Engineering Commons^™

Oligodimethylsiloxanes With Charged Chain Ends: Synthesis, Characterization, And Properties, Tianyu Li

Doctoral Dissertations

Charged polymers have been intensively studied because of their scientific and industrial importance. In certain cases, a single charged group in the chain end can alter the structure and properties of a polymer dramatically. On the other hand, oligomers, which are different from both discrete small molecules and higher molecular weight polymers, have become an emergent class of materials. There are several charged chain-end functionalized oligomers reported, but this area has been largely unexplored. The work described in this dissertation is aimed at using well-characterized end-group functionalized oligodimethylsiloxane (oDMS) as model materials to understand the effects of charged end groups …

Interactions Between Soft Nanoparticles And Mammalian Cells, Mitchell Raith

Doctoral Dissertations

Nanoparticles have been of interest to the pharmaceutical industry since the 1980s. The first FDA approved nanoparticle-based therapies included liposomal anesthesia agents. Since then, the amount of FDA-approved nanoparticle therapies remains low. This is because nanoparticle-patient interactions can be very complex and are not well understood. Complicating factors also include increasing obesity rates among the patient population and many small animal pre-clinical trials are completed with healthy, lean animals. The biochemical differences between lean and obese patients prevents early studies from accurately predicting nanoparticle clinical behaviors. Many nanoparticles fail in trails. In this thesis, I aimed to uncover how nanoparticles …

Accelerated Catalyst Diffusion In Chemically Amplified Resists, Christopher M. Bottoms

Doctoral Dissertations

Quantitative reaction-diffusion models are critical for the development of high-resolution lithographic processes based on chemically amplified resists (CARs). CARs consist of a glassy polymer resin with a photoacid generator. Patterns are formed through a coupled reaction-diffusion process. It is known that reaction kinetics is controlled by the slow diffusion of acid-anion pairs (catalysts), and catalyst diffusion lengths partly control the pattern resolution and uniformity. However, it is difficult to quantify the diffusivity during reaction, let alone examine the roles of polymer-ion and ion-ion interactions on catalyst mobility, using direct measurements. This work presents a concerted experimental and computational effort to …

Improving The Biocompatibility Of The Bio-Inorganic Interface For Enhanced Photosystem I-Based Biophotovoltaic Device Performance, Alexandra H. Teodor

Doctoral Dissertations

The world’s energy demands are projected to increase by nearly 50% by the year 2040, and consumption of carbon-based fuels continues to release greenhouse gases such as carbon dioxide and methane into the atmosphere. This has been causally linked with climate change and increased extreme weather events, which has been further linked to adverse health outcomes and negative effects on biodiversity, food security, and increased disease transmission. Clearly, there is a need for a sustainable, carbon-free, and cost-effective method of energy production to meet growing energy production demands. The sun irradiates Earth’s surface annually with ~80,000 terawatts (TW), making solar …

Modeling Chain Packing In Complex Phases Of Self-Assembled Block Copolymers, Anugu Abhiram Reddy

Doctoral Dissertations

Block copolymer (BCP) melts undergo microphase seperation and form ordered soft matter crystals with varying domain shapes and symmetries. We study the con- nection between diblock copolymer molecular designs and thermodynamic selection of ordered crystals by modeling features of variable sub-domain geometry filled with individual blocks within non-canonical sphere-like and network phases that together with layered, cylindrical and canonical spherical phases forms “natural forms” of self- assembled amphiphilic soft matter at large. First, we present a model to revise our understanding of optimal Frank-Kasper sphere-like morphologies by advancing the- ory to account for varying domain volumes. We then develop generic …

New Isomeric Silicones: Synthesis, Compositions And Surface Properties, Yan Cong

Doctoral Dissertations

This dissertation presents research performed in the field of silicone polymer science, which refers to polymers with alternating silicon-oxygen backbones. Three research topics will be explored. The first topic involves the synthesis of trimethylsiloxysilsesquioxane (MT) copolymers with vinyl and hydride functionalities as reactive liquid silicone precursors. The second topic describes titration of dimethylsiloxy (D) composition into trimethylsiloxysilsesquioxane (MT) copolymers for the purpose of controlling the mechanical properties and thermal stabilities of the material. The last topic explores the modification of hydrophobic silicone surfaces with oxygen plasma to form silica-like, hydrophilic surfaces and the behaviors of hydrophobic recovery. The first chapter …

Computational Rational Design Of Electrocatalysts For Electrochemical Ammonia And Hydrogen Synthesis, Akash Jain

Doctoral Dissertations

The electrochemical hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR) offer fossil-fuel-free routes for hydrogen and ammonia synthesis, respectively. However, currently, both processes lack suitable electrocatalysts for practical applications. Thus, this dissertation focuses on the computational rational design of HER and NRR electrocatalysts. HER is most efficiently catalyzed by platinum (Pt), which is expensive. To reduce the catalyst cost, we investigate core-shell nanoparticles of inexpensive tungsten-carbide (WC) and Pt (WC@Pt). Using first-principles density functional theory (DFT) calculations, we compare the suitability of two WC phases, α-WC and β-WC as support materials for Pt overlayers. We dope WC with titanium …

Development Of Crosslinking Technologies For Waterborne & Powder Coatings, Mengfei Huang

Doctoral Dissertations

Waterborne coatings and powder coatings are fast-growing sectors of the world coating market due to their environmentally friendliness as they have low or zero volatile organic compounds (VOCs) emission. However, compared with solventborne coatings, significant limitations need to be overcome to enable their broad applications. My dissertation will discuss several novel crosslinking strategies for waterborne and powder coating that could enable curing on-demand at ambient conditions, with facile polymerization and easy processing, and ultimately, exhibit a high degree of crosslinking and excellent performance that is comparable to solventborne coatings. We introduced and demonstrated the anionic polymerization mechanism and the high …

The Kanarra Fold-Thrust System -- The Leading Edge Of The Sevier Fold-Thrust Belt, Southwest Utah, William Joseph Michael Chandonia

Doctoral Dissertations

“The Jurassic to Eocene Sevier fold-thrust belt is the subject of continued scientific curiosity in tectonics, stratigraphy, and industry. Understanding its development in southwest Utah is hindered in part due to the multiple origins proposed for the Kanarra anticline, a major leading edge structure -- a drag fold along the Hurricane fault, Laramide monocline, Sevier fault propagation fold, or a combination of these -- which have confused its tectonic significance and regional context. This confusion results from the structural complexity of its exposed eastern limb, as well as displacement and burial of its crest and western limb beneath Neogene sediments …

Engineering Ni/Al2o3 Catalysts By Atomic Layer Deposition For Methane Reforming, Baitang Jin

Doctoral Dissertations

"Dry reforming of methane (DRM) could be a promising choice to utilize natural gas (mainly methane or CH₄), recycle captured CO₂, and produce valuable syngas. Promoters (e.g., CeO₂ and MgO) on Ni/Al₂O₃ prepared by atomic layer deposition (ALD) and ALD-prepared ultrathin overcoating (e.g., ZrO₂ and CeO_x) on Ni/Al₂O₃ prepared by incipient wetness method were investigated for methane reforming.

MgO and CeO₂ prepared by traditional incipient wetness method were used to promote the performance of ALD-prepared Ni nanoparticles (NPs) supported on four-channel α-Al₂O_{3 …}

Computational Fluid Dynamics Techniques For Multiphase Flow Systems, Jose Sebastian Uribe Lopez

Doctoral Dissertations

"Mathematical modelling of multiphase flow systems has been a major and persistent challenge over the last decades. Vast attempts to obtain predictive models can be found reported in literature, where major advances can be recognized in recent years, paired to enhancements in computer science and engineering. Notwithstanding, universally valid models with a mechanistic development are far from being achieved. The current status of modelling any multiphase flow system relies on the model order reduction of purely theoretical models. Such reductions and simplifications become the source of deviations in the predictions of the experimentally measured parameters and will constrain the applicability …

Evaluation Of Novel Preformed Particle Gels For Conformance Control And Acid Stimulation Through Core Flooding Tests, Shuda Zhao

Doctoral Dissertations

"Acid stimulation and conformance control are two major methods to improve oil production. This study systematically evaluates two newly developed gels: Degradable Preformed Particle Gel (DPPG) and Re-crosslinkable Preformed Polymer Gel (RPPG). DPPG is designed to be a temporary plugging agent for acid stimulation and can self-degrade into a water-like fluid. RPPG is designed for reservoir sweep efficiency improvement and can re-crosslink to each other and form an immobile bulk gel after being placed in fractures or fracture-like conduits.

For DPPG, this study evaluates the effect of monomer, crosslinker, and initiator concentration on the swelling and degradation performance. Results show …

The Utilization And Loss Of Available Energy In Aerospace Systems, Mohammad Abbas

Doctoral Dissertations

“Theoretical principles and analytical methodology for the control volume-based energy availability methodology for aerospace vehicles are developed; applications are made to jet-propelled and rocket-propelled vehicles as well as to stand-alone engine systems. Energy availability utilization characteristics of a modeled turbojet engine are studied across a wide range of operating conditions of throttle setting, flight altitude, and flight Mach number. The method is also extended to consider jet-powered vehicles. Fundamental principles regarding entropy generation and energy availability are developed, including directly linking entropy generation and maximum range and endurance of a powered aircraft. Theory and application of the energy utilization methodology …

Numerical Simulation Study Of Gel Treatment For Conformance Control From Lab To Field, Jianqiao Leng

Doctoral Dissertations

“Gel treatment has been widely applied to control reservoir conformance and thus improve the sweep efficiency of injection fluids. Quite a few numerical simulations have been conducted to investigate the factors impacting gel treatment and assist to optimize treatment design and predict the performance. However, there exists significant barrier between the simulation approaches and lab experiments. In this study, two comprehensive reviews have been conducted to identify the gaps between lab and current simulations for in-situ polymer treatment and preformed particle gel treatment, separately.

Based on the identified gaps, the effect of a few major factors which are very important …

Evaluation Of Recrosslinkable Preformed Particle Gel (Rppg) As A Fluid Loss Control Material During Drilling Operations, Mohamed Saad M. Ahdaya

Doctoral Dissertations

"One of the most intense, expensive, and time-consuming problems during drilling operations is the loss of circulation, which could result in several consequences, including wellbore collapse, fluid inflow, formation damage, environmental issues, and nonproductive time. This research aims to evaluate novel materials that can mitigate lost circulation and overcome the limitation of other materials. In this research, a comprehensive evaluation of a re-crosslinkable preformed particle gel (RPPG) has been conducted to determine the extent to which it can be used to control drilling fluid losses during drilling operations. The RPPG consists of swellable gel particles that can self-crosslink to form …

Development And Testing Of A New Air-Assisted Flare System For Low Flow Conditions, Hayder Alhameedi

Doctoral Dissertations

"Flare systems provide a safe, efficient, and reliable way to treat unwanted flammable gases that come from relief devices of various chemical processing equipment to ensure the safety of personnel and equipment. Flare systems are classified according to the assist media type as non-assisted (utility), steam-, air-, and pressure-assisted flares. The assist medium enhances mixing between flare gases and surrounding air and induces more air into the combustion zone. An air-assisted flare system is the preferred flare type in regions where steam is unavailable or is costly to supply or ambient temperatures are too low. The environmental protection agency (EPA) …

Advanced Materials And Processes For Gas Separation And Storage Applications, Qasim Mohammed Al-Naddaf

Doctoral Dissertations

"Transition to a clean, renewable energy future requires departure from thermally driven separation processes. In that regard, development of new materials that exhibit high adsorption capacity and selectivity, fast kinetics, and long-term durability under multicomponent conditions is becoming attractive for the applications in clean energy. Moreover, novel sorbents and separation systems that can store gases at normal conditions offer a promising approach for stationary or onboard gas storage. Due to the limitations on the surface area and biding energy restrict commercial materials effectiveness as a potential adsorption and storage material. There is significant interest in the properties of hybrid materials …

Surface Modification To Improve The Electrochemical Performance Of Cathode Materials For Lithium-Ion Batteries And Sodium-Ion Batteries, Han Yu

Doctoral Dissertations

"The specific capacity of active materials as well as their cycling stability are the main limiting factors for the performance of lithium-ion batteries (LIBs) and sodium-ion batteries (SIB). Atomic layer deposition (ALD) is considered as a promising surface modification method to enhance the electrochemical performance of active materials for LIBs and SIBs.

In this research, we are committed to using ALD to modify the cathode materials of LIB, by coating different films on the surface of different cathode materials and constructing a stable and favorable interface layer for lithium-ion transport, so that we can protect the active materials from the …

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 …

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 …