Master of Science / Department of Chemical Engineering / John Schlup / This study investigated the specular reflectance properties of 6061-T6 aluminum alloy anodized in accordance with military specification MIL-A-8625 as a function of both etch process time and anodization process potential. Both process parameters affect the specular reflectance characteristics when measured using a 660 nm, collimated diode laser source. The etch process time, when varied between 0.5 to 20 minutes, resulted in a decrease in specular reflectivity with increasing time. The anodization process potential was varied between 10 and 21 volts, with a 15 volt condition producing samples with the greatest specular reflectivity. Between the two parameters, the etch time had the greater effect. Additionally, the dependence of the incident beam angle on specular reflectivity was shown not to have a significant effect when compared to the etch process time and process potential.

Master of Science / Department of Chemical Engineering / Larry Erickson / Oxy-fired boilers are receiving increasing focus as a potential response to reduced boiler emissions limits and greenhouse gas legislation. Among the challenges in cleaning boiler gas for sequestration is attaining the necessary purity of the CO[subscript]2. A key component in the oxy-fired cleaning path is high purity SO[subscript]x and NO[subscript]x removal, often through absorption using the lead-chamber or similar process. Aerosol formation has been found to be a source of product contamination in many flue gas absorption processes. A number of authors presented simulation methods to determine the formation of aerosols in gas absorption. But these methods are numerically challenging and not suitable for day-to-day analysis of live processes in the field. The goal of this study is to devise a simple and practical method to predict the potential for and effect of aerosol formation in gas absorption using information from Aspen Plus, a commonly used process simulation tool. The NO[subscript]x absorber in an oxy-fired boiler CO[subscript]2 purification system is used as a basis for this investigation. A comprehensive review of available data suitable for simulating NO[subscript]x absorption in an oxy-fired boiler slipstream is presented. Reaction rates for eight reactions in both liquid and vapor phases are covered. These are entered into an Aspen Plus simulation using a RadFrac block for both rate-based and equilibrium reactions. A detailed description of the simulation format is given. The resulting simulation was compared to a previously published simulation and process data with good agreement. An overall description of the aerosol formation mechanism is presented, along with an estimate of expected aerosol nuclei reaching the NO[subscript]x absorption process. A method to estimate aerosol quantities produced based on inlet gas nuclei concentration and available condensable water vapor is presented. To estimate aerosol composition and emissions, an exit gas slipstream is used to equilibrate with a pure water aerosol using an Aspen Plus Equilibrium Reactor block. Changing the composition of the initial aerosol feed liquid suggests that the location of aerosol formation may influence the final composition and emissions.

Master of Science / Department of Chemical Engineering / John Schlup / In this study, life cycle analysis (LCA) of shea butter biodiesel from Well-to-Pump (WTP) is considered utilizing information gathered from Anuanom Industrial Bio Products Ltd. (AIBP) in Ghana, West Africa. The information presented in this report starts with shea plant cultivation, proceeds through harvesting of shea fruits, extraction of shea butter from shea kernels, and finishes with the production of shea butter biodiesel via homogenous acid–alkali transesterification reactions utilizing methanol. After researching the conversion of shea butter to biodiesel, the GREET software was explored as a tool to perform LCA. Shea butter is an excellent alternative feedstock to produce biodiesel on an industrial scale. Though research into shea plant cultivation and subsequent conversion into biodiesel in Ghana has not received formal attention, it has huge potential in the biodiesel industry. The tree originates in Africa and is tropical and drought-resistant. Although even some basic agronomic characteristics of shea butter are not yet fully understood, the plant enjoys a booming interest, which may hold the risk of unsustainable practice. The GREET software from the Argonne National laboratory of the US Department of Energy (DOE) was used in LCA. The software is a very useful tool specifically designed for LCA focused on energy and emissions of different production processes, including biodiesel production. This software is managed by DOE research laboratory and is made available for public use. The GREET software allow users perform many existing fuel production processes. To perform an LCA on shea butter biodiesel which is a new feedstock to the GREET software, some of the requisite information, and data input has to be sent to the Argonne National Laboratory personnel for input. For a new biodiesel feedstock such as shea butter which is not part of the GREET software database, it is important to work with the Argonne National laboratory to perform the LCA.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / Semiconducting icosahedral boron arsenide, B[subscript]12As[subscript]2, is an excellent candidate for neutron detectors and radioisotope batteries, for which high quality single crystals are required. Thus, the present study was undertaken to grow B[subscript]12As[subscript]2 crystals by precipitation from metal solutions (nickel) saturated with elemental boron and arsenic in a sealed quartz ampoule. B[subscript]12As[subscript]2 crystals of 8-10 mm were produced when a homogeneous mixture of the three elements was held at 1150 °C for 48-72 hours and slowly cooled (3°C/hr). The crystals varied in color and transparency from black and opaque to clear and transparent. X-ray topography (XRT), Raman spectroscopy, and defect selective etching confirmed that the crystals had the expected rhombohedral structure and a low density of defects (5x10[superscript]7 cm[superscript]-2). The concentrations of residual impurities (nickel, carbon, etc) were found to be relatively high (10[superscript]19 cm[superscript]-3 for carbon) as measured by secondary ion mass spectrometry (SIMS) and elemental analysis by energy dispersive x-ray spectroscopy (EDS). The boron arsenide crystals were found to have favorable electrical properties (μ = 24.5 cm[superscript]2 / Vs), but no interaction between a prototype detector and an alpha particle bombardment was observed. Thus, the flux growth method is viable for growing large B[subscript]12As[subscript]2 crystals, but the impurity concentrations remain a problem.

Doctor of Philosophy / Department of Chemical Engineering / Stefan H. Bossmann / Both chemotherapy for cancer treatment and antibiotic therapy for bacterial infections require systemic applications of the drug and a systemic application is always linked to a number of disadvantages. To circumvent these a targeted drug delivery system was developed. It utilizes the ability of phagocytes from the hosts own immune system to recognize and internalize antigens. Deactivated M. luteus, a non-pathogenic gram positive bacteria was loaded with high concentrations (exceeding the IC50 at least 60 fold in local intracellular concentration) the chemotherapeutics doxorubicin or DP44mt or with the bactericidal chlorhexidine. The modified bacteria is fed to phagocytes (Monocytes/Macrophages or neutrophils) and serves as protective shell for the transporting and targeting phagocyte. The phagocyte is recruited to the tumor site or site of infection and releases the drug along with the processed M. luteus via the exosome pathway upon arrival. The chlorhexidine drug delivery system was successfully tested both in vitro and in vivo, reducing the pathogen count and preventing systemic spread of a F. necrophorum infection in a mouse model. The doxorubicin drug delivery system reduced the viability of 4T1 cancer cells to 20% over the course of four days in vitro.

Master of Science / Department of Chemical Engineering / Keith Hohn / The study will utilize a probabilistic reaction modeling method for ring-opening reactions of epoxide. In particular, to elucidate the reaction mechanism by the methods presented, focus will be placed on the nucleophillic attack of ethylene oxide by ammonia and its anion. This focus was chosen because of the potential to gain significant advantage in computational intensity required to model the epoxy-amino macromolecular curing reactions and resulting thermochemical and physical properties of the cured resin. The method employed utilizes the combinatorial probability that 1. Two molecules will approach a transition state with sufficient energy to drive reaction 2. Any reaction will occur for a given penetration into the potential energy surface. The concept of a transition state is relaxed to allow a dynamic probability that any reaction will proceed given a position on the intrinsic reaction coordinate (IRC) rather than searching for a specific transition state of theoretical reaction probability. 3. The reaction that occurs yields a desired stable or semi-stable molecular complex This study will focus on identifying possible stable and semi-stable products and corresponding rate constants. The technique developed here is novel in that it provides an unsupervised method to identify all structures corresponding to minima on the potential energy surface. The technique provides a pragmatic and efficient approach to sample a molecular system for different reaction mechanisms and provides a relative energy requirement to achieve these mechanisms with no presupposition of the mechanism, product, or transition state. It is possible from this data to derive rate constants for a reacting system, however, the rate constant derived for the EO/NH2 molecular system yielded significantly understated reaction probabilities and therefore rate constants.

Doctor of Philosophy / Department of Chemical Engineering / Vikas Berry / Nanoscale materials invite immense interest from diverse scientific disciplines as these provide access to precisely understand the physical world at their most fundamental atomic level. In concert with this aim of enhancing our understanding of the fundamental behavior at nanoscale, this dissertation presents research on three nanomaterials: Gold nanoparticles (GNPs), Graphene and ultra-thin Boron Nitride sheets (UTBNSs). The three-fold goals which drive this research are: incorporating mobility in nanoparticle based single-electron junction constructs, developing effective strategies to functionalize graphene with nano-forms of metal, and exfoliating ultrathin sheets of Boron Nitride. Gold nanoparticle based electronic constructs can achieve a new degree of operational freedom if nanoscale mobility is incorporated in their design. We achieved such a nano-electromechanical construct by incorporating elastic polymer molecules between GNPs to form 2-dimensional (2-D) molecular junctions which show a nanoscale reversible motion on applying macro scale forces. This GNP-polymer assembly works like a molecular spring opening avenues to maneuver nano components and store energy at nano-scale. Graphene is the first isolated nanomaterial that displays single-atom thickness. It exhibits quantum confinement that enables it to possess a unique combination of fascinating electronic, optical, and mechanical properties. Modifying the surface of graphene is extremely significant to enable its incorporation into applications of interest. We demonstrated the ability of chemically modified graphene sheets to act as GNP stabilizing templates in solution, and utilized this to process GNP composites of graphene. We discovered that GNPs synthesized by chemical or microwave reduction stabilize on graphene-oxide sheets to form snow-flake morphologies and bare-surfaces respectively. These hybrid nano constructs were extensively studied to understand the effect and nature of GNPs’ interaction with graphene, and applied to address the challenge of dispersing bare-surfaced GNPs for efficient liquid-phase catalysis. We also revisited the functionalization of graphene and present a non-invasive surface introduction of interfaceable moieties. Isostructural to graphene, ultrathin BN sheet is another atomic-thick nanomaterial possessing a highly diverse set of properties inconceivable from graphene. Exfoliating UTBNSs has been challenging due to their exceptional intersheet-bonding and chemical-inertness. To develop applications of BN monolayers and evolve research, a facile lab-scale approach was desired that can produce processable dispersions of BN monolayers. We demonstrated a novel chlorosulfonic acid based treatment that resulted in protonation assisted layer-by-layer exfoliation of BN monolayers with highest reported yields till date. Further, the BN monolayers exhibited extensively protonated N centers, which are utilized for chemically interfacing GNPs, demonstrating their ability to act as excellent nano-templates. The scientific details obtained from the research shown here will significantly support current research activities and greatly impact their future applications. Our research findings have been published in ACS Nano, Small, Journal of Physical Chemistry Letters, MRS Proceedings and have gathered >45 citations.

Doctor of Philosophy / Department of Chemical Engineering / Jennifer L. Anthony / Zeolites and zeolite-like materials are a group of porous materials with many applications in industry including but not limited to detergent builders and catalyst in the oil refining and petrochemical industry, due to their unique properties such as uniform pore size, large surface area and ion-exchange capacity. Researchers are constantly seeking new methods to synthesize zeolites. Zeolites are commonly synthesized in water. Then in 2004, a new method called ionothermal synthesis was invented by Dr. Morris and his colleagues, using ionic liquids (ILs) and eutectic mixtures as the solvent. In contrast to water, ILs and eutectic mixtures have negligible vapor pressure, thus making the use of high-pressure vessel unnecessary. In addition, they have various structures which could render new structures to frameworks of zeolite. Furthermore, since the cations of some ILs have structures which are similar to common structure directing agents, they theoretically could be used both as solvent and structure directing agent in ionothermal synthesis, possibly simplifying the synthesis process. This project is aimed at investigating the behavior of precursors of zeolites in ionic liquids and the interaction between precursors and ionic liquids in ionothermal synthesis because these fundamental properties could be useful in the current and future synthesis of zeolites. First, solubilities of different precursors, including Syloid 63 silica particles, aluminium isopropoxide (Al(OiPr)3) and phosphoric acid (H3PO4) in ILs with different structures are reported. Parameters such as activity coefficient and Henry’s constant are calculated from the solubility result. Second, interaction between precursors and ILs are studied. It is found that the addition of ILs in Al(OiPr)3 could change the structure of Al(OiPr)3, especially with the presence of H3PO4. Both ILs’ structures and temperature are capable of influencing the structure change of Al(OiPr)3. Third, hydrochloric acid is used for the first time as the mineralizer to synthesize aluminophosphates in ILs and it could lead to both dense and porous materials. Regardless of the acid used, frameworks synthesized after several hours always undergo a dramatic change after further heating. A slightly longer alkyl chain of ILs could accelerate the formation of crystalline materials. Increasing concentration of precursors in the reaction gel could increase the yield, but the same framework is not retained. Researches have also been done on stability of ILs in the synthesis process and it is found that heat and the presence of H3PO4 could decompose ILs, but the decomposed amount is extremely small.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The sublimation recondensation crystal growth of aluminum nitride, titanium nitride, and yttrium nitride were explored experimentally and theoretically. Single crystals of these nitrides are potentially suitable as substrates for AlGaInN epitaxial layers, which are employed in ultraviolet optoelectronics including UV light-emitting diodes and laser diodes, and high power high frequency electronic device applications. A thermodynamic analysis was applied to the sublimation crystal growth of aluminum nitride to predict impurities transport (oxygen, carbon, and hydrogen) and to study the aspects of impurities incorporation for different growth conditions. A source purification procedure was established to minimize the impurity concentration and avoid degradation of the crystal’s properties. More than 98% of the oxygen, 99.9% of hydrogen and 90% of carbon originally in the source was removed. The AlN crystal growth process was explored in two ways: self-seeded growth with spontaneous nucleation directly on the crucible lid or foil, and seeded growth on SiC and AlN. The oxygen concentration was 2 ~ 4 x 1018cm-3, as measured by secondary ion mass spectroscopy in the crystals produced by self-seeded growth. Crystals grown from AlN seeds have visible grain size expansion. The initial AlN growth on SiC at a low temperature range (1400°C ~1600°C) was examined to understand the factors controlling nucleation. Crystals were obtained from c-plane on-axis and off-axis, Si-face and C-face, as well as m-plane SiC seeds. In all cases, crystal growth was fastest perpendicular to the c-axis. The growth rate dependence on temperature and pressure was determined for TiN and YN crystals, and their activation energies were 775.8±29.8kJ/mol and 467.1±21.7kJ/mol respectively. The orientation relationship of TiN (001) || W (001) with TiN [100] || W [110], a 45o angle between TiN [100] and W [100], was seen for TiN crystals deposited on both (001) textured tungsten and randomly orientated tungsten. Xray diffraction confirmed that the YN crystals were rock-salt structure, with a lattice constant of 4.88Å. Cubic yttria was detected in YN sample from the oxidation upon its exposed to air for limited time by XRD, while non-cubic yttria was detected in YN sample for exposures more than one hour by Raman spectra.

Master of Science / Department of Mechanical and Nuclear Engineering / Kirby S. Chapman / The increased emissions monitoring requirements of industrial gas turbines have created a demand for less expensive emissions monitoring systems. Typically, emissions monitoring is performed with a Continuous Emissions Monitoring System (CEMS), which monitors emissions by direct sampling of the exhaust gas. An alternative to a CEMS is a system which predicts emissions using easily measured operating parameters. This system is referred to as a Parametric Emissions Monitoring System (PEMS). A review of the literature indicates there is no globally applicable PEMS. Because of this, a PEMS that is applicable to a variety of gas turbine manufacturers and models is desired. The research presented herein includes a literature review of NOx reduction techniques, NOx production mechanisms, current PEMS research, and combustor modeling. Based on this preliminary research, a combustor model based on first-engineering principles was developed to describe the NOx formation process and relate NOx emissions to combustion turbine operating parameters. A review of available literature indicates that lean-premixed combustion is the most widely-used NOx reduction design strategy, so the model is based on this type of combustion system. A review of the NOx formation processes revealed four well-recognized NOx formation mechanisms: the Zeldovich, prompt, nitrous oxide, and fuel-bound nitrogen mechanisms. In lean-premixed combustion, the Zeldovich and nitrous oxide mechanisms dominate the NOx formation. This research focuses on combustion modeling including the Zeldovich mechanism for NOx formation. The combustor model is based on the Siemens SGT-200 combustion turbine and consists of a series of well-stirred reactors. Results show that the calculated NOx is on the same order of magnitude, but less than the NOx measured in field tests. These results are expected because the NOx calculation was based only on the Zeldovich mechanism, and the literature shows that significant NOx is formed through the nitrous oxide mechanism. The model also shows appropriate trends of NOx with respect to various operating parameters including equivalence ratio, ambient temperature, humidity, and atmospheric pressure. Model refinements are suggested with the ultimate goal being integration of the model into a PEMS.