Digital Commons Network^™

Processing Of Preceramic Polymers For Direct-Ink Writing, James W. Kemp

Doctoral Dissertations

Preceramic polymers are organosilicon polymers that, when pyrolyzed to above 1000°C, convert from a polymer to an amorphous ceramic. These polymers have been used for fiber spinning, polymer infiltration, and casting of materials but have recently gained interest for use as the feedstock material for additive manufacturing techniques. This work explores preceramic polymers being used for direct-ink writing (an additive manufacturing method) and many of the issues that occur with the polymers during curing and pyrolysis.

The first chapter of this dissertation provides a review of preceramic polymers, while the second and third chapters focus on the development of inks …

Nuclear Fuel Materials Under Extremes: Redox Behavior And Resulting Defect Structure, William Cureton

Doctoral Dissertations

Oxide nuclear fuel materials and analogues are often subject to complex structural and chemical changes when exposed to extreme environments. For example, oxidation and buildup of fission products cause changes to the local- and long-range structure as well as the chemistry and stoichiometry of UO₂ during operation in light water reactors. Highly ionizing energetic fission fragments have been shown to cause redox effects and associated defect structures in oxide nuclear fuel-type materials. The underlying mechanisms that lead to defect structures produced in a wider range of nuclear fuel material compositions and microstructures is not well understood.

This research project …

Structural Stability Of Thermosets During Material Extrusion Additive Manufacturing, Stian K. Romberg

Doctoral Dissertations

Over the past decade, the scale of polymer additive manufacturing has been revolutionized with machines that print massive thermoplastic parts with greater geometric complexity than can be achieved by traditional manufacturing methods. However, the heat required to print thermoplastics consumes energy and induces thermal gradients that can reduce manufacturing flexibility and final mechanical properties. With the ability to be extruded at room temperature and excellent compatibility with fibers and fillers, thermoset resins show promise to decrease the energy consumption, expand the manufacturing flexibility, and broaden the material palette offered by large-scale polymer additive manufacturing. However, structural instability in the uncured …

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 …

Interfacial Bonding Between Thermoset And Thermoplastic Polyurethane Reinforced Textile Grade Carbon Fiber: Structure Property Relationships, Surbhi Subhash Kore

Doctoral Dissertations

The research work focused on examining the interfacial adhesion of unsized, epoxy, and urethane-sized textile grade carbon fiber (TCF) reinforced in different classes of polyurethane (PU) thermoplastic (TPU) and thermoset (TSU) polyurethane (PU) through the structure-property relationship. The Carbon Fiber Technology Facility (CFTF) at Oak Ridge National Laboratory (ORNL) has produced TCF to reduce the cost of commercial-grade carbon fiber. The first part of the research examined the fundamental relationships between (a) soft segment thermoplastic polyurethane (S-TPU), (b) hard segment thermoplastic polyurethane (H-TPU), (c) thermoset polyurethane (TSU) and TCF reinforcement’s molecular behavior at the interface using the surface and thermal …

Fundamentals Of Cavity Formation In Α-Fe And Fe-Cr Alloys, Yan-Ru Lin

Doctoral Dissertations

Ferritic-martensitic steels are attractive candidate materials for fusion and advanced fission reactors primarily due to their low swelling characteristic, attractive thermo-mechanical properties, and the potential for development of nanostructured ferritic alloys. However, significant discrepancies exist regarding the effect of solutes and irradiation temperature on cavity swelling under ion versus neutron irradiation conditions. Several mechanisms have been proposed that may affect cavity swelling, but no general theory or model has received complete acceptance to explain these phenomena.

To better understand the formation of cavities in ferritic steels, we have performed multi-temperature (400-550°C) single-beam and simultaneous dual-beam irradiations (ex-situ and in-situ) on …

Innovations In Aligned And Overmolded Long Fiber Thermoplastic Composites, Shailesh P. Alwekar

Doctoral Dissertations

Long fiber thermoplastic (LFT) composite materials are increasingly used in high performance lightweight automotive, sporting, and industrial applications. LFT composites are processed with extrusion-compression molding (ECM) and/or injection molding (IM). Melt extrusion offers unique opportunities to align long fibers in a thermoplastic polymer melt. The properties of LFT materials are highly influenced by processing techniques which leads to different porosity content, fiber length distribution, and fiber orientation distribution. Hence, it is important to understand the various LFT processing techniques and their effect on mechanical, thermal, and microscopic properties.

The fundamental process-property relationships in LFT composites are investigated in this dissertation. …

Assessing Mechanical Performance Of Dissimilar Steel Systems Made Via Wire-Arc Additive Manufacturing, Obed Daniel Acevedo

Masters Theses

Hot stamping is part of a specific type of metalworking procedure widely used in the automotive industry. This research seeks to help make hot stamp tooling component production more cost-effective by using large-scale additive manufacturing. Additive manufacturing can produce dissimilar steel components that can be more cost-effective and time-efficient and allow for complex geometries to be made. A dissimilar steel system consisting of 410 martensitic stainless steel and AWS ER70S-6 mild steel is proposed to make hot stamps, making them more cost-efficient. However, the material interface's mechanical behavior in 410SS-mild steel additively manufactured material systems is not well understood. This …

Radiation Effects On Lithium Indium Diselenide Semiconductors As Neutron Imaging Detectors, Robert M. Golduber

Masters Theses

The studies presented in this work aim to improve upon the knowledge base of lithium indium diselenide (LISe) semiconductors to understand how the material behaves in high radiation environments and refine the process of turning it into a neutron detector. LISe has great potential as neutron imaging detector because of the high neutron absorption efficiency of its enriched ⁶Li component and its ability to discriminate between gamma-rays and neutrons. Its ability to remain functional after being irradiated with large amounts of neutron fluence has been tested and the change in its electro-optical properties with relation to fluence has been …

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 …

Studies Of Creep Damage In The Heat-Affected Zone Of 9cr-1mo-Vnb Steel Weldments, John William Bohling

Doctoral Dissertations

Creep strength enhanced ferritic (CSEF) steels are used in power plants for high temperature, pressure-containing welded components such as steam headers. One CSEF steel, 9Cr-1Mo-VNb or Grade 91, often exhibits localized creep deformation and cavitation in the weld heat-affected zone (HAZ), identified as Type IV creep damage. Three Grade 91 weldments were evaluated by creep testing and microstructural characterization using optical and scanning electron microscopy, combined with image analysis, to investigate microstructure evolution and creep damage. Two weldments fabricated from dissimilar base metals were used for direct comparison of creep damage in two materials simultaneously during cross-weld testing. Longitudinal creep …

High Resolution Electron Energy Loss Spectroscopy Of Plasmonic Nanostructures, Grace Pakeltis

Doctoral Dissertations

This dissertation discusses developing fabrication techniques to study the plasmonic phenomena of nanostructures utilizing high spatial and energy resolution of monochromated aberration-corrected scanning transmission electron. While standard lithography has been widely used to create planar nanostructures, investigation into 3-dimensional nanostructures is lacking. A robust synthesis approach utilizing focused electron beam induced deposition, atomic layer deposition, and thin film sputter deposition to fabricate complex 3D plasmonic architectures is described and characterization of single nanoresonators is presented. Additionally, this dissertation discusses the use of high-resolution electron energy loss spectroscopy to investigate the hybridization of gold nanorod oligomers. Experiment and simulation resolve magnetic …

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 …

Transients In Plastic Instabilities During Thermo-Mechanical Reversals In An Additively Manufactured Ti6al4v, Sabina C. Kumar

Doctoral Dissertations

A complex interaction of process variables in an evolving geometry during Additive Manufacturing (AM), can bring about spatial and temporal transients of temperature and stress within each layer in a part. Although AM shares commonalities with conventional processing techniques such as casting, welding, and thermo-mechanical process, published literature has shown that the steady-state conditions are not strictly valid during AM process. Macro-scale fluctuations of thermal gradients (dT/dx: 10³ to 10⁷ K/m) combined with local changes in thermal expansion coefficients, crystallographic strains and localized stress-strain constitutive properties in conjunction with thermal cycles, can bring about a plastic strain gradient …

Understanding Colloidal And Surface Phenomena To Manufacture Energy-Dense Lithium-Ion And Solid-State Battery Cathodes, William B. Hawley

Doctoral Dissertations

Lithium-ion batteries (LIB) are a technology that have been commercialized since 1991 for portable electronics. Research and development have dramatically reduced the cost of LIBs over the past ten years such that it is becoming more feasible that electric vehicles utilizing LIBs can compete with vehicles using the internal combustion engine. To continue to reduce the cost of LIBs, novel cathode processing strategies must be pursued and the impact of these strategies on the cathode’s microstructure and performance must be well-understood. Moving beyond LIBs, solid-state lithium metal batteries (SSLMBs) are a safer, more energy-dense alternative due to non-flammable, thin solid …

Microstructural Characterization And Analysis Of Laser-Powder Bed Fusion Grcop-84 By Metallurgical And Neutron Scattering Methods, Robert Minneci

Doctoral Dissertations

GRCop-84 or Cu-8Cr-4Nb (atomic %) is a structural high-heat-flux Cu alloy that is dispersion strengthened by C15 Laves Cr₂Nb [Niobium Chromide] that has seen significant development with laser additive manufacturing (AM), specifically laser-powder bed fusion (L-PBF) in recent years. A review of the development, properties, and performance of GRCop alloys has been conducted and provides pertinent background. The body of research provides fundamental understanding regarding microstructure evolution and phase interaction of GRCop-84 through characterization by neutron and X-ray scattering and metallographic techniques. This research is intended to bridge fundamental research of L-PBF, Cu alloys, structural thermal conductors, and …

3d Printing Of Hybrid Architectures Via Core-Shell Material Extrusion Additive Manufacturing, Robert Cody Pack

Doctoral Dissertations

Biological materials often employ hybrid architectures, such as the core-shell motif present in porcupine quills and plant stems, to achieve unique properties and performance. Drawing inspiration from these natural materials, a new method to fabricate lightweight and stiff core-shell architected filaments is reported. Specifically, a core-shell printhead conducive to printing highly loaded fiber-filled inks, as well as a new low-density syntactic foam ink, are utilized to 3D-print core-shell architectures consisting of a syntactic epoxy foam core surrounded by a stiff carbon fiber-reinforced epoxy composite shell. Effective printing of test specimens and structures with controlled geometry, composition, and architecture is demonstrated …

Local Dynamics And Atomic-Level Structures In Metallic Liquids And Glasses, Zengquan Wang

Doctoral Dissertations

Structure and dynamics at the atomic level in metallic glasses and liquids are poorly understood when compared to the crystalline solids. For instance, even though viscosity is the basic property of liquids, its atomistic origin is not well elucidated. Also, the physics of the fragility of liquids and the crossover phenomenon is far from full understanding. Earlier, through molecular dynamics (MD) simulations a direct connection was found between the timescale describing the macroscopic viscous behavior, the Maxwell relaxation time (t_M = h/G_∞, h is the shear viscosity and G_∞ is the high-frequency shear modulus) and …

Microstructural Investigation Of Hydride Reorientation In Zirconium Based Spent Nuclear Fuel Cladding, Tyler S. Smith

Doctoral Dissertations

Hydride embrittlement and the impact of hydride reorientation are failure phenomena of particular interest during the transportation process of spent nuclear fuel from wet storage to dry storage. This process exposes the cladding to elevated temperatures and high pressure-induced hoop stresses that can release the hydride platelets back into solution and cause them to radially precipitate upon cooling. Though the impact of high temperature and high-pressure conditions on hydride reorientation have been investigated for many nonirradiated specimens, a data gap remains for the coupling effects of irradiation at these conditions in high burnup spent nuclear fuel rods. To simulate this …

Biofabricated Constructs Of Carbon-Based Nanoparticles With Mesenchymal Stem Cells For Orthopedic Repair, Steven D. Newby

Doctoral Dissertations

Breakthroughs in tissue engineering are moving at a rapid rate especially in the regenerative bone biofabrication. Technology growth in the field of additive manufacturing (AM) such 3D bioprinting which provides the ability to create biocompatible 3D construct on which a cell source could be seeded is an encouraging substitute to autologous grafts.

This present research aims to biofabricate a construct for bone tissue engineering using AM technology. The biocompatible material was chosen corresponding to bones extracellular matrix (ECM) composition, which demonstrates an inorganic and organic development phase: Poly (lactic-glycolic acid) was chosen as the polymeric matrix of the compound, due …

Next Generation Energy Storage: An Examination Of Lignin-Based Carbon Composite Anodes For Sodium Ion Batteries Through Modeling And Simulation, Dayton G. Kizzire

Doctoral Dissertations

The current energy market relies heavily on fossil fuel sources; however, we are amidst a momentous shift towards wind, solar, and water based renewable energies. Large-scale energy storage allows renewable energy to be stored and supply the grid with consistent energy despite changing weather conditions. Improvements to large-scale energy storage in terms of cost, safety, and sustainability are crucial to wide-scale adoption. A promising candidate for large-scale energy storage are sodium-ion batteries using hard carbon anodes. Sodium is globally available, cheaper, and more sustainable than lithium, but requires a different anode structure. A sustainable hard carbon anode with excellent Li-ion …

Process-Structure-Property Relationships In 3d-Printed Epoxy Composites Produced Via Material Extrusion Additive Manufacturing, Nadim S. Hmeidat

Doctoral Dissertations

Extrusion-based additive manufacturing (AM) technologies, such as direct ink writing (DIW), offer unique opportunities to create composite materials and novel multi-material architectures that are not feasible using other AM technologies. DIW is a novel 3D-printing approach in which viscoelastic inks, with favorable rheological properties, are extruded through fine nozzles and patterned in a filament form at room temperature.

Recent developments in DIW of polymer composites have led to expanding the range of materials used for printing, as well as introducing novel deposition strategies to control filler orientation and create improved functional/structural composite materials. Despite these substantial advancements, the successful and …

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 …

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 …

Microscopic And Image Processing Characterization Of Aggregates To Predict Asr Expansion Potential Of Concrete, Ammar Elfatih Abdelssamd Elhassan

Doctoral Dissertations

Preventing ASR occurrence in new concrete structures requires reliable and quick methods to identify reactive aggregates and to evaluate proper mitigation alternatives. The current accelerated mortar-bar expansion tests (ASTM C 1260 or ASTM C1567) and the concrete prism expansion test (ASTM C 1293) have been reported to have several limitations. Assessment of the extend of ASR damage in existing affected structures requires more understanding on how ASR expansion and damage develop in field conditions such as under confinements and under relatively slow rate of ASR reaction.

The significance of ASR expansion rate and bi-axial restrain on concrete degradation has been …

Synthesis And Physical Properties Of High Entropy Oxide Ceramics, Brianna L. Musicó

Doctoral Dissertations

Utilizing entropy as the driving force for stabilizing oxide materials offers a path for the discovery of innovative compounds with unique structure-property relations. The multi-cation approach inherent to high entropy oxides (HEOs) is expected to allow for the tailoring of physical properties that meet the requirements of potential applications. However, the intrinsic disorder and highly localized chemical environments of HEOs bring along new challenges. In order to shed light on the complexities associated multi-cation oxides, we have initiated a systematic study of polycrystalline HEO samples across multiple crystal systems. This work expands the multi-component concept to new compositions and crystal …

Rare Earth-Doped Glass-Ceramic Scintillators As X-Ray Flat Panel Detector Substrates, Austin M. Thomas

Masters Theses

Digital radiography (DR) is an important two-dimensional imaging technique in the field of medicine that utilizes x-rays to form a digital image. DR employs a flat panel detector that converts incident x-rays, that have passed through the subject, to an electrical signal, which is used to create a digital image. The conversion from x-rays to electrical signals can be done either directly or indirectly. The direct method involves the x-rays being converted to an electrical signal via an array of semiconductors. The indirect method utilizes scintillators to absorb the x-rays and produce light in the visible spectrum, which is then …

Spin Effects Of Excited States In Organic Semiconductors And Hybrid Perovskites For Optoelectronics And Spintronics, Miaosheng Wang

Doctoral Dissertations

Organic semiconductors and organic-inorganic hybrid perovskites have demonstrated versatile functionalities for optoelectronic and spintronic applications. Research in this dissertation focuses on the spin effects of excited states in emerging organic semiconductor and hybrid perovskite systems to understand the fundamental working principle. The investigation on the spin effects in excited states can provide insightful guidance for the development of the next-generation organic and hybrid perovskite optoelectronics and spintronics.

In organic semiconductors, the excited states, namely, excitons can be characterized by the total spin angular momentum S=S_e+S_h of the constituent electron and hole, which determines the …

Development Of Data Science Tools For Part Qualification In Additive Manufacturing, Sujana Chandrasekar

Doctoral Dissertations

In recent years, metal additive manufacturing processes have become popular choices for part production especially for low volume, high complexity parts. To enable widespread adoption of these methods, it is essential to understand the link between process parameters and part properties. This is particularly because additive manufacturing processes cause inherently complex thermo-mechanical cycles and drastically different local process conditions within a part, compared to conventional manufacturing processes like casting and forging. Additionally, properties of feedstock material like metal powder impact final part properties. The focus of this dissertation is on development of data-driven methods using in situ monitoring, as a …

Manipulation Of Excited States In Organic-Inorganic Hybrid Perovskite Optoelectronic Devices, Jia Zhang

Doctoral Dissertations

In recent years, a huge success on photovoltaic and light emitting has been achieved in the field of organic-inorganic hybrid perovskites owing to the superior optoelectronic properties of excited states. Regulating the primary excited states is the foundation of developing multi-functional optoelectronics, including the light-emitting, photovoltaic and lasing actions. By revisiting the photophysical processes of excited states, some new strategies are suggested to further pushing the efficiency of perovskites forward. This thesis focuses on the manipulation of excited states through combining optoelectronic devices, from excited states generation to excited charge carrier transport.

Chapter 1 presents a basic introduction to excited …