Engineering Commons^™

Novel Fission Track Detection For Identification And Characterization Of Special Nuclear Materials, Jonathan Allen Gill

Doctoral Dissertations

Fission track detection and analysis is used primarily in nuclear safeguards to identify special nuclear material. Identification of isotopic ratios is a crucial step in understanding the intended use of nuclear material and the nature of the materials production cycle. Unfortunately, this methodology uses etchable track detectors that require significant expertise and intensive labor to process.

This study developed a novel method using lithium fluoride (LiF) as a fluorescing nuclear track detector to conduct fission track analysis for isotopic prediction of uranium enrichment. Individual latent tracks produced by fission products were observed in LiF for the first time. These tracks …

Computational Studies Of Structure–Function Relationships Of Supported And Unsupported Metal Nanoclusters, Hongbo Shi

Doctoral Dissertations

Fuel cells have been demonstrated to be promising power generation devices to address the current global energy and environmental challenges. One of the many barriers to commercialization is the cost of precious catalysts needed to achieve sufficient power output. Platinum-based materials play an important role as electrocatalysts in energy conversion technologies. In order to improve catalytic efficiency and facilitate rational design and development of new catalysts, structure–function relationships that underpin catalytic activity must be understood at a fundamental level. First, we present a systematic analysis of CO adsorption on Pt nanoclusters in the 0.2-1.5 nm size range with the aim …

Correlating Long-Term Lithium Ion Battery Performance With Solid Electrolyte Interphase (Sei) Layer Properties, Seong Jin An

Doctoral Dissertations

This study was conducted to understand effects of some of key factors (i.e., anode surface properties, formation cycling conditions, and electrolyte conditions) on solid electrolyte interphase (SEI) formation in lithium ion batteries (LIBs) and the battery cycle life. The SEI layer passivates electrode surfaces and prevents electron transfer and electrolyte diffusion through it while allowing lithium ion diffusion, which is essential for stable reversible capacities. It also influences initial capacity loss, self-discharge, cycle life, rate capability and safety. Thus, SEI layer formation and electrochemical stability are primary topics in LIB development. This research involves experiments and discussions on key factors …

Excitations Of Quasi-Particles In Nanostructured Systems, Jingxuan Ge

Doctoral Dissertations

The excitation of quasiparticles, like the investigated excitons and plasmons here, are the optically most prominent responses of materials. In nanostructured system, the sample quality is crucial for quantitative investigations of these optical excitations. We used electron beam evaporation, nano-second laser dewetting, and electron metalorganic chemical vapor deposition techniques to prepare well-defined and “clean” transmission electron microscopy (TEM) samples. Electron energy-loss microscopy (EELS) performed in STEM mode was employed to investigate the structural and electro-optical properties. Quantifit software was used to analyze the EELS spectra quantitatively in terms of inelastic scattering probability, energy and lifetime.

We found that the ferroplasmon …

Surface Energy In Bond-Counting Models On Bravais And Non-Bravais Lattices, Tim Ryan Krumwiede

Doctoral Dissertations

Continuum models in computational material science require the choice of a surface energy function, based on properties of the material of interest. This work shows how to use atomistic bond-counting models and crystal geometry to inform this choice. We will examine some of the difficulties that arise in the comparison between these models due to differing types of truncation. New crystal geometry methods are required when considering materials with non-Bravais lattice structure, resulting in a multi-valued surface energy. These methods will then be presented in the context of the two-dimensional material graphene in a way that correctly predicts its equilibrium …

Strategies For Controlling Bulk Heterojunction Morphology, Zach Daniel Seibers

Doctoral Dissertations

Organic photovoltaic devices have been extensively studied as a means to produce sustainable energy. However, the performance of organic-photovoltaic (OPV) devices is dependent upon a number of factors including the morphology of the active layer, device architecture, and processing conditions. Recent research has indicated that fullerenes in the bulk heterojunction are entropically driven to the silicon and air interfaces upon crystallization of P3HT, which occurs during thermal annealing. The first chapter of this research focuses on investigating the structure and function of end-tethered poly(3-hexylthiophene) chains to a transparent electrode as an anode buffer layer. Neutron reactivity reveals that these P3HT …

Temperature Dependent Mechanical Behavior Of Solid Acids, Ryan Scott Ginder

Doctoral Dissertations

Existing literature data on the creep behavior of superprotonic solid acids, which is important for their use in fuel cell applications, is scant and unreliable. Steady state creep behavior for the model material system cesium hydrogen sulfate (CHS) is probed using nanoindentation and corroborated using uniaxial compression testing. To facilitate nanoindentation creep result interpretation, a radial flow model of power law indentation creep is developed. This model is compared with the related model from Bower, et. al. for several pre-existing literature datasets showing that the nonlinear, steady state creep law underpinning both appears valid for power law indentation creep.

Characterizing Local Order And Physical Properties Of Rare Earth Complex Oxides, Thomas Jacob Shamblin

Doctoral Dissertations

With more than 500 compositions, materials possessing the pyrochlore structure have a myriad of technological applications and physical phenomena. Three of the most noteworthy properties are the structure’s ability to resist amorphization making it a possible host matrix for spent nuclear fuel, its exotic magnetic properties arising from geometric frustration, and fast ionic conductivity for solid-oxide fuel cell applications. This work focuses on these three aspects of the pyrochlore’s many potential uses. Structural characterization revealed that pyrochlore-type oxides have a tendency to disorder from a high symmetry cubic structure to a lower symmetry orthorhombic arrangement in response to a variety …

Lignin-Based Li-Ion Anode Materials Synthesized From Low-Cost Renewable Resources, Nicholas William Mcnutt

Doctoral Dissertations

In today’s world, the demand for novel methods of energy storage is increasing rapidly, particularly with the rise of portable electronic devices, electric vehicles, and the personal consumption and storage of solar energy. While other technologies have arguably improved at a rate that is exponential in accordance with Moore’s law, battery technology has lagged behind largely due to the difficulty in devising new electric storage systems that are simultaneously high performing, inexpensive, and safe.

In order to tackle these challenges, novel Li-ion battery anodes have been developed at Oak Ridge National Laboratory that are made from lignin, a low-cost, renewable …

Enzyme Stabilization In Hierarchical Biocatalytic Food Packaging And Processing Materials, Dana Erin Wong

Doctoral Dissertations

The partnership of biocatalysts and solid support materials provides many opportunities for bioactive packaging and bioprocessing aids beneficial to the agricultural and food industries. Biocatalysis, or reactions modulated by enzymes, allows bioactive materials to assist in bringing a substrate to product. Enzymes are proteins which catalyze reactions by lowering the activation energy required to drive the production of a desired product. Enzymes are commonly utilized in food processing as catalysts with specificity in order to enhance product quality through the production of beneficial food components, and to break down undesirable components that may be harmful or may decrease product quality. …

Pulsed-Laser Induced Dewetting Of Metallic Nanostructures, Christopher Aidan Hartnett

Doctoral Dissertations

This dissertation explores the fluid dynamics of nano and microscale liquid metal filaments, with an emphasis on experimentally investigating the influences and causes of filament breakup and metallic nanostructure formation. Understanding and manipulating the liquid state properties of materials, especially metals, have the potential to advance the development of future technology, particularly nanoscale technology. The combination of top-down nanofabrication techniques with bottom-up, intrinsic self-assembly mechanisms are a powerful fusion, because it permits new and unusual nanostructures to be created, whilst revealing interesting nanoscale physics.

In fluid dynamics, wetting and dewetting is the spontaneous natural process that occurs when a liquid …

Rational Development Of Solid Lewis Acid Catalysts For Biomass Conversion, Chun-Chih Chang

Doctoral Dissertations

The need for sustainable production of everyday materials in addition to declining reserves of petroleum-based feedstocks has motivated research into the production of renewable aromatic chemicals from biomass. We have proposed a multistep pathway to produce renewable p-xylene from lignocellulosic biomass using heterogeneous catalysts. The pathway includes formation of glucose by saccharification of cellulose, isomerization of glucose into fructose, dehydration/hydrogenolysis for production of 2,5-dimethylfuran (DMF), and final step for producing p-xylene from reacting DMF with ethylene. Lewis acid zeolite catalysts (e.g. Sn-BEA, a tin containing molecular sieve with zeolite BEA structure) exhibited critical roles in the pathway because …

Development And Improvement Of Cerium Activated Gadolinium Gallium Aluminum Garnets Scintillators For Radiation Detectors By Codoping, Fang Meng

Doctoral Dissertations

Ce doped Gd3Ga3Al2O12 [gadolinium gallium aluminium oxides] is considered as a promising candidate for the next generation Positron Emission Tomography material due to its high light yield in theory. This dissertation is focused on studying the Gd3Ga3Al2O12:Ce crystals by codoping, aiming to improve the light yield and decay time experimentally and understand the underlying mechanism.

The work starts from prescreening appropriate codopants for Gd3Ga3Al2O12:Ce crystals. A cost-effective method is developed to predict the performance of the single crystals by characterizing the radioluminescence intensity and photoluminescence decay of the small polycrystalline pellets. This method is demonstrated by showing that the results …

The Experimental And Theoretical Study Of Plasticity Improvement Of Zr-Based Bulk Metallic Glasses, Xie Xie

Doctoral Dissertations

Bulk metallic glasses (BMGs) attract more and more attention for their great mechanical properties, such as high strength, good corrosion resistance, etc. However, even though extensive studies have been made, their deformation mechanisms are still not well understood. Their limited plasticity and catastrophic failure after yielding severely prevent their broad applications in industry and daily life. To improve their plasticity, some work has been done through miscellaneous processing methods, e.g., thin-film coating, surface treatment, and ion irradiation. The present work also focuses on the plastic deformation of BMGs, and is expected to deepen the fundamental understanding of the deformation mechanisms …

Engineering The “Pluripotency” Of Zr-Based Bulk Metallic Glasses As Biomedical Materials, Lu Huang

Doctoral Dissertations

Bulk metallic glasses (BMGs) are a family of novel alloys with amorphous microstructures. The combination of their excellent mechanical properties, good chemical stability, high thermal formability, and general biocompatibility has brought up new opportunities for biomaterials. Research in this dissertation was focused on exploring multiple biomedical functionalities of Zr-based BMGs over a wide spectrum, combining materials and biological characterizations, through experimental and computational approaches. Four distinct yet interconnected tasks were endeavored, involving inflammation, hard-tissue implant, soft-tissue prosthesis, and pathogenic infection.

The inflammation that can be potentially triggered by Zr-based BMGs was investigated using macrophages. Lower level or comparable macrophage activations …

Energy Selective Neutron Imaging For The Characterization Of Polycrystalline Materials, Robin Woracek

Doctoral Dissertations

This multipart dissertation focuses on the development and evaluation of advanced methods for material testing and characterization using neutron diffraction and imaging techniques. A major focus is on exploiting diffraction contrast in energy selective neutron imaging (often referred to as Bragg edge imaging) for strain and phase mapping of crystalline materials. The dissertation also evaluates the use of neutron diffraction to study the effect of multi-axial loading, in particular the role of applying directly shear strains from the application of torsion. A portable tension-torsion-tomography loading system has been developed for in-situ measurements and integrated at major user facilities around the …

Single Fiber Mechanical Properties Using Nano-Tensile Testing And Carbon Fiber Structure-Property Relationship, Matthew Erich Kant

Doctoral Dissertations

Single carbon fibers are studied using a nano-tensile testing system. This system has unprecedented load and displacement resolution, nN and nm respectively, and the ability to perform dynamic testing for storage and loss modulus during quasi-static tensile extension. Furthermore, improved fiber mounting and alignment procedures coupled with the precision of the nano-tensile testing system assist in unprecedented resolution in single fiber mechanical testing for axial modulus and strength. Hence, using these unique capabilities, the moduli and their statistical distribution of many high performance carbon fibers are reported here. From this, a simplified single parameter model describing the strain dependent modulus …

Monte Carlo Modeling Of Ion Beam Induced Secondary Electrons, Uk Huh

Doctoral Dissertations

Modeling ion beam induced secondary electron (iSE) production within matter for simulating ion beam induced images has been studied. When the complex nature of ion beam interactions with matter is account for, a detailed quantitative model of the ion interactions with matter, Monte Carlo simulation will be the best choice to be able to compute and predict iSE yields faster and more accurately. In order to build Monte Carlo simulation software incorporated with a reliable database of stopping power tables, for wide variety of range of materials, there have been numerous attempts to experimentally measure ion stopping power tables and …

Ab Initio Studies Of Proton Transport In Proton Exchange Membranes, Jeffrey Keith Clark

Doctoral Dissertations

A molecular-level understanding of the factors that contribute to transport properties of proton exchange membranes (PEMs) for fuel cell applications is needed to aid in the development of superior membrane materials. Ab initio electronic structure calculations were undertaken on various PEM ionomer fragments to explore the effects of local hydration, side chain connectivity, protogenic group separation, and specific side chain chemistry on proton dissociation and transfer at low hydration. Cooperative interactions between both intra- and inter-molecular acidic groups and hydrogen bond connectivity were found to enhance proton dissociation at very low degrees of hydration. The energetics associated with proton transfer …

Synthesis And Characterization Of Magnetic Nanowires Prepared By Chemical Vapor Deposition, Siwei Tang

Doctoral Dissertations

Various metal silicide and germanide magnetic nanowires were synthesized using a home-built CVD [chemical vapor deposition] system. The morphology, composition, and magnetic properties of the nanowires were studied and correlated with growth parameters such as temperature, pressure, time, and source-substrate distance.

One of the compositions targeted for synthesis was MnSi [manganese silicide]. In bulk, this material orders helimagnetically at T_c [curie temperature] = 30K, with a helical pitch of about 20 nm. After extensive study, we learned that the thickness of the silicon dioxide layer on the substrate is a critical parameter for the growth of MnSi nanowires. An …

An Investigation Of Energy Migration In Rare Earth Oxyorthosilicate Scintillation Materials, Harold Edward Rothfuss

Doctoral Dissertations

In most scintillator applications, the energy resolution is an important scintillation property and is related to other scintillator properties. In order to observe how these properties relate to the energy resolution, a simulation was created to quantify most of these characteristics for a LSO:Ce scintillator. These results were validated with good agreement to experimental results. From the separable components of the simulation, an understanding of the contributions to the energy resolution broadening was developed. A thought to improve the energy resolution by improving the energy migration was tested by observing and modifying the scintillation kinetics of YSO:Ce. The scintillation kinetics …

Plasmonics Resonance Enhanced Active Photothermal Effects In Aluminum Nanoenergetics For Propulsion Applications, Jacques Abboud

Doctoral Dissertations

In this dissertation, aluminum nanoparticles (Al NPs) are shown capable to on-demand enhance and control the local photothermal energy deposition, both spatially and temporally, via active photothermal effects initiated by the localized surface plasmon resonance (LSPR) phenomenon, and amplified by the Al exothermal oxidation reactions. Experiments in dry and wet environments along with computational modeling of the photothermal process are very desirable for gaining fundamental understanding, ignition optimization and parameter exploration.

Combined phenomena of motion and ignition of Al NPs are explored first in this study. Both resulting from exposing a pile of the nanoenergetics in hand to a single …

Structural And Kinetic Studies Of Structure I Gas Hydrates Via Low Temperature X-Ray Diffraction And High Resolution Neutron Diffraction, Susan Michelle Everett

Doctoral Dissertations

Gas hydrates are materials of interest as sources for clean energy, carbon sequestration, greenhouse gas mitigation, and gas storage. This body of work presents two projects that each separately explore one aspect of the potential found in gas hydrates. Chapter 1 tackles the structural changes found to occur over the CO₂ [carbon dioxide] - CH₄ [methane] hydrate solid solution. The application here pertains to the sequestration of CO₂ in natural gas hydrates found in permafrost regions and ocean floors. As CO₂ is injected into the hydrate reservoir, CH₄ is released and recovered for energy use. …

Understanding Size Effects In Small Scale Deformation: A Statistical Perspective, Sudharshan Phani Pardhasaradhi

Doctoral Dissertations

Recent experimental observations of micro-compression / tension tests indicate that as the size of test specimen decreases the yield strength increases. This raises a fundamental question: Why is smaller stronger? Is there a fundamental relationship between the size of a specimen and its intrinsic strength? This simple question pushes the limit of the current understanding of the physical mechanisms underlying material deformation, especially at small scales. In order to explain the experimental observations of the strength of small specimens containing a limited number of dislocations, a simple statistical model is developed. Two different types of randomness are introduced, viz., randomness …

Structure And Dynamics Of High Temperature Superconductors, Jennifer Lynn Niedziela

Doctoral Dissertations

High temperature superconductivity in iron based compounds has presented a series of complex problems to condensed matter physics since being discovered in 2008. The stalwart basis of condensed matter physics is the “strength in numbers" aspect of crystalline periodicity. Perfect crystalline periodicity has made possible the reduction of the questions of structural and electronic properties to single dimensions, increasing the tractability of these problems. Nevertheless, modern complex materials stretch these assumptions to their limits, and it is at this point where our work starts. Using neutron and x-ray scattering, we have conducted a series of studies on the structural disorder …

Magnetic And Elastic Properties Of Magnetostrictive Tb6fe1-Xcoxbi2, Michael Richard Koehler

Doctoral Dissertations

The Tb6[6 sub]Fe1-x[1-x sub]Cox[x sub]Bi2[2 sub] (x = 0, 0.125, 0.25, and 0.375) family of compounds has been synthesized and investigated for magnetostrictive behavior using capacitance dilatometry. These measurements have been complemented by measurements of the elastic moduli using Resonant Ultrasound Spectroscopy (RUS), magnetization measurements (with a vibrating sample magnetometer (VSM)), as well as powder X-ray diffraction (XRD) and powder neutron diffraction measurements and heat capacity measurements.

Each of the compounds studied shows little magnetostriction at the Curie temperature but shows pronounced amounts of magnetostriction at temperatures below 100 K. Magnetostriction values of up to ~980 ppm have been discovered …

Computational And Experimental Study Of Structure-Property Relationships In Nial Precipitate-Strengthened Ferritic Superalloys, Shenyan Huang

Doctoral Dissertations

Ferritic superalloys strengthened by coherent ordered NiAl B2-type precipitates are promising candidates for ultra-supercritical steam-turbine applications, due to their superior resistance to creep, coarsening, oxidation, and steam corrosion as compared to Cr ferritic steels at high temperatures. Combined computational and experimental tools have been employed to investigate the interrelationships among the composition, microstructure, and mechanical behavior, and provide insight into deformation micromechanisms at elevated temperatures.

Self and impurity diffusivities in a body-centered-cubic (bcc) iron are calculated using first-principles methods. Calculated self and impurity diffusivities compare favorably with experimental measurements in both ferromagnetic and paramagnetic states of bcc Fe. The calculated …

Study Of Mechanical Behaviors And Structures Of Bulk Metallic Glasses With High-Energy Synchrotron X-Ray Diffraction, Feng Jiang

Doctoral Dissertations

This dissertation addresses two critical issues in the mechanical behaviors and structures of bulk-metallic glasses (BMGs): (1) the effect of composition, fabrication method, and pretreatment of plastic deformation on mechanical properties and structures of BMGs; (2) the mechanical response and structural evolution of BMGs in the elastic and plastic region.

(Cu₅₀Zr₅₀)₉₄Al₆ and (Cu₅₀Zr₅₀)₉₂Al₈ amorphous alloys were used to study the effect of composition on mechanical properties and structures of BMGs. The (Cu₅₀Zr₅₀)₉₄Al₆ alloy exhibits lower yield stress and Young’s …

Acoustic Emission And X-Ray Diffraction Techniques For The In Situ Study Of Electrochemical Energy Storage Materials, Kevin James Rhodes

Doctoral Dissertations

Current demands on lithium ion battery (LIB) technology include high capacity retention over a life time of many charge and discharge cycles. Maximizing battery longevity is still a major challenge partly due to electrode degradation as a function of repeated cycling. The intercalation of lithium ions into an active material causes the development of stress and strain in active electrode materials which can result in fracture and shifting that can in turn lead to capacity fade and eventual cell failure. The processes leading to active material degradation in cycling LIBs has been studied using a combination of acoustic emission (AE) …

Discovery And Development Of Rare Earth Activated Binary Metal Halide Scintillators For Next Generation Radiation Detectors, Kan Yang

Doctoral Dissertations

This work focuses on discovery and development of novel binary halide scintillation materials for radiation detection applications. A complete laboratory for raw materials handling, ampoule preparation, material rapid synthesis screening, single crystal growth, sample cutting, polishing and packaging of hygroscopic halide scintillation materials has been established. Ce³⁺ and Eu²⁺ activated scintillators in three binary systems: Alkali Halide – Rare Earth Halide (AX–REX₃), Alkali Halide – Alkaline Earth Halide (AX–AEX₂) and Alkalin Earth Halide – Rare Earth Halide (AEX₂–REX₃) were systematically studied. Candidates for new scintillation materials in the three systems …