Engineering Commons^™

Theory And Improved Methods For Probing The Cavitation To Fracture Transition, Christopher Barney

Doctoral Dissertations

A material is considered soft when its bulk modulus is significantly greater than its shear modulus. Rubbery polymers are a class of soft materials where resistance to extension is mainly entropic in nature. Polymeric soft solids differ from liquids due to the presence of a percolated network of strong bonds that resist deformation and flow on a given time scale. The incompressible nature, entropically driven elasticity, and molecular scale network structure of soft polymeric solids combine to impart unique mechanical behavior that often results in complex material responses to simple loading situations. An important example of this is cavitation in …

Engineered Carbon Materials With Nano-Graphitic Domains Derived From Lignin, Valerie Garcia Negron

Doctoral Dissertations

This work focuses on establishing a comprehensive understanding of lignin-derived materials as a function of carbonization with the goal of identifying processing-structure-property-performance relationships. A combination of modeling, statistical, and empirical materials characterization techniques are applied to lignin materials varying in feedstock source, extraction method, and processing conditions. The first part of this study evaluates the structure of carbon composite materials, possessing both crystalline and amorphous domains, using scattering techniques. One approach performs atomistic simulations of a proposed structure, from which the analogous scattering pattern can be obtained for validation. An alternative approach based on a hierarchical decomposition of the radial …

Discontinuous Recycled And Repurposed Carbon Fiber Reinforced Thermoplastic Organosheet Composites, Philip R. Barnett

Doctoral Dissertations

There is a significant need for low cost, high volume composites in the automotive industry to aid in vehicle lightweighting and safety. The current state-of-the-art severely compromises the mechanical properties of composites to achieve cost and cycle time goals. In this dissertation, a novel composite format, termed discontinuous carbon fiber organosheets, using recycled and repurposed carbon fibers in a thermoplastic matrix is developed and studied. Unlike traditional composites, the long fiber length and rapid processing time yield mechanical properties and cycle times competitive with automotive metals.

Several studies were performed to characterize this new material format. First, samples were manufactured …

Chemico-Physical Interactions In Metal Halide Perovskites, Yongtao Liu

Doctoral Dissertations

Metal halide perovskite (MHP) has attracted tremendous attention due to its success in optoelectronics, largely due to outstanding photovoltaic performance. A wide variety of characterization approaches have been used to explore the fundamentals behind the outstanding optoelectronic properties of MHP, which has yet to be unambiguously established despite considerable efforts to do so. Given the high ionic mobility in MHP, when physical phenomena are coupled with chemical changes, all behaviors will become very complex due to the strong ion migration. Therefore, chemico-physical interactions in MHP can no longer be ignored, which will be the focus of the researches in this …

Development Of A Novel Casting Alloy Composed Of Aluminum And Cerium With Other Minor Additions, Zachary Cole Sims

Doctoral Dissertations

Eutectic casting alloys of aluminum and cerium are a recent discovery and early research describes an alloy with great potential to meet the growing demand for a lightweight, economical, high specific strength material for use in high-temperature or extremely corrosive environments. The broad application of aluminum alloys across industry sectors is driven by their collection of balanced properties including economical cost, high specific strength, and flexibility of their production pathways. Additionally, their high corrosion resistance makes them a good choice for structural materials. Despite this, the push to use aluminum alloys in ever more extreme environments with higher temperatures, stresses, …

Processing-Structure-Performance Relationships In Fused Filament Fabricated Fiber Reinforced Abs For Material Qualification, William Howard Ferrell

Doctoral Dissertations

This dissertation uses the processing-structure-performance relationships to elucidate future needs in qualification of materials manufactured by fused filament fabrication and also introduces a previously unused testing method for the determination of fracture toughness in these materials. Fused filament fabrication (FFF) is an additive manufacturing technique that utilizes the layering of deposited molten plastic in two dimensional shapes to create three dimensional objects. This technique has gained traction over the past two decades as a disruptive manufacturing technology that promises many benefits. In order for FFF to truly be a staple in manufacturing spaces across the world for the production of …

Thermoplastic Additive Manufacturing For Composites And Molds, Pritesh S. Yeole

Doctoral Dissertations

Recent inventions in the ability of additive manufacturing (AM) to use carbon fiber (CF) reinforced pellets as a feedstock material to manufacture components has complemented its purpose from prototypes to structural load-bearing parts. In the first part of this research, we investigated the processability, microstructure, and mechanical performance of twin-screw compounded short CF reinforced polyphenylene sulfide (PPS) pellets as a feedstock material for extrusion deposition fabrication-additive manufacturing (EDF-AM) using big area AM (BAAM). The performance of the BAAM components was compared to that of traditional processing methods, namely injection molding (IM) and extrusion-compression molding (ECM). It was found that the …

Local Structure And Dynamic Studies Of Mixed Ch4-Co2 Gas Hydrates Via Computational Simulation And Neutron Scattering, Bernadette Rita Cladek

Doctoral Dissertations

Permeated throughout the ocean floor and arctic permafrost, natural gas hydrates contain an estimated 3000 trillion cubic meters, over three times that of traditional shale deposits, of CH₄ that is accessible for extraction. Gas hydrates are a crystal structure in which water molecules form a cage network, the host, through hydrogen bonds while trapping a guest molecule such as CH₄ in the cavities. These compounds form naturally where the appropriate low temperature and high pressure conditions occur. A promising and tested method of methane recovery is through exchange with CO₂, which energetically takes place of the …

Characterization Of A Digital Holography Diagnostic For In Situ Erosion Measurement Of Plasma-Facing Components In Fusion Devices, Cary Dean Smith

Doctoral Dissertations

Fusion energy devices, particularly tokamaks, face the challenge of interior surface damage occurring over time from the heat flux of the high-energy plasma they generate. The ability to monitor the rate of surface modification is therefore imperative, but to date no proven technique exists for real-time erosion measurement of planar regions of interest on plasma-facing components in fusion devices. In order to fill this diagnostic gap, a digital holography system has been established at ORNL [Oak Ridge National Laboratory] for the purpose of measuring the erosion effects of plasma-material interaction in situ.

The diagnostic has been designed with the …

Market-Conscious Strategies To Improve The Performance And Stability Of Planar, P-I-N Hybrid Organic-Inorganic Metal Halide Perovskite Solar Cells, Brandon Dunham

Doctoral Dissertations

Planar, p-i-n (inverted) hybrid organic-inorganic perovskite solar cells that use low-temperature, solution-processable charge-transport layers have garnered much attention due to their direct compatibility with flexible substrates and cost-effective roll-to-roll manufacturing. Nevertheless, this architecture has failed to repeatedly achieve the superior power conversion efficiencies frequently attained by its n-i-p counterpart. Additionally, the perovskite active layer has poor stability in the presence of prolonged light exposure, high temperatures, and moisture. In this study, we propose commercially viable strategies to improve the performance and stability of inverted methylammonium lead iodide perovskite solar cells. First, we show that a simple two-step method comprising evaporation-induced …

Design And Development Of Strong And Ductile Single Bcc Refractory High-Entropy Alloys For High-Temperature Applications, Chanho Lee

Doctoral Dissertations

The objectives of this proposed study are to (1) design and develop single BCC phase refractory high-entropy alloys (HEAs) for the high-temperature applications, (2) investigate the deformation mechanisms of refractory HEAs, (3) improve an integrated approach, coupling focused experiments and theoretical modeling, to design, discover, and develop HEAs, and (4) understand the alloy design-microstructure-property-performance links underlying the mechanical behavior of refractory HEA systems for gas-turbine applications

A traditional alloy system generally includes one or two principal elements that form the matrix with other additional elements, e.g., iron or aluminum alloys, to strengthen some specific properties, such as strength and corrosion …

Cracking And Earing Phenomenon In Deep-Drawn Stainless Steel Alloys: Role Of Transformation Kinetics, Microstructure, And Texture, Peijun Hou

Doctoral Dissertations

The enhancement of formability of advanced high-strength TRIP-assisted steel alloys is a challenging assignment for industrial application due to the cracking phenomenon. The critical factor governing the cracking behavior is residual-stress concentration resulting from the inhomogeneous plastic deformation and microstructural evolution during the forming processes. Martensitic phase transformation kinetics, constituent phases, and crystallographic texture in TRIP-assisted steel alloys are correlated to the microstructure evolution, resulting in phase-specific stress concentration. In the current study, we are aiming at understanding the fundamental mechanisms responsible for the cracking phenomenon and thus improving the formability of TRIP-assisted steel alloys. Four stainless steel (SS) alloys …

Exploration Of Thin Films For Neuromorphic, Electrofluidic, And Magneto-Plasmonic Applications, Walker L. Boldman

Doctoral Dissertations

Due to the limit in computing power arising from the Von Neumann bottleneck, computational devices are being developed that mimic neuro-biological processing in the brain by correlating the device characteristics with the synaptic weight of neurons. We demonstrate a platform that combines ionic liquid gating of amorphous indium gallium zinc oxide (aIGZO) thin film transistors and electrowetting for programmable placement/connectivity of the of the ionic liquid. In this platform, both short term potentiation (STP) and long-term potentiation (LTP) are realized via electrostatic and electrochemical doping of the aIGZO, respectively, and pulsed bias measurements are demonstrated for low power considerations. Using …

Nano- And Micro-Structured Temperature-Sensitive Hydrogels For Rapidly Responsive Devices, Qi Lu

Doctoral Dissertations

This thesis aims to extend the understanding and explore the application of temperature-responsive hydrogel systems by integrating microelectromechanical systems (MEMS). Stimuli-responsive hydrogel systems are immensely investigated and applied in numerous fields, and interfacing with micro- and nano-fabrication techniques will open up more possibilities. In Chapter 2, the first biologically relevant, in vitro cell stretching device based on hydrogel surface instability was developed. This dynamic platform is constructed by embedding micro-heater devices under temperature-responsive surface-attached hydrogels. The fast and regional temperature change actuates the stretching and relaxation of the seeded human artery smooth muscle cell (HASMC) via controllable surface creasing instability. …

Resistive Switching Characteristics Of Nanostructured And Solution-Processed Complex Oxide Assemblies, Zimu Zhou

Doctoral Dissertations

Miniaturization of conventional nonvolatile (NVM) memory devices is rapidly approaching the physical limitations of the constituent materials. An emerging random access memory (RAM), nanoscale resistive RAM (RRAM), has the potential to replace conventional nonvolatile memory and could foster novel type of computing due to its fast switching speed, high scalability, and low power consumption. RRAM, or memristors, represent a class of two terminal devices comprising an insulating layer, such as a metal oxide, sandwiched between two terminal electrodes that exhibits two or more distinct resistance states that depend on the history of the applied bias. While the sudden resistance reduction …

Characterizing Non-Linear Structural, Mechanical, And Volumetric Properties Of Aliphatic And Aromatic Thermosets, Brendan Robert Ondra

Doctoral Dissertations

A unifying theme throughout this dissertation employs advanced experimental mechanics, including the design and development of new instruments, testing techniques, and analysis strategies. Chapter 1 covers the design and development of a new instrument for polymer and composite characterization. More specifically, a bi-fluidic, confining-fluid, pressurizable dilatometer (referred to herein as the BFCF-PVT). Whereas both classical and contemporary confining-fluid type pressurizable dilatometers utilize a bellows and / or piston system along with a Linear Variable Displacement Transducer to apply pressure and track volume changes, the BFCF-PVT that was designed and built utilizes a fluid-fluid interface (composed of two immiscible fluids that …

Surface Driven Flows : Liquid Bridges, Drops And Marangoni Propulsion, Samrat Sur

Doctoral Dissertations

Molecules sitting at a free liquid surface against vacuum or gas have weaker binding than molecules in the bulk. The missing (negative) binding energy can therefore be viewed as a positive energy added to the surface itself. Since a larger area of the surface contains larger surface energy, external forces must perform positive work against internal surface forces to increase the total area of the surface. Mathematically, the internal surface forces are represented by surface tension, defined as the normal force per unit of length. One common manifestation of surface tension is the difference in pressure it causes across a …

Engineered Nanoparticles For Site-Specific Bioorthogonal Catalysis: Imaging And Therapy, Riddha Das

Doctoral Dissertations

Bioorthogonal catalysis offers a strategy for chemical transformations complementary to bioprocesses and has proven to be a powerful tool in biochemistry and medical sciences. Transition metal catalysts (TMCs) have emerged as a powerful tool to execute selective chemical transformations, however, lack of biocompatibility and stability limits their use in biological applications. Incorporation of TMCs into nanoparticle monolayers provides a versatile strategy for the generation of bioorthogonal nanocatalysts known as “nanozymes”. We have fabricated a family of nanozymes using gold nanoparticles (AuNPs) as scaffolds featuring diverse chemical functional groups for controlled localization of nanozymes in biological environments, providing unique strategies for …

Nanoengineered Core-Shell Structures Using Tubile Halloysite Clay, Yusuf A. Darrat

Doctoral Dissertations

Halloysite nanotubes are a versatile nanomaterial that can be used in a wide variety of applications. They have a unique structure which could be described as a flat material that consists of silica on one side and alumina on the other; this structure is rolled up in a way naturally forming an internal 10-15 nm lumen and interlayer spacing. This could lead to many potential applications for example incorporating halloysite as a template material or as a support structure. They are an inexpensive clay material that is available in large quantities (thousands of tons), so they may be practically used …

Enhanced Electrochemical Performance Of Li-Ion Battery Cathodes By Atomic Layer Deposition, Yan Gao

Doctoral Dissertations

”Li-ion battery now plays an irreplaceable role in supplying green and convenient energy. In this work, atomic layer deposition (ALD) was used to modify Li-ion battery cathode particles for performance enhancement.

An ultrathin and conductive CeO₂ ALD film was deposited on Li-rich layered cathode particles, of which the specific capacity and cyclic stability were significantly improved. On the same cathode particles, FeO_x ALD and post-annealing resulted in a stable and conductive surface spinel phase to improve the performance.

Synergetic TiN coating and Ti doping were performed on a LiFePO₄ (LFP) cathode and extended its cycle life. The …

Studying The Effects Of Various Process Parameters On Early Age Hydration Of Single- And Multi-Phase Cementitious Systems, Rachel Cook

Doctoral Dissertations

”The hydration of multi-phase ordinary Portland cement (OPC) and its pure phase derivatives, such as tricalcium silicate (C₃S) and belite (ß-C₂S), are studied in the context varying process parameters -- for instance, variable water content, water activity, superplasticizer structure and dose, and mineral additive type and particle size. These parameters are studied by means of physical experiments and numerical/computational techniques, such as: thermodynamic estimations; numerical kinetic-based modelling; and artificial intelligence techniques like machine learning (ML) models. In the past decade, numerical kinetic modeling has greatly improved in terms of fitting experimental, isothermal calorimetry to kinetic-based modelling …

Thermodynamic Investigations Of Pure And Blended Cement Mixtures, Jonathan Lapeyre

Doctoral Dissertations

” This research is made up of several studies. The first study focused on understanding the reaction kinetics of Ca₃SiO₅ and metakaolin (MK) mixtures compared to Ca₃SiO₅ and silica fume (SF) mixtures. It was shown that MK was a more effective additive than SF at small replacement levels (i.e. ≥ 10% by mass) while higher replacement levels of MK became a detriment due to excess (Al(OH)₄¯) ions preventing the nucleation and growth of C-S-H. In a follow-up study where the MK particle size distribution (PSD) was modified, similar effects were observed but …

Understanding The Deformation Mechanisms In Ni-Based Superalloys With Using Crystal Plasticity Finite Element Method, Tianju Chen

Doctoral Dissertations

“Ni-based superalloy is considered as a good candidate due to its excellent resistance to elevated temperature deformation for long term period application. Understanding the deformation and failure mechanisms of Ni-Based superalloys is very helpful for providing design guidelines for processing Ni-based superalloys. Experimental characterization indicates that the deformation mechanisms of Ni based superalloy is strongly microstructure dependent. Besides, damage transform from the void nucleation to the macro cracks by voids growth leading to the failure of the Ni-based superalloys are also showing strong microstructure sensitivity. Therefore, this work focuses on the prediction and comprehension of the deformation and void growth …

Removal Of Non-Metallic Inclusions From Molten Steel By Ceramic Foam Filtration, Soumava Chakraborty

Doctoral Dissertations

”Ceramic filters are routinely used in steel foundries to remove non-metallic inclusions from steel melt. Removal efficiency for both solid and liquid inclusions by magnesia-stabilized zirconia foam filters (10ppi) were evaluated and distribution of the captured inclusions through the filter thickness was also investigated. A mold design was developed using a commercial computational fluid dynamics software package to produce two castings that fill simultaneously, one with a filter and the other without a filter, from a single ladle pour, while also matching the fill rates and avoid turbulence and reoxidation during pouring. An industrial-scale experiment was also performed to investigate …

Development Of Lightweight Materials By Meso- And Microstructure Control, Myranda Shea Spratt

Doctoral Dissertations

”In this work, two lightweight structures – lattice structures and metal matrix syntactic foams (MMSF) – were studied. Honeycomb lattices were manufactured by powder bed selective laser melting (SLM) from 304L stainless steel. The wall thicknesses of these structures ranged from 0.2 to 0.5 mm. Surface roughness was the primary cause of dimensional mismatch between the expected and as-built structures with an average wall thickness increase of 0.12 mm. The strength of the honeycombs increased with increasing wall thickness. A feature of the SLM microstructure, the melt pool boundary, was also studied as a part of this work. 3D models …

Transition Metal Chalcogenide Hybrid Systems As Catalysts For Energy Conversion And Biosensing, Siddesh Umapathi

Doctoral Dissertations

"Generation of hydrogen and oxygen through catalyst-aided water splitting which has immense applications in metal air batteries, PEM fuel cells and solar to fuel energy production, has been one of the critical topics in recent times. The state of art oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) catalysts are mostly comprised of precious metals. The current challenge lies in replacing these precious metal-based catalysts with non-precious earth-abundant materials without compromising catalytic efficiency.

This research explores mixed metal selenides containing Fe-Ni, Fe-Co and RhSe which were hydrothermally synthesized and/or electrodeposited and tested for OER and ORR …