Polymer samples of polytetrafluoroethylene (PTFE) and a PTFE-glass weave (RF- 35P) are exposed to low pressure, non-equilibrium glow discharge plasmas for enhanced wettability as measured by static contact angles. Plasma treatments are performed in two parallel plate RF plasma systems, a downstream microwave plasma and a barrel etcher using feed gases composed of H₂, N₂, Ar, He, and 0₂. Surface analysis of the topography and chemical composition of treated samples is performed by atomic force microscopy (AFM), attenuated total reflection infrared (ATR-IR) spectroscopy, x-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (ToF SIMS). Optical emission spectroscopy is used to correlate wettability to reactive species in the plasma, and plasma parameters to species emission. In the parallel plate plasma systems, the contact angle can change from approximately 95° to 5° with treatment while treatments in the downstream and barrel etcher systems do not result in a contact angle change. The difference in plasma performance is attributed to ion bombardment. Plasmas composed of 20 to 80% H₂O in (H₂ + N₂) give the best wettability improvement. Plasma exposure significantly reduces the surface fluorine content followed by incorporation of nitrogen, oxygen and hydrogen, apparently as amino, hydroxyl and carbonyl functional groups with evidence of an amide. The incorporation of oxygen likely originates through peroxy radicals subsequent to plasma exposure. It is proposed that using a higher applied power creates a more reactive surface. A larger percentage of H₂ in the plasma tends to passivate the surface, leading to a smaller wettability improvement which is correlated to the atomic hydrogen concentration in the plasma. The addition of He or Ar into the H₂/N₂ plasma tends to dilute or weaken the plasma effect on wettability. To a much greater extent, the addition of oxygen also decreases the wettability. This latter effect is attributed to etching reactions which result in a more hydrophobic surface. An etch rate of approximately 0.2 μ/min is observed, and this is the first report of PTFE etching with 0₂/H₂/N₂. The distance between the parallel plate electrodes (gap) is a significant factor for the wettability of treated polymers, while power, pressure and flow rate are not. The optimal storage conditions to retain the wettability of H₂/N₂ plasma-treated RF-35P are low pressure and low temperature. The following model of PTFE surface modification is proposed. Ion bombardment creates reactive sites that initiate surface reactions. Reactive species from the H₂/N₂ plasma modify the surface through incorporation of amino, hydroxyl and carbonyl surface groups. These new groups increase the polymer wettability. Atomic hydrogen in the mixture is required to improve the wettability, but too high of a concentration will passivate the surface and lessen the wettability improvement. If oxygen is present, the modified surface is etched away leaving a refreshed, more hydrophobic surface. / Graduation date:2006

Controlled radical polymerization has proven to be a viableroute to obtain polymers with narrow polydispersities (PDI's)and controlled molecular weights under simple reactionconditions. It also offers control over the chain-]ends of thesynthesized polymer. Atom transfer radical polymerization(ATRP) is the most studied and utilized of these techniques. Inthis study ATRP has been utilized as a tool to obtain differentcomplex macromolecular structures. In order to elaborate a system for which a multitude ofchains can polymerize in a controlled manner and in closeproximity to one another, a multifunctional initiator based onpoly(3-ethyl-3-(hydroxymethyl)oxetane was synthesized. Themacroinitiator was used to initiate ATRP of methyl acrylate(MA). The resulting dendritic-]linear copolymer hybrids hadcontrolled molecular weights and low PDI's. Essentially thesame system was used for the grafting of MA from a solidsubstrate, cellulose. A filter paper was used as cellulosesubstrate and the hydroxyl groups on the cellulose weremodified into bromo-]ester groups, known to initiate ATRP.Subsequent grafting of MA by ATRP on the cellulose made thesurface hydrophobic. The amount of polymer that was attached tothe cellulose could be tailored. In order to control that thesurface polymerization was -eliving-f and hence that thechain-]end functionality was intact, a second layer of ahydrophilic monomer, 2-hydroxyethyl methacrylate, was graftedonto the PMA- grafted cellulose. This dramatically changed thehydrophilicity of the cellulose. Dendronized polymers of generation one, two and three weresynthesized by ATRP of acrylic macromonomers based on2,2-bis(hydroxymethyl)propionic acid. In the macromonomerroute, macromonomers of each generation were polymerized byATRP. The polymerizations resulted in polymers with low PDI's.The kinetics of the reactions were investigated, and thepolymerizations followed first-order kinetics when ethyl2-bromopropionate was used as the initiator. In the-egraft-]onto-f route dendrons were divergently attached to adendronized polymer of generation one, that had been obtainedby ATRP.

Arborescent polymers are characterized by a tree-like architecture and a high branching functionality. This type of polymer can be synthesized by different techniques, but the ‘grafting onto’ method is attractive because it provides good control over the molecular weight of the graft polymer and the side-chains used as building blocks. This method was applied to the synthesis of arborescent polybutadiene, using cycles of epoxidation and anionic grafting reactions. The research focused on optimization of the grafting yield for the synthesis of the G0 polymers, obtained by grafting side-chains onto a linear epoxidized substrate, with the ultimate goal of synthesizing successive generations of graft polymers using these optimized conditions. Two additives potentially useful as reactivity modifiers, N,N,N’,N’-tetramethylethylenediamine (TMEDA) and lithium bromide (LiBr), were investigated to increase the grafting yield. The influence of solvent polarity was also examined, and the reaction time was varied from one day to one week while monitoring the grafting yield. Optimal results (with grafting yields reaching up to 85% in one week) were obtained in cyclohexane-tetrahydrofuran mixtures, in the presence of LiBr, with only small (2-3%) yield increases observed after 24 h of reaction. These optimal conditions, when applied to the synthesis of G1 and G2 polymers, led to grafting yields of 78-80% when using a 1:1 ratio of epoxide groups to living ends. The influence of excess substrate was also examined individually for each generation, and likewise led to small (2-4%) increases in grafting yield. The results obtained showed that the grafting reaction was successful on the basis of 1H NMR spectroscopy and size exclusion chromatography analysis, and was sensitive to parameters such as the substitution level of the epoxidized substrate, the solvent composition, and the presence of additives.

No description available.

The thermodynamic parameters associated with the copolymerization of ethylene and carbon dioxide were calculated using bond dissociation energies, the Benson additivity method and density functional theory calculations (DFT). In all cases, the formation of an alternation copolymer was found to be endergonic at any reasonable polymerization temperatures (the ceiling temperature is calculated to be -159 °C). However, the polymerization was calculated to be exergonic at room temperature, as long as the incorporation of CO2 is less than 29.7 mol%. Experiments failed to provide evidence of any CO2 incorporation, despite previously published reports claiming up to 30 mol%. Octamethyloctahydrodibenzofluorenyl (Oct) has profound steric consequences when incorporated into metallocene olefin polymerization catalysts – including increased catalytic activity and stereoselectivity. However, the electronic effect of the ligand’s four electron-donating tertiary alkyl groups is less understood. NMR and DFT calculations were used to study the electronic nature of the Oct moiety – both as a part of ansa-metallocene pre-catalysts and as an independent molecule. The results show that Oct is more electron rich than other cyclopentadienyl analogues and that the electronics of the ligand are readily conveyed to the metal center. Upon activation, the steric bulk of the Oct moiety dominates the immediate environment around the metal center. Evidence is presented that supports previous theories about Oct’s ability to influence the counteranion distance, thereby increasing the catalytic activity. In addition, excess trimethyl aluminum (TMA) is known to be detrimental to catalytic activity and results uphold this belief – although the magnitude of the effect varies depending on the metallocene being studied. However, UV-Vis data do not support the theory that TMA binds to the catalytically-active metal center, thereby decreasing the catalytic activity; but does not offer an alternate mechanism.

<p>Controlled radical polymerization has proven to be a viableroute to obtain polymers with narrow polydispersities (PDI's)and controlled molecular weights under simple reactionconditions. It also offers control over the chain-]ends of thesynthesized polymer. Atom transfer radical polymerization(ATRP) is the most studied and utilized of these techniques. Inthis study ATRP has been utilized as a tool to obtain differentcomplex macromolecular structures.</p><p>In order to elaborate a system for which a multitude ofchains can polymerize in a controlled manner and in closeproximity to one another, a multifunctional initiator based onpoly(3-ethyl-3-(hydroxymethyl)oxetane was synthesized. Themacroinitiator was used to initiate ATRP of methyl acrylate(MA). The resulting dendritic-]linear copolymer hybrids hadcontrolled molecular weights and low PDI's. Essentially thesame system was used for the grafting of MA from a solidsubstrate, cellulose. A filter paper was used as cellulosesubstrate and the hydroxyl groups on the cellulose weremodified into bromo-]ester groups, known to initiate ATRP.Subsequent grafting of MA by ATRP on the cellulose made thesurface hydrophobic. The amount of polymer that was attached tothe cellulose could be tailored. In order to control that thesurface polymerization was -eliving-f and hence that thechain-]end functionality was intact, a second layer of ahydrophilic monomer, 2-hydroxyethyl methacrylate, was graftedonto the PMA- grafted cellulose. This dramatically changed thehydrophilicity of the cellulose.</p><p>Dendronized polymers of generation one, two and three weresynthesized by ATRP of acrylic macromonomers based on2,2-bis(hydroxymethyl)propionic acid. In the macromonomerroute, macromonomers of each generation were polymerized byATRP. The polymerizations resulted in polymers with low PDI's.The kinetics of the reactions were investigated, and thepolymerizations followed first-order kinetics when ethyl2-bromopropionate was used as the initiator. In the-egraft-]onto-f route dendrons were divergently attached to adendronized polymer of generation one, that had been obtainedby ATRP.</p>

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Dissertation (Ph. D.)--University of Akron, Dept. of Polymer Science, 2009. / "May, 2009." Title from electronic dissertation title page (viewed 11/29/2009) Advisor, Judit E. Puskas; Committee members, Roderic P. Quirk, Joseph P. Kennedy, Li Jia, Chrys Wesdemiotis; Department Chair, Ali Dhinojwala; Dean of the College, Stephen Z. D. Cheng; Dean of the Graduate School, George R. Newkome. Includes bibliographical references.

Thesis (Ph. D.)--Lehigh University, 2002. / Includes bibliographical references and vita.

Thesis (Ph. D.)--School of Chemistry and Biochemistry, Georgia Institute of Technology, 2004. Directed by Andrew Lyon. / Vita. Includes bibliographical references.