Chemical Engineering Commons^™

Hybrid Monomers & Resins For High-Performance Thermosetting Polymers, Thermoplastics, & Additive Manufacturing, Alexander William Bassett

Theses and Dissertations

Vinyl ester and epoxy resins are used to produce thermosetting polymeric materials for a variety of commercial and military applications due to their relatively high moduli (2-3 GPa at 25 deg C), glass transition temperatures (Tgs) (greater than or equal to 120 deg C), and adequate fracture toughness (G1C approx. 200-250 J m-2). Most commercially available vinyl ester and epoxy resins are typically cured via traditional manufacturing techniques such as resin transfer molding and thermal curing. However, additive manufacturing (AM) has gained significant traction as a favorable manufacturing technique over traditional methods due to the ability to create customizable parts …

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 …

Formulation And Validation Of Nanoparticle Controlled Delivery For Chemotherapeutic Drug Products, Shani L. Levit

Theses and Dissertations

Taxol, a formulation of paclitaxel (PTX), is one of the most widely used anticancer drugs, particularly for treating recurring ovarian carcinomas following surgery. Clinically, PTX is used in combination with other drugs such as lapatinib (LAP) to increase treatment efficacy. Delivering drug combinations with nanoparticles has the potential to improve chemotherapy outcomes. In this study, we use Flash NanoPrecipitation, a rapid, scalable process to encapsulate weakly hydrophobic drugs (logP in vitro. Encapsulating either PTX or LAP into nanoparticles increases drug potency. When PTX and LAP are co-loaded in the same nanoparticle, they have a synergistic effect that is greater than …

Dendrimer-Based Therapeutic Delivery Vehicle For The Treatment Of Ocular Diseases, Remy C. Cooper

Theses and Dissertations

The treatment of ocular diseases poses a significant challenge to drug delivery design, due to the eye’s complex anatomy, with a semi-permeable blood-ocular barrier and associated immune privilege. To address some of the delivery challenges, polycationic dendrimers are explored as vehicle for the treatment of posterior chamber disease. Dendrimers are a class of polymeric nanoparticles that are highly branched, multivalent and monodisperse, whose three-dimensional globular architecture has given them the nickname of “synthetic proteins”. Dendrimers are synthesized by reacting monomers in a step-wise fashion to produce generationally and radially increasing structures, with core, interior and surface chains that are highly …

Reaction Profiling Of Extracellular Protein Phosphorylation Through A Microfluidic Reactor Coupled With Raman Spectroscopy, Abigail Casey

Theses and Dissertations

Diseases and disorders in the human body are considered abnormalities of proper cellular function. Understanding the signal transduction mechanisms that cause these abnormalities is crucial to developing earlier detection methods, better treatment options and effective cures. While current diagnostic procedures are powerful tools in diagnosing diseases, they are ineffective in informing physicians on the real-time behavior of the signal transduction mechanisms associated with diseases and disorders. Currently, disease progression is monitored over time through routine patient visits and testing by one or more of the above techniques. By developing an approach that can monitor structural and conformational changes of proteins …

Structure, Morphology And Composition-Property Elucidation Of Ni–Mo And Ni−Mo−P Nanocrystals For Water Splitting Reactions And Group Iv Alloy And Silicate Nanocrystals For Visible To Near Ir Optoelectronics, Ebtesam Hassan Abuelenein Eladgham

Theses and Dissertations

Abstract

Structure, Morphology and Composition-Property Elucidation of Ni–Mo and Ni−Mo−P Nanocrystals for Water Splitting Reactions and Group IV Alloy and Silicate Nanocrystals for Visible to Near IR Optoelectronics

by

Ebtesam Hassan Abuelenein Eladgham

A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University.

Advisor: Indika U Arachchige

Associate Professor, Department of Chemistry

Nanomaterials have gained a great attention because of their unique physical properties with size intermediate between molecular materials and extended solids. They have a large surface to volume ratio and display size tunable physical properties that was not …

Higher Tensile Forces Across Cellular Junctions And An Intact Nuclear Linc Complex Is Required For Epithelial Function And Stability, Fnu Vani Narayanan

Theses and Dissertations

Recent advances in three-dimensional (3D) cell culture systems have provided key insights into the understanding of biochemical and physiological states of native tissue. A significant progress in the field of mechanobiology involves measuring cellular traction forces in a more native 3D environment. However, the effects of mechanical forces exerted across cellular junctions and the nuclear LINC complex, in an organized 3D system has not been investigated thus far. Epithelial cells spontaneously form acini (also known as cysts or spheroids) with a single, fluid-filled central lumen, when grown in 3D matrices. The size of the lumen is dependent on apical secretion …

Beneficiation Of Coal Using Supercritical Water And Carbon Dioxide Extraction, Matthew Decuir Virginia Commonwealth University Cl

Theses and Dissertations

This work explores the use of carbon dioxide, water, and their mixtures as solvent for the pre-combustion beneficiation of raw coal without using any toxic mineral acids in the temperature range of 200-400℃. The fluid polarity, ionic constant, and supercritical point can be adjusted by H₂O/CO₂ ratio and temperature. Adding carbon dioxide to hydrothermal fluid also increases the ionization by forming carbonic acid. Extractions with supercritical fluids have several benefits including enhanced mass transport, ease of separation and recycle, wide range of extractive capability and tunability, better inherent safety, and in the case of carbon dioxide and …

Self-Assembled Metal Nanoparticle/Polymer Nanocomposites As Nanoreactors For One-Pot Reactions, Andrew Harrison

Theses and Dissertations

Polymer nanoreactors incorporating gold nanoparticle catalysts were self-assembled via Flash Nanoprecipitation. The incorporated gold nanoparticles maintained catalytic activity, which was evaluated using reduction of 4-nitrophenol with sodium borohydride as a model reaction. The diffusion coefficient for 4-nitrophenol was determined by NMR and used to calculate the second Damköhler number, which indicated that the systems were not diffusion limited. Despite similar diffusion coefficients, catalytic performance was strongly affected by the co-precipitant. For example, the apparent reaction rate per surface area using castor oil was over 8-fold greater than polystyrene. Thus, we measured the partition coefficient of 4-nitrophenol between water and castor …

Design Of A System For Inexpensive Underwater Fiber Optic In Vivo Imaging And Mass Balance Accounting Of Tissue Engineering Candidates, Nicole Melissa Bueno Guerrero

Theses and Dissertations

The goal of this project is to create a prototype bioreactor that mimics a cell’s microenvironment. The ultimate goal is to set up an array of 36 bioreactors in parallel and monitor them with an array of sensors that will enable full mass and energy balance accounting and in vivo imaging. This thesis will analyze the various options available for cell imaging, as well as describe the construction of a bioreactor design in which cell images can be obtained without removing the cells from the bioreactor. The hypothesis for this project is that imaging of unstained cells in an aquarium …

Quantifying And Elucidating The Effect Of Co2 On The Thermodynamics, Kinetics And Charge Transport Of Aemfcs, Yiwei Zheng

Theses and Dissertations

Anion exchange membrane fuel cells (AEMFCs) have shown significant promise to provide clean, sustainable energy for grid and transportation applications – and at a lower theoretical cost than more established proton exchange membrane fuel cells (PEMFCs). Adding to the excitement around AEMFCs is the extremely high peak power that can now be obtained (> 3 W cm-2) and continuously improving durability (1000+ h), which has made the future deployment of AEMFCs in real-world applications a serious consideration. For some applications (e.g. automotive), the most critical remaining practical issue with AEMFCs is understanding and mitigating the effects of atmospheric CO2 (in …

Discovery Of Materials Through Applied Machine Learning, Travis Williams

Theses and Dissertations

Advances in artificial intelligence technology, specifically machine learning, have cre- ated opportunities in the material sciences to accelerate material discovery and gain fundamental understanding of the interaction between certain the constituent ele- ments of a material and the properties expressed by that material. Application of machine learning to experimental materials discovery is slow due to the monetary and temporal cost of experimental data, but parallel techniques such as continuous com- positional gradients or high-throughput characterization setups are capable of gener- ating larger amounts of data than the typical experimental process, and therefore are suitable for combination with machine learning. A …

Molecular Modeling Of Tethered Polyelectrolytes For Novel Biomedical Applications, Merina Jahan

Theses and Dissertations

Current research trends throughout the world focus on designing intelligent materi- als and systems for diverse applications in all courses of life. Biomaterials research encompasses a major part in this revolution due to the increased effort in fulfilling unmet medical needs to treat complex physiological and neurodegenerative disorders. Polymers play inevitable roles in these research endeavors for their ubiquitous pres- ence in biological systems. Therefore, it is crucial to understand how the polymeric molecules interact within diverse biological environments, to efficiently engineer them for various drug delivery and biosensing systems. The use of experimental design and selection of different polymers …

Improving And Modeling Bacteria Recovery In Hollow Disk System, Clifton Anderson

Theses and Dissertations

Identifying antibiotic resistance in blood infections requires separating bacteria from whole blood. A hollow spinning disk rapidly removes suspended red blood cells by leveraging hydrodynamic differences between bacteria and whole blood components in a centrifugal field. Once the red cells are removed, the supernatant plasma which contains bacteria is collected for downstream antibiotic testing. This work improves upon previous work by modifying the disk design to maximize fractional plasma recovery and minimize fractional red cell recovery. V-shaped channels induce plasma flow and increase fractional plasma recovery. Additionally, diluting a blood sample spiked with bacteria prior to spinning it increased the …

Correlating Pressure, Fluidization Gas Velocities, Andsolids Mass Flowrates In A High-Pressurefluidized Bed Coal Feed System, Jacob Talailetalalelei Tuia

Theses and Dissertations

The goal of this thesis was to understand what parameters would be most impactful when delivering dry, pulverized coal in a dilute-phase, with a high-pressure feed-system to a pressurized oxy-combustion (POC) reactor. Many studies have conveyed materials in dense-phase plugs at high-pressure or in dilute-phase flows at atmospheric pressure. Very few studies have fluidized and conveyed materials in dilute-phase flows at high pressure, as we needed to. Additionally, studies which might have been applicable based upon system -pressure and -phase delivered findings that were empirically based and therefore not specifically applicable to non-similar systems. 220 different tests were ran using …

Enabling High Energy Density Aluminum Anodes For Alkaline Batteries, Xinyi Zhao

Theses and Dissertations

Zn-MnO₂ primary alkaline batteries stood out immediately among all batteries after it was introduced in the late 1980s and has attracted world-wide attention. These batteries have dominated the portable power market for decades as a highly effective energy storage system with high energy density, long life and low self-discharge, dependable safety and other superiorities.

In order to achieve higher cell-level energy density, Aluminum has long been considered a very attractive anode material for alkaline batteries because of its high theoretical capacity (2980 mAh/g; 2.60 Ah/cm³) and low price. However, some early efforts to utilize aluminum anodes did …

Liquid Phase Modeling In Heterogeneous Catalysis, Mohammad Shamsus Saleheen

Theses and Dissertations

Conversion of lignocellulosic biomass into transportation fuels or commodity and specialty chemicals will be an important and fast-growing industry within the United States over the coming decades. Its growth will be driven by a variety of factors, including increased energy demands, environmental considerations, national security, and government mandates. To achieve the desired energy efficiency and economic impact, the emerging biorefining industries need novel heterogeneous catalysts with exceptional activity, selectivity, and stability. Catalytic materials developed in the petrochemical industries are generally not suitable for processing highly functionalized feedstocks typical of the biorefinery landscape. Due to the characteristics of this biomass feedstock …

Flame Spray Pyrolysis Of Ce-Mn Solid Solutions For Catalytic Applications, Nicole Cordonnier

Theses and Dissertations

Flame spray pyrolysis (FSP) is a method of quickly synthesizing active particles in a flame. Precursors are dissolved in a flammable organic solvent before being sprayed into the flame environment where they rapidly burn. Particle formation occurs on the order of 10 milliseconds. FSP has been shown to be a viable method of producing materials on an industrial scale, capable of producing grams of particles per minute. Metastable structures which exist in the liquid phase, but are difficult to synthesize using traditional impregnation methods can be formed with FSP due to fast quenching times. For example, solid solutions of Ce-Zr …

The Development Of A Multi-Objective Optimization And Preference Tool To Improve The Design Process Of Nuclear Power Plant Systems, Paul Richard Wilding

Theses and Dissertations

The complete design process for a new nuclear power plant concept is costly, long, complicated, and the work is generally split between several specialized groups. These design groups separately do their best to design the portion of the reactor that falls in their expertise according to the design criteria before passing the design to the subsequent design group. Ultimately, the work of each design group is combined, with significant iteration between groups striving to facilitate the integration of each of the heavily interdependent systems. Such complex interaction between experts leads to three significant problems: (1) the issues associated with knowledge …

Replacement Rates Of Initially Hydrocarbon-Filled Microscopic Cavities With Water, Hans Christian Larson

Theses and Dissertations

Wetting behaviors influence many aspects of life and industry from consumer product goods to oil recovery to cosmetics. While the traditional solid-liquid-vapor (SLV) system has been studied for many years now, wetting transitions in the solid-liquid-liquid (SLL) system has remained relatively unexplored. The purpose of this work is to bring light to the wetting transition of the solid-liquid-liquid system and to understand the replacement rates of initially hydrocarbon-filled microscopic cavities with water and the factors affecting these rates. Factors studied were viscosity, density, diffusion related properties, and surface related properties in both hydrocarbon-saturated and hydrocarbon-non-saturated conditions. Cylindrical microscopic cavities were …

Electrochemical Fabrication Of Elastin-Containing Bi-Layered Scaffold For Vascular Tissue Engineering Applications, Thuy-Uyen Ky Nguyen

Theses and Dissertations

Lack of a viable vascular graft for the replacement of diseased small diameter blood vessels (< 4 mm) has encouraged the development of a self-repairing tissue engineered vascular graft (TEVG) as a promising alternative source. Although many different fabrication approaches have been devised to generate TEVGs using both natural and synthetic biomaterials, a functional TEVG that can serve as an effective replacement of diseased small-diameter blood vessels (< 4 mm) is still elusive mainly due to concerns associated with thrombosis and intimal hyperplasia. One approach to improve the clinical outcome of vascular grafts is to develop a 3D biomimetic scaffold that provides the essential physicochemical cues (i.e., compositional, topographical) to modulate cellular response (i.e., cell phenotype, endothelialization, de novo elastic matrix production) and thereby aid in tissue repair and remodeling. This approach entails the development of a novel 3D scaffold that provides an aligned collagen platform to guide smooth muscle cell (SMC) orientation

and insoluble elastic matrix (i.e., native form of elastin) to promote SMC contractility and thereby prevent overproliferation and hence alleviate concerns with intimal hyperplasia. In addition, the scaffold must comprise of a smooth luminal side to support the formation of a continuous endothelium that is essential to prevent thrombosis. Most existing biofabrication methodologies to generate vascular scaffolds (e.g., extrusion, electrospinning) have limited scope because of the inability to incorporate insoluble elastic matrix within the aligned collagen framework due to the disparity in the size …

Fabrication Of Enhanced Carbon Based Biocompatible And Biodegradable Microelectronic Materials Derived From Lignocellulosic Biomass, Harrison Thomas Hawkins

Theses and Dissertations

The development of materials capable of harmlessly being broken down and removed from the body is a crucial step towards the development of short-term application electronic biomedical implants. Once developed, these implants, known as bioresorbable electronics, will open a wide array of temporary applications in the field of biomedical implantable devices. Necessary to the operation of bioresorbable electronics within the body is a power source that is similarly biocompatible and biodegradable. To this end, enhanced carbon-based materials and a bio-ionic liquid were developed for the fabrication of a preliminary implantable and bioresorbable battery and tested for functional properties. Electrodes were …

Residence Time Distribution (Rtd) Analysis Of A Bioreactor's External Recirculation Loop For A Tissue Engineering Test Bed, Adrien Hosking

Theses and Dissertations

Currently, in tissue engineering, the focus is on morphing cells into a particular type of tissue by hand, rather than automating the process. Automating cell feeding and waste removal, alone, still requires the removal of cells from their culture to perform imaging and analysis. Without the ability to automate the imaging in a way that does not risk cell death, the advantages of automating the feeding and waste removal are largely lost. By building a fully automated tissue engineering test bed, the capacity for cell reproducibility and cell yield increases significantly. This thesis outlines the design, some initial testing, and …

Validation Of An External Bioreactor Filtration Loop Prototype For A Tissue Engineering Test Bed, Jonah Martin Melegrito

Theses and Dissertations

As a cell line thrives within a culture, some of the cells undergo the natural process of death. Whether it is due to apoptotic or necrotic causes, cell death is a significant hurdle for tissue engineering and cell cultivation. When cells attached to a scaffold die, they slough off from the scaffold into the bloodstream. If left unchecked, these dead cells and any cellular waste products accumulate and could affect the living cells’ ability to survive. The objective of this thesis was to construct a separation system that can filter away any unwanted suspended solids while allowing nutrients to recycle …

Heterogeneous Catalysis For The Upgrading Of Biomass Derived Chemicals Via Hydrodeoxygenation, Elizabeth Barrow

Theses and Dissertations

An important step in the upgrading of biomass derived chemicals is the removal of excess oxygen. The works reported here are focused on studying the heterogeneous catalysts that can be utilized for that upgrading through hydrodeoxygenation. This work begins with a discussion of the alkylation of short chain platform chemicals for chain growth and also demonstrates the proof of concept of combining alkylation and hydrodeoxygenation in a single step. Then, because of the promising nature of ReOx- Pd/CeO2 for selective hydrodeoxygenation, a detailed study of ReOx/CeO2 is presented. Finally, a new surface structure interpretation is presented for P/Ni(111) which could …

The Use Of Multi-Targeting Natural Products For The Treatment Of Cancer, Wesley Taylor

Theses and Dissertations

The paradigm shift in cancer treatments from traditional chemotherapeutics to targeted therapies has rapidly improved prognoses for patients for whom cancer was once a death sentence. This is especially true in the case of targeted immune therapies which activate the body’s own natural defense system to fight cancer. Despite these advances, however, cancer remains the second leading cause of death in the United States. The promise of targeted therapeutics has faced significant hurdles in providing effective cancer treatments, namely the limited percentage of susceptible cancers for each treatment, high cost burden, high toxicities, and significant risk of treatment induced resistance. …

Electrode Development And Electrocatalysts Design For Polymer Electrolyte Membrane Fuel Cells, Xiong Peng

Theses and Dissertations

Because of environmental issues and national conflicts caused by overuse of fossil fuels, there is a need to seek renewable ways to utilize energy. In the transportation sector, hydrogen-based polymer electrolyte membrane fuel cells, including proton exchange membrane fuel cells (PEMFCs) and anion exchange membrane fuel cells (AEMFCs), have been considered as a promising alternative to conventional combustion engines. However, the widespread commercialization of both PEMFCs and AEMFCs has been hindered by several factors, including cost and performance. In this thesis, a series of topics including electrode fabrication, electrocatalyst development for both PEMFCs and AEMFCs, as well as the water …

Bio-Based Thiol-Ene Polymer Electrolytes, Elyse Antonia Baroncini

Theses and Dissertations

Industrial and consumer demand for smaller and safer technologies motivates a global research effort to improve electrolytic polymer separators in lithium-ion batteries (LIBs). To incorporate the aromatic structural advantages of lignin, an abundant and renewable resource, into polymer electrolytes, molecules that can be derived from lignin are functionalized and UV-polymerized with multifunctional thiol monomers. Monomer aromaticity, thiol molecular weight, and total functionality are varied, allowing for analysis of the relationships between polymer structure and electrochemical properties.

The synthesized polymers display conductivities on the order of 10^-5 S/cm for gel polymer electrolytes and 10^-4 S/cm for solid polymer electrolytes, comparable to …

Examination Of Flow Dynamics And Passive Cooling In An Ultra Compact Combustor, Tylor C. Rathsack

Theses and Dissertations

The Ultra Compact Combustor (UCC) promises to greatly reduce the size of a gas turbine engine’s combustor by altering the manner in which fuel is burnt. Differing from the common axial flow combustor, the UCC utilizes a rotating flow, coaxial to the engine’s primary axis, in an outboard circumferential cavity as the primary combustion zone. The present study investigates two key UCC facets required to further this combustor design. The first area of investigation is cooling of the Hybrid Guide Vane (HGV). This UCC specific hardware acts as a combustor center body that alters the exit flow angle and acts …

Scaling Film Cooling Adiabatic Effectiveness With Mass Transfer And Thermal Experimental Techniques, Luke J. Mcnamara

Theses and Dissertations

With increasing engine temperatures, it is becoming more important to design effective film cooling schemes. Low temperature, large scale tests are often implemented in the design process to reduce cost and complexity. A nondimensional adiabatic effectiveness can be used as an indication of the performance of a film cooling scheme. However, the coolant flow rate must be properly scaled between the low temperature tests and engine temperatures to accurately predict film cooling effectiveness. This process is complicated by gas property variation with temperature. Tests are commonly conducted using thermal measurement techniques with infrared thermography (IR), but the use of pressure …