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Raman spectroscopy is often used for material identification but may be used for characterization. This document focuses on using Raman measurements to characterize polymers, specifically the curing and aging mechanism for hydroxyl-terminated polybutadiene (HTPB). HTPB is a well-known elastomer used in sealants, non-slip surfaces, rocket repellants and plastic explosives. Raman spectroscopy was used to monitor urethane linkages that form from curing HTPB with a cyanate curing agent to suggest a curing mechanism for HTPB. Since this polymer is highly susceptible to oxidation, the methods used to characterize curing were also used for the aging process to see if urethane breakages could be observed. Raman measurements were compared to elongation-at-break measurements to assess the short-term aging process. Results showed that oxidation of the urethane linkage seemed to be the primary source of degradation during early thermal aging. Patterns seen in Raman data may be studied to suggest an oxidation mechanism at the urethane site as a starting point to unravel the network of aging mechanisms for HTPB. Additionally, a recently published mount design is discussed for sustained tensile strain. The mount setup was used to mechanically extend samples while taking real-time spectroscopic data. Testing for the mount was done on HTPB and high-density polyethylene, but the design may accommodate a large variety of materials and is compatible with many spectroscopic methods including Raman spectroscopy.

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L’objet de ces travaux de thèse est d’étudier la synthèse de polybutadiène au moyen de systèmes d’amorçage multi-métalliques. L’utilisation d’alcoolates de potassium en association avec des dérivés d’alkyllithium a été étudiée afin d’obtenir du polybutadiène de façon contrôlée avec 50% d’unités vinyliques en milieu apolaire. Dans un second temps, ces travaux démontrent que des systèmes d’amorçage sans lithium permettent la synthèse de polybutadiène par voie anionique. Lorsque le dialkylmagnesium est associé à un alcoolate de potassium, il permet l’obtention de polybutadiène avec 50% d’unités vinyliques, alors que le système dialkylmagnesium / alcoolate de baryum permet la synthèse de polybutadiène à fort taux de 1,4-trans (65%). / The goal of this research work is to find original ways to obtained polybutadiene with defined microstructure by developing multimetallic initiation systems. The aim of the first experimental chapter was to obtain polybutadiene with a 50% vinyl content in a controlled way in apolar media. This objective was achieved by using a bimetallic system based on potassium alkoxide and alkyllithium. The goal of the last experimental chapter was to prospect multimetallic initiation systems allowing obtention of polybutadiene without using lithium derivatives. The use of dialkylmagnesium in association with potassium alkoxide was found relevant to produce polybutadiene with a 50% vinyl content, while the association of dialkylmagnesium and barium alkoxide allows the synthesis of polybutadiene with a high 1,4-trans content (up to 65%).

Cationic photopolymerization of multifunctional epoxides is very useful for efficient cure at room temperature and has been widely used in coatings and adhesives. Despite excellent properties of the final cured polymers, cationic photopolymerizations of epoxides have seen limited application due to slow reactions (relative to acrylates) and brittleness associated with a highly crosslinked, rigid network. To address these issues, two reaction systems were studied in this thesis: photoinitiated cationic copolymerizations of a cycloaliphatic diepoxide with epoxidized elastomers and acrylate/epoxide hybrid photopolymerizations. Oligomer/monomer structures, viscosity, compositions, and photoinitiator system were hypothesized to play important roles in controlling photopolymerizations of the epoxide-based mixtures. A fundamental understanding of the interplay between these variables for the chosen systems will provide comprehensive guidelines for the future development of photopolymerization systems comparable to the epoxide-based mixtures in this research. For diepoxide/oligomer mixtures, the observed overall enhancement in polymerization rate and ultimate conversion of the cycloaliphatic diepoxide was attributed to the activated monomer mechanism associated with hydroxyl terminal groups in the epoxidized oligomers. This enhancement increased with increasing oligomer content. The mixture viscosity influenced the initial reactivity of the diepoxide for oligomer content above 50 wt.%. Real-time consumption of internal epoxides in the oligomers was successfully determined using Raman spectroscopy. Initial reactivity and ultimate conversion of the internal epoxides decreased with increasing the diepoxide content. This trend was more pronounced for the oligomer containing low internal epoxide content. These results indicate that the reactivity of the hydroxyl groups is higher toward cationic active centers of the diepoxide than those of the internal epoxides in the oligomers. These conclusions are consistent with physical property results. The enhanced fracture toughness and impact resistance were attributed to multimodal network chain-length distribution of copolymers containing the oligomer content between 70% and 80%. For acrylate/epoxide hybrid mixtures, diacrylate oligomers significantly suppressed reactivities of cycloaliphatic mono/diepoxides, which was attributed to high mixture viscosity and highly crosslinked acrylate network. In this case, the dual photoinitiator system did not favor the epoxide reaction. Depending on the monovinyl acrylate secondary functionalities, enhanced reactivity and ultimate conversion of the diepoxide were attributed to a combined effect of a reduced viscosity and the radical-promoted cationic polymerization associated with the dual photoinitiator. The retarded and inhibited diepoxide reactivities with ether and urethane secondary groups were attributed to solvation and nucleophilicity/basicity effects, respectively. The influence of the diepoxide on the acrylate reactivity was attributed to dilution and polarity effects. In this case, high concentration of the free-radical photoinitiator is required for the dual photoinitiator system. Physical properties of hybrid polymers also varied with acrylate structures and monomer composition. Dynamic modulation methods were proposed to enhance the diepoxide reactivity and final properties in the presence of urethane acrylates.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta Dissertação foi utilizado um sistema catalítico Zieger-Natta à base de neodímio para avaliar a influência do agente de halogenação e da razão molar halogênio:Nd sobre a atividade catalítica, a constante de velocidade de propagação, a conversão da polimerização, a microestrutura, a massa molecular e a polidispersão do polibutadieno 1,4-cis. O sistema utilizado era constituído por versatato de neodímio (NdV), hidreto de diisobutilalumínio (DIBAH) e um agente de halogenação. Os agentes halogenantes estudados foram: cloreto de t-butila (t-BuCl), sesquicloreto de etilalumínio (EASC) e cloreto de dietilalumínio (DEAC), em valores de razão molar Cl:Nd que variaram entre 0,5:1 e 5:1 e o dietil-eterato de trifluoreto de boro (BF3.Et2O), na razão molar F:Nd = 3:1. Os polímeros foram caracterizados por espectroscopia na região do infravermelho para determinação da microestrutura e por cromatografia de exclusão por tamanho para determinação das massas moleculares. O teor de unidades 1,4-cis variou de 90 a 98%, a massa molecular numérica média ( ) permaneceu na faixa entre 0,2 e 2x105, e a massa molecular ponderal média ( ) variou de 1,4 a 4x105 / In this Dissertation a catalyst system based on neodymium was employed to evaluate the influence of halogen source and the halogen:Nd molar ratio on the catalyst activity, polymerization constant rate, polymerization conversion, molecular weight characteristics and microstructure of polybutadiene. The catalyst systems were formed by diisobutylaluminium hydride (DIBAH), neodymium versatate (NdV) and a halogen source. The halogenating agents studied were t-butyl chloride (t-BuCl), ethylaluminium sesquichloride (EASC) and diethylaluminium chloride (DEAC) in a nCl:nNd molar ratio in the range from 0,5 to 5, and boron trifluoride diethyl ether (BF3.Et2O). The polymers were characterized by infrared espectroscopy for determining the microstructure and by size exclusion chromatography to obtain the molecular mass characteristics. The cis-1,4 units contents varied from 90 to 98%, the number-average molecular mass ( ) varied from 0,2 to 2x105 and the weight-average molecular mass ( ) varied from 1,4 to 4x105

Les traitements plasma sont devenus des moyens incontournables et puissants pour modifier les propriétés de surface de nombreux matériaux sans intervenir sur les propriétés massiques et ceci en étant respectueux de l’environnement. Si ces traitements ont été appliqués à de nombreuses reprises aux élastomères réticulés pour améliorer leurs propriétés d’adhérence, ils n’ont quasiment jamais été appliqués à des élastomères non réticulés. Les expositions plasma ont été réalisées à basse pression, en décharge radiofréquence dans un environnement d’air. Pour limiter la complexité de l’étude et pour obtenir une meilleure compréhension des mécanismes d’interaction plasma-surface, un SBR et un polybutadiène (BR) non chargés et non réticulés ont été utilisé comme élastomères modèles. Le rôle d’un d’antioxydant (6PPD) classiquement utilisé a également été étudié. L’influence de la configuration du réacteur plasma sur les modifications surface a été suivie par mouillabilité et spectroscopie XPS. La cartographie des espèces plasmagènes a été obtenue par spectroscopie d’émission optique.L’augmentation du caractère hydrophile des surfaces avec l’énergie du plasma jusqu’à un seuil énergétique a pu être mise en évidence. Au-delà les phénomènes d’ablation et de réticulation de surface deviennent prépondérants. Les modifications de surface et leur cinétique de réorganisation de surface des chaînes polymère dépendent essentiellement de la température, l’environnement est un paramètre secondaire. L’influence de ces modifications physico-chimiques de surface induite sur les propriétés de tack est clairement mise en évidence. L’augmentation du caractère hydrophile conduit à une augmentation importante des performances adhésives instantanées (temps courts de contact 100s) au contact du verre. Par contre, la réticulation superficielle consécutive à des expositions plasma trop énergétiques diminue de façon drastique l’autohésion, ie le contact entre deux surfaces élastomères traitées. Le rôle de l’antioxydant sur la recombinaison des radicaux macromoléculaires formés lors du traitement a été montré. Le succès de la mise en œuvre d’un traitement de surface par plasma repose sur le contrôle du seuil énergétique à ne pas dépasser de sorte à minimiser les phénomènes de réticulation superficielle. / Plasma treatment has become a powerful candidate to modify surface properties without any change in bulk properties. It combines high chemical reactivity with low operational costs, in environmentally friendly processes. Plasma treatment has been intensively applied for surface modification of vulcanized rubbers. Almost no studies have been dedicated to plasma treatment of unvulcanized rubbers. The role of each additive during plasma exposure is poorly understood. It is also admitted that surface crosslinking occurs easily on rubber surfaces exposed to plasmas. This impacts the adhesive properties of the rubbers because it mimics chain interdiffusion. In this context, determining the key plasma parameters that have a significant effect on the surface properties is a prerequisite for further process control. To limit the complexity of the study, we concentrated our efforts on unvulcanized filler-free styrene butadiene rubber (SBR) and polybutadiene rubber (BR) which has been used for the first time as rubber models. The effect of three main parameters that directly impact the amount of energy and the nature of the excited species in the plasma phase (i.e. the RF source power, the exposure time and the distance between the rubber samples and the plasma) was analyzed. Optical Emission Spectroscopy was used to characterize the plasma phase. Surface modifications were investigated by wettability measurements and X-Ray Photoelectron Spectroscopy. Surface aging was investigated under ambiant and inert atmosphere at different temperatures and finally tack properties were measured and connected to surface properties determined with optical emission spectroscopy.

The marked increase in surface-to-volume ratio associated with microscale devices for hemodialysis leads to problems with hemocompatibility and blood flow distribution that are more challenging to manage than those encountered at the conventional scale. In this work, stable surface modifications with pendant polyethylene oxide (PEO) chains were produced on polycarbonate microchannel and polyacrylonitrile membrane materials used in construction of microchannel hemodialyzer test articles. These coatings were evaluated in relation to protein repulsion, impact on urea permeability through the membrane, and impact on bubble retention through single-channel test articles. PEO layers were prepared by radiolytic grafting of PEO-PBD-PEO (PBD = polybutadiene) triblock copolymers to microchannel and membrane materials. Protein adsorption was detected by measurement of surface-bound enzyme activity following contact of uncoated and PEO-coated surfaces with ��-galactosidase. Protein adsorption was decreased on PEO-coated polycarbonate and polydimethyl siloxane (PDMS) materials by 80% when compared to the level recorded on uncoated materials. Protein adsorption on membrane materials was not decreased with PEO-PBD-PEO treatment; a PEI (polyethylene imide) layer exists on the AN69 ST membrane which is intended to trap heparin during membrane pre-treatment. It is still unclear how this PEI layer interacts with PEO-PBD-PEO. Neither the PEO-PBD-PEO triblocks nor the irradiation process was observed to have any effect on polyacrylonitrile membrane permeability to urea, nor did the presence of additional fibrinogen and bovine serum albumin (BSA) in the urea filtrate. The PEO-PBD-PEO treatment was not able to visibly reduce bubble retention during flow through single-channel polycarbonate test articles, however, the rough surfaces of the laser-etched polycarbonate microchannels may be causing this bubble retention. This surface treatment holds promise as a means for imparting safe, efficacious coatings to blood processing equipment that ensure good hemocompatibility and blood flow distribution, with no adverse effects on mass transfer. / Graduation date: 2013

The object of this research was to investigate dispersion in surface phononic crystals (PnCs) for application to a newly developed passive surface acoustic wave (SAW) ozone sensor. Frequency band gaps and slow sound already have been reported for PnC lattice structures. Such engineered structures are often advertised to reduce loss, increase sensitivity, and reduce device size. However, these advances have not yet been realized in the context of surface acoustic wave sensors. In early work, we computed SAW dispersion in patterned surface structures and we confirmed that our finite element computations of SAW dispersion in thin films and in one dimensional surface PnC structures agree with experimental results obtained by laser probe techniques. We analyzed the computations to guide device design in terms of sensitivity and joint spectral operating point. Next we conducted simulations and experiments to determine sensitivity and limit of detection for more conventional dispersive SAW devices and PnC sensors. Finally, we conducted extensive ozone detection trials on passive reflection mode SAW devices, using distinct components of the time dispersed response to compensate for the effect of temperature. The experimental work revealed that the devices may be used for dosimetry applications over periods of several days.