Engineering Commons^™

Engineering Ionomer Materials For Addressing Ohmic Resistances In Electrochemical Desalination And Waste Heat Recovery, Varada Menon Palakkal

LSU Doctoral Dissertations

Water scarcity and energy availability present important challenges that need to be addressed in the coming centuries. In the front of water technologies, desalting brackish water is of extreme importance for thermal electric power plants, chemical manufacturing plants, and other industrial operations that treat and reuse their water utilities. Membrane capacitive deionization (MCDI) is an energy efficient desalination technique that has drawn attention from commercial entities. Most material research studies on MCDI focus on enhancing electrode performance while little emphasis is given to rationale design of ion-exchange membranes (IEMs). In this work, the ionic conductivity, permselectivity, and thickness for three …

Theoretical Investigation Of Fundamental Cathode Processes In Metal-02 Batteries, Saurin Hiren Rawal

LSU Doctoral Dissertations

In this thesis we theoretically explore the different fundamental phenomena associated with metal-air batteries (where the metal can be Li, Na or K) using first principles density functional theory. We start by investigating the adsorption of the starting reactants/primary intermediates i.e. metal superoxides and superoxide anion on Au(111) and Au(211). We elucidate the influence of electric fields and the importance of including explicit solvents on the adsorption energy of these intermediates. We show that these effects are considerable and should be included for future reaction modeling of these batteries. Following this we investigate the reaction of M⁺ and O …

Multi-Component Material For Solar Energy Conversion And Fundamentals Of Lead Acid Batteries, Crystal Ferels

Graduate Research Theses & Dissertations

Synthesis of complex inorganic materials is desirable because their complex composition allows more degrees of freedom and tunability, whose properties differ from their parent components. As an expansion on this concept, we synthesized a quinary compound Ce3FeWS3O6, using a molten flux method and a solvothermal method. The compound crystallizes into a hexagonal crystal system with space group P63/m. Its electric partition shows an anion with the form [(Ce3+)3W6+(S2-)3(O2-)6]3- forcing the transition metal Fe3+ state and leaving no conduction electrons, making the material a semiconductor. This compound is the right candidate as photoelectric material capable of absorbing photons from the solar …

Application Of Immobilized Palladium Monolithic Catalysts In Suzuki-Miyaura And Tsuji-Wacker Redox Reactions, Sajjad Ghobadi

Theses and Dissertations

Herein, a wholistic analysis of the viability of monolithic catalysts for redox reactions is presented. The interdisciplinary approach taken in this systematic study included preparation and investigation on Pd-on-carbon monoliths as catalysts in a flow and electrochemical settings.

The Suzuki-Miyaura reaction-focused study led to rational design, preparation, and successful application of Pd⁰-on-graphene oxide (GO) monolithic catalysts in flow conditions. In this study a combination of chemical reduction, freeze-casting, and vapor-phase reduction processes was applied to Pd-GO structures leading to the preparation of these monoliths. The Suzuki flow synthesis reactions revealed that the monolithic structure led to significantly improved …

Transition Metal Chalcogenide Hybrid Systems As Catalysts For Energy Conversion And Biosensing, Siddesh Umapathi

Doctoral Dissertations

"Generation of hydrogen and oxygen through catalyst-aided water splitting which has immense applications in metal air batteries, PEM fuel cells and solar to fuel energy production, has been one of the critical topics in recent times. The state of art oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) catalysts are mostly comprised of precious metals. The current challenge lies in replacing these precious metal-based catalysts with non-precious earth-abundant materials without compromising catalytic efficiency.

This research explores mixed metal selenides containing Fe-Ni, Fe-Co and RhSe which were hydrothermally synthesized and/or electrodeposited and tested for OER and ORR …

Anion Exchange And Bipolar Membranes For Electrochemical Energy Conversion And Storage, Zhongyang Wang

McKelvey School of Engineering Theses & Dissertations

Anion exchange and bipolar membrane fuel cells generate electrical energy directly from chemical fuels and have attracted considerable interests as alternate power sources for large market applications, such as transportation (hydrogen fuel cells) and unmanned vehicles (sodium borohydride fuel cells). Anion exchange membrane (AEM), generally composed of a polymer with covalently tethered ionic groups, is the central component of the fuel cell serving as the electrolyte, conducting hydroxide ions from cathode to anode, where fast ionic conduction is directly related to power output. However, AEMs currently used in fuel cells (H2 fuel cells and sodium borohydride fuel cells) exhibit ion …

Design, Microfabrication And Characterization Of Concentric Gold Nanoring Electrode For Neurochemical Sensing, Haocheng Yin

Doctoral Dissertations

Nanoelectrodes have become widely used in electrochemical sensing in recent decades. When compared to microelectrodes, it has many unique advantages such as high signal to noise ratio, small sample volume requirement, and lower detection limits.

This work reports on the microfabrication and characterization of a gold nanoring electrode (Au NRE) patterned on top of a silicon (Si) micropillar. An NRE of 165  10 nm in width was micropatterned on 4.6  1 µm diameter  17.5  2.5 µm long Si micropillar with an intervening 50 nm thick hafnium oxide insulating layer. Scanning electron microscopy and energy dispersive spectroscopy …

Modification And Optimization Of Conducting Polymer-Modified, Redox-Magnetohydrodynamics (R-Mhd) Pumping For Enhanced And Sustained Microfluidics Applications, Md Foysal Zahid Khan

Graduate Theses and Dissertations

In this work, a novel microfluidic pumping approach, redox-magnetohydrodynamics (R-MHD) has improved by materials and device optimization to use in lab-on-a-chip applications. In R-MHD, magnetic flux (B) and ionic current density (j) interacts to generate body force (FB) in between active electrodes, according to the equation FB = j×B. This unique fluid pumping approach is scalable, tunable, generates flat flow profile, and does not require any channels or valves. Pumping performance, such as speed scales with the ionic current density (j) and duration depends on the total charge (Q). The ionic current density (j) results from the conversion of electronic …

Morphology And Detection Of Corrosion On Stainless Steel Reinforcement In Concrete, Julio J. Saire Yanez

USF Tampa Graduate Theses and Dissertations

Stainless steel (SS) has emerged as an alternative corrosion-resistant reinforcement in concrete instead of the commonly used carbon steel (CS). The biggest advantage of SS is that it takes more time for corrosion to initiate than for CS. An additional benefit from the use of SS in concrete may be derived from the period after the corrosion started until the concrete structure reaches a limit state. This period is called corrosion propagation stage (CPS) and it has been hardly studied in SS reinforced structures. The duration of this period could be related, among other factors, to the morphology of corrosion …

Surface Immobilization Of Terpyridine Compounds, Elizabeth Hallett

Chemical Engineering Undergraduate Honors Theses

The deoxydehydration (DODH) of polyols to alkenes is a promising method of producing high-value chemical feedstocks from biomass-derived materials. Current catalytic systems for DODH require the use of costly reducing agents that generate stoichiometric amounts of chemical waste. Immobilizing catalysts on electrode surfaces using chemical linking groups eliminates the need for sacrificial reductants. In this work, glassy carbon electrodes were modified with 4’-(3,4-dihydroxyphenyl)-2,2’:6’,2’’-terpyridine to investigate o-benzoquinone as a potential linking group for DODH, and possibly for other reactions. Previous studies involving electrodes modified with quinone-containing compounds have primarily been focused on catalyzing the oxidation of NADH; the nature or …

An Experimental And Numerical Investigation Of Flow Accelerated Flibe Corrosion, David B. Weitzel

Nuclear Engineering ETDs

Renewed interest in molten salt reactor technology has brought to light the need for a better understanding of FLiBe corrosion. To this end a flowing FLiBe corrosion test loop was designed to test the flow effects of FLiBe corrosion. The loop consists of a pump, melt tank, and stainless-steel tubing assembly that heats the molten salt to high temperatures and circulates it over test specimens. The experiment has been constructed and has completed initial shakedown testing.

To support the flowing FLiBe experiment, a numerical corrosion model that couples FLiBe electrochemistry, solid metal diffusion, and mass transport was implemented. The model …

Engineering Of Earth-Abundant Electrochemical Catalysts, Dylan D. Rodene

Theses and Dissertations

Alternative energy research into hydrogen production via water electrolysis addresses environmental and sustainability concerns associated with fossil fuel use. Renewable-powered electrolyzers are foreseen to produce hydrogen if energy and cost requirements are achieved. Electrocatalysts reduce the energy requirements of operating electrolyzers by lowering the reaction kinetics at the electrodes. Platinum group metals (PGMs) tend to be utilized as electrocatalysts but are not readily available and are expensive. Ni_1-xMo_x alloys, as low-cost and earth-abundant transition metal nanoparticles (NPs), are emerging as promising electrocatalyst candidates to replace expensive PGM catalysts in alkaline media. Pure-phase cubic and hexagonal Ni_{1-x …}

Novel Cathode Framework, Effective Electrolyte Modification, And Electrode Structural Modification Of High Performance Lithium Sulfur Batteries, Wenduo Zeng

Wayne State University Dissertations

Firstly, TiN nanotube arrays have been investigated as an effective skeleton in the cathode of lithium-sulfur batteries. A series of TiN nanotubes with various diameter and length have been synthesized and tested. Moreover, graphene nanoplatelets have been utilized as a structural anchor to support the TiN nanotubes, and the synergetic effect of composite material and its enhancement on Li-S battery electrochemical performance and cycling stability have been studied. Secondly, the improvement of electrode structural design has been evaluated for their effectiveness by using an in-situ characterization method with other electrochemical characterization. Lastly, the facile method of using transition metal cations …

Chronoamperometry Analysis Of Sweat Sensor Technology, Evan Fritz

Williams Honors College, Honors Research Projects

Due to the demand for in-situ electrolyte sodium sensors, prototype sensors have been produced to create a product for athletes and marathoners to monitor hydration levels. These senors address a desire in the marketplace for athletic monitoring for overall athlete wellness and performance. Sweat sensor samples were created using Multi-walled Carbon Nanotubes functionalized on a Nylon-6 fiber mat using cyclo-oligomeric Calixarene. This production process produces sensors capable of detecting sodium ion concentration present in human sweat in presence of an electric current. Chronoamperometry analysis is used in this manner to determine the functionality of the sensors. Much of the research …

Electrochemical Separation Of Multivalent Species On A Liquid Bismuth Cathode In Licl-Kcl Eutectic For Used Nuclear Fuel Reprocessing, Michael Woods

Theses and Dissertations

The presence of group I/II fission products (Cs-137, Sr-90, and Ba-137) within molten salt nuclear processes degrades operational efficiencies by contributing to increased radiation levels in the case of material handling processes or to loss of criticality in the case of a reactor. While methods such as zone freezing and ion exchange have been proven for the separation of these fission products in LiCl-KCl salts, they require extra equipment and processing steps. Addition of a liquid metal electrode to molten salt media, such as the electrorefiner of a pyroprocessing scheme or the salt cleaning stage of a molten salt fast …

Development Of Flexible Nickel-Zinc And Nickel-Iron Batteries, Xianyang Meng

Dissertations

The fabrication of flexible nickel-zinc batteries using a facile mixing of electroactive components for electrode preparation is presented. Polytetrafluoroethylene (PTFE) is found to be an effective binder by reducing concentration polarization, providing chemical/physical stability and enhancing flexibility. The zinc electrode containing PTFE maintains its original porous morphology even after hundreds of cycles while polymers such as PEO show morphology change. Each component, as well as the assembled flexible cells show desired flexibility and stability even under bending conditions.

The fabrication of flexible nickel-iron batteries using printable composite electrodes embedded with multiwalled carbon nanotubes (CNT) is also presented. All the metal …

Corrosion Dynamics Of Carbon Steel In Used Fuel Container Environments, Dan Guo

Electronic Thesis and Dissertation Repository

The current Canadian used nuclear fuel container (UFC) design uses a pressure‑grade carbon steel (CS) vessel with its outer surface coated with a thin layer of copper. One concern regarding the structural integrity of the UFC design is the potential internal corrosion of the CS vessel. Moisture trapped inside a UFC could condense within the gap between the hemispherical head and the cylindrical body of the vessel. The internal UFC environment will be exposed to a continuous flux of ionizing radiation arising from the decay of radionuclides trapped in the used UO₂ fuel matrix.

This thesis research project investigates …

Investigating The Electrodeposition Of Plutonium And Curium For Safeguarding The Electrorefiner, Chantell L. Murphy

Nuclear Engineering ETDs

This research investigated the electrochemical deposition behavior of plutonium (Pu) and curium (Cm) for safeguarding the electrorefiner (ER) in a pyroprocessing facility. The main goal of this investigation was to evaluate the feasibility of using a safeguards concept called the neutron balance method to account for Pu in the ER. The neutron balance method relies on a known Pu/Cm ratio and measures neutrons from Cm-244 coming into and leaving a unit operation to track Pu. The application of the neutron balance approach for pyroprocessing facilities requires that Pu and Cm remain together in all extraction, product recovery, and waste streams. …

Design And Synthesis Of Novel Nanometallic Catalysts And Electrode Materials For Green Fuel Cells, Jing Zhang

Graduate Dissertations and Theses

The United Nations formally adopted 17 sustainable development goals (SDGs) at its 2015 summit. Many of these goals addressed issues such poverty, hunger, health, education, climate-change, gender equality, water, sanitation, energy, urbanization, environment and social justice. The seventh SDG seeks to ensure access to affordable, reliable, sustainable and modern energy for all. So among all renewable forms of energy, fuel cells with high efficiency have attracted a lot of attention recently. In particular, the direct ethanol fuel cells (DEFCs) and microbial fuel cells (MFCs) are significant due to their green fuel, less waste generated and environmental friendliness. Hence the overall …

Spectro-Electrochemical Platforms For Dynamic Analyses Of Catalytic Cascade Systems, Nalin I. Andersen

Nanoscience and Microsystems ETDs

The development of spectro-electrochemical platforms that facilitate the dynamic analyses of complex catalytic cascade systems was explored in this research. These systems facilitated multiple modalities of catalysts and were used as platforms for monitoring catalytic transformations quasi-in situ. The analytical platforms allowed for the characterization of intermediates and products using surface-enhanced Raman spectroscopy (SERS). The design and fabrication of these devices proved to be reproducible, made of materials that can be manipulated for multiple applications, and incorporate fluid mechanics, electrochemistry, and multimodal catalysis. Microfluidic technology offers capabilities for understanding catalytic cascade systems by providing precise dynamic control of …

Non-Precious Metal Catalysts For Oxygen Reduction Reaction In Alkaline Solutions, Zhewen Yin

USF Tampa Graduate Theses and Dissertations

Mesoporous WO3 powders were prepared via sol-gel processing synthesis using nonionic surfactant Pluronic (P-123) as the template. The influences of heating temperature on the pore structure and properties of WO3 powders were investigated. Three kinds of modifications were compared and evaluated after finding out the best heating condition. Different amount of lanthanum was doped into mesoporous WO3 to improve its Oxygen Reduction Reaction (ORR) activity. Several factors contributing to the increase of catalytic performance were discussed. Vulcan carbon powder was also used as a support to increase the catalysts’ electrical conductivity as well as dispersity. The component, microstructure and specific …

Vanadium Redox Flow Batteries: Design And Experimentation, Matthew George

Williams Honors College, Honors Research Projects

Vanadium flow batteries (VFB) are a type of battery that has potential as a grid-scale energy storage solution. An original design for a lab-scale VFB is presented herein, along with a procedure for electrolyte preparation from V₂O₅ using oxalic acid. The flow cell is constructed from Delrin, Teflon, Kynar, Santoprene, Nafion, graphite plate, and porous carbon. Two diaphragm pumps along with polyethylene, PVC, and Santoprene tubing are used. The active area is 58 cm². The battery was charged using a DC power supply at a constant current of 4 A with corresponding initial voltage of …

Corrosion Performance Of Zirconium-Based Passivations On Electroplated Zinc Nickel, Madison Morgan Reed

Masters Theses

“Performance requirements for Department of Defense (DoD) electrical components include corrosion and electrical contact resistance. Historically, electroplated cadmium with a chromate conversion coating (CrCC) has been used to meet corrosion and contact resistance standards. However, replacements are needed for these materials because they are toxic and carcinogenic. Electroplated γ-ZnNi has been identified as an acceptable alternative to Cd. This study evaluated commercially available Zr-based thin films and sealers as passivations for potential replacement of CrCCs. Ten different passivations were tested and compared with bare γ-ZnNi. X-Bond and Zircobond passivations were found to provide some improvement to the bare ZnNi corrosion …

Controlled Electrochemical Reduction Of Gold And Palladium Metal Precursors In Polyaniline, Nicole Goodwin

UNLV Theses, Dissertations, Professional Papers, and Capstones

Polyaniline (PANI) has been extensively studied due to its unique electrochemical properties. The conjugated polymer is conductive with high chemical stability below 100°C, mechanical strength, and large surface area. The applications of PANI have included chemical sensing, corrosion inhibition coatings, light emitting diode and as a substrate for metal composite catalysts. Both chemical and electrochemical methods have been developed and utilized in the synthesis of PANI/metal composites. The simultaneous reduction of aniline and metal precursor produces a composite of PANI encapsulated metal, reducing the active surface area available for catalysis. Alternatively, chemical reduction of the metal precursor into preformed PANI …

Graphite And Graphene-Oxide Based Pgm-Free Model Catalysts For The Oxygen Reduction Reaction, Joseph Henry Dumont

Nanoscience and Microsystems ETDs

The world currently relies heavily on fossil fuels such as coal, oil, and natural gas for its energy. Fossil fuels are non-renewable, that is, they draw on finite resources that will eventually dwindle, becoming too expensive or too environmentally damaging to retrieve. One alternative source of energy are fuel cells, electrochemical devices that convert chemical energy to cleanly and efficiently produce electricity. They can be used in a wide range of applications, including transportation, stationary, portable and emergency power sources. Their development has been slowed by the high cost of PGM electrocatalysts needed at both electrodes as well as sluggish …

Design, Material And Surgical Assembly Effects On Fretting Corrosion Behavior Of Modular Tapers In Orthopedic Implants, David Pierre

Dissertations - ALL

Mechanically assisted crevice corrosion (MACC) has become a significant problem in the orthopedic device industry, particularly in modular devices with metal-on-metal (MoM) tapered interfaces. Oxide film abrasion, leading to fretting corrosion in the presence of a crevice, accelerates the corrosion process and in some instances may lead to failure of the implant. Failure is defined as the need for revision surgery. The basic processes of oxide film abrasion and repassivation, and the associated effects (chemical, transport, mechanical and electrical) of these processes have been well described and studied over time.

Despite these advancements, there is much that is still not …

A Study Of Lignin And Lignin Models In Chemical And Electrochemical Systems, Luke Thomas Servedio

Doctoral Dissertations

The use of biomass as a viable, renewable feedstock for the production of energy and as a surrogate for the petrochemical industry has generated a tremendous amount of research over the last 40 years. With lignin comprising 25- 35% by weight of the dry mass of much of that material, much time and energy has been devoted to investigating a viable, scalable value-added proposition for the use of lignin and lignin pre-cursor materials. The bulk of lignin produced today comes as a by-product of the de-pulping process in the production of paper – most of which is used as a …

Processing-Property-Structure Relationships Of Carbonaceous Materials Derived From Renewable Lignin Products, Valerie García-Negrón

Masters Theses

Efforts to effectively use lignin, a by-product of paper and biofuels production, have been carried out for several decades. This renewable resource has potential for use as a carbonaceous material due to its aromatic structure and high carbon content, reminiscent of graphite. The search for new carbon-based materials is extremely active, because they are necessary components in many applications, such as energy storage, electronics, catalysis, and lubricants. Traditional carbon-based materials are derived or mined from petroleum or coal, thus, contributing to pollution, national security risks, and anthropogenic climate change. Lignin, a carbon-rich component found in the tissues of vascular plants, …

Biomimetic Devices To Drive A Thermodynamically Uphill Reaction Using Light And To Degrade Industrial Waste Stream Components, Madison Joanne Sloan

Theses and Dissertations--Chemistry

Given the amount of industrial waste produced each year, as well as the accruing amount of greenhouse gases in our atmosphere produced by the burning of fossil fuels, it is imperative that humanity develop environmentally-sustainable sources of energy and methods of remediation. Nature achieves both of these by use of enzymes as catalysts, inspiring interest in designing biomimetic systems capable of harnessing clean energy and remediating industrial waste. This study examined the ability of enzymes in electrochemical and convective flow systems to achieve these tasks. The first portion studied the incorporation of enzymes into an electrochemical system to drive the …

Corrosion Of Aluminum Current Collector In Cost Effective Rechargeable Lithium-Ion Batteries, Shengyi Li

Theses and Dissertations

Rechargeable lithium ion batteries (LIB) have been widely used as commercial energy storage systems for portable equipment, electronic devices and high power applications (e.g. electronic vehicles). One issue with the commercialized LIB is that expensive, highly toxic and flammable organic solvents are used in the electrolyte and the fabrication process of electrodes. The toxic organic based solvents increase the production cost and lead to significant safety concerns in the event of a battery overcharge or short circuit. The recent development of “green manufacturing” technology allows manufacturers to replace the organic solvents used in the cathode coating process by aqueous based …