Physical Sciences and Mathematics Commons^™

Ultrasound-Driven Fabrication Of Nanosized High-Entropy Materials For Heterogeneous Catalysis, Francis Uchenna Okejiri

Doctoral Dissertations

High-entropy materials (HEMs) have emerged as a new class of multi-principal-element materials with great technological prospects. As a unique class of concentrated solid-solution materials, HEMs, formed on the premise of incorporating five or more principal elements into a single crystalline phase, provide an excellent opportunity to access superior catalytic materials ‘hiding’ in the unexplored central regions of a multicomponent phase space of higher orders.

However, the fabrication of HEMs is energy-intensive, typically requiring extreme temperatures and/or pressures under which agglomeration of particles occurs with a commensurate decrease in surface area. For most catalytic applications, non-agglomerated particles with high surface areas …

Interfaces And Dynamics In Polymeric 3d Printing And Crystalline Polymer Blends, Stevenson C. Perryman

Doctoral Dissertations

This dissertation presents experimental work that provide a foundation to rationally improve fused filament fabrication (FFF) and immiscible blend compatibilization. Objects generated from additive manufacturing processes, such as FFF, have intrinsic structural weaknesses which include two project specific examples: structural anisotropy and irreversible thermal strain. Due to low adhesion between individual print layers that results in macroscopic defects, the mechanical strength of printed objects when force is applied perpendicular to the build orientation is drastically reduced. In the first dissertation chapter, we present a protocol to produce interlayer covalent bonds by depositing multi-amine additives between individual layers of a print …

Using Applied Field, Pressure, And Light To Control Magnetic States Of Materials, Amanda J. Clune

Doctoral Dissertations

Due to their low energy scales, flexible architectures, and unique exchange pathways, molecule-based multiferroics host a number of unique properties and phase transitions under external stimuli. In this dissertation, we reveal the magnetic- and pressure-driven transitions in [(CH₃)₂NH₂]Mn(HCOO)₃ and (NH₄)₂[FeCl₅(H₂O)], present a detailed investigation of these materials away from standard equilibrium phases, and develop rich two- and three-dimensional phase diagrams.

The first platform for exploring phase transitions is [(CH₃)₂NH₂]Mn(HCOO)₃. This type-I multiferroic contains Mn centers linked by …

Interdomain Route Leak Mitigation: A Pragmatic Approach, Benjamin Tyler Mcdaniel

Doctoral Dissertations

The Internet has grown to support many vital functions, but it is not administered by any central authority. Rather, the many smaller networks that make up the Internet - called Autonomous Systems (ASes) - independently manage their own distinct host address space and routing policy. Routers at the borders between ASes exchange information about how to reach remote IP prefixes with neighboring networks over the control plane with the Border Gateway Protocol (BGP). This inter-AS communication connects hosts across AS boundaries to build the illusion of one large, unified global network - the Internet. Unfortunately, BGP is a dated protocol …

Characterization Techniques And Cation Exchange Membrane For Non-Aqueous Redox Flow Battery, Kun Lou

Doctoral Dissertations

The motivation of this work comes from one of the major problems of emerging non-aqueous flow battery (NAFB) that a separator or membrane which facilitates conductivity and blocks redox species crossover does not exist. Although many aspects of principles can be mirrored from mature fuel cell and aqueous flow battery, it is found that some well-defined membrane properties in aqueous systems such as swelling, transport and interactions are different in non-aqueous solvents to some extent. However, the approach of this work does follow the way perfluorosulfonate ion exchange membrane (PFSA) facilitated development of fuel cell and aqueous flow battery in …

Stimuli-Responsive Polyelectrolytes: Thermosensitive Zwitterionic Polymers And Charged Shape-Changing Star Molecular Bottlebrushes, Evan M. Lewoczko

Doctoral Dissertations

This dissertation work investigated two classes of stimuli-responsive polyelectrolytes: thermosensitive zwitterionic poly(sulfobetaine methacrylate)s (PSBMAs) and charged shape-changing star molecular bottlebrushes (SMBs). While zwitterionic polymers are explored for numerous applications, their structure-solution behavior relationship was poorly understood. The first part of this dissertation focused on the effects of N-substituents of PSBMAs on their behavior in water. A series of PSBMAs were synthesized, with systematically changed N-substituents, including symmetric N-n-alkyl substituents of various lengths and asymmetric N-substituents comprising one methyl and either one cyclohexyl, phenyl or 2-hydroxyethyl group. The behavior of PSBMAs with symmetric N-substituents …

Fabrication Of Specialized Scintillators For Nuclear Security Applications, Cordell James Delzer

Doctoral Dissertations

Radiation detectors are important for a variety of fields including medical imaging, oil drilling, and nuclear security. Within nuclear security, they can serve a multitude of purposes whether that be imaging, localization, isotopic identification, or even just activity measurement. Even without directly seeing a nuclear material it is often able to notice their existence without a detector. Scintillators make up an important part of these detectors due to their large intrinsic efficiency, low cost, large volume, and relatively low upkeep. Due to the importance of the large number of purposes these scintillators may be used for, it can often be …

Neutron Star Structure From Electromagnetic And Gravitational Wave Observations, Mohammad Al-Mamun

Doctoral Dissertations

Neutron star (NS) research primarily relied on spectral observations before the first gravitational wave (GW) detection from the binary neutron star merger was done by the LIGO-VIRGO collaboration. The GW170817 merger event provided mass and tidal deformability Λ˜ constraints for neutron stars. This project used these constraints and associated them with the constraints made by the NS X-ray observations to construct neutron star models. Selective X-ray sources were used in this work, which showed reliable uncertainties from their previous uses. The mass-radius constraints from the electromagnetic (EM) observations were constructed from seven quiescent low-mass X-ray binaries (QLMXBs), three photospheric radius …

Extending Core-Collapse Supernova Simulations: From The Onset Of Explosion To Shock Breakout, Michael A. Sandoval

Doctoral Dissertations

A core-collapse supernova (CCSN) is the result of a massive star’s core collapsing due to the inability of electron degeneracy pressure to provide sufficient support against gravity. Currently, there is a disconnect between when most three-dimensional CCSN simulations end (seconds) and when the explosion would reach the surface of the star and become visible (hours to days). We present three-dimensional simulations of CCSNe using the FLASH code that follow the progression of the explosion to the stellar surface, starting from neutrino-radiation hydrodynamic simulations of the first seconds performed with the Chimera code. We consider a 9.6-M_⊙ zero-metallicity progenitor, starting …

Development Of Density-Functional Tight-Binding Methods For Chemical Energy Science, Quan Vuong

Doctoral Dissertations

Density-functional tight-binding (DFTB) method is an approximation to the popular first-principles density functional theory (DFT) method. Recently, DFTB has gained considerable visibility due to its inexpensive computational requirements that confer it the capability of sustaining long-timescale reactive molecular dynamics (MD) simulations while providing an explicit description of electronic structure at all time steps. This capability allows the description of bond formation and breaking processes, as well as charge polarization and charge transfer phenomena, with accuracy and transferability beyond comparable classical reactive force fields. It has thus been employed successfully in the simulation of many complex chemical processes. However, its applications …

Roughening Interfaces In Spatial Population Dynamics, Clarisa E. Castillo

Doctoral Dissertations

The spatial structure and geometry of biological systems can have a strong effect on that system’s evolutionary dynamics. In particular, spatially structured populations may invade one another, giving rise to invasion fronts that may exhibit qualitatively different evolutionary dynamics in different dimensions or geometric configurations. For examples of invasion fronts arising in nature, one might think of a thin layer of bacteria cells growing on a Petri dish, an animal species expanding into new territory, or a cancerous tumor growing into and competing with the surrounding healthy tissue. Perhaps the most well-studied class of invasion fronts in population genetics is …

A Study Of Systematic Uncertainties For A Photon-Like Low Energy Excess Search At Microboone, Gray Yarbrough

Doctoral Dissertations

The premise of this dissertation is the study of and reduction of systematic uncertainties in the MicroBooNE experiment at the Fermi National Accelerator Laboratory. MicroBooNE is a short-baseline oscillation experiment using the innovative liquid argon time projection chamber technology to study, with unprecedented detail, neutrino interactions. The primary goal of MicroBooNE is the investigation of the MiniBooNE low energy excess (LEE) of electron neutrino events, a result which raised fundamental questions on the existence of sterile neutrinos with broad implications to the field of particle physics. The principal study of this dissertation is a study of systematics as part of …

Planetary Processes Active And Ancient: Hollowing On Mercury, Ancient Crust Formation On Mars, And Identifying Mars-Analog Habitats., Michael Steven Phillips

Doctoral Dissertations

This dissertation comprises a thermophysical model that shows elemental sulfur may be involved in the potentially active processes that form enigmatic features called hollows on the Mercurian surface, a suite of remote sensing techniques that unveil anorthositic rocks in ancient martian crust, and deep learning to discover the spatial resolutions necessary to identify astrobiology targets in images of Mars analog landscapes.

On Mercury, hollows are high-reflectance, flat-floored depressions observed nearly globally. Hollows are thought to form via sublimation, or a “sublimation-like” process, but the identity of the sublimating phase is poorly constrained. To better understand which phase might be responsible …

Birds And Bioenergy: A Modeling Framework For Managed Landscapes At Multiple Spatial Scales, Jasmine Asha Kreig

Doctoral Dissertations

This dissertation examines the design and management of bioenergy landscapes at multiple spatial scales given numerous objectives. Objectives include biodiversity outcomes, biomass feedstock yields, and economic value.

Our study examined biodiversity metrics for 25 avian species in Iowa, including subsets of these species related to ecosystem services. We used our species distribution model (SDM) framework to determine the importance of predictors related to switchgrass production on species richness. We found that distance to water, mean diurnal temperature range, and herbicide application rate were the three most important predictors of biodiversity overall. We found that 76% of species responded positively to …

Collector Probe Measurements Of Sol Impurity Accumulation And The Implications Of Sol Flows On The Accumulation Amount, Shawn Zamperini

Doctoral Dissertations

A collector probe in its simplest form is a rod inserted into a plasma so that impurities are deposited onto it. These probes are then removed and analyzed to determine the deposition profile both along the length of probe and across the width of it. This dissertation covers a series of collector probes experiments and accompanying interpretive modelling all with the main goal of providing evidence for long-hypothesized near scrape-off layer (SOL) accumulation of impurities that can lead to efficient core contamination. The structure of this dissertation is as follows. A brief outline of fusion energy and why we need …

Coarse Proximity Spaces, Jeremy D. Siegert

Doctoral Dissertations

This work is meant to present the current general landscape of the theory of coarse proximity spaces. It is largely comprised of two parts that are heavily interrelated, the study of boundaries of coarse proximity spaces, and the dimension theory of coarse proximity spaces. Along the way a study of the relationships between coarse proximity spaces and other structures in coarse geometry are explored.

We begin in chapter 2 by going over the necessary preliminary definitions and concepts from the study of small scale proximity spaces as well as coarse geometry. We then quickly proceed to the introduction of coarse …

Physical Adsorption Of Linear Hydrocarbon Quadrupoles On Graphite And Mgo (100): Effects Of The Compatibility Of Surface And Molecular Symmetries, Andrew J. Pedersen

Doctoral Dissertations

The process of physical adsorption finds a practical role in wide-ranging fields from catalysis, to lubrication, and even optoelectronics. Furthermore, it provides a mechanism to probe the fundamental understanding of intermolecular forces and how symmetries can play a role in the behavior of a system. Linear quadrupoles preferentially adopt square-T configurations when confined in two dimensions. This would lead the system to adopt a four-fold symmetry in the molecular lattice.

Two archetypal surfaces often studied in physisorption research are MgO (100), which has a four-fold symmetry of alternating charges, and the basal plane of graphite, which has a six-fold symmetry …

Development Of Catalysts For The Ring-Opening Polymerization Of Cyclic Esters And The Coordination-Insertion Polymerization Of Olefins, Alicia Doerr

Doctoral Dissertations

Over the past few decades, interest in the design and synthesis of tailorable polymeric materials has grown due to the well documented correlation between structure, property, and function. However, in order to obtain polymers with desired microstructures, well controlled synthetic methods are needed. Therefore, the continued investigation of homogeneous, single-site polymerization catalysts is important to gain a deeper understanding of how systematic modifications of polymerization conditions, ligand scaffold, metal center identity, cocatalyst or activator identity, etc. affect the catalytic activity, selectivity, and/or polymer topology obtained when using these catalysts for the polymerization of a variety of monomers. This dissertation will …

In Situ Cosmogenic Backgrounds In The Majorana Demonstrator, Andrew Lopez

Doctoral Dissertations

Neutrino-less double-beta decay is a proposed type of radioactive decay that, if observed, could answer several outstanding physics questions, such as "Is the neutrino its own antiparticle otherwise known as a Majorana particle?", "What is the mass of the neutrino?", and "What is the neutrino mass hierarchy?" As technology and experimental techniques improve, the sensitivity of experiments looking for rare events becomes more dependent on the backgrounds. Some of these backgrounds can be reduced using shielding techniques such as implementing a veto system, selecting radiopure components, and conducting the experiment deep underground. However some amount of cosmogenically induced backgrounds remain …

Preconditioned Nesterov’S Accelerated Gradient Descent Method And Its Applications To Nonlinear Pde, Jea Hyun Park

Doctoral Dissertations

We develop a theoretical foundation for the application of Nesterov’s accelerated gradient descent method (AGD) to the approximation of solutions of a wide class of partial differential equations (PDEs). This is achieved by proving the existence of an invariant set and exponential convergence rates when its preconditioned version (PAGD) is applied to minimize locally Lipschitz smooth, strongly convex objective functionals. We introduce a second-order ordinary differential equation (ODE) with a preconditioner built-in and show that PAGD is an explicit time-discretization of this ODE, which requires a natural time step restriction for energy stability. At the continuous time level, we show …

Small Molecule Activation By Transition Metal Complexes: Studies With Quantum Mechanical And Machine Learning Methodologies, Justin Kyle Kirkland

Doctoral Dissertations

One of the largest areas of study in the fields of chemistry and engineering is that of activation of small molecules such as nitrogen, oxygen and methane. Herein we study the activation of such molecules by transition metal compounds using quantum mechanical methods in order to understand the complex chemistry behind these processes. By understanding these processes, we can design and propose novel catalytic species, and through the use of data-driven machine learning methods, we are able to accelerate materials discovery.

Fine Tuning Rhii Complexes With Tethered, Axial Coordination: Structural Studies And Application To Diazo-Mediated Cyclopropanation Reactions, Derek Cressy

Doctoral Dissertations

The cyclopropane moiety is an attractive synthetic target due to its application in pharmaceuticals and medicinal research. One effective strategy involves the formation of metal carbenoid species from diazo reagents. The carbenoid then reacts with an olefin substrate to generate the cyclopropane ring. Of the metal complexes that can facilitate this reaction, dirhodium(II) paddlewheel complexes are arguably the most prevalent catalysts. This is because modification of the bridging ligands enables control to be exerted over the catalyst’s chemoselectivity and enantioselectivity. Exploiting the axial site as a control element is often overlooked as strongly coordinated Lewis bases inhibit catalysis. Despite this, …

Spectroscopic Investigations Of Complex Van Der Waals Systems, Sabine N. Neal

Doctoral Dissertations

Complex chalcogenides are superb platforms for revealing the interplay between structure, charge, and magnetism as well as the unusual states of matter that develop under external stimuli. These van der Waals solids can also be exfoliated into few- and single-layer sheets that sport a number of unexpected properties, including quantum confinement, magnetic excitations and size-induced magnetic states, and symmetry breaking. A commonality amongst sheet studies is the role of Raman scattering to assure sample quality, probe even-symmetry vibrational modes, and uncover single-layer properties. Odd-symmetry modes were, however, completely underexplored in few-layer materials. Infrared spectroscopy is well suited for examining the …

Synthesis, Characterization, And Applications Of Nucleobase-Functionalized Conjugated Polymers, Sina Sabury

Doctoral Dissertations

Understanding the effect of the functional groups at the terminus of the side chains is important for developing conjugated polymers through side chain engineering. Nucleobases, which are known for their multi-functionality, have not been deeply studied as functionality in conjugated polymers due to synthetic challenges. The overarching goal of my dissertation is to design, synthesize, characterize conjugated polymers bearing nucleobase functionality in their side chains and demonstrate their utility in various applications. Stille cross-coupling and direct arylation polymerization are used to synthesize adenine- and thymine-containing conjugated polymers. Monomer design requirements for successful polymerization are studied and conditions that optimize polymerization …

Motor Control-Based Assessment Of Therapy Effects In Individuals Post-Stroke: Implications For Prediction Of Response And Subject-Specific Modifications, Ashley Rice

Doctoral Dissertations

Producing a coordinated motion such as walking is, at its root, the result of healthy communication pathways between the central nervous system and the musculoskeletal system. The central nervous system produces an electrical signal responsible for the excitation of a muscle, and the musculoskeletal system contains the necessary equipment for producing a movement-driving force to achieve a desired motion. Motor control refers to the ability an individual has to produce a desired motion, and the complexity of motor control is a mathematical concept stemming from how the electrical signals from the central nervous system translate to muscle activations. Exercising a …

Hazardous Weather And Human Response In The Southeastern United States, Daniel Burow

Doctoral Dissertations

Effectively mitigating the human costs of future hazardous weather events requires examining meteorological threats, their long-term patterns, and human response to these events. The southeastern United States is a region that has both a high climatological risk and a high societal vulnerability to many different meteorological hazards. In this dissertation, I study hazardous weather and human response in the Southeast through three different lenses: identifying uniquely simultaneous hazards posed by tropical cyclones, assessing precipitation and synoptic weather patterns on hazardous weather days, and examining patterns in intended response to tornado watches. I find that simultaneous and collocated tornado and flash …

Spectroscopic Properties Of Ferroic Superlattices, Shiyu Fan

Doctoral Dissertations

The interplay between charge, structure, magnetism, and orbitals leads to rich physics and exotic cross-coupling in multifunctional materials. Superlattices provide a superb platform to study the complex interactions between different degrees of freedom. In this dissertation, I present a spectroscopic investigation of natural and engineered superlattices including Fe_xTaS₂ and (LuFeO₃)_m/(LuFe₂O₄)₁ under external stimuli of temperature and magnetic field as well as chemical substitution. Studying the phase transitions, symmetry-breaking, and complex interface interactions from a microscopic viewpoint enhances fundamental understanding of coupling mechanism between different order parameters and the …

Susceptibility Of Riverine Fishes To Anthropogenically-Linked Trauma: Strikes From Hydropower Turbine Blades, Ryan K. Saylor

Doctoral Dissertations

Hydropower accounts for nearly 40% of renewable electricity generation in the US; however, dams significantly impact the surrounding aquatic ecosystems. One of the most visible impacts of hydropower―beyond the dam itself―is the direct negative impacts (injury or death) to fish populations that must pass through hydropower turbines to access desired downstream habitat. During passage, fishes face many potential stressors that can cause severe injuries and often leads to high rates of mortality. In this dissertation, I have focused on quantifying how fishes respond to impacts from turbine blades that may occur during turbine passage. Laboratory research into blade strike impact …

Characterization And Benchmarking Of Quantum Computers, Megan L. Dahlhauser

Doctoral Dissertations

Quantum computers are a promising technology expected to provide substantial speedups to important computational problems, but modern quantum devices are imperfect and prone to noise. In order to program and debug quantum computers as well as monitor progress towards more advanced devices, we must characterize their dynamics and benchmark their performance. Characterization methods vary in measured quantities and computational requirements, and their accuracy in describing arbitrary quantum devices in an arbitrary context is not guaranteed. The leading techniques for characterization are based on fine-grain physical models that are typically accurate but computationally expensive. This raises the question of how to …

Stretching The Applications Of Biomass: Development Of Lignin Based Thermoplastic Elastomers And Composite Materials, Anthony Stephen Bova

Doctoral Dissertations

Bio-based plastics and composites have seen increased industry adoption in recent years due to growing demand for materials with a low carbon footprint. The use of lignin as a feedstock for polymers has seen growing interest as the concept of an integrated cellulosic biorefinery gains traction and advances the need to use all components of separated biomass for value-added applications. Historically, use of lignin in thermoplastic and elastomeric copolymers and blends has been bottlenecked by the inability to introduce lignin content above 30 weight percent due to difficulties with interfacial adhesion of lignin with other soft segments. Efforts to overcome …