Chemistry Commons^™

Study Of Thermal Frontal Polymerization Utilizing Reactive And Non-Reactive Additives, Veronika Grace Viner

Dissertations

Thermal frontal polymerization is a process that involves a propagating front travelling through a monomer/initiator solution and converting monomer into polymer. The effects of different reactive and non-reactive additives on front temperature, front velocity, and pot life were studied in a thermal frontal polymerization system of multifunctional acrylates. One issue with thermal frontal polymerization of acrylate monomers is the amount of smoke and fumes produced due to high front temperatures. The effect of thermally-expandable microspheres was studied utilizing a variety of monomers. Solid additives including fillers, inert phase changer materials, and high thermal conductive fillers were investigated. The addition of …

Off-Metal Synthesis Of Some Aryl Substituted Rhenium N5-Cyclopenta [C] Pyridazyl Complexes, James Leif Neathery

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (e.g. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to non-aromatic analogs (e.g. polyacetylene). Our current interests focus upon the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. Pyridazines, 6-membered aromatic rings with two adjacent nitrogens, are promising candidates for a variety of materials and commercial applications. These molecular electronic materials posses several advantages over traditional inorganic semiconducting materials including lower cost of production, higher processibility, and the ability to function on flexible …

Investigation Of Novel Thiol "Click" Reactions, Justin William Chan

Dissertations

The thio-Michael addition reaction is traditionally considered a base catalyzed reaction which involves high catalyst concentrations and long reaction times. This reaction utilizes potent, simple nucleophiles to catalyze the reaction, decreases the catalyst concentration and greatly increases the reaction times. The free radical mediated thiol-ene click reaction uses light or heat and an initiator to catalyze the rapid and quantitative addition of thiols to most electron rich enes without the formation of side products and in the absence of solvent. Recently, the thiol-ene click reaction has been exploited for these reasons in materials science and organic synthesis. The research herein …

Investigation Of The Relationship Between Polymer Structures And Thermal, Mechanical, Viscoelastic Properties, Ethem Kaya

Dissertations

The research presented in this dissertation involves four distinct areas: physical crosslinking systems, UV curable coatings for enhanced oxygen and carbon dioxide barrier properties, synthesis, and investigation of melting behavior/crystallinity relations of linear polyamides with long alkyl chains, and synthesis and characterization of cyclic diamides as precursors to linear polyamides 6 4.

The physical crosslinking section involves synthesis of monomers and polymers bearing cyclodextrin and adamantane pendent groups, and investigation of non-covalent interactions between these polymers (Chapter II). Two methacrylate monomers bearing cyclodextrin and adamantane were synthesized, and copolymerized with poly(ethylene glycol) methyl ether methacrylate. The specific interaction between copolymers …

Random And Block Copolymers Of Poly(Dodecamethyleneterephthalamide), Theodore Frank Novitsky Jr.

Dissertations

The following dissertation focuses on the synthesis and characterization of poly(dodecamethylene terephthalamide) (PA-12,T) and novel copolymers. Chapter I details the synthesis of PA-12,T homopolymer by melt condensation polymerization. A series of homopolymers with different molecular weights were obtained by adjusting the stoichiometry of the polymerization using 1,12-diaminododecane, terephthalic acid and benzoic acid. End group 13C NMR spectroscopy resonances were obtained by correlating peak intensities with intrinsic viscosity values. From the NMR data, total end group concentrations and molecular weights were determined for each sample. The data exhibited a linear trend when plotting log (IV) versus log (Mn), and previously unknown …

Preparation And Characterization Of Thiol Based Polymeric Materials, Junghwan Shin

Dissertations

The thiol click-type reaction is one of the most efficient chemical processes that can undergo at room temperature in the benign organic solvent providing excellent opportunity in the fabrication of new materials as well as development of new manufacturing processes. Moreover, the versatility of thiol click-type reactions with many different functional groups such as ene, yne, epoxy, isocyanate, and alkyl halide is the important aspect that should be differentiated from the classic azide-alkyne click chemistry. Although, there are tremendous studies on many areas using thiol click-type reactions, the efficiency and utilities for the material applications have been barely explored. Especially, …

A Characterization Of Caffeine Imprinted Polypyrrole Electrode, Deepika Mandadi

Masters Theses & Specialist Projects

Nanotechnology holds great potential for improving our lives by creating many new materials and devices in medical sciences, electronics and also in energy production. Molecularly imprinted polymers (MIPs) are highly stable synthetic polymers that possess molecular recognition properties due to cavities created in the polymer matrix that are complementary to an analyte both in shape and in positioning of functional groups. These MIPs have been widely employed for diverse applications (e.g., in chromatographic separation, drug screening, chemosensors, catalysis, immunoassays etc) due to their specificity towards the target molecules and high stability against physicochemical perturbations. Conductive polymers, (CPs) such as polypyrrole, …

Interface Slippage Study Between Polyamide 12 And Ethylene Butene Copolymer Melt In Capillary Extrusion, Jinhai Yang, James L. White

Faculty Publications

Extrusion of a polyamide 12 (PA12) material through a capillary die coated with an ethylene butene copolymer (EBM) was studied. The EBM coated die significantly increased the flow rates of the PA12 melt compared to a clean die at the same extrusion pressure. Introducing a maleic anhydride grafted ethylene-octene copolymer (EOM-g-MAH) into the EBM suppressed the effect. This behavior seems only explained by significant interface slippage between PA12 and EBM melts, which could be eliminated by introducing covalent chemical bonds across the interface. A mathematical analysis was carried out to calculate the interface slippage. The shear stress where slippage began …

Development Of Improved Torsional Potentials In Classical Force Field Models Of Poly (Lactic Acid), James Mcaliley

All Dissertations

In this work, existing force field descriptions of poly (lactic acid), or PLA, were improved by modifying the torsional potential energy terms to more accurately model the bond rotational behavior of PLA. Extensive calculations were carried out using density functional theory (DFT), for small PLA molecules in vacuo, and also using DFT with a continuum model to approximate the electronic structure of PLA in its condensed phase. From these results, improved force field parameters were developed using a combination of the OPLS and CHARMM force fields. The new force field, PLAFF2, is an update to the previously developed PLAFF model …

Synthesis Of Polymers Featuring Novel Diphosphines, Eleanor Tennyson

All Theses

This report details the synthesis of functionalized platinum-based metallopolymers featuring m-terphenyl-scaffolded and light-harvesting phosphine ligands. Substituents placed on both the phosphine and pendant alkynyl units can enhance the optical activity of the metallopolymers depending on their inherent properties. The presence of the platinum metal atom can be exploited to increase conductivity of the molecule and promises to be a unique and valuable modification for polymers to be used in light emitting diodes and photovoltaics. Light-harvesting phosphines prepared in the course of the metallopolymer development have also been used to prepare luminescent polyelectrolytes that prove valuable for well-defined composite film formation …

Synthesis And Characterization Of Some Rhenium Complexes, Joseph Brian Scott

Masters Theses & Specialist Projects

Plastics or polymers are thought to behave oppositely from metals. Ideally, polymers behave as insulators while metals conduct electricity. Shirakawa and coworkers discovered conductive polymers in 1977.1 These conductor polymers have been extensively studied, discovering that charge transfer oxidative doping of polyacteylene could increase its conductivity by 12 orders of magnitude. Polyacetylene, although showing promise as an organic conductor, because it is highly air-sensitive and oxidizes when exposed to molecular oxygen, therefore making this an unattractive use for commercial products. Attention has been focused on heterocylic aromatic polymers such as polythiophene and polypyrrole, in efforts to produce conductive polymers that …

Raft Synthesis Of Water-Soluble, Stimuli-Responsive (Co)Polymers And Post-Polymerization End Group Modification Via The Thiol-Ene Reaction, Bing Yu

Dissertations

A series of water-soluble, stimuli-responsive (co)polymers was synthesized via the reversible addition-fragmentation chain transfer (RAFT) polymerization. The end group of a RAFT polymer, poly(jV-isopropylacrylamide), was modified to ene or yne function via thiol-ene click chemistry. The ene or yne end group subsequently underwent thiol-ene or thiol-yne addition affording mono- or di-functional end group. First, three methacrylic monomers containing 2 or 3 pendent tertiary amine functional groups, l,3-bis(dimethylamino)propan-2-yl methacrylate (Ml), l-(bis(3-(dimethylamino)propyl)amino)propan-2-yl methacrylate (M2), and 2-((2-(2-(dimethylamino)ethoxy)ethyl)methylamino)ethyl acrylate (M3), were synthesized via an acylation reaction between methacryloyl chloride and the corresponding aminoalcohol. All of these three monomers were successfully homopolymerized under RAFT conditions …

Design, Synthesis, And Film Formation Of Fluorine Containing Colloidal Dispersions, Anuradha Misra

Dissertations

Fluoropolymers (FPs) have been subject of interest for many years, however due to extreme synthetic and processing conditions their applications have been limited. This dissertation focuses on design and synthesis of fluorine containing colloidal dispersions to advance limited knowledge and to gain further understanding of fluorine containing colloidal dispersions. Fluoroacrylates and fluoro methacrylates consisting of varying chain length of perfluoroalkyl side chain were copolymerized with methylmethacrylate (MMA) and n-butylacrylate (n-BA) under aqueous environment utilizing phospholipids (PLs) as dispersing agent. Morphologies of colloids, coalescence, and film formation processes after water evaporation was investigated using various microscopic probes such as transmission electron …

Influence Of Functional Components On The Film Formation Of Colloidal Dispersions, Kevin Lee Rhudy

Dissertations

A number of colloidal dispersions were synthesized to advance knowledge and gain understanding regarding interactions between individual components and for elucidation of complex processes governing their film formation. These studies show that for methyl methacrylate/n-butyl acrylate (MMA/nBA) colloidal dispersions, the presence of functional components significantly affects film formation. The incorporation of polyvinyl alcohol (PVOH) into pMMA/nBA colloidal dispersions creates competing environments between the copolymer particle surfaces, aqueous phases, and dispersing agents which results in migration with self-induced stratification occuring during coalescence. pMMA/nBA/PVOH films stratify to form sodium dodecyl sulfate (SDS) rich film-air (F-A) interfaces, and the -SO3" moieties exhibit preferential …

Magnetic And Dielectric Properties Of Sulfonated (S) Poly[(Styrene)-(Ethylene-Co-Butylene)-(Styrene)] (Sebs) Block Copolymer/Magnetic Metal Oxide Nanocomposites Synthesized Via An In-Situ Precipitation Method, Sateesh Kumar Peddini

Dissertations

Block copolymer/magnetic metal oxide nanocomposites were synthesized by growing metal oxide nanoparticles (cobalt ferrite, CoFe204 and iron oxide, a-Fe203) in sulfonated (s) poly (styrene) (PS) block domains of sulfonated poly [(styrene)-(ethyleneco- butylene)-(styrene)] (SEBS) BCP preformed films via an in-situ precipitation method by dissolving the salts of respective metal chloride (s) in a suitable solvent that selectively swells the sPS regions. Inorganic uptake was determined using thermogravimetric analysis (TGA), and it was observed that none of the samples incorporated more than 5 wt % of the inorganic component. Dynamical mechanical analysis was used to observe the changes in the glass transition …

Multi-Walled Carbon Nanotubes-Modified Polymer Organic Photovoltaics, Tzu-Fan Chen

Masters Theses & Specialist Projects

Since the carbon nanotubes were first discovered by Iijima in 1991, CNTs have been the focus of intense research by many groups. Nearly 7000 papers and 700 theses on carbon nanotubes can be found from the eminent journals such as Nature and Science in the last decade. Since carbon nanotubes show impressive mechanical, physical and electronic properties such as high stiffness, high strength, low density, and excellent thermal conductivity, suggesting its role in light-weight high strength material application. A great quantity of important research has evidently been done in this field. The purpose of this thesis research is to investigate …

The Synthesis And Systematic Evaluation Of Modified Polymeric Foams And Electrically Conductive Polyimide/Carbon/Metal Films, John Macharia Kinyanjui

UNLV Theses, Dissertations, Professional Papers, and Capstones

Thermally processed PU foams are examined as a function of processing temperatures (25, 45, 65, and 85°C) at the side, middle, and center of a simple cylindrical mold. The PU foams show both chemical and morphological differences as a function of the processing temperature and radial position within the mold. Thermal degradation of uretoneimine structures, the emergence of carbodiimide structures, and extent of reaction of isocyanate groups are measured using photoacoustic FTIR spectroscopy. Chemical gradients and morphology differences between the side, middle, and center of the molded foam are observed for all processing temperatures. The data indicate that thermal activation …

Chasing Μ, Joseph P. Cannon

Doctoral Dissertations

Conducting and semiconducting, π-conjugated polymers are promising materials for micro- and nano-optoelectronic applications because of their widely tunable physical, electrical, and optical properties. These polymers have been used to fabricate a number of electronic devices including field-effect transistors, light-emitting diodes, and photovoltaic cells. However, widespread commercial application of these devices has yet to be realized, due in part to poor electronic transport characteristics and device degradation.

Nanostructuring of conjugated polymers by various methods has demonstrated marked improvements in molecular ordering and electronic transport. In this research, nanoscale, tubular structures of semiconducting polymers fabricated by template wetting nanofabrication procedures are explored. …

Meine Jugend In Traiskirchen, Otto Vogl

Emeritus Faculty Author Gallery

No abstract provided.

Silver Doped Perfluoropolyether-Urethane Coatings: Antibacterial Activity And Surface Analysis, Niall Stobie, Brendan Duffy, Steven Hinder, Patrick Mchale, Declan Mccormack

Articles

The colonisation of clinical and industrial surfaces with pathogenic microorganisms has prompted increased research into the development of effective antibacterial and antifouling coatings. There is evidence that implanted biomedical surfaces coated with metallic silver can be inactivated by hysiological fluids, thus reducing the bioactivity of the coating. In this work, we report the biofilm inhibition of Staphylococcus epidermidis using a roomtemperatureprocessedsilver dopedperfluoropolyether-urethane coating. The release of silver ions from these fluoropolymers over a six-day period inhibited bacterial encrustation – as observed by scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS) analysis indicated differences in carbon, fluorine and sodium surface composition …

Surface Investigation Of Chitosan Film With Fatty Acid Monolayers, M Misran

Misni Misran

The surface pressure-molecular area (pi-A) isotherm curves of two fatty acids of different chain lengths, i.e. stearic (C(18)) and arachidic (C(20)) acids, were obtained by using Langmuir-Blodgett (LB) technique. Results showed clear isotherm plots with limiting mean molecular area around 21 angstrom(2) for both acids. However, the monolayer was found to collapse at higher than 33 mN m(-1) and 21 mN m(-1) for stearic acid and arachidic acid respectively. The effect of Langmuir-Blodgett monolayers of the acids was investigated by atomic force microscopy (AFM). Chitosan film, before and after dipping in water, was also studied by means of AFM so …

Meine Jugend In Traiskirchen, Otto Vogl

Otto Vogl

No abstract provided.

Effect Of Organic Chelates On The Performance Of Hybrid Sol–Gel Coated Aa2024-T3 Aluminium Alloys, Rajath Varma, John Colreavy, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, Brendan Duffy

Articles

Sol–gels are organic–inorganic polymers formed by hydrolysis/condensation reactions of alkoxide precursors, primarily silanes, which have found applications as electronic, optical and protective coatings. These coatings possess important characteristics such as chemical stability, physical strength and scratch resistance. Further performance improvement is achieved through the incorporation of zirconium and titanium based nanoparticles, also formed through the sol–gel process. However due to the inherent difference in the reactivity of the precursors, the hydrolysis of each precursor must be carried out separately before being combined for final condensation. Zirconium precursors are commonly chelated using acetic acids, prior to hydrolysis, to lower the hydrolysis …

Influence Of Magnesium Nitrate On The Corrosion Performance Of Sol-Gel Coated Aa2024-T3 Aluminium Alloy, Rajath Varma, Brendan Duffy, John Cassidy

Articles

Traditional anti-corrosion technology has relied heavily on using reducible metal species, predominantly hexavalent chromium (Cr(VI)), for protecting reactive metal alloys such as aluminium which is extensively used in the aerospace sector. However, the impending changes in the use of Cr(VI) in Europe and the United States have forced aerospace manufacturers to examine alternative materials for protecting aluminium. One of the most promising alternatives being investigated are organosilane based sol-gels containing anticorrosion additives. In this work the anti-corrosion properties of magnesium (II) nitrate (Mg(NO3)2) as a inhibitor was investigated at different concentrations (0.1% - 1.0 wt %) in a methyltriethoxysilane (MTEOS) …

Lipid Metal Organic Networks, Maria Eugenia Martinez

Open Access Theses & Dissertations

Metal–organic frameworks (MOFs) first appeared in the literature in 1991 and consist of three dimensional structures constructed by linking transition metal ions together through highly directional bonding with organic ligands. MOF materials offer the ability to choose from variety of metal centers that allow the tailoring of optical or magnetic properties, as well as control, to some extent, the size of the coordination sphere. Another advantage is the numerous organic ligands form which suitable pore geometries may be constructed with customized functionality among many applications in other areas such a gas storage chemical separations and selective catalysis. The primary objective …

Genetically Engineered Repetitive Polypeptides : Design, Synthesis, Characterization, And Applications, Natalya I. Topilina

Legacy Theses & Dissertations (2009 - 2024)

This work is dedicated to the investigation of protein folding with the emphasis on the aggregation and amyloid fibrils formation. The focus of the research is to elucidate the relationship between polypeptide chain sequence and folding/aggregation properties. For this purpose, i) libraries of the de novo macromolecular repetitive β-sheet forming polypeptides were designed, and ii) the strategy for their rapid creation was developed. The strategy enables retention of a basic polypeptide core, yet allowing variations in the repetitive sequence, degree of polymerization and distribution of specific amino acids. The polypeptides were expressed in E. coli, purified, and characterized by various …

Controlled Functionalization Of Crystalline Polyolefins And Their Application In Soluble Polymer Support, Jihoon Shin

UNLV Theses, Dissertations, Professional Papers, and Capstones

Functionalization of polyolefins has been recognized as a useful methodology for the generation of new materials with a wide range of applications. Recently, crystalline or semi-crystalline polyolefins have drawn increasing attention in both industrial and academic fields as one of the most interesting engineering plastics, due to their remarkable physical and mechanical properties. This dissertation describes: (1) novel methods for the direct postfunctionalization of crystalline polyolefins to introduce functionality, (2) characterizations for the functionalized polymers to analyze their structures, molecular-weight properties, thermal properties, and hydrophilicity, and (3) an application of the modified crystalline polystyrene as a soluble polymer support for …

The Synthesis And Spectroscopic Study Of A Spirooxazine-Functionalized Poly(Phenylenevinylene), Jordan Thomas Walk

Dissertations, Theses, and Masters Projects

No abstract provided.