Chemistry Commons^™

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 …

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 …

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 …

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 …

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 …

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 …

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. …

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 …

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 …

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 …

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) …

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 …

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 …

Investigation Of The Interactions Of Cationic Polyelectrolytes With Anionic Surfactants: Effects Of Polymer, Surfactant And Solution Properties, Lisa Renee Huisinga

Dissertations

The intent of this research is to explore and understand the effects that a range of polymer, surfactant and solution parameters have on the interaction of oppositely-charged polymers and surfactants. Cationic polysaccharides were chosen for this research because they are known to interact with anionic surfactants, and they offer a wide range of adjustable polymer properties, including molecular weight, charge substitution, and backbone structure. Cationic poly(vinylpyridinium hydrochloride) polymers were chosen for these studies because they provide the opportunity to explore the effects of charge position on the interaction of cationic polymers with anionic surfactants and how this influences the mechanism …

Examination Of An Aloe Vera Galacturonate Polysaccharide Capable Of In Situ Gelation For The Controlled Release Of Protein Therapeutics, Shawn David Mcconaughy

Dissertations

A therapeutic delivery platform has been investigated with the ultimate goal of designing a sustained protein release matrix utilizing an in-situ gelling, acidic polysaccharide derived from the Aloe vera plant. The Aloe vera polysaccharide (AvP) has been examined in order to determine how chemical composition, structure, molecular weight and solution behavior affect gelation and protein/peptide delivery. Correlations are drawn between structural characteristics and solution behavior in order to determine the impact of polymer conformation and solvation on gel formation under conditions designed to simulate nasal applications. Steady state and dynamic rheology, classic and dynamic light scattering, zeta potential, pulse field …

Dispersion States And Surface Characteristics Of Physically Blended Polyhedral Oligomeric Silsesquioxane/Polymer Hybrid Nanocomposites, Rahul Misra

Dissertations

Control of dispersion and segregation states of nanostructured additives is one of the biggest challenges in realizing the optimum potential of high-performance hybrid polymer nanocomposites. Polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals, with their hybrid organic-inorganic nature and flexible functionalization with a variety of organic substituents, yield possibilities to control dispersion and tune compatibility in a wide range of polymer systems. The overall goal of this research is to investigate the fundamental parameters that influence the dispersion and segregation states of POSS nanostructured chemicals and to understand chain dynamics and conformations in physically blended POSS hybrid polymer nanocomposites (HPNC's). Multiple structural …

Synthesis, Propagation Kinetics, And Characterization Of D,L-Lactide-Based Polyols And Polyurethanes Therefrom, Scott Joseph Moravek

Dissertations

In order to expand the usefulness of degradable polyesters, degradable polyurethanes were synthesized using a mixed polyol system including poly(D,L-lactideco- glycolide) (PLGA), a well-known degradable polyester. Two isocyanate systems, methyl 2,6-diisocyantocaproate (LDI) and dicyclohexylmethane-4,4'- diisocyanate(Hi2MDI), were studied in order to achieve optimal physical and thermal properties of the thermoplastic polyurethane (TPU) while maintaining degradablity. The LDI based systems had excellent physical properties as well as thermal properties that may make them suitable for biomedical devices. The H12MDI based TPUs also had excellent physical properties as well as a higher melting temperature. The aforementioned TPUs were synthesized in small batches. Another …

Preparation Of Carboxylic Acid Functionalized Glycopolymers Through Raft And Post-Polymerization Modification For Biomedical Application, Husnu Alp Alidedeoglu

Dissertations

The primary theme of this dissertation involves the synthesis of well-defined primary amine functionalized polymers, subsequent modification of the polymers to produce novel carboxylic acid functionalized glycopolymers and surface polymerization of these systems utilizing controlled polymerization techniques. Additionally, the synthesis of new water-based allylic copolymer latexes is described. Carbohydrates are natural polymers which possess unlimited structural variations. They carry a huge density of information, and play major roles in recognition events and complex biological operations. For example, hyaluronic acid (HA), an anionic glycosaminoglycan, provides lubricating and cushioning properties in the extracellular matrix and has been found to be involved in …

Photopolymerization And Characterization Of Thiol-Enes And Thiourethanes, Qin Li

Dissertations

Compared to conventional acrylic monomer systems, thiol-ene photopolymerization, an efficient click process leading to the formation of dense and uniform molecular networks, has several distinct advantages including relative insensitivity to oxygen inhibition, high monomer conversion and low shrinkage. Although there has been a revival of interest in thiol-enes in the past 6 years, the structure-property relationship of these networks has not been explored in detail. For future applications, thiol-enes with higher shelf-life stability and glass transition temperatures need to be used. Sulfur containing urethanes, thiourethanes and dithiourethanes are a class of widely used materials due to their distinct properties such …

The Relationship Betweeen Dynamic And Chemical Factors On The Morphology In Aot-Water-Polymer Systems, Jolanta Elzbieta Marszalek

Dissertations

Photopolymerization of reverse microemulsion demonstrates strong influences from dynamical and chemical factors on morphology of formed polymer systems. Upon polymerization the clear microemulsion with nanoscale structures transforms into opaque films with larger aggregates that scatter light. Studied here were microemulsions based on acrylate and on thiol-ene chemistries. The difference in the two reaction mechanisms results in the phase separation occurring at different stages of the material formation. Consequently, the morphology of the material demonstrates distinct dissimilarities in the two systems. In addition, the chemical structure of the monomers promotes these morphological differences. When the microemulsion is composed of acrylate and …

Synthesis And Characterization Of Biodegradable Polyurethanes For Biomedical Application, Changhong Zhang

All Dissertations

This dissertation constitutes the studies about the biomedical materials research of novel polyurethanes. These elastic and degradable polyurethanes exhibited the potential for drug delivery, scaffold fabrication by novel ink-jet printing technology or other biomedical applications. This dissertation includes two parts about two different types of polyurethanes.
In the first part of this dissertation, we studied a polyurethane that was synthesized from methylene di-p-phenyl-diisocyanate (MDI), polycaprolactone diol (PCL-diol) and N, N-bis (2-hydorxyethyl)-2-aminoethane-sulfonic acid (BES). MDI, PCL-diol and BES were polymerized into polyurethane and served as the hard segment, soft segment and chain extender respectively. The effects of the chain extender BES …

Electrochemical Synthesis And Characterization Of Polymers From Bis(3,4-Ethylenedioxythiophene)-Thiophenes (Bedot-Ts) And Bis(3,4-Ethylenedioxythiophene)-Benzenes (Bedot-Bs) As Optoelectronic Materials, Kalya Eaiprasertsak

All Dissertations

ABSTRACT


A series of bis(3,4-ethylenedioxythiophene)-thiophene derivatives (BEDOT-Ts) and bis(3,4-ethylenedioxythiophene)-benzene derivatives (BEDOT-Bs) monomers were electrochemically polymerized onto glassy carbon or ITO-coated glass electrodes. Cyclic voltammetry (CV), infrared (IR), UV-vis-NIR and photoluminescence (PL) spectroscopy were employed to investigate and characterize properties of resulting polymers. dc-conductivities of these polymers were measured by the four-point probe method.
Cyclic voltammetry studies show that the redox half potentials of PBEDOT-3BT, PBEDOT-3OT, PBEDOT-3TBS and PBEDOT-3MPT are -290, -297, -325 and -284 mV versus Ag/Ag+, respectively. The redox half potentials of PBEDOT-TOL, PBEDOT-BOB and PBEDOT-FB are -130, -147 and -327 mV vs. Ag/Ag+, respectively, and a bit higher …

Proposed Route To Cyclopenta[C]Thiophenes Via Activated Methylene, Vineet V. Karambelkar

Masters Theses & Specialist Projects

The synthesis of cyclopenta[c]thiophenes has been sparsely reported in the literature owing to several difficulties involved in their synthesis. The present work involves the proposed synthesis of cyclopenta[c]thiophenes and their precursors using activated methylene. Cyclopenta[c]thiophene compounds show promise in the field of polymer and catalysis chemistry. These substituted polythiophenes are potential organic semiconductors and anti-tumor agents. The research presented shows the successful and novel conversion of 3,4-bis(chloromethyl)-2,5-dimethylthiophene and 3,4-bis(bromomethyl)-2,5-dimethylthiophene to a fused 5,5'-fused membered ring which is the precursor to cyclopenta[c]thiophene the sulfone ester, 5-carbomethoxy-5- phenylsulfonyl-1,3-dimethyl-5,6-dihydro-4H-cyclopenta[c]thiophene, in just two steps as compared to four steps previously reported in the literature. …

A Selectivity Study On The Use Of Caffeine And Theobromine Imprinted Polypyrrole Surface Electrodes, Anil Kiran Kumar Vinjamuri

Masters Theses & Specialist Projects

Molecularly imprinted polymers (MIPs) are proving to be very effective in development of synthetic recognition systems and are of great interest to those interested in the field of sensor technology. The use of MIPs is receiving considerable interest due to the ability to prepare recognition matrices that possess high substrate selectivity and specificity. Conducting polymers (CP) have proved to be an excellent tool for the preparation of nano-structured biologically selective systems. Polypyrrole (Ppy) is one such CP that is extensively used for the construction of bioanalytical sensors. Ppy has shown great promise primarily due to its biocompatibility and thermal stability …

Optimization Of Microwave-Assisted Acid Digestion Method For Determination Of Trace Elements In Coal And Coal Fly Ash, Dejan Savic

Masters Theses & Specialist Projects

In most of the analytical and environmental laboratories today inductively coupled plasma (ICP) is a method of choice for analysis of trace metal elements present in coal and coal combustion products. This method requires use of liquid samples, so all coal and coal combustion products must be digested prior to analysis by ICP. Traditionally an open-air hot-plate acid digestion method published as ASTM D6357-04 was used to extract all trace metal elements into solution.

Recent development of microwave systems designed for digestions under extreme acidic conditions and high temperatures and pressures shifted focus toward more rapid and precise microwave-assisted digestion …

Poly(Ethylenedioxythiophene) Based Electronic Devices For Sensor Applications, Jie Liu

Doctoral Dissertations

Organic electronic devices, based on Poly (3,4-ethylenedioxythiophene)-Poly (styrene sulfonic acid) (PEDOT-PSS) as the active layer for sensor applications, have been studied. Two sets of sensors have been developed. In one case, sensors consisting of PEDOT-PSS resistors have been realized and demonstrated for soil moisture monitoring. The resistor model for the soil moisture sensor enables the sensor device to be fabricated at low cost and easily tested with a simple structure. Unlike the large dimension device used in Time Domain Reflectometry (TDR), the sensors are small and are capable of capturing microscale behavior of moisture in soil which is useful for …

Perfluorocyclobutyl Aryl Ether Polymers For Proton Exchange Membranes, Raul Hernandez

All Theses

Over the last decades Nafion¨ has emerged as the polymer of choice for the fabrication of Proton Exchange Membranes (PEM)s, due to its excellent proton conductivity and long-term stability. However, high temperatures and low relative humidity decrease fuel cell efficiency, due to the highly hydrated conditions required for proton conductivity. To overcome these issues, different types of sulfonated polymers have been proposed as promising substitutes for Nafion ¨, these include; Poly(arylene ether sulfones) (PAES) and Perfluorocyclobutyl (PFCB) aryl ether polymers among others.
Chapter 2 of this thesis describes the synthesis of a new class of sulfonated PAESs containing the perfluorocyclobutyl …

Broadband Dielectric Spectroscopy Studies Of Nafion, David Walter Rhoades

Dissertations

In light of available literature regarding Nafion® materials, it is apparent that an information gap exists between the current state of understanding of Nafion relaxations and the dielectric behavior of these materials. Although the currently available dielectric relaxation data is accurate it is very limited in its scope—specifically in-depth broadband analyses are not available. As a result, very little information is available regarding the dependence of the relaxation processes on frequency and temperature. This presents an important opportunity for the exploration of the dielectric broadband relaxation behavior of Nafion® materials. The primary intent of this research is to quantify the …

Photopolymerization And Characterization Of Crosslinked Thiol-Ene Networks And Poss/Thiol-Ene Nanocomposites, Tolecia Sharonda Shaunee Clark

Dissertations

Interests in the area of thiol-ene photopolymerization are rapidly expanding due to the numerous advantages over the polymers produced by traditional solvent based polymerizations. Although current research of photoinitiated thiol-ene polymerization is diverse, numerous opportunities are available for investigating structure/property and structure/reactivity relationships and novel material applications. This research in this dissertation includes a fundamental study of the effect of monomelic thiol functionality on thiol-ene polymerization kinetics and formation of the thiol-ene network structure, and an investigation of the development of novel silicate based thiol-ene nanocomposites. The first fundamental study investigates the effect of thiol functionality on the kinetics and …

The Design, Synthesis, And Controlled Polymerization Of Cationic And Zwitterionic Norbornene Derivatives, David Allen Rankin

Dissertations

Ring-opening metathesis polymerization (ROMP) has been exploited for the controlled polymerization of cationic and zwitterionic norbornene-based monomers and employed in the preparation of homo- and block-copolymer systems in homogeneous organic media without the use of post-polymerization modification or protecting group chemistries. Relying on previous knowledge of certain halogenated alcoholic organic solvents capable of solubilizing hydrophilic monomers, the first study, describes the synthesis and controlled polymerization of a series of new permanently cationic ammonium exo-7- oxanorbornene derivatives M31 via ROMP, with the first generation Grubbs catalyst 17, in a novel solvent mixture comprised of 1:1 vol/vol 2,2,2-trifluoroethanol (TFE)/methylene chloride (CH2CI2). This …