Chemical Engineering Commons^™

Shale Softening Based On Pore Network And Laboratory Investigations, Di Zhang

Dissertations

This dissertation consists of two major parts: Firstly, experimental investigation of four major shale softening mechanisms and quantifications of structural parameters. Secondly, numerical simulations of nano-scale flow behaviors using the previous experiments determined parameters based on modified pore network modeling.

Hydraulic fracturing is widely applied to economical gas production from shale reservoirs. Still, the gradual swelling of the clay micro/nano-pores due to retained fluid from hydraulic fracturing causes a gradual reduction of gas production. Four different gas-bearing shale samples are investigated to quantify the expected shale swelling due to hydraulic fracturing. These shale samples are subject to heated deionized (DI) …

Feedstock Powders For Reactive Structural Materials, Daniel Hastings

Dissertations

Metals as fuels have higher energy density per unit mass or volume compared to any hydrocarbon. At the same time, metals are common structural materials. Exploring metals as reactive structural materials may combine their high energy density with attractive mechanical properties. Preparing such materials, however, is challenging. Requirements that need to be met for applications include density, strength, and stability enabling the component to sustain the structure during its desired operation; added requirements are the amount and rate of the energy release upon impact or shock. Powder technology and additive manufacturing are approaches considered for design of reactive structural materials. …

Towards Quality By Design (Qbd) Of Pharmaceutical Oral Films Loaded With Poorly Watersoluble Drugs, Eylul Cetindag

Dissertations

Oral films are an emerging drug delivery dosage form with numerous advantages such as ease of handling, the possibility to circumvent the first-pass metabolism, better patient compliance, capability for continuous manufacturing, and as a platform for personalized medicine. As films are different from other final dosages by their dimensions and their matrix form, further research is required to better understand the impact of excipient and drug on product performance to assure a consistent and good quality product. Therefore, this dissertation aims to contribute towards the processability and manufacturability of films by examining the impact of the materials and processes. First, …

Exploring Fused Deposition Modeling (Fdm) Three-Dimensional Printing Tablet Design Options For Pharmaceutical Dosage Forms, Guluzar Gorkem Buyukgoz

Dissertations

This dissertation examines the use of Fused Deposition Modeling (FDM) based three-dimensional (3D) printing approach for developing patient-specific dosage forms and addressing related technical challenges in such drug delivery systems. The first main objective is to explore pharmaceutical tablet design options using novel FDM 3D printing technology as the drug delivery platform such that drug form and tablet properties are tailored by considering patient age-specific formulations and dissolution control. Of the five different design options, two proposed options meet the main objective of providing similar drug release, whereas the popular option of fixed drug concentration but differing tablet size could …

Development And Characterization Of Composite Membranes For Use In Countercurrent Solvent Extraction, Lydia Neves Rodrigues

Dissertations

Porous membranes having a particular wetting characteristic, hydrophobic or hydrophilic, are used for nondispersive membrane solvent extraction (MSX) where two immiscible phases flow on two sides of the membrane. The aqueous-organic phase interface across which solvent extraction/back extraction occurs remains immobilized on one surface of the membrane. This process requires the pressure of the phase not present in membrane pores to be either equal to or higher than that of the phase present in membrane pores; the excess phase pressure should not exceed a breakthrough pressure. In countercurrent MSX with significant flow pressure drop in each phase, this often poses …

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.

Membrane-Based Removal Of Ammonia From A Waste Stream And Its Recovery, Philip A. Aligwe

Dissertations

At neutral pH levels, ammonia in aqueous streams exists in two forms: ammonium ion (NH₄⁺) and dissolved ammonia gas molecules (NH₃). Membrane separation serves as a viable option for treatment of ammonia containing effluents. This can be achieved via by stripping NH₃ from an ammonia feed solution at feed solution pH > 11 via hollow fiber supported gas membrane (SGM) or removing NH₄⁺ from an ammonia feed solution at feed solution pH < 7 via liquid or polymeric membranes.

The first study reported here examines the influence of feed volumetric flow rates on outlet NH₃ concentrations in parallel flow …

Graphene Based Barrier Membrane For Gas Separation Processes, Cheng Peng

Dissertations

Novel graphene oxide (GO) flake-based composite lamellar membrane structure is being developed as a potential component of a garment for protection against chemical warfare agents (CWAs) represented here by simulants, dimethyl methyl phosphonate (DMMP) (a sarin-simulant) and 2-chloroethyl ethyl sulfide (2-CEES) (a simulant for sulfur mustard), yet allowing a high moisture transmission rate. GO flakes of dimensions 300-800 nm, 0.7-1.2 nm thickness and dispersed in an aqueous suspension are formed into a membrane by vacuum filtration on a porous polyethersulfone (PES) or poly (ether-ether-ketone) (PEEK) support membrane for noncovalent π-π interactions with GO flakes. After physical compression of such a …

Moisture Permeable Barrier Membranes For Toxic Gases And Vapors, Yufeng Song

Dissertations

Defense against small molecule toxic gases is an important aspect of protection against chemical and biological threat as well as chemical releases from industrial accidents. Current protective respirators/garments cannot effectively block small molecule toxic gases and vapors and retain moisture transmission capability without a heavy burden.

Metal organic frameworks (MOFs) have been used as highly effective adsorbents and catalysts to remove ammonia, cyanogen chloride, and sulfur dioxide from air. A nanopacked bed of nanoparticles of MOF by synthesizing them in the pores of microporous membranes is developed in the study. The submicron scale size of membrane pores ensures a large …

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 …

Particle Engineering Via Surface Modification: Model Based Analysis, Kai Zheng

Dissertations

Size reduction, an important step in particle engineering, leads to downstream processing problems because of fine powders are cohesive. This research aims to improve the fine particle properties through surface modification and develop better understanding of such processes by model-based analysis. Four case studies concerning surface modification are systematically investigated.

First, enhancement of dissolution behavior of griseofulvin is investigated via combination of amorphization and particle size reduction. The dissolution behavior is affected by the particle size and polymer loading. Finest size amorphous solid dispersions dissolve fast enough to negate the higher recrystallization rate and enhance drug loading by reducing the …

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. …