Materials Science & Engineering
Permanent URI for this communityhttp://hdl.handle.net/1903/2260
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Item Magnetic nanoparticle inks for syringe printable inductors(2023) Fedderwitz, Rebecca; Kofinas, Peter; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Direct Ink Writing (DIW) additive manufacturing (AM) has the transformative potential to construct complex shapes and devices with a single apparatus by exchanging the printable material at the print head. Iron cobalt (FeCo), permalloy (Ni80Fe20), and iron (II,III) oxide (Fe2O3·FeO) nanoparticles with varying magnetic properties were incorporated in resins to explore the influence of particle loading on printability and inductor device performance. It was generally found that increasing particle loading increased ink viscosity, with a loading maximum approaching 29 – 42 vol% depending on the particle type and resin mixtures due to differences in particle shape and size and resin viscosity. With more magnetic content, composites had higher magnetic permeability and inductance. Syringe printable, colloidal, aqueous magnetic inks were made using both stabilized iron oxide and MnZn doped ferrite nanoparticles with added free polymers. MnZn doped ferrite inks are printed into toroids, sintered to improve magnetic permeability and mechanical robustness, and constructed into an inductor device. Inductors with high magnetic permalloy nanoparticle content were also syringe printed into toroids and hand-wound to demonstrate their viability in fabricating three-dimensional inductors. The effect of particle size on stability and printability was observed. The research presented in this thesis investigates various methods for formulating magnetic nanoparticle inks and evaluates the contributions of particle stabilization, free polymer content, solvent composition, and particle loading on the rheological behavior required for syringe printing. Material properties and device performances were characterized using methods such as zeta potential and settling studies to observe particle functionalization and stability, rheology to study viscoelastic flow behavior, and vector network analysis to measure inductance and device efficiency to showcase the viability of this technique to manufacture passive electronic devices.Item Radiation-Induced Modification of Aramid Fibers: Optimizing Crosslinking Reactions and Indirect Grafting of Nanocellulose for Body Armor Applications(2022) Gonzalez Lopez, Lorelis; Al-Sheikhly, Mohamad; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The goal of this dissertation was to design, synthesize, and analyze novel aramid fibers by covalently grafting nanocellulose through electron beam irradiation. These nanocellulose functionalized fibers showed enhanced strength and larger surface areas, which improves their performance and applicability in fiber-reinforced composites. Unmodified aramid fibers have smooth and chemically inert surfaces, which results in poor adhesion to many types of resins. Nanocellulose was chosen as the ideal filler to functionalize the fibers due to its reactive surface and high strength-to-weight ratio. Aramid fibers were further modified by radiation-induced crosslinking reactions as a means to avoid scission of the polymeric backbone and to further increase the fiber strength.An indirect radiation-induced grafting approach was used for synthesizing these novel nanocellulose-grafted aramid fibers while avoiding the irradiation of nanocellulose. The fibers were irradiated using the e-beam linear accelerator (LINAC) at the Medical Industrial Radiation Facility (MIRF) at the National Institute of Standards and Technology (NIST). After the irradiation, the fibers were kept in an inert atmosphere and then mixed with a nanocellulose solution for grafting. The grafted fibers were evaluated by gravimetric analysis, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and nuclear magnetic resonance (NMR) spectroscopy. The mechanical properties of the synthesized fibers were studied by single fiber tensile tests. Aramid fibers were also irradiated at the MIRF in the presence of acetylene gas and triacrylate solution as a means to induce crosslinking reactions. These fibers were irradiated at both low doses and high dose rates at room temperature. A mechanism for the crosslinking of aramid fibers was proposed in this dissertation. Mechanical testing of the fibers after crosslinking showed an increase in the strength of the fibers of up to 15%. Ultra-high molecular weight polyethylene (UHMWPE) fibers were also studied, but due to an issue of entanglement of the fibers during the grafting process, their mechanical properties could not be analyzed. Future work will focus on using a better set up to avoid entanglement of these fibers. To complete the study of the radiation effects on polymers, this thesis explored the radiation-induced degradation of aromatic polyester-based resins. The composition of the resins studied included phenyl groups and epoxies, which complicate radiation-induced grafting and crosslinking reactions. Unlike aramid and polyethylene fibers, polyester-based resins have a C-O-C bond that is susceptible to degradation. The resins were irradiated at high doses in the presence of oxygen. The scission of the polymeric backbone of the polymers was studied using Electron Paramagnetic Resonance (EPR) analysis. EPR showed the formation of alkoxyl radicals and C-centered radicals as the primary intermediate products of the C-O-C scissions. The degradation mechanisms of the resins in the presence of different solvents were proposed. Changes in the Tg of the polymers after irradiation, as an indication of degradation, were studied by Dynamic Mechanical Analysis (DMA). The results obtained from this work show that irradiation of these resins results in continuous free radical-chain reactions that lead to the formation of recyclable oligomers.Item Processing and structural characterization toward all-cellulose nanocomposites(2021) Henderson, Doug A; Briber, Robert M; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Cellulose is the most abundant biopolymer on the planet and is used in a variety of industry sectors including paper, coatings, medicine, and food. A deep understanding of cellulose is important for its development as an alternative polymer to those based on petroleum. This work focuses on two cellulose systems. The first of these, cellulose nanofibers, are the basic structural elements of naturally-occurring cellulosic materials; they exhibit excellent mechanical characteristics due to high crystallinity and a dense network of hydrogen bonding. These fibers can be separated from bulk cellulose via a TEMPO oxidation reaction followed by mechanical homogenization into a suspension in water. In this work, the production of these fibers is investigated by monitoring the change in structure of cellulose as a function of TEMPO reaction time and mechanical homogenization using small angle neutron scattering, atomic force microscopy, and optical microscopy. The second cellulose system is a molecular solution of cellulose formed using a binary solvent mixture consisting of ionic liquid and an aprotic solvent. Cellulose is difficult dissolve due to a dense hydrogen bonding network, and ionic liquids have been shown to be an effective alternative to more hazardous and energy-intensive dissolution methods for cellulose currently used in industry. The phase behavior of these solutions has been investigated using small angle neutron scattering as a function of temperature. The process of regenerating cellulose from these solutions is also investigated, as dense gels of cellulose and ionic liquid were produced with a unique multiscale ordered structure. The ultimate goal of this work is to combine cellulose nanofibers and molecular cellulose solutions in order to create all-cellulose nanocomposite films. These films are characterized using tensile testing, atomic force microscopy, and water uptake measurements in order to understand the interaction between cellulose nanofibers and molecular cellulose solutions, water resistance and tunability of mechanical properties.Item RADIATION SYNTHESIS OF IONIC LIQUID POLYMER ELECTROLYTE MEMBRANE FOR HIGH TEMPERATURE FUEL CELL APPLICATIONS(2020) Mecadon, Kevin; Al-Sheikhly, Mohamad; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The purpose of this thesis was to design, synthesize and analyze innovative anhydrous fuel cell membranes that can operate at temperatures above 100°C. Operating at this higher temperature region improves performance and reliability of fuel cells: increasing proton mobility, enhancing reaction kinetics, increasing catalysis activity and reducing carbon monoxide poisoning. Traditional polymer electrolyte membrane fuel cells (PEMFCs) do not operate efficiently above 100°C because water is used as a proton conductive medium though the Grotthuss hopping mechanism. Through substituting water with protic ionic liquids and grafting onto fluorocarbon films, a new proton conductive network solid state PEM has been developed. These membranes can perform at high temperature above 100°C. Polymers were selected for grafting based on the following properties: high proton conductivity, low electrical conductivity, high mechanical properties, high chemical resistance, and high temperature and humidity stability. The method used to synthesize these anhydrous polymer electrolyte membranes (PEMs) was radiation grafting using heterocyclic protic ionic liquid monomers and fluorocarbon substrates. PEMs were prepared at the Medical Industrial Radiation Facilities (MIRF) at the National Institute of Standards and Technology (NIST). MIRF is a 10.5 MeV electron beam accelerator, which was used to radiate the fluorocarbon substrate and then indirectly graft heterocyclic protic ionic liquids to create PEMs. After synthesis, the extent and uniformity of PEM composition was analyzed using FTIR microscopy, SEM/EDS, SANS and their proton conductivity as measured by EIS. Through this research, indirect radiation grafting was shown to covalently bond ionic liquids onto fluorocarbon substrates to synthesize PEMs. The resulting ionic liquid PEMs showed proton conductivities greater than 10-3 S/cm above 100°C that behaved independent of humidity. The ionic liquid PEMs also demonstrated a positive correlation of increasing proton conductivity with increasing temperatures above 100°C even after the PEMs are dehydrated. The chemical properties and structure of the grafted ionic liquids greatly affects the proton conductive mechanisms present in the PEMs. These trends found through the course of this research will help the development of future anhydrous PEM with higher proton conductivity, performance, and reliability.