The alloy containing 20 wt.% Zr, however, did not demonstrate ?-U decomposition even though Mo2Zr was observed after heat treatments. The formation of Mo2Zr effectively reduced the stability of the metastable ?-U phase by depleting the ?-stabilizing Mo. The destabilization of ?-U phase into the ?-U phase is not favorable due to anisotropic and poor irradiation behavior of ?-U phase. Therefore the formation of Mo2Zr at the interface between U10Mo fuel and Zr diffusion barrier must be carefully controlled during the fabrication of monolithic LEU fuel system for successful implementation.

Currently, there are two major driving forces for considering alternative materials to lead- based products, specifically interconnections, in electronics applications, including the impending legislation or regulations which may tax, restrict, or eliminate the use of lead and the trend toward advanced interconnection technology, which may challenge the limits of present soldering technology. The reliability of solder joints is a concern because fracture failures in solder joints accounts for 70% of failures in electronic components. Lead-free solders are being investigated as replacements for lead solders currently used in electronics. Thermo-mechanical properties describe the stresses accumulated due to thermal fatigue as a result of CTE mismatch within the system. By understanding the failure mechanisms related to lead-free solders, the application of lead- free solders could be more strategically designed for specific applications. The objective of this thesis is to observe microstructural change in large-area solder joints caused by thermal cycling and relate these changes to reliability issues in large-area lead and lead-free solder constructed semiconductor power devices. This study focused on the microstructural changes within the solder alloy of a large-area solder joint under thermal cycling conditions. Two major primary observations were made from this research, they are: 1) due to a combination of testing conditions and material properties, the lead-free solders, Sn/3.5Ag and Sn/Ag/0.7Cu, sustained the most severe damage as compared to Sn/37Pb, and 2) due to elevated stresses at the solder/substrate interface in a simulated power semiconductor device sample damage was found to be most severe. / Master of Science

Alumina-to-alumina brazed joints were formed using 96.0 and 99.7 wt.% Al2O3 ceramics in as-ground and in ground and heat treated conditions using TICUSIL® (68.8Ag-26.7Cu-4.7Ti wt.%) braze preforms of thicknesses ranging from 50 to 250 μm. Brazing was conducted in a vacuum of 1 x 10-5 mbar at 850 °C for 10 minutes. Joint strengths were evaluated using four-point bend testing and were compared to the flexural strengths of standard test bars according to ASTM C1161-13. Post-grinding heat treatment, performed at 1550 °C for 1 hour, did not affect the average surface roughness or grain size of either grade of alumina but affected their average flexural strengths, with a small increase for 96.0 wt.% Al2O3 and a small decrease for 99.7 wt.% Al2O3. Post-grinding heat treatment led to secondary phase migration, creating a fissured 96.0 wt.% Al2O3 surface. This affected the reliability of 96.0 wt.% Al2O3 brazed joints, in which braze infiltration was observed. As the TICUSIL® braze preform thickness was increased from 50 to 150 μm, the average strengths of both 96.0 and 99.7 wt.% Al2O3 brazed joints improved. This occurred due to a microstructural evolution, in both sets of joints, which was studied using SEM, TEM and nanoindentation techniques. An increase in the TICUSIL® braze preform thickness increased the amount of Ti which was available to diffuse to the joint interfaces. This led to increases in both, reaction layer and braze interlayer thicknesses. Excess Ti in joints that were made using TICUSIL® braze preforms thicker than 50 μm, led to relatively hard Cu-Ti phases in an Ag-Cu braze interlayer. Cu-Ti phase formation, which may have reinforced joint strength whilst also reducing CTE mismatch at the joint interface, also led to Ag-rich braze outflow at the joint edges. Brazed joints made using as-ground 96.0 wt.% Al2O3 consistently outperformed brazed joints made using as-ground 99.7 wt.% Al2O3, due to the formation of Ti5Si3 phases at locations where the Ti-rich reaction layer intersected with the triple pocket grain boundary regions of the as-ground 96.0 wt.% Al2O3 surface.