Engineering Commons^™

Electrochemical Hydrogen Separation Via The Solid Acid Electrolyte Cesium Dihydrogen Phosphate, David Leon Wilson

Doctoral Dissertations

Abundant, inexpensive, high purity molecular hydrogen as a medium for energy distribution is potentially enabling for adoption of alternative electricity generation schemes. Steam reforming of natural gas remains the dominant method of producing large amounts of hydrogen. However, this process also creates by-products, most notably, carbon monoxide and carbon dioxide. Separation to ultra-high purity hydrogen from these syngas reformate streams by traditional methods, such as pressure swing absorption, has its disadvantages including long cycle times, contamination and a large equipment footprint. Alternative methods of hydrogen separation, such as electrochemical pumping, are a viable alternative to this separation dilemma due to …

An Exploration Of Basic Processes For Aqueous Electrochemical Production Of Hydrogen From Biomass Derived Molecules, Brian Fane

Doctoral Dissertations

Polymer electrolyte membrane fuel cells(PEMFCs) are energy conversion devices with significant potential. The factors preventing them from becoming widespread concern production and distribution of hydrogen. Developing an efficient hydrogen infrastructure with an approachable rollout plan is an essential step towards the future of fuel cells. Water electrolysis is limited by the thermodynamics of the process, which leads to high electrical consumption and significant materials challenges. Alternative methods for cleanly generating hydrogen while using a lower cell voltage are required. PEM based electrolyzers can operate with a "depolarized anode", whereby they become significantly less power hungry.

This thesis explores two techniques …

Multiscale Modeling Approach To Understand Active Sites In Non-Conventional Catalyst Layers For Fuel Cell Applications, Diana Constanza Orozco Gallo

Doctoral Dissertations

Fuel cells development required stable, active and more abundant catalytic materials. Oxygen reduction reaction (ORR) is the key process to enhance better activity and reduce the fabrication costs. Pt-based has proven to be the best catalyst for ORR and greater efforts has been made in terms of reducing the Pt content in the electrodes, reduce electrode thickness and enhance better catalytic activities. To overcome many of the challenges present, the catalyst layer studies are the great importance in the fuel cell community. Understanding catalyst layer with new catalytic materials, and configurations requires the development of methodological approach to relate structure, …

Transport Of Water And Ions Through Single-Walled Armchair Carbon Nanotubes: A Molecular Dynamics Study, Michelle Patricia Aranha

Doctoral Dissertations

The narrow hydrophobic interior of a carbon nanotube (CNT) poses a barrier to the transport of water and ions, and yet, unexpectedly, numerous experimental and simulation studies have confirmed fast water transport rates comparable to those seen in biological aquaporin channels. These outstanding features of high water permeability and high solute rejection of even dissolved ions that would typically require a lot of energy for separation in commercial processes makes carbon nanotubes an exciting candidate for desalination membranes. Extending ion exclusion beyond simple mechanical sieving by the inclusion of electrostatics via added functionality to the nanotube bears promise to not …

The Rheology And Roll-To-Roll Processing Of Shear-Thickening Particle Dispersions, Sunilkumar Khandavalli

Doctoral Dissertations

Particle dispersions are ubiquitous in our daily lives ranging from food and pharmaceutical products to inks. There has been great interest in the recent years in formulation of functional inks to fabricate myriad flexible electronic devices through high-throughput roll-to-roll technologies. The formulations often contain several functional additives or rheological modifiers that can affect the microstructure, rheology and processing. Understanding the rheology of formulations is important for tuning the formulation for optimal processing. This thesis presents investigations on the rheology of particle dispersions and their impact on roll-to-roll technologies. Shear-thickening behavior is common in particle dispersions, particularly, concentrated particulate inks. We …

The Role Of Chain Configuration In Governing The Rational Design Of Polymers For Adhesion, Onyenkachi Wamuo

Doctoral Dissertations

ABSTRACT THE ROLE OF CHAIN CONFIGURATION IN GOVERNING THE RATIONAL DESIGN OF POLYMERS FOR ADHESION SEPTEMBER 2017 ONYENKACHI C. WAMUO, B.Eng., FEDERAL UNIVERSITY OF TECHNOLOGY, OWERRI (FUTO), NIGERIA M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Shaw Ling Hsu The chain configurational control of polymers used in adhesion can be utilized as a means of tuning the cohesive properties of hot melt adhesives (HMAs). The cohesive properties control the solidification, strength, setting speed. Propylene-Ethylene copolymers (PP-co-PE) and thermoplastic polyurethanes (TPUs) were studied. In the first project, the effects of sequence distribution of the two types …

Computational Studies Of Structure–Function Relationships Of Supported And Unsupported Metal Nanoclusters, Hongbo Shi

Doctoral Dissertations

Fuel cells have been demonstrated to be promising power generation devices to address the current global energy and environmental challenges. One of the many barriers to commercialization is the cost of precious catalysts needed to achieve sufficient power output. Platinum-based materials play an important role as electrocatalysts in energy conversion technologies. In order to improve catalytic efficiency and facilitate rational design and development of new catalysts, structure–function relationships that underpin catalytic activity must be understood at a fundamental level. First, we present a systematic analysis of CO adsorption on Pt nanoclusters in the 0.2-1.5 nm size range with the aim …

Analyses Of Densely Crosslinked Phenolic Systems Using Low Field Nmr, Jigneshkumar Patel

Doctoral Dissertations

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multi-components, especially for the crosslinking of rigid high-performance materials. In these reactions, miscibility is crucial for curing efficiency. This miscibility is typically enhanced by adding a third component, a plasticizer. For the reaction of the highly crystalline crosslinking agent hexamethylenetetramine (HMTA) with a strongly hydrogen-bonded phenol formaldehyde resin, furfural has been traditionally used as the plasticizer. However, the reason for its effectiveness is not clear. In this doctoral thesis work, miscibility and crosslinking efficiency of plasticizers in phenolic curing reactions are studied by thermal analysis and spectroscopic …

Nanocomposite Polymer Networks For Reconfigurable Materials, Adam W. Hauser

Doctoral Dissertations

This thesis broadly aims to design reconfigurable materials through complementary combinations of nanoparticles and polymers. Understanding nanoparticle dispersion pathways and mechanisms is a critical first step in any polymer nanocomposite work as it continues to be a non-trivial subject. To this end, Chapter 2 describes a simple method to control nanoparticle dispersion within polymer melts by photografting random copolymers to selectively reactive nanoparticle ligands. The chapters following focus on harnessing the functionality of well dispersed nanocomposite networks to elicit macro-scale responses. Chapter 3 exploits the unique optical properties of gold nanoparticles in combination with thermally responsive hydrogels and liquid crystalline …

Modeling Of Nanoscale Transport In Mesoporous Membranes, Ashutosh Rathi

Doctoral Dissertations

Mesoporous membranes with pore sizes in the range 2-50 nm provide an energy efficient alternative for separation of mixtures such as CO₂ from stack effluents and volatile organic compounds (VOC) from air. Transport mechanisms such as capillary condensation, Knudsen diffusion and surface adsorption help in enrichment of a more condensable component based on the bulk mixture thermodynamics, surface chemistry and geometry of the mesopores. Despite the progress in synthesis techniques, design of better mesoporous materials for targeted separations is still a challenge due to the absence of clear design rules. Modeling techniques can be used to quantify the relevant …

Metabolic Modeling And Engineering Of Gas Fermentation In Bubble Column Reactors, Jin Chen

Doctoral Dissertations

Gas fermentation is an attractive route to produce alternative fuels and chemicals from non-food feedstocks, such as waste gas streams from steel mills and synthesis gas (mainly CO and H₂) produced from municipal solid waste through gasification. While commercial development of gas fermentation technology is underway, many research problems must be addressed to further advance the technology towards economic competitiveness. A particularly important challenge is to develop integrated metabolic and transport models that describe gas fermentation in industrially relevant bubble column reactors. I have developed and evaluated a spatiotemporal metabolic model for bubble column reactors with the syngas …

Interactions At The Aqueous Interface Of Large-Area Graphene: Colloidal-Scale And Protein Adsorption, Aaron Chen

Doctoral Dissertations

This thesis addresses the interactive interfacial character of large-area supported graphene in an aqueous environment near neutral pH. Studies of molecular bio-interactions with proteins and colloidal interactions with microparticles probe the role of hydrophobicity, van der Waals, and electrostatic contributions with varied ionic strength. The respective roles of the silica support and the graphene itself are identified. Results are benchmarked against other systems directly in experiments, and against published behavior with other materials, especially self-assembled monolayers. The adhesive and adsorption behavior of supported graphene is also put into context by calculations of surface and interaction potentials. Interest in graphene is …

Correlating Long-Term Lithium Ion Battery Performance With Solid Electrolyte Interphase (Sei) Layer Properties, Seong Jin An

Doctoral Dissertations

This study was conducted to understand effects of some of key factors (i.e., anode surface properties, formation cycling conditions, and electrolyte conditions) on solid electrolyte interphase (SEI) formation in lithium ion batteries (LIBs) and the battery cycle life. The SEI layer passivates electrode surfaces and prevents electron transfer and electrolyte diffusion through it while allowing lithium ion diffusion, which is essential for stable reversible capacities. It also influences initial capacity loss, self-discharge, cycle life, rate capability and safety. Thus, SEI layer formation and electrochemical stability are primary topics in LIB development. This research involves experiments and discussions on key factors …

Nanoporous Solid Acid Materials For Biomass Conversion Into Value-Added Chemicals: Synthesis, Catalysis, And Chemistry, Hong Je Cho

Doctoral Dissertations

Growing environmental concerns associated with diminishing reserves of fossil fuels has led to accelerated research efforts towards the discovery of new catalytic processes for converting renewable lignocellulosic biomass into value-added chemicals. For this conversion, nanoporous solid acid materials have been widely used because of their excellent hydrothermal stability and molecular sieving capability. In the thesis, hierarchical Lewis acid zeolites with ordered mesoporosity and MFI topology (three dimensionally ordered mesoporous imprinted (3DOm-i) Sn-MFI) were successfully synthesized within the confined space of three dimensionally ordered mesoporous (3DOm) carbon by a seeded growth method. The obtained 3DOm-i Sn-MFI showed at least 3 times …

Vitreous Gel Physics, Svetlana Morozova

Doctoral Dissertations

The transparent vitreous, which fills the posterior cavity of the eye, is incredibly engineered. The charged polyelectrolyte hyaluronic acid (HA) network swells to maintain the pressure in the eye, while stiff collagen type II bundles help absorb any external mechanical shock. Our investigations have contributed to a few key developments related to the physical properties of the vitreous: (1) The stiff collagen network that supports the soft gel network is self-assembled from single triple-helix collagen proteins. Electrostatic interactions drive this assembly, such that the size and concentration are optimized at physiological salt concentrations. The width of the assemblies remarkably changes …

Electrochemical Behavior Of Dense Electrodes For Impedancemetric Nox Sensors, Nabamita Pal

Doctoral Dissertations

NOx (NO and NO2) exhaust gas sensors for diesel powered vehicles have traditionally consisted of porous platinum (Pt) electrodes along with a dense ZrO2 based electrolyte. Advancement in diesel engine technology results in lower NOx emissions. Although Pt is chemically and mechanically tolerant to the extreme exhaust gas environment, it is also a strong catalyst for oxygen reduction, which can interfere with the detection of NOx at concentrations below 100 ppm. Countering this behavior can add to the complexity and cost of the conventional NO x sensor design. Recent studies have shown that dense electrodes are less prone to heterogeneous …

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 …

Morphological And Photoelectrochemical Characterization Of Membrane Reconstituted Photosystem I (Psi), Seyedeh Hanieh Niroomand

Doctoral Dissertations

The robust structural and photoactive electrochemical properties of Photosystem I (PSI), a transmembrane photosynthetic protein complex, make it an ideal candidate for incorporation into solid state bioelectronic or hybrid photovoltaic devices. However, the first step towards the successful fabrication of such devices requires systematic assembly of oriented and functional PSI onto desired bio-abio interfaces via suitable protein scaffoldings. Hence, this dissertation focuses on utilizing the cyanobacterial PSI for integration into organic/inorganic interfaces that mediate photo-electrochemical energy conversions for electricity and/or solar fuel production. To this end, in this study the effect of systematic incorporation of PSI complexes into synthetic membrane-bound …

Catalytic Hydrodeoxygenation And Dehydration Of Bioderived Oxygenates To Renewable Hydrocarbon Building Block Molecules: Enabling Renewable Carbon Fiber, Andrew Walter Lepore

Doctoral Dissertations

It is our goal to develop inexpensive catalytic pathways that can effectively remove oxygen from bio-derived carboxylic acids and alcohols under mild reaction conditions to produce propene which can be converted to renewable carbon fibers. Carboxylic acid hydrodeoxygenation and alcohol dehydration are necessary for successfully producing propene from bio-mass derived precursors and are also broadly relevant to bio-oil upgrading. This body of research adds to the understanding of both known and novel catalyst materials and develops and optimizes pathways for valorizing oxygenates. Dehydration and hydrodeoxygenation catalysts were examined under both batch and continuous flow operation. Product selectivity and reactant conversion …

Improving Predictive Capabilities Of Classical Cascade Theory For Nonproliferation Analysis, David Allen Vermillion

Doctoral Dissertations

Uranium enrichment finds a direct and indispensable function in both peaceful and nonpeaceful nuclear applications. Today, over 99% of enriched uranium is produced by gas centrifuge technology. With the international dissemination of the Zippe archetypal design in 1960 followed by the widespread illicit centrifuge trafficking efforts of the A.Q. Khan network, traditional barriers to enrichment technologies are no longer as effective as they once were. Consequently, gas centrifuge technology is now regarded as a high-priority nuclear proliferation threat, and the international nonproliferation community seeks new avenues to effectively and efficiently respond to this emergent threat.

Effective response first requires an …

All Acrylic Based Thermoplastic Elastomers: Design And Synthesis For Improved Mechanical Performance, Wei Lu

Doctoral Dissertations

Thermoplastic elastomers (TPEs) have been widely studied because of their recyclability, good processability, low production cost and distinct performance. Compared to the widely-used styrenic TPEs, acrylate based TPEs have potential advantages including exceptional chemical, heat, oxygen and UV resistance, optical transparence, and oil resistance. However, their high entanglement molecular weight lead to “disappointing” mechanical performance as compared to styrenic TPEs. The work described in this dissertation is aimed at employing various approaches to develop the all acrylic based thermoplastic elastomers with improved mechanical performance.

The first part of this work focuses on the introduction of acrylic polymers with high glass …

The Self-Assembly Of Lamellae-Forming Block Copolymer For High Resolution Nanolithography, Zhiwei Sun

Doctoral Dissertations

This thesis will be focused on the thin film self-assembly and high resolution nanolithography of lamellae-forming PS-b-P2VP block copolymer. Some of the scientific and engineering problems of block copolymer self-assembly will be studied using the state-of-the-art characterization facilities including AFM, SEM and synchrotron radiation X-ray scattering, pushing forward the application of block copolymer in high resolution nanolithography, storage media, and separation membranes, etc. The first challenge is the design of BCP with small domain spacing, which defines the resolution of BCP nanolithography. Small domain spacing can be achieved by reducing the degree of polymerization, but order-to-disorder transition happens …

Deformation And Adhesion Of Soft Composite Systems For Bio-Inspired Adhesives And Wrinkled Surface Fabrication, Michael Imburgia

Doctoral Dissertations

The study of soft material deformation and adhesion has broad applicability to industries ranging from automobile tires to medical prosthetics and implants. When a mechanical load is imposed on a soft material system, a variety of issues can arise, including non-linear deformations at interfaces between soft and rigid components. The work presented in this dissertation embraces the occurrence of these non-linear deformations, leading to the design of functional systems that incorporate a soft elastomer layer with application to bio-inspired adhesives and wrinkled surface fabrication. Understanding the deformation of a soft elastomer layer and how the system loading and geometry influence …

Synthesis Of Biopolymer Materials Tailored For Biological Applications, Nathan P. Birch

Doctoral Dissertations

Biopolymers are able to address a wide variety of medical concerns from chronic wounds to stem cell cultivation to antibacterial and antifouling applications. They are non-toxic, biodegradable, and biocompatible, making them ideal candidates for creating green materials for biological applications. In this thesis, we cover the synthesis of two novel materials from the biopolymers, chitosan and pectin. Chitosan is a biocompatible antibacterial polycation and pectin is an anti-inflammatory polyanion with a strong propensity for hydrogen-bonding. The two chitosan:pectin materials, particles and hydrogels, explore some of the structures that can be created by tuning the electrostatic interactions between chitosan and pectin. …

Investigation Of Hydraulic Fracture Complexity And The Benefits Of Maximizing Or Minimizing Complexity In Unconventional Resources, Rashid Sheikh Kassim

Doctoral Dissertations

"This dissertation discusses two separate, yet inter-related studies. The first study was an extension of historical work comparing transversely fractured versus longitudinally fractured horizontal wells in multiphase flow environment. The second study investigated hydraulic fracture complexities and the benefits of maximizing or minimizing complexities in unconventional resources and tight reservoirs.

The main objective of this research was to investigate fracture complexity and its impact on well performance and economics. To achieve that objective, three different integrated completions and reservoir models were built. Two of the three models, a hybrid reservoir model and micro-seismic based SRV (stimulated reservoir volume) model, were …

Investigation Of Local Velocities And Phase Holdups, And Flow Regimes And Maldistribution Identification In A Trickle Bed Reactor, Mohd Fitri Bin Abdul Rahman

Doctoral Dissertations

"Trickle bed reactors are packed beds of catalyst on which gas and liquid reactants flow concurrently downward. In this work, the experimental work was carried out in 0.14 m diameter Plexiglas column using air-water system flowing over a packed bed of 3 mm glass bead particles. The local liquid and gas velocities, phase saturation and their time series have been investigated for the first time by developing, validating, and implementing a new two-tip optical fiber probe technique. It was found the radially and axially the liquid and gas velocities and their saturation vary and they also vary with times. In …

Screening Guidelines And Data Analysis For The Application Of In-Situ Polymer Gels For Injection Well Conformance Improvement, Munqith Naeem Rashak Aldhaheri

Doctoral Dissertations

"Excessive water production represents a major industry challenge because of its serious economic and environmental impacts. Polymer gels have been effectively applied to mitigate water production and extend the productive lives of mature oilfields. However, selecting a proper gel technology for a given reservoir is a challenging task for reservoir engineers because of the associated geological and technical complexities and the absence of efficient screening tools.

A comprehensive review for the worldwide gel field projects was conducted to develop an integrated systematic methodology that determines the applicability of three injection well gel technologies including bulk gels, colloidal dispersion gels, and …

The Effect Of Testing Conditions On Lost Circulation Materials' Performance In Simulated Fractures, Montri Jeennakorn

Doctoral Dissertations

"Lost circulation (LOC) problems increase costs of drilling significantly. It is not only the cost of the drilling fluid that is lost into the formation but also the costs of subsequent problems that can be higher than the cost of the drilling fluids. LOC also possibly leads to a serious risk of blowout incident.

Lost circulation materials (LCM) are regularly added to the drilling fluids with an expectation of plugging the flow path. Due to the difficulties of testing and monitoring LCM sealing processes in the field, LCM evaluation in the laboratory is often used to prove and assure successful …

Synthesis, Characterization, And Activity Of Co/Fe Alumina/Silica Supported Ft Catalysts And The Study Of Promoter Effect Of Ruthenium, Sunday Azubike Esumike

Doctoral Dissertations

The alumina and hybrid alumina-silica FT catalyst were prepared by one-step solgel/oil-drop methods using metal-nitrate-solutions (method-I), and nanoparticle-metaloxides (method-2). The nanoparticle-metal-oxides did not participate in solubility equilibria in contrast to metal nitrate in method-1 causing no metal ion seepage; therefore, method-2 yields higher XRF metal loading efficiency than method-1. The thermal analysis confirmed that the metal loading by method-1 and method-2 involved two different pathways. Method-1 involves solubility equilibria in the conversion of metal-nitrate to metal- hydroxide and finally to metal-oxide, while in method-2 nanoparticle-metal-oxide remained intact during sol-gel-oil-drop and calcination steps.

The alumina supported catalysts were dominated by γ-alumina …

Impact Of Vertical Internals On The Hydrodynamics And Heat Transfer Coefficient In A Gas-Solid Fluidized Bed, Haidar Moafaq Taofeeq

Doctoral Dissertations

"This research studied the impact of the dense vertical immersed heat exchanging tubes on the gas and solids hydrodynamic characteristics, flow regime, pressure drop, and heat transfer in a 0.14 m inside diameter gas-solid fluidized bed column of. Two sizes of vertical internal tube bundles (0.0127 and 0.0254 m) of circular arrangement have been implemented to represent the heat exchange tubes covering 25% of the column cross-sectional area. The experimental work was achieved at different operating conditions and various solids particle types that differ in average particle size, solids density, particles shape, and particles sphericity. The experimental measurements were performed …