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Mechanochemical Investigation Of A Glassy Epoxy-Amine Thermoset Subjected To Fatigue, Stephen Finley Foster

Dissertations

Covalent bonds in organic molecules can be produced, altered, and broken through various sources of energy and processes. These include photochemical, thermochemical, chemical, and mechanochemical processes. Polymeric materials derive their physical properties from the time scale of motion, summation of intermolecular forces, and number of chain entanglements and crosslinks. Glassy thermoset polymers experience mechanical fatigue during dynamic stress loading and properties diminish with inevitable material failure at stress levels below the ultimate tensile strength (UTS). Damage modeling has been successful in predicting the number of cycles required to induce failure in a specimen due to stress. However, it does not …

Aqueous Raft Polymerization Of Glycopolymers For Peptide Interaction Studies And Antimicrobial Peptide Mimics For Antimicrobial Activity And Selectivity Studies, Sarah Elizabeth Exley

Dissertations

The first section of this work describes the synthesis and characterization of novel glycopolymers synthesized to model GM1 gangliosides, a glycolipid found in neuronal cells. Glucose and galactose were attached to N-hydroxyethyl acrylamide, using chemistry that granted control over the stereochemistry at the C1’ carbon of each saccharide, and polymerized via aqueous RAFT (aRAFT). Homopolymers, targeting either 30 or 300 DP, and copolymers, with N-dimethyl acrylamide, were prepared as a glycopolymer platform for investigation of amyloid β (Aβ), a naturally occurring peptide associated with Alzheimer’s disease, aggregation. Aβ aggregation kinetics and aggregate size in the presence of glycopolymer were determined. …

Polymerization Of Blocked Isocyanate Functional Polymer Surfaces And Post-Polymerization Modification By Thiol-Isocyanate Reactions, Chase A. Tretbar

Honors Theses

Direct polymerization of isocyanate-functional monomers has been achieved with controlled radical polymerizations (CRP) for precisely engineered modification platforms with highly reactive side chains. However, despite the success of these strategies, the inherent reactivity of isocyanates still leads to adverse side reactions, such as hydrolysis, that are difficult to suppress. Phenol, lactam, and oxime-based blocking agents have been used to limit the reactivity of isocyanates in applications such as multicomponent urethane coating systems. The reactivity of these blocked isocyanates can be restored by thermal deprotection of the blocking agent to achieve the desired reactions. In this work, we use blocked isocyanate-functional …

Biomimetic Adhesive Thiol-Ene Films For Improved Adhesion, Laken L. Kendrick

Honors Theses

Current dental restoration materials fall short in adhesion and often pull away from the surface of the tooth upon curing. This project seeks to design polymers that can adhere to wet, heterogeneous surfaces as potential materials for dental restoration applications. The goal of this project is to mimic the structure and adhesive properties of natural adhesives containing 3,4-dihydroxyphenyl-L-alanine (DOPA). We will synthesize mono- and di-functional DOPA derivatives with catechol functionality and investigate their adhesion compared to their non-catechol-containing alternative through incorporation into a model thiol-ene photopolymerization. Functional group conversion, real time kinetics, and adhesion data will be used to analyze …

Analysis Of The Mechanical Properties Of Dgebf/4,4’-Dds Thermoset Systems As A Function Of Cure Rate, Chase B. Thompson

Honors Theses

The relationship between macroscopic mechanical and thermal properties and ramp rate during cure of epoxy-amine systems consisting of the epoxide resin digylcidyl ether of bisphenol F (DGEBF, provided Hexion specialty chemicals) and 4,4-diaminodiphenyl sulfone (4,4-DDS, provided by Atul Sulpho) were probed using Dynamic Mechanical Analysis (DMA), Positron Annihilation Lifetime Spectroscopy (PALS), and compression testing. These systems were cured in a programmable oven; the samples were heated from 35°C to 180°C at ramp rates of 0.5, 1.0, 1.5, 2.0, 2.5, 5.0, 10, and 15°C/min. Even as the ramp rates during the cure of these materials was changed, there was very little …

A New Synthesis Of Bis (4-Tert-Butylphenyl) Iodonium Hexafluoroantimonate; A Known Catalyst For Photopolymerization, Matthew C. Salvi

Chemistry Master’s Theses

This thesis describes a novel reaction protocol for the synthesis of bis (4-tert-butylphenyl) iodonium (BtPhI) hexafluoroantimonate (2) via the formation of diacetoxy (t-butylphenyl)-λ3-iodane (1). It is also important to provide a safe and robust reaction procedure for future scaled-up production.

Bio-Crosslinking Of Starch Films With Oxidized Sucrose, Hazal Canisag

Department of Textiles, Merchandising, and Fashion Design: Dissertations, Theses, and Student Research

In this work, corn starch films were crosslinked with a novel bio-based agent; oxidized sucrose and their strength and stability were improved. Although starch is an inexpensive, biodegradable and abundant source, industrial applications of starch films are limited due to their poor mechanical properties. Crosslinking is one of the most common methods to enhance the mechanical properties of starch films. However, most of the available crosslinkers, such as gluteraldehyde, phosphorus oxychloride, sodium trimetaphosphate, and epichlorohydrin, are either toxic, expensive or with low crosslinking efficiencies. Oxidized sucrose, which is derived by periodate cleavage, has aldehyde groups in the structure and this …

In Vivo Near Ir Fluorescent Imaging Of Hollow Polymeric Nanocapsules, Venkata Suresh Patthipati

Biological Sciences Theses & Dissertations

Medical Imaging has been an integral component in medical diagnosis and therapeutics. It is frequently used in conjunction with other treatment modalities and has been used for developing applications that range from cancer management to clinical practice. Nanotechnology and its applications are foreseen to have a profound impact on life sciences. Nanomaterial based imaging has a significant potential in addressing medical challenges such as tumor localization, targeted delivery of drugs and real time diagnosis and management of circulation pathology. In particular, polymer based nanoparticles are increasingly being developed as they can be customized according to the diagnostic and/or therapeutic requirements. …

Thermal Fluctuations Tunneling In Doped Conjugated Polymers, Troy C. Stedman

USF Tampa Graduate Theses and Dissertations

The possibility of using conducting polymers as organic alternatives to widely used inorganic materials for thermoelectric (TE) applications has received much attention in the past few decades. Since conducting polymers are generally inefficient compared to inorganic TE materials, research into their underlying transport mechanisms is required to improve their efficiency. We use a model based on the effects of local thermal fluctuations to characterize the transport in conducting polymer composites. With this model, full linear responses for the current and electronic heat current are obtained. From these responses, the local temperature dependent conductivity, electronic contribution to the thermal conductivity, and …

Design, Synthesis And Applications Of Polymer Biomaterials, Frankie Costanza

USF Tampa Graduate Theses and Dissertations

The emergence of antibiotic resistant bacteria has prompted the research into novel kinds of antibacterial small molecules and polymers. Nature has solved this issue with the use of cationic antimicrobial peptides, which act as nonspecific antibiotics against invading species. Herein, we have tried to mimic this general mechanism in a biocompatible and biodegradable polymer micelle based on the polymerization of naturally occurring amino acids lysine and phenylalanine linked to a PEG tether. This amphiphilic structure allows for the spontaneous collapse into stable nanoparticles in solution, which contains a hydrophilic outer layer and a hydrophobic core. Our polymers have shown activity …

Cationic Amphiphilic Synthetic Macromolecules With Superior Antibacterial Activity, Ashish Punia

Dissertations, Theses, and Capstone Projects

The increasing prevalence of antibiotic resistant bacteria (superbugs) has created a pressing need for new systems of antimicrobial agents. In this dissertation, I report on my extensive research on the design, synthesis, and development of synthetic amphiphilic macromolecules with antimicrobial activity and very low hemolytic impact. Synthetic amphiphilic polymers attack bacteria directly to rupture the cell membrane through electrostatic and hydrophobic interactions. However, the toxicity of such synthetic amphiphilic polymers against mammalian cells have impeded their therapeutic applications. We investigated the systematic structure/activities relationships for antibacterial and hemolytic activities of amphiphilic polyacrylates and poly(vinyl esters). Acrylate homopolymers with various lengths …

Synthesis And Characterization Of A Novel Polyacetal & Design And Preparation Of Superhydrophobic Photocatalytic Surfaces, Yuanyuan Zhao

Dissertations, Theses, and Capstone Projects

Polyacetal polymers are thermoplastic resins that play an important role in industry because of numerous industrial applications including automobile; household appliance; etc. The first part of this thesis (Chapter 2) is about the synthesis of a new acetal copolymer that exhibits superior thermal stability. The second part of this thesis (Chapter 3) is about the preparation and applications of TiO₂-based polymer nanocomposite films, where the reactive oxygen species (ROS) are generated on the solid surface. Catalytic nanocomposite films are an active area of research because of their potential uses for environmental remediation and chemical synthesis. Furthermore, to …

Multi-Mode And Single Mode Polymer Waveguides And Structures For Short-Haul Optical Interconnects, Kevin L. Kruse

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

Single mode and multi-mode polymer optical waveguides are a viable solution for replacing copper interconnects as high speed and large bandwidth short-haul optical interconnects in next-generation supercomputers and data servers. A precision laser direct writing method is implemented for producing various single mode and multi-mode polymer waveguide structures and their performance is evaluated experimentally showing agreement with theoretically developed models. The laser direct writing method is the optimal solution for low-rate cost-effective prototyping and large area panel production.

A single mode polymer waveguide bridge module for silicon to glass optical fibers is designed, modeled, fabricated, and measured. The bridge module …

Biological Materials: Part A. Temperature-Responsive Polymers And Drug Delivery And Part B. Polymer Modification Of Fish Scale And Their Nano-Mechanical Properties, Xu Xiang

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

This research has three parts. Two parts deal with novel nanoparticle assemblies for drug delivery, and are described in Part A, while the third part looks at properties of fish scales, an abundant and little-used waste resource, that can be modified to have value in medical and other areas.

Part A describes fundamental research into the affects of block sequence of amphiphilic block copolymers prepared from on a new and versatile class of monomers, oligo(ethylene glycol) methyl ether acrylate (OEGA) and the more hydrophobic di(ethylene glycol) methyl ether methacrylate (DEGMA). Polymers from these monomers are biologically safe and give polymers …

Development Of Boron-Containing Polyimide Materials And Poly(Arylene Ether)S For Radiation Shielding, Brittani May Collins

Dissertations, Theses, and Masters Projects

No abstract provided.

Burst Pressure Properties And Ex Vivo Analysis Of Alginate-Based Hydrogels For Tissue Sealant Applications, Patrick Nelson Charron

Graduate College Dissertations and Theses

Lung diseases, cancers, and trauma can result in injury to the connective tissue lining the lung, i.e., the pleura. Pleural injuries lead to pneumothoraxes or pleural effusions, i.e., air or fluid leaking out of the lung respectively, and potential lung collapse - an immediately life threatening condition. While several bioengineered soft tissue sealants exist on the market, there is only one sealant FDA-approved for use in pulmonary surgery. In addition, very limited techniques are presented in the literature for characterizing the burst properties of hydrogel tissue sealants. For my thesis, I proposed to develop a protocol for characterizing the burst …

Initiated Chemical Vapor Deposition (Icvd) Polymer Thin Films : Structure-Property Effects On Thermal Degradation And Adhesion, Vijay Jain Bharamaiah Jeevendrakumar

Legacy Theses & Dissertations (2009 - 2024)

Opportunities and challenges for chemical vapor deposition (CVD) of polymer thin films stems from their applications in electronics, sensors, and adhesives with demands for control over film composition, conformity and stability. Initiated chemical vapor deposition (iCVD) is a subset of the CVD technique that conjoins bulk free-radical polymerization chemistry with gas-phase processing. The novelty of iCVD technique stems from the use of an initiator that can be activated at low energies (150 – 300 °C) to react with surface adsorbed monomer to form a polymer film. This reduces risk for potential unwarranted side-reactions.

Synthesis, Characterization And Application Of Acrylic Colloidal Unimolecular Polymer (Cup), Ameya Manohar Natu

Doctoral Dissertations

"Colloidal Unimolecular Polymer (CUP) particles were prepared by the process of water reduction on amphiphilic acrylic copolymers prepared via free radical polymerization technique. The formation of CUP particles was driven by the polymer-polymer interaction being greater than the polymer-solvent interaction and entropically favored by release of the water. It was demonstrated by Dynamic Light Scattering technique that CUP particles based on copolymers below 13,000 MW were unstable and the particles aggregated to a higher particle size. For the polymers with molecular weight (MW) above 13,000, a good correlation between the theoretical and experimental CUP particle size was observed. The rheology …

Inhalable Nanocomposites And Anticancer Agents For Cancer Therapy, Nathanael A. Stocke

Theses and Dissertations--Chemical and Materials Engineering

Cancer is designated as the leading cause of mortality worldwide and lung cancer is responsible for nearly 30% of all cancer related deaths. Over the last few decades mortality rates have only marginally increased and rates of recurrence remain high. These factors, among others, suggest the need for more innovative treatment modalities in lung cancer therapy. Targeted pulmonary delivery is well established for treating pulmonary diseases such as asthma and provides a promising platform for lung cancer therapy. Increasing local deposition of anticancer agents (ACAs) and reducing systemic exposure of these toxic moieties could lead to better therapeutic outcomes and …

Application Of Colloidal Unimolecular Polymer (Cup) Particles In Coatings, Sagar Vijay Gade

Doctoral Dissertations

"Colloidal unimolecular polymer (CUP) particles were prepared by the process of water reduction on copolymers containing hydrophobic and hydrophilic monomers at definite ratio using free radical polymerization. The CUPs are formed by the effect of hydrophilic /hydrophobic interactions of the polymer with a change in the solvent environment around them. Once formed these colloidal particles are thermodynamically stable with collapsed hydrophobic groups forming a spheroidal core and hydrophilic charges on the surface stabilizing the particle by the charge repulsion. CUPs contain only the charged CUP particles, water and counterions with all the functionality on the surface for further chemistry. CUP …

Mechanical Characteristics Of Organically Modified Fly Ash-Kaolinite Mixtures, Xin Kang

Doctoral Dissertations

"Fly ash is a hazardous waste material to the environment. Beneficial reuse of fly ash, however, brings economic and environmental benefits, i.e., decreases the cost of disposal, reduces greenhouse gas emission, and improves mechanical properties of construction materials. Due to the lack of pozzolanic properties, the reuse rate of Class F fly ash in geotechnical engineering is relatively low (ACAA 2013). In order to promote the effectiveness and sustainability of high volume reuse of class F fly ash in geotechnical engineering, biopolymers (Chitosan, and Xanthan gum) and synthetic polymers (Polyethylene Oxide, PEO) were used instead of the traditional stabilizers to …

The Synthesis And Characterization Of Water-Reducible Nanoscale Colloidal Unimolecular Polymer (Cup) Particles, Cynthia J. Riddles

Doctoral Dissertations

"The coatings industry has adapted to more stringent guidelines in paint formulations. Current VOC (volatile organic compound) limits placed by the federal government have pushed the industry toward the development of paint formulations which have very little to no VOC's. The development of Colloidal Unimolecular Polymer (CUP) particles is a step in the direction of providing a resin system which exists in zero VOC aqueous dispersion.

The CUP particles are a part of the polymer field of Single Chain Nano Particles (SCNP) and ranged in diameters of 3-9 nm. The research presented in this dissertation describes the synthesis and design …

Biodegradable Poly(Ester Urea's) Scaffold Sponges Containing Platelet-Rich Plasma For Targeted Tendon-Bone Fixation, Alex B. Ellenberger Mr.

Williams Honors College, Honors Research Projects

In this report the synthesis and characterization of L-valine and L-isoleucine poly(ester ureas) (PEUs) for future use in the synthesis of biodegradable PEUs sponges will be discussed. The method of monomer and polymer synthesis will be explained along with the characterization of the monomer and polymer products. This characterization will be done by the use of Nuclear Magnetic Resonance (NMR) and Size Exclusion Chromatography (SEC). NMR is a quick and convenient method for determining structure and purity of the monomer and polymer products. SEC gives the number average molecular weight, which is the statistical average molecular weight of all the …

Humidity And Rest Period Effects On Viscid Silk Recovery, Catherine Donley

Williams Honors College, Honors Research Projects

Spider silk applications, and applications of composite materials generally, are limited due to lack of recovery once damaged. Viscid silk, however, is known to have self-healing capabilities which restore, at least partially, its initial properties. If maximized, this ability could potentially increase viscid silk’s practicality and ultimately, provide insight into a self-healing system of use in synthetics. To that end, samples of viscid silk spun by female Larinioides cornutus spiders were tested via cyclical loading at 3 different relative humidities, with 3 different rest period lengths between complete cycles. Data from previously-performed tensile tests conducted at the same 3 humidities …

The Effects Of Substrate Roughness In Air And Water On The Gecko Adhesive System, Amanda Palecek

Williams Honors College, Honors Research Projects

In an effort to better understand the fascinating gecko adhesive system, scientists have long tested the abilities of the gecko in controlled conditions that mimic the gecko’s native environment. The effects of humidity, environmental temperature, and exposure to water have all been tested. Roughness, however has not been studied in great detail. Surfaces of varying roughnesses are all over the gecko’s natural environment. We tested geckos on hydrophilic silicon carbide sandpapers of varying roughnesses in both air and water to attempt to better study the effects of roughness on gecko adhesion. When tested on the rougher (1 µm) surface, the …

Characterization Of Noncovalent Complexes Of Polyelectrolytes By Mass Spectrometry, Anthony J. Marino

Williams Honors College, Honors Research Projects

Various ions of poly-L-lysine and polystyrene sulfonic acid were successfully observed first within a matrix-assisted laser desorption/ionization mass spectrometer and subsequently in an electrospray ionization mass spectrometer. The successful ionization of these polymers allowed for studies to be performed on the noncovalent interactions between the two. Noncovalent interactions were effectively studied on both instruments, but further quantified using tandem mass spectrometry found within the MALDI system and ion-mobility mass spectrometry found within the electrospray ionization system. As a result of employing the use of ion-mobility, various different stoichiometries and charges of polyelectrolyte complexes could be distinguished.

Gene Expression Of Tissue-Engineered Distal Phalanx Models Utilizing Polymer Scaffolds With Hydroxyapatite And Beta-Tricalcium Phosphate, Kristrun H. Kristinsdottir, William J. Landis Ph.D., Robin Jacquet M.S.

Williams Honors College, Honors Research Projects

Tissue engineering is a scientific methodology that provides the means for fabrication of vital tissues in a laboratory with the ultimate goal of translating the tissue to a patient in a clinic. It is a desirable technique in clinical medicine because it eliminates the need for patient tissue grafts and transplants, which have the potential for donor site morbidity and rejection. In tissue engineering, the scaffolding material, typically a polymer upon which tissue is grown, is important. The goal of this research is to investigate optimization of tissue-engineered polymer scaffold constructs for cell proliferation and gene expression. This work includes …

Fabrication Of Tissue Precursors Induced By Shape-Changing Hydrogels, Olukemi O. Akintewe

USF Tampa Graduate Theses and Dissertations

Scaffold based tissue reconstruction inherently limits regenerative capacity due to inflammatory response and limited cell migration. In contrast, scaffold-free methods promise formation of functional tissues with both reduced adverse host reactions and enhanced integration. Cell-sheet engineering is a well-known bottom-up tissue engineering approach that allows the release of intact cell sheet from a temperature responsive polymer such as poly-N-isopropylacrylamide (pNIPAAm). pNIPAAm is an ideal template for culturing cell sheets because it undergoes a sharp volume-phase transition owing to the hydrophilic and hydrophobic interaction around its lower critical solution temperature (LCST) of 32°C, a temperature close to physiological temperature. Compared to …

Diazaborole Linked Porous Polymers: Design, Synthesis, And Application To Gas Storage And Separation, Zafer Kahveci

Theses and Dissertations

The synthesis of highly porous organic polymers with predefined porosity has attracted considerable attention due to their potential in a wide range of applications. Porous organic polymers (POPs) offer novel properties such as permanent porosity, adjustable chemical nature, and noteworthy thermal and chemical stability. These remarkable properties of the POPs make them promising candidates for use in gas separation and storage. The emission of carbon dioxide (CO₂) from fossil fuel combustion is a major cause of global warming. Finding an efficient separation and/or storage material is essential for creating a cleaner environment. Therefore, the importance of the POPs …