Chemical Engineering Commons^™

Studies On Silicon Nmr Characterization And Kinetic Modeling Of The Structural Evolution Of Siloxane-Based Materials And Their Applications In Drug Delivery And Adsorption, Jyotrhirmai Ambati

University of Kentucky Doctoral Dissertations

This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane- materials can be engineered for drug delivery and adsorption.

The phase behavior of polymerizing …

Synthesis And Energy Applications Of Oriented Metal Oxide Nanoporous Films, Qingliu Wu

University of Kentucky Doctoral Dissertations

This dissertation mainly addresses the synthesis of well-ordered mesoporous titania thin films by dip coating with PEO-PPO-PEO triblock copolymer surfactant template P123. Because P123 is composed of poly(ethylene oxide) [PEO] and poly(propylene oxide) [PPO] blocks, concentrations of ingredients are adjusted to tune the films’ wall thickness, pore size and mesophase. Structural changes are consistent with partitioning of species among PEO blocks, PPO blocks, and the PEO/PPO interface. Titanates localize near PEO and increase wall thickness (by 5 nm to 7 nm). Depending on aging temperature, PPG either swells the PPO cores (when it is hydrophobic) or introduces large (>200 …

Diffuse-Charge Dynamics Of Ionic Liquids In Electrochemical Systems, Hui Zhao

Mechanical Engineering Faculty Research

We employ a continuum theory of solvent-free ionic liquids accounting for both short-range electrostatic correlations and steric effects (finite ion size) [Bazant et al., Phys. Rev. Lett. 106, 046102 (2011)] to study the response of a model microelectrochemical cell to a step voltage. The model problem consists of a 1-1 symmetric ionic liquid between two parallel blocking electrodes, neglecting any transverse transport phenomena. Matched asymptotic expansions in the limit of thin double layers are applied to analyze the resulting one-dimensional equations and study the overall charge-time relation in the weakly nonlinear regime. One important conclusion is that our …

Characterizations Of Partially Reduced Polyoxometalate Catalysts Using Ammonia Adsorption Microcalorimetry And Methanol Oxidation Studies / By Suresh Babu Bommineni., Suresh Babu Bommineni

Dissertations, Master's Theses and Master's Reports - Open

Phosphomolybdic acid (H₃PMo₁₂O₄₀) along with niobium,pyridine and niobium exchanged phosphomolybdic acid catalysts were prepared. Ammonia adsorption microcalorimetry and methanol oxidation studies were carried out to investigate the acid sites strength acid/base/redox properties of each catalyst. The addition of niobium, pyridine or both increased the ammonia heat of adsorption and the total uptake. The catalyst with both niobium and pyridine demonstrated the largest number of strong sites. For the parent H₃PMo₁₂O₄₀ catalyst, methanol oxidation favors the redox product. Incorporation of niobium results in similar selectivity to redox products but also …

Development And Testing Of An Asymmetric Capacitor With A Nickel-Carbon Foam Positive Electrode, Wen Nee Yeo

Dissertations, Master's Theses and Master's Reports - Open

Electrochemical capacitors (ECs), also known as supercapacitors or ultracapacitors, are energy storage devices with properties between batteries and conventional capacitors. EC have evolved through several generations. The trend in EC is to combine a double-layer electrode with a battery-type electrode in an asymmetric capacitor configuration. The double-layer electrode is usually an activated carbon (AC) since it has high surface area, good conductivity, and relatively low cost. The battery-type electrode usually consists of PbO₂ or Ni(OH)₂.

In this research, a graphitic carbon foam was impregnated with Co-substituted Ni(OH)₂ using electrochemical deposition to serve as the positive electrode …

Graphite Exfoliation By Supercritical Carbon Dioxide Extraction, Chaiyaporn Wattanaprayoon

Dissertations, Master's Theses and Master's Reports - Open

Supercritical carbon dioxide is used to exfoliate graphite, producing a small, several-layer graphitic flake. The supercritical conditions of 2000, 2500, and 3000 psi and temperatures of 40°, 50°, and 60°C, have been used to study the effect of critical density on the sizes and zeta potentials of the treated flakes. Photon Correlation Spectroscopy (PCS), Brunauer-Emmett-Teller (BET) surface area measurement, field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM) are used to observe the features of the flakes. N-methyl-2-pyrrolidinone (NMP), dimethylformamide (DMF), and isopropanol are used as co-solvents to enhance the supercritical carbon dioxide treatment. As a result, the …

Modeling Of Diesel Particulate Filter Filtration And Regeneration For Transient Driving Schedules, Di Huang

Dissertations, Master's Theses and Master's Reports - Open

Due to their high thermal efficiency, diesel engines have excellent fuel economy and have been widely used as a power source for many vehicles. Diesel engines emit less greenhouse gases (carbon dioxide) compared with gasoline engines. However, diesel engines emit large amounts of particulate matter (PM) which can imperil human health. The best way to reduce the particulate matter is by using the Diesel Particulate Filter (DPF) system which consists of a wall-flow monolith which can trap particulates, and the DPF can be periodically regenerated to remove the collected particulates.

The estimation of the PM mass accumulated in the DPF …

Synthesis And Characterization Of Polymeric Antioxidant Delivery Systems, Paritosh P. Wattamwar

Theses and Dissertations--Chemical and Materials Engineering

Even though the role of oxidative stress in a variety of disease states is known, strategies to alleviate this oxidative stress by antioxidants have not been able to achieve clinical success. Particularly, treatment of oxidative stress by small molecule antioxidants has not received due attention because of the challenges associated with its delivery. Antioxidant polymers, where small molecule antioxidants are incorporated into the polymer backbone, are an emerging class of materials that can address some of these challenges.

In this work, biodegradable polymers incorporating phenolic antioxidants in the polymer backbone were synthesized. Antioxidant polymers were then characterized for their in …

Stability Of Affinity Based Layer-By-Layer Polymeric Self-Assemblies For Oral Wound Applications, Sundar Prasanth Authimoolam

Theses and Dissertations--Chemical and Materials Engineering

Oral mucositis is a painful and debilitating chronic inflammatory condition that can result from chemo and/or radiotherapy. While current treatment strategies which provide temporary relief exist, there is still an unmet clinical need for a robust long active barrier strategy which can simultaneously provide protection and release drug to enhance the wound healing response. It is proposed that an affinity based layer-by-layer self-assembled barrier administered as a series of mouth rinses can allow for wound specific drug delivery, providing an effective regenerative therapy.

In this work, biotinylated poly(acrylic acid) is used to develop LBL assemblies based upon biotin-streptavidin affinity interactions. …

Dynamic Relaxation Properties Of Aromatic Polyimides And Polymer Nanocomposites, Anthony C. Comer

Theses and Dissertations--Chemical and Materials Engineering

The dynamic relaxation characteristics of Matrimid^® (BTDA-DAPI) polyimide and several functionalized aromatic polyimides have been investigated using dynamic mechanical and dielectric methods. The functionalized polyimides were thermally rearranged to generate polybenzoxazole membranes with controlled free volume characteristics. All polyimides have application in membrane separations and exhibit three motional processes with increasing temperature: two sub-glass relaxations (ƴ and β transitions), and the glass-rubber (α) transition. For Matrimid, the low-temperature ƴ transition is purely non-cooperative, while the β sub-glass transition shows a more cooperative character as assessed via the Starkweather method. For the thermally rearranged polyimides, the ƴ transition is a …

Strength Adjustable Preformed Particle Gels For Conformance Control, Jia Zhou

Doctoral Dissertations

"Reservoir heterogeneity and early water breakthrough (also known as fingering) represent two of the greatest challenges to recover crude oil efficiently. Gel treatments have been implemented as a cost-effective method to plug high permeability zones and thus improve sweep efficiency in reservoirs. However, when extensive cross-flows exist between formation layers, gel treatments become less efficient. Polymer was used in polymer flooding to increase the viscosity of the injected fluids and to correct the fingering problem. However, such treatment may be uneconomical since dramatic viscosity loss (80-90%) is caused by shearing degradation during the injection process near the wellbore.

This research …

Scaling Properties At Freeze-Out In Relativistic Heavy-Ion Collisions, M. M. Aggarwal, Z. Ahammed, A. V. Alakhverdyants, I. Alekseev, J. Alford, B. D. Anderson, S. Bueltmann, I. Koralt, D. Plyku, Star Collaboration

Physics Faculty Publications

Identified charged pion, kaon, and proton spectra are used to explore the system size dependence of bulk freeze-out properties in Cu+Cu collisions at √sNN=200 and 62.4 GeV. The data are studied with hydrodynamically motivated blast-wave and statistical model frameworks in order to characterize the freeze-out properties of the system. The dependence of freeze-out parameters on beam energy and collision centrality is discussed. Using the existing results from Au + Au and pp collisions, the dependence of freeze-out parameters on the system size is also explored. This multidimensional systematic study furthers our understanding of the QCD phase diagram revealing the importance …

Effect Of Hydrophobicity And Surface Roughness On Two-Phase Flow In Rectangular Microchannels, Gautham C. Unni

Doctoral Dissertations

"Two-phase flows in microchannels have received significant attention recently, and have become the cornerstone of numerous microfluidic devices. Microscale devices used for bioengineering applications, oil recovery, and chemical and catalytic microreactor applications involve the transport of bubbles in confined fluidic networks in channels of micrometer length scale. These types of two-phase flows result in pressure variations, leading to an overall increase in pressure drop. Among various flow parameters, pressure drop is extensively used in design of microfluidic devices. There are several parameters that affect the pressure drop across two-phase flow in microchannels. In the present study, the goal is to …

Biodegradable Polymer/Clay Nanocomposites Based On Poly(Butylene Adipate-Co-Terephthalate) And Polylactide, Mahin Shahlari

Doctoral Dissertations

"In offering a scientifically succinct methodology which leads to property-enhanced biodegradable polymer products for broader application, as well as in promoting the use of bio-sourced renewable polymers such as Polylactide (PLA) in biodegradable polymers with desirable properties from petroleum based polymers such as PBAT, this study and its results both directly and indirectly contribute to the technological solutions that address growing environmental and energy problems caused by the increased use of and reliance upon nondegradable, nonrenewable, petroleum-based plastics. This work studied blends of PBAT and PLA compounded with organoclay through direct melt mixing in a twin-screw extruder and a batch …

Surface Modification Of Micro-Fluidic Devices, Zhan Gao

Doctoral Dissertations

"The surface modification, fabrication and characterization of microfluidic sensor systems for oxygen and glucose measurements with the use of polymeric materials were investigated in this dissertation. This dissertation is prepared in publication format. The first manuscript focuses on the surface modification of SU -8 layer to enhance the wettability. The improvement of wettability is critical since biofouling can be minimized during bioanalysis. A novel in situ photopattemable grafting technology was used to attach biocompatible polymer layers on SU-8 surface, changing its property from hydrophobicity to hydrophilicity. The results were confirmed by contact angle measurement and Fourier Transform Infrared (FTIR) spectra. …

Enhanced Heavy Oil Recovery By Alkali-Surfactant In The Pennsylvania Warner Sandstone, Rabia Mohamed Hunky

Doctoral Dissertations

"In this research, a study of the non-thermal method of alkaline-surfactant (AS) flooding to enhance heavy oil recovery from the Pennsylvanian Warner sandstone reservoir in Western Missouri was conducted. This work includ [sic] testing approximately 30 commercial surfactants and using a heavy oil sample with an API of 17. It was found that a number of surfactants could create stable emulsions. The viscosity of heavy oil could be reduced from 18,518 cp to 2.5 cp at 25⁰C through emulsification of certain surfactants. One of the major findings was that the emulsion created by the commercial surfactant, Igepalʼ CO-530 was stable …

Oxygen Diffusion Characterization Of Frp Composites Used In Concrete Repair And Rehabilitation, Chandra K. Khoe

USF Tampa Graduate Theses and Dissertations

Many independent studies have conclusively demonstrated that fiber reinforced polymers (FRP) slow down chloride-induced corrosion of steel in concrete. The mechanism for this slow down is not well understood but it has been hypothesized that FRP serves as a barrier to the ingress of chloride, moisture, and oxygen that sustain electrochemical corrosion of steel.

This dissertation presents results from an experimental study that determined the oxygen permeation rates of materials used in infrastructure repair. In the study, the oxygen permeation constants for epoxy, carbon and glass fiber laminates, concrete, epoxy-concrete and FRP-concrete systems were determined and a method developed to …

Catalytic Hydrodehalogenation And Hydrogenation Of Halogenated Aromatic Organic Contaminants For Application To Soil Remediation, Claire J. Osborn

USF Tampa Graduate Theses and Dissertations

The objective of this research was to aid in the development of a new method for removing and destroying soil contaminants. In particular, 1,2,4,5-tetrachlorobenzene (TeCB) was selected for this research. Hydrodehalogenation (HDH) was paired with hydrogenation for remedially destroying TeCB without generating a secondary waste stream in a single batch reactor. Palladium- and rhodium-catalyzed HDH and hydrogenation were applied in a batch reactor at room temperature and moderate hydrogen pressure. Cyclohexane was formed as an end product with benzene as an intermediate reactant.

An analytical method was developed to measure TeCB, benzene, and cyclohexane in a solution of water and …

Cactus Mucilage-Assisted Heavy Metal Separation: Design And Implementation, Dawn Iona Fox

USF Tampa Graduate Theses and Dissertations

Natural contamination of groundwater by arsenic (As) has become a critical public health threat in many parts of the world. The well-known regions associated with As contamination of groundwater are Bangladesh and West Bengal, India where approximately 100 million people are exposed to high levels of arsenic by drinking arsenic-contaminated groundwater and about 35 million are already affected. Long-term drinking of arsenic-contaminated water leads to arsenicosis, which is characterized by cancers of the skin, organ disease and certain other types of cancer. Affected developing communities are at higher risk because they may not have access to conventional water treatment facilities. …

Characterization Of Foam Flow In Pipes Using Two Flow Regime Concept, Rahul Narayanrao Gajbhiye

LSU Doctoral Dissertations

The objective of this study is to investigate the characteristics of foam flow behavior in pipes in a wide range of experimental conditions, including two pipe materials (stainless steel and nylon pipes with about 0.36 - 0.38 inch in inner diameter and 12 ft in length), three surfactant formulations (Cedepal FA-406, Stepanform-1050, and Aquet-944), and three surfactant concentrations (0.1, 0.5, and 5 wt%). The concept of “two foam-flow regimes”, consisting of high-quality regime and low-quality regime, is at the heart of interpreting the experimental data. The experimental results in horizontal pipes showed the presence of two distinct high-quality and low-quality …