Materials Science and Engineering Commons^™

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 …

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 …

Advanced Materials Design Using Application-Based Processing Techniques, Daniel S. Camarda

Doctoral Dissertations

This dissertation pertains to generating advanced materials using application-based processing techniques. First, billets consisting of PTFE sintering powders are evaluated using Thermomechancal Analysis. It was found that both shape change and volume change are associated with enthalpic and entropic recoil, respectively. These phenomena, due to melting and stored energy during the powder compaction process, were found to be molecular weight dependent. Additionally, kinetics of the recovery and sintering process were found to be slower in blended specimens than pure samples. Next, the creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer …

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 …

Designing Stimuli-Responsive Nanocomposites To Investigate Interface Dynamics, Huyen Vu

Doctoral Dissertations

Inspired by nature, this research focuses on designing multifunctional renewable nanocomposites with high toughness and stimuli-responsiveness. In recent years, cellulose nanocrystals (CNCs) have been explored due to their abundance, renewable resource, and unique mechanical strength and structural coloration. CNCs naturally self-assemble into the helicoidal (Bouligand) structure that effectively endure high impacts but is brittle without an attendant soft phase. A thermoresponsive polymer, poly(diethylene glycol methyl ether methacrylate) (PMEO₂MA), was incorporated into CNCs via evaporation-induced self-assembly to improve toughness of the resulting nanocomposites and to study responses in polymer dynamics under varying temperature and humidity conditions. To study microscopic …

Thermoelectric Transport In Disordered Organic And Inorganic Semiconductors, Meenakshi Upadhyaya

Doctoral Dissertations

The need for alternative energy sources has led to extensive research on optimizing the conversion efficiency of thermoelectric (TE) materials. TE efficiency is governed by figure-of-merit (ZT) and it has been an enormously challenging task to increase ZT > 1 despite decades of research due to the interdependence of material properties. Most doped inorganic semiconductors have a high electrical conductivity and moderate Seebeck coefficient, but ZT is still limited by their high lattice thermal conductivity. One approach to address this problem is to decrease thermal conductivity by means of alloying and nanostructuring, another is to consider materials with an inherently low …

Engineering Advanced Material Properties For Polymeric Materials Through Miscible And Immiscible Additives, Chinmay M. Saraf

Doctoral Dissertations

This dissertation focuses on engineering polymeric formulations using strategically selected additives or novel processes to achieve advanced material properties. The first chapter reviews the state-of-the-art impact modification and discusses micro-mechanics associated with soft particle toughening of polymeric materials. We present an analytical solution to elucidate the effect of concentration of rubbery domains on matrix yielding and energy absorption. Soft particle toughening relies on particle size, interparticle spacing, and concentration of rubbery phase. The second chapter demonstrates developing impact modified stereolithography (SLA) resins for the superior energy absorption of the SLA printed thermosets. SLA resins are engineered using additives that remain …

Direct Printing/Coating/Plating Of Key Components For Electronic Devices, Xiyu Hu

Doctoral Dissertations

Miniaturization has been a technological trend for several decades for electronic devices. From the practical point of view, the successful miniaturization of fully integrated systems mainly depends on their components. This dissertation examines the inkjet printing of copper oxide inks on flexible substrates for applications in microfluidic valving systems. We expand the knowledge of low-cost and high-performance electrowetting valves and fabricate the microfluidic device for fluidic control, which is necessary to enable the next-generation microfluidic devices. In addition, we also study the electromagnetic interference (EMI) shielding material, which is a crucial part of electronic devices. The basic theory of EMI …

Surface Modification Of Cellulose Nanocrystals: Imparting Non-Native Properties On Sustainable Substrates, Allen C. Chang

Doctoral Dissertations

Governments and scientists all over the planet have recognized the importance of pursuing and achieving sustainability. As the human population grows and technologies advance, the planet’s limited resources become less and less able to support our taxing demands. In 2015, the United Nations set forth 17 Sustainable Development Global Goals. Goal 12 “Responsible Production and Consumption” can be addressed quite readily by the integration of sustainable materials into advanced technologies; however, such materials have yet to be developed. Cellulose nanocrystals (CNCs) – an abundant, well-known sustainable nanomaterial hydrolyzed from bulk cellulose with high surface functionality and high strength properties – …

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 …

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 …

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 …