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Understanding The Influence Of Non-Covalent Interactions And Nanoparticle Geometries In Carbon Based Polymer Nanocomposites, Bradley Carroll Miller

Doctoral Dissertations

Low-loading polymer nanocomposites (PNC) are an area of great interest in polymer science. As nanoparticles (NP) are typically expensive in comparison to matrix materials; the low loading regime makes the most efficient use of materials, and represents the optimum for realizing cost effective, high-performance PNCs. However, formulating effective low-loading composites is not without challenges. In addition to the typical requirement of good dispersion for efficient translation of NP properties to the bulk, low-loading composites can sometimes exhibit anomalous (non-classical) dynamics, and unpredictable properties. It is within this context that this thesis aims to examine the effects of NP geometry and …

Rare Earth Production And Characterization Studies, Jake Anson Stewart

Doctoral Dissertations

The rare earths include elements Sc, Y, and La through Lu are important in many modern technologies. With the exception of Sc and Ce the rare earths are all have similar chemical behaviors with the preferred oxidation state in aqueous solution being +3. Currently, industrial purification of the rare earths is completed by counter current solvent extraction (CCSX). In most CCSX separations, Y extracts with Ho making their separation difficult. However, in a few systems Y exhibits an itinerant behavior. Carboxylic acids of varying sizes and substitutions were investigated in a study of Y itinerant behavior. It was found when …

Interface And Morphology Engineering In Solution-Processed Electronic And Optoelectronic Devices, Sanjib Das

Doctoral Dissertations

The first part of this dissertation focuses on interface and morphology engineering in polymer- and small molecule-based organic solar cells. High-performance devices were fabricated, and the device performance was correlated with nanoscale structures using various electrical, spectroscopic and microscopic characterization techniques, providing guidelines for high-efficiency cell design.

The second part focuses on perovskite solar cells (PSCs), an emerging photovoltaic technology with skyrocketing rise in power conversion efficiency (PCE) and currently showing comparable PCEs with those of existing thin film photovoltaic technologies such as CIGS and CdTe. Fabrication of large-area PSCs without compromising reproducibility and device PCE requires formation of dense, …

Solution And Surface Properties Of Architecturally- And Compositionally-Complex Block Copolymers And Their Binary Mixtures, Jesse Lawrence Davis

Doctoral Dissertations

The spontaneous generation of complex structures from polymeric building blocks provides a simple yet effective route to create useful soft matter structures having potential application in a variety of nanotechnologies. The topology, chemical structure, block composition, and sequence of the constituent building blocks of polymers are tunable through synthetic chemistry. This tunability offers attractive opportunities to generate complex, yet well-defined structures with control over the geometry, packing symmetry, and microdomain structure. This thesis work involves the study of the self-assembly behaviors of architecturally complex amphiphilic block copolymers (ABCs). ABCs are composed of two or more chemically distinct blocks that are …

Novel Thermoplastic Elastomers Based On Benzofulvene: Synthesis And Mechanical Properties, Weiyu Wang

Doctoral Dissertations

Thermoplastic elastomers (TPEs) are of great importance both academically and technologically. Currently TPEs are the predominated form of styrene-diene copolymers. However, these styrenic TPEs have serious limitations in applications, especially at higher temperature, because of their low upper service temperature (UST). The work described in this dissertation aimed to developing thermoplastic elastomers with a higher UST and lower cost.

In order to develop TPEs with a higher UST, we employed benzofulvene, an anionically polymerizable monomer in hydrocarbon solvent at room temperature, as the glassy block and copolymerized it with isoprene to prepare polybenzofulvene-polyisoprene-polybenzofulvene (FIF) triblock copolymers. Among all triblock copolymers …

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 …

Chemical Investigations Of Diabetes Mellitus, Malaria, And Castrate-Resistant Prostate Cancer, Maggie Sparks Lookadoo

Masters Theses

This work studies a variety of molecules and the systems they are involved in to further understand disease and treatment of diabetes mellitus, malaria, and castrate resistant prostate cancer. The first system studied, diabetes mellitus, involves synthesis of 5 different steroidal compounds, while the other two systems, malaria and castrate-resistant prostate cancer, apply mass spectrometric-based untargeted metabolomics to study both known metabolites and unknown spectral features.

Diabetes mellitus is a result of the dysfunction and death of islet beta cells caused by the transcription of pro-inflammatory cytokines resulting in reduced insulin secretion and uncontrollable blood glucose levels. Glucocorticoids can reduce …

Rapid Dissolution For Destructive Assay Of Nuclear Melt Glass, Jonathan Allen Gill

Masters Theses

This study evaluates four methods for dissolving complex glassy debris resulting from nuclear detonations. The samples of interest simulate the glassy debris generated from a nuclear detonation’s fireball coming in contact with solid masses. Each method attempts to achieve dissolution through different approaches involving either acid digestion, alkaline digestion, or molten salt fusion. Two of the four methods were modified to retain all elements of the debris or surrogate debris. This retention is critical to the proportional relationships used in identifying fuel types and designs of nuclear weapons. Analysis is conducted with an inductively coupled time of flight mass spectrometer …

Preparation And Characterization Of Thermodynamically Controlled Polymer Nanocomposites, Jiadi Hou

Masters Theses

The mechanical and physical properties of polymeric materials can be greatly improved by adding nanoscale additives. To mediate the dispersion of nanoparticles in polymers, it is often necessary to modify their surfaces to prevent aggregation. While polymer nanocomposites system consisting of homopolymer-grafted nanoparticles are well understood, copolymer-functionalized nanoparticles are less well understood but provide additional ways to alter dispersion through the use of chemically different comonomers. In this thesis, polystyrene nanocomposites blended with copolymer-grafted nanoparticles were prepared and studied. The particular comonomers used were methyl methacrylate and cyclohexyl methacrylate, which provides miscibility with polystyrene. Polymers with varying comonomer ratios were …

Siloxane And Silane-Functionalized Polynorbornenes As Membranes For Passive Carbon Dioxide Separation, Eunice Koheun Hong

Masters Theses

In 2012, carbon dioxide (CO₂) [carbon dioxide] accounted for approximately 82% [percent] of all U.S greenhouse gas emissions.¹ These excessive CO2 levels have been attributed to climate changes that have a range of negative effects on human health and welfare.1 In an effort to decrease these emissions, polymeric membranes consisting of silane- and siloxane-functionalized norbornene units have been targeted as a potential solution for the passive separation of CO2 from other non-greenhouse gases. These substituted norbornene-based polymers were synthesized via vinyl-addition polymerization. Through a series of catalyst trials, commercially available palladium and nickel catalysts were compared along …

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 …

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 …

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 …

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 …

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) …

Real-Time Spectroscopic Analysis Of Microalgal Adaptation To Changing Environmental Conditions, Robert Ked Byrd

Masters Theses

Increases in anthropogenic pollution are causing many environmental problems; understanding their impact on the environment has become an important issue. Industrialization and the burning of fossil fuels have caused increased levels of carbon dioxide to enter the atmosphere, which is contributing to global warming and ocean acidification. Agricultural runoff has caused levels of inorganic nitrogen and phosphorus to rise, where they have been noted to cause harmful algal blooms. Marine ecosystems have been particularly affected as both of these forms of pollution accumulate in bodies of water. Microalgae are important organisms in these ecosystems because they sequester these pollutants and …

Biodegradable Nano-Hybrid Polymer Composite Networks For Regulating Cellular Behavior, Charles Henley Sprague

Masters Theses

Photo-crosslinkable polymeric biomaterials have emerged in the field of biomedical research to promote tissue regeneration. For example, scaffolds that can be crosslinked and hardened in situ have been known to make suitable implant alternatives. Since injectable and photo-crosslinkable biomaterials offer the advantage of being minimally invasive, they have emerged to compete with autografts, a current highly invasive method to repair diseased tissue. A series of novel photo-crosslinkable, injectable, and biodegradable nano-hybrid polymers consisting of poly(ε-caprolactone fumarate) (PCLF) and polyhedral oligomeric silsesquioxane (POSS) has been synthesized in our laboratory via polycondensation. To engineer the material properties of the nano-hybrid networks, varied …

Correlating Morphology To Performance In Conjugated Polymer Nanocomposite Thin Films, Siddharth Pradhan

Masters Theses

The morphology and performance of thin films that consist of conjugated polymers and nanoparticles are investigated in this thesis. In the first system, the morphology of the nanocomposite that consists of low band gap alternating copolymers with a methano-fullerene are determined by neutron scattering and correlated to their photovoltaic performance as polymer solar cells. These results show that the conjugated alternating copolymers have high miscibility relative to other conjugated polymers. The analysis of the scattering data shows that the morphology of the conjugated polymer-fullerene bulk heterojunction can be described as the formation of aggregates on two length scales. Important parameters …

Comparison Of Activation Enthalpies For Aminoglycoside Modification Reactions, Brittany Sterling Soto

Masters Theses

At highly elevated temperatures, many biological reactions can proceed spontaneously from the ground state to the transition state. However, due to the long half-life of these reactions, catalysts are required to catalyze these reactions at modern day temperatures by lowering the activation energy. Wolfenden et al. has previously shown that catalysts enhance the rate of the reaction by reducing the enthalpy of activation. Therefore, the activation energies have been determined for three aminoglycoside modifying enzymes, APH(3’)-IIIa, AAC(3)-IIIb, and AAC(3)-VIa, to determine whether these three enzymes distinguish between the two classes of aminoglycoside antibiotics by reducing the enthalpy of activation during …

Microfluidic Syntheses Of Pet Radiotracers Via Fluorodenitration, Thomas Madison Moore

Doctoral Dissertations

This research study is focused on the syntheses of radiotracers for use in positron emission tomography [PET] via fluorodenitration and fluorodehalogenation under microfluidic conditions. Methodology has been developed for radiolabeling via fluorodenitration under microfluidic conditions and comparisons made to dehalogenation reactions. Developmental work was carried out on commercially available compounds containing a variety of functional groups. Subsequent production of radiotracers has been performed with precursors provided by collaborators as well as those synthesized in our laboratory.

Synthesis And Characterization Of Support-Modified Nanoparticle-Based Catalysts And Mixed Oxide Catalysts For Low Temperature Co Oxidation, Andrew Justin Binder

Doctoral Dissertations

Heterogeneous catalysts are responsible for billions of dollars of industrial output and have a profound, if often understated, effect on our everyday lives. New catalyst technologies and methods to enhance existing catalysts are essential to meeting consumer demands and overcoming environmental concerns. This dissertation focuses on the development of catalysts for low temperature carbon monoxide oxidation. CO [carbon monoxide] oxidation is often used as a probe reaction to test overall oxidation activity of a given catalyst and is an important reaction in the elimination of toxic pollutants from automotive exhaust streams. The work included here presents three new heterogeneous catalysts …

Studies Of Metalloporphyrins And Tantalum Amide Imide Compounds, Seth Carlton Hunter

Doctoral Dissertations

The focus of this dissertation is on two different subjects. The first examines the magnetic and structural properties of metalloporphyrins. In these studies, neutrons were used to probe the magnetic properties of metalloporphyrins. Insight on the structural properties of metalloporphyrins was also gained by examining the intermolecular interactions in the solid state. The second subject is the synthesis and characterization of new tantalum complexes and studies of their reactions with O₂ [dioxygen]. These complexes are potential precursors to make metal oxide and metal nitride thin films.

In the first part of this dissertation, the zero-field parameters D have been …

An Investigation Of Inorganic Compound Scattering., Karl Jay Bernstein

Doctoral Dissertations

Raman and its associated forms of spectroscopy are powerful tools that have been under-utilized. Presented within are three inorganic compounds studied with some form of Raman spectroscopy: normal Raman, hyper-Raman (HR), surface-enhanced Raman spectroscopy (SERS), surface-enhanced hyper-Raman spectroscopy (SEHRS), or resonance Raman spectroscopy (RR).

The first study involves the investigation of phosphine binding with silver metal. Phosphines find wide use in synthetic circles yet have had little study into their method of binding, unlike similar compounds comprised of sulfur. In order to understand the binding of phosphines, several tertiary phosphines, secondary phosphines and secondary phosphine oxides are examined with SERS. …

Oxygen Reduction Reaction By Copper Complex Based Electrocatalysts, Congling Zhang

Doctoral Dissertations

My research focuses on catalysis of oxygen reduction reaction (ORR) by a series of Cu(II) [copper with positive two valence] -1,2,4-triazole complex-based electrocatalysts at the cathode of PEMFC (polymer electrolyte membrane fuel cell), an efficient and environmental friendly energy conversion system compared to internal combustion engines in use today. The sluggish kinetics of ORR considerably limited the performance of PEMFCs. Understanding of ORR mechanism is important for developing affordable, active and durable ORR catalysts for such devices.

The first part of my work focused on improving the ORR performance of Cu(II)-1,2,4-triazole complex-based catalysts in an acidic environment by exploring synthesis …

The Fabrication Of Micro- And Nano- Scale Deterministic And Stochastic Pillar Arrays For Planar Separations, Teresa Byers Kirchner

Doctoral Dissertations

Planar chromatography, unlike high performance liquid chromatography (HPLC), has not experienced a significant evolution in stationary phase media since the development of the technique. This has lead HPLC to become a much more popular and robust analytical method. Main factors that contribute to improved performance of chromatographic systems include a reduction in particle size, homogeneity of the stationary phase, and an increase in velocity of the mobile phase. In general, a reduction in particle size should lead to an improvement in the performance of all chromatography systems. However, the main obstacle of improving the performance of planar chromatography systems is …

Development And Demonstration Of Critical Components Of Aluminum Based Energy Storage Devices Using The Chloroaluminate Ionic Liquids, Mengqi Zhang

Doctoral Dissertations

This dissertation considers the development of porous carbon materials as the substrates for Al deposition/dissolution in an Al based ionic liquid flow battery (ILFB) and demonstration of an Al based hybrid supercapacitor. The Aluminum chloride/ 1-ethyl-3-methylimidazolium chloride chloroaluminate ionic liquid is utilized as the electrolyte for these Al based energy storage devices. The ILFB has less capital cost than the all-vanadium redox flow battery because of the inexpensive AlCl₃. The feasibility to equip a tank of solid aluminum chloride in an ILFB system aiming to improve energy density is investigated. A critical range of temperature data (50-130 celsius …

Computational Electrodynamics And Second Hyper-Raman Scattering, Philip Dwaine Simmons Jr.

Doctoral Dissertations

Surface-enhanced second hyper-Raman spectroscopy is a type of nonlinear light scattering in which three photons are simultaneously annihilated to produce one photon whose color is slightly shifted from its third harmonic. This process, while incredibly weak, can be magnified by many orders of magnitude with the aid of plasmonic substrates. In this dissertation, three different studies are presented probing both the nature of plasmonics and nonlinear Raman scattering. In the first, nanoparticle aggregates were dosed with two isotopologues of Rhodamine 6G to determine single-molecule activity. Plasmon maps of the aggregates were then generated from electron energy-loss spectroscopy (EELS) and 3D …