Doctor of Philosophy / Department of Chemistry / Jun Li / Nanostructured electrode materials for electrochemical energy storage systems have been shown to improve both rate performance and capacity retention, while allowing considerably longer cycling lifetime. The nano-architectures provide enhanced kinetics by means of larger surface area, higher porosity, better material interconnectivity, shorter diffusion lengths, and overall mechanical stability. Meanwhile, active materials that once were excluded from use due to bulk property issues are now being examined in new nanoarchitecture. Silicon was such a material, desired for its large lithium-ion storage capacity of 4,200 mAh g[superscript]-1 and low redox potential of 0.4 V vs. Li/Li[superscript]+; however, a ~300% volume expansion and increased resistivity upon lithiation limited its broader applications. In the first study, the silicon-coated vertically aligned carbon nanofiber (VACNF) array presents a unique core-shell nanowire (NW) architecture that demonstrates both good capacity and high rate performance. In follow-up, the Si-VACNFs NW electrode demonstrates enhanced power rate capabilities as it shows excellent storage capacity at high rates, attributed to the unique nanoneedle structure that high vacuum sputtering produces on the three-dimensional array. Following silicon’s success, titanium dioxide has been explored as an alternative highrate electrode material by utilizing the dual storage mechanisms of Li+ insertion and pseudocapacitance. The TiO[subscript]2-coated VACNFs shows improved electrochemical activity that delivers near theoretical capacity at larger currents due to shorter Li[superscript]+ diffusion lengths and highly effective electron transport. A unique cell is formed with the Si-coated and TiO[subscript]2-coated electrodes place counter to one another, creating the hybrid of lithium ion battery-pseudocapacitor that demonstrated both high power and high energy densities. The hybrid cell operates like a battery at lower current rates, achieving larger discharge capacity, while retaining one-third of that capacity as the current is raised by 100-fold. This showcases the VACNF arrays as a solid platform capable of assisting lithium active compounds to achieve high capacity at very high rates, comparable to modern supercapacitors. Lastly, manganese oxide is explored to demonstrate the high power rate performance that the VACNF array can provide by creating a supercapacitor that is highly effective in cycling at various high current rates, maintaining high-capacity and good cycling performance for thousands of cycles.

Master of Science / Mechanical and Nuclear Engineering / Kevin B. Lease / Gurpreet Singh / Energy has always been one of the most important factors in any type of human or industrial endeavor. Clean energy and alternative energy sources are slowly but steadily replacing fossil fuels, the over-dependence on which have led to many environmental and economic troubles over the past century. The main challenge that needs to be addressed in switching to clean energy is storing it for use in the electrical grid and transportation systems. Lithium ion batteries are currently one of the most promising energy storage devices and tremendous amount of research is being done in high capacity anode and cathode materials, and better electrolytes and battery packs as well, leading to overall high efficiency and capacity energy storage systems. Polymer derived ceramics (PDCs) are a special class of ceramics, usually used in high temperature applications, but some silicon based PDCs have demonstrated good electrochemical properties in lithium ion batteries. The goal of this research is to explore a special hybrid ceramic of titanium dioxide (TiO₂) and silicon oxy carbide (SiOC) ceramic derived from 1,3,5,7 -- tetravinyl -- 1,3,5,7 -- tetramethylcyclotetrasiloxane (TTCS) polymer for use in lithium ion batteries and investigate the source of its properties which might make the ceramic particularly useful in some highly specialized energy storage applications.

Doctor of Philosophy / Chemical Engineering / Mary E. Rezac / Membrane contact reactors (MCRs) have been evaluated for the selective hydro-treating of model reactions; the partial hydrogenation of soybean oil (PHSO), and the conversion of lactic acid into commodity chemicals. Membranes were rendered catalytically active by depositing metal catalyst onto the polymer "skin" of an asymmetric membrane. Hydrogen was supplied to the support side of the membrane and permeated from the support side to the skin side, where it adsorbed directly onto the metal surface. Liquid reactant was circulated over the membrane, allowing the liquid to come into direct contact with the metal coated surface of the membrane, where the reaction occurred. Our membrane contact reactor approach replaces traditional three-phase batch slurry reactors. These traditional reactors possess inherent mass transfer limitations due to low hydrogen solubility in liquid and slow diffusion to the catalyst surface. This causes hydrogen starvation at the catalyst surface, resulting in undesirable side reactions and/or extreme operating pressures of 100 atmospheres or more. By using membrane reactors, we were able to rapidly supply hydrogen to the catalyst surface. When the PHSO is performed in a traditional slurry reactor, the aforementioned hydrogen starvation leads to a high amounts of trans-fats. Using a MCR, we were able to reduce trans-fats by over 50% for equal levels of hydrogenation. It was further demonstrated that an increase in temperature had minimal effects on trans-fat formation, while significantly increasing hydrogenation rates; allowing the system to capture higher reaction rates without adversely affecting product quality. Additionally, high temperatures favors the hydrogenation of polyenes over monoenes, leading to low amounts of saturated fats. MCRs were shown to operator at high temperatures and: (1) capture high reaction rates, (2) minimize saturated fats, and (3) minimize trans-fats. We also demonstrated lactic acid conversion into commodity chemicals using MCRs. Our results show that all MCR experiments had faster reaction rate than all of our controls, indicating that MCRs have high levels of hydrogen coverage at the catalyst. It was also demonstrated that changing reaction conditions (pressure and temperature) changed the product selectivities; giving the potential for MCRs to manipulate product selectivity.

Master of Science / Department of Mechanical and Nuclear Engineering / Steven J. Eckels / Christopher M. Sorensen / Large specific surface areas and high concentrations of reactive edge and defect sites make NanoActive™ metal oxide powders ideal chemical adsorbents. These powders are dispersed in aerosol form to remediate toxic wastes and neutralize chemical and biological warfare agents. In the destructive adsorption of toxic chemicals, effective application requires particles be as small as possible, thus, maximizing surface area and number of edge and defect sites. Other applications, e.g. smoke clearing, require particles be large so they will settle in a timely manner. Ideally, particle size control could be engineered into powder dispersion devices. The purpose of this study was to explore particle cohesion and aerodynamic deaggregation mechanisms to enhance the design of powder dispersion devices. An aerosol generator and four experimental nozzles were designed to explore the most commonly referenced deaggregation mechanisms: particle acceleration, particles in shear and turbulent flows, and particle impaction. The powders were then dispersed through the nozzles with increasing flow rates. A small angle light scattering device was used to make in situ particle size measurements. The nozzle designed for impaction deaggregated the NanoActive™ MgO particles to a lesser degree than the other three nozzles, which deaggregated the particles to a similar degree. Flows in three of the four nozzles were simulated in a commercial computational fluid dynamics package. Theoretical particle and aggregate stresses from the literature were calculated using simulated data. These calculations suggest particle acceleration causes internal stresses roughly three orders of magnitude larger than shear and turbulent flows. These calculations, coupled with experimental data, lead to the conclusion that acceleration was the most significant cause of particle deaggregation in these experiments. Experimental data also identified the dependence of deaggregation on primary particle size and agglomerate structure. NanoActive™ powders with smaller primary particles exhibited higher resistance to deaggregation. Small primary particle size was thought to increase the magnitude of van der Waals interactions. These interactions were modeled and compared to theoretical deaggregation stresses previously mentioned. In conclusion, deaggregation is possible. However, the ideas of particle size control and a universal dispersion device seem elusive considering the material dependent nature of deaggregation.

Doctor of Philosophy / Department of Chemical Engineering / Larry E. Erickson / Over the past decade, nanomaterials have been the subject of enormous interest. Their defining characteristic is a very small size in the range of 1-100 nm. Due to their nanometer size, nanomaterials are known to have unique mechanical, thermal, biological, optical and chemical properties, together with the potential for wide-ranging industrial applications. Here, we synthesized nanocrystalline metal oxides through the sol-gel process and used these materials as desulfurization adsorbents and photocatalysts. Deep desulfurization of fuels has received more and more attention worldwide, not only because of health and environmental consideration but also due to the need for producing ultra-low-sulfur fuels, which can only be achieved under severe operating conditions at high cost using hydrodesulfurization (HDS). Consequently, development of new and affordable deep desulfurization processes to satisfy the decreasing limit of sulfur content in fuels is a big challenge. Sol-gel derived Cu/Al[subscript]2O[subscript]3 and Zn/Al[subscript]2O[subscript]3 adsorbents have been demonstrated to be effective in the removal of thiophene from a model solution. Results showed that Cu[superscript]+ was the active site and thermal treatment under vacuum was critical for Zn/Al[subscript]2O[subscript]3 since a defective, less crystalline spinel led to stronger interaction between zinc ions and thiophene molecules in the adsorption process. The kinetic study suggested that most of the adsorption occurred in the first 30 min, and adsorption equilibrium was attained after 1.5 h. Both adsorbents showed good regenerative property. TiO2 is considered the most promising photocatalyst due to its high efficiency, chemical stability, non-toxicity, and low cost for degradation and complete mineralization of organic pollutants. However, the use of TiO[subscript]2 is impaired because it requires ultraviolet (UV) activation ([Lambda]<387 nm). The shift of optical response of TiO[subscript]2 from the UV to the visible light region would have a profound positive effect on the efficient use of solar energy in photocatalytic reactions. We shifted the optical response of TiO[subscript]2 and improved the photocatalytic efficiency through size modification and transition metal ion and nonmetal atom doping. Experimental results showed that C and V co-doped TiO[subscript]2 catalysts had much higher activity than commercial P25 TiO[subscript]2 towards the degradation of acetaldehyde under visible light irradiation. For the first time, we reported that activities were comparable in the dark and under visible light irradiation for co-doped TiO[subscript]2 with 2.0 wt% V. C and N co-doped TiO[subscript]2 exhibited higher activity for the degradation of methylene blue than pure TiO[subscript]2 under visible light and UV irradiation. Possible mechanisms were discussed based on the experimental results.

Master of Science / Department of Civil Engineering / Hayder A. Rasheed / Throughout history natural fiber was used as one of the main building materials all over the world. Because the use of such materials has decreased in the last century, not much research has been conducted to investigate their performance as a reinforcing material in cement and concrete. In order to investigate one of the most common natural fibers, wheat fibers, as a reinforcing material, 156 mortar specimens and 99 concrete specimens were tested. The specimens were tested in either uniaxial compression or flexure. The uniaxial compression test included 2 in (50.8 mm) mortar cubes and 4x8 in (101.6 x 203.2 mm) concrete cylinders. As for the flexure test, they were either 40x40x160 mm cementitious matrix prisms or 6x6x21 in (152.4x152.4x533.4 mm) concrete prisms. Several wheat fibers percentages were studied and compared with polypropylene fiber as a benchmarking alternative. The average increase in the uniaxial compression strength for cementitious matrix cubes reinforced with 0.5% long wheat fiber exceeded that of their counterparts reinforced with polypropylene fiber by 15%. Whereas for concrete cylinders reinforced with 0.75% long wheat fiber, their strength exceeded that of their counterparts reinforced with polypropylene fiber by 5% and that of the control by 7%. The flexural strength of cementitious matrix prisms reinforced with 0.75% long wheat fiber exceeded that of their counterparts reinforced with polypropylene fiber by 27%. Meanwhile, concrete prisms reinforced with both long wheat fiber and polypropylene fiber showed deterioration in strength of up to 17%. Finally, ABAQUS models were developed for concrete cylinders and prisms to simulate the effect of inclusion of the wheat fibers.