Chemical Engineering Commons^™

Integrating 3d Layered Manufacturing With Photonic Sintering, Precision Machining And Smart Coating Techniques For Rapid Casting Applications, Hemant Bohra

Dissertations

Developments in rapid casting technologies have led to a new era of inclusion of 3D printing. Three-Dimensional (3D) printing provides the flexibility and ease of reproducing a sand mold directly from CAD models, eliminating patterning steps, thus reducing the process time for creating prototypes. In addition to minimizing processing steps, 3D printing provides the advantages of higher precision and the ability to produce complex shaped sand molds, but it simultaneously possesses some limitations and concerns related to throughput, safety and logistics.

This study proposes an alternative method for creating sand molds by introducing a hybrid rapid prototyping approach to overcome …

A Soft Condensed Matter Approach Towards Mathematical Modelling Of Mass Transport And Swelling In Food Grains, Michael Chapwanya, N. Misra

Articles

Soft condensed matter (SCM) physics has recently gained importance for a large class of engineering materials. The treatment of food materials from a soft matter perspective, however, is only at the surface and is gaining importance for understanding the complex phenomena and structure of foods. In this work, we present a theoretical treatment of navy beans from a SCM perspective to describe the hydration kinetics. We solve the transport equations within a porous matrix and employ the Flory–Huggin’s equation for polymer–solvent mixture to balance the osmotic pressure. The swelling of the legume seed is modelled as a moving boundary with …

Replacement Of Solvent Based Ink By Water Based Inks For Gravure Presses With Low Efficiency Ink Driers, Viraj Suresh Dalvi

Masters Theses

Rotogravure printing of decorative laminates, wall coverings, or vinyl floorings process often uses solvent based inks. The main constraining factor with solvent based ink is presence of volatile organic compounds (VOC’s). Due to the environmental norms on Volatile Organic Compounds (VOCs), and restrictions on using solvent based inks, the ink industry came up with water based ink as more environmentally friendly alternative. Organizations which print decorative laminates, wall coverings, or vinyl floorings with solvent based inks have gravure printing infrastructure, which is often equipped with low efficiency driers capable of drying solvent based inks. In order to comply with environmental …

Self-Supported Printed Multi-Layer Capacitors, Michael James Joyce

Masters Theses

The increasing demand for miniaturized electronic devices has increased the need for rechargeable micro-power sources. Although lithium and lithium ion batteries have been utilized in these applications since the late 1990s, other energy harvesting technologies, such as thermal, mechanical, and solar, are now being used to augment batteries to enable systems to be self-powered. However, the lifetime of any battery is finite, which may be a major problem when the application is in a permanent structure or medical implant device. For power or significant energy storage applications, printed multilayer capacitors or supercapacitors are being explored as an enhancement, or replacement …

Photo-Sensitivity Of Large Area Physical Vapor Deposited Mono And Bilayer Mos2, Baoming Wang, Christopher Muratore, Andrey A. Voevodin, M. Amanul Haque

Chemical and Materials Engineering Faculty Publications

We present photosensitivity in large area physical vapour deposited mono and bi-layer MoS2 films. Photo-voltaic effect was observed in single layer MoS2 without any apparent rectifying junctions, making device fabrication straightforward. For bi-layers, no such effect was present, suggesting strong size effect in light-matter interaction. The photo-voltaic effect was observed to highly direction dependent in the film plane, which suggests that the oblique deposition configuration plays a key role in developing the rectifying potential gradient. To the best of our knowledge, this is the first report of any large area and transfer free MoS2 photo device with performance comparable to …

Interfacial Interactions Between Carbon Nanoparticles And Conjugated Polymers, Yanqi Luo

Master's Theses

Conjugated polymer based electronics, a type of flexible electronic devices, can be produced from solution by traditional printing and coating processes in a roll-to-roll format such as papers and graphic films. This shows great promise for the emerging energy generation and conversion. The device performance of polymer electronics is largely dependent of crystalline structures and morphology of photoactive layers. However, the solution crystallization kinetics of conjugated polymers in the presence of electron acceptor nanoparticles has not been fully understood yet. In this study, solution crystallization kinetics of poly (3-hexylthiophene) in the presence of carbon nanotubes and graphene oxide has been …

Hydraulic Fracturing Water Recycle Through Optimal Ultrafiltration And Nanofiltration Membranes System Design, Long Tran

Graduate Theses and Dissertations

Innovations in hydraulic fracturing technology have created opportunities for petroleum and natural gas production. This technology injects water, sand, and additives to create fissures in rock formations and discharge oil and gas to the surface. The average amount of water used per well is approximately 4.4 million gallons. The large water demand and the complexities involved in wastewater treatment make this process very expensive and not sustainable as far as water use is concerned. Flexible membrane technology has not been developed to process fracking water for re-use across the U.S. The objective of this project is to compare and analyze …

Fundamental Investigations Of Clay/Polymer Nanocomposites And Applications In Co-Extruded Microlayered Systems, Jeremy John Decker

Dissertations

The second and fourth generations of hydroxylated dendritic polyesters (HBP2, HBP4) were combined with unmodified sodium montmorillonite clay (Na+MMT) in water to generate a broad range of polymer clay nanocomposites from 0 to 100% wt/wt Na+MMT. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to investigate intercalation states of the clay galleries. It was shown that interlayer spacings were independent of generation number and changed over the composition range from 0.5 nm to 3.5 nm in 0.5 nm increments that corresponded to a flattened HBP conformation within the clay tactoids.

The HBP4/Na+MMT systems were investigated to study the …

Improved Efficiency Organic Photovoltaic Cells Through Morphology Control And Process Modification, Qi Wu

Dissertations

Organic photovoltaic (OPV) cells have drawn great attention due to the potential to produce flexible, light weight, affordable solar cells using polymer organic photovoltaic materials; however, the current power conversion efficiency achieved for these systems is too low for widespread implementation of the technology. Morphology and phase separation are key factors determining the performance of organic photovoltaic cells. Precise control of the size and distribution of the phase-separated photoactive domains is necessary for optimum photon-electron conversion. Polyhedral oligomeric silsesquioxane (POSS) nanostructered chemicals have the potential to provide enhanced control of morphology, crystallinity, and phase dispersion in polymeric blend systems. In …

Fluorine Containing Uv-Curable Materials For Advanced Transport Applications, James Thomas Goetz

Dissertations

The characterization of structure, thermal, gas transport, and free volume properties of two unique UV cured polymeric systems are studied and reported. In the initial pursuit of waterproof high water vapor transport membranes, it became apparent that the UV curing of fluorinated materials yielded routes to develop unique materials that fundamentally challenge conventional models for free volume and light gas transport behavior. UV-curing provides a means to rapidly “lock-in” morphologies that are accessible in the small molecule, monomer phase but rapidly become kinetically inaccessible when constraints such as covalent bonding and cross linking limit motion in the polymer system. This …

An Investigation Of Heat Transfer Enhancement In Nanofluids Containing Core And Shell Nanoparticles., Cory Adam Milligan

Electronic Theses and Dissertations

The purpose of this research is to determine the differences in heat transfer enhancement of poly alpha olefin oil after the addition of two types of carbon coated nanoparticles, specifically carbon coated cobalt and carbon coated copper nanoparticles. The carbon shell allows for the nanoparticles to be homogenously dispersed in the oil and remain stable throughout the experimental procedure. The nanofluids were prepared in concentrations of 0.5, 1.0, and 1.5 wt%. A constant surface heat flux testing rig is used to determine the heat transfer coefficients of the base fluids and the nanofluids. Inlet temperatures to the heat transfer section …

Investigation Of Stabilization Mechanisms For Colloidal Suspension Using Nanoparticles., Qingwen He

Electronic Theses and Dissertations

Over the past decade, charged nanoparticles have been found to enhance the stability of colloidal suspensions. One promising explanation of this stabilization mechanism is “Nanoparticle Haloing”- the formation of a non-adsorbing nanoparticle layer surrounding neutral colloids that would induce an effective electrostatic repulsion between them. The objective of this work was to investigate the effect of additional charged nanoparticles on the interaction between neural colloids in nanoparticle-regulated complex fluids. Firstly, colloidal probe Atomic Force Microscopy (CP-AFM) is used to directly measure the interaction force in such system with nanoparticle volume fractions varying from 10-6 to 10-2. It is found that …

Application Of Membrane Processes For Concentration And Separation Of Sugar Streams In Biofuel Production, Mohammadmahdi Malmali

Graduate Theses and Dissertations

The overall objective of this study was identification and development of a sugar concentration/separation membrane filtration unit to improve the bioconversion of lignocellulosic biomass into chemicals and fuels. This thesis is divided into three main parts. The first part is about our studies on the use of nanofiltration membranes for concentration of sugars in a lignocellulosic biomass hydrolysate. In addition, the feasibility of simultaneous removal of acetic acid, 5-(hydroxymethyl)furfural and furfural from the hydrolysate has also been investigated. The results obtained indicate that both concentration of sugars and removal of hydrolysis degradation products is feasible. However, careful selection of the …

Production Of Recombinant Human Coagulation Factor Ix By Transgenic Pig, Weijie Xu

Department of Chemical and Biomolecular Engineering: Dissertations, Theses, and Student Research

Hemophilia B is the congenital bleeding disorder caused by deficiency in functional coagulation factor IX (FIX) and about 28,000 patients worldwide in 2012. And current treatment is restricted to protein-replacement therapy, which required FIX concentrates for patients’ life-time. Approximately 1 billion units FIX were consumed in 2012. However, still about 70-80% patients, mostly in developing countries, received inadequate or no treatment because of the unavailable and/or unaffordable FIX concentrates. Considering safety reasons, e.g. transmission of blood-borne diseases, the recombinant human FIX (rFIX) is recommended other than the plasma-derived FIX. However, only one rFIX is currently available on the market. The …

Opto-Electronic Devices With Nanoparticles And Their Assemblies, Chieu Van Nguyen

Department of Chemical and Biomolecular Engineering: Dissertations, Theses, and Student Research

Nanotechnology is a fast growing field; engineering matters at the nano-meter scale. A key nanomaterial is nanoparticles (NPs). These sub-wavelength (< 100nm) particles provide tremendous possibilities due to their unique electrical, optical, and mechanical properties. Plethora of NPs with various chemical composition, size and shape has been synthesized. Clever designs of sub-wavelength structures enable observation of unusual properties of materials, and have led to new areas of research such as metamaterials. This dissertation describes two self-assemblies of gold nanoparticles, leading to an ultra-soft thin film and multi-functional single electron device at room temperature. First, the layer-by-layer self-assembly of 10nm Au nanoparticles and polyelectrolytes is shown to behave like a cellular-foam with modulus below 100 kPa. As a result, the composite thin film (~ 100nm) is 5 orders of magnitude softer than an equally thin typical polymer film. The thin film can be compressed reversibly to 60% strain. The extraordinarily low modulus and high compressibility are advantageous in pressure sensing applications. The unique mechanical properties of the composite film lead to development of an ultra-sensitive tactile imaging device capable of screening for breast cancer. On par with human finger sensitivity, the tactile device can detect a 5mm imbedded object up to 20mm below the surface with low background noise. The second device is based on a one-dimensional (1-D) self-directed self-assembly of Au NPs mediated by dielectric materials. Depending on the coverage density of the Au NPs assembly deposited on the device, electronic emission was observed at ultra-low bias of 40V, leading to low-power plasma generation in air at atmospheric pressure. Light emitted from the plasma is apparent to the naked eyes. Similarly, 1-D self-assembly of Au NPs mediated by iron oxide was fabricated and exhibits ferro-magnetic behavior. The multi-functional 1-D self-assembly of Au NPs has great potential in modern electronics such as solid state lighting, plasma-based nanoelectronics, and memory devices.

Adviser: Ravi F. Saraf

Catalytic Performance Of An Iron-Based Catalyst In Fischer–Tropsch Synthesis, Majid Sarkari, Farhad Fazlollahi, Hossein Ajamein, Hossein Atashi, William C. Hecker, Larry L. Baxter

Faculty Publications

This paper documents the performance and kinetics of an iron/manganese oxide catalyst in a fixed-bed reactor by Fischer–Tropsch synthesis (FTS) under conditions favoring the formation of gaseous and liquid hydrocarbons (P: 1–12 bar; T: 513–543 K; H2/CO:1, 1.5, 2 mol/mol; gas hourly space velocity: 4200–7000 cm3 (STP)/h/gcat). Based on the hypothesis that water inhibits the intrinsic FTS reaction rate, eight kinetic models are considered: six variations of the Langmuir–Hinshelwood–Hougen–Watson representation and two empirical power-law models. The kinetic expression/mechanism that most precisely fits the data assumes the following: (1) CO dissociation is reversible and does not involve hydrogen; (2) all hydrogenation …

Nanoparticle Cerium Oxide And Mixed Cerium Oxides For Improved Fuel Cell Lifetime, Stephen Stewart

Chemical and Biological Engineering ETDs

While there is a rich body of literature concerning of properties of bulk cerium oxide and cerium cations in solution, the discussion has been inappropriately applied to nanoscale cerium oxide resulting in many unexpected or unexplained results. In particular, there is very limited understanding about the properties of cerium oxide and its potential use as a radical scavenger, and how the catalytic properties of cerium oxide change as the particle size approaches the nanoscale. For example, the involvement of Ce+4 and Ce+3 cations in reactions such as hydrogen peroxide decomposition have been investigated for both cerium cations and bulk cerium …

Poly(N-Isopropyl Acrylamide)-Coated Surfaces: Investigation Of Cytotoxicity With Mammalian Cells And The Mechanism Of Cell Detachment, Marta Cooperstein

Chemical and Biological Engineering ETDs

With the increase in life expectancy and with growing numbers of an aging population, there is a rising need worldwide for replacement tissues and organs. One way to address this growing need is through engineered tissues, such as those generated from stimulus-responsive polymers. Stimulus-responsive polymers undergo a physical or chemical change when a stimulus is applied. One such material is poly(N-isopropyl acrylamide), (pNIPAM), which undergoes a conformation change in a physiologically relevant temperature range to release intact mammalian cell monolayers capable of being used to engineer tissues. Two factors currently limit the use of cell sheets for this purpose: 1) …

Modeling Of Kinetically Limited Growth Rate For Solution-Synthesized Germanium Nanocrystals, Nicholas Shoop

Chemical and Biological Engineering ETDs

Solution synthesis is a common method of generating semiconductor nanocrystals. For solution synthesis, many studies have assumed that the growth rate is diffusion-limited with an unphysically low diffusion constant. In this thesis, a model is developed that considers both diffusion and surface kinetics. The diffusion coefficient of Ge monomers through the solvent, octadecene, at elevated synthesis temperatures is estimated to be on the order of 10-5 to 10-4 cm2/sec, while the mass transfer boundary layer thickness is estimated to be on the order of a few nanometers, similar to the nanocrystal size. These two realistic conditions strongly suggest that the …

Development Of Novel Synthetic Methods For Size-Tunable Synthesis Of Superparamagnetic Iron Oxide Nanoparticles, Erika Vreeland

Chemical and Biological Engineering ETDs

The properties of magnetic nanoparticles vary dramatically with size, so reproducibly controlling size is critical for practical applications. This is particularly true when moving into clinical settings, where regulatory approval requires demonstrated reproducibility in efficacy that can only be achieved with excellent size control. A number of methods for the synthesis of magnetic nanoparticles have been published, although the thermal decomposition of iron(III) precursors in organic solvents has been shown to yield high quality particles with low shape and size dispersity. Currents methods lack reproducibility resulting from non-stoichiometric starting materials, and reliance on reaction parameters, such as temperature ramp rate, …

Fundamental Studies On Copper Zeolites For Catalytic No X Abatement, Anuj Arun Verma

Open Access Dissertations

Stringent regulations in mobile NOx emissions have resulted in the development of Standard Selective Catalytic Reduction (SCR) as the dominant NOx abatement technology in lean burn diesel engines. Standard SCR is a reaction of nitric oxide (NO) with ammonia (NH₃), in the presence of oxygen (O ₂) to form nitrogen (N₂) and water (H₂O). Copper containing zeolites show commercially viable SCR performance. Cu-SSZ-13 (CHA framework), a member of this family, is a preferred catalyst for SCR applications because it shows exceptional hydrothermal stability in addition to commercially viable SCR performance. Our work focuses …

Correlation Between Microstructure And Thermionic Electron Emission From Os-Ru Thin Films On Dispenser Cathodes, Phillip D. Swartzentruber, Thomas John Balk, Michael P. Effgen

Chemical and Materials Engineering Faculty Publications

Osmium-ruthenium films with different microstructures were deposited onto dispenser cathodes and subjected to 1000 h of close-spaced diode testing. Tailored microstructures were achieved by applying substrate biasing during deposition, and these were evaluated with scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray spectroscopy before and after close-spaced diode testing. Knee temperatures determined from the close-spaced diode test data were used to evaluate cathode performance. Cathodes with a large {10-11} Os-Ru film texture possessed comparatively low knee temperatures. Furthermore, a low knee temperature correlated with a low effective work function as calculated from the close-spaced diode data. It is proposed …

Preparation & Characterization Of High Purity Cu2 Znsn(Sxse1-X)4 Nanoparticles, Bethlehem G. Negash

Open Access Theses

Research in thin film solar cells applies novel techniques to synthesize cost effective and highly efficient absorber materials in order to generate electricity directly from solar energy. Of these materials, copper zinc tin sulfoselenide (Cu₂ZnSn(S_xSe_1-x) ₄) nanoparticles have shown great promise in solar cell applications due to optimal material properties as well as low cost & relative abundance of materials.^1,2 Sulfoselenide nanoparticles have also a broader impact in other industries including electronics³, LED ⁴, and biomedical research⁵. Of the many routes of manufacturing these class of semiconductors, …

Solvent System Selection For Xylooligosaccharides Separation By Centrifugal Partition Chromatography Using Conductor-Like Screening Model For Real Solvents, He Zhang

Open Access Theses

The production of value-added, bio-based industrial commodity chemicals is an important area in science right now and this study provides an initial step in the recovery of bio-based chemicals from hemicellulose. Hemicellulose is a long chain polymer mostly consisting of xylose, which is a five-carbon sugar, and a variety of other compounds that are ubiquitous in plant life. The hemicellulose polymer chain can be depolymerized into smaller components, called xylooligosaccharides (XOS) with different chain lengths of xylose linked by beta-1-4 glycosidic bonds, using either hot water, or dilute sulfuric acid. The xylooligosaccharides can then be purified from one another from …

Correlating Molecular Architecture Of A Radical Polymer Based Copolymer With Its Electrical Transport Properties, Holly Chan

Open Access Theses

The design and synthesis of electrically-conductive macromolecules can lead to significant improvements in the performance of polymer-based energy conversion devices (e.g., thermoelectric devices). For these organic electronic devices, conjugated polymers have dominated the area of conductive polymers; however, these materials are usually synthesized using conditions that lead to poorly-defined polymers. Furthermore, in these increasingly-standard polymers, the charge transport ability of the polymer thin films is largely affected by the degree of crystallinity, which is a difficult property to control in a reproducible fashion. Therefore, we seek to explore a new class of amorphous, non-conjugated polymers containing a stable radical …

Measurement And Modeling Of Fire Behavior In Leaves And Sparse Shrubs, Dallan R. Prince

Theses and Dissertations

Wildland fuels and fire behavior have been the focus of numerous studies and models which provide operational support to firefighters. However, fuel and fire complexity in live shrubs has resulted in unexpected and sometimes aggressive fire behavior. The combustion of live fuels was studied and modeled, and the results were assimilated into a shrub-scale fire behavior model which assumes fire spread by flame-fuel overlap. Fire spread models have usually assumed that radiation heat transfer is responsible for driving fire spread, but that assumption is a topic of continuing debate, and appears to contradict some experimental observations. A convection-based shrub-scale fire …

Pharmacokinetic Characterization Of Procoagulation Proteins, Nicholas C. Vanderslice

Department of Chemical and Biomolecular Engineering: Dissertations, Theses, and Student Research

The cessation of bleeding in mammals occurs due to a well-conserved sequence of protein activation known as the coagulation cascade. However, people who have a deficiency in one or more proteins in this cascade, whether due to genetics or blood loss, struggle to maintain hemostasis. In order to aid patients in the restoration of hemostasis, exogenous proteins are often administered in response to bleeding events. However, these proteins are limited and costly due to limited supply of donor blood available for the production of plasma-derived proteins and the high cost of mammalian cell bio-reactors required for the production of recombinant …

Optimal Aggregation Of Fcεri With A Structurally Defined Trivalent Ligand Overrides Negative Regulation Driven By Phosphatases, Avanika Mahajan, Dipak Barua, Patrick Cutler, Diane S. Lidke, Flor A. Espinoza, Carolyn Pehlke, Rachel Grattan, Yuko Kawakami, Chang-Shung Tung, Andrew R. M. Bradbury, William S. Hlavacek, Bridget S. Wilson

Chemical and Biochemical Engineering Faculty Research & Creative Works

To investigate why responses of mast cells to antigen-induced IgE receptor (FcεRI) aggregation depend nonlinearly on antigen dose, we characterized a new artificial ligand, DF3, through complementary modeling and experimentation. This ligand is a stable trimer of peptides derived from bacteriophage T4 fibritin, each conjugated to a hapten (DNP). We found low and high doses of DF3 at which degranulation of mast cells sensitized with DNP-specific IgE is minimal, but ligand-induced receptor aggregation is comparable to aggregation at an intermediate dose, optimal for degranulation. This finding makes DF3 an ideal reagent for studying the balance of negative and positive signaling …

Horseradish Peroxidase-Attapulgite Clay Nanocomposites: Fabrication And Application To Sensing The Extracellular H2O2 Released From Cells, Ping Wu, Chen-Xin Cai

Journal of Electrochemistry

The nanostructured attapulgite clay was employed as a support matrix for immobilizing horseradish peroxidase (HRP). FTIR and electrochemical methods demonstrated that HRP had been effectively assembled on attapulgite surface with the formation of HRP-attapulgite nanocomposites. The HRP-attapulgite hybrid was deposited on the glassy carbon (GC) electrode forming the HRP-attapulgite/GC electrode. Cyclic voltammetric results showed a pair of well-defined redox peaks, which were ascribed to direct electron transfer (DET) of HRP, with the formal potential E₀′ = -335 mV (vs. SCE) in the phosphate buffer solution (PBS, pH 7.0). The dependence of E₀′ on solution pH indicated …

The Ionic Diffusion Model For The Solid Oxide Cathode And Its Verification By The Electrolysis Of Ta2O5 In Molten Cacl2, Hua-Lin Chen, Zhi-Yong Wang, Xian-Bo Jin, George Z. Chen

Journal of Electrochemistry

The deoxidation speed of a solid oxide cathode in molten CaCl₂ can be estimated by the PRS steady diffusion model of O^2-, which correlates the deoxidation speed with the precursor porosity, P, the metal-to-oxide molar volume ratio, R, and the cathode volume shrinkage S. The PRS model indicates that the porosity of the oxide cathode has important influence on the deoxidation speed, and provides a very simple equation for the prediction of the optimal cathode porosity. For the electrolysis of Ta₂O₅, the porosity of the cathode is better to be within 50%. …