Engineering Commons^™

Surface Modification Of Nanoplatelets In Polymer Nanocomposites, Shailesh K. Shori

Theses and Dissertations

In polymer nanocomposites (PNCs), it is very important that the nanofiller (typically an inorganic) is well-dispersed in an organic polymer matrix. Optimal compatibility results in end-use products such as packaging materials with enhanced properties. In practice, however, this is challenging to achieve because “ideal” dispersions require the complete uniform separation, termed exfoliation, of the nanofiller within the matrix. As a result, different nanofillers including calcium niobate (CN) and montmorillonite (MMT) are first studied for their ability to exfoliate in aqueous suspensions by measuring the organic cation uptake. The cation exchange capacity, or CEC, determined that CN needs further work before …

Theoretical Investigation Of The Catalytic, Liquid-Phase Hydrodeoxygenation Of Organic Acids And Esters, Sina Behtash

Theses and Dissertations

With worldwide fossil fuel resources dwindling and greenhouse gas emissions rising, it is urgent to find renewable liquid fuel alternatives from e.g. biomass to meet the world’s growing energy demand. Lipid feedstocks and pyrolysis oils from woody biomass can be utilized for the production of second-generation biofuels via a catalytic hydrodeoxygenation (HDO) process. The conversion of fatty acids and esters plays an important role in the activity and selectivity of these processes. Understanding the HDO reaction mechanism of organic acids and esters on metal surfaces is a prerequisite for the rational design of new HDO catalysts specifically designed for upgrading …

Synthesis Of Au And Ag Catalysts With Controlled Sizes Of Metal Particles, Eleni A. Kyriakidou

Theses and Dissertations

The performance of supported metal catalysts largely depends on the structure and composition of the metal particles and the nature of the support. In order to achieve better control over these parameters, synthetic route based on the use of templating agents has been proposed. Among the different templating agents, poly(amidoamine) (PAMAM) dendrimers have attracted a lot of recent attention as nanoparticle stabilizers. In this thesis, Au/G4OH nanocomposites were synthesized in aqueous solutions and used as precursors for the preparation of SiO2-supported Au nanoparticles. Elemental analysis, UV-Vis, and STEM measurements were used to estimate the extent of the Au-dendrimer interactions and …

Quantifying Individual Losses In A Direct Methanol Fuel Cell, Jennifer Rae Ruffing

Theses and Dissertations

The performance of a direct methanol fuel cell (DMFC) is complicated due to the complex interactions of kinetic and transport processes. As a result, changes in one aspect of the cell have consequences in other aspects, which are difficult to elucidate from the full-cell polarization (i.e. voltage vs. current) behavior that fuel cell researchers often use to characterize the performance of their systems. The objective of this work was to develop a strategy to use current and voltage relationships from anode half cells, cathode half-cells, and a hydrogen pump, coupled with methanol crossover data and a mathematical model, to quantify …

Novel Biofabrication Technologies To Recapitulate In Vivo Geometries In Collagen Hydrogels, Veronica Rodriguez-Rivera

Theses and Dissertations

Tissue engineering and regenerative medicine aims to restore form and function to tissues that have been lost or damaged due to disease, congenital defect, or trauma. Biomaterials suitable to restore these complex tissues need to provide a balance between chemical and mechanical properties, providing accurate cell-matrix interaction and induce in vivo behaviors such as proliferation, differentiation and migration. It also requires that physical and chemical cues be presented to the body in the proper temporal and spatial pattern. The extracellular matrix exerts forces that are transmitted through focal adhesion causing changes in the cell behavior. The hypothesis for this dissertation …

A Three-Dimensional-Engineered Matrix To Study The Microenvironment Of Cancer Stem Cells, Samaneh Kamali Sarvestani

Theses and Dissertations

Maintenance of cancer stem cells (CSCs) is regulated by their microenvironment. As cancer cells are affected by many factors in their microenvironment, a major challenge is to isolate the effect of a specific factor on CSCs while keeping other factors unchanged. We developed a synthetic inert 3D Poly Ethylene Glycol Di-Acrylate (PEGDA) gel culture system as a unique tool to study the effect of microenvironmental factors on CSCs response. Synthetic hydrogels provide the flexibility to design three-dimensional (3D) matrices to isolate and study individual factors in the tumor microenvironment. The first objective of this work was to investigate the effect …

Bio-Active Degradable Micellar Hydrogels For Osteogenic Differentiation Of Mesenchymal Stem Cells, Seyedsina Moeinzadeh

Theses and Dissertations

A feasible approach to the restoration of injured bone tissue is the use of tissue engineering strategies to deliver mesenchymal stem cells (MSCs) to the site of regenration in degradable, in-situ gelling, bio-active hydrogels. Although inert Polyethylene glycol (PEG) hydrogels provide flexibility in controlling the cell microenvironment, their use for in vivo applications in tissue regeneration is limited by their persistence (nondegradability) in the site of regeneration. In an attempt to produce inert hydrolytically degradable matrices for encapsulation of MSCs, hydrogels based on star PEG macromonomers chain-extended with short hydroxy acid (HA) segments (SPEXA) were synthesized and characterized with respect …

Novel Nanostructured Materials For Solar Fuel Production And Advanced Rechargeable Batteries, Cunyu Zhao

Theses and Dissertations

Non-renewable fossil fuels are the major sources to meet the energy, electricity and transportation demands of today's world. The over consumption of fossil fuels will lead to the increasing energy crisis and disastrous effects such as air pollution, global warming etc.

The primary greenhouse gas is CO2 mainly emits from the combustion of fossil fuels. Photocatalytic reduction of CO2 using sunlight as the energy input is a promising way to reduce CO2 level in the atmosphere and in the meantime produce alternative fuels such as CO, methane, methanol, etc. Among the various photocatalyst materials reported, nanomaterial TiO2 is the most …

Optimized Photogrammetric Network Design With Flight Path Planner For Uav-Based Terrain Surveillance, Ivan Yair Rojas

Theses and Dissertations

This work demonstrates the use of genetic algorithms as a stochastic optimization technique for developing a camera network design and the flight path for photogrammetricapplications using Small Unmanned Aerial Vehicles. This study develops a Virtual Optimizer for Aerial Routes (VOAR) as a new photogrammetric mapping tool for acquisition of images to be used in 3D reconstruction. 3D point cloud models provide detailed information on infrastructure from places where human access may be difficult. This algorithm allows optimized flight paths to monitor infrastructure using GPS coordinates and optimized camera poses ensuring that the set of images captured is improved for 3D …

Kinetic Experimental And Modeling Studies On Iron-Based Catalysts Promoted With Lanthana For The High-Temperature Water-Gas Shift Reaction Characterized With Operando Uv-Visible Spectroscopy And For The Fischer-Tropsch Synthesis, Basseem Bishara Hallac

Theses and Dissertations

The structural and functional roles of lanthana in unsupported iron-based catalysts for the high-temperature water-gas shift reaction and Fischer-Tropsch synthesis were investigated. The performance of the catalysts with varying lanthana contents was based on their activity, selectivity, and stability. With regard to the former reaction, extent of reduction of the iron in Fe2O3/Cr2O3/CuO/La2O3 water-gas shift catalysts is a key parameter that was characterized using UV-visible spectroscopy. Minor addition of lanthana (<0.5 wt%) produces more active and stable catalysts apparently because it stabilizes the iron-chromium spinel, increases the surface area of the reduced catalysts, enhances the reduction of hematite to the magnetite active phase, and facilitates the adsorption of CO on the surface of the catalyst modeled by an adsorptive Langmuir-Hinshelwood mechanism. Statistical 95% confidence contour plots of the adsorption equilibrium constants show that water adsorbs more strongly than CO, which inhibits the reaction rate. A calibration curve that correlates the oxidation state of surface iron domains to normalized absorbance of visible light was successfully generated and applied to the water-gas shift catalysts. UV-visible studies indicated higher extent of reduction for surface Fe domains for the catalysts promoted with 1 wt% of lanthana and showed potential to be a more convenient technique for surface chemistry studies than X-ray absorption near edge spectroscopy (XANES). Lanthana addition to iron-based Fischer-Tropsch catalysts enhances the olefin-to-paraffin ratio, but decreases their activity, stability, and selectivity to liquid hydrocarbons. Adding lanthana at the expense of potassium reduces the water-gas shift selectivity and enhances the activity and stability of the catalysts. Finally, a model that simulates heat and mass transfer limitations on the particle scale for the Fischer-Tropsch reaction applicable at lab-scale suggests optimal operating and design conditions of 256°C, 30 bar, and 80 mirons are recommended for higher selectivity to liquid hydrocarbons. The model considers pressure drop, deactivation, pore diffusion, film heat transfer, and internal heat transfer when solving for the optimal conditions, and maps them as functions of design variables. This model can be up-scaled to provide guidance for optimal design of commercial-size reactors.

Preparation Of Active, Stable Supported Iron Catalysts And Deactivation By Carbon Of Cobalt Catalysts For Fischer-Tropsch Synthesis, Kamyar Keyvanloo

Theses and Dissertations

The first half of this dissertation reports the development of supported Fe FT catalysts including the effects of various, carefully chosen preparation methods on the performance of alumina-supported iron/copper/potassium (FeCuK/Al2O3); it was determined that non-aqueous slurry impregnation and co-impregnation yielded catalysts with activities as high as any reported in the literature. Furthermore, the effects of support properties including pore size, hydroxyl group concentration, and support stabilizer were investigated for FeCuK/Al2O3 catalysts containing 20 or 40% Fe. For the first time, we report the performance of a supported Fe FT catalyst that is not only more active and stable than any …

Gasification Of Biomass, Coal, And Petroleum Coke At High Heating Rates And Elevated Pressure, Aaron D. Lewis

Theses and Dissertations

Gasification is a process used to convert any carbonaceous species through heterogeneous reaction to obtain the desired gaseous products of H2 and CO which are used to make chemicals, liquid transportation fuels, and power. Both pyrolysis and heterogeneous gasification occur in commercial entrained-flow gasifiers at pressures from 4 to 65 atm with local gas temperatures as high as 2000 °C. Many gasification studies have been performed at moderate temperatures, heating rates, and pressures. In this work, both pyrolysis and char gasification experiments were performed on coal, petroleum coke, and biomass at conditions pertinent to commercial entrained-flow gasifiers. Rapid biomass pyrolysis …

Development Of Experiments Involving Pharmaceutical Manufacturing Principles, Alexander Struck Jannini

Theses and Dissertations

Laboratory experiments were developed to incorporate pharmaceutical engineering concepts into Freshman-level engineering courses. The goal is to increase the interest of pharmaceutical engineering in students and provide the necessary background for more advanced courses in the field. The experiments can be used on an individual basis, or to be grouped into themes for more focused learning objectives. The laboratory experiments are available at the pharmaceutical knowledge and training website www.PharmaHUB.org under the Teaching Resources tab.

Use Of Blood Oxygenator Membrane Units In Teaching Mass Balances, Friction Factor And Mass Transfer Analysis, Keith Mciver

Theses and Dissertations

Many applications of chemical engineering principles are biomedical but traditional chemical engineering education does not focus on these applications. New laboratory experiments with hollow fiber blood oxygenators allow integration of concepts into already full programs. This work describes three new educational experiments that have been developed to introduce students to concepts of mass balances, mass transfer and momentum transfer as applied to a hollow fiber blood oxygenator. In addition, a new mass transfer correlation is presented for the Medtronic Affinity NT blood oxygenator, which has not been reported previously in the literature. Mass transfer of oxygen through the hollow fiber …

Theoretical Investigation Of Heterogeneous Catalysis At The Solid–Liquid Interface For The Conversion Of Lignocellulosic Biomass Model Molecules, Muhammad Faheem

Theses and Dissertations

Catalytic conversion of biomass-derived oxygenates to fuels and value-added chemicals is a promising strategy in the search for renewable and sustainable energy sources. Most relevant catalytic processes are carried out in an aqueous environment using supported transition metal catalysts. The reaction network consists of multiple series and parallel pathways leading to formation of hydrogen, alkanes, and lighter oxygenates. The final product distribution ultimately depends on the sequence and competition of C−C, C−O, C−H, and O−H bonds scissions. Ethylene glycol (EG) is the simplest model molecule of various biomass-derived polyols that has a C:O stoichiometry of 1:1 and contains all relevant …

Synthesis, Characterization And Evaluation Of Ir-Based Bimetallic Catalysts, You Jung Song

Theses and Dissertations

This dissertation considers effective bimetallic preparation for supported Ir-based bimetallic catalysts and their catalytic activity. Since bimetallic catalysts exhibit significantly different catalytic and chemical properties than their corresponding monometallic components by providing enhanced selectivity, stability and /or activity, many monometallic catalysts in industrial processes have been replaced by bimetallic catalysts. However, conventional synthetic methods used to produce monometallic and bimetallic catalysts often result in wide particle size distributions and non-uniform materials which can be difficult to characterize on a fundamental level. Two alternate preparation methods, dendrimer templating and electroless deposition, are developed and compared with conventional incipient wetness method. In …

Synthesis Of Graphitic Carbon Nanostructures And Use As Electrocatalyst For Oxygen Reduction Reaction, Daniel A. Moniot

Theses and Dissertations

Graphitic carbon nanostructure (GCN) was synthesized by a simple procedure using cobalt(II) gluconate as a precursor and used as a catalyst support for polymer electrolyte membrane (PEM) fuel cell cathode. A novel stabilization procedure was developed to enhance the thermal stability of the GCN support. Support stabilization resulted in well-defined crystalline graphitic hollow structures as confirmed by highresolution transmission electron microscope (HRTEM). The prepared GCNs are used as support for depositing platinum nanoparticles (size) by modified polyol process. Rotating ring disk electrode (RRDE) and fuel cell studies were carried out to evaluate the catalyst performance. Cycling studies (0.6-1.0 V vs. …

Ultrathin Graphene Oxide Membranes/Coatings For Separations, Hang Li

Theses and Dissertations

Graphene oxide (GO) was utilized as a novel material for making ultrathin membranes for gas separation and for making functional coatings for nano-/ultra-filtration in oil/water separation. Fundamental separation mechanisms by ultrathin GO membranes/coatings and potential applications were explored. This work can be divided into three parts. In the first part, ultrathin GO membranes supported on flat and smooth anodic aluminum oxide (AAO) substrates, with thickness down to 1.8 nm, were prepared by a facile vacuum filtration method. The as-prepared GO membranes were then studied for single-gas permeation and hydrogen mixture separation. It was revealed that the separation mechanism for the …

Gas-Phase, Catalytic Hydrodeoxygenation Of Propanoic Acid Over Supported Group Viii Noble Metals, Yuliana K. Lugo José

Theses and Dissertations

Recent advances for the deoxygenation of biomass, have demonstrated that hydrodeoxygenation (HDO) is one of the most promising route for the upgrading pyrolysis bio-oils. Catalytic hydrodeoxygenation of pyrolysis bio-oil have shown to be an efficient and economical process, since the raw materials consist mainly of waste. Propanoic Acid (PAc) is considered as one of the main constituents of pyrolysis bio-oils. However, these carboxylic acids are extremely corrosive and difficult to deoxygenate. Therefore, much effort have been given to the development of novel catalytic techniques, to improve the activity, stability and selectivity for the HDO of carboxylic acids.

This dissertation explores …

Polymer Nano-Dielectrics For High Density Energy Storage, Sayful Islam Md

Theses and Dissertations

Military and commercial users require next-generation polymer dielectric materials for pulse power and power conditioning applications with rise times less than 1 ms and AC power at frequencies ranging from kHz to MHz. These power density and rate capability requirements necessitate the use of dielectric capacitors that store energy via polarization of electrons in molecular scale dipoles. Multiphase polymer composites and all-polymer dielectrics could be new kinds of materials to meet this acute need for capacitors with compact size and high rate capability.

The polymer nanocomposite (PNC) approach to achieve high energy density employed a “colossal” dielectric constant material, calcium …

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 …

Design Of A Light-Weight Low-Volume High Oxygen Storage Density Material, Nicholas Robert Schwartz

Theses and Dissertations

A compact, lightweight, dense and safe method for storing and supplying oxygen remains a large hurdle for closed-circuit self-contained breathing apparatus (SCBA) and respiratory protective equipment. No filter that can protect against airborne chemical, biological, radiological, and nuclear (CBRN) contaminants exists, which presents the need for an isolated oxygen source. Heavy and high maintenance oxygen cylinders are typically used. The most important criteria for a smart and effective CBRN protection device are safety, weight, size, and cost, level of maintenance, ease-of-use and reliability. This study focused on nanomaterials for high capacity gas storage. Nanocapillary arrays composed of anodic aluminum oxide …

Enhancement Of Mass Transfer And Electron Usage For Syngas Fermentation, James J. Orgill

Theses and Dissertations

Biofuel production via fermentation is produced primarily by fermentation of simple sugars. Besides the sugar fermentation route, there exists a promising alternative process that uses syngas (CO, H2, CO2) produced from biomass as building blocks for biofuels. Although syngas fermentation has many benefits, there are several challenges that still need to be addressed in order for syngas fermentation to become a viable process for producing biofuels on a large scale. One challenge is mass transfer limitations due to low solubilities of syngas species. The hollow fiber reactor (HFR) is one type of reactor that has the potential for achieving high …

Engineering Cell-Free Systems For Vaccine Development, Self-Assembling Nanoparticles And Codon Reassignment Applications, Mark T. Smith

Theses and Dissertations

This dissertation reports on the technology of cell-free protein synthesis (CFPS) including 1) stabilized lyophilized cell-free systems and 2) enhanced heterogeneous cell extracts. This work further considers applications of CFPS systems in 1) rapid vaccine development, 2) functional virus-based nanoparticles, 3) site-specific protein immobilization, and 4) expanding the language of biology using unnatural amino acids. CFPS technology is a versatile protein production platform that has many features unavailable in in vivo expression systems. The primary benefit cell-free systems provide is the direct access to the reaction environment, which is no longer hindered by the presence of a cell-wall. The “openness" …

A New Software Tool To Environmentally And Economically Evaluate Solvent Recovery In The Pharmaceutical Industry, Eduardo Cavanagh

Theses and Dissertations

The environmental impact reduction and operating costs savings associated with the purification and reuse of solvent waste in the manufacture of active pharmaceutical ingredients (API's) were investigated. A software toolbox has been developed that combines Aspen Plus(R) process simulation with SimaPro(R) and Ecosolvent life cycle assessment (LCA) databases. The feasibility of a relatively small flexible skid capable of recovering multiple solvent waste streams was evaluated. Fractional distillation and pervaporation were considered to separate binary solvent waste mixtures. Optimum distillation reflux ratio and feed stage were determined to maximize the environmental impact reductions and operating cost savings. The optimum reflux ratio …

Toward Polymer Coating With Easy Ice Release, Chenyu Wang

Theses and Dissertations

Minimizing adhesion of ice has been the subject of extensive studies for applications such aircraft wings, wind turbine blades spacecraft, power transmission wires, while a growing interest concerns coatings for aerospace applications. The work described here describes progress for coatings and ice release test method development over the last few years. Major achievements include: (1) New Rigid Adherent-Resistant Elastomers (RARE), (2) A new Epoxied Cylinder (EC) adhesion test, (3) Validation of an ice release test, and (4) Study of ice adhesion strength on coating thickness for a PDMS elastomer. Rigid Adhesion-Resistance Elastomers (RARE) are comprised of 3F 1 terminated with …

Electrochemical, Interfacial, And Surface Studies Of The Conversion Of Carbon Dioxide To Liquid Fuels On Tin Electrodes, Jingjie Wu

Theses and Dissertations

The electrochemical reduction of carbon dioxide (CO2) into liquid fuels especially coupling with the intermittent renewable electricity offers a promising means of storing electricity in chemical form, which reduces the dependence on fossil fuels and mitigates the negative impact of anthropogenic CO2 emissions on the planet. Although converting CO2 to fuels is not in itself a new concept, the field has not substantially advanced in the last 30 years primarily because of the challenge of discovery of structural electrocatalysts and the development of membrane architectures for efficient collection of reactants and separation of products. An efficient catalyst for the electrochemical …

High Fidelity Chemistry And Radiation Modeling For Oxy-Combustion Scenarios, Hassan A. Abdul Sater

Theses and Dissertations

To account for the thermal and chemical effects associated with the high CO₂ concentrations in an oxy-combustion atmosphere, several refined gas-phase chemistry and radiative property models have been formulated for laminar to highly turbulent systems. This thesis examines the accuracies of several chemistry and radiative property models employed in computational fluid dynamic (CFD) simulations of laminar to transitional oxy-methane diffusion flames by comparing their predictions against experimental data. Literature review about chemistry and radiation modeling in oxy-combustion atmospheres considered turbulent systems where the predictions are impacted by the interplay and accuracies of the turbulence, radiation and chemistry models. Thus, …

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 …

Development Of A Pressure Swing Adsorption Process For Co2 Capture From Flue Gas Using Solid Amine Sorbents, Anahita Abdollahi Govar

Theses and Dissertations

Solid amines are comprised of adsorbent materials, like silica gel, that contain amine based organic compounds, either physically or chemically, attached within their pores. The major characteristic of these sorbents that makes them interesting for CO₂ capture from flue gas is that unlike zeolites they are not negatively affected by the presence of water. The current work has been focusing on the development of a novel PSA cycle for CO₂ capture from flue gas using a solid-amine sorbent composed of PEI physically immobilized on a commercial silica substrate. The goal was to achieve > 90% recovery and > 95 vol. …