Physical Sciences and Mathematics Commons^™

Large Scale Brownian Dynamics Simulation Of Dilute And Semidilute Polymeric Solutions, Amir Saadat

Doctoral Dissertations

Excluded Volume (EV) and Hydrodynamic Interactions (HI) play a central role in static and dynamic properties of macromolecules in solution under equilibrium and nonequilibrium settings. The computational cost of incorporating HI in mesoscale Brownian dynamics (BD) simulations, particularly in the semidilute regime has motivated significant research aimed at development of high-fidelity and efficient techniques.

In this study, I have developed several algorithms for the mesoscale bead-spring representation of a macromolecular solution in dilute and semidilute regimes. The Krylov subspace method enables fast calculation of single chain dynamics with simulation time scaling of O(N_b²) [order N …

Preliminary Investigation For The Development Of Surrogate Debris From Nuclear Detonations In Marine-Urban Environments, Adam G. Seybert

Masters Theses

No nuclear weapon has ever been detonated in a United States city. However, this also means the nuclear forensic community has no actual debris from which to develop analytical methods for source attribution, making the development of surrogate nuclear debris a vital undertaking. Moreover, the development of marine-urban debris presents an unusual challenge because unlike soil and urban structures, which remain compositionally consistent, the elemental composition of harbor and port waters fluctuates considerably due to natural phenomenon and human activity. Additionally, marine vessel composition and cargo can vary dramatically. While early US nuclear tests were carried out in shallow-water coastal …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Photocatalytic Reduction Of Co2 With Tunable Bandgap And Bandedge Materials, Thuhuong T. Ngo

USF Tampa Graduate Theses and Dissertations

Solar energy is a sustainable resource which has substantial potential to meet the increasing demand for renewable energy. Though there has been some success in harvesting solar energy for electricity production, converting solar energy to chemical energy as fuels is still a challenge due to low efficiency.

Since the discovery of TiO₂ photocatalysts for splitting water (4) and reducing CO₂ (5) to form useful chemical feedstock such as H₂, CO and CH₄, much research has been done to increase the efficiency of photocatalysts. However, the current conversion efficiency of photocatalysts remains low (~5%) (6, …

Kinetics And Dynamics Of Electrophoretic Translocation Of Polyelectrolytes Through Nanopores, Harshwardhan Katkar

Doctoral Dissertations

The idea of sequencing a DNA based on single-file translocation of the DNA through nanopores under the action of an electric field has received much attention over the past two decades due to the societal need for low cost and high-throughput sequencing. However, due to the high speed of translocation, interrogating individual bases with an acceptable signal to noise ratio as they traverse the pore has been a major problem. Experimental facts on this phenomenon are rich and the associated phenomenology is yet to be fully understood. This thesis focuses on understanding the underlying principles of polymer translocation, with an …

Polymer And Small Molecule Designs For Anion Conducting Membranes: Connected Ion-Channel Morphologies And Highly Alkaline Stable Ammonium Cations, Sedef P. Ertem

Doctoral Dissertations

Fuel cells are one of the oldest sustainable energy generation devices, converting chemical energy into electrical energy via reverse-electrolysis reactions. With the rapid development of polymer science, solid polymer electrolyte (SPE) membranes replaced the conventional liquid ion transport media, rendering low-temperature fuel cells more accessible for applications in portable electronics and transportation. However, SPE fuel cells are still far from commercialization due to high operation cost, and insufficient lifetime and performance limitations. Anion exchange membrane fuel cells (AEMFCs) are inexpensive alternatives to current proton exchange membrane fuel cell (PEMFC) technology, which relies on utilizing expensive noble-metal catalysts and perfluorinated SPE …

Modeling Pyrolysis Of Large Coal Particles With Many Species, Jianqing Li

Master's Theses (2009 -)

Coal currently supplies 40% of the world’s electricity needs, and is one of the most important energy sources. As the initial stage of coal combustion, pyrolysis is a thermal decomposition process which converts coal into light gases and tars, which are subsequently consumed in combustion reactions, as well as solid char. Recently there has been interest in using slow pyrolysis as a stand-alone process for the production of chemicals and fuels from large (mm-scale) coal particles. Simulations can be used to efficiently study the impact of pyrolysis conditions on gas, tar and char yields, as well as gas and tar …

Development Of Ultrasonic Techniques For Characterization Of Liquid Mixtures, William A. Cooke

Electronic Thesis and Dissertation Repository

To evaluate the suitability of ultrasonic techniques for on-line process monitoring applications, an ultrasonic probe was used to measure acoustic velocity, acoustic impedance, and isentropic compressibility of hydrocarbons (including n-, iso-, and cycloalkanes, toluene, mineral oil, and crude oil) and polar liquids (alcohols, water, salt water) over a temperature range of 25-60°C. Temperature, carbon chain length, molecular shape, and intermolecular forces had significant effects on ultrasonic parameters. Relationships between media characteristics and observed ultrasonic parameters were modeled using empirical-least squares equations. The same parameters were measured in binary mixtures of hydrocarbons in heptane, as well as polar liquids in ethanol. …

Nanostructured Thin Film Synthesis By Aerosol Chemical Vapor Deposition For Energy Storage Applications, Tandeep Singh Chadha

McKelvey School of Engineering Theses & Dissertations

Renewable energy sources offer a viable solution to the growing energy demand while mitigating concerns for greenhouse gas emissions and climate change. This has led to a tremendous momentum towards solar and wind-based energy harvesting technologies driving efficiencies higher and costs lower. However, the intermittent nature of these energy sources necessitates energy storage technologies, which remain the Achilles heel in meeting the renewable energy goals. This dissertation focusses on two approaches for addressing the needs of energy storage: first, targeting direct solar to fuel conversion via photoelectrochemical water-splitting and second, improving the performance of current rechargeable batteries by developing new …

Mechanism Of Ethanol Partial Oxidation Over Titania Supported Vanadia Catalysts: Geometric And Electronic Structure Consequences On Reaction Kinetics, Dongmin Yun

Electronic Thesis and Dissertation Repository

Supported vanadium oxide catalysts (VO_x) are used for a wide range of industrial processes. A significant amount of research has been carried on this specific system with the aim to identify the critical parameters involved in catalytic activity. The results on this relative large body of research indicate that the catalyst support plays a critical role in determining the catalytic activity of vanadia and the use of titanium dioxide as support renders a catalyst with superior activity. Studies on supported vanadia on titanium oxide (VO_x/TiO₂) have provided an understanding on support interactions that result …

Adsorption Kinetics Of Bovine Serum Albumin To Strong Anion Exchange Adsorbents: Application Of The Pore Diffusion Model To Resins And Membranes, Sarah Catherine Jensen

Graduate Theses - Chemical Engineering

The replacement of traditional bead-based chromatography by membranes has gained recent interest in the bioseparations industry. However, membranes have drawbacks such as lower binding capacity that make them unrealistic for some applications. The goal of this work is to compare the adsorption kinetics of anion exchange bead-based resin and membranes both on a theoretical modeling level and experimental level. Bovine serum albumin (BSA) was adsorbed to Q Sepharose FastFlow resin and Sartobind Q membrane to obtain adsorption equilibrium characteristics and kinetic data. A numerical solution was used to fit the pore diffusion model to the data and estimate a pore …

Enabling A Sustainable Economy Through Energy Systems Modeling: Solar-Centric, Efficient, Integrated And Continuous Process Synthesis And Optimization, Emre Gencer

Open Access Dissertations

The expected increase in food, energy and water demand due to increase in population and change in consumption habits in conjunction with diminishing fossil fuel reserves and increasing greenhouse gas emissions urge the development and implementation of alternative energy conversion techniques using renewable energy for a sustainable economy. Among renewable energy sources, solar energy is prominent due to its abundance. A sustainable economy can be created by producing building blocks foundational to meeting all basic human needs of daily existence. However, intermittencies and limitations on land area dedicated to harness solar energy are the major obstacles on widespread implementation of …

Enhancing Silymarin Fractionation Via Molecular Modeling Using The Conductor-Like Screening Model For Real Solvents, Emma C. Brace

Open Access Theses

The market for bio-based products from plant sources is on the rise. There is a global challenge to implement environmentally clean practices for the production of fuels and pharmaceuticals from sustainable resources. A significant hurdle for discovery of comparable plant-derived products is the extensive volume of trial-and-error experimentation required. To alleviate the experimental burden, a quantum mechanics based molecular modeling approach known as the COnductor-like Screening Model for Real Solvents (COSMO-RS) was used to predict the best biphasic solvent system to purify silymarins from an aqueous mixture. Silymarins are a class of flavonolignans present in milk thistle ( Silybum marianum …

Initial Structural Subsidence As Reflected In Morrowan And Atokan (Pennsylvanian) Subsurface Stratigraphy, Northern Arkoma Basin, North-Central Arkansas, Fatimah Taher Nahi Al Asadi

Graduate Theses and Dissertations

The Arkoma Basin is a carboniferous foreland basin that is known for its prolific gas production. The objective of this research is to study the initial subsidence of the basin by analyzing the strati-graphic and structural features of the study area. This was accomplished through IHS Petra, Surf-er 13, and Win-Tensor software. Field work studies comprised a large part of this study. Also, a seismic profile and Google earth elevation profiles are among the methods used to study the initial subsidence of the Arkoma Basin. The study area within the basin represents a transitional zone from the shelf into the …

Electrodeionization Versus Electrodialysis: A Clean-Up Of Produced Water In Hydraulic Fracturing, Brigitte Marie Rodgers

Graduate Theses and Dissertations

Electrodeionization (EDI) is a widely studied process ranging from applications in wastewater clean-up in the food and beverage industry to purifying organic compounds. To date, there are no apparent studies on applying this technology to produced wastewater recovered from hydraulic fracking sites. Water consumption within hydraulic fracturing sites can reach in the upwards of millions of gallons per site, so a need for a water recycling process becomes necessary within areas where water requirements are scarce. Implementation of an EDI module that is capable of handling high salt solutions from produced wastewater in subsequent fracturing practices will decrease overall water …

Synthesis And Characterization Of Polymeric Anion Exchange Membranes, Wenxu Zhang

Doctoral Dissertations

As alkaline anion exchange membrane fuel cells (AAEMFC) are regarded as promising and important energy devices, the development of high performance anion exchange membranes are in urgent need, as well as fundamental investigation on the structure-property relationship, which are the motivation of this dissertation. Three different polymer systems are presented and focused on polymer synthesis, material morphology, and ion transport phenomena. Crosslinked membranes are promising as practical materials, however, the understanding and further improvement of its performance is hindered by the lack of an ordered morphology or well-defined chemical structure. In Chapter 2, a series of crosslinked membranes were design …

The Design And Testing Of A Novel Batch Photocatalytic Reactor And Photocatalyst, Shawn Sasser

USF Tampa Graduate Theses and Dissertations

With an ever-increasing human population, the importance in having sustainable energy resources is becoming increasingly evident, as the current energy habits have brought about massive atmospheric pollution in the form of CO₂ emissions, resulting in a rise in the average global temperature. To battle the effects of climate change, many alternative energy resources have been investigated. Among these, photocatalytic conversion of CO₂ to renewable hydrocarbon fuels such as methane and methanol is one of the most desirable, as it provides the opportunity to utilize the sun’s energy to convert CO₂ to renewable fuels. The work in this …

Atomic Force Microscopy Of Poly(Ethylane-Oxide) Crystalization, Xavier Capaldi

Honors Theses

Polymer crystallization is a complex process which is influenced by a variety of factors. Atomic force microscopy is used to explore the material properties of polymer crystals. Poly(ethylene-oxide) is used in a variety of molecular weights as the sample. In addition, a variety of sample preparation methods and microscopy modes were tested. A relatively new imaging technique was identified for the characterization of polymer crystals: amplitude modulation-frequency modulation viscoelastic mapping. This mode was used to measure material properties such as stiffness and dissipation.

Gasoline Confined In Nano-Porous Media, Matthew Giso

Honors Theses

The heat of combustion was determined for gasoline confined in nano-porous media of differing pore size by bomb calorimetry. The heat of combustion of the confined fuels was comparable to that of bulk within the experimental uncertainty. This suggests that all of the confined fuel burns without any flame quenching and no chemical interactions at the interface between pore walls and fuel mitigate combustion.

Nano-Photonic Waveguides For Chemical And Biomedical Sensing, Surya Venkatasekhar Cheemalapati

USF Tampa Graduate Theses and Dissertations

In this dissertation, advances in the fields of Photonics, and Plasmonics, and specifically, single cell analysis and waveguide sensing will be addressed. The first part of the dissertation is on Finite Difference Time Domain (FDTD) optimization and experimental demonstration of a nano-scale instrument that allows sensing at the cellular and subcellular levels. A new design of plasmonic coupler into a nanoscale waveguide is proposed and optimized using FDTD simulations. Following this, a subcellular nanoendoscope that can locally excite fluorescence in labelled cell organelles and collect the emitted fluorescent light for detailed spectrum analysis is fabricated and tested. The nanoendoscope has …

Modeling, Simulation, And Analysis Of Lithium-Ion Batteries For Grid-Scale Applications, Matthew Thomas Lawder

McKelvey School of Engineering Theses & Dissertations

Lithium-ion batteries have become universally present in daily life, being used across a wide range of portable consumer electronics. These batteries are advantageous compared to other forms of energy storage due to their high energy density and long cycle life. These characteristics make lithium-ion batteries advantageous for many new and developing applications that require large scale energy storage such as electric vehicles and the utility grid. Typical uses for lithium-ion batteries require consistent cycling patterns that are predictable and easy to approximate across all uses, but new large scale applications will have much more dynamic demands. The cycling patterns for …

A Characterization Study On Catalyst Layers In Proton Exchange Membrane Fuel Cells, Luyue Li

Doctoral Dissertations

This thesis describes the work for the catalyst layer (CL) characterization study of proton exchange membranes (PEM) for fuel cells. In particular, both the structure and performance of catalyst layers with alternative ionomers were studied. Structure wise, the morphology, surface area and pore size distribution studies were accomplished with scanning electron microscopy (SEM), transmission electron microscope (TEM) and nitrogen adsorption processed through Brunauer–Emmett–Teller (BET) and Barrett-Joyner-Halenda (BJH) theory. Water uptake isotherms of the CLs have been developed under well controlled relative humidity (RH) levels. The performance characterization focuses on polarization study, catalyst layer proton conductivity measurement and estimation of the …

Particle Image Velocimetry Design & Installation, Zach Ritchie

Mechanical Engineering Undergraduate Honors Theses

This work will mainly focus on the design, construction, and installation of the Particle Image Velocimetry (PIV) system in the Chemical Hazards Research Center wind tunnel. The PIV system utilizes a Class IV (double pulsed) laser, optics to produce a light sheet, timing circuitry, and a high-resolution camera (with buffered output) to measure a system’s velocity (two-dimensional) field by determining the displacement of particles over the time between laser pulses. For maximum mobility and functionality, the PIV system was installed in the center of the tunnel on a moveable cart with the laser and camera mounted to an adjustable support. …

Haul Truck Tires Recycling, Jessica N. Lizarazu

Chemical Engineering Undergraduate Honors Theses

The disposal of large Off-the-Road (OTR) tires is an increasingly important concern. These tires can weigh up to 8,450 pounds with an overall diameter and width of approximately 140.7 inches and 45.1 inches respectively. OTR tires are used for mining vehicles such as haul trucks, wheel loaders, backhoes, graders, and trenchers. These new tires cost between $38,000 and $50,000 each, depending on multiple factors including oil prices and the cyclical nature of the industry. Haul trucks contain six tires per vehicle, and mines replace these tires around every 9-12 months. Statistics regarding discarded OTR tires are not provided by the …

Cd Transport In Eutectic Licl-Kcl And Contamination Of Zr Metal And Thermal Dehydration Of Bulk Licl-Kcl, Nicholas Azoy Earle

Masters Theses

Researchers at Idaho National Labs have noted unexpectedly high Cd content in empty cladding hulls after processing in the Mark-IV ER. It has been theorized that Cd metal is transporting from the LCC pool through the eutectic LiCl-KCl salt bath to the anode baskets containing the empty hull where it is retained as a Zr-Cd intermetallic. This study sought to replicate the Cd contamination in a dry Ar glovebox using small-scale analogue of the Mark-IV ER salt-Cd metal system.

Anhydrous eutectic LiCl-KCl was an essential regent in this research and experiments were conducted to investigate the feasibility of dehydrating nominally …

Direct Band Gap Gallium Antimonide Phosphide (Gasbxp1-X) For Solar Fuels., Harry Benjamin Russell

Electronic Theses and Dissertations

Photoelectrochemical water splitting has been identified as a promising route for achieving sustainable energy future. However, semiconductor materials with the appropriate optical, electrical and electrochemical properties have yet to be discovered. In search of an appropriate semiconductor to fill this gap, GaSbP, a semiconductor never tested for PEC performance is proposed here and investigated. Density functional theory (DFT+U) techniques were utilized to predict band gap and band edge energetics for GaSbP alloys with low amount of antimony. The overall objective of this dissertation is to understand the suitability of GaSb_xP_1-x alloys for photoelectrochemical water splitting application. Specifically, …

Doped Tio2 Nanowires For Applications In Dye Sensitized Solar Cells And Sacrifical Hydrogen Production, Qasem Alsharari

Electronic Thesis and Dissertation Repository

This thesis explores the synthesis of metal oxide 1-D nanowires using a sol-gel method in supercritical carbon dioxide (sc-CO₂), as an environmental friendly enabling solvent. Porous nanowires were synthesized and their performance was tested in dye sensitized solar cell and sacrifical hydrogen production. Titanium isopropoxide (TIP) was used as a precursor for titania synthesis while copper, bismuth and indium were examined as dopants, respectively. The sol-gel reactions were catalyzed by acetic acid in CO₂ at a temperature of 60 °C and pressure of 5000 psi. It was observed that acetic acid/monomer ratio > 4 produced nanowires while a …

Targeted Metabolomics On The Shikimate And Aromatic Amino Acid Biosynthetic Pathways, Robert E. Wheeler

Open Access Theses

The shikimate and aromatic amino acid biosynthesis pathways are some of the most studied biosynthetic pathways in nature due to their fundamental importance. Interest in this field stems from synthesis of the essential amino acids, tryptophan, tyrosine and phenylalanine. The pathways also are important as generating the precursors of thousands of secondary metabolites and lignin. Inhibiting the pathway has led to discovery of herbicides, pesticides as well as tuberculosis drugs. However there is currently a lack of a comprehensive targeted method for detecting and quantifying the majority of the intermediates in these pathways. Often multiple extraction and detection methods are …

Investigation Of The Use Of A Plasticizer-Polymer Sensor Coating With Improved Long-Term Stability In The Liquid Phase, Laura Jeanne Alderson

Master's Theses (2009 -)

Benzene is one of the volatile organic compounds present in crude oil and gasoline. Leakage from underground storage tanks or hazardous waste sites can introduce benzene contamination into nearby groundwater. Benzene is a known carcinogen and its exposure is limited by the Environmental Protection Agency to 5 parts per billion (ppb) in drinking water. Early, accurate detection of the presence of benzene contamination in groundwater supplies is extremely important. Shear horizontal surface acoustic wave (SH-SAW) devices with a chemically sensitive coating can be used for the detection of volatile organic compounds in liquid, such as BTEX (benzene, toluene, ethylbenzene and …

Low-Temperature Artificial Maturation Studies Of Type Ii And Type Iii Kerogens: Implications For Biogenic Gas Production, Albert Willy Nguena Kamga

Chemistry & Biochemistry Theses & Dissertations

Ancient organic matter (OM) in shales and coals, known mainly as Type II and Type III OM are known to produce both biogenic, thermogenic gas and oil. In this dissertation, mild artificial maturation, via closed system pyrolysis, is employed to determine the thermal reactivity of Type II and Type III OM beyond diagenesis. We select three Type II kerogens: i) Type II kerogen isolated from recent cores (3.3 Ma, Ro = 0.28) recovered from an upwelling basin in Namibia, Africa referred to as ODP Sediment, ii) Type II-S isolated from sediments (150 Ma, Ro = 0.38) recovered from an outcrop …