Digital Commons Network^™

Structural Stability Of Thermosets During Material Extrusion Additive Manufacturing, Stian K. Romberg

Doctoral Dissertations

Over the past decade, the scale of polymer additive manufacturing has been revolutionized with machines that print massive thermoplastic parts with greater geometric complexity than can be achieved by traditional manufacturing methods. However, the heat required to print thermoplastics consumes energy and induces thermal gradients that can reduce manufacturing flexibility and final mechanical properties. With the ability to be extruded at room temperature and excellent compatibility with fibers and fillers, thermoset resins show promise to decrease the energy consumption, expand the manufacturing flexibility, and broaden the material palette offered by large-scale polymer additive manufacturing. However, structural instability in the uncured …

Advanced Materials Design Using Application-Based Processing Techniques, Daniel S. Camarda

Doctoral Dissertations

This dissertation pertains to generating advanced materials using application-based processing techniques. First, billets consisting of PTFE sintering powders are evaluated using Thermomechancal Analysis. It was found that both shape change and volume change are associated with enthalpic and entropic recoil, respectively. These phenomena, due to melting and stored energy during the powder compaction process, were found to be molecular weight dependent. Additionally, kinetics of the recovery and sintering process were found to be slower in blended specimens than pure samples. Next, the creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer …

Spectroscopic Investigations Of Zeolite-Catalyzed Carbenium Ion Chemistry, Eric David Hernandez

Doctoral Dissertations

The catalytic conversion of methanol to olefins on zeolites is an industrially important process, yet the mechanistic details remain unresolved. Enylic cations (unsaturated carbenium ions) are active intermediates in the production of olefins and aromatics. However, these long-lived species are also precursors to carbonaceous deposits, the accumulation of which is responsible for catalyst deactivation. The aim of this work is to develop a mechanistic understanding that will ultimately allow steering the surface chemistry toward active intermediates. An in situ spectroscopic approach is applied to determine the nature of the relevant surface species and to track their transformations. The UV–vis and …

Characterization Techniques And Cation Exchange Membrane For Non-Aqueous Redox Flow Battery, Kun Lou

Doctoral Dissertations

The motivation of this work comes from one of the major problems of emerging non-aqueous flow battery (NAFB) that a separator or membrane which facilitates conductivity and blocks redox species crossover does not exist. Although many aspects of principles can be mirrored from mature fuel cell and aqueous flow battery, it is found that some well-defined membrane properties in aqueous systems such as swelling, transport and interactions are different in non-aqueous solvents to some extent. However, the approach of this work does follow the way perfluorosulfonate ion exchange membrane (PFSA) facilitated development of fuel cell and aqueous flow battery in …

Thermochemical And Continuum Modeling To Understand The Chemical Composition Of Pwr Fuel Crud, Jason T. Rizk

Doctoral Dissertations

Computational modeling of Chalk River Undesirable Deposits (CRUD) allows for the prediction of associated phenomena that impact nuclear power plant performance, reliability, and safety. It also provides insight into the physical mechanisms by which CRUD forms and affects plant performance. A major concern in pressurized water reactors (PWRs) is Axial Offset Anomaly (AOA) which is caused by CRUD’s proficiency at trapping boron within the reactor core. The ability to predict AOA and other phenomena requires a detailed explanation of the chemical composition of CRUD. By pairing computational models that can simulate the structure and species trapping with detailed thermochemical models, …

Experimental And Computational Study Of Determining Mass Transport Parameters In Vanadium Redox Flow Batteries, Tugrul Y. Ertugrul

Doctoral Dissertations

Vanadium redox flow batteries are a promising large-scale energy storage technology, but a number of challenges must be overcome for commercial implementation. At the cell level, mass transport contributes significantly to performance losses, limiting VRFB performance. Therefore, understanding mass transport mechanisms in the electrode is a critical step to mitigating such losses and optimizing VRFBs.

In this study, mass transport mechanisms (e.g. convection, diffusion) are investigated in a VRFB test bed using a strip cell architecture, having 1 cm² active area. It is found that diffusion-dominated cells have large current gradients; convection-dominated cells have relatively uniform current distribution from …

Development Of Density-Functional Tight-Binding Methods For Chemical Energy Science, Quan Vuong

Doctoral Dissertations

Density-functional tight-binding (DFTB) method is an approximation to the popular first-principles density functional theory (DFT) method. Recently, DFTB has gained considerable visibility due to its inexpensive computational requirements that confer it the capability of sustaining long-timescale reactive molecular dynamics (MD) simulations while providing an explicit description of electronic structure at all time steps. This capability allows the description of bond formation and breaking processes, as well as charge polarization and charge transfer phenomena, with accuracy and transferability beyond comparable classical reactive force fields. It has thus been employed successfully in the simulation of many complex chemical processes. However, its applications …

Direct Printing/Coating/Plating Of Key Components For Electronic Devices, Xiyu Hu

Doctoral Dissertations

Miniaturization has been a technological trend for several decades for electronic devices. From the practical point of view, the successful miniaturization of fully integrated systems mainly depends on their components. This dissertation examines the inkjet printing of copper oxide inks on flexible substrates for applications in microfluidic valving systems. We expand the knowledge of low-cost and high-performance electrowetting valves and fabricate the microfluidic device for fluidic control, which is necessary to enable the next-generation microfluidic devices. In addition, we also study the electromagnetic interference (EMI) shielding material, which is a crucial part of electronic devices. The basic theory of EMI …

Novel Approaches Towards Improved Purity In High Yield Transcription Reactions, Elvan Cavac

Doctoral Dissertations

High yields of RNA (e.g., mRNA, gRNA, lncRNA) are routinely prepared following a two-step approach: high yield in vitro transcription using T7 RNA polymerase, followed by extensive purification using gel or chromatic methods. In high yield transcription reactions, as RNA accumulates in solution, T7 RNA polymerase rebinds and extends the encoded RNA (using the RNA as a template), resulting in a product pool contaminated with longer than desired, (partially) double stranded impurities. Current purification methods often fail to fully eliminate these impurities which, if present in therapeutics, can stimulate the innate immune response with potentially fatal consequences. This study establishes …

Surface Modification Of Cellulose Nanocrystals: Imparting Non-Native Properties On Sustainable Substrates, Allen C. Chang

Doctoral Dissertations

Governments and scientists all over the planet have recognized the importance of pursuing and achieving sustainability. As the human population grows and technologies advance, the planet’s limited resources become less and less able to support our taxing demands. In 2015, the United Nations set forth 17 Sustainable Development Global Goals. Goal 12 “Responsible Production and Consumption” can be addressed quite readily by the integration of sustainable materials into advanced technologies; however, such materials have yet to be developed. Cellulose nanocrystals (CNCs) – an abundant, well-known sustainable nanomaterial hydrolyzed from bulk cellulose with high surface functionality and high strength properties – …

Elucidating Mechanisms And Genotypes Underlying Robust Phenotypes In Yarrowia Lipolytica, Caleb M. Walker

Doctoral Dissertations

Robustness is an important phenotype for bioenergy microbes to acquire but is difficult to engineer. Hence, tools for engineering microbial robustness are critical to unlock novel phenotypes for innovative bioprocessing strategies. The oleaginous yeast, Yarrowia lipolytica, is an exceptionally robust microbe that can tolerate stressful environments, assimilate a wide range of substrates, and produce high-value chemicals. In this doctoral dissertation, the impacts of systems biology and metabolic engineering to reveal mechanisms and identify genotypes- underlying robust phenotypes are addressed.

The first approach employs adaptive laboratory engineering to generate a platform strain by which to study superior robust mechanisms. This …

Engineering Modularity Of Ester Biosynthesis Across Biological Scales, Hyeongmin Seo

Doctoral Dissertations

Metabolic engineering and synthetic biology enable controlled manipulation of whole-cell biocatalysts to produce valuable chemicals from renewable feedstocks in a rapid and efficient manner, helping reduce our reliance on the conventional petroleum-based chemical synthesis. However, strain engineering process is costly and time-consuming that developing economically competitive bioprocess at industrial scale is still challenging. To accelerate the strain engineering process, modular cell engineering has been proposed as an innovative approach that harnesses modularity of metabolism for designing microbial cell factories. It is important to understand biological modularity and to develop design principles for effective implementation of modular cell engineering. In this …

Stretching The Applications Of Biomass: Development Of Lignin Based Thermoplastic Elastomers And Composite Materials, Anthony Stephen Bova

Doctoral Dissertations

Bio-based plastics and composites have seen increased industry adoption in recent years due to growing demand for materials with a low carbon footprint. The use of lignin as a feedstock for polymers has seen growing interest as the concept of an integrated cellulosic biorefinery gains traction and advances the need to use all components of separated biomass for value-added applications. Historically, use of lignin in thermoplastic and elastomeric copolymers and blends has been bottlenecked by the inability to introduce lignin content above 30 weight percent due to difficulties with interfacial adhesion of lignin with other soft segments. Efforts to overcome …

Unraveling The Effects Of Molecular Confinement On The Dynamics Of Polymeric Systems: I. Block Copolymer Architecture Ii. Silica Nanopores, Thomas P. Kinsey

Doctoral Dissertations

In this dissertation, broadband dielectric spectroscopy (BDS) is employed as an experimental tool to probe dipolar relaxations in polymeric systems under two types of molecular confinement. First a series of miktoarm star copolymers are used to explore how branching block copolymer architectures constrain polymer relaxations within self-assembled domains in relation to linear systems. Secondly, the effects of hard spatial confinement on the dynamics of polymer chains and of ions in polymerized ionic liquids (PILs) are studied after infiltration into silica nanochannels. Complementary techniques such as transmission electron microscopy, small angle x-ray scattering, and Raman spectroscopy are used to determine various …

Valorization Of Secondary Agriculture Residues, Narendra Kumar

Doctoral Dissertations

Secondary agriculture residues have the potential to be major contributors as resources for energy and sustainably sourced materials production. Separating secondary agricultural residues, which have already been transported to processing centers, into individual biomass components could convert these wastes into bioproducts. Many types of pretreatments to achieve this separation involve chemicals that are hazardous for the environment. Several deep eutectic solvents (DES) that are biocompatible have been investigated for their ability to deconstruct rice hulls and sugarcane bagasse. Mass yield, enzymatic hydrolysis of the pretreated biomass, fiber analysis, and Fourier transform infrared spectroscopy have confirmed that the DES formic acid:choline …

Engineered Switch Protein Inspired By Novel Protein Affinity Transition Mode, Liang Fang

Doctoral Dissertations

Many natural proteins involved in complex biological processes such as ligand binding and protein folding demonstrate multiple, allosterically-regulated conformational states, with protein activity regulated by effector molecules. The alpha L integrin and its inserted domain (I domain) is one example of such a protein. The binding of the effector molecule such as talin or filamin to the cytoplasmic domain of the integrin increases the binding affinity between I- domain and its ligand intercellular adhesion molecule-1, known as ICAM-1.There are multiple models attempting to describe the mechanism responsible for the change in binding affinity. According to research conducted by our lab, …

The Controlled Synthesis Of Hydrogen Electrocatalysts For Alkaline Exchange Membrane Fuel Cell And Electrolysis Applications Via Chemical Vapor Deposition, Stefan Thurston Dubard Williams

Doctoral Dissertations

The development of catalysts for the electrochemical processes of hydrogen systems (e.g., fuel cells and electrolyzer systems) continues to be an attractive area of research for renewable energy technologies. One significant challenge has been developing hydrogen catalysts suitable for alkaline environments, mainly due to the sluggish kinetics of hydrogen reactions. In alkaline environments, the kinetics are decreased by two orders of magnitude when compared to acidic environments. Chemical vapor deposition (CVD) is a conventional method used to synthesize these types of catalysts. This effort discusses extending work being done using a modified CVD process known as “Poor Man’s” CVD (PMCVD) …

Synthesis Of Inorganic Porous Materials With Tunable Morphology For Molecular Adsorption And Separation, Sanket Sabnis

Doctoral Dissertations

Global industrial and economic development over the past century has largely relied on combustion of non-renewable fossil fuels, such as petroleum, coal, and natural gas, which are also harmful to environment because of the release of CO₂, responsible for global warming and climate change. Establishing eco-friendly, energy-efficient and cost-effective processes to reduce environmental impact is currently one of the most urgent issues for the sustainable development of our society. Inorganic porous materials have found applications in the fields of renewable energy and environmental protection such as biomass conversion, fuel cells, thermal energy storage, CO₂ capture and conversion, …

Electrospinning Fibers Via Complex Coacervation, Xiangxi Meng

Doctoral Dissertations

Electrospun fibers are high-surface-area materials widely used in applications ranging from batteries to wound dressings. Typically, an electrospinning precursor solution is prepared by dissolving a high-molecular-weight polymer in an organic solvent to form a sufficiently entangled solution. Our approach bypasses the requirement for entanglements and completely avoids toxic chemicals by focusing on using an aqueous complex coacervates solution. Coacervates are a dense, polymer-rich liquid phase resulting from the associative electrostatic complexation of oppositely charged macroions. We were the first to demonstrate that liquid complex coacervates could be successfully electrospun into polyelectrolyte complex (PEC) fibers. A canonical coacervate system was formed …

Metabolic Modeling Of Gas Fermentation For Renewable Fuel And Chemical Production, Xiangan Li

Doctoral Dissertations

Gas fermentation has emerged as a technologically and economically attractive option for producing renewable fuels and chemicals from carbon monoxide (CO) rich waste streams. As compared to traditional catalyst technologies, microbial systems have several advantages including operation near ambient temperature and pressure, high conversion efficiencies, robustness to gas impurities and high product yields that have motivated both fundamental research and commercial development. While microbial production of high-value products from waste gases is challenging because wild-type strains capable of gas consumption tend to synthesize these products at low yields, strategy like metabolically engineering the gas fermenting acetogens have been studied to …

Catalytic Carbon Dioxide Hydrogenation To Methanol/Dimethyl Ether Over Copper-Based Catalysts, Xiao Fan

Doctoral Dissertations

Direct synthesis of dimethyl ether (DME) via CO₂ hydrogenation has received great attention, owing to the global warming caused by CO₂ emission and increasing energy demand worldwide. In this works, three major aspects of bifunctional catalysts development were studied: (1) investigation of the roles of interaction in the CuO-ZnO-ZrO₂-Al₂O₃/HZSM-5 bifunctional catalysts, (2) deactivation and regeneration of CuO-ZnO-ZrO₂-Al₂O₃ with different zeolitic catalysts for one-step CO₂ hydrogenation to dimethyl ether, and (3) study on the enhancement of activity and stability of CZZA/HZSM-5 bifunctional catalysts via the introduction of …

3d-Printed Adsorbents For Gas Separations: A Material Development, Kinetic Assessment, And Process Performance Investigation, Shane Lawson

Doctoral Dissertations

“Adsorbent materials are promising for various gas purification processes, however, forming them into structured contactors is paramount in enhancing mass transfer properties and reducing pressure losses. In this research, various adsorbents were engineered into structured contactors with 3D printing. The overall goal of this research was to improve the formulation methods of 3D-printed adsorbents and understand their performances in gas separation processes. The specific objectives were to 1) develop new adsorbent 3D-printing strategies, 2) understand the kinetic properties of printed adsorbent monoliths, and 3) assess their process performances. Objective one was addressed by developing five 3D printing techniques: i) oxide …

Evaluation Of Robust Epoxy Resin Sealants For Wellbore Integrity Applications, Mohammed Mousa M Alkhamis

Doctoral Dissertations

"During the drilling and completion phases of oil and gas wells, cement is placed in the wellbore as a barrier between the casing and the formation. All casing strings must be cemented to protect and support the casing, and to isolate production zones. The primary cement must prevent the wellbore fluids from migrating in an annular flow path so as to allow the wells to be utilized without any control problems. The primary cement may fail to deliver full zonal isolation due to several reasons such as insufficient mud removal before the cementing, casing expansion, and contraction, high fluid losses, …

Cyclic Sequential Adsorption Desorption/Thermal-Catalytic Oxidation Of Volatile Organic Compounds: Material Development, Process Advancement/Improvement, And Numerical Modeling, Simulation And Optimization, Busuyi Ojo Adebayo

Doctoral Dissertations

"Volatile organic compounds (VOCs) are a group of useful organic chemicals but when emitted have contributed to air pollution. They affect human health, cause environmental degradation and contaminate our waters and soils, so they need to be controlled. When they exist in dilute concentrations, abatement becomes challenging, thus requiring advanced abatement methods, e.g., sequential adsorption desorption/thermal-catalytic oxidation process. The overall goal of this research was to abate dilute streams of VOCs via the process. The specific objectives were to 1) develop novel adsorbent/catalyst dual-function materials (DFMs) for the process, 2) improve the operability of a one-bed-one-column reactor configuration for the …

Convective-Diffusive Transport In Krogh Cylinders: A Model For Pharmacokinetics, Xianjie Qiu

Doctoral Dissertations

"Drug delivery to inside of the tumor is the important problem. The dynamics of drug delivery is presented here. Previously and particularly for directed delivery, a stirred tank model has been used, which appears to have worked well when compared to experiments. However, the stirred tank models do not include all the mass transfer resistances and towards that end we have used a distributed system called Krogh cylinder. This study focuses on the Krogh cylinder model simulation, both on the fluid flow and the mass transfer. The capillary network is broken down into cylindrical cells, each containing a capillary and …

Investigation Of Packed Bed And Moving Bed Reactors With Benchmarking Using Advanced Measurement And Computational Techniques, Binbin Qi

Doctoral Dissertations

"Trickle bed reactors (TBR), as typical packed bed reactors (PBR), are widely used in various fields. Very limited information regarding the flow behaviors, hydrodynamic, and mathematical models in extrudate catalyst shapes, such as cylinders, trilobes, and quadrilobes, can be found in literatures because the major focus was on spherical shape. Therefore, a hybrid pressure drops and liquid holdup phenomenological model for extrudate catalyst shapes was developed based on two-phase volume averaged equations, which showed high accuracy against experimental data. The maldistribution and dynamic liquid holdup were investigated in quadrilobe catalyst using gamma-ray computed tomography. A pseudo-3D empirical model was developed …

Studies On Protein Solubility, Ke Li

Doctoral Dissertations

"Solubility is a critical factor of protein-based drugs during processing and patient administration. This study focused on two aspects of solubility: one was the poly (ethylene) glycol (PEG) precipitation of monoclonal antibodies (mAbs) and another was crystallins aggregation that is associated with cataracts. Protein precipitation by PEG is a common technique for downstream processing. The effects of pH, ionic strength and the exclude volume effect on the protein precipitation by PEG were extensively studied, but the effects of glycosylation on protein precipitation by PEG has not been examined. Protein aggregation is not only a problem in downstream processing, but it …

Enhanced Heavy Oil Recovery By Low Salinity Polymer Flood Combined With Microgel Treatment, Yang Zhao

Doctoral Dissertations

“Heavy oil resources account for a large portion of the total oil reserves around the world. The target heavy oil reservoir is located on Alaska’s North Slope (ANS). Advantages of low-salinity HPAM polymer (LSP) over high-salinity polymer (HSP) were demonstrated. LSP could recover more oil with 40% less polymer consumption. No additional oil was recovered by HSP after LSP flood. The first-ever polymer flood pilot on ANS showed remarkable success regarding water cut reduction, oil production increase, delayed breakthrough, and projected oil recovery improvement. Polymer alone was insufficient to achieve satisfactory recovery as the reservoirs were highly heterogeneous. Microgels could …

Extracting Metallurgy Contaminants And Hydrocarbons Removing From Water And Industrial Wastewater Using Enhanced Emulsion Liquid Membrane With Nanoparticles And Ionic Liquid, Qusay Al-Obaidi

Doctoral Dissertations

It is an uphill battle to extract pollutants such as heavy metals, hydrocarbons, and radioactive metals from water and industrial wastewater. Emulsion liquid membrane (ELM) is an emerging technology that combines extraction/recover and stripping in one stage to extract/recover heavy metals and/or hydrocarbons from water and wastewater. ELM devised a way to clean up heavy metals and/or hydrocarbons from the water and wastewater where its primary chemicals can be recycled and reused.

In this work, the Emulsion Liquid Membrane (ELM) has been enhanced by adding nanoparticles and ionic liquid to significantly improve the recovery of the water-based contaminants of heavy …