Polymer composite has been under rapid development with advancements in polymer chemistry, synthetic fibers, and nanoparticles. With advantages such as lightweight, corrosion resistance, and tunable functionalities, polymer composite plays a significant role in various applications such as aerospace, wearable electronics, energy storage systems, robotics, biomedicine, and microelectronics. In general, polymer composite can be divided into particulate-filled, fiber-filled, or network-filled types depending on the manufacturing process and internal structure. Over the years, fabrication processes on the macro- and micro-scales have been extensively explored. For example, lamination, fiber tow steering, and fiber spinning correspond to meter, millimeter, and micrometer scales, respectively. With the development of nanoparticles and their exceptional material properties, polymer nanoparticle composite has shown promising material property enhancements. However, the lack of economical solutions to achieve nanoscale nanoparticle morphology control limits the reinforcement efficiency and industrial applications. This dissertation focuses on utilizing additive manufacturing as a tooling method to achieve nanoparticle morphology control in polymer nanocomposite fibers. Chapter 1 gives a thorough background review regarding fiber composite, additive manufacturing, and the importance of nanoparticle orientation. Two types of nozzle designs, concentrical and layer-by-layer, are 3D printed and combined with the dry-jet-wet fiber spinning method to create continuous fibers with internal structures. Chapters 2 to 5 correspond to four stages of my research, namely, (2) multi-material fiber spinning, (3) interfacial-assisted nanoparticle alignment, (4) microscale patterning, and (5) nanoscale patterning. The achieved feature resolution also improves from 100 µm, 10 µm, 2 µm, to 170 nm, respectively. The process-structural-property relationship of polymer nanocomposite fibers is also investigated with applications demonstrations including sensors, electrically conductive fibers, thermally conductive fibers, and mechanically reinforced fibers. At last, Chapter 6 gives a summary and some future perspectives regarding fiber composites.

In recent years, the scientific community around the synthesis and processing of nanoporous metals is striving to integrate them into powder metallurgy processes such as additive manufacturing since it has a potential to fabricate 3D hierarchical high surface area electrodes for energy applications. Recent research in dealloying – a versatile method for synthesizing nanoporous metals – emphasized the need in understanding its process-structure relationships to independently control the relative density, ligament and pore sizes with good process reproducibly. In this dissertation, a new understanding of the dealloying process is presented for synthesizing (i) nanoporous gold thin-films and (ii) nanoporous Cu spherical powders with an emphasis on understanding variability in their process-structure relationships and process scalability. First, this work sheds the light on the nature of the dealloying front and its percolation along the grain boundaries in nanocrystalline gold-silver thin films by studying the early stages of ligament nucleation. Additionally, this work analyses its variability by investigating new process variables such as (i) equilibration time and (ii) precursor aging and their impacts in achieving process reproducibility. The correlation of relative density with ligament size is contextualized with state-of-the-art data mining research. Second, this work provides a new methodology for large scale production of nanoporous Cu powder and demonstrates its integration with powder casting to fabricate porous conductive electrode. By understanding the influence of etching solution concentration and titration methodology on the structure and composition of nanoporous Cu, it was possible to fabricate precipitate-free powders at high throughputs. Further, the nature of oxygen incorporation into porous Cu powder was studied as a function of surface-to-volume ratio of powder in atmospheric conditions. To consolidate powders into parts via open-die casting, this work harvests Ostwald Ripening phenomena associated with thermal coarsening in nanoporous metals to weld them at low temperatures (approximately one-third of its melting temperature). This work represents a major step towards the integration of nanoporous Cu feedstocks into additive manufacturing.

The current Li-ion batteries with organic liquid electrolytes are limited by their safety and energy density. Therefore, ceramic electrolytes are proposed in developing next-generation, energy-dense Li-metal batteries by replacing organic liquid electrolytes to improve safety and performance. Among numerous ceramic Li-ion conductors, garnet-based solid electrolyte c-Li7La3Zr2O12 (c-LLZO) is considered one of the most promising candidates to enable Li metal batteries due to its high ionic conductivity, chemical stability, and wide electrochemical stability window against Li metal. However, synthesis and processing of c-LLZO through conventional solid-sate reaction methods requires long periods of calcination (> 6 h) at high reaction temperatures (> 1000 °C). The need for high reaction temperature results to attain cubic-LLZO phase results in large aggerated LLZO particles and causes Li-loss from the garnet structure, making them unfavorable to process further as bulk pellets or thin films. To overcome processing challenges with solid-state reaction method, two novel facile synthesis approaches molten salt (flux growth method), and solution combustion are employed to produce submicron-sized LLZO powders at low reaction temperatures (< 1000 °C) in a short time. In the first case, molten salt synthesis method with LiCl-KCl eutectic mixture is employed to produce sub-micron sized Ta-doped LLZO (LLZTO) powders at low temperatures (900 °C, 4 h). In addition, a detailed investigation on effect of sintering medium and sintering additives on the structural, microstructural, chemical, and Li-ion transport behavior of the LLZTO pellets are investigated. Sintered LLZTO pellets prepared using molten salt synthesis route exhibited high Li-ion conductivity up to 0.6 mS cm-1 and high relative density (> 95 %) using Pt-crucible. In the second case, a facile solution-combustion technique using an amide-based fuel source CH6N4O is utilized to produce submicron-sized Al-doped LLZO (Al-LLZO) powders at low reaction temperatures 600-800 °C in a short duration of 4 h. In addition, effect of fuel to oxidizer ratio on phase purity, particle growth size, and formation mechanism of conductive Al-LLZO are reported and discussed. The Al-LLZO pellets sintered at 1100 °C/ 6 h exhibited high Li-ion conductivity up to 0.45 mS cm-1 with relative densities (> 90 %).

The purpose of this project is to assess how well today’s youth is able to learn new skills<br/>in the realm of engineering through online video-conferencing resources. Each semester of this<br/>last year, a class of students in both 3rd and 6th grade learned about computer-aided design (CAD)<br/>and 3D printing through their laptops at school. This was done by conducting online lessons of<br/>TinkerCAD via Zoom and Google Meet. TinkerCAD is a simple website that incorporates easy-to-learn skills and gives students an introduction to some of the basic operations that are used in<br/>everyday CAD endeavors. In each lesson, the students would learn new skills by creating<br/>increasingly difficult objects that would test both their ability to learn new skills and their overall<br/>enjoyment with the subject matter. The findings of this project reflect that students are able to<br/>quickly learn and retain new information relating to CAD. The group of 6th graders was able to<br/>learn much faster, which was expected, but the class of 3rd graders still maintained the<br/>knowledge gained from previous lessons and were able to construct increasingly complicated<br/>objects without much struggle. Overall, the students in both classes enjoyed the lessons and did<br/>not find them too difficult, despite the online environment that we were required to use. Some<br/>students found the material more interesting than others, but in general, the students found it<br/>enjoyable to learn about a new skill that has significant real-world applications

Photocatalytic activity of titanium dioxide (titania or TiO2) offers enormous potential in solving energy and environmental problems. Immobilization of titania nanoparticles on inert substrates is an effective way of utilizing its photocatalytic activity since nanoparticles enable high mass-transport, and immobilization avoids post-treatment separation. For competitive photocatalytic performance, the morphology of the substrate can be engineered to enhance mass-transport and light accessibility. In this work, two types of fiber architectures (i.e., dispersed polymer/titania phase or D-phase, and multi-phase polymer-core/composite-shell fibers or M-phase) were explored as effective substrate solutions for anchoring titania. These fibers were fabricated using a low-cost and scalable fiber spinning technique. Polymethyl methacrylate (PMMA) was selected as the substrate material due to its ultraviolet (UV) transparency and stability against oxidative radicals. The work systematically investigates the influence of the fiber porosity on mass-transport and UV light scattering. The properties of the fabricated fiber systems were characterized by scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), UV-vis spectrophotometry (UV-vis), and mechanical analysis. The photocatalytic performance was characterized by monitoring the decomposition of methylene blue (MB) under UV (i.e., 365 nm) light. Fabrication of photocatalytic support structures was observed to be an optimization problem where porosity improved mass transport but reduced UV accessibility. The D-phase fibers demonstrated the highest MB degradation rate (i.e., 0.116 min-1) due to high porosity (i.e., 33.2 m2/g). The M-phase fibers reported a better degradation rate compared to a D-phase fibers due to higher UV accessibility efficiency.

Precursors of carbon fibers include rayon, pitch, and polyacrylonitrile fibers that can be heat-treated for high-strength or high-modulus carbon fibers. Among them, polyacrylonitrile has been used most frequently due to its low viscosity for easy processing and excellent performance for high-end applications. To further explore polyacrylonitrile-based fibers for better precursors, in this study, carbon nanofillers were introduced in the polymer matrix to examine their reinforcement effects and influences on carbon fiber performance. Two-dimensional graphene nanoplatelets were mainly used for the polymer reinforcement and one-dimensional carbon nanotubes were also incorporated in polyacrylonitrile as a comparison. Dry-jet wet spinning was used to fabricate the composite fibers. Hot-stage drawing and heat-treatment were used to evolve the physical microstructures and molecular morphologies of precursor and carbon fibers. As compared to traditionally used random dispersions, selective placement of nanofillers was effective in improving composite fiber properties and enhancing mechanical and functional behaviors of carbon fibers. The particular position of reinforcement fillers with polymer layers was enabled by the in-house developed spinneret used for fiber spinning. The preferential alignment of graphitic planes contributed to the enhanced mechanical and functional behaviors than those of dispersed nanoparticles in polyacrylonitrile composites. The high in-plane modulus of graphene and the induction to polyacrylonitrile molecular carbonization/graphitization were the motivation for selectively placing graphene nanoplatelets between polyacrylonitrile layers. Mechanical tests, scanning electron microscopy, thermal, and electrical properties were characterized. Applications such as volatile organic compound sensing and pressure sensing were demonstrated.

Polymer fibers have broad applications in wearable electronics, bulletproof vests, batteries, fuel cells, filters, electrodes, conductive wires, and biomedical materials. Polymer fibers display light density and flexibility but are mostly weak and compliant. The ceramic, metallic, and carbon nanoparticles have been frequently included in polymers for fabricating continuous, durable, and functional composite fibers. Nanoparticles display large specific areas, low defect density and can transfer their superior properties to polymer matrices. The main focus of this thesis is to design, fabricate and characterize the polymer
anocarbon composite fibers with unique microstructures and improved mechanical/thermal performance. The dispersions and morphologies of graphene nanoplatelets (GNPs), the interactions with polyvinyl alcohol (PVA) molecules and their influences on fiber properties are studied. The fibers were fabricated using a dry-jet wet spinning method with engineered spinneret design. Three different structured fibers were fabricated, namely, one-phase polymer fiber (1-phase), two-phase core-shell composite fiber (2-phase), and three-phase co-axial composite fiber (3-phase). These polymer or composite fibers were processed at three stages with drawing temperatures of 100˚C, 150˚C, and 200˚C. Different techniques including the mechanical tester, wide-angle X-Ray diffraction (WAXD), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and differential scanning calorimeter (DSC) have been used to characterize the fiber microstructures and properties.

The goal of our research was to develop and validate a method for predicting the mechanical behavior of Additively Manufactured multi-material honeycomb structures. Multiple approaches already exist in the field for modeling the behavior of cellular materials, including the bulk property assumption, homogenization and strut level characterization [1]. With the bulk property approach, the structure is assumed to behave according to what is known about the material in its bulk formulation, without regard to its geometry or scale. With the homogenization technique, the specimen that is being tested is treated as a solid material within the simulation environment even if the physical specimen is not. Then, reduced mechanical properties are assigned to the specimen to account for any voids that exist within the physical specimen. This approach to mechanical behavior prediction in cellular materials is shape dependent. In other words, the same model cannot be used from one specimen to the next if the cell shapes of those lattices differ in any way. When using the strut level characterization approach, a single strut (the connecting member between nodes constituting a cellular material) is isolated and tested. With this approach, there tends to be a significant deviation in the experimental data due to the small size of the isolated struts. Yet it has the advantage of not being shape sensitive, at least in principle. The method that we developed, and chose to test lies within the latter category, and is what we have coined as the Representative Lattice Element (RLE) Method. This method is modeled after the well-established Representative Volume Element (RVE) method [2]. We define the RLE as the smallest unit over which mechanical tests can be conducted that will provide results which are representative of the larger lattice structure. In other words, the theory is that a single member (or beam in this case) of a honeycomb structure can be taken, tests can be conducted on this member to determine the mechanical properties of the representative lattice element and the results will be representative of the mechanical behavior whole structure. To investigate this theory, we designed specimens, conducted various tensile and compression tests, analyzed the recorded data, conducted a micromechanics study, and performed structural simulation work using commercial Finite Element Analysis software.