Chemical Engineering Commons^™

Effects Of Confinement On Ionic Liquids And Deep Eutectic Solvents For The Design Of Catalytic Systems, Electrochemical Devices, And Separations, Andrew Drake

Theses and Dissertations--Chemical and Materials Engineering

Confinement of ionic liquids (ILs) and deep eutectic solvents (DESs) within mesoporous materials such as silica helps to control the local environment within the pores for applications such as catalysis, electrochemistry, and absorption. Silica thin films with 2.5 and 8 nm pores and micron-sized silica particles with pore diameters of 5.4 and 9 nm were synthesized to study the effect of nanoconfinement on ILs 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]), 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), and DESs reline and ethaline (choline chloride and urea or ethylene glycol). Silica thin films with vertically aligned, well ordered, and accessible pores were synthesized via the evaporation-induced …

A Detailed Parameter Study Into The Dermal Absorption Of Chemical Warfare Agents And The Effects Of Pharmacokinetics, Koko Lear

Theses

Chemical warfare agents (CWAs) are substances of varying toxicity profiles. These chemicals exhibit complex dynamics and pose a serious health risk when released into the environment. A mathematical model based on Fick’s second law of diffusion was developed to comprehend how these compounds were absorbed into the skin. The analysis applied to both small and large doses and, successfully, predicted experimental results. This work also includes the effects of CWA physicochemical properties on evaporation and dermal absorption through the stratum corneum. A sensitivity analysis was conducted to assess the impacts of small variations in the initial dose, environmental conditions, and …

Diffusion Of A Salt In An Aqueous Media, Aldaly Pineda Hernandez

Chemical Engineering Undergraduate Honors Theses

Diffusion is defined as the net transfer of a molecule from a high concentration region to a low concentration region. The concept of diffusion is used in a very important process called "desalination." Desalination is a separation process used to reduce the salt content dissolved in brackish water to make it suitable for human consumption, irrigation, and industrial use.

In desalination plants, it is important to monitor the constantly changing salt content of water, partly due to the diffusive effect. The main purpose of this experiment was to study the diffusion of NaCl in water at two NaCl concentrations. The …

Enhanced Oil Recovery In Tight Rocks Using The “Slot-Drill” Completion, Hassan Amer

LSU Master's Theses

Enhanced oil recovery (EOR) is essential in shale/tight formations because primary recovery typically produces less than 10% of the original hydrocarbon in-place (OHIP). This work presents a novel “slot-drill” EOR technology, which involves injecting gas through a horizontal fracture that is cut into the formation near the top of the reservoir (using a tensioned abrasive cutting cable mounted to the drillstring) and producing oil from a second slot-drilled horizontal fracture near the bottom of the reservoir.

The dusty-gas diffusion model was implemented in a compositional simulator to account for the diffusion mechanism expected during the injection of gases in this …

Establishing Independent Tunability Of The Mechanical And Transport Properties Of Polymer Gels, Lucas Rankin

Master’s Theses

Polymer gels can be used in the fabrication of materials for filtering liquid and gaseous media, solid-state electrolytes, and transdermal medical patches. This diverse range of applications primarily relies on the transport and mechanical properties of polymer gels. Both sets of properties have shown excellent tunability, but typically in a coupled fashion. Establishing the independent tunability of the transport and mechanical properties of polymer gels (using simple, cost-effective methods) is paramount if polymer gels are to be used to their full potential. Specifically, block copolymer gels self-assemble into organized nanoscale networks within the gel solvent, which allows for facile control …

Complementary Techniques To Study The Behavior Of Water And The Effect On Diffusion And Degradation In Hydrogels, Paige Rockwell

Master’s Theses

Hydrogels exhibit biocompatibility in a range of biomedical applications, including drug delivery. This thesis aims to develop complementary techniques to measure the diffusion and degradation behaviors within an injectable, hydrolytically degradable hydrogel, formed via the covalent crosslinking of ethoxylated trimethylolpropane tri-3- mercaptopropionate (ETTMP) and poly(ethylene glycol) diacrylate (PEGDA), to determine its suitability as a drug delivery matrix. The characterization of water as either free, within the network openings of the hydrogel, or bound, tightly associated with the polymer chains, was determined using differential scanning calorimetry (DSC). The mobility of each type of water within the hydrogels was determined via nuclear …

Effects Of Microporous Structure On The Enzymatic Conversion Of Biomass Using A Multiscale Model, Saketh Merugu

Dissertations, Master's Theses and Master's Reports

The generation of biofuels from lignocellulosic biomass involves innovative process technology that is being investigated worldwide. Enzymatic hydrolysis is a major step in the contemporary process of the generation of biofuels. Guided by pore size distribution measured using NMR cryoporometry, we developed pore-enzyme diffusion and adsorption models at the particle level coupled with a kinetic model for cellulose, cellobiose, and glucose production at flask level. By simulating these models in MATLAB, COMSOL, and Polymath software packages, we investigate the effects of various biomass particle-related parameters (particle dimensions, porosity, enzyme accessibility) on the characteristic time of enzyme diffusion and adsorption and …

Assessing The Impact Of Block-Selective Homopolymers On The Diffusion Of Payload Through Polymeric Organogels, Ian Coates

Honors Theses

Styrenic polymer gels have received recent attention for their application in transdermal patches due to their unique properties. Previous research in the pharmaceutical industry has identified that polymeric gels, specifically styrenic gels, have the potential to encompass multiple functions of the transdermal delivery patch including controlling mechanical and delivery properties. To tailor styrenic gels either the gel nanostructure or the drug complex can be controlled. Specifically, this thesis investigated the effect of gel nanostructure in an attempt to control the gel diffusivity and mechanical properties. To control gel nanostructure a phase selective styrene homopolymer was used at varying concentrations. It …

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 …

Elucidating The Properties And Mechanism For Cellulose Dissolution In Tetrabutylphosphonium-Based Ionic Liquids Using High Concentrations Of Water, Brad Crawford

Graduate Theses, Dissertations, and Problem Reports

The structural, transport, and thermodynamic properties related to cellulose dissolution by tetrabutylphosphonium chloride (TBPCl) and tetrabutylphosphonium hydroxide (TBPH)-water mixtures have been calculated via molecular dynamics simulations. For both ionic liquid (IL)-water solutions, water veins begin to form between the TBPs interlocking arms at 80 mol % water, opening a pathway for the diffusion of the anions, cations, and water. The water veins allow for a diffusion regime shift in the concentration region from 80 to 92.5 mol % water, providing a higher probability of solvent interaction with the dissolving cellulose strand. The hydrogen bonding was compared between small and large …

Polymeric Impulsive Actuation Mechanisms: Development, Characterization, And Modeling, Yongjin Kim

Doctoral Dissertations

Recent advances in the field of biomedical and life-sciences are increasingly demanding more life-like actuation with higher degrees of freedom in motion at small scales. Many researchers have developed various solutions to satisfy these emerging requirements. In many cases, new solutions are made possible with the development of novel polymeric actuators. Advances in polymeric actuation not only addressed problems concerning low degree of freedom in motion, large system size, and bio-incompatibility associated with conventional actuators, but also led to the discovery of novel applications, which were previously unattainable with conventional engineered systems. This dissertation focuses on developing novel actuation mechanisms …

Synthesis And Molecular Transport Studies In Zeolites And Nanoporous Membranes, Vivek Vattipalli

Doctoral Dissertations

The advent of nanoporous materials such as zeolites and nanoporous membranes has provided cost-effective solutions to some of the most pressing problems of the 20^th century such as the conversion of crude oil into fuels and valuable chemicals. Hierarchical zeolites and mesoporous inorganic membranes are showing great promise in addressing new problems such as the conversion of biomass into value-added chemicals and development of energy-efficient separation processes. The synthesis and fundamental aspects of molecular transport in these new materials with hierarchical porosities need to be better understood in order to rationally develop them for these desired applications. Pore narrowing …

Spatiotemporal Modeling And Model Restructuration Approaches In Studies Of Intracellular Signalling Pathways, Md Shahinuzzaman

Doctoral Dissertations

"The main focus of the research is to understand the complex phenomena of cell transduction pathways and cell biology in a single cell. Mathematical modeling and experimental evaluation are widely used approaches for this kind of research. Firstly, A multiscale framework for protein-protein interaction has been established using Brownian dynamics algorithm. Sit specific feature, steric collision, diffusion, co-localization and complex formation with time and space has been included in this spatial modeling framework. By implementation of the time adaptive feature in this framework, the computation time reduces in an order of magnitude compared with traditional modeling framework. This multiscale Brownian …

Influence Of Natural Convection During Dendritic Array Growth Of Metal Alloys (Gradient Freeze Directional Solidification), Suyog N. Mahajan

ETD Archive

Purpose of this study was to examine the microstructural evolution of primary dendrites during Gradient Freeze Directional Solidification process in cylindrical Pb-5.8% Sb alloy samples to generate the ground- based research data to support a future microgravity experiment on the Space Station in a convection free environment. Pb-5.8Sb was selected for this study because of its ease of processing and availability of physical property data which will be required for predicting the dendrite morphology parameters, such as, primary dendrite spacing and dendrite trunk diameter. This alloy is also susceptible to thermosolutal convection caused by density inversion of the met in …

Fluid Flow In A Krogh Cylinder: A Model For A Single Capillary And Surrounding Tissue, Xianjie Qiu

Masters Theses

"A model describing the flow of plasma from the capillaries to the interstitial space in the extravascular tissue and back into the capillaries is constructed and solved. The flow through the tissue or the interstitial spaces is described by the Brinkman equation for porous medium, modified to account for the presence of cells considered as spheres. The flow of blood through the capillaries is considered to be that of a Newtonian fluid. The flow between capillary and tissue is coupled by the permeability of the capillary wall. The nature of flow and its magnitude was found to be highly dependent …

Microbial Desalination Cells With Efficient Platinum Group Metal-Free Cathode Catalysts, Morteza Rezaei Talarposhti

Chemical and Biological Engineering ETDs

Iron-nitrogen-carbon based catalyst was used at the cathode of a microbial desalination cell (MDC) and compared with platinum (Pt) and activated carbon (AC) cathode. Fe-N-C catalyst was prepared using nicarbazin (NCB) as organic precursor by sacrificial support method (SSM). Rotating ring disk electrode (RRDE) experiments shows that Fe-NCB had higher electrocatalytic activity compared to AC and Pt. The utilization of Fe-NCB into the cathode improved substantially the performance output with initial maximum power density of 49±2 μWcm^-2 in contrast to Pt and AC catalysts which have shown lower values of 34±1 μWcm^-2 and 23.5±1.5 μWcm^-2, respectively. …

Diffusion-Mediated Deposition Of Proteins, Ruiqian Zhan

Theses and Dissertations--Mechanical Engineering

Gradients of proteins play a prominent role in many biological processes, from development of multicellular organisms to chemical signaling in the immune system. Deposition of surface gradients is a way to permanently modifying a surface’s properties, resulting in the creation of novel materials which have widespread applications in biologically relevant fields, such as directed cell growth, production of biocompatible implantable materials, and creation of functional biosensors. These types of surfaces can also be used as an ex vivo tool to help understand many biological processes by mimicking the environment in gradient-related phenomena in a controllable way. However, despite the large …

Transport Limitations In Zeolites And Biomass Pyrolysis, Andrew Robert Teixeira

Doctoral Dissertations

Biomass pyrolysis has been widely explored for its potential to generate a sustainable chemical source capable of producing synthetic fuels and chemicals. Lignocellulosic biomass is the carbon rich, inedible fraction of wood that is comprised of long oxygenated biopolymers, primarily cellulose, hemicellulose and the highly aromatic lignin. High temperature thermal conversion of biomass to bio-oil (pyrolysis oil) occurs on the order of milliseconds and converts long chain biopolymers to a carbon-rich liquid crude. The chemistry of biomass pyrolysis is greatly complicated by significant heat and mass transport challenges. The complex fluid dynamics of the reactive liquid intermediate are examined in …

Microanalysis Of Polymer Chain Diffusion In Heat Seals, Russell Cooper

All Theses

Heat sealing is an integral method for the closure and protection of packaging. Previous work has shown that seal strength is developed by the interdiffusion of polymer chains within heat seals. Heat seals were made between two dissimilar materials. Poly(ethylene-co-acrylic acid) (EAA) was heat sealed to ionomer. Diffusion within the EAA-ionomer heat seals was estimated. The diffusion estimates were then related to resulting seal strength in the EAA-ionomer sealant system. Heated tooling sealing was utilized to make heat seals at 40 psi (275.79 kPa), 0.5 seconds, and a range of temperatures between 180˚F (82.22˚C) and 300˚F (148.89˚C). Scanning electron microscopy …

Volume Swing Frequency Response Method For Determining Mass Transfer Mechanisms In Microporous Adsorbents, Mohammad Iftekhar Hossain

Theses and Dissertations

Because of their numerous important applications in industrial catalytic, separation, and purification processes, miroporous materials have attracted considerable attention. Understanding the dynamic behavior of various gases in these porous materials is a critical step in designing, developing and effective operation of such kind of industrial processes. Frequency response (FR) methods have proven to be one of the best recently developed techniques and have been widely used to investigate kinetics behavior of various gas-solid systems due to their ability to discriminate among different rate limiting mechanisms. The current work has been focusing on the development of a volume swing frequency response …

Adsorption And Diffusion Of Gases In Nano-Porous Materials, Nethika Sahani Suraweera

Doctoral Dissertations

In this work, a systematic computational study directed toward developing a molecular-level understanding of gas adsorption and diffusion characteristics in nano-porous materials is presented. Two different types of porous adsorbents were studied, one crystalline and the other amorphous. Physisorption and diffusion of hydrogen in ten iso-reticular metal-organic frameworks (IRMOFs) were investigated. A set of nine adsorbents taken from a class of novel, amorphous nano-porous materials composed of spherosilicate building blocks and isolated metal sites was also studied, with attention paid to the adsorptive and diffusive behavior of hydrogen, methane, carbon dioxide and their binary mixtures. Both classes of materials were …

Novel Ceria-Zirconia-Yttria Mesostructures: Synthesis, Characterization, Diffusional Studies And The Effects Of Morphology On Their Properties, Alma Cordova Morales

All Dissertations

Ceria-zirconia-yttria (CZY) mixed oxides are used as catalyst supports for three-way catalysts for automotive exhaust emission control and in solid oxide fuel cells. By improving the morphology of CZY mesopores it is possible to reduce the sintering of supported noble metals and enhance overall catalyst lifetime and performance. However, limited studies have been published on the synthetic control of the morphology of CZY materials and the effects that CZY pore geometry has on catalyst operation.
To create optimized CZY catalyst supports, novel mesoporous CZY oxides were synthesized via classical sol-gel and evaporation induced self-assembly (EISA) methods, obtaining mesostructures that exhibited …

Computational Studies Of Ion Transport In Polymer Electrolytes, Hui Wu

Doctoral Dissertations

Improving ionic conductivity and lithium mobility in polymer electrolytes is important for their practical use for battery electrolytes. In this study, a combination of molecular dynamics and Monte Carlo simulations was used to bring insight into lithium ion transport in poly(ethylene oxide) (PEO) with plasticizers and also next to alumina solid surface doped with lithium salt. The simulations were performed using a moderately high molecular weight polymer (Mn = 10,000 g/mol) at an EO:Li ratio of 15. For the plasticized system, the PEO with LiN(CF3SO 2)2 (LiTFSI) was mixed with 10 wt% plasticizers that included either cyclic ethylene carbonate …

Modeling Small Molecule Elution From A Hydrogel Using A Microfluidic Technique, Stephanie Evans

Master’s Theses

Drug release from a fluid-contacting biomaterial is simulated using a microfluidic device with channels defined by solute-loaded hydrogel. In order to mimic a drug delivery device, a solution of poly(ethylene glycol) diacrylate (PEG-DA), solute, and photoinitiator is cured inside a microfluidic device with a channel through the center ofthe hydrogel. As water is pumped through the channel, solute diffuses out of the hydrogel and into the water. Channel sizes within the devices range from 300 µm to 1000 µm to simulate vessels within the body. The properties of the PEG hydrogel were characterizedby the extent of crosslinking, the swelling ratio, …

Molecular Simulations Of Adsorption And Diffusion In Metal-Organic Frameworks (Mofs), Ruichang Xiong

Doctoral Dissertations

Metal-organic frameworks (MOFs) are a new class of nanoporous materials that have received great interest since they were first synthesized in the late 1990s. Practical applications of MOFs are continuously being discovered as a better understanding of the properties of materials adsorbed within the nanopores of MOFs emerges. One such potential application is as a component of an explosive-sensing system. Another potential application is for hydrogen storage.

This work is focused on tailoring MOFs to adsorb/desorb the explosive, RDX. Classical grand canonical Monte Carlo (GCMC) and molecular dynamic (MD) simulations have been performed to calculate adsorption isotherms and self-diffusivities of …

Quantifying Defects In Zeolites And Zeolite Membranes, Karl Daniel Hammond

Open Access Dissertations

Zeolites are crystalline aluminosilicates that are frequently used as catalysts to transform chemical feedstocks into more useful materials in a size- or shape-selective fashion; they are one of the earliest forms of nanotechnology. Zeolites can also be used, especially in the form of zeolite membranes (layers of zeolite on a support), to separate mixtures based on the size of the molecules. Recent advances have also created the possibility of using zeolites as alkaline catalysts, in addition to their traditional applications as acid catalysts and catalytic supports. Transport and catalysis in zeolites are greatly affected by physical and chemical defects. Such …

A Microfluidic Method To Measure Diffusion In Hydrogels, Andrew Lee Litzenberger

Master’s Theses

A novel microfluidic method is proposed for studying diffusion of small molecules in a hydrogel. Microfluidic devices were prepared with semi-permeable microchannels defined by crosslinked poly(ethylene glycol) (PEG). Uptake of dye molecules from aqueous solutions flowing through the microchannels was observedoptically and diffusion of the dye into the hydrogel was quantified. To complement the diffusion measurements from the microfluidic studies, nuclear magnetic resonance(NMR) characterization of the diffusion of dye in the PEG hydrogels was performed. The diffusion of small molecules in a hydrogel is relevant to applications such asdrug delivery and modeling transport for tissue-engineering applications. The diffusion of small …

Simulation Of Particle Size Distribution In Continuous Emulsion Polymerization Through A Modified Population Balance Approach, Ying-Yuh Lu

Theses

A detailed mathematical model for particle size distribution in continuous emulsion polymerization of styrene and vinyl acetate is proposed on the basis of the population balance in the presence of several kinetic and mass transfer processes. This study is limited to the Smith-Ewart case II, which assumes instantaneous free radical termination within polymer particles. Radical desorption mechanism from polymer particles is included in the model and the desorption rate is formulated from the diffusion theory which suggests that the rate coefficient should be inversely proportional to the surface area of polymer particles.

Correlation And Prediction Of Diffussion Coefficients In Binary Gas Systems, Raymond Gerald Bailey

Theses

A correlation was developed for estimating binary gas diffusion coefficients by the reference substance method, in this case using the viscosity of air and subsequently its corresponding temperature. The derivation was made by the linear least square analysis of 65 different binary systems comprising 161 separate data points at temperatures ranging from 193°K. to 1200°K. At any given temperature only the critical molal volume and the molecular weights of the two gases of interest are required to calculate the diffusion coefficient. The correlation based on the viscosity of air had an average error of 7.67%. The correlation using temperature had …

Interphase Gas-Liquid Mass Transfer Study In A Horizontal Channel, Bruce R. Marx

Theses

The rate of transfer of hydrogen sulfide and of carbon dioxide from an atmosphere of the gas saturated with water to a flowing stream of water in a horizontal channel was investigated over a range of water flow velocities and absolute pressures.

Mathematical models describing the system in terms of the penetration and boundary layer theories were inadequate when used to calculate the diffusivity of each gas in water at various conditions. The results of the hydrogen sulfide-water system study shows a relationship between the diffusivity, the interfacial concentration and the liquid flow rate. The calculated diffusivity of the carbon …