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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Using Core-Shell Nanocatalysts to Unravel the Impact of Surface Structure on Catalytic Activity:

Williams, Benjamin Parker January 2020 (has links)
Thesis advisor: Udayan Mohanty / The high surface area and atomic-level tunability offered by nanoparticles has defined their promise as heterogeneous catalysts. While initial studies began with nanoparticles of a single metal assuming thermodynamic shapes, modern work has focused on using nanoparticle composition and geometry to optimize nanocatalysts for a wide variety of reactions. Further optimization of these refined nanocatalysts remains difficult, however, as the factors that determine catalytic activity are intertwined and a fundamental understanding of each remains elusive. In this work, precise synthetic methods are used to tune a number of factors, including composition, strain, metal-to-metal charge transfer, atomic order, and surface faceting, and understand their impact on catalysis. The first chapter focuses on current achievements and challenges in the synthesis of intermetallic nanocatalysts, which offer long-range order that allows for total control of surface structure. A particular focus is given to the impact of the synthetic approach on the activity of the resulting nanoparticles. In the second chapter, multilayered Pd-(Ni-Pt)x nanoparticles serve as a controlled arena for the study of metallic mixing and order formation on the nanoscale. The third chapter controls the shell thickness of Au@PdPt core-alloyed shell nanoparticles on a nanometer scale to isolate strain at the nanoparticle surface. In the fourth chapter, the synthetic approaches of chapters two and three are applied to catalysis. In totality, the work presented here represents a brick in the foundation of understanding and exploiting structure-function relationships on the nanoscale, with an eye toward the rational design of tailored nanocatalysts. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
2

Effect of Process Parameters on Deformation of Zr-2.5wt%Nb Alloy

Cochrane, Christopher James 15 October 2013 (has links)
Zirconium and its alloys are used extensively in the nuclear industry. In the Canadian Deuterium Uranium reactor, the primary containment in the primary coolant system is composed of Zr-2.5wt%Nb in the form of a pressure tube. The permissible chemical composition of Zr-2.5wt%Nb for use in the pressure tube in nuclear reactors is dictated by ASTMB353. Oxygen and iron are the highest content controlled elements in the standard alloy, after zirconium and niobium. Oxygen is an alpha-stabilizer, and diffuses preferentially to the alpha phase, leading to a well established increase in the yield strength of the alpha phase. Iron is a beta-stabilizer, and is concentrated in the beta phase, as well as near alpha-beta grain boundaries. While the mechanical properties of standard Zr-2.5wt%Nb alloy are well understood, there is a dearth of knowledge on the individual effect of these alloying additions, especially at non-standard concentrations. Additionally, the experimental evidence that does exist does not directly take into account the two-phase nature of the alloy, or the effect of impurities on specific deformation modes. Notably absent is experimental evidence on the effect of interstitial impurities on twinning in the hexagonal close-packed alpha phase. This work seeks to complement the present understanding of these phenomena. Mechanical tests have been performed on three specially prepared Zr-2.5wt%Nb alloys to clarify the contributions of oxygen and iron to Zr-2.5wt%Nb deformation properties. Traditional mechanical measurements were complemented by in situ and ex situ diffraction measurements. Tests were performed at a range of temperatures (77K - 673K) and strain rates (quasi-static to 10^-2/s). Increasing oxygen content from 1176wppm to 3300wppm increases the macroscopic yield stress at room temperature, and results in a transition in work hardening behaviour at low strain rates. Increasing iron content from 547wppm to 1080wppm has no effect on the macroscopic yield stress, but increases the work hardening rate at room temperature. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2013-10-11 20:06:57.655
3

Synthesis of Strained Metal Nanocrystal Architectures for Energy Conversion Electrocatalysis

Sneed, Brian Thomas January 2015 (has links)
Thesis advisor: Chia-Kuang F. Tsung / Thesis advisor: Dunwei Wang / In order to understand the lattice strain effect and its relationship to size, shape, composition, and catalytic performance, novel well-defined nanocrystal archetypes were designed and synthesized by taking advantage of wet chemical, seed-mediated (mild) reduction routes developed by our lab. First, the current synthesis challenges are addressed in creating smaller monometallic shape-controlled metal nanocrystals, and novel cuboctopods via a hybrid nanoparticle stabilizer. A look at the relationship between lattice strain and morphology is then shown in a single-component system, where still new features have been observed for the first time by the traditional technique of powder x-ray diffraction. Synthesis methods for differently strained Pd surfaces are described and catalysis by these surfaces is discussed. Finally, studies of the synthesis, characterization, electrocatalytic activity, and restructuring of novel and more sophisticated strained architectures are presented: core-island-shell nanocrystals, phase-segregated nanoboxes, island nanoframeworks, and core-sandwich-shell nanoparticles. Lattice strain and composition effects were studied in carbon monoxide, small alcohol, and formic acid electrocatalytic oxidations as well as in oxygen reduction, the latter of which, governs the commercial viability of automotive fuel cells, a sustainable energy and zero-emission technology. Here it is demonstrated how a tunable thickness of Ni sandwich layers can be used to improve catalytic performance by increasing lattice strain on the Pt surface. The sandwich archetype offers a new platform for the investigation of lattice strain and could be a promising, industrially relevant, catalyst design concept, to help address the need for a more sustainable energy future. The results help paint a new picture of catalysis by metal nanocrystals; one which brings lattice strain to the forefront of the discussion, as an important parameter for further study and for use in developing higher-performing catalysts. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
4

The mechanical alloying of sub-stoichiometric titanium carbonitride-tungsten-aluminium by high energy ball milling.

Kasonde, Maweja. 27 January 2012 (has links)
The transformations occurring in the sub-stoichiometric Ti(C,N) – W - Al system processed by high energy ball mill were investigated. The milling parameters included the milling time and the temperature comprising milling at subzero temperature and above 25°C. Two sub-stoichiometric Ti(C,N) stocks were selected, the Ti(C0.5N0.05) containing more interstitial elements than the Ti(C0.5N0.5)0.6.The transformation stages and mechanisms of alloying are discussed with respect to the changes in crystal structures of the powder constituents. The milling atmosphere had an effect on the lattice strain of milled products, and hence on the kinetics of solid state dissolution between the powder constituents, but it did not affect the fracturing process. The release of the stored crystallite lattice strain energy was the major determinant in mechanical alloying, with particle size reduction playing a necessary, but less significant role. The strain energy and the fine particle size contributed to the increased chemical reactivity with oxygen of the powders milled for shorter times. The affinity of the powders with oxygen decreased after W dissolution in Ti(C,N), and the subsequent decrease in lattice strains. The annealing behaviour of Ti(C0.5N0.05) - 40wt% W and Ti(C0.5N0.5)0.6 - 40wt% W mechanically alloyed powders were investigated using XRD, TEM, SEM and DTA techniques. It was observed that the reaction start and finish temperatures between constituents were lower in the system that had higher residual lattice strains after milling. The compositions of the intermetallic compounds and the solid solutions formed were dependent on the milling conditions and the annealing temperature. Thermal alloying was observed during annealing of Ti(C0.5N0.05) - 40wt% W mechanically alloyed products, whereas de-mixing of W-rich phases from the metastable solid solution occurred during annealing of the Ti(C0.5N0.5)0.6 - 40wt% W milled powders. The effects of Al addition and milling at subzero temperatures on the transformation of Ti(C0.5N0.05)-W powder mixtures were investigated. Addition of Al powder improved the kinetics of solid solution between powder constituents. The effect of Al was ascribed to the increase of lattice strain during short milling time followed of relaxation at longer time, and to the fast diffusion of atoms. Also, it was noticed that the high viscosity of the process control agent could inhibit the alloying process. Multiple three-component compounds could be formed. Aluminium preferably reacted with tungsten. The W(Al,C) and W(Al,Ti) formed were stable, thus solubility of W in Ti(C0.5N0.05) in the presence of Al was limited. The evolution of the morphologies of Ti(C,N)-W mixtures show that fracturing of hard particles dominated in the early stage of milling in the absence of Al, whereas with Al, plastic deformation of particles and cold welding of Ti(C,N) and W particles by the softer Al prevailed at the same time. Longer milling time improved the homogeneity and the formation of nanostructured binder pools in the sintered products. Lower oxygen contents in sintered PcBN were achieved by mechanically alloying Ti(C,N), W and Al in the high energy ball milling stage. Low level of Co in the infiltration layer was also achieved when sintering PcBN with this type of binder. A link was established between the addition of Al at the attrition milling stage and high oxygen content in the sintered PcBN, thus should be avoided. The pressure and temperature applied during sintering or annealing had a strong effect on the compositions and the crystal structures of the phases formed in the mechanically alloyed binder. The lattice strains of the binder and the PcBN were higher in the sintered materials prepared with the Ti(C0.5N0.5)0.6-W binder than in those made using the Ti(C0.5N0.05)-W alloys.
5

Lattice Strain and Texture of Plastically Deformed Zircaloy-2 at 77K

Judge, COLIN 07 December 2009 (has links)
Zircaloy-2 is used extensively in the nuclear industry as a structural material for the reactor core in both light and heavy water reactors. The intergranular strains and texture greatly affect the mechanical properties of the material while in operation. Understanding the plastic deformation of Zircaloy-2 will improve on current plastic deformation models, particularly for twinning mechanisms, which are more active at lower temperatures, and are not yet well understood. For this study, neutron diffraction was used to track the lattice spacing and peak intensity in warm-rolled and recrystallized Zircaloy-2 slab for various crystallographic orientations at 77 K. Tests were performed in all three principle directions under tension and compression. The texture was measured for the deformed samples to help interpret the dominant deformation systems and then Electron Back Scattering Diffraction was used to identify and image the active twinning modes. Prism <a> slip, basal <a> slip, {10-12} and {11-2 1} tensile twinning, and {11-2 2} compression twinning were found to be contributing deformation systems in Zircaloy-2 at 77K. In this study, the diffraction elastic constants for Zircaloy-2 at room temperature and 77K are reported for the first time in open literature. These values will be useful in future experimental work by allowing a conversion between lattice spacing and residual stress. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2009-09-24 13:41:25.371
6

Lattice Strain Development in Inconel-690 under Bi-axial Compression and Tension

TODA, Rebecca 02 September 2010 (has links)
Nuclear reactor steam generator tubes, manufactured from Nickel alloys such as Inconel 690 (INC690), are potentially susceptible to failure by Stress Corrosion Cracking where crack initiation may be exacerbated by internal stress fields. A more comprehensive understanding of this potential failure mechanism was gained via an exploration of a model of INC690’s behaviour under Constrained loading conditions in compression and tension. An Elasto-Plastic Self-Consistent (EPSC) model was used to predict the lattice stresses and strains resulting from Constrained loading in INC690 for four crystallographic planes. The internal strain fields generated under such conditions were shown to be markedly different from those developed under Uniaxial loading. Finite Element Modeling was used to design tensile and compression samples as well as a testing rig that would allow the application of a compressive load along one axis of the specimen with simultaneous constraint along another and free-deformation along the third. Lattice strain measurements were done for both compressive and tensile loading using Time-Of-Flight neutron diffraction. The predicted and experimental values showed reasonable agreement; mainly in terms of crystallographic plane interaction and behaviour. Iterative computer modeling was used to achieve a more realistic depiction of the lattice strains developed. This research allowed for an extension on the Uniaxial findings by examining the material’s behaviour under more complex loading that better approximates steam generator tube operating conditions. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2010-08-31 16:19:23.331
7

Controlling Coherency Phase Boundary for High Performance Batteries / 蓄電池の高性能化に資する相境界面制御

Yoshinari, Takahiro 25 March 2019 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第21877号 / 人博第906号 / 新制||人||216(附属図書館) / 2018||人博||906(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 吉田 寿雄, 准教授 藤原 直樹 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM
8

Effect of Chemistry on the Transformation of Austenite to Martensite for Intercritically Austempered Ductile Iron

Banerjee, Sayanti 11 January 2013 (has links)
Intercritically austempered ductile iron (IADI) with a matrix microstructure of ferrite plus metastable austenite has an excellent combination of strength and toughness. The high strength and good ductility of this material is due to the transformation of metastable austenite to martensite during deformation. In the present study, the transformation of austenite to martensite for intercritically austempered ductile irons of varying alloy chemistry (varying amounts of nickel and/or manganese) were examined using in-situ neutron diffraction under strain-controlled loading at VULCAN at the Spallation Neutron Source at Oak Ridge National Laboratory (ORNL). Both diffraction and tensile data were collected and synced using the VDRIVE software (a proprietary ORNL software package). The single peak fit method was employed in the analysis of the diffraction data. In this thesis, the stress and strain for the start of the transformation of metastable austenite to martensite were determined. The development of residual stresses during deformation and the elastic diffraction constants for both the ferrite and austenite phases were also determined. The material was characterized using optical microscopy, backscattered imaging in the scanning electron microscopy, energy dispersive spectroscopy and transmission electron microscopy. / Master of Science
9

Fluorine and chlorine fractionation in the sub-arc mantle : an experimental investigation / Fractionemment du fluor et du chlore dans le manteau sub-arc : une approche expérimentale

Dalou, Célia 21 January 2011 (has links)
Les éléments volatils libérés de la plaque plongeante lors de la subduction jouent un rôle fondamental durant la formation des magmas d'arc dans le coin mantellique. Depuis quelques années, les développements des techniques d'analyse par sonde ionique ont permis l'analyse de ces éléments, en particulier F et Cl, dans les magmas d'arc, et notamment dans les magmas d'arc primaires grâce aux avancées des études sur les inclusions magmatiques. Une récente étude des inclusions magmatiques du Mont Shasta (E. U.) (Le Voyer et al., 2010) a montré que le fractionnement du F et du Cl apportait des informations sur la genèse des magmas d'arc. Afin de caractériser la source de ces magmas, j'ai étudié les coefficients de partage du fluor et du chlore. Dans cette étude, je présente les premiers coefficients de partage du F et du Cl, entre des liquides de fusions silicatés anhydres et hydratés et des minéraux mantelliques tels que olivine, orthopyroxène, clinopyroxène, plagioclase, grenat ainsi que pargasite et phlogopite. Les valeurs sont issues de 300 mesures dans 24 expériences de fusion, réalisées entre 8 et 25 kbars et, 1180 et 1430˚C. Les faibles concentrations en F et Cl dans les minéraux ont été analysées par la sonde ionique Cameca IMF 1280 de WHOI en utilisant le mode d'ions secondaires négatifs. Les résultats montrent que DOpx/meltF varient de 0.123 à 0.021 et DCpx/meltF de 0.153 à 0.083, tandis que DOpx/meltCl varient de 0.002 à 0.069 et DCpx/meltCl de 0.008 à 0.015. De plus, DOl/meltF de 0.116 à 0.005 et DOl/meltCl de 0.001 à 0.004 ; DGrt/meltF de 0.012 à 0.166 et DGrt/meltCl de 0.003 à 0.087 avec l'augmentation de la teneur en eau et la diminution de la température dans les expériences. Je montre aussi que le F est compatible dans la phlogopite (DPhl/meltF >1.2) alors qu'il est incompatible dans la pargasite (DAmp/meltF de 0.36 à 0.63). A l'inverse, Cl est plus incompatible dans la phlogopite (DPhl/meltCl en moyenne 0.09±0.02), que dans la pargasite (DAmp/meltCl de 0.12 à 0.38). Cette étude démontre que F et Cl sont substitués dans des sites spécifiques de l'oxygène, ce qui les rend plus sensibles que les éléments traces aux variations de chimie des cristaux et de la quantité d'eau, et donc aux conditions de fusion. En utilisant ces nouveaux coefficients de partage, j'ai modélisé la fusion de lithologies potentielles du manteau sub-arc permettant de 1) déterminer la quantité de fluide aqueux impliqué dans la fusion, 2) distinguer la fusion induite par apport de fluides de la fusion d'une source à minéraux hydratés et 3) la fusion d'une lithologie à pargasite de celle à phlogopite, et montre que la source de certains magmas primaires d'arc, par exemple d'Italie, contient de la pargasite et de la phlogopite, tandis d'autres magmas primaires d'arc résultent d'une fusion par apport de fluides. / Volatile elements released from the subducting slab play a fundamental role during the formation of arc magmas in the mantle wedge. Advances of melt inclusion studies enlarged the data on volatile abundance in arc magmas, and it is now possible to characterize some volatile contents in arc primary magmas, in particular F and Cl. A recent study of Mt Shasta melt inclusions (LeVoyer et al., 2010) shows that fractionation of F and Cl potentially contains information about arc magma genesis. In order to trace the source of arc magmas, fluorine and chlorine partitioning was investigated. Here, I present new experimental determinations of Cl and F partition coefficients between dry and hydrous silicate melts and mantle minerals: olivine, orthopyroxene, clinopyroxene, plagioclase, garnet and also pargasite and phlogopite. The values were compiled from more than 300 measurements in 24 melting experiments, conducted between 8 and 25 kbars and between 1180 and 1430˚C. The low abundance F, Cl measurements in minerals were done by Cameca IMF 1280 at WHOI using the negative secondary ion mode. The results show that DOpx/meltF ranges from 0.123 to 0.021 and DCpx/meltF ranges from 0.153 to 0.083, while Cl partition coefficient varies from DOpx/meltCl from 0.002 to 0.069 and DCpx/meltCfrom 0.008 to 0.015, as well. Furthermore, DOl/meltF ranges from 0.116 to 0.005 and DOl/meltCl from 0.001 to 0.004; DGrt/meltF ranges from 0.012 to 0.166 and DGrt/meltCl from 0.003 to 0.087 with the increasing water amount and decreasing temperature. I also show that F is compatible in phlogopite DPhl/meltF > 1.2) while DAmp/meltF is incompatible in pargasite DAmp/meltF from 0.36 to 0.63). On the contrary, Cl is more incompatible in phlogopite (DPhl/meltCl > 1.2 on average 0.09 ± 0.02), than in pargasite (DPhl/meltCl from 0.12 to 0.38). This study demonstrates that F and Cl are substituted in specific oxygen site in minerals that lead then to be more sensitive than trace elements to crystal chemistry and water amount variations thus melting conditions. Using those new partition coefficients, I modelled melting of potential sub-arc lithologies with variable quantity aqueous-fluid. This model is able to decipher 1) amount of aqueous-fluid involved in melting, 2) melting induced by fluid or melting of an hydrous mineral-bearing source and 3) melting of either pargasite-bearing lithology or phlogopite-bearing lithology and shows that sources of some primitive melts, for instance from Italy, bear pargasite and phlogopite, while some primitve melts seem to be the results of fluid-induced melts.
10

Atomic-scale Structural Characterizations of Functional Epitaxial Thin Films

Zhu, Yuanyuan 16 December 2013 (has links)
A precise understanding of the fundamental correlation between synthesis, microstructure and physical properties is of vital importance towards rational design of improved functional epitaxial thin films. With the presence of heterogeneous interface and associated inhomogeneous lattice strain, film microstructure becomes sensitive to subtle interfacial perturbations and hence may exhibit intriguing physical properties. Control of the epitaxial film functionality requires accurate knowledge of the actual film chemistry, interfacial defects and associated strain field. This dissertation reports in-depth microstructural characterization of the intrinsic chemical inhomogeneity in selected epitaxial thin films including superconducting Fe1+yTe1-xSex/SrTiO3(STO) heterogeneous systems, the flux-pinning defects at both of conversional YBa2Cu3O7-δ (YBCO)/substrate lateral interfaces and vertical interfaces of YBCO&BaSnO3(BSO) nanocomposite films, and the misfit dislocation core configurations of STO/MgO and MgO/STO heterostructures pair, using the state-of-the-art aberration-corrected scanning transmission electron microscopy (CS-corrected STEM) in combination with geometric phase analysis (GPA). For the first time, the local atomic arrangement of Te and Se as well as interstitial Fe(2) has been clearly revealed in superconducting Fe1+yTe1-xSex/STO epitaxial films. We found that the film growth atmosphere can greatly affect the film stoichiometry, the homogeneity of Se/Te ordering and thus the overall film superconductivity. YBCO/substrate interface mismatch and YBCO&BSO vertical interface contact have been explored through substrate selection and doping-concentration variation. We observed a diverse nature of intrinsic defects in different YBCO/substrate heterosystems; thermal stable defects capable of maintaining individual strain field have been found effective in flux-pinning. Along the vertical heterointerface of YBCO/BSO, misfit dislocations were found throughout the film thickness. It adds another dimension to the flux-pinning landscape design. Four basic misfit dislocation core configurations of a STO/MgO heterosystem have been identified, and found strongly dependent on the actual interface disordering such as substrate atomic-height steps and interdiffussion. To precisely quantify the heterointerface lattice strain, we first conducted systematic investigations on the accuracy of STEM-based GPA. Follow our protocol, 1 pm accuracy has been proven in the STEM fast-scan direction with a spatial resolution less than 1 nm. The effectiveness and reliability of this optimized GPA strain profile were demonstrated in both applications of a relaxed STO/MgO and a partially strained LaAlO3/STO heterointerfaces, respectively.

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