Engineering Commons^™

Volume-Phase Transitions In Responsive Photo-Cross-Linked Polymer Network Films, Leena Patra

USF Tampa Graduate Theses and Dissertations

The overall thrust of this project is to gain an insight into a class of surface-tethered cross-linked thin films of poly(N-alkylacrylamides) that display a lower critical solution temperature (LCST).The structure of the alkyl group and the modification of the amide groups determine the LCST and resultant volume-phase transition behavior. The aim of this study involves synthesis and characterization of thin films and to correlate the volume-transition behavior to the structure of the alkyl group. For better understanding the volume-transition behavior, the polymer films are perturbed by the Hofmeister salt series to examine trends between different alkyl groups. While most of …

Novel Blends Of Sulfur-Tolerant Water-Gas Shift Catalysts For Biofuel Applications, Timothy Michael Roberge

USF Tampa Graduate Theses and Dissertations

As traditional sources of energy become depleted, significant research interest has gone into conversion of biomass into renewable fuels. Biomass-derived synthesis gas typically contains concentrations of approximately 30 to 600 ppm H2S in stream. H2S is a catalyst poison which adversely affects downstream processing of hydrogen for gas to liquid plants. The water-gas shift reaction is an integral part of converting CO and steam to H2 and CO2. Currently, all known water-gas shift catalysts deactivate in sulfur concentrations typical of biomass-derived synthesis gas. Novel catalysts are needed to remain active in the presence of sulfur concentrations in order to boost …

Catalytic Tri-Reforming Of Biomass-Derived Syngas To Produce Desired H2:Co Ratios For Fuel Applications, Devin Mason Walker

USF Tampa Graduate Theses and Dissertations

This study focuses on upgrading biomass derived syngas for the synthesis of liquid fuels using Fischer-Tropsch synthesis (FTS). The process includes novel gasification of biomass via a tri-reforming process which involves a synergetic combination of CO2 reforming, steam reforming, and partial oxidation of methane. Typical biomass-derived syngas H2:CO is 1:1 and contains tars that deactivate FT catalyst. This innovation allows for cost-effective one-step production of syngas in the required H2:CO of 2:1 with reduction of tars for use in the FTS. To maximize the performance of the tri-reforming catalyst, an attempt to control oxygen mobility, thermal stability, dispersion of metal, …

Smart Packaging: A Novel Technique For Localized Drug Delivery For Ovarian Cancer, Eva Christabel Williams

USF Tampa Graduate Theses and Dissertations

Localized drug delivery is emerging as an effective technique due to its ability to administer therapeutic concentrations and controlled release of drugs to cancer sites in the body. It also prevents the contact of harsh chemotherapy drugs to healthy regions in the body that otherwise would become exposed to current treatments.

This study reports on a model chemotherapy drug delivery system comprising non-ionic surfactant vesicles (niosomes) packaged within a temperature-sensitive chitosan network. This smart packaging, or package-within-a package system, provides two distinct advantages. First, the gel prevents circulation of the niosomes and maintains delivery in the vicinity of a tumor. …

Aggregation Of Sediment And Bacteria With Mucilage From The Opuntia Ficus-Indica Cactus, Audrey Lynn Buttice

USF Tampa Graduate Theses and Dissertations

Flocculants are commonly used in industrial settings where solid-liquid separations are desired including industrial and municipal wastewater management and potable water production facilities. Conventional flocculants include inorganic metal salts and synthetic organic polymers. The cost, availability, and harmful effects of the non-biodegradable nature of these flocculants have led to the widespread study of natural flocculants. Current natural flocculants being studied include polysaccharides cultivated from microbial extracellular matrix products and plant based materials. In this study, the mucilage of Opuntia ficus-indica cactus was evaluated as a natural flocculant for sediments and bacteria. The O. ficus-indica cactus is also known as the …

Shape-Shifting Surfaces For Rapid Release And Direct Stamping Of Organized Micro-Tissues, Samuel James Dupont

USF Tampa Graduate Theses and Dissertations

The primary aim of the research in this study is to develop a robust and simple platform for the in vitro organization of cells on surfaces which facilitate rapid cell release and allows for the direct stamping of highly organized micro-tissues. Current approaches towards this goal have been very successful but are lengthy and subject cells to harsh conditions for extended periods of time raising questions regarding cell health and maintenance of physiological state. To address these concerns a platform was developed to allow for rapid cell release by utilizing a release mechanism different from previous work.

Micron-scale structures comprised …

Precipitation Of Phosphate Minerals From Effluent Of Anaerobically Digested Swine Manure, Alex Y. Lin

USF Tampa Graduate Theses and Dissertations

Swine production represents approximately 40% of the world's meat production, and its wastes contain high concentrations of organic carbon, nitrogen (N), and phosphorus (P). Anaerobic digestion is an increasingly popular technology for treating animal wastes while simultaneously generating energy. Its propagation and ability to solubilize organic N and P make adding a struvite recovery process attractive. Recovering struvite (MgNH4PO4) from anaerobically digested swine waste can address global P shortages, meet P discharge guidelines, and produce slow-release fertilizer, which can be sold for revenue.

Anaerobic digesters were operated with at organic loading rates of 3.4-3.9 g volatile solids per liter per …

Design Of Colloidal Composite Catalysts For Co2 Photoreduction And For Co Oxidation, Bijith D. Mankidy

USF Tampa Graduate Theses and Dissertations

In this doctoral dissertation, novel colloidal routes were used to synthesize nanomaterials with unique features. We have studied the impact of nanoparticle size of catalyst, role of high surface area of a photocatalyst, and the effect of varying elemental composition of co-catalytic nanoparticles in combination with core-shell plasmonic nanoparticles. We have demonstrated how physical and chemical characteristics of nanomaterials with these unique features play a role in catalytic reactions, specifically the oxidation of CO and the photoreduction of CO2. The first objective of this doctoral dissertation involved the preparation of CoO nanoparticles with discrete nanoparticles sizes (1-14 nm) using a …

Prediction Of Tar And Light Gas During Pyrolysis Of Black Liquor And Biomass, Thomas H. Fletcher, Harland R. Pond, Jarom Webster, Judson Wooters, Larry L. Baxter

Faculty Publications

A generalized model for describing the pyrolysis behavior of low-grade fuels is being developed for incorporation into larger combustion simulation models. Light gas and tar yields from black liquor or biomass pyrolysis can be predicted using the chemical percolation devolatilization (CPD) model originally developed for coal. The initial approach is to measure the average chemical structures in a black liquor sample using 13C NMR spectroscopy. These chemical structures are then used in pyrolysis model predictions. With few changes from the coal-derived kinetic parameters, the model describes the organic pyrolysis behavior of black liquor samples obtained in a nitrogen-purged furnace. It …

A Cfd Model For Thermal Conversion Of Thermally Thick Biomass Particles, Ramin Mehrabian, Selma Zahirovic, Robert Scharler, Ingwald Obernberger, Stefan Kleditzsch, Siegmar Wirtz, Victor Scherer, Hong Lu, Larry L. Baxter

Faculty Publications

A one-dimensional model for the thermal conversion of thermally thick biomass particles is developed for the simulation of the fuel bed of biomass grate furnaces. The model can be applied for cylindrical and spherical particles. The particle is divided into four layers corresponding to the main stages of biomass thermal conversion. The energy and mass conservation equations are solved for each layer. The reactions are assigned to the boundaries. The model can predict the intra-particle temperature gradient, the particle mass loss rate as well as the time-dependent variations of particle size and density, as the most essential features of particle …

Critical And Phase-Equilibrium Properties Of An Ab Initio Based Potential Model Of Methanol And 1-Propanol Using Two-Phase Molecular Dynamics Simulations, Sonal Patel, W. Vincent Wilding, Richard L. Rowley

Faculty Publications

Two-phase molecular dynamics simulations employing a Monte Carlo volume sampling method were performed using an ab initio based force field model parameterized to reproduce quantum-mechanical dimer energies for methanol and 1-propanol at temperatures approaching the critical temperature. The intermolecular potential models were used to obtain the binodal vapor-liquid phase dome at temperatures to within about 10 K of the critical temperature. The efficacy of two all-atom, site-site pair potential models, developed solely from the energy landscape obtained from high-level ab initio pair interactions, was tested for the first time. The first model was regressed from the ab initio landscape without …

Formation Of Organized Nanostructures From Unstable Bilayers Of Thin Metallic Liquids, Mikhail Khenner, Sagar Yadavali, Ramki Kalyanaraman

Mathematics Faculty Publications

Dewetting of pulsed-laser irradiated, thin (< 20 nm), optically reflective metallic bilayers on an optically transparent substrate with a reflective support layer is studied within the lubrication equations model. A steady-state bilayer film thickness (h) dependent temperature profile is derived based on the mean substrate temperature estimated from the elaborate thermal model of transient heating and melting/freezing. Large thermocapillary forces are observed along the plane of the liquid-liquid and liquid-gas interfaces due to this h-dependent temperature, which, in turn, is strongly influenced by the h-dependent laser light reflection and absorption. Consequently the dewetting is a result of the competition between thermocapillary and intermolecular forces. A linear analysis of the dewetting length scales established that the non-isothermal calculations better predict the experimental results as compared to the isothermal case within the bounding Hamaker coefficients. Subsequently, a computational non-linear dynamics study of the dewetting pathway was performed for Ag/Co and Co/Ag bilayer systems to predict the morphology evolution. We found that the systems evolve towards formation of different morphologies, including core-shell, embedded, or stacked nanostructure morphologies.

Analysis Of Biomass/Coal Co-Gasification For Integrated Gasification Combined Cycle (Igcc) Systems With Carbon Capture, Henry A. Long Iii

LSU New Orleans Theses and Dissertations

In recent years, Integrated Gasification Combined Cycle Technology (IGCC) has become more common in clean coal power operations with carbon capture and sequestration (CCS). Great efforts have been spent on investigating ways to improve the efficiency, reduce costs, and further reduce greenhouse gas emissions. This study focuses on investigating two approaches to achieve these goals. First, replace the subcritical Rankine steam cycle with a supercritical steam cycle. Second, add different amounts of biomass as feedstock to reduce emissions. Finally, implement several types of CCS, including sweet- and sour-shift pre-combustion and post-combustion.

Using the software, Thermoflow®, this study shows that utilizing …

Chemical Templating By Afm Tip-Directed Nano-Electrochemical Patterning, Kyle A. Nelson

Theses and Dissertations

This work has examines the creation and use of chemical templates for nanocircuit and other nanodevice fabrication. Chemical templating can be useful in attachment, orientation and wiring of molecularly templated circuits. DNA origami provides a suitable method for creating molecularly templated circuits as DNA can be folded into complex shapes and functionalized with active circuit elements, such as semiconducting nanomaterials. Surface attachment of DNA origami structures can be accomplished by hybridization of dangling single-stranded DNA (ssDNA) on the origami structures with complementary surface-bound strands. Chemical templating provides a pathway for placing the patterned surface-bound attachment points needed for surface alignment …

Modeling Solid Propellant Ignition Events, Daniel A. Smyth

Theses and Dissertations

This dissertation documents the building of computational propellant/ingredient models toward predicting AP/HTPB/Al cookoff events. Two computer codes were used to complete this work; a steady-state code and a transient ignition code Numerous levels of verification resulted in a robust set of codes to which several propellant/ingredient models were applied. To validate the final cookoff predictions, several levels of validation were completed, including the comparison of model predictions to experimental data for: AP steady-state combustion, fine-AP/HTPB steady-state combustion, AP laser ignition, fine-AP/HTPB laser ignition, AP/HTPB/Al ignition, and AP/HTPB/Al cookoff. A previous AP steady-state model was updated, and then a new AP …

Proteome Based Development Of Novel Affinity Tail For Immobilized Metal Affinity Chromatography And Hydrophobic Interaction Chromatography, Neha Tiwari

Graduate Theses and Dissertations

At industrial scale, reducing the step in purification and recovery is desired; this not only decreases the cost but also increases the yield. Hydrophobic Interaction Chromatography (HIC) and Immobilized Metal Affinity Chromatography (IMAC) both are not harsh on biological structure or activity of proteins; also both the techniques are economical and therefore a suitable choice at industrial level. This dissertation comprises of three parts. Purpose for the Part I was to identify and characterize Escherichia coli proteins which display affinity towards both IMAC and Hydrophobic Interaction Chromatography (HIC). Co (II) IMAC was chosen as the primary capture step, followed by …

Nanoparticle Necklace Network Arrays Exhibiting Room Temperature Single-Electron Switching, Jennifer L. Kane

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

A single nanoparticle is one of the most sensitive electronic devices for sensing chemicals in a gas or liquid. The conductivity of a single Au nanoparticle is significantly modulated by the binding of a molecule that alters charge by just one electron. However, the single-electron sensitivity requires cryogenic temperatures and interconnection is not easy. A patterned two-dimensional network of one-dimensional nanoparticle necklaces made up of 10 nm Au particles are fabricated and shown to exhibit similar single-electron effect at room temperature. Furthermore, the long range conductivity of over 10’s of microns makes the structure easy to self-assemble onto conventional microelectronics …

Chlorine Absorption Utilizing Caustic Sodium Sulfite, Henry Mcdonald

All Theses

A scrubber was required to abate a waste stream containing chlorine gas created in the electrolytic dissolution step of the aqueous polishing process at the Mixed Oxides Fuel Fabrication Facility at Savannah River Site, South Carolina. A method of absorption that utilized caustic sodium sulfite as the scrubbing agent was studied for implementation in the process. This method was found to be highly efficient with respect to process requirements, and it was also found to provide enhanced performance over the more conventional method of chlorine scrubbing which uses only aqueous sodium hydroxide as a reagent. Sulfite provides an additional advantage …

Optofluidic Glucose Sensor Utilizing An Epoxy-Based, Transparent Dry Film Resist, Zhan Gao, Sijia Gong, Chang Soo Kim, David B. Henthorn

Electrical and Computer Engineering Faculty Research & Creative Works

An enzymatic, fluorescent glucose sensor was constructed with a novel epoxy-Based, optically transparent dry film resist (PerMX 3000 series, DuPont). This material was utilized as the main active material for fluidic structure and optical interrogation. This sensor was based on the enzymatic reaction of glucose oxidase (GOD) and utilized a ruthenium complex fluorophore as the reporting agent. Both the oxygen-sensitive ruthenium complex and GOD were incorporated into poly (ethylene glycol) (PEG)-Based hydrogel materials, which were lithographically patterned and embedded inside the PerMX fluidic channel after wafer-bonding process. the optofluidic sensing platform with this embedded sensing elements exhibited a wide dynamic …

Degradation Of Polystyrene Foam Under Radiant Heat Flux, James Butler

Graduate Theses and Dissertations

As the demand for liquefied natural gas has increased, safety concerns about the performance of transport vessels under fire conditions have been raised. Current codes for the sizing of the pressure relief systems require that the vessels are able to withstand an emmissive heat flux of 108kW/m2 and do not take into account the effects of insulation loss due to thermal decomposition of the insulation materials. To address this possible oversight in the current code models were presented to a working group organized by the Society of International Gas Tanker and Terminal Operators Ltd. focusing on the decomposition rate of …

Visual, Spectrophotometric, And Colorimetric Measurement Of Red Wine And Wine Blends, Zachary Fricke

Chemical Engineering Undergraduate Honors Theses

Partially due to prevalence and popularity around the world, much research has been done in the field of enology and wine analysis. The visual aspect of wine is one of the key features of wine. This research focused on how blending and storage affected the color and composition of wine. Visual, sensory, color, and composition data were collected. Three primary red wine varietals (Cabernet Sauvignon, Merlot, and Zinfandel) and seven blends were analyzed for color, acidity, polymeric color, and optical density. The ten wine treatments were composed based on a mixture design model. The color and composition results were compared …

Clean Energy Water Disinfection For Small Rural Remote Communities, Nathan Bearden

Chemical Engineering Undergraduate Honors Theses

The University of Arkansas competed in the 2011 Waste-Management Education and Research Consortium (WERC) competition. The U of A team participated in Task 7, which was titled “Clean Energy Water Disinfection for Small, Remote Rural Communities”. The task looks for a solution to a continuing problem throughout the world: disinfecting water. The task’s problem statement was to develop and a standalone disinfection system that could be used for a small community. It will need at least 3000 gallons of water per day. The solution must address only bacterial disinfection and must be powered by a non-fossil based energy source. Other …

Quantitative Analysis And Structural Characterization Of Carbonaceous Pitches, Sourabh Kulkarni

All Dissertations

Both petroleum pitches and pitches derived from pure polycyclic aromatic hydrocarbons (PAHs) are oligomeric materials that can serve as precursors for a wide variety of advanced carbon materials. The goal of this study was the structural characterization and quantitative analysis of the dominant constituent oligomers and species present in these pitches.
A key requirement for such work is the ability to fractionate these complex mixtures into samples of narrow molecular weight distribution (mol wt; MWD) that can be used as standards. To this end, semicontinuous (or semibatch) dense-gas/supercritical extraction (DGE/SCE) was used to produce monomer, dimer, and trimer fractions of …

Modeling And Synthesis Of Functionalized Meta-Poly(Phenylene Ethynylene) Helical Structures, Ha Nguyen

All Dissertations

The ability of meta-poly(phenylene ethynylene) (mPPE) materials to undergo random coil to helix conformational changes under select conditions affords many opportunities for their use in sensor, separation, catalysis, and bio-related applications. Thus, to advance the development of these materials, a modeling procedure based on replica exchange molecular dynamics (REMD) simulation was developed to reliably assess factors affecting the folding behaviors of functionalized mPPE variants in solution. A combinational modeling study of 20 functionalized mPPEs in five solvent conditions provided insight into how mPPE secondary structure is impacted by the complex relationship between mPPE functional groups and solvent moieties. Further, these …

Pitch-Based Activated Carbon Fibers: The Effect Of Precursor Composition On Pore Structure, Halil Tekinalp

All Dissertations

Although researchers have previously investigated the effect of precursor differences on the final properties of activated carbon fibers (ACFs), those precursors were not well-characterized. In particular, detailed information about their molecular composition and anisotropy was not available.
In this study, seven oligomeric fractions, each of well-defined composition and molecular weight (mol wt) distribution, were isolated from a commercially produced isotropic petroleum pitch (i.e., Marathon M–50) and used for the production of ACFs. Four of these precursors of varying oligomeric composition were fully isotropic and three contained different levels of mesophase, so that the effects of molecular composition and molecular order …

Light-Emitting Nanocomposites And Novel Amorphous Polymers For Optical Applications, Kyle Gipson

All Dissertations

Polymeric optical materials generally are comprised of amorphous polymers that are transparent in at visible wavelengths but exhibit strong absorption bands in the near-infrared making them less useful for many optical applications. Attenuation, which is the absorption per unit length, largely results from the high vibrational energy associated with carbon-hydrogen bonds contained in the polymer backbone. Attenuation can be mitigated by optical amplification utilizing light emitting additives. Investigated in this dissertation are synthesis techniques for the fabrication of light-emitting polymer nanocomposites and their resultant thermal and rheological characteristics for potential use as polymer optical fibers or films.
Inorganic nanocrystals doped …

Selective Deposition Of Metallic And Semiconductor Materials Onto Dna Templates For Nanofabrication, Jianfei Liu

Theses and Dissertations

This work examines the selective deposition of metallic and semiconductor materials onto DNA templates for the fabrication of nanodevices. DNA origami provides a simple and robust method for folding DNA into a variety of shapes and patterns and makes it possible to create the complex templates needed for nanodevices, such as nanoelectronic circuits, plasmonics, and nanosensors. Metallization of DNA origami templates is essential for the fabrication of such nanodevices. In addition, selective deposition of semiconductor materials onto the DNA template is of importance for making many nanodevices such as nanocircuits. Metallization of DNA origami presents several challenges beyond those associated …

Microemulsion Preparation And Electrochemical Characterization Of Pt/C, Ptir/C Electrocatalysts, Ya-Ping Zeng, Sheng Sui

Journal of Electrochemistry

The Pt/C electrocatalysts were prepared by three different systems and the PtIr/C electrocatalysts were prepared with four different Ir contents. The samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), cyclic voltammetry (CV), potentiostatic and potentiodynamic polarizations measurements. The experimental results confirmed that the electrocatalyst particles prepared by the microemulsion method were well distributed on XC-72R supports with the active particle sizes of 5～10nm and good electrocatalysts activity. The Pt85Ir15/C electrocatalysts showed the highest overall electrochemical activity in unitized regenerative fuel cell.

Electrochemical Properties Of Tungstogermanate And Electrocatalysis Of H2O2 On Gew11Co/P-Opd/Gc Electrode, Li-Li Zhu, Jian-Ying Qu, Jue Wang, Hao-Yue Feng

Journal of Electrochemistry

The electrochemical properties of Co-substituted trimeric tungstogermanate containing Keggin fragments were studied. Cyclic voltammograms revealed two couples of reversible redox peaks on glassy carbon (GC) electrode in acid solutions. They corresponded to two-electron reductions accompanying by the additions of four protons and three protons, respectively, both were controlled by adsorption. The differences in the peak potentials of 2-electron-4-proton and 2-electron-3-proton reactions were 31 mV and 35 mV, respectively..Furthermore, the tungstogermanate (GeW11Co) modified GC electrode with functionalization by poly(o-phenylenediamine) (P-oPD) was prepared readily by electropolymerization. The GeW11Co/P-oPD/GC electrode could electrocatalyze the reduction of hydrogen peroxide, which showed good stability and quick …

Preparation And Characterization Of The Lani0.6Fe0.4O3-δ Cathode For Intermediate Temperature Solid Oxide Fuel Cell, Hang Liu, Bo Huang, Xin-Jian Zhu

Journal of Electrochemistry

The LaNi_0.6Fe_0.4O_3-δ as cathode material for intermediate temperature solid oxide fuel cell was prepared using a combustion synthesis technique. The X-ray diffraction (XRD) pattern showed that the single-phase LaNi_0.6Fe_0.4O_3-δ perovskite could be obtained after heat treatment at 600°C. The TEM and SEM images of the synthesized powders revealed that the grains were 50-100nm. According to the electrochemical impedance spectra (EIS), the polarization resistance of the symmetric cell LaNi_0.6Fe_0.4O_3-δ/ScSZ/LaNi_0.6Fe_0.4O_3-δ sintered at 1050°C was the smallest (0.70Ω·cm², 0.27Ω·cm^{2 …}