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.

This dissertation undertakes theoretical research into the adsorption, pattern formation, and reactions of atoms, molecules, and layered materials on catalyst surfaces. These investigations are carried out from first-principles calculations of electronic and geometric structures using density functional theory (DFT) for predictions and simulations at the atomic scale. The results should be useful for further study of the catalytic activities of materials and for engineering functional nanostructures. The first part of the dissertation focuses on systematic first-principles simulations of the energetic pathways of CO oxidation on the Cu2O(100) surface. These simulations show CO to oxidize spontaneously on the O-terminated Cu2O(100) surface by consuming surface oxygen atoms. The O-vacancy on Cu2O(100) then is subsequently healed by dissociative adsorption of atmospheric O2 molecules. The second part discusses the pattern formation of hydrogen on two and three layers of Co film grown on the Cu(111) surface. It is found that increasing the pressure of H2 changes the hydrogen structure from 2H-(2 × 2) to H-p(1 × 1) through an intermediate structure of 6H-(3 × 3). The third part compares the results of different ways of introducing van der Waals (vdW) interactions into DFT simulations of the adsorption and pattern formation of various molecules on certain substrates. Examinations of the physisorption of five nucleobases on iii graphene and of n-alkane on Pt(111) demonstrate the importance of taking vdW interactions into account, and of doing so in a way that is best suited to the particular system in question. More importantly, as the adsorption of 1,4 diaminebenzene molecules on Au(111) shows inclusion of vdW interactions is crucial for accurate simulation of the pattern formation. The final part carries out first-principles calculations of the geometric and electronic structure of the Moir´e pattern of a single layer of Molybdenum disulfide (MoS2 ) on Cu(111). The results reveal three possible stacking types. They also demonstrate that the MoS2 layer to be chemisorbed, albeit weakly, and that, while Cu surface atoms are vertically disordered, the layer itself is not strongly buckled.

<p>The properties and microstructure of Ti-5Al-5V-5Mo-3Cr were characterized under various stress states after the following heat treatments: 1) annealing above the β transus, followed by cooling at various rates and ageing for different times; 2) solution heat treatment in the α-β range, fan-cooling and ageing for various temperatures and times.</p> <p>Heat treatment above the ptransus temperature causes complete recrystallization of the as-forged microstructure. The as-cooled microstructure consists of equiaxed β grains with an average grain size of 200μm. Water quenching from above the β transus results in precipitation of a dispersion of nano-sized ω phase; while the fan-cooled microstructure contains nano-sized ω and α precipitates. Ageing of the fan-cooled microstructure at 790°C or 600°C precipitates sub micron acicular α throughout the β grains. The tensile properties of this condition could not be determined using standard tensile specimens due to brittle failure at the grips.</p> <p>Controlled cooling from above the β transus to the ageing temperature at slower rates produces a coarser α+β microstructure. Acicular α laths are produced with cooling rates of 1°C/min, while lamellar α develops at cooling rates of 3.4°C/min. The β annealed and fan-cooled condition is characterized by relatively low strength (~850MPa) and low ductility (~6% elong.).The fracture mode is by intensely localized slip and the creation of transgranular cracks. Localization of slip is attributed to shearing of the nano-scale ω precipitates by dislocations. A linear relationship between the grain size, d⁻¹/² , and the yield and fracture stresses was established, as described by the Hall-Petch relation. With controlled cooling, the strength and ductility improve by precipitation of lamellar α within the β matrix. Improvements in ductility and strength are achieved by reducing the slip length.</p> <p>Solution heat treatment below the β transus and fan-cooling results in complete dissolution of the as-forged acicular α phase. Solutionizing at 50°C below the ptransus yields a volume fraction of 16.5% primary α in a matrix of retained β. Low angle grain boundaries and globular primary α, each measuring 2-4μm average in diameter, are uniformly distributed throughout the retained β matrix. The tensile strength in this condition is relatively low, i.e. (900MPa) and the ductility relatively high (~16% elong.). With ageing in the 500°C to 600°C temperature range, precipitation of α within the retained β begins within 5 minutes of the start of ageing. Precipitating is heterogeneously nucleated at dislocations and grain boundaries. The yield and ultimate tensile strengths reach values of roughly 1200 and 1300MPa, respectively, and remain relatively constant for up 48 hours ageing</p> <p> The fracture stresses for the solution treated condition and for material subsequently aged at 500°C and 600°C are quite similar in magnitude. This similarity is due to the fact that the fracture mechanism, which controls the fracture stress, is the same for all these conditions. The fracture mechanism for all the solution treated conditions begins with shear decohesion of the primary α/β interfaces.</p> <p>For each condition, the damage mechanisms and final fracture modes were evaluated and rationalized on the basis of microstructural features. The yield and fracture stresses for the various conditions were calculated and plotted on a two-principal stress axis coordinate system, thus creating the failure envelope for Ti-5553. For the β annealed and fan cooled and for the α-β solution heat treated and aged conditions the yield and fracture envelopes are two concentric ellipses in good agreement with the shear strain energy (van Mises) model for failure.</p> <p>The fracture toughness and stress corrosion cracking behaviour for the STA condition were evaluated and compared against other β titanium alloys.</p> / Thesis / Doctor of Philosophy (PhD)

<p>Long-term stability and chromium (Cr) contamination are two major concerns for application of chromium-bearing metallic materials as interconnects of solid oxide fuel cells (SOFCs) at intermediate temperature (~800°C). Copper-manganese (Cu-Mn) and cobalt-manganese (Co-Mn) spinel can be promising coating materials for the metallic interconnects as they show high electrical conductivities. The first objective of this research is to develop an economical and convenient method through which the spinel coatings can be applied to the metallic substrates. The investigations on the crystal structure of CuᵪMn₃₋ᵪO₄ spinel, e.g., structure symmetry and cation distributions, have always been controversial, which hinders the total understanding of the detailed structure of the material. In order to resolve the inconsistency, in-situ neutron and X-ray diffraction were employed to determine the structure of the spinel.</p> <p>A novel method was developed to obtain high quality manganese coating without any additives (sulphur or selenium compounds). Cu-Mn and Co-Mn spinel coatings were applied to metallic coupons by electrodeposition and subsequent annealing. The method is convenient and easy to control. The performance testing showed that the area specific resistances (ASRs) of the coated samples (0.003 Ω•cm²) are much lower than that of the uncoated UNS 430 (0.189 Ω•cm²) after oxidation at 750°C for 1500 hours. Moreover, both spinel coatings can effectively suppress the outward diffusion of Cr, which resulted in reduction of Cr contamination significantly. The oxidation studies of Cu-Mn coating revealed the transformation mechanisms of Cu-Mn coating to the spinel. In-situ neutron and X-ray diffraction analysis clarified the crystal symmetry of CuᵪMn₃₋ᵪO₄ spinel and CuMnO₂ at high temperatures. Rietveld refinement revealed the cation distribution of Cu and Mn ions on tetrahedral and octrahedral sites of CuᵪMn₃₋ᵪO₄ spinel, which was compared to values in the literatures. / Thesis / Doctor of Philosophy (PhD)

<p> This investigation is concerned with the development of a general ternary diffusion analysis for the diffusion-controlled oxidation of binary alloys based on the concept of local equilibrium and phenomenological diffusion theory and its application to appropriate experimental systems. </p> <p> The theoretical analysis is in two parts. In the first part diffusion equations for the alloy and oxide phases are obtained and tested against experiments for Ni-10.9% Co alloy at 1000°C. In the second part phenomena observed in binary alloy oxidation such as supersaturation, internal oxidation and morphological instability are qualitatively discussed and the concept ot the stationary diffusion path on the isotherm is applied to binary alloy oxidation. In general the ternary diffusion analysis satisfactorily accounts for the diffusion-controlled oxidation properties of several binary alloys. </p> <p> An experimental investigation of the oxidation of nickel-iron alloys at 1000°C is described. In the first part of the experimental investigation, thermodynamics of the ternary iron-nickel-oxygen system at 1000°C has been investigated in support of the oxidation studies. The second part is comprised of a detailed kinetic and metallographic study of nickel-iron alloys containing upto 25% iron exposed to oxygen atmospheres at 1000°C and determination of the metal concentration profiles in the oxide and alloy phases. The experimental results for these alloys are in good agreement with the theoretical calculations. </p> / Thesis / Doctor of Philosophy (PhD)

<p> Iron-vanadium alloys were levitation melted and equilibrated at controlled temperatures with water vapour/hydrogen atmospheres of controlled composition, quenched and analysed for oxygen. The effect of vanadium on the behaviour of oxygen has been expressed in terms of first order free energy, enthalpy and entropy interaction parameters. </p> <p> The reduction of phosphorus from synthetic blast furnace slags by carbon saturated iron was studied under laboratory conditions. The rate of phosphorus transfer was determined and the results have been interpreted in terms of chemical reaction control at the slag/metal interface. </p> <p> The dephosphorisation of induction melted mild steel by synthetic basic slags was investigated. The rate of dephosphorisation was determined and the results have been interpreted in terms of mass transfer control in the slag phase. </p> / Thesis / Doctor of Philosophy (PhD)

Cellulose wet adhesives are applied to enhance the wet strength of paper products by binding individual paper fibers together. However, the recycling of the wet strength paper is a challenge as the fibers are hard to re-disperse in water. This project demonstrates new strategies for developing cellulose wet adhesives with controllable degradability, facilitating the recycling of wet strength papers. In this project, regenerated cellulose membranes were used to simulate paper fibers. In adhesion measurements, two wet cellulose membranes were laminated with a thin layer of adhesive (1–30 mg/m2), and the 90-degree wet-peel was used as a measure of cellulose wet adhesion. It was shown that the wet-peel was a simple and reliable method to evaluate the wet adhesives for paper products. Cellulose wet adhesives, in the form of microgels or linear polymers, were synthesized by incorporation of hydrazide, amine or azetidinium functional groups that can form covalent bonds to cellulose surfaces. Two strategies to design degradable adhesives were demonstrated in this project. 1) Reductant-responsive microgel adhesives were created by introducing cleavable disulfide linkages, either in the polymer chains tethering adhesive groups or as the microgel crosslinks. More than 70% reduction in wet adhesion was achieved after exposure to a reductant. 2) Degradable polymer cohesive bonds were used to “switch off” the cellulose wet adhesion. This adhesive was created by introducing labile boronate-dextran complexes to the PVAm adhesive layer between cellulose surfaces. The introduction of this new interaction between PVAm chains enhanced the cellulose wet adhesion. In response to subtle pH changes or the presence of monosaccharides, the wet adhesion decreased by 60%. / Thesis / Doctor of Philosophy (PhD) / Wet strength is important for paper products such as paper towels and paper packaging. In paper manufacturing, cellulose wet adhesives are applied to enhance the strength of wet papers by “gluing” together individual cellulose fibers. However, the recycling of wet strength papers is a challenge because the current adhesives prevent the easy disintegration of waste paper back to a suspension of discrete cellulose fibers. As an important part of the bio-based economy, the next generation of paper products are required to be both strong in water and easy to recycle. This thesis explores new designs for wet-strength adhesives that will facilitate recycling. Both nanoparticles and linear polymers were synthesized in this study as cellulose wet adhesives. Many important properties of wet adhesives were probed, including the size of nanoparticles, the pre-treatment of cellulose surfaces, the dosage of adhesives and the choice of adhesive chemistries. A few types of novel cellulose wet adhesives with controllable degradability were synthesized and evaluated. I demonstrated that the cellulose wet adhesion can be “switched off” in response to subtle pH changes, reducing agents or sugars, showing a promising start for the recycling of wet strength papers.

Metal additive manufacturing (AM) provides a platform for microstructure optimization via process control, the ability to model the evolution of microstructures from changes in processing condition or even predict the microstructures from given processing condition would greatly reduce the time frame and the cost of the optimization process. In 1, we present a deep learning framework to quantitatively analyze the microstructural variations of metals fabricated by AM under different processing conditions. We also demonstrate the capability of predicting new microstructures from the representation with deep learning and we can explore the physical insights of the implicitly expressed microstructure representations. We validate our framework using samples fabricated by a solid-state AM technology, additive friction stir deposition, which typically results in equiaxed microstructures. In 2, we further improve and generalize the generating framework, a set of metrics is used to quantitatively analyze the effectiveness of the generation by comparing the microstructure characteristics between the generated samples and the originals. We also take advantage of image processing techniques to aid the calculation of metrics that require grain segmentation. / Master of Science / Different from the traditional manufacturing technique which removes material to form the desired shape, additive manufacturing (AM) adds material together to form the shapes usually layer by layer. AM which is sometimes also referred to as 3-D printing enables the optimization of material property through changing the processing conditions. The microstructure is structures formed by materials on a microscopic scale. Crystals like metal usually form a crystalline structure composed of grains where atoms have the same orientation. Especially for metal AM, changes in the processing condition will usually result in changes in microstructures and material properties. To better optimize for the desired material properties, in 1 we present a microstructure representation method that allows projection of microstructure onto the representation space and prediction from an arbitrary point from the representation space. This representation method allows us to better analyze the changes in microstructure in relation to the changes in processing conditions. In 2, we validate the representation and prediction using EBSD data collected from copper samples manufactured with AM under different processing conditions.

L’électrochimie bipolaire est un phénomène générant une réactivité asymétrique à la surface d’objets conducteurs, sans contact électrique direct. Ce concept est basé sur le fait que lorsqu’un objet conducteur est localisé dans un champ électrique, il se polarise. Par conséquent, une différence de potentiel est générée entre ses deux extrémités, et peut être utilisée pour induire des réactions redox localisées. Dans cette thèse, l’utilisation de l’électrochimie bipolaire pour la science des matériaux et pour la locomotion d’objets est présentée.Jusqu’à présent, la plupart des méthodes ou procédés utilisés pour générer des objets asymétriques,appelés aussi objets « Janus », nécessitent l’introduction d’une interface pour briser la symétrie. Nous avons développé une nouvelle approche basée sur l’électrodéposition bipolaire pour générerce type d’objet en grande quantité. Grâce à cette technologie différents matériaux tels que des métaux, des polymères et des semi‐conducteurs ont pu être déposés sur diverses particulesconductrices. Il a été aussi démontré que l’électrochimie bipolaire pouvait être utilisée pour lamicrostructuration de substrats conducteurs.Nous avons induit des mouvements à des objets conducteurs en exploitant le phénomèned’électrochimie bipolaire. Certains objets Janus synthétisés par l’approche précédente ont pu être utilisés comme micronageurs. La brisure de symétrie qui est générée par l’électrochimie bipolaire peut être aussi utilisée directement pour générer un mouvement de particules isotropes. En employant ce concept, nous avons pu provoquer des mouvements de translation, rotation et lévitation pour des particules de carbones ou métalliques. / The phenomenon of bipolar electrochemistry generates an asymmetric reactivity on the surface ofconductive objects in a wireless manner. This concept is based on the fact that when a conducingobject is placed in an electric field, it gets polarized. Consequently, a potential difference appearsbetween its two extremities, that can be used to drive localized redox reactions. In the presentthesis, bipolar electrochemistry was used for material science and the locomotion of objects.So far, the majority of methods and processes used for the generation of asymmetric objects, alsocalled “Janus” objects, is based on using interfaces to break the symmetry. We developed a newapproach based on bipolar electrodeposition for generating this type of objects in the bulk. Using thistechnology, various materials like metals, polymers and semiconductors could be deposited ondifferent types of conducting particles. We also showed that bipolar electrochemistry can be used forthe microstructuration of conducting substrates.Motion generation by bipolar electrochemistry has also been demonstrated. Some of the Janusobjects synthesized by the previous approach can be used as microswimmers. The asymmetricreactivity that is induced by bipolar electrochemistry can also be used directly to generate motion ofnon‐hybrid objects. With this concept we induced translations, rotations and levitations of carbonand metal particles.

A superfície (001) dos compostos III-V têm grande importância para as modernas tecnologias de crescimento de materiais, assim o estudo da formação dessa superfície, de suas propriedades e dos processos de adsorção de moléculas que ocorrem sobre ela é essencial para o desenvolvimento da ciência de materiais. Sabe-se que o InP, a exemplo de outros compostos III-V, apresenta uma variedade de padrões de reconstrução para superfície (001) que dependem das condições iniciais que prevalecem durante o seu crescimento. Neste trabalho estudamos os padrões da superfície InP(001) originados em ambientes com concentração máxima de átomos de índio e de fósforo e os processos envolvidos com a adsorção da molécula H2S sobre estas superfícies. Usamos cálculos de primeiros princípios dentro do formalismo da Teoria do Funcional da Densidade (DFT) associados à pseudopotenciais de norma conservada com aproximação generalizada do gradiente para o termo da energia de troca e correlação (DFT-GGA) e correlação não linear de caroço (NLCC). Fizemos a adsorção da molécula de H2S sobre os padrões mais estáveis da superfície InP(001), considerando os casos com a molécula dissociada e não dissociada. No padrão reconstrução 2x2 com dois dímeros, superfície originada em ambientes ricos em átomos de fósforo, fizemos o cálculo das barreiras de energia entre as configurações energeticamente mais favoráveis e encontramos um mecanismo de adsorção para a molécula de H2S dissociada Na superfície com padrão de reconstrução 2x4, crescida em ambientes ricos em átomos de índio, com formação de um dímero misto, verificamos que a molécula não dissociada adsorve sobre os sítios formados por átomos de fósforo e que adsorve sobre os sítios formados por átomos de índio. O átomo de enxofre da molécula dissociada adsorve sobre os sítios formados por átomos de fósforo e de índio e as moléculas de hidrogênio permanecem desorvidas, porém as estruturas são desfavoráveis energeticamente. / The (001) surface of the III-V compounds have great importance for modern technologies of materials growth thus the study of these surfaces formation, its properties and the absorption process of the molecules are essential for the development of materials science. It is well known that the InP, as well others III-V compounds, present a variety of reconstruction patterns for (001) surface that depend on the initial growth conditions. In this work we studied the patterns of InP(001) surface considering an environment with high concentration ln and P atoms and the interaction of the H2S molecule with these surfaces. Using first-principles calculations within the Density Functional Theory (DFT) formalism, norm-conserving pseudopotentials with the generalized gradient approximation for the exchange and correlation energies (GGA) and non-linear core-correction (NLCC). We have studied the H2S molecule adsorption on different reconstruction of the InP(001) surface, considering the cases in which the H2S molecule was dissociated and non-dissociated. In the 2x2 pattern with two dimmers, the energy barriers were calculated between the more energetically favorable configurations and a possible mechanism of adsorption of dissociated H2S molecule is proposed. The non-dissociated molecule does not bind over phosphorus sites but over indium sites, for all considered reconstructions. The sulfur atom of dissociated molecule adsorbs over phosphorus and indium sites and the hydrogen molecules stands not joint, however the structure are energetically unfavorable.