Engineering Commons^™

Photosystem I-Based Applications For The Photo-Catalyzed Production Of Hydrogen And Electricity, Rosemary Khuu Le

Doctoral Dissertations

The aim of this dissertation was to optimize systems integrating the photosystem I (PSI) redox protein, which is involved in photosynthesis, with noble metals for electron transfer to show its versatility: 1) in solution coupled with platinum to mediate hydrogen evolution and 2) on a planar gold surface for electricity production.

Response surface methodology was utilized to study variables that affect hydrogen (H₂) yield from platinized-PSI. Light intensity, temperature, and platinum concentration were varied during the platinum-photo-reduction process. Analysis of the effects of the variables on H₂ yield allowed for determination of a condition for optimized hydrogen …

Thermodynamic Modeling Of Uranium And Oxygen Containing Ternary Systems With Gadolinium, Lanthanum, And Thorium, Jacob Wesley Mcmurray

Doctoral Dissertations

The CALPHAD method is used to assess the thermodynamic properties and phase relations in the U-M-O system where M = Gd, La, and Th. A compound energy formalism (CEF) model for fluorite UO_2±x [urania] is extended to represent the complex U_1-yM_yO_2±x [urania solid solution] phases. The lattice stabilities for fictive GdO₂ [gadolinia] and LaO₂ [lanthana] fluorite structure compounds are calculated from density functional theory (DFT) for use in the CEF for U_1-yM_yO_2±x [urania solid solution phase] while U⁶⁺ [uranium 6 plus cation] is introduced into the …

The Structure And Function Of Photosystem I And Photosystem I – Hydrogenase Protein Fusions: An Experimental And Computational Study, Bradley Jordan Harris

Doctoral Dissertations

Photosystem I (PSI) is a membrane protein involved in the photosynthetic cycle of plants, algae, and cyanobacteria that is of specific interest due to its ability to harness solar energy to generate reducing power. This work seeks to form an in vitro hybrid protein fusion between the membrane integral PSI protein and the membrane-bound hydrogenase (MBH) enzyme, in an effort to improve electron transport between these two proteins.

Small-angle neutron scattering (SANS) was used to characterize the detergent-solubilized solution structure of trimeric PSI from the cyanobacterium Thermosynechococcus elongatus, which showed that the detergent interacts primarily with the hydrophobic periphery …

Evaluating Effects Of Molecular Heterogeneity On The Non-Linear Mechanical Behavior Of Epoxy Networks, Zhan Hang Yang

Doctoral Dissertations

This thesis describes synthetic and processing strategies to formulate epoxies resins with molecular heterogeneity to achieve enhanced engineering properties. The network heterogeneities include chemical differences in stiffness and crosslink density, as well as mechanical difference in baseline energy state. The focus is to understand the fundamental structure-process-property relationships in these unusual network polymers, especially the post-yield responses and fracture toughness. The main characterization techniques to probe the complex network architectures are dynamic mechanical spectroscopy and compression tests. Ductility and governing parameters are also proposed to describe the relationships between molecular structures and physical properties. Three different staged fabrication strategies are …

Production Of Sustainable Aromatics From Biorenewable Furans, Christopher Luke Williams

Doctoral Dissertations

Increasing demand for renewable and domestic energy and materials has led to an accelerated research effort in developing biomass-derived fuels and chemicals. The North American shale gas revolution can provide a domestic source for the manufacture of four of the five major products of the world chemical industry: methanol, ethylene, ammonia, and propylene. However this emerging domestic resource lacks a conversion pathway to the fifth major chemical building block; the larger C6 aromatics benzene, toluene, and xylene (BTX). One sustainable feedstock for renewable C6 aromatic chemicals is sugars produced by the saccharification of biopolymers (e.g., cellulose, hemicellulose). The catalytic conversion …

Primary And Secondary Reactions Of Cellulose Melt Pyrolysis, Alex D. Paulsen

Doctoral Dissertations

Fast pyrolysis of biomass is a next-generation biofuels production process that is capable of converting solid lignocellulosic materials (in their raw form) to a transportable liquid (bio-oil) which can be catalytically hydrogenated to fuels and chemicals. Pyrolysis reactors depolymerize solid biomass by heating the feedstock (in the absence of oxygen) up to high temperatures (400 – 600 °C) to produce a short-lived intermediate liquid phase (only a few seconds), which ultimately breaks down to form small (1-6 carbon) oxygenates. These vapor-products can then be condensed at room temperature to produce liquid bio-oil. While biomass fast pyrolysis has enormous potential to …

Production Of Renewable Fuels And Chemicals From Biomass-Dervied Furan Compounds, Sara K. Green

Doctoral Dissertations

Growing concern over the petroleum supply, energy independence, and environmental impacts associated with fossil fuels, has motivated research into the production of renewable fuels and aromatic chemicals from biomass resources. Specifically, furan-based feedstocks such as furfural, 2-methylfuran (MF) and, 2,5-dimethylfuran (DMF) can be derived from biomass and used to produce a wide variety of desired compounds. These furan-based feedstocks are produced by: (a) the hydrolysis of cellulose and hemicellulose form to glucose and xylose, (b) the dehydration of these carbohydrates to form 5-hydroxymethylfurfural (HMF) and furfural, and (c) the reduction of HMF and furfural to DMF, MF, and furan. The …

Production Of Renewable Chemicals And Energy From Waste Biomass, Sheng Chu

Doctoral Dissertations

With the rapid growth of world population and developing industries, the production of wastes has dramatically increased in the past decades. Due to environmental concerns and limited landfill space, the disposal of wastes has been subjected to strict regulations. Beneficial uses of wastes such as recycling/reuse, land applications, energy production, and resource recovery have been advocated greatly. This thesis presents the utilization of two types of solid waste: lignin and waste paper/plastic. Through thermochemical conversion, wastes can be converted to chemicals and energy. This aims at reducing the energy dependence on fossil fuels while achieving effective waste management. Lignin is …

Computational Study Of Sodium Magnesium Hydride For Hydrogen Storage Applications, Fernando Antonio Soto Valle

Doctoral Dissertations

Hydrogen offers considerable potential benefits as an energy carrier. However, safe and convenient storage of hydrogen is one of the biggest challenges to be resolved in the near future. Sodium magnesium hydride (NaMgH 3) has attracted attention as a hydrogen storage material due to its light weight and high volumetric hydrogen density of 88 kg/m3. Despite the advantages, hydrogen release in this material occurs at approximately 670 K, which is well above the operable range for on-board hydrogen storage applications. In this regard, hydrogen release may be facilitated by substitution doping of transition-metals. This dissertation describes first-principles computational methods that …

Structure Of Nearly Ideal And Multi-Component Polymeric Biomaterials, Erika Saffer

Doctoral Dissertations

Hydrogels have long been considered ideal candidates for biomaterial and tissue engineering applications due to their many desirable properties, such as high water content and tunable gelation conditions. Although these materials have undergone extensive research and development, some mechanical and physical properties are still difficult to achieve. The reason for this is often related to the structure of the hydrogel network. Understanding how network structures are influenced by changes in formulation parameters (i.e. polymer molecular weight, initial polymer concentration, ratio of hydrophilic to hydrophobic polymer), and correlating these results to known mechanical and physical properties would yield well characterized systems …

Design Of A Targeted Bacterial Drug Delivery Vector For The Treatment Of Cancer And Metastases, Charles Alexander Swofford

Doctoral Dissertations

Engineered Salmonella possess unique capabilities that make them ideal drug delivery vectors for tumors. Targeted bacterial delivery of anticancer proteins has the ability to overcome therapeutic resistance in tumors that limits the efficacy of chemotherapeutics. In my doctoral research, I identified a protein-drug that can be expressed by bacteria and rapidly kills cancer cells. I also created a density dependent switch that initiates gene expression in tumors and prevents expression in healthy tissue. Combining these two systems has created a potent anti-cancer system that targets tumors with minimal toxicity. I cloned genes for five potential anti-cancer proteins into Salmonella. …

Composition Dependence Of The Flory-Huggins Interaction Parameter In Polymer Blends: Structural And Thermodynamic Calculations, Travis H. Russell

Doctoral Dissertations

Flory-Huggins Theory has been the basis for understanding polymer solvent and blended polymer thermodynamics for much of the last 60 years. Within this theory, a parameter (χ) [chi] was included to quantify the enthalpic energy of dispersion between distinct components. Thin film self-assembly of polymer melts and block copolymers depends critically on this parameter, and in application, χ has generally been assumed to be independent of the concentrations of the individual components of the system. However, Small-Angle Neutron Scattering data on isotopic polymer blends, such as polyethylene and deuterated polyethylene, have shown a roughly parabolic concentration dependency for …

Ab Initio Studies Of Proton Transport In Proton Exchange Membranes, Jeffrey Keith Clark

Doctoral Dissertations

A molecular-level understanding of the factors that contribute to transport properties of proton exchange membranes (PEMs) for fuel cell applications is needed to aid in the development of superior membrane materials. Ab initio electronic structure calculations were undertaken on various PEM ionomer fragments to explore the effects of local hydration, side chain connectivity, protogenic group separation, and specific side chain chemistry on proton dissociation and transfer at low hydration. Cooperative interactions between both intra- and inter-molecular acidic groups and hydrogen bond connectivity were found to enhance proton dissociation at very low degrees of hydration. The energetics associated with proton transfer …

Nanolayer Polymeric Coatings To Enhance The Performance And Service Life Of Inorganic Membranes For High Temperature-High Pressure Biomass Pretreatment And Other Applications, Vincent C. Kandagor

Doctoral Dissertations

Membrane technology has become increasingly attractive in several applications including water filtration, food industry, oil and gas, and biomedical applications. Most recently the quest for renewable, bioenergy has called for use of membranes in biomass pretreatment and other stages of producing biofuel. The success and advancement of the membrane technology for these various applications has, however, been impeded by the fouling of membranes, which causes the pores in the microporous structure to block, resulting in reduced efficiency, and in some cases, total failure of the membranes system. This challenge leads to a tremendous increase in the cost of using membranes …

Transport Resistance In Polymer Electrolyte Fuel Cells, Jon Patrick Owejan

Doctoral Dissertations

Fuel cells offer the potential for high efficiency energy conversion with only water and heat as significant products of the electrochemical reaction. For a cost-competitive product, fuel cell researchers are exploring the limits of the Pt catalyst loading in parallel with performance and durability trade-offs. A significant portion of the performance loss in low-cost PEMFCs is associated with the partial pressure of oxygen (for an air cathode) at the Pt surface. This dissertation explores the main components of oxygen transport resistance which are associated with diffusion through partially saturated porous media and the ionomer coating in the catalyst layer.

Under …

Strategies For Improving Oxygen Transport And Mechanical Strength In Alginate-Based Hydrogels, Joseph C. White

Doctoral Dissertations

Hydrogels have attracted significant interest over the past several decades due to their outstanding versatility as biomaterials. Alginate-based hydrogels are among the most popular studied due to their low cost, biocompatibility, and tunable physical properties. However, as with all hydrogels, persistent oxygen solubility and poor mechanical strength limits their utility for creating macroscopic devices for biomedical use. This thesis presents two strategies for improving oxygen transport and mechanical properties of alginate-based hydrogel. The former involves incorporating perfluorocarbons, hydrophobic compounds with very high oxygen solubility, into the formulation. The perfluorocarbons are stabilized by nonionic surfactants, Pluronics®, and the emulsion is entrapped …

Study And Development Of Sulfated Zirconia Based Proton Exchange Fuel Cell Membranes, Brittany Wilson Kemp

Doctoral Dissertations

With the increasing consumption of energy, fuel cells are among the most promising alternatives to fossil fuels, provided some technical challenges are overcome. Proton exchange membrane fuel cells (PEMFCs) have been investigated and improvements have been made, but the problem with Nafion®, the main membrane for PEMFCs, has not been solved. Nafion® restricts the membranes from operating at higher temperatures, thus preventing them from working in small electronics. The problem is to develop a novel fuel cell membrane that performs comparably to Nafion® in PEMFCs.

The membranes were fabricated by applying sulfated zirconia, via template wetting, to porous alumina membranes. …

Experimental And Computational Investigation Of Flow Of Pebbles In A Pebble Bed Nuclear Reactor, Vaibhav B. Khane

Doctoral Dissertations

"The Pebble Bed Reactor (PBR) is a 4th generation nuclear reactor which is conceptually similar to moving bed reactors used in the chemical and petrochemical industries. In a PBR core, nuclear fuel in the form of pebbles moves slowly under the influence of gravity. Due to the dynamic nature of the core, a thorough understanding about slow and dense granular flow of pebbles is required from both a reactor safety and performance evaluation point of view.

In this dissertation, a new integrated experimental and computational study of granular flow in a PBR has been performed. Continuous pebble re-circulation experimental set-up, …

Degradable Nanocomposite Preformed Particle Gel For Chemical Enhanced Oil Recovery Applications, Paul Tongwa

Doctoral Dissertations

”This work presents two new materials that can be potentially used in conformance control to increase ultimate oil recovery from mature oilfields.

The first product is a degradable nanocomposite preformed particle gel for enhanced in-depth mobility control. Three different types of degradable nanocomposite preformed particle gels were synthesized. These three nanocomposite hydrogels were made using Laponite XLG, Calcium Montmorillonite, and Sodium Montmorillonite nanomaterials. It was observed that after degradation, Laponite XLG nanocomposite hydrogels had the highest post-degradation viscosity (4437 cp), followed by sodium nanocomposite hydrogels (129 cp), and lastly calcium nanocomposite hydrogels (75.5 cp). Thus, degradable Laponite XLG nanocomposite hydrogels …

Investigating And Modeling Tar-Mats In A Kuwaiti Carbonate Reservoir And Their Role In Understanding Oil Reserves And Recovery Economics, Abdullah Owidah Almansour

Doctoral Dissertations

"Tar-mat columns exist in many carbonate reservoirs in the Middle East. Historically, tar-mats have been thought to impede primary oil extraction, thus necessitating further improved oil recovery (IOR) technology applications. However, this research considers tar-mats as potential sources for unlocking extremely difficult crude oil, less than 5 ⁰API. The main objective of the study was to understand the qualitative physical and chemical properties of extremely viscous tar-mat oil and the quantitative potential of tar-mats to extract difficult oil.

The physical and chemical geneses of the tar-mat oil were analyzed utilizing several experimental geochemical techniques, including rock evaluation pyrolysis, liquid extracts …

Study And Pilot Test On A Novel Eor Method - Coupling Ppg Conformance Control And Surfactant Flooding, Farag Awadh Muhammed

Doctoral Dissertations

"The interest in enhanced oil recovery (EOR) methods has re-emerged in recent years; however, significant challenges remain for the widespread deployment of these methods. One major downside to the successful application of EOR technologies in mature reservoirs is conformance problems (e.g. heterogeneity). To mitigate these problems, a novel EOR method which couple preformed particle gel (PPGs) conformance treatment with traditional surfactant flooding in one process is introduced.

This dissertation provides a comprehensive study for the proposed method. A series of laboratory tests were carried out to understand the chemical interaction between PPGs and surfactants. A new method to evaluate PPGs …

Carbon Dioxide - Heavy Oil Systems: Thermodynamics, Transport And Interfacial Stability, Truynh Quoc My Duy Tran

Doctoral Dissertations

"Conventional oil recovery leaves behind around 67% of original oil in place for light oils and all of it for heavy oils. The carbon dioxide flooding process is the cheapest among the recovery methods for the next stage. The interest here lies in recovering heavy oil. When CO₂ dissolves in oil, it increases the volume of oil, squeezes it out of narrow capillaries and the viscosity of oil drops by up to an order of magnitude. Starting with the available data with and without CO₂ in heavy oil, the free volume theory is used to predict these physical …

Impact Of Slickwater Fracturing Fluid Compositions On The Petrophysical Properties Of Shale And Tightsand, Yongpeng Sun

Doctoral Dissertations

"A tight reservoir always requires hydraulic fracturing before production to increase production rate. The additives in hydraulic fluids are highly considerable for a successful stimulation. A friction reducer is often used to reduce the flowing friction in the wellbore during hydraulic fracturing. Extensive researches have been conducted to examine the extent it can reduce the fluid friction in tubings; however, no research has been reported on its behavior in a reservoir, which is related to the fracture extension. A breaker is also pumped into the formation to degrade the friction reducer. However, it is not clear that what is the …

Multiscale Modeling Study Of Methanol Oxidation By Ion-Modified Mdh Enzymes, Purnima Kharidehal

Doctoral Dissertations

Enzymes have been considered as molecular electrocatalysts due to their extraordinary characteristics such as their ability to accelerate reactions enormously, to operate under physiological conditions, and to produce fewer by-products during a catalytic reaction. However, enzyme based fuel cells have been reported to have power output and stability limitations, which are restricting the use of this kind of fuel cell to small electronic devices. Methanol dehydrogenase (MDH) is one such enzyme, which oxidizes methanol and other primary alcohols to their corresponding aldehydes. The active site of MDH contains a divalent cation (Ca2+), a co-factor pyrrolo-quinoline quinone (PQQ), several amino acids, …

Preformed Particle Gel Transport Through Fractures, Hao Zhang

Doctoral Dissertations

"Polymer gel treatment is one of the most cost-effective methods to control water production in mature oil fields. The main objective of gel treatments is to reduce water or gas flow through high-permeability channels or fractures without damaging productive zones. Preformed particle gels (PPGs) have been applied for conformance control because they can overcome some potential drawbacks inherent in an in-situ gelation system.

In this study, lab experiments were performed to quantify PPG propagation through fractures and fracture-like channels by using screen models and open fracture models. The main findings in these experiments can guide the selection of best particle …

Semantic Model And Updated Screening Criteria For Polymer Flooding, Laila Dao Saleh

Doctoral Dissertations

"Enhanced oil recovery (EOR) processes produce oil that conventional methods leave behind, where interfacial forces, heavy oil viscosity, and reservoir heterogeneity make it difficult to produce. Many EOR methods are available but usually cannot be used at the same time for a candidate reservoir. Therefore, it is important to select the most appropriate EOR process from among the possible techniques. EOR screening criteria have been created using EOR datasets and serve as the first step to compare the suitability of each technique for a specific reservoir. Most of these datasets are based on field data collected from EOR surveys published …