Engineering Commons^™

Effects Of Polymer-Nanoparticle Interactions On The Dynamics Of Attractive Polyhedral Oligomeric Silsesquioxane Nanocomposites, Walter W. Young

Doctoral Dissertations

Polyhedral oligomeric silsesquioxane (POSS) had long been recognized as a critical building block for inorganic-organic hybrid materials with unique and desirable properties and performance. Through synthesis and characterization of polymer/POSS nanocomposites, direct insights into the significant effects of the polymer/POSS interactions on the resulting material properties are obtained. Random copolymers of a hydrogen-bond accepting monomer and a non-interacting monomer are synthesized and loaded with a model amine-functionalized hydrogen bond donating POSS molecule via solution casting, to create a material with well-controlled dynamical heterogeneity. The increase in the glass transition temperature (Tg) of these materials is found to strongly depend on …

Stress Relaxation Cracking In 347h Austenitic Steel Weldments Under Various Heat Treatments: Experiments And Modeling, Yi Yang

Doctoral Dissertations

347H austenitic stainless steel exhibits exceptional creep and corrosion resistance, rendering it an exemplary candidate for pipeline materials, particularly in mid- to high-temperature working conditions. However, due to constraints in component dimensions, welding has been chosen as the preferred method for joining pipeline systems extensively employed in nuclear power plants, fossil fuel plants, and petrochemical companies. The welding process entails the accumulation of residual stress during the cooling stage, along with the introduction of microstructure evolution. Moreover, the residual stress field and microstructure continuously evolve under service conditions, thereby intensifying the susceptibility of crack initiation and propagation. The initial residual …

Atomic-Level Mechanisms Of Fast Relaxation In Metallic Glasses, Leo W. Zella

Doctoral Dissertations

Glasses are ubiquitous in daily life and have unique properties which are a consequence of the underlying disordered structure. By understanding the fundamental processes that govern these properties, we can modify glasses for desired applications. Key to understanding the structure-dynamics relationship in glasses is the variety of relaxation processes that exist below the glass transition temperature. Though these relaxations are well characterized with macroscopic experimental techniques, the microscopic nature of these relaxations is difficult to elucidate with experimental tools due to the requirements of timescale and spatial resolution. There remain many questions regarding the microscopic nature of relaxation in glass …

3d Experimental Studies Of Temperature And Crystallographic Effects On Creep And Strength In Rock Salt, Amirsalar Moslehy

Doctoral Dissertations

Salt domes utilization as storage reservoirs in the energy sector has led to extensive studies on rock salt’s mechanical and geothermal behavior. These important facilities’ safety and serviceability rely on understanding rock salt’s compressive strength and creep behavior under various loading directions, water contents, in-situ stresses, and temperatures. Despite numerous studies on rock salt’s mechanical behavior in the literature, there are still many unanswered questions about rock salt’s behavior. This dissertation was aimed at utilizing state-of-the-art experimental techniques such as 3D synchrotron micro-computed tomography (SMT) and 3D x-ray diffraction (3DXRD) along with hundreds of compression and creep experiments to enhance …

Additive Manufacturing Of Magnetic Materials For Electric Motor And Generator Applications, Haobo Wang

Doctoral Dissertations

This work details the research into the 3D Printing, also known as Additive Manufacturing (AM), of both impermanent and permanent magnets. This work also details the research in enabling such AM magnets in electrical machine applications, primarily motors and generators. The AM processes of many types of magnets are described in detail. The material properties of such AM magnets are also described. The two main types of AM magnets that are discussed in detail are AM NdFeB, and AM Silicon Steel. The implementation of AM NdFeB as rotor magnets, and the implementation of AM Silicon Steel as rotor and stator …

Characterizing The Structure And Radiation Resistance Of Weberite-Type Complex Oxides, Igor M. Gussev

Doctoral Dissertations

Weberite-type A₃BO₇ oxides, where A is a trivalent rare earth and B is a pentavalent element like Ta, have been a focus of research due to the discovery of the weberite-type local atomic arrangement in ceramics with a defect-fluorite structure. Earlier studies primarily examined their long-range structures, leaving gaps in understanding their short-range atomic behavior. This thesis investigates various weberite-type tantalates across all structural scales. There has been debate over the long-range structure of Y₃TaO₇, a medium-sized rare earth tantalate oxide, particularly regarding its spacegroup symmetry. This work identifies Y₃TaO_{7 …}

Additive Manufacturing Of High-Performance Nanolamellar Eutectic High-Entropy Alloys, Jie Ren

Doctoral Dissertations

Additive manufacturing, also called three-dimensional (3D) printing, is an emerging technology for printing net-shaped components layer by layer for applications in automotive, aerospace, biomedical and other industries. In addition to the vast design freedom offered by this approach, metal 3D printing via laser powder-bed fusion (L-PBF) involves large temperature gradients and rapid cooling and provides exciting opportunities for producing microstructures and mechanical properties beyond those achievable by conventional processing routes. Although these extreme printing conditions enable microstructural refinement to the nanoscale for achieving high strength. However, high-strength nanostructured alloys by laser additive manufacturing often suffer from limited ductility. Eutectic high-entropy …

Characterization Of Residual Stress And Precipitate Evolution In Aluminum 2xxx Self-Reacting Friction Stir Welds, Benjamin Joe Wing

Doctoral Dissertations

2xxx series aluminum alloys possess attractive properties for structural aerospace applications including high strength to weight ratio, corrosion resistance, and stable cryogenic performance. Solid state joining processes are often employed to reduce weld defects and improve weld performance/consistency as many alloys of this range have poor weldability for traditional fusion based joining techniques. One such process, self-reacting friction stir welding (SRFSW) allows for consistent high-quality, welding of large and curved articles is often used in the construction of large structures such as launch vehicle liquid propellant tanks.

Despite the merits of this process, joint softening (a decrease in mechanical properties …

Evaluation Of Biomass As Bio-Additive In 3d Printing, Shuyang Zhang

Doctoral Dissertations

The petrol-based polymer has been widely applied in current daily life. The end-of-life of polymeric products has drawn environmental concerns. One of the solutions to such issues is to use bio-renewable materials to replace or reduce the use of petrol-based materials. Lignocellulosic materials are one of the potential candidates. Along with the features of 3D printing and the unique properties of biomass, 3D-printed biomass-based materials could be promising in preparing sustainable alternatives.

In this dissertation, lignin and other biomass were applied to various 3D printing techniques for sustainable composites. Stereolithography (SLA) was first used, and the kraft softwood lignin was …

The Synthesis And Optimization Of Sulfide And Halide Solid Electrolytes For All Solid-State Batteries, Teerth Brahmbhatt

Doctoral Dissertations

Countries and organizations around the world have established ambitious targets to transition away from fossil fuel-based energy sources and devices. The transition is focused on cleaning up power generation by converting coal, natural gas, and oil-based power generation to renewables and nuclear energy. Decarbonizing other sectors of energy use, transportation for example, will require broader electrification. To drive this move away from fossil fuel powered transportation will require portable energy storage devices. Conventional lithium-ion batteries are a popular candidate to lead this shift. However, these batteries often rely on flammable liquid electrolytes and carbon anodes that suffer from low energy …

Investigation Of Microstructure And Mechanical Behavior Of Novel Powder-Extruded Al-Ce-Mg Alloys, Mairym Vazquez

Doctoral Dissertations

Pursuing advanced structural materials with enhanced performance, reduced weight, and lower costs is a constant endeavor in the aerospace and automotive industries. Conventional structural alloys, such as cast irons, carbon steels, and titanium alloys, have strength, weight, and cost limitations. Aluminum-based alloys, known for their lightweight and high strength, have gained popularity in these industries. This dissertation focuses on investigating microstructure and mechanical behavior of novel powder-extruded Al-Ce-Mg alloys as potential candidates for high-performance structural materials.

This research explores using powder extrusion, a well-established forging methodology in the steel industry, to produce Al-Ce-Mg alloys with improved properties and aims to …

A Study Of The Effect Of Machine Parameters On Defects Produced In Eos Additive Manufacturing Builds, Tina White Malone

Doctoral Dissertations

⁵Additive Manufacturing (AM) is defined in the American Society for Testing and Materials (ASTM) standard F2792 as “a process of joining materials to make objects from 3D model data, usually layer upon layer, as opposed to subtractive manufacturing methodologies. It provides an advanced method for building complex geometries and parts for high performance with a significant cost savings. ⁵⁵It’s advantages include the reduced need for tools and molds commonly used in manufacturing, a large reduction in wasted material, much shorter manufacturing cycles for the building of hardware, and its uniquely inherent ability to produce much more complex shapes. …

Al-Ce-Mn Solidification Phase Selection And Solid-State Phase Transformations, Kevin Dean Sisco

Doctoral Dissertations

The design of Al alloys has become an important topic in Additive Manufacturing (AM). The adoption of Al alloys to AM has been difficult because traditional alloys are prone to processing related defects such as solidification cracking. The Al-10Si-Mg alloy was initially adopted because of its resistance to solidification cracking. However, the Al-10Si-Mg alloy has reduced tensile properties especially at high temperatures, where the silicon phase coarsens readily. Therefore, efforts have been made to design new Al alloys that can take advantage of the AM processing. The goal of new alloys is to optimize based on rapid solidification conditions, while …

Non-Collinear Magnetic Textures Studied By Neutron Scattering, Nan Tang

Doctoral Dissertations

Non-collinear magnetic structures, where the magnetic moments do not align along a single axis, can lead to interesting physical phenomena and potential device applications. In this dissertation, two specific non-collinear magnetic textures are studied which includes soft/hard bilayer and skyrmions. Soft/hard magnetic bilayer thin films have been widely used in data storage technologies and permanent magnet applications. Here, we use polarized neutron reflectometry (PNR) to study magnetic configuration in soft-hard bilayer heterostructure thin films designed with different sample geometry and material properties under a range of temperatures and fields. Comparing the PNR results to the micromagnetic simulations reveals that the …

Polyesters Derived From Biobased 1,5-Pentanediol For Coatings, Adhesives, And Biodegradable Plastics, Lei Zheng

Doctoral Dissertations

Biomass-derived polymers are drawing increased attention from researchers due to unique performance attributes, potential for biodegradability, new low-cost feedstocks, and improved sustainability. Biobased feedstocks are employed in both major applications of polymers thermosets and thermoplastics. For thermoset coatings and adhesives, biobased resins such as biobased alkyds, epoxy resins, benzoxazine resins, starch derivatives, and proteins from plants and animals, are promising candidates to replace petroleum-derived counterparts. Thermoplastics such as polyethylene are mainly produced from fossil resources, generally have poor degradability and are difficult to effectively recycle. Currently, in the United States, less than 10% plastics are recycled, and more than 70% …

Polymer Based Energy Storage And Thermal Management On Textile Devices, Wesley A. Viola

Doctoral Dissertations

Humans developed textiles to manage thermal energy transfer with the environment and support homeostasis in a wide range of climates. With the anticipation of wearable technologies to transform healthcare via early, pre-symptomatic detection of illness, there is now a demand for electrical energy storage to support such on-body devices. Finding energy materials to merge seamlessly with textiles is basic requirement to ensure widespread adoption of wearable health monitors. Here we use a vapor deposition process to conformally coat ordinary fabrics with the doped conjugated polymer poly(3,4 ethylenedioxythiophene) (PEDOT-Cl), a soft material which possesses electronic and redox capabilities. We demonstrate PEDOT-Cl …

Controlling Mechanical Properties Of Well-Defined Polymer Networks, Ipek Sacligil

Doctoral Dissertations

Polymer networks are one of the most versatile and highly studied material class that revolutionized many aspects of life. Connecting the final network properties to the molecular parameters of its building blocks remains a major research thrust. Recent advances in network synthesis techniques allowed for accurate predictions of elastic modulus in model networks. Tew Group has developed highly efficient, thiol-norbornene networks with controllable mechanical properties. Chapter 2 focuses on modifying the gel fracture energy predicted by Lake-Thomas theory by accounting for loop defects. This study allowed for a priori estimates of gel fracture energy by combining theory, experiments, and simulations. …

Bottom-Up Morphological Control Of Biphasic Polymer Particles Via Heterogeneous Polymerization, Heather S.C. Hamilton

Doctoral Dissertations

Heterogeneous polymerization techniques are industrially relevant, scalable methods to synthesize polymer colloids and they have emerged in recent decades as viable methods to produce biphasic and morphologically complex polymer particles. The overarching goal of this thesis is to understand how heterogeneous polymerization techniques can be modified and optimized to control particle morphology through the systematic study of process parameters. Chapter 1 introduces relevant nomenclature and provides a brief historical perspective on the development of heterogeneous polymerization. This chapter also reviews the state-of-the-art techniques used to prepare morphologically complex polymer particles, with an emphasis on the heterogeneous polymerization processes studied in …

Effect Of Chemical Identity And Morphology On Amphiphilic-Zwitterionic Block Copolymer Membranes, Ria Ghosh

Doctoral Dissertations

Amphiphilic block copolymers have gained a broad research interest attributed to their self-assembly properties over a range of pH, temperature, and ionic strength. Polyzwitterions have attracted special attention due to their hydrophilicity, charge sensitivity and coulombic attraction of the opposite charges over a range of environments making them a popular material of study in the field of stimuli responsive systems, for example in self-healing hydrogels, and water transport membranes. Combining the stimuli responsiveness and higher hydrophilicity of zwitterionic polymers with self-assembly behavior of amphiphilic block copolymers created an interest to study the effect of composition and identity of the zwitterionic …

Structure-Function Relationships Of Bighorn Sheep Horncore Bone And Horn-Horncore Interface Materials For Energy Absorption Applications, Luca H. Fuller

Doctoral Dissertations

Bighorn sheep rams do not show overt signs of traumatic brain injury from head impacts experienced during intraspecific combat. Rams’ cranial appendages bear the brunt of ramming impacts and are composed of a keratin-rich horn anchored to a bony horncore via a soft connective tissue interface. The horncore is filled with velar bone which has a unique porous architecture with a comparable bone volume fraction, but larger strut thickness and separation than typical mammalian trabecular bone. Velar bone absorbs more energy than the horn and substantially reduces post-impact brain cavity accelerations in computational models of bighorn sheep ramming. These findings …

Vapor Deposition Of Self-Wrinkling Polymer Films, Robert N. Enright

Doctoral Dissertations

Initiated chemical vapor deposition is used to grow polymer films on substrates of various three-dimensional shapes which exhibit wrinkling during film growth, termed self-wrinkling. Self-wrinkling avoids separate film growth and compression steps and more-closely mimics processes observed in nature. The self-wrinkling process is elucidated on flat elastic substrates, revealing control over the amount of compressive stress by changing deposition conditions. Next, a study of films grown on liquid substrates with interface profiles that either resemble cylinders or contain repeating concave cones, saddles, and bowls affirms the principle that the wrinkle roundness increases with interface curvature. The selection of high versus …

Synthesis Of Zeolites With Controlled Defects By Understanding The Role Of Charge Balance In Zeolite Crystallization, Song Luo

Doctoral Dissertations

Zeolites are well-defined and ordered microporous crystalline materials constructed by the continuous linkage of corner sharing TO4 tetrahedra (taking T atoms (e.g., Si or Al) as the tetrahedral center). Due to the structural and compositional diversities and superior hydrothermal stability, zeolites have been broadly utilized to many industrial fields, including gas separation and catalysis heterogeneous catalysis. However, understanding zeolite crystallization mechanisms remains a tantalizing challenge, which causes challenges in tailoring this material for advanced applications. Raman spectroscopy has emerged as a powerful tool for probing medium-range (0.35 - 1 nm) structures. Since this scale is consistent with the micropore size …

Intragranular Tungsten-Titanium Carbide Composite Ceramics Via Gas-Solid Displacement Reactions, Ryan Daniel Dempsey

Doctoral Dissertations

"Research presented herein details the synthesis and characterization of nanocomposite ceramics featuring novel heterogeneous microstructures of potential interest in a variety of electrical and structural applications. Specifically, W-TiCy composite ceramics featuring tungsten nanoprecipitates located primarily within TiCy grains have been produced via sintering of intragranular nanocomposite powders produced via reaction processing-based techniques. This dissertation details the thermodynamic basis and applied kinetics of a processing scheme for fabricating nanocomposite ceramics whose morphological heterogeneity reflects that originally developed in the powder state. The first study in this series overviews the motivation for applying metallothermic displacement reactions, conducted through gaseous intermediates, to solid …

Phosphate And Borophosphate Glasses For Optical And Biomedical Applications, Parker Tracy Freudenberger

Doctoral Dissertations

"The goal of this work was to connect the network structures of phosphate and borophosphate glasses to the compositional dependence of properties related to biomedical applications. The glasses were characterized by a variety of techniques, including phosphate ion chromatography, Raman spectroscopy, and ¹¹B and ³¹P Magic Angle Spinning Nuclear Magnetic Resonance spectroscopy, which provide qualitative and quantitative information about the phosphate and borate moieties that constitute the network structures. The systematic addition of borate to a phosphate glass initially creates tetrahedral borate sites that replace P-O-P linkages with B-O-P linkages, and the properties of the resulting borophosphate glasses …

A Study On Early Age Properties Of Concrete For Precast And 3d Printing, Debalina Ghosh

Doctoral Dissertations

Concrete is the second-most consumed material, leading the global Portland cement production of 4.1 billion tons in 2020 and 5-8% of global Carbon dioxide (CO₂) emission annually. As with any other material and practice, the construction industry is also ever-changing to meet market demand, evolving technology, and resource limitation. In the case of concrete construction, one of the main concerns is the lack of automation. In the last few decades, some new construction methods have risen to address this concern. Some of these economic and successful practices are precast construction, self-compacting concrete (SCC), and 3D printing of concrete(3DPC). …

Compositional Effects On The Mechanical Properties And Deformation Mechanisms Of Face-Centered Cubic High-Entropy Alloys, Joshua L. Cicotte

Doctoral Dissertations

High entropy alloys, HEAs, have expanded the compositional spaces of modern metallurgy into highly concentrated and chemically complex alloys, previously believed to be unproductive. With this newfound compositional freedom, comes additional control, allowing for new investigations into previously established mechanisms. To discover new and potentially useful alloys, the HEA field is continually expanding away from the equiatomic solid solutions that dominated early work. The work presented in this dissertation utilizes two, intuitive, pseudo-binary HEA systems to investigate compositional effects on solid solution strengthening in highly concentrated alloys and twinning and transformation induced plasticity. It furthers the understanding of the mechanical …

Fabrication, Thermophysical, And Mechanical Properties Of Cermet And Cercer Fuel Composites For Nuclear Thermal Propulsion, Neal D. Gaffin

Doctoral Dissertations

Nuclear thermal propulsion (NTP) utilizes nuclear fission to double the efficiency of
in-space propulsion systems compared with traditional combustion rocket systems.
NTP systems are limited primarily by the fuel material choice, due to the extreme
conditions they will need to endure, including temperatures up to 3000 K, multiple
thermal cycles with rapid heating and cooling, exposure to hot flowing hydrogen,
large thermal gradients, and high neutron flux. Particle based fuels, namely ceramic-
metallic (cermet) and ceramic-ceramic (cercer) composites are both promising fuel
element material candidates for NTP. Given the high temperature nature, these
materials are difficult to fabricate and very …

Synthesis And Assembly Of Polymer Materials At Interfaces, Xiaoshuang Wei

Doctoral Dissertations

The overarching goal of the thesis is to understand growth and assembly of polymer materials at interfaces. Chapter 2 and Chapter 3 study simultaneous polymer growth and assembly at fluid interfaces, where in-situ photopolymerization and vapor phase deposition were utilized to grow polymers, respectively. Chapter 4 leverages capillary condensation to pattern polymer growth at solid substrates. Chapter 1 provides background information on polymer materials at interfaces, and vapor phase deposition method (initiated chemical vapor deposition, iCVD) to grow polymers. This chapter also reviews polymer thin film wetting, and colloidal assemblies at interfaces. In Chapter 2, we demonstrate the preparation …

Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian

Doctoral Dissertations

The self-assembly of charged macromolecules forms the basis of all life on earth. From the synthesis and replication of nucleic acids, to the association of DNA to chromatin, to the targeting of RNA to various cellular compartments, to the astonishingly consistent folding of proteins, all life depends on the physics of the organization and dynamics of charged polymers. In this dissertation, I address several of the newest challenges in the assembly of these types of materials. First, I describe the exciting new physics of the complexation between polyzwitterions and polyelectrolytes. These materials open new questions and possibilities within the context …

Quantifying Elasto-Adhesion And Fluid-Elastic Dynamics For Ultra-Soft Hydrogel Interfaces, Hongbo Fu

Doctoral Dissertations

Hydrogels are constructed with polymer networks swollen with water, which are soft and with much smaller shear moduli than bulk moduli. Due to the similar moduli to biological tissues, synthetic hydrogels have been used for biological applications. While interfacial properties are important for many of the applications of soft materials, quantifying these properties is challenging for ultra-soft materials. Ultra-softness causes difficulties in measuring interfacial properties with conventional force-based methods. For example, soft specimens deform largely under gravity and external forces, and thus the assumptions of the established methods are invalid. Additionally, many of the applications for hydrogels require them to …