Physical Sciences and Mathematics Commons^™

All-Acrylic Multigraft Copolymers: Synthesis And Structure-Property Relationship For Producing Next Generation Thermoplastic Elastomers, Andrew Brown Goodwin

Doctoral Dissertations

Polymer architecture and the advancement of molecular design using anionic and other controlled polymerization methods continues to be of significant research interest because of the tunable approach it provides, which can impact numerous applications ranging from thermoplastics to drug delivery systems. Among the numerous branched structures currently investigated, comb and graft copolymers continue to provide tailored materials which exhibit superior mechanical properties when compared to their di- and triblock linear counterparts. More specifically, the incorporation of two or more monomers into graft and multigraft constructions where the side chains are composed of a plastic (high T_g [glass transition temperature]) …

The Effect Of Composition And Architecture On Polymer Behavior In Homopolymer Blends And Inter-Filament Bonding In 3d Printed Models, Edward Roy Duranty

Doctoral Dissertations

This dissertation presents work that increases our understanding of the effects of composition and architecture on copolymer structure and dynamics and how they affect material diffusion between filaments in a 3D printed model. Copolymers are polymer chains made up of at least two different monomers. The ordering and arrangement of the two monomer species within a copolymer can have drastic effects on the behavior and properties of the copolymer.

The first chapter of this dissertation examines how the copolymer composition affects the structure and dynamics of the chain in a homopolymer blend. This study used a modified Monte Carlo BFM …

Batched Linear Algebra Problems On Gpu Accelerators, Tingxing Dong

Doctoral Dissertations

The emergence of multicore and heterogeneous architectures requires many linear algebra algorithms to be redesigned to take advantage of the accelerators, such as GPUs. A particularly challenging class of problems, arising in numerous applications, involves the use of linear algebra operations on many small-sized matrices. The size of these matrices is usually the same, up to a few hundred. The number of them can be thousands, even millions.

Compared to large matrix problems with more data parallel computation that are well suited on GPUs, the challenges of small matrix problems lie in the low computing intensity, the large sequential operation …

Bacterial Diversity And Function Within An Epigenic Cave System And Implications For Other Limestone Cave Systems, Kathleen Merritt Brannen-Donnelly

Doctoral Dissertations

There are approximately 48,000 known cave systems in the United States of America, with caves formed in carbonate karst terrains being the most common. Epigenic systems develop from the downward flow of meteoric water through carbonate bedrock and the solutional enlargement of interconnected subsurface conduits. Despite carbonate karst aquifers being globally extensive and important drinking water sources, microbial diversity and function are poorly understood compared to other Earth environments. After several decades of research, studies have shown that microorganisms in caves affect water quality, rates of carbonate dissolution and precipitation, and ecosystem nutrition through organic matter cycling. However, limited prior …

Spontaneously Generated Inhomogeneous Phases Via Holography, Kübra Yeter Aydeniz

Doctoral Dissertations

We discuss a holographic model consisting of a U(1) gauge field and a scalar field coupled to a charged AdS (anti-de Sitter) black hole under a spatially homogeneous chemical potential. By turning on a higher-derivative interaction term between the U(1) gauge field and the scalar field, a spatially dependent profile of the scalar field is generated spontaneously. We calculate the critical temperature at which the transition to the inhomogeneous phase occurs for various values of the parameters of the system. We solve the equations of motion below the critical temperature, and show that the dual gauge theory on the boundary …

Algorithm-Based Fault Tolerance For Two-Sided Dense Matrix Factorizations, Yulu Jia

Doctoral Dissertations

The mean time between failure (MTBF) of large supercomputers is decreasing, and future exascale computers are expected to have a MTBF of around 30 minutes. Therefore, it is urgent to prepare important algorithms for future machines with such a short MTBF. Eigenvalue problems (EVP) and singular value problems (SVP) are common in engineering and scientific research. Solving EVP and SVP numerically involves two-sided matrix factorizations: the Hessenberg reduction, the tridiagonal reduction, and the bidiagonal reduction. These three factorizations are computation intensive, and have long running times. They are prone to suffer from computer failures.

We designed algorithm-based fault tolerant (ABFT) …

Investigating Advection Control In Competitive Pde Systems And Environmental Transmission In Johne's Disease Ode Models, Kokum Rekha De Silva

Doctoral Dissertations

We extend the work on optimal control of advective direction in a reaction-diffusion population model to a system representing two competing populations. We investigate the choice of movement direction to benefit a population. First, the advective direction in one of the populations in a competition model is the control. Next, we extend the work by taking the advective directions of both populations as controls. In both these cases the objective is to maximize a weighted combination of the two populations while minimizing the cost involved in the species movement. Mathematical analysis is completed to derive the optimality system and numerical …

Designing Novel 1,2,3- And 1,2,4-Triazoles For Coordination Complexes And Frameworks, Brianna Celiese Hughes

Doctoral Dissertations

Triazoles are a versatile ligand that forms a variety of compounds and extended materials within the field of coordination chemistry. The reaction of triazoles with metals leads to the synthesis of homoleptic complexes, coordination polymers and metal-organic frameworks (MOFs). These triazole compounds and materials have been employed for a variety of applications in chemistry ranging from nanomaterials to anion recognition.

The synthesis of tris(1,2,3-triazolyl)borate completed and complemented the initial research began by Trofimenko in 1966. This ligand was used in metal reactions and found to form both homoleptic complexes and coordination polymers. The connectivity of the tris(1,2,3-triazolyl)borate varied dependent on …

Versatile Three-Phase Power Electronics Converter Based Real-Time Load Emulators, Jing Wang

Doctoral Dissertations

This dissertation includes the methodology, implementation, validation, as well as real-time modeling of a load emulator for a reconfigurable grid emulation platform of hardware test-bed (HTB). This test-bed was proposed by Center of Ultra-wide-area Resilient Electric Energy Transmission Network (CURENT) at the University of Tennessee, at Knoxville in 2011, to address the transmission level system challenges posed by contemporary fast changing energy technologies.

Detailed HTB introduction, including design concept, fundamental units and hardware construction, is elaborated. In the development, current controlled three-phase power electronics converter based emulator unit is adopted to create desired power system loading conditions.

In the application, …

Engineering Photosystem I Complexes For Use In Bio-Hybrid Dye-Sensitized Solar Cells, Richard Franklin Simmerman

Doctoral Dissertations

Increasing global population, growing per capita energy needs, diminishing fossil fuels, and climate change collectively will require new, innovative, and sustainable alternatives to meet the world’s growing energy needs. One of the most promising yet simple approaches are dye-sensitized solar cells (DSSCs). However, conventional DSSCs use semi-conductor anodes sensitized with complex synthetic organometallic dyes. Most dyes utilize ruthenium complexes to absorb photons, which upon excitation, inject electrons into the anode, while holes migrate to the cathode via liquid electrolyte. However, these dyes are expensive, difficult to make, and resource-limited. This dissertation focuses on replacing synthetic dyes with the naturally occurring, …

Measurements Of Methyl Radicals And Temperatures By Using Coherent Microwave Rayleigh Scattering From Resonance Enhanced Multiphoton Ionization, Yue Wu

Doctoral Dissertations

This thesis includes two main parts: (I) The CH₃[methyl radical] detection in methane/air flames and (II) the rotational temperature measurement of O₂[molecular oxygen] in a variety of environments by using coherent microwave Rayleigh scattering from resonance enhanced multiphoton ionization (Radar REMPI).

In first the part, from Chapter I to Chapter III, the methyl radical detection and quantitative measurements have been conducted in hydrocarbon flame with one-dimensional and two-dimensional spatial-resolved concentration distribution. Due to the proximity of the argon resonance state (4+1 REMPI by 332.5 nm) with the CH₃ state (2+1 REMPI by 333.6 nm), in …

Examination Of Banded Iron Formation Through Petrographic, Geochemical And Iron Isotope Analyses, Melissa Margaret Hage

Doctoral Dissertations

Banded iron formation (BIF) has the potential to preserve geochemical signatures critical to interpretation of early Earth because: (1) it is found within the Precambrian when fundamental changes in Earth’s physical, biological and chemical evolution occurred, and (2) it may preserve a record of the depositional environment. Rare earth elements (REE) are useful for investigating BIF because they have characteristic features. One goal of this study was to evaluate the calculation of certain REE ratios to determine if the calculation affected the interpretation. It was concluded that the method for calculating certain ratios may affect the interpretation of redox conditions …

Developing An Optimal Model For Infant Home Visitation, Isaac Atuahene

Doctoral Dissertations

The United States, Great Britain, Denmark, Canada and many other countries have accepted home visitation (HV) as a promising strategy for interventions for infants after births and for their mothers. Prior HV studies have focused on theoretical foundations, evaluations of programs, cost/benefit analysis and cost estimation by using hospital/payer/insurance data to prove its effectiveness and high cost. As governments and private organizations continue to fund HVs, it is an opportune time to develop and formulate operations research (OR) models of HV coverage, quality and cost so they might be used in program implementation as done for adult home healthcare (HHC) …

Evaluating The Effects Of Standardized Patient Care Pathways On Clinical Outcomes, Anna V. Romanova

Doctoral Dissertations

The main focus of this study is to create a standardized approach to evaluating the impact of the patient care pathways across all major disease categories and key outcome measures in a hospital setting when randomized clinical trials are not feasible. Toward this goal I identify statistical methods, control factors, and adjustments that can correct for potential confounding in observational studies. I investigate the efficiency of existing bias correction methods under varying conditions of imbalanced samples through a Monte Carlo simulation. The simulation results are then utilized in a case study for one of the largest primary diagnosis areas, chronic …

Evidence Of Late Quaternary Fires From Charcoal And Siliceous Aggregates In Lake Sediments In The Eastern U.S.A., Joanne P. Ballard

Doctoral Dissertations

The late-glacial transition to the Holocene, 15,000–11,600 cal yr BP, is an enigmatic period of dynamic global changes and a major extinction event in North America. Fire is an agent of disturbance that transforms the environment physically and chemically, and affects plant community composition. To improve understanding of the linkages between fire, vegetation, and climate over the late glacial and Holocene in the eastern U.S., I analyzed lake-sediment cores for charcoal and indicators of wood ash, and compared results to existing pollen records. A new microscopic charcoal record from Anderson Pond, Tennessee revealed high fire activity from 23,000–15,000 cal yr …

On The Spin Evolution Of Isolated Pulsars, Oliver Quinn Hamil

Doctoral Dissertations

Neutron stars are the remnants of supernova explosions, and harbor the densest matter found in the universe. Because of their extreme physical characteristics, neutron stars make superb laboratories from which to study the nature of matter under conditions of extreme density that are not reproducible on Earth. The understanding of QCD matter is of fundamental importance to modern physics, and neutron stars provide a means of probing into the cold, dense region of the QCD phase diagram.

Isolated pulsars are rotating neutron stars that emit beams of electromagnetic radiation into space which appear like lighthouses to observers on Earth. Observations …

Timing And Extent Of The Little Ice Age Glacial Advances In The Eastern Tian Shan, China, Yanan Li

Doctoral Dissertations

Located in Central Asia, one of the most continental regions on Earth, the Tian Shan’s glaciers contribute critical fresh water to populated areas in the lowland. These glaciers are sensitive to climate change, and knowledge of contemporary glaciers and their changes in the past is of critical importance for sustainable development in this region. Constraining glacial fluctuations in recent centuries will fill a gap in numerical constraints on glacial history and paleoclimate information, and provide important evidence on the spatio-temporal changes of the climate systems in the Tian Shan. This doctoral dissertation investigates the timing and extent of Little Ice …

Nanoscaled Cellulose And Its Carbonaceous Material: Application And Local Structure Investigation, Yujie Meng

Doctoral Dissertations

In this dissertation, cellulose nanocrystals three-dimensional morphology, size distribution, and the crystal structure were statistically and quantitatively investigated. Lognormal distribution was identified as the most likely for cellulose nanocrystals’ size distribution. Height and width dimensions were shown to decrease toward the ends from the midpoint of individual CNCs, implying a spindle-like shape. XRD analysis of crystallite size accompanied with TEM and AFM measurements revealed that the cross-sectional dimensions of individual switchgrass CNC were either rectangular or elliptical shape, with an approximately 3~5 nm [nanometer] lateral element length range. A sponge-like carbon aerogel from microfibril cellulose with high porosity, ultra-low density, …

Synthesis, Characterization And Evaluation Of Lectin-Binding Properties Of 1,2-Cis-Glycosides, Bo Meng

Doctoral Dissertations

This dissertation presents a state-of-the-art research of 1,2-cis-glycosides, including synthetic methodology development, combinatorial total synthesis of galactoside ligands, construction of glycomicroarray surfaces, and quantitative evaluation of carbohydrate–lectin binding properties.

In Chapter 1, as a general introduction, various strategies that have been developed for the stereoselective construction of 1,2-cis-O-glycosidic bond are reviewed. 1,2-cis-O-Glycoside structural units are ubiquitous in nature, and they are extensively involved in numerous biological activities. The systematic identification and evaluation of the roles of carbohydrates usually relies on practical synthetic approaches to afford pure carbohydrates in considerable quantities. …

Vapor Synthesis And Thermal Evolution Of Supportless, Metal Nanotubes And Application As Electrocatalysts, Robert William Atkinson

Doctoral Dissertations

One of the major limitations of proton exchange membrane fuel cells (PEMFCs) is the high cost and poor durability of the currently preferred catalyst design, small Pt nanoparticles supported on high surface area carbon (Pt/C). Unsupported, high-aspect ratio nanostructured catalysts, or extended surface catalysts, are a promising paradigm as electrocatalysts for a number of electrochemical reactions. These extended surface catalysts generally exhibit higher specific activities compared to their carbon-supported nanoparticle counterparts that have been ascribed to their unique electronic, surface and structural properties. Extended surface catalysts frequently maintain enhanced durability over supported catalysts during fuel cell operation because they are …

Ion Transport In Polymer Electrolytes, Fei Fan

Doctoral Dissertations

Batteries with superior performance will advance many technologies, such as the field of energy storage and electrochemical devices. Traditional lithium ion batteries based on liquid electrolytes have intrinsic problems such as leaking, dendrite growth, and those problems are associated with fire or even explosion hazard. Extensive efforts have been devoted into the development of solid polymer electrolytes (SPEs), which would not only reduce the size and weight of the batteries, but also solve safety related issues. However, none of current dry SPEs have reached the desired conductivity of 10^-3 [0.001] S/cm at ambient temperature. The ion conductivity is controlled …

The Effects Of Realistic Nuclear Kinetics, Dimensionality, And Resolution On Detonations In Low-Density Type Ia Supernovae Environments, Thomas L. Papatheodore

Doctoral Dissertations

Type Ia supernovae are most likely thermonuclear explosions of carbon/oxygen white dwarves in binary stellar systems. These events contribute to the chemical and dynamical evolution of their host galaxies and are essential to our understanding of the evolution of our universe through their use as cosmological distance indicators. Nearly all of the currently favored explosion scenarios for these supernovae involve detonations. However, modeling astrophysical detonations can be complicated by numerical effects related to grid resolution. In addition, the fidelity of the reaction network chosen to evolve the nuclear burning can alter the time and length scales over which the burning …

Experimental And Ab Initio Computational Study Of Azobenzene And Several Of Its Derivatives, Mohammadreza Rezaee

Doctoral Dissertations

In this dissertation we studied azobenzene and seven of its derivatives experimentally in addition to comprehensive ab initio computational investigation. Gas phase ion chemistry studies sre a rich and important area of chemical physics. We used an energy resolved collision induced dissociation technique to study the chemical bonding of these molecule negative or positive ions. We studied the fragment ions which we have detected in the mass spectrum computationally as well. Doing so we experimentally measured the bond dissociation energies and compared them with those resulting from the quantum chemistry computations. We also performed other experiments such as Raman spectroscopy, …

Nucleosynthesis In Self-Consistent Core-Collapse Supernova Models Using Multidimensional Chimera Simulations, James Austin Harris

Doctoral Dissertations

Observations of nuclear abundances in core-collapse supernova (CCSN) ejecta, highlighted by γ-ray [gamma-ray] observations of the ⁴⁴Ti [titanium-44] spatial distribution in the nearby supernova remnants Cassiopeia A and SN 1987A, allow nucleosynthesis calculations to place powerful constraints on conditions deep in the interiors of supernovae and their progenitor stars. This ability to probe where direct observations cannot makes such calculations an invaluable tool for understanding the CCSN mechanism. Unfortunately, despite knowing for two decades that supernovae are intrinsically multi-dimensional events, discussions of CCSN nucleosynthesis have been predominantly based on spherically symmetric (1D) models, which employ a contrived energy source …

Investigations Into The Tectonics Of Uranian And Saturnian Icy Satellites, Chloe Brett Beddingfield

Doctoral Dissertations

This dissertation reports a range of analyses of tectonic structures on various icy satellites and the implications of these analyses for each satellite’s geologic history. On Miranda, I tested the hypothesis that faults of the Arden Corona boundary and the 340º [degree] Chasma are listric in geometry. A listric fault geometry implies the presence of a subsurface detachment, which likely marked Miranda’s brittle-ductile transition (BDT) at the time of faulting. Results support the hypothesis for the Arden Corona boundary, although not for the 340˚ [degree] Chasma. Using the Arden Corona fault system geometry, the BDT depth, thermal gradient, and heat …

Insights Into Planetesimal Evolution: Petrological Investigations Of Regolithic Howardites And Carbonaceous Chondrite Impact Melts, Nicole Gabriel Lunning

Doctoral Dissertations

Asteroidal meteorites are the only available geologic samples from the early part of our solar system’s history. These meteorites contain evidence regarding how the earliest protoplanetary bodies formed and evolved. I use petrological and geochemical techniques to investigate the evolution of these early planetesimals, focusing on two meteorite types: Howardites, which are brecciated samples of a differentiated parent body (thought to be the asteroid 4 Vesta), and CV chondrites, which are primitive chondrites that have not undergone differentiation on their parent body.

Quantitative petrological analysis and characterization of paired regolithic (solar wind-rich) howardites indicate that this large sample of the …

Polymer Additives Effects On Structure And Dynamics, Adam Eugene Imel

Doctoral Dissertations

This dissertation presents work that expands the understanding of the effect additives have on the structure and dynamics of a polymer matrix. Polymer additives are molecules, nanoparticles or fibers that are added to a polymer to modify the properties of the host polymer. Due to the vast amount of additives available, our studies were limited to C₆₀ (C60), soft polystyrene nanoparticles, and poly(ethylene oxide).

The first part of this project examined the influence that C₆₀ nanoparticles have on the assembly of polyacrylonitrile using small angle and wide-angle x-ray scattering techniques and viscometry. The addition of C₆₀ (C60) …

Daq Software Contributions, Absolute Scale Energy Calibration And Background Evaluation For The Nova Experiment At Fermilab, Eric Flumerfelt

Doctoral Dissertations

The NOvA (NuMI Off-axis ν_e [nu_e] Appearance) Experiment is a long-baseline accelerator neutrino experiment currently in its second year of operations. NOvA uses the Neutrinos from the Main Injector (NuMI) beam at Fermilab, and there are two main off-axis detectors: a Near Detector at Fermilab and a Far Detector 810 km away at Ash River, MN. The work reported herein is in support of the NOvA Experiment, through contributions to the development of data acquisition software, providing an accurate, absolute-scale energy calibration for electromagnetic showers in NOvA detector elements, crucial to the primary electron neutrino search, and through an …

Advances In High-Throughput Analysis: Automated Radiochemical Separations And Nanopillar Based Separations And Field Enhanced Spectroscopy, Jennifer Jeanne Charlton

Doctoral Dissertations

Often the need to analyze a large number of samples coincide with critical time consternates. At such times, the implementation of high-throughput technologies is paramount. In this work we explore some viable pathways for high-throughput analysis and develop advancements in novel forms of detection of materials that are vital in the environmental, biological as well as national security arenas. Through the use of new protocols with high sensitivity and specificity as well as simplified chemical processing and sample preparation we aim to allow for improved throughput, fieldable detection, and rapid data acquisition of extensive sample sets. The methods developed in …

Crystal Growth And Physical Property Characterization Of Complex Perovskite Oxides, Ling Li

Doctoral Dissertations

Bulk EuTiO₃ [europium titanate], a quantum paraelectric antiferromagnet, is shown to exhibit multiferroic behavior in strained thin film form, which highlights the spin-phonon coupling in this system. We have investigated the structural, elastic, magnetic, thermal and transport properties of single crystals of EuTiO₃ as well as doped system EuTi_1-xB_xO₃ (B = Zr, Nb) [Zr and Nb doped europium titanate] utilizing various experimental techniques and theoretical calculations.

The cubic to tetragonal structural transition in pure EuTiO₃ is characterized by a pronounced step-like softening of the elastic moduli near 288 K [kelvin], which resembles …