Nesta tese procuramos caracterizar o Policarbonato Bisfenol-A, Durolon&#174 sob o ponto de vista elétrico, separando a reação dipolar e os processos de condução. Apesar de preparadas de forma análoga, as amostras (&#8773 30&#956m de espessura) mostraram comportamento pouco reprodutível, principalmente da componente condutiva. Várias anomalias foram detectadas embora não estudadas em detalhe pela pobre reprodutibilidade já mencionada. Além das técnicas usuais de polarização e despolarização isotérmicas, despolarização termoestimulada e de polarização termoestimulada, empregou-se pela primeira vez, em medidas desta natureza, a técnica de oscilação senoidal da temperatura, estando o campo elétrico aplicado. Media-se a corrente daí decorrente, procurando-se trabalhar sempre com uma mesma amostra. Na região de 50&#176C a 70&#176C, diferenças de fase superiores a 90&#176 foram encontradas (o sinal de corrente atrasado em relação ao de temperatura). Uma análise simples destes resultados indica que, neste caso, tanto a condutividade como a suscetibilidade diminuem com o crescimento da temperatura (dX/dT&#8773 -1x10-3/&#176C). Medidas de polarização termoestimulada, também, mostram uma inversão da corrente em relação ao campo aplicado desde cerca da temperatura ambiente ate &#8773 90&#176C. Um estudo sistemático da condução a 120&#176C indica que portadores são emitidos do eletródio, e que o trânsito dos mesmos é rápido (menor do que o tempo em que a polarização se estabelece, &#8773 2 min). Tensões e correntes espontâneas foram detectadas mesmo em amostras providas de eletródios de mesmo metal (uma correlação com a ordem empregada na metalização foi suspeitada, seguindo observação anteriormente feita pelo Prof. B. Gross). Algumas medidas com eletródios Al-Al, Al-Au e Au-Au foram feitas. Finalmente, sugestões para trabalhos futuros são feitas. / In this work the electrical characterization of the Polycarbonate Bisphenol-A, Durolon &#174 was attempted, trying to separate the dipole and the conduction processes. However, poor reproducibility, mainly in the conductivity, was achieved even for samples (&#8773 30&#956m thick usually) taken from the same batch. Anomalies were detected but not studied in detail owing the poor reproducibility referred above. Beside the usual techniques like the isothermal polarization and depolarization in short-circuit, thermally depolarization currents and thermally stimulated polarization, in a new one, employed by the first time for the study of transport and polarization, the temperature was oscillated and the ensuing current oscillation was monitored. Large phase shifts (the current lagging the temperature oscillation), even greater &#8773 90&#176 were found in the range 50&#176C 70&#176C. A simple analysis indicates that in this case both the conductivity as well as the susceptibility are decreased for increasing temperature (dX/dT&#8773 -1x10-3/&#176C). Accordingly thermally stimulated polarization shows a current reversal with respect to the electric field from room temperature to &#8773 90&#176C. A systematic study of the conduction process at 120&#176C was carried out, the analysis of which indicates that carriers are emitted from the electrode, whose transit across the sample is shorter than the duration of the polarization current (&#8773 2 min). Spontaneous tensions and currents were detected even for samples provisioned with similar electrodes (a correlation with the actual sequence of metallization, following a suggestion by Prof. B. Gross, was surmised). A few measurements with Al-Al, Al-Au and Au-Au electrodes were carried out. Finally suggestions for future work are given.

There has been a growing demand for specific linear alpha olefins in the polyethylene industry in order to control polymer rheology. This growing demand thereby increases the need for highly active and selective ethylene oligomerization catalysts. Chromium-based catalysts continue to be of high interest for this application due to this metal’s versatility in both selective and non selective ethylene oligomerization. Ligand design is an important consideration in oligomerization chemistry: the ability of the ligand to stabilize low valent chromium and to support a two-electron redox process will allow the catalytic systems to follow the selective ring expansion mechanism for oligomerization. Chelating aminophosphane based ligands, previously studied by our group, have been shown to support both tri- and tetramerization of ethylene. We have explored modifications of one of the NP arms by replacing with a different coordinating group in an attempt to further stabilize the monovalent state of chromium and increase selectivity. Other ligands explored in this work are pyrrole based ligands, which have shown high activity and selectivity towards ethylene oligomerization. One example of this is the commercial Chevron-Phillips system. Recently, the co-polymerization of CO2 with epoxides has been studied as an environmentally friendly route to convert CO2 into biodegradable polymers. The first successful catalytic system to achieve these results consisted of a diethyl-zinc complex. More recently, aluminum, chromium, cadmium and cobalt have been studied as polycarbonate catalysts. To date, the only reported chromium catalysts for CO2-epoxide copolymerization are Cr-salen and Cr-porphyrin complexes, studied by Darrensbourg and Holmes, respectively. We were particularly interested in finding new chromium-based complexes able to catalyze epoxide/CO2 copolymerization by using molecules with the nitrogen donor motif embedded in different functions such as neutral pyridines with anionic pendants, pyrroles with either imine or amine pendants, or a combination of these.

"Chain walking” catalytic polymerization CWCP is a powerful tool for the one-pot synthesis of a unique class of hyperbranched polyethylene HBPE-based macromolecules with a controllable molecular weight, topology, and composition. This dissertation focuses on new synthetic routes to prepare HBPE-based macromolecular architectures by combining the CWCP technique with ring opening polymerization ROP, atom–transfer radical polymerization ATRP, and “click” chemistry. Taking advantage of end-functionalized HBPE, and a new ethynyl-soketal star-shape agent, we were able to synthesize different types of the HBPE-based architectures including hyperbranched-on-hyperbranched core-shell nanostructure, and miktoarm-star-HBPE-based block copolymers. The first part of the dissertation provides a general introduction to the synthesis of polyethylene types with controllable structures. Well-defined polyethylene with different macromolecule architectures were synthesized either for academic or industrial purposes. In the second part, the HBPE with different topologies was synthesized by CWCP, using a α-diimine Pd (II) catalyst. The effect of the temperature and pressure on the catalyst activity and polymer properties, including branch content, molecular weight, distribution, and thermal properties were studied. Two series of samples were synthesized: a) serial samples (A) under pressures of 1, 5, and 27 atm at 5˚C, and b) serial samples (B) at temperatures of 5, 15, and 35 ˚C under 5 atm. Proton nuclear magnetic resonance spectroscopy, 1H NMR, and gel permeation chromatography, GPC, analysis were used to calculate the branching content, molecular weight, and distribution, whereas differential scanning calorimetry, DSC, was used to record the melting and glass transition temperatures as well as the degree of the crystallinity. Well-defined HBPE-based core diblock copolymers with predictable amphiphilic properties are studied in the third part of the project. Hyperbranched polyethylene-b-poly(N-isopropylacrylamide), HBPE-b-PNIPAM, and hyperbranched polyethylene-b-poly(solketal acrylate), HBPE-b-PSA, were successfully synthesized by combining CWCP and ATRP. The synthetic methodology includes the following steps; a) synthesis of multifunction hyperbranched polyethylene initiators HBPE-MI by direct copolymerization of ethylene with 2-(2-bromoisobutyryloxy)ethyl acrylate BIEA in the presence of a α-diimine Pd(II) catalyst, and b) HBPE-MI with α-bromoester groups used as initiation sites for ATRP. Proton nuclear magnetic resonance spectroscopy, 1H NMR, gel permeation chromatography,GPC, and Fourier transform infrared, FT-IR, spectroscopy, were used for determining the molecular and composition structures. Also, differential scanning calorimetry, DSC, and thermogravimetric analysis, TGA, were used to record the melting temperature and to study the thermal stability, respectively. In the fourth part, a well-defined 3-miktoarm star copolymer 3μ-HBPE(PCL)2 (HBPE: hyperbranched polyethylene, PCL: poly(ε-caprolactone) was synthesized by combining CWCP, ring opening polymerization, ROP, and “click” chemistry. The synthetic methodology includes the following steps: a) synthesis of azido-functionalized hyperbranched polyethylene HBPE-N3 by CWCP of ethylene with the α-diimine Pd(II) catalyst, followed by quenching with an excess of 4-vinylbenzyl chloride and transformation of –Cl to the azido group with sodium azide, b) synthesis of in-chain ethynyl-functionalized poly(ε-caprolactone), (PCL)2-C≡CH by ROP of ε-CL with ethynylfunctionalized solketal [3-(prop-2-yn-1-yloxy) propane-1,2-diol] as a bifunctional initiator, in the presence of P2-t-Bu phosphazene super base, and c) “clicking” HBPE-N3 and (PCL)2-C≡CH using the copper(I)-catalyzed alkyne–azide cycloaddition CuAAC. Proton nuclear magnetic resonance spectroscopy, 1H NMR, gel permeation chromatography, GPC, and Fourier transform infrared, FT-IR, spectroscopy, were used to determine the molecular and composition structures. Also, the differential scanning calorimetry, DSC, was used to record the melting point temperature. The fifth part illustrates the self-assembly behavior of the HBPE-based block copolymers of poly(N-isopropylacrylamide), NIPAM, and poly(ε-caprolactone), PCL, at room temperature in water and a petroleum ether-selective solvent for NIPAM and PCL respectively. The synthesized copolymers HBPE-b-NIPAM and 3μ-HBPE(PCL)2 revealed either core-shell nanostructure in vesicles or worms and worm-likes branches, as confirmed by combining the analysis of dynamic light scattering, DLS, transmission electron microscopy, TEM, and atomic force spectroscopy, AFM. All the findings presented in this dissertation emphasize the utility of "living" CWCP to synthesize end-functionalized HBPE, and new star-linkage HBPE-based complex architectures. The summary and future works concerning predictable properties and applications are discussed in the sixth part.

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This work investigates processing-microstructure-property relationships of a model cryogenically mechanically alloyed polymer-polymer system: polycarbonate (PC) and poly (ether ether ketone) (PEEK). Mechanically milled and alloyed powders were characterized using a variety of techniques including microscopy and thermal analysis. Cryogenically mechanically alloyed powders processed for 10 hours were shown to have a sub-micron level two-phase microstructure. These powders were processed into testable coupons using a mini ram-injection molder; microstructure and bulk mechanical properties of the coupons were investigated as a function of mechanical alloying and injection molding parameters. Atomic force microscopy, transmission electron microscopy, and scanning transmission X-ray microscopy revealed that the intimate blending achieved during the mechanical alloying process is not retained upon post-processing using a conventional polymer processing technique. Injection molded coupons were tested in 3-point bend mode via dynamic mechanical and quasi-static mechanical testing. Results demonstrated that no improvement in energy to break, strain at failure, or failure strength was achieved in coupons made from cryogenically mechanically alloyed powders compared to those of coupons made from non-mechanically alloyed samples. / Ph. D.

The purpose of this study was to characterize the craze growth behavior of polycarbonate (PC) as a function of stress level, model the residual mechanical properties of PC at various craze levels and strain rates, and determine if the total surface area of crazing is the sole factor in residual properties or if the crazing stress plays a role. To obtain these goals, a new in-situ reflective imaging technique was developed to quantify the craze severity in transparent polymers. To accomplish the goal of craze growth rate characterization, polycarbonate samples were placed under a creep load in a constant temperature, constant humidity environment. Using the new technique, the relative craze density was measured as a function of time under load at stresses of 40, 45, and 50 MPa. The craze growth rates were found to increase exponentially with stress level, and the times to 1% relative craze density were found to decrease exponentially with stress level. One exception to this behavior was found at a crazing stress of 50 MPa at which over half of the samples tested experienced delayed necking, indicating competitive mechanisms of crazing and shear yielding. The draw stress was found to be a lower bound below which delayed necking will not occur in a reasonable time frame. The yield stress, elastic modulus, failure stress, and ductility were correlated to crazing stress, relative craze density, and strain rate using a Design of Experiments (DOE) approach. The yield stress was found to correlate only to the strain rate, appearing to be unaffected by the presence of crazes. No correlation was found between the elastic modulus and the experimental factors. The failure stress was found to decrease with an increase in relative craze density from 0 to 1%, increase with an increase in crazing stress from 40 to 45 MPa, and correlate to the interaction between the crazing stress and the strain rate. The ductility of polycarbonate was found to decrease significantly with an increase in relative craze density, a decrease in crazing stress, and an increase in strain rate. The craze microstructure was correlated to the magnitude of stress during craze formation. The area of a typical craze formed at 40 MPa was measured to be more than 2.5 times larger than the area of a typical craze formed at 45 MPa. The fewer, but larger, crazes formed at the lower stress level were found to decrease the failure strength and ductility of polycarbonate more severely than the large number of smaller crazes formed at the higher stress level. / Ph. D.

Crystallization and multiple melting behavior of bisphenol-A polycarbonate (PC) was investigated using differential scanning calorimetry (DSC) for the monitoring of thermal behavior and atomic force microscopy (AFM) for the morphology study. The exceedingly slow crystallization kinetics of PC and the feasibility of obtaining near monodisperse fractions provide distinct advantages for the elucidation of the effects of crystallization time, temperature, and molar mass on crystallization kinetics. The effects of molar mass on the glass transition temperature (Tg) and heat capacity change at Tg, and the amorphous density of PC were investigated. Similar to many semicrystalline polymers, PC exhibits a multiple melting behavior upon heating. While for each PC sample, the coexistence of low and high temperature endothermic regions in the DSC heating traces is explained by the melting of populations of crystals with different stabilities, melting-recrystallization-remelting effects are observed only for the lowest molar mass samples. The effects of crystallization temperature and molar mass distribution on overall crystallization kinetics were studied for some of the fractions, including the commercial PC-28K (Mw = 28,000 g.mol-1) sample. Regarding the kinetics of secondary crystallization, particular attention was placed on understanding the effects of molar mass, initial degree of crystallinity prior to the secondary crystallization, and secondary crystallization time and temperature. The secondary crystallization of PC follows the same laws discovered in previous studies of PEEK, PET, it-PS and ethylene copolymers, and the results are discussed in the context of a bundle-like secondary crystallization model. During isothermal annealing of semicrystalline PC-28K around the high melting endotherm, a significant increase of melting temperature along with peak broadening with time was observed. Independently, morphological studies using AFM showed that mean lamellar thickness increases with time during isothermal annealing. These results are discussed in light of isothermal thickening of lamellar crystals. Lastly, almost 200 DSC melting traces of varying molar mass PC samples thermally treated under various conditions were analyzed to calculate crystallinity (Xc), rigid fraction (RF), and rigid amorphous fraction (RAF). The correlation between RAF vs Xc, Tg, and Tg broadening are discussed. / Ph. D.

L‟objectif de cette thèse est de valoriser les polymères styréniques issus des déchets d‟équipements électroniques et électriques. Les polymères considérés sont le polystyrène (PS), le polystyrène choc (HIPS), le poly(acrylonitrile-butadiène-styrène) (ABS), l'ABS couplé avec du polycarbonate (ABS/PC) et le poly(styrène-acrylonitrile) (SAN). Une étude préliminaire a permis de définir deux mélanges à compatibiliser : le mélange PS/ABS et le mélange PS/PC. Pour le mélange PS/ABS, la voie de compatibilisation ionique est étudiée. L‟ajout d‟un copolymère présentant une structure ionique et la création d‟un réseau in-situ sont tentés. Ces deux voies n‟ont pas donné de résultats concluants en termes d‟amélioration des propriétés finales du mélange. Le mélange PS/PC est lui compatibilisé par ajout d‟un copolymère polystyrène bloc-poly(éthylène-butylène)-bloc-polystyrène greffé PC. Ce copolymère est tout d‟abord créé en mélangeur interne, afin d‟étudier différents catalyseurs susceptibles d‟initier le greffage, puis l‟extrusion réactive est utilisée pour synthétiser ce copolymère à grande échelle. Plusieurs taux de copolymère sont alors introduits dans le mélange PS/PC et l‟amélioration des propriétés et des microstructures prouve son effet compatibilisant / The aim of this work consists in the recycling of the styrenic polymers coming from waste of electric and electronic equipments. Polystyrene (PS), high impact polystyrene (HIPS), poly(acrylonitrile-butadiene-styrene) (ABS), its alloy with the polycarbonate (ABS/PC) and poly(styrene-acrylonitrile) (SAN) are considered. A preliminary study permits to choose two blends to study: PS/ABS and PS/PC. In the case of PS/ABS blend, the ionic way of compatibilization was studied. The addition of a copolymer containing an ionic structure and the creation of an ionic network in-situ are investigated. Both these attempts are not conclusive about the improvement of the final properties of the blend. The PS/PC blend is then compatibilized by adding a polystyrene-block-poly(ethylene-butylene)-block-polystyrene grafted polycarbonate. This copolymer is first created in an internal mixer, in order to study different catalysts able to initiate the grafting, and then the reactive extrusion is used to synthesize it on a large scale. Several amounts are introduced in the PS/PC blend and the improvement of the properties and microstructures proves its compatibilizing effect