Chemical Engineering Commons^™

Epoxy Curing: Paramount Or Trivial? A Cure Path Dependent Inquiry, Jared Bates

Dissertations

The presented research delves into epoxy network formation corroborating reactant concentration profiles and physical property development throughout cure, providing an experimental basis for burgeoning molecular dynamics and coarse-grained simulation methodologies. Herein, three primary subjects were investigated: the first two examine neat and toughened epoxide/amine network formation with respect to various cure profiles aimed at altering reaction pathways, the final chapter intends to augment traditionally utilized activation energy (E_a) methodologies.

Neat and toughened epoxide/amine slurries were monitored in-situ throughout cure via near infrared (NIR) spectroscopy and rheological techniques. Functional group conversion and moduli development were related with specific attention …

Fluorine-Based Inorganic Oxidizers For Use In Metal-Based Reactive Materials, Siva Kumar Valluri

Dissertations

This work explores inorganic fluorides as oxidizers for fuel-rich reactive materials. A preliminary assessment of metal fluorides accounting for their enthalpy of formation points to bismuth (III) fluoride, BiF3 and cobalt (II) fluoride, CoF2 as oxidizers of interest. Initially, composite powders of aluminum with chosen fluorides at 50-50 wt. % are prepared by arrested reactive milling. Despite an increase in reactivity and lowtemperature ignition, the prepared composite powders are insensitive to initiation by electro-static discharge (ESD), making them attractive alternative to analogous thermites having very high ESD sensitivity. In air, the composite powder particles burn faster than reference aluminum particles …

Conversion Of Lignocellulose Biomass From Date Palm Waste To High Value Chemicals, Emmanuel Galiwango

Dissertations

Lignocellulose biomass has gained growing popularity because of its low cost of production compared to food crops, it solves problems of food and energy security, can grow in various climates and land, and it is CO₂ neutral. Date palm trees produce large amounts of fibrous wastes that are good sources of lignocellulose. There are over 40 million date palm trees in UAE and most of their lignocellulosic wastes (i.e., leaves, surface fibers, bunches, etc.) are currently used for low value applications such as compost or electric generation. However, the lignocellulosic components of this waste stream have the potential to …

Development Of Novel Inks And Approaches For Printing Tissues And Organs, Shen Ji

Dissertations

Tissue engineering is a multidisciplinary field that investigates and develops new methods to repair, regenerate and replace damaged tissues and organs, or to develop biomaterial platforms as in vitro models. Tissue engineering approaches require the fabrication of scaffolds using biomaterials or fabrication of living tissues using cells. As the demands of customized, implantable tissue/organs are increasing and becoming more urgent, conventional scaffold fabrication approaches are difficult to meet the requirements, especially for complex large-scale tissue fabrication. In this regard, three-dimensional (3D) printing attracted more interest over the past decades due to its unrivaled ability to fabricate highly customized tissues or …

The Aging And Impacts Of Atmospheric Soot: Closing The Gap Between Experiments And Models, Ogochukwu Yvonne Enekwizu

Dissertations

The main goal of this dissertation is to generate data and parameterizations to accurately represent soot aerosols in atmospheric models. Soot from incomplete combustion of fossil fuels and biomass burning is a major air pollutant and a significant contributor to climate warming. The environmental impacts of soot are strongly dependent on the particle morphology and mixing state, which evolve continuously during atmospheric transport via a process known as aging. To make predictions of soot impacts on the environment, most atmospheric models adopt simplifications of particle structure and mixing state, which lead to substantial uncertainties. Using an experimentally constrained modeling approach, …

Modeling Mass Transfer And Chemical Reaction In Industrial Nitrocellulose Manufacturing Processes, Francis Patrick Sullivan

Dissertations

A series of models are proposed to describe the production of military grade nitrocellulose from dense cellulose materials in mixtures of nitric acid, sulfuric acid, and water. This effort is conducted to provide a predictive capability for analyzing the rate and extent of reaction achieved under a range of reaction conditions used in the industrial nitrocellulose manufacturing process for sheeted cellulose materials. Because this capability does not presently exist, nitrocellulose producers have historically relied on a very narrow range of cellulose raw materials and resorted to trial and error methods to develop processing conditions for new materials. This tool enables …

Development Of Novel Membranes For Nanocarbon Enhanced Separation With Application In Biofuels And Solvent Recover, Oindrila Gupta

Dissertations

Pharmaceutical industries historically have had one of the highest amounts of solvent waste generated per unit of drug manufactured. Energy requirements and carbon footprint of current solvent recycling processes tend to be quite high, and the incineration of the solvents for waste disposal produces toxic air emissions. Also, rapidly increasing demand for energy and strict regulation on engine pollutant emissions have necessitated the use of alcohol as carbon-neutral fuels. Thermal distillation is one of the most common methods for the separation of alcohol-water mixtures. However, its application is limited due to energy requirements and high operating costs, and heating to …

Predicting Bulk-Scale Properties Of Pharmaceutical Powders From Their Particle-Scale Dimensionless Measures, Kuriakose T. Kunnath

Dissertations

Loose powder packing and flowability are both important bulk properties to consider in relation to pharmaceutical tablet and capsule manufacturing. These properties as well as cohesive powder agglomeration tendency impact the efficiency of various processes such as feeding, blending, conveying, and compaction, and could have an adverse effect on final drug product. Pharmaceutical powders are often milled to fine sizes (<100 gm) for dissolution improvements via increased available surface area. However, such particle size reductions lead to inadequate bulk powder properties due to high cohesion among the individual particles. Recent work has demonstrated the ability of nano-silica dry coating techniques to significantly decrease interparticle forces without changes in particle size. In this work, the ability to predict properties such as powder bed porosity, flowability, and particle agglomeration both before and after nano-silica dry coating is examined, along with assessment of the extent of property enhancements after dry coating. Previous studies have utilized empirical approaches to build property prediction models. However, such approaches lack physical fundamentals which dictate bulk powder behavior and would be unable to account for the effects of dry powder coating. Incorporation of physics can be done via computation of the granular Bond number, as is done in this study for a large dataset of commonly used pharmaceutical powders, with wide variations in particle size, shape, density, and surface roughness. Predictive capability of current Bond number models is investigated, reasons for outliers are elucidated, and amendments to improve prediction is attempted. Overall, the aim of this work is to expand generalizability of Bond number models to a wider variety of particles, and extend its use from single powders to multi-component mixtures. The major outcome of this work is the development of a predictive framework that is expected to simplify pharmaceutical dry powder formulation development, reduce required experimental testing, and provide quantifiable estimates to aid processing route decision making.

Stress-State And Injection-Rate Dependent Damage Processes During The Hydraulic Fracturing Of Granite, Gayani Sasendrika Gunarathna

Dissertations

Hydraulic fracturing is a well-stimulation technique that is employed in field applications, such as enhanced geothermal systems (EGS) and shale oil/gas extraction. This research experimentally investigates the effect of the state of stress and injection rate on the hydraulic fracturing processes. In addition, a displacement discontinuity method (DDM) code, FROCK, is used to model the crack initiation and propagation in a granite specimen under hydraulic fracturing conditions. In order to conduct the experimental work, a test setup capable of applying a triaxial state of stress and water pressure inside pre-fabricated flaws cut in prismatic granite specimens is developed. Additionally, the …

Calculating Elastic Properties Of Confined Simple Fluids, Christopher D. Dobrzanski

Dissertations

Confinement in nanoporous materials is known to affect many properties of the fluids confined within their pores. The elastic properties are no exception. This dissertation begins with an overview of the relevant literature on ways of obtaining elastic properties of confined fluids. It outlines some fundamental gaps in our understanding. The chapters following address some of these gaps in understanding elastic properties of the confined fluid, in particular, how the shape of the confining pore matters, how supercriticality effects the properties, how an equation of state designed for confined fluids can be used to calculate elastic properties, and if an …

Bulk Properties Correlated To The Hydrogen Bond Organization In Dendrimers, Hyperbranched Polymers, And Linear Polymers, Beibei Chen

Dissertations

Although a lot of research was conducted on dendritic polymers, our understanding of their structure-property is still limited. Our previous study, which focused on a family of dendritic polymers based on 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) as a monomer, discovered unique hydrogen bond organizations contributed by their dendritic structures. However, the influence of the H-bond organization on bulk properties has yet to be understood. The goal of this dissertation is to elucidate the correlation between the H-bond organization with the dielectric and volumetric properties of bis-MPA based dendritic polymers, with an emphasis on developing a fundamental understanding of to what extent …

Customized Boron And Magnesium-Based Reactive Materials Prepared By High Energy Mechanical Milling, Xinhang Liu

Dissertations

New reactive materials need to be developed having biocidal combustion products. When ignited, such material can add chemical biocidal effects to the common effects of high temperature and pressure. Biocidal combustion products are capable of deactivating harmful spores or bacteria, which can be released by targets containing biological weapons of mass destruction. Research showed that halogens, especially iodine, are effective as biocidal components of reactive material formulations. Recently, magnesium combustion product MgO is also found to have a biocidal effect. Thus, advanced formulations containing both magnesium and iodine are of interest; such formulations are prepared and investigated here.

Reactive materials …

The Effect Of Precursor Design And Processing On The Semi-Crystalline Morphologies Of Polyacrylonitrile-Based Carbon Fiber, Katelyn Cordell

Dissertations

Basic research to control the morphology of polyacrylonitrile (PAN)-based carbon fiber is crucial for next generation composites as it determines their mechanical properties and final use. Poor molecular design of PAN-based precursors and fiber processing causes morphological defects and mechanical limitations.^1,2 This research focused on utilizing the controlled polymerization technique, reversible addition-fragmentation chain transfer (RAFT), of novel acrylamide comonomers to afford well-defined precursors with precisely controlled molecular design. This controlled RAFT technique improved the overall precursor graphitic structure as evident by the increased extent of stabilization and reduced activation energy as compared to precursors prepared by traditional free radical …

Modelling In Vitro Dissolution And Release Of Sumatriptan Succinate From Polyvinylpyrrolidone-Based Microneedles Aided By Iontophoresis, James Paul Ronnander

Dissertations

A novel dissolving microneedle array system is developed to investigate permeation of a sumatriptan succinate formulations through the skin aided by iontophoresis. Three formulations consisting of hydrophilic, positively charged drug molecules encapsulated in a water-soluble biologically suitable polymer, polyvinylpyrrolidone (PVP), have been accepted by the U.S. Food and Drug Administration (FDA). The microneedle systems are fabricated with 600 pyramid-shaped needles, each 500 µm tall, on a 0.785-cm² circular array. In vitro transdermal studies with minipig skin and vertical Franz diffusion cells show > 68% permeation of sumatriptan over a 24-hour period. A combination of microneedle and electrical current density ranging …

Improving Boron For Combustion Applications, Kerri-Lee Annique Chintersingh

Dissertations

Boron has received much attention as a potential additive to explosives and propellants due to its high theoretical gravimetric and volumetric heating values. The challenge, however, is that boron particles tend to agglomerate, have lengthy ignition delays and very low combustion rates. Prior research indicates that boron’s long ignition delays are due to its inhibiting naturally occurring oxide layer, impeding the diffusion of reactants for oxidation. For combustion, current studies report that boron particles have two consecutive stages, but the actual reaction mechanism is poorly understood. Despite many years of relevant research, quantitative combustion data on micron-sized boron particles are …

Analyzing Evolution Of Rare Events Through Social Media Data, Xiaoyu Lu

Dissertations

Recently, some researchers have attempted to find a relationship between the evolution of rare events and temporal-spatial patterns of social media activities. Their studies verify that the relationship exists in both time and spatial domains. However, few of those studies can accurately deduce a time point when social media activities are most highly affected by a rare event because producing an accurate temporal pattern of social media during the evolution of a rare event is very difficult. This work expands the current studies along three directions. Firstly, we focus on the intensity of information volume and propose an innovative clustering …

Roles Of Surfactant And Binary Polymers On Dissolution Enhancement Of Bcs Ii Drugs From Nanocomposites And Amorphous Solid Dispersions, Md Mahbubur Rahman

Dissertations

Drug nanocomposites and amorphous solid dispersions (ASDs) are two major formulation platforms used for the bioavailability enhancement of BCS Class II drugs. The major drawback of nanocomposites is their inability to attain high drug supersaturation during in vitro (<50% relative supersaturation) and in vivo dissolution. On the other hand, formulating an amorphous solid dispersion (ASD) with high drug loading (>20%) that releases drug rapidly, while generating and maintaining high supersaturation over at least three hours is challenging. The goal of this thesis is to develop a fundamental understanding of the impact of anionic surfactants–polymers on in vitro drug release from nanocomposites and ASDs, while addressing the above challenges. To achieve this goal, the following objectives are set: (1) compare griseofulvin …

Enzymatic Biofuel Cells In A Sandwich Geometry With Compressed Carbon Nanotubes/Enzyme Electrodes & Hybrid Patch Applications, Biao Leng

Dissertations

Enzymatic biofuel cells (EBFCs) convert the chemical energy of biofuels, such as glucose and methanol, into electrical energy by employing enzymes as catalysts. In contrast to conventional fuel cells, EBFCs have a simple membrane-free fuel cell design due to the high catalytic specificity of the enzymes, but the power densities obtained are lower. Although the primary goal of research on EBFCs has been to develop a sustainable power source that can be directly implanted in the human body to power bio-devices, other applications such as the use of a flexible film or fuel cell patch as a wearable power source …

Electrochemically Reactive Membranes For Efficient Biomass Recovery, Pollutant Degradation And Commercialization, Likun Hua

Dissertations

Micropollution in natural waters such as rivers and groundwater aquifers is a widespread problem that prevents these potentially potable sources from being used as drinking water. In the United States, approximately two-thirds of the over 1,200 most serious hazardous waste sites in the nation are contaminated with trichloroethylene (TCE), a potentially carcinogenic compound. Other emerging and environmentally persistent organic micropollutants include polyromantic hydrocarbons (PAHs), organophosphate flame retardants, endocrine disrupting compounds (EDCs), pesticides, herbicides, pharmaceuticals and personal care products (PPCPs). Membrane filtration is one of the most efficient separation processes widely used for water treatment and pollutant removal. However, traditional membrane …

Speciation Of Gaseous Oxidized Mercury Molecules Relevant To Atmospheric And Combustion Environments, Francisco J. Guzman

Dissertations

Mercury is a pervasive and highly toxic environmental pollutant. Major anthropogenic sources of mercury emissions include artisanal gold mining, cement production, and combustion of coal. These sources release mostly gaseous elemental mercury (GEM), which upon entering the atmosphere can travel long distances before depositing to environmental waters and landforms. The deposition of GEM is relatively slow, but becomes greatly accelerated when GEM is converted to gaseous oxidized mercury (GOM) because the latter has significantly higher water solubility and lower volatility. Modeling GOM deposition requires the knowledge of its molecular identities, which are poorly known because ultra-trace (tens to hundreds part …

N8- Polynitrogen Stabilized On Carbon-Based Supports As Metal-Free Electrocatalyst For Oxygen Reduction Reaction In Fuel Cells, Zhenhua Yao

Dissertations

The sluggish oxygen reduction reaction (ORR) kinetics at the cathode is one of the key factors limiting the performance of polymer electrolyte membrane fuel cell (PEMFC). Platinum-based materials are the most widely studied catalysts for this ORR reaction while their large-scale practical application in fuel cells is hindered due to their scarcity and low stability. Therefore, highly active, low cost and robust non-Pt catalysts are being developed to overcome the drawbacks. Recently, a novel polynitrogen N8- (PN) stabilized on multiwall carbon nanotube (MWNT) was synthesized under ambient condition for the first time by our group and demonstrated high ORR activities. …

Engineered Excipients Via Dry Particle Coating, Liang Chen

Dissertations

Excipients with good flowability, bulk density as well as compaction properties are desired for use in tableting since they play important roles in formulation development and processing, including, handling, mixing, feeding and compaction. However, it is often difficult to manufacture excipients that simultaneously possess all three desirable properties, particularly if their size is fine. In addition, it is desirable that the excipients promote direct compression of poorly compactable fine cohesive drug powders at sufficiently high drug loading, and not just achieve the desired high functional properties in placebo formulations. This dissertation aims to developed engineered excipients towards this unmet industry …

Enzyme-Assisted Development Of Hydrogels As Medical Materials With Injectable, Biodegradable And Biocompatible Properties, Yung-Hao Tsou

Dissertations

Hydrogels were first discovered in the year 1960 by Wichterle and Lim [1], and in the following decades, they have been widely studied because of their unique characteristics including their hydrophilic nature, biocompatibility, and capacity to mimic the extracellular matrix (ECM). Hydrogels based on natural or synthetic polymers have continued to be of interest for tissue engineering and drug delivery due to their ability to encapsulate living cells and control the release rate of drugs or other bioactive molecules such as pharmaceutical proteins.

In the first part of this dissertation, dopant-free photoluminescent hydrogels formed in situ by crosslinking of biocompatible …

“Polysoaps” Via Raft Copolymerization To Form Well-Defined Micelles For Water Remediation And Targeted Drug Delivery Applications, Phillip Pickett

Dissertations

Amphiphilic copolymers have become increasingly important for environmental and biological applications due to their behavioral characteristics in aqueous solution. For example, structurally-tailored statistical amphiphilic copolymers or “polysoaps” can self-assemble into micelles or other architectures in water at various concentrations. Polysoaps may be differentiated from small molecule surfactant micelles in their capability to self-assemble into unimolecular associates (unimolecular micelles) with no dependence on concentration. Such micelles offer enormous potential for dispersion of hydrophobic species in water at high dilution. Importantly, each polymer chain forms its own micelle and upon dilution, these micelles remain intact and capable of dispersing hydrocarbon material in …

Chemical And Physical Modification Of Thiol-Ene And Epoxy-Amine Networks For Advanced Control Of Gas Transport And Flame Retardant Behavior, Vivek Vasagar

Dissertations

Crosslinked polymers are widely used due to its several advantages not limited to high mechanical strength combined with the easy processability. Despite of its popular usage, the fundamental understanding of polymer structure affecting the desired properties is still lacking. This PhD thesis is in two parts, the first part is devoted to the design and developing a basic understanding of structure and chemical composition dependencies of gas transport, whereas in the second part a fundamental relationship between structure to the fire-retardant properties is established.

Membrane based gas separation technique has attracted interest of selective removal of carbon dioxide gas from …

Bioinspired Glycopolymers: Models To Investigate The Effect Of Saccharide Structure And Concentration On Amyloid Beta Aggregation, Pradipta Kumar Das

Dissertations

Aggregation and subsequent deposition of amyloid-β (Aβ) peptide on neuronal cell membranes have been implicated as a cause of Alzheimer’s disease. Gangliosides in their clustered form seed and promote the Aβ aggregation process. However, the effects of the structure and the concentration of ganglioside saccharides on Aβ aggregation are not well understood. We investigated how the specific structure of saccharides (β-D-galactose and β-D-glucose) affect the aggregation pathways, kinetics, and the aggregated structures of Aβ via in vitro experiments. The effects of the local concentration of saccharides on the Aβ aggregation were also investigated.

To mimic the multivalent effect of the …

The Cooperative Effects Of Channel Length-Bias, Width Asymmetry, Gradient Steepness, And Contact-Guidance On Fibroblasts’ Directional Decision Making, Quang Long Pham

Dissertations

Cell migration in complex micro-environments, that are similar to tissue pores, is important for predicting locations of tissue nucleation and optimizing scaffold architectures. Firstly, how fibroblast cells - relevant to tissue engineering, affect each other’s directional decisions when encountered with a bifurcation of different channel lengths was investigated. It was found that cell sequence and cell mitosis influence the directional choices that the cells made while chemotaxing. Specifically, the fibroblasts chose to alternate between two possible paths - one longer and the other shorter - at a bifurcation. This finding was counter-intuitive given that the shorter path had a steeper …

Experimental And Numerical Characterization Of Multiphase Subsurface Oil Release, Feng Gao

Dissertations

Subsurface oil release is commonly encountered in the natural environment and engineering applications and has received the substantial attention of researchers after the disastrous Deepwater Horizon Blowout oil spill in 2009. The main focus on the present research is to systematically study the hydrodynamics of underwater oil jet under a variety of conditions, including the effect of dispersant and different gas to oil ratios (GOR) by using experimental measurement as well as a Computational Fluid Dynamics (CFD) approach, from which the measured turbulent characteristics (e.g., velocity, turbulent kinetic energy, turbulence dissipation rate, etc.) of underwater oil jet are thoroughly examined …

Overcoming Conventional Modeling Limitations Using Image- Driven Lattice-Boltzmann Method Simulations For Biophysical Applications, Olufemi E. Kadri

Dissertations

The challenges involved in modeling biological systems are significant and push the boundaries of conventional modeling. This is because biological systems are distinctly complex, and their emergent properties are results of the interplay of numerous components/processes. Unfortunately, conventional modeling approaches are often limited by their inability to capture all these complexities. By using in vivo data derived from biomedical imaging, image-based modeling is able to overcome this limitation.

In this work, a combination of imaging data with the Lattice-Boltzmann Method for computational fluid dynamics (CFD) is applied to tissue engineering and thrombogenesis. Using this approach, some of the unanswered questions …

Screen Printed Moisture Sensor On Barrier Coated Sbs Board: The Characterizations Of The Hemicellulose-Based Biofilms And Their Applications For Smart Packaging, Ruoxi Ma

Dissertations

Fiber-based packaging materials have many advantages over their petroleum-based plastic competitors, such as sustainability, recyclability and stiffness/weight ratio. However, the poor barrier properties and sensitivity towards moisture are the main challenges for their extended use. Therefore, there has been a need to provide a biodegradable and biocompatible biopolymer packaging material with improved barrier properties for food and pharmaceutical packaging. Also, the moisture loss/gain problem causes a lot of waste every year. Therefore, there is a need of better tracking and sensing methods attached to the package in order to control the moisture level along the supply chain. To accomplish these …