Physical Sciences and Mathematics Commons^™

Dust Control Examination Using Computational Fluid Dynamics Modeling And Laboratory Testing Of Vortecone And Impingement Screen Filters, Ashish R. Kumar

Theses and Dissertations--Mining Engineering

Heavy industries, such as mining, generate dust in quantities that present an occupational health hazard. Prolonged exposure to the respirable dust has been found to result in many irreversible occupational ailments in thousands of miners. In underground mining applications, a variety of scrubbing systems are used to remove dust near the zones of generation. However, the wire-mesh type fibrous screens in the flooded-bed dust scrubbers used on continuous miners, are prone to clogging due to the accumulation of dust particles. This clogging results in a reduced capture efficiency and a higher exposure to the personnel. This research establishes the Vortecone, …

Improved Standard Error Estimation For Maintaining The Validities Of Inference In Small-Sample Cluster Randomized Trials And Longitudinal Studies, Whitney Ford Tanner

Theses and Dissertations--Epidemiology and Biostatistics

Data arising from Cluster Randomized Trials (CRTs) and longitudinal studies are correlated and generalized estimating equations (GEE) are a popular analysis method for correlated data. Previous research has shown that analyses using GEE could result in liberal inference due to the use of the empirical sandwich covariance matrix estimator, which can yield negatively biased standard error estimates when the number of clusters or subjects is not large. Many techniques have been presented to correct this negative bias; However, use of these corrections can still result in biased standard error estimates and thus test sizes that are not consistently at their …

Synthesis, And Structural, Electrochemical, And Magnetic Property Characterization Of Promising Electrode Materials For Lithium-Ion Batteries And Sodium-Ion Batteries, Ruixin Han

Theses and Dissertations--Chemistry

Iron oxides, have been widely studied as promising anode materials in lithium-ion batteries (LIBs) for their high capacity (≈ 1000 mA h g^-1 for Fe₂O₃ and Fe₃O_4,), non-toxicity, and low cost. In this work, β-FeOOH has been evaluated within a LIB half-cell showing an excellent capacity of ≈ 1500 mA h g^-1 , superior to Fe₂O₃ or Fe₃O_4. Reaction mechanism has been proposed with the assistance of X-ray photoelectron spectroscopy (XPS). Various magnetic properties have been suggested for β-FeOOH such as superparamagnetism, antiferromagnetism and complex …

Catalytic Conversion Of Monosaccharides Into 5-(Hydroxymethyl)Furfural In Ionic Liquids Using Aluminum Complexes Bearing Bidentate (Aminomethyl)Phenolate Ligands, Daudi Sayialel Saang'onyo

Theses and Dissertations--Chemistry

Currently, the major sources of fuel, energy, and chemicals are nonrenewable fossil resources such as petroleum, natural gas, and coal. Additionally, petroleum is used for the production of most transportation fuels and for the production of about 95% of organic chemicals. However, the production and use of non-renewable fossil fuels are unsustainable. For economic and environmental sustainability, there is a need to search for new and/or renewable resources and technologies for energy, fuels, and chemicals production that have the potential of effectively substituting fossil resources. In this context, lignocellulosic biomass is one of the candidates that meet these requirements due …

New Approaches To Cyclopentadienyl-Fused Thiophene Complexes Of Iron And Synthesis And Characterization Of Carbonic Anhydrase Active-Site Mimics For Co2 Hydration, Deepshikha Gupta

Theses and Dissertations--Chemistry

Polyheterocycles such as polythiophene and its derivatives comprise an important class of conducting polymers used for electronic applications. They have been of great interest for use in electronic materials due to their increased environmental stability as well as novel electronic properties in their polymer states. We have been interested in exploring the electronic properties of organometallic analogues of the low-band-gap polymer poly(benzo[3,4-c]thiophene) (polyisothianaphthene) that incorporates η⁵-cyclopenta[c]thienyl monomers such as ferroceno[c]thiophene. First chapter of this dissertation involved synthetic attempts to ferroceno[c]thiophene. Exploring a shorter synthetic route to starting material, 1,2-di(hydroxymethyl)ferrocene was …

Oxidation Of Β-O-4 Lignin Model Compounds And Application To Lignin Linkage Degradation Facilitated By Mechanochemical Treatment And Two-Step Oxidative Depolymerization, Soledad G. Yao

Theses and Dissertations--Chemistry

The oxidation of lignin model compounds was studied in conventional solvents in parallel with oxidations in ionic liquid solvents. Catalyst systems were investigated in ionic liquid solvents to determine how reaction rates and the selectivity for benzylic carbon oxidation were affected. Oxidation rates were often lower in ionic liquids than in conventional solvents ‒ as indicated by lower conversion in a standard reaction time ‒ likely due, at least in part, to the higher viscosity of ionic liquids. Mechano chemical treatment of Indulin AT kraft lignin by ball milling with KOH and toluene produced significant carbonyl functionality, among other changes. …

Carbon Quantum Dots: Bridging The Gap Between Chemical Structure And Material Properties, Timothy J. Pillar-Little Jr.

Theses and Dissertations--Chemistry

Carbon quantum dots (CQDs) are the latest generation of carbon nanomaterials in applications where fullerenes, carbon nanotubes, and graphene are abundantly used. With several attractive properties such as tunable optical property, edge-functionalization, and defect-rich chemical structure, CQDs have the potential to revolutionize optoelectronics, electro- and photocatalysis, and biomedical applications. Chemical modifications through the addition of heteroatoms, chemical reduction, and surface passivation are found to alter the band gap, spectral position, and emission pathways of CQDs. Despite extensive studies, fundamental understanding of structure-property relationship remains unclear due to the inhomogeneity in chemical structure and a complex emission mechanism for CQDs.

This …

Spectroscopy And Formation Of Lanthanum-Hydrocarbon Complexes, Wenjin Cao

Theses and Dissertations--Chemistry

Lanthanum-mediated bond activation reactions of small hydrocarbon molecules, including alkenes, alkynes, and alkadienes, were carried out in a laser vaporization metal cluster beam source. Time-of-flight mass spectrometry and mass-analyzed threshold ionization (MATI) spectroscopy, in combination with quantum chemical and multi-dimensional Franck-Condon factor calculations, were utilized to identify the reaction products and investigate their geometries, electronic structures, and formation mechanisms.

La-hydrocarbon association was only observed in the reaction of La with isoprene. C-H bond activation was observed in all reactions, hydrogen elimination was observed as the prominent reaction for the alkenes (2-butene, isobutene, 1-pentene, and 2-pentene), alkynes (1-butyne, 2-butyne, and 1-pentyne), …

Spherulitic Growth And Thermodynamic Equilibrium In Multicomponent Elastic Films Under Solvent-Vapor Annealing, Ding Zhao

Theses and Dissertations--Mathematics

In this dissertation, we will study solvent-vapor induced spherulitic growth in multicomponent thin films modeled as prestressed elastic solids. The interface between the crystalline phase and the amorphous phase will be treated as an evolving thermodynamic system and no diffusion of any component will be considered.

The dissertation is divided into three parts. In Part I we will determine necessary conditions of thermodynamic equilibrium between the two solid phases, the inter- face, and the vapor. In Part II we will derive the thermodynamic driving force for spherulitic growth in multicomponent elastic thin films. In Part III we will investigate the …

A Representation Theorem For Material Tensors Of Textured Thin Sheets With Weak Planar Anisotropy, Yucong Sang

Theses and Dissertations--Mathematics

Herein we consider material tensors that pertain to thin sheets or thin films, which we model as two-dimensional objects. We assume that the thin sheet in question carries a crystallographic texture characterized by an orientation distribution function defined on the rotation group SO(3), which is almost transversely-isotropic about the sheet normal so that mechanical and physical properties of the thin sheet have weak planar-anisotropy. We present a procedure by which a special orthonormal basis can be determined in each tensor subspace invariant under the action of the orthogonal group O(2). We call members of such special bases irreducible basis tensors …

Recurrent Neural Networks And Their Applications To Rna Secondary Structure Inference, Devin Willmott

Theses and Dissertations--Mathematics

Recurrent neural networks (RNNs) are state of the art sequential machine learning tools, but have difficulty learning sequences with long-range dependencies due to the exponential growth or decay of gradients backpropagated through the RNN. Some methods overcome this problem by modifying the standard RNN architecure to force the recurrent weight matrix W to remain orthogonal throughout training. The first half of this thesis presents a novel orthogonal RNN architecture that enforces orthogonality of W by parametrizing with a skew-symmetric matrix via the Cayley transform. We present rules for backpropagation through the Cayley transform, show how to deal with the Cayley …

Magneto-Optical Properties Of Thin Permalloy Films: A Study Of The Magneto-Optical Generation Of Light Carrying Angular Momentum, Patrick D. Montgomery

Theses and Dissertations--Electrical and Computer Engineering

Magneto-optical materials such as permalloy can be used to create artificial spin- ice (ASI) lattices with antiferromagnetic ordering. Magneto-optical materials used to create diffraction lattices are known to exhibit magnetic scattering at the half- order Bragg peak while in the ground state. The significant drawbacks of studying the magneto-optical generation of OAM using x-rays are cost, time, and access to proper equipment. In this work, it is shown that the possibility of studying OAM and magneto-optical materials in the spectrum of visible light at or around 2 eV is viable. Using spectroscopic ellipsometry it is possible to detect a change …

A Combinatorial Miscellany: Antipodes, Parking Cars, And Descent Set Powers, Alexander Thomas Happ

Theses and Dissertations--Mathematics

In this dissertation we first introduce an extension of the notion of parking functions to cars of different sizes. We prove a product formula for the number of such sequences and provide a refinement using a multi-parameter extension of the Abel--Rothe polynomial. Next, we study the incidence Hopf algebra on the noncrossing partition lattice. We demonstrate a bijection between the terms in the canceled chain decomposition of its antipode and noncrossing hypertrees. Thirdly, we analyze the sum of the 𝑟th powers of the descent set statistic on permutations and how many small prime factors occur in these numbers. These results …

Polytopes Associated To Graph Laplacians, Marie Meyer

Theses and Dissertations--Mathematics

Graphs provide interesting ways to generate families of lattice polytopes. In particular, one can use matrices encoding the information of a finite graph to define vertices of a polytope. This dissertation initiates the study of the Laplacian simplex, P_G, obtained from a finite graph G by taking the convex hull of the columns of the Laplacian matrix for G. The Laplacian simplex is extended through the use of a parallel construction with a finite digraph D to obtain the Laplacian polytope, P_D.

Basic properties of both families of simplices, P_G and P …

Bounded Point Derivations On Certain Function Spaces, Stephen Deterding

Theses and Dissertations--Mathematics

Let 𝑋 be a compact subset of the complex plane and denote by 𝑅^𝑝(𝑋) the closure of rational functions with poles off 𝑋 in the 𝐿^𝑝(𝑋) norm. We show that if a point 𝑥₀ admits a bounded point derivation on 𝑅^𝑝(𝑋) for 𝑝 > 2, then there is an approximate derivative at 𝑥₀. We also prove a similar result for higher order bounded point derivations. This extends a result of Wang, which was proven for 𝑅(𝑋), the uniform closure of rational functions with poles off 𝑋. In addition, we show that if …

The Effect Of The Total Maximum Daily Loads(Tmdl) Management Implementation Plan On Total Phosphorus(Tp), Jaejeong Ma April

MPA/MPP/MPFM Capstone Projects

The Ministry of Environment of the Republic of Korea has been making efforts to improve water quality and the health of the aquatic ecosystems of the inland waters. Establishing water quality standards for point sources and permissible wastewater emission standards to achieve the target environmental standard were part of the efforts. Nevertheless, water quality indexes such as Biochemical Oxygen Demand(BOD) and Chemical Oxygen Demand(COD) has not improved significantly. Also, harmful cyanobacteria blooms have frequently been occurred, which, in particular, has brought people to lose faith in the environmental policy and has created anxiety about drinking water. As the solution, the …

Structural, Transport, And Topological Properties Induced At Complex-Oxide Hetero-Interfaces, Justin K. Thompson

Theses and Dissertations--Physics and Astronomy

Complex-oxides have seen an enormous amount of attention in the realm of Condensed Matter Physics and Materials Science/Engineering over the last several decades. Their ability to host a wide variety of novel physical properties has even caused them to be exploited commercially as dielectric, metallic and magnetic materials. Indeed, since the discovery of high temperature superconductivity in the “Cuprates” in the late 1980’s there has been an explosion of activity involving complex-oxides. Further, as the experimental techniques and equipment for fabricating thin films and heterostructures of these materials has improved over the last several decades, the search for new and …

Surficial Geologic Map Of The Patriot 7.5-Minute Quadrangle, Kentucky, Maxwell L. Hammond Iii, Antonia E. Bottoms, Steven L. Martin

Contract Reports--KGS

The Patriot 7.5-minute quadrangle is located in Boone, Gallatin, and Grant Counties of northern Kentucky in the Outer Bluegrass physiographic province (McFarlan, 1943). Broad to narrow ridges, steep hillsides, and the Ohio River Valley characterize the topography of the quadrangle. The Ohio River has been made navigable by a series of high-level dams, and the Markland Locks and Dam controls the river level in this area (Ray, 1974). The bedrock geology, originally mapped by Swadley (1969), consists, from oldest to youngest, of the Point Pleasant Formation, the Kope Formation, the Fairview Formation, the Bellevue Tongue of the Grant Lake Limestone, …

High-Order Integral Equation Methods For Quasi-Magnetostatic And Corrosion-Related Field Analysis With Maritime Applications, Robert Pfeiffer

Theses and Dissertations--Electrical and Computer Engineering

This dissertation presents techniques for high-order simulation of electromagnetic fields, particularly for problems involving ships with ferromagnetic hulls and active corrosion-protection systems.

A set of numerically constrained hexahedral basis functions for volume integral equation discretization is presented in a method-of-moments context. Test simulations demonstrate the accuracy achievable with these functions as well as the improvement brought about in system conditioning when compared to other basis sets.

A general method for converting between a locally-corrected Nyström discretization of an integral equation and a method-of-moments discretization is presented next. Several problems involving conducting and magnetic-conducting materials are solved to verify the accuracy …

Self-Image Multimedia Technologies For Feedforward Observational Learning, Nkiruka M. A. Uzuegbunam

Theses and Dissertations--Electrical and Computer Engineering

This dissertation investigates the development and use of self-images in augmented reality systems for learning and learning-based activities. This work focuses on self- modeling, a particular form of learning, actively employed in various settings for therapy or teaching. In particular, this work aims to develop novel multimedia systems to support the display and rendering of augmented self-images. It aims to use interactivity (via games) as a means of obtaining imagery for use in creating augmented self-images. Two multimedia systems are developed, discussed and analyzed. The proposed systems are validated in terms of their technical innovation and their clinical efficacy in …

Efficacy Of Herbivore Exclusion On Planted Tree Seedling Vitality On A Reclaimed Surface Mine In Eastern Kentucky, Zachary J. Hackworth

Theses and Dissertations--Forestry and Natural Resources

Conventional Appalachian surface-mine reclamation techniques repress natural forest regeneration, and tree plantings are often necessary for reforestation. Reclaimed Appalachian surface mines harbor a suite of mammal herbivores that forage on recently planted seedlings. Anecdotal reports across Appalachia have implicated herbivory in the hindrance and failure of reforestation efforts, yet empirical evaluation of herbivory impacts on planted seedling vitality in this region remains relatively uninitiated. First growing-season survival, height growth, and mammal herbivory damage of black locust (Robinia pseudoacacia L.), shortleaf pine (Pinus echinata Mill.), and white oak (Quercus alba L.) are presented in response to varying intensities …

Performance Of The Grout Curtain At The Kentucky River Lock And Dam No. 8, Robert C. Hatton

Theses and Dissertations--Civil Engineering

Karst bedrock conditions and deterioration of the lock and dam structures have resulted in significant leakage through, underneath, and around Lock and Dam No. 8 on the Kentucky River. During severe droughts, the water surface in Pool No. 8 has been observed to drop below the crest of the dam, resulting in water supply shortages and water quality issues for surrounding communities reliant on the pool. Presently, the primary purpose of Lock and Dam No. 8 is water supply. Pool No. 8 is currently where the cities of Nicholasville (Jessamine County, KY) and Lancaster (Garrard County, KY) draw their water. …

Study Of The Effect Of Steric Bulk Of Side Chains On The Properties Of Conjugated Polymers, Bei Zhang

Theses and Dissertations--Chemistry

Donor-acceptor conjugated polymers opened a new era for conjugated polymer research due to the abundant selection and combination of different conjugated units. This class of polymers function as semiconductor materials with potential application in plastic consumer electronics. The frontier molecular orbital energies of the polymers are generally determined by the selection of donor and acceptor units in the backbone structure, and their substituents. The side chains attached to the backbone not only affect the solubility of the materials, but also their self-assembly and morphological characteristics, which indirectly govern optoelectronic properties. It is important therefore to consider backbone architectures and the …

Applications Of Cell-Derived Vesicles: From Single Molecule Studies To Drug Delivery, Faruk H. Moonschi

Theses and Dissertations--Chemistry

Single molecule studies can provide information of biological molecules which otherwise is lost in ensemble studies. A wide variety of fluorescence-based techniques are utilized for single molecule studies. While these tools have been widely applied for imaging soluble proteins, single molecule studies of transmembrane proteins are much more complicated. A primary reason for this is that, unlike membrane proteins, soluble proteins can be easily isolated from the cellular environment. One approach to isolate membrane proteins into single molecule level involves a very low label expression of the protein in cells. However, cells generate background fluorescence leading to a very low …

Enhanced Analysis Of Lignin Dehydrogenation Oligomers Via Mass Spectrometry, Amber Suzanne Bowman

Theses and Dissertations--Chemistry

Effective analytical techniques need to be developed to characterize the products of lignin degradation experiments to be able to generate renewable products from lignin. Mass spectrometry is an valuable analytical approach for lignin characterizaion, but it is hindered by lignin’s poor ionization efficiency, especially in the positive ion mode. In this work, we attempt to improve lignin’s ionization by utilizing electrospray and laser desorption mass spectrometry coupled with the addition of cations and chemical derivatives. We confronted the ionization problem from both a top-down and bottom-up analytical approach by analyzing synthesized monomers, dimers, and polymers along with natural lignin extracts …

Heterogeneous Catalytic Deoxygenation Of Lipids To Fuel-Like Hydrocarbons Over Improved Bimetallic Nickel Catalysts, Ryan Andrew Loe

Theses and Dissertations--Chemistry

Diminishing petroleum reserves and environmental considerations have strengthened the demand for developing renewable fuel technologies. One alternative is deoxygenating plant oils, animal fats, and waste lipid streams to fuel-like hydrocarbons. These fuels offer a drop-in replacement to petroleum products while potentially becoming carbon neutral, satisfying both fuel and environmental concerns. This fuel is obtained through catalytic deoxygenation via either hydrodeoxygenation (HDO) or decarboxylation/ decarbonylation (deCO_x). HDO requires problematic sulfided catalysts and extreme hydrogen pressures to convert lipids to fuel-like hydrocarbons. Therefore, this work focuses on the deCO_x pathway, where hydrogen is not required for deoxygenation to take …

Design And Synthesis Of Functional Organic Materials, Anthony Joseph Petty Ii

Theses and Dissertations--Chemistry

Control of solid state ordering in conjugated small molecules is paramount to the continued development and implementation of organic materials in electronic devices. However, there exists no reliable method on which to predicatively determine how a change to the molecular structure will impact the solid-state packing. As such, the molecule must be synthesized before its solid-state packing can be definitively evaluated. However, once the packing structure of a material is known there exist both qualitative structure- function relationships derived from the literature, as well as quantitative computational methods that can be employed to suggest if a material will perform well …

Protein Suppression Of Flavin Semiquinone As A Mechanistically Important Control Of Reactivity: A Study Comparing Flavoenzymes Which Differ In Redox Properties, Substrates, And Ability To Bifurcate Electrons, John Patrick Hoben

Theses and Dissertations--Chemistry

A growing number of flavoprotein systems have been observed to bifurcate pairs of electrons. Flavin-based electron bifurcation (FBEB) results in products with greater reducing power than that of the reactants with less reducing power. Highly reducing electrons at low reduction midpoint potential are required for life processes of both aerobic and anaerobic metabolic processes. For electron bifurcation to function, the semiquinone (SQ) redox intermediate needs to be destabilized in the protein to suppress its ability to trap electrons. This dissertation examines SQ suppression across a number of flavin systems for the purpose of better understanding the nature of SQ suppression …

Aqueous Photochemistry Of 2-Oxocarboxylic Acids, Alexis Eugene

Theses and Dissertations--Chemistry

Atmospheric aerosols affect climate change by altering the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. While the formation of secondary organic aerosol (SOA) from gas phase precursors is relatively well understood, it does not account for the abundance of SOA observed during field measurements. Recently it has become apparent that in-aerosol aqueous chemical reactions likely provide some of the missing sources of SOA production, and many studies of aqueous phase processes are underway.

This work explores the fates of the simplest 2-oxocarboxylic acids, glyoxylic acid (GA) and pyruvic acid (PA), …

Can Increasing Grass-Fungal Endophyte Symbiotic Diversity Enhance Grassland Ecosystem Functioning?, Mahtaab Bagherzadeh

Theses and Dissertations--Plant and Soil Sciences

The relationship between biodiversity and ecosystem functioning is important in maintaining agroecosystem sustainability. Plant-microbe symbioses, such as exists between the grass tall fescue (Schedonorus arundinaceum) and the asexual fungal endophyte Epichloë coenophiala, can be utilized to enhance agroecosystem functions, such as herbivore resistance. “Novel” E. coenophiala strains that vary in the production of mammal- and insect-toxic compounds have been identified, inserted into tall fescue cultivars, and are planted in pastures globally. Novel fungal endophyte-tall fescue associations may have divergent ecosystem function effects. This study assessed effects of different fescue-endophyte symbiotic combinations on pasture ecosystem function, including aboveground …