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Analysis Of Physicochemical Properties And Terrestrial Dynamics Of Mechanically Formed Micro-Nano Scaled Particles From Agricultural Plastic Mulches, Anton Friedrich Astner

Doctoral Dissertations

Release of microplastics (MPs) and nanoplastics (NPs) into agricultural fields is of great concern due to their reported ecotoxicity to organisms that provide beneficial service to the soil such as earthworms, and the potential ability of MPs and NPs to enter the food chain. Most fundamental studies of the fate and transport of plastic particulates in terrestrial environments employ idealized MP materials as models, such as monodisperse polystyrene spheres. In contrast, plastics that reside in agricultural soils consist of polydisperse fragments resulting from degraded films employed in agriculture. There exists a need for more representative materials in fundamental studies of …

Confinement And Interface Effects In Self Assembly Of Functional Block Copolymers, Jonathan P. Coote

Doctoral Dissertations

Functional block copolymers are of increasing interest for their ability to combine the functional properties of one polymer, such as a polymer electrolyte or semiconductor, with the mechanical properties of another polymer. Balancing properties in this way can be challenging, however, due to the complex relationship between self-assembled morphology and resulting properties. Interface effects in particular, whether due to confinement within a self-assembled domain or at macroscopic boundary, are poorly understood in such functional block copolymers. This dissertation consists of two main thrusts, each investigating confinement or interfacial effects in a different functional block copolymer system. The first thrust focuses …

Synthesis And Assembly Of Polymer Materials At Interfaces, Xiaoshuang Wei

Doctoral Dissertations

The overarching goal of the thesis is to understand growth and assembly of polymer materials at interfaces. Chapter 2 and Chapter 3 study simultaneous polymer growth and assembly at fluid interfaces, where in-situ photopolymerization and vapor phase deposition were utilized to grow polymers, respectively. Chapter 4 leverages capillary condensation to pattern polymer growth at solid substrates. Chapter 1 provides background information on polymer materials at interfaces, and vapor phase deposition method (initiated chemical vapor deposition, iCVD) to grow polymers. This chapter also reviews polymer thin film wetting, and colloidal assemblies at interfaces. In Chapter 2, we demonstrate the preparation …

Frontiers In The Self-Assembly Of Charged Macromolecules, Khatcher O. Margossian

Doctoral Dissertations

The self-assembly of charged macromolecules forms the basis of all life on earth. From the synthesis and replication of nucleic acids, to the association of DNA to chromatin, to the targeting of RNA to various cellular compartments, to the astonishingly consistent folding of proteins, all life depends on the physics of the organization and dynamics of charged polymers. In this dissertation, I address several of the newest challenges in the assembly of these types of materials. First, I describe the exciting new physics of the complexation between polyzwitterions and polyelectrolytes. These materials open new questions and possibilities within the context …

Functional Bottlebrush Polymer Additives For Thin Films And Coatings, Travis S. Laws

Doctoral Dissertations

Bottlebrush polymers are a class of highly branched polymers consisting of polymeric side chains that are densely grafted to a linear backbone. Their highly branched architecture results in surface enrichment across a broad range of materials. The goal of my research has been centered around the design of functional bottlebrush polymers and their use as surface active additives in blend films and coatings.

In the first chapter, we examine the segregation behavior of polystyrene bottlebrushes that are blended with linear polystyrene. We systematically vary the lengths of the bottlebrush backbone (Nb), side-chain (Nsc), and the linear matrix (Nm) in order …

Elucidating Mammalian Cellular Responses To The Uptake Of Nanoparticles (Nps), Pathogens, And Lipoproteins: Similarities And Differences, Monireh Asoudeh

Doctoral Dissertations

Soft poly-ethylene-glycol (PEG)-based soft nanoparticles (NPs) including cylindrical (CNPs) micelles, spherical (SNPs) micelles, and lipid bilayer vesicles (LNPs) are thought to be treated as foreign objects by mammalian phagocytes. If this hypothesis is true, NPs should trigger a proinflammatory, autophagic phenotype that is similar to the one seen when macrophages phagocytose pathogens or when macrophage surface expressed proteins bind pathogen surface factors such as lipopolysaccharide (LPS). Here, we show that macrophage responses to the above NPs are almost completely unique from those triggered by group A streptococcus (GAS) pathogens (JRS4 cells) and LPS. Instead, macrophages treat these soft NPs more …

Studies Of Multiphase Distribution And Flow In Bubble/ Slurry Bubble Columns With /Without Internals And Advanced Sustainable Construction Materials Using Sophisticated Measurement Techniques, Omar Farid

Doctoral Dissertations

"Bubble/slurry bubble columns have been widely studied and employed as multiphase flow reactors with and without vertical heat-exchanging tubes. In order to understand more deeply the effect of the dense internals on the hydrodynamics of bubble/slurry bubble column, systematic experiments were performed to visualize and quantify using the radioactive particle tracking (RPT) technique. A new methodology for implementing the radioactive particle tracking (RPT) technique has been developed to investigate the effect of the dense internals on the hydrodynamics of the bubble/slurry column reactor. Monte Carlo N-Particle (MCNP) simulation has been implemented to simulate the system to generate a large number …

A Rapid And Ultra-Sensitive Biosensing Platform Based On Tunable Dielectrophoresis For Robust Poc Applications, Yu Jiang

Doctoral Dissertations

With the ongoing pandemic, there have been increasing concerns recently regarding major public health issues such as abuse of organophosphorus compounds, pathogenic bacterial infections, and biosecurity in agricultural production. Biosensors have long been considered a kernel technology for next-generation diagnostic solutions to improve food safety and public health. Significant amounts of effort have been devoted to inventing novel sensing mechanisms, modifying their designs, improving their performance, and extending their application scopes. However, the reliability and selectivity of most biosensors still have much to be desired, which holds back the development and commercialization of biosensors, especially for on-site and point-of-care (POC) …

Crowd Control: Regulating The Spatial Organization Of Biopolymers And Gene Expression By Macromolecular Crowding, Gaurav Chauhan

Doctoral Dissertations

The intracellular environment is crowded with macromolecules that can occupy a significant fraction of the cellular volume. This can give rise to attractive depletion interactions that impact the conformations and interactions of biopolymers, as well as their interactions with confining surfaces. We used computer simulations to study the effects of crowding on biologically-inspired models of polymers. We showed that crowding can lead to attractive interactions between two flexible ring polymers, and we further characterized the adsorption of both flexible and semiflexible polymers onto confining surfaces. These results indicate that crowding-induced depletion interactions could play a role in the spatial organization …

Biomass Conversion To Bio-Derived Materials And Their Applications, Luna Liang

Doctoral Dissertations

Nowadays, fossil fuels still serve as the primary global energy resource. Replacing fossil fuels with renewable sources of energy and developing efficient energy storage technology is an urgent problem to solve. Lignocellulosic biomass has been investigated as a promising alternative for the production of biofuels, chemicals, and materials. In this dissertation, we studied the thermochemical biomass conversion strategies via different pretreatments strategies (e.g. dilute acid, ethanol, tetrahydrofuran, gamma-valerolactone) and genetic modification to overcome the biomass recalcitrance and achieve efficient conversion process. The biomass component structure of lignin and cellulose after thermal treatments were characterized and analyzed.

To further explore the …

Electrode Development Of Water Electrolyzer Cells For Low-Cost And High-Efficiency Hydrogen Production, Shule Yu

Doctoral Dissertations

A worldwide increase in energy demand and a latent crisis in the fossil fuel supply have spurred broad research in the renewable energy. Currently, most renewable energy resources (e.g., hydro, wind, solar, tide) face supply challenges as they are known to be intermittent, unstable, and locally shackled, which calls for urgent development in energy storage and conversion. Hydrogen is regarded as an ideal energy carrier with its advantages (e.g., high energy density, environmentally friendliness, and low weight). In practice, the proton exchange membrane electrolyzer cell (PEMEC) is considered to be one of the optimal hydrogen production and energy storage devices …

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 …

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 …

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 …

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 …}

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 …

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 …

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) …

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 …

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 …