Supercritical carbon dioxide (scCO2) was used as a processing aid to improve the level of exfoliation achievable in a PET-layered silicate nanocomposite produced from melt compounding. Layered silicate and scCO2 were allowed to mix for a period of time before being released into the second stage of a single screw extruder. The rapid expansion forced silicate particles into a modified hopper containing neat PET pellets. The mixture of layered silicate and PET was immediately melt mixed in a single screw extruder, cooled in a water bath and pelletized. Two sets of samples each containing layered silicate with different surface chemistries were produced with this method at 1, 3 and 5 wt% silicate. For comparison, samples of the same weight fraction and type of silicate were produced from a traditional melt compounding method. Wide angle x-ray diffraction (WAXD), mechanical testing and rheological analysis were used in order to characterize the silicate morphology, the composite mechanical properties and the relative amount of degradation between the various samples. Results show that scCO2 processed samples contain a higher degree of layered silicate exfoliation than samples produced with traditional melt compounding. Mechanical property improvements are shown to be dependent on the type of silicate surface modification employed. Finally, degradation of the PET matrix appears to be far less extensive in the scCO2 processed samples as shown from rheological data. / Master of Science

A reação de hidrodescloração catalítica (HDC) de bifenilas policloradas (PCB) foi estudada em diversos sistemas reacionais: solventes orgânicos, dióxido de carbono supercrítico, presença e natureza de aditivos (bases e co-solventes) a temperaturas na faixa de 25 °C a 100 °C e pressões de 1 bar até 250 bar. Os reagentes utilizados foram um composto modelo (2,4- diclorobifenil), misturas comerciais de PCB (Aroclor, Ascarel) e outros compostos halogenados (clorobenzenos e bromoclorobenzeno). Os catalisadores avaliados, paládio suportado em carvão ativo (Pd/C), paládio suportado em sílica mesoporosa (Pd/SiO2), nanopartículas ferromagnéticas de paládio (FFSiNH2Pd), e nanopartículas ocas de paládio (PdNP) e de platina (PtNP), mostraram-se versáteis nas mais diversas condições, quer sejam condições supercríticas, presença ou não de água, presença e natureza da base e diferentes doadores de hidrogênio. Em dióxido de carbono, dois regimes reacionais foram avaliados: dióxido de carbono subcrítico, onde o gás atua como agente expansor da fase líquida ao se dissolver nela permitindo que a reação ocorra em uma fase líquida rica em gás hidrogênio; e dióxido de carbono supercrítico, sistema onde a temperatura influencia fortemente a reação e a pressão tende a ter efeito negativo sobre a velocidade de reação, devido a efeitos de diluição e de competição das moléculas do gás com as moléculas dos reagentes. A condição reacional ótima foi determinada para o regime supercrítico e dados cinéticos foram obtidos para os regimes sub- e supercrítico. / The catalytic hydrodechlorination reaction (HDC) of polychlorinated biphenyls (PCB) was studied in several reactional systems: organic solvents, supercritical carbon dioxide, presence and nature of additives (bases and co-solvents), in temperatures of 25 °C to 100 °C and pressures of 1 bar to 250 bar. The reagents used were: a model compound, 2,4-dichlorobiphenyl, commercial mixtures of PCB (Aroclor, Ascarel) and other halogenated compounds (chlorobenzenes and bromochlorobenzene). The catalysts evaluated, palladium supported in activated carbon (Pd/C), palladium supported in mesoporous silica (Pd/SiO2), palladium ferromagnetic nanoparticles (FFSiNH2Pd), and hollow palladium ((PdNP) and platinum (PtNP) nanoparticles, showed to be versatile in several conditions, either supercritical conditions, presence or not of water, nature of the base, and different hydrogen donors. In carbon dioxide, two reaction regimes were evaluated: subcritical carbon dioxide, where the gas acts as an expansion agent of the liquid phase when it dissolves in it, allowing that the reaction happens in a liquid phase rich in hydrogen; and supercritical carbon dioxide, a system where the temperature has a strong influence over the reaction and the pressure has a negative effect on the rate of the reaction, due to dilution and the competition of gas molecules with the reagents molecules for the catalyst. The optimal reaction condition was determined for the supercritical regime and kinetic data were obtained for both the sub and supercritical regimes.

La capture du dioxyde de carbone (CO2) est devenu un enjeu mondial majeur et notre but est d’identifier des usages positifs du CO2, par exemple comme solvant alternatif pour la synthèse de polymères. La polymérisation en dispersion est un procédé industriel permettant de produire des particules de polymères avec une taille et une morphologie définies. L’utilisation du CO2 supercritique (scCO2) comme solvant pour ce type de polymérisation est toutefois limitée par l’existence et la disponibilité de stabilisants très solubles, peu chers et respectueux de l’environnement.Dans cette thèse, la synthèse de stabilisants hydrocarbonés est décrite. Jusqu’à récemment, l’utilisation de polymères fluorocarbonés ou à base de silicone était privilégiée car ces polymères présentent une bonne solubilité dans le scCO2. Cependant, ils demeurent coûteux et peu respectueux de l’environnement. Les stabilisants hydrocarbonés comme les poly(acétate de vinyle-stat-pivalate de vinyle) (P(VAc-stat-VPi)) constituent une alternative viable pour la polymérisation de la N-vinyl pyrrolidone (NVP) en dispersion dans le scCO2. Le but de cette étude est d’en étendre les potentialités à la polymérisation d’autres monomères comme le méthacrylate de méthyle (MMA). Une série de copolymères à blocs P(VAc-stat-VPi)-block-PNVP avec différentes masses molaires et compositions a été synthétisée par polymérisation radicalaire contrôlée (RAFT/MADIX) et caractérisée par plusieurs techniques telles que la résonance magnétique nucléaire (RMN) et la chromatographie d’exclusion stérique (SEC).Les copolymères à blocs ont été testés pour la polymérisation en dispersion du MMA / Carbon capture has become a major global process and our aim is to make positive use of the captured carbon dioxide (CO2) as an alternative green solvent. Supercritical carbon dioxide (scCO2) presents many advantages over other conventional solvents employed in polymer synthesis. It is nonflammable, has a very low toxicity and allows an easy recovery of the polymer. Dispersion polymerisation is a technique that provides polymer particles with defined morphology and size and it is therefore industrially relevant. However, the main limitation for using scCO2 as a solvent in this technique is the availability of highly CO2-soluble, environmentally friendly and affordable stabilisers. In this thesis the synthesis of hydrocarbon based stabilisers for dispersion polymerisation is explored. Until very recently, only fluorocarbon and silicone based polymers showed any significant solubility in scCO2 but these are expensive and not environmentally friendly. Hydrocarbon stabilisers constitute a viable alternative, however they have only worked successfully for one monomer system, NVP.1A range of P(VAc-stat-VPi)-block-PNVP block copolymers with different molar masses and molar ratios were synthesised using controlled radical polymerisation techniques (RAFT/MADIX) and characterised by different techniques (NMR, SEC) showing narrow dispersities. The NVP block was incorporated to act as an anchor to the growing polymer particles during dispersion. Solubility of the stabilisers was tested using a variable volume view cell.Finally, block copolymers of different DP of PNVP were tested in dispersion polymerisation of MMA

Textile processing methods such as conventional exhaustion dyeing, pre-treatments and printing consume high amounts of water and use partly toxic and hazardous chemicals which are non-degradable. These chemicals (e.g. excess amount of dye, additives and catalysts) remain partially in the waste-water which is drained out and ends up polluting the environment. The supercritical carbon dioxide dyeing technology presents an eco-friendly and water-free method with reduced use of chemicals and energy. The benefits of such technology are currently not overcoming the relative high investment costs which impede its full implementation into the textile industry. This study presents an approach to extent the application of the eco-friendly supercritical carbon dioxide technology. It combines the well-studied supercritical carbon dioxide dyeing process for polyester with the functionalisation process to obtain water repellent surface properties. As water repellent (substance) environmentally benign silicones are used. Results showed that the simultaneous dyeing and functionalisation process was feasible assessed by the compatibility of the dye and silicone in the system. Silicone and dye did not interfere in each other’s functionality (colour strength and water contact angle). Further the process temperature and silicone molecular weight showed no influence on the colour strength of the fabric whereas the water contact angle (water repellence) increased with increasing temperature. The resulting polyester fabric showed acceptable colour strength yet did not obtain sufficient water repellent properties despite the increase in water contact angle of the treated samples to the untreated reference sample. The poor water repellence is suggested to be caused by the hydrophobic functional groups of the silicones oriented towards each other rather than toward the outer fabric surface. Overall the thesis is promoting research which combines eco-friendly technologies including environmental benign chemicals for the textile industry. Silicones are widely used in textile processing not only as water repellents, but also as anti-foaming agents, lubricants and softeners. Therefore a water-free and eco-friendly application method can benefit a wide range of finishing processes.

This study covers the extraction of antioxidants from wheat germ / which is the byproduct of the flour-milling industry and a rich source of antioxidants / with Ultrasound Assisted (UAE) and Supercritical Carbon Dioxide (SC-CO2) extractions. Extraction conditions were ultrasonication time (1&ndash / 11 min), temperature (20&ndash / 60&deg / C) and ethanol level (5&ndash / 95%) for UAE, and pressure (148&ndash / 602 bar), temperature (40&ndash / 60&deg / C) and time (10&ndash / 60 min) for SC-CO2 extraction. The extraction conditions were optimized based on yield (%), total phenolic contents (TPC, mg GAE/g extract) and antioxidant activities (AA, mg scavenged DPPH&amp / #729 / /g extract) of the extracts, using Central Composite Rotatable Design. Total tocopherol contents (TTC) of the extracts were determined, as well. UAE (at 60&deg / C) with low ethanol level (~5-30%) and short times (1-3 min) provided protein rich extracts with high yield, medium TPC and AA. On the other hand, with high ethanol level (~90%) and long times (6-11 min), waxy structured extracts with low yield but high TPC and AA were obtained. SC-CO2 extraction at 442 bar, 40&ordm / C and 48 min. enabled almost 100% recovery of wheat germ oil (9% yield) but TPC and AA of the extracts were low. On the contrary, the extracts obtained at lower pressures (~150bar) and shorter times (~10 min) at 50-60&ordm / C had high TPC and AA since the oil yield was low. However, TPC and AA of these extracts were only half of those extracted by UAE. Maximum tocopherol (7.142 mg tocopherol/g extract) extraction was achieved at 240 bar, 56&ordm / C for 20 min. Both of the methods extracted high amounts of tocopherols from roasted wheat germ (SC-CO2 extraction / 0.31 mg tocopherol/g germ, UAE / 0.33 mg tocopherol/g germ) but TTC of the extracts obtained by SC-CO2 extraction was superior compared to 1.170 mg tocopherol/g extract obtained by UAE at 9 min, 58&ordm / C and 95% ethanol level. All these extracts with different characteristics have potential uses in cosmetic and food industry depending on the targeted specific application.

Traditional fluorosilicones contain a siloxane backbone and pendant fluorinated group leading to low temperature ductility and excellent thermal stability. However, acidic or basic catalysts can reduce the thermal stability from a potential 350 °C to 150 °C. The predominant decomposition mechanism is through chain scission and it is hypothesized that preventing this will result in polymers with higher thermal stability. Three approaches were taken to prevent chain scission. First, a series of hybrid fluorosilicones based on (trifluorovinyl)benzene were synthesized through condensation polymerization with initial decomposition temperatures of approximately 240 °C. These were compared to similar aromatic polyethers and removal of the ether oxygen lowered the initial decomposition temperature by approximately 190 °C demonstrating the importance of this oxygen to the stability of polyethers. Second, reverse fluorosilicone (fluorinated backbone and pendant siloxane) terpolymers of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc) and methacryloxypropyl-terminated polydimethylsiloxane (PDMSMA) were synthesized in supercritical CO2 (scCO2) or by emulsion polymerization. Chain scission was prevented as initial decomposition occurred between 231 and 278 °C. In both the emulsion and scCO2 cases, VAc was essential in facilitating cross-propagation between CTFE and PDMSMA and the branching was similar suggesting polymerization media does not affect polymer structure. Emulsion-based polymers had higher molar masses and thermal stability whereas comparable scCO2 polymers had higher yields and incorporated more PDMSMA. Third, a series of homo-, co-, and terpolymers of CTFE, VAc and methacryloxypropyl-terminated silsesquioxane (POSSMA) were synthesized representing the first synthesis of POSSMA containing polymers in scCO2 and demonstrating reverse fluorosilicones can be synthesized without VAc. Chain scission was prevented as initial decomposition occurred from 244 to 296 °C with thermal stability increasing with CTFE content to a limit. Decomposition of the polymers was examined and mechanism elucidated. In air, the copolymers give 40 to 47 wt% char since the silsesquioxane oxidizes to SiO2 while in N2, no residue is seen. In contrast, the terpolymers give a carbonaceous residue of approximately 20 wt% in N2. The flammability and surface properties of the polymers were examined with the terpolymers having flammability similar to p(CTFE) and surface properties comparable to p(POSSMA) giving a low-flammability, hydrophobic polymer.

Traditional fluorosilicones contain a siloxane backbone and pendant fluorinated group leading to low temperature ductility and excellent thermal stability. However, acidic or basic catalysts can reduce the thermal stability from a potential 350 °C to 150 °C. The predominant decomposition mechanism is through chain scission and it is hypothesized that preventing this will result in polymers with higher thermal stability. Three approaches were taken to prevent chain scission. First, a series of hybrid fluorosilicones based on (trifluorovinyl)benzene were synthesized through condensation polymerization with initial decomposition temperatures of approximately 240 °C. These were compared to similar aromatic polyethers and removal of the ether oxygen lowered the initial decomposition temperature by approximately 190 °C demonstrating the importance of this oxygen to the stability of polyethers. Second, reverse fluorosilicone (fluorinated backbone and pendant siloxane) terpolymers of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc) and methacryloxypropyl-terminated polydimethylsiloxane (PDMSMA) were synthesized in supercritical CO2 (scCO2) or by emulsion polymerization. Chain scission was prevented as initial decomposition occurred between 231 and 278 °C. In both the emulsion and scCO2 cases, VAc was essential in facilitating cross-propagation between CTFE and PDMSMA and the branching was similar suggesting polymerization media does not affect polymer structure. Emulsion-based polymers had higher molar masses and thermal stability whereas comparable scCO2 polymers had higher yields and incorporated more PDMSMA. Third, a series of homo-, co-, and terpolymers of CTFE, VAc and methacryloxypropyl-terminated silsesquioxane (POSSMA) were synthesized representing the first synthesis of POSSMA containing polymers in scCO2 and demonstrating reverse fluorosilicones can be synthesized without VAc. Chain scission was prevented as initial decomposition occurred from 244 to 296 °C with thermal stability increasing with CTFE content to a limit. Decomposition of the polymers was examined and mechanism elucidated. In air, the copolymers give 40 to 47 wt% char since the silsesquioxane oxidizes to SiO2 while in N2, no residue is seen. In contrast, the terpolymers give a carbonaceous residue of approximately 20 wt% in N2. The flammability and surface properties of the polymers were examined with the terpolymers having flammability similar to p(CTFE) and surface properties comparable to p(POSSMA) giving a low-flammability, hydrophobic polymer.

The purpose of this research was to determine the solubility of apricot (Prunus armeniaca L.) oil in supercritical carbon dioxide (SC-CO2), effects of parameters (particle size, solvent flow rate, pressure, temperature and co-solvent (ethanol) concentration) on extraction yield and to investigate the possibility of fractionation. Solubility, increased with pressure and increased with temperature above the crossover pressure, which was found between 200 and 300 bar, and decreased with temperature below the crossover pressure. Appropriate models were fitted to data. Extraction of apricot kernel oil occurred in two extraction periods as fast and slow extraction periods. Most of the oil was extracted in the fast extraction period and the oil recovered in the slow extraction period was negligible. Extraction yield increased with decrease in particle size and recovery of more than 99 % of the oil was possible if particle diameter decreased below 0.425 mm. Extraction rate increased with increase in flow rate, pressure, temperature and ethanol concentration. The volume mass transfer coefficient in the fluid phase changed between 0.6 and 3.7 /min, whereas the volume mass transfer coefficient in the solid phase changed between 0.00009 and 0.00048 /min. Extraction yield at 15 min for particle diameter smaller than 0.85 mm was formulated as a function of solvent flow rate, pressure, temperature, and ethanol concentration by using Response Surface Methodology. According to the model yield was highest (0.26 g /g) at 4 g/min flow rate, 60 oC, 450 bar and 3 % ethanol concentration. Fractionation was not possible at significant levels.

Membrane separations are rapidly growing alternatives to traditionally expensive gas separation processes. For natural gas purification, membranes are used to remove carbon dioxide to prevent pipeline corrosion and increase the heating value of the natural gas. The robust chemical and physical properties of polyimide membranes make them ideal for the numerous components and high pressures associated with natural gas production. Typically, the performance of membranes changes over time as a result of physical aging of the polymer. Previous work shows that the thin selective layer of an asymmetric hollow fiber membrane, the morphology of choice for gas separations, ages differently than a thick dense film of the same material. Also, carbon dioxide, which is highly soluble in most polymers, can actively swell and plasticize polymer membranes at higher pressures. In this work, free acid groups present in the model polyimide are covalently crosslinked to stabilize the matrix against plasticization. Physical aging of two different crosslinked derivatives are compared to the free acid polyimide through gas permeation, gas sorption, and refractive index measurements. Thick (~50 m) and thin (~650 nm) films are examined to determine the effects of sample dimension on physical aging. The crosslinking mechanism employs diol substituents to form ester linkages through the free acid group. However, the annealing treatment, above the glass transition temperature, used to "reset" the thermal history of the films is found to form a new crosslinked polymer. Characterization of this new crosslinking mechanism reveals a high-temperature decarboxylation of the free acid creates free-radical phenyl groups which form covalent crosslinks through other portions of the polymer structure. Since ester crosslinks may be vulnerable to hydrolysis in aggressive gas feed streams, this new mechanism of crosslinking may create a more robust membrane for aggressive separations. In addition to the physical aging study, supercritical carbon dioxide conditioning of the two glycol crosslinked polyimides is compared to the free acid polymer. In this case, the free acid polymer is not crosslinked since the esterification crosslinking reaction occurs at much lower temperature than the decarboxylation mechanism. The free acid polymer displays an atypical permeation response under supercritical carbon dioxide conditions which suggests a structural reorganization of the polymer occurs. The crosslinked polymers do not exhibit this type of response. Mixed gas permeation confirms a substantial decrease in the productivity of the free acid polyimide and reveals the enhanced stability of the crosslinked polyimides following the supercritical carbon dioxide conditioning. Finally, examination of structurally similar fluorine-containing polyimides following approximately 18 years of aging allows the study of polymer structure on physical aging. A 6FDA-based polyimide is compared to a BPDA-based polyimide to understand the effects of bulky, CF3 groups on physical aging, and polyimides with diamine isomers reveal the effects of structural symmetry on physical aging.

A reação de hidrodescloração catalítica (HDC) de bifenilas policloradas (PCB) foi estudada em diversos sistemas reacionais: solventes orgânicos, dióxido de carbono supercrítico, presença e natureza de aditivos (bases e co-solventes) a temperaturas na faixa de 25 °C a 100 °C e pressões de 1 bar até 250 bar. Os reagentes utilizados foram um composto modelo (2,4- diclorobifenil), misturas comerciais de PCB (Aroclor, Ascarel) e outros compostos halogenados (clorobenzenos e bromoclorobenzeno). Os catalisadores avaliados, paládio suportado em carvão ativo (Pd/C), paládio suportado em sílica mesoporosa (Pd/SiO2), nanopartículas ferromagnéticas de paládio (FFSiNH2Pd), e nanopartículas ocas de paládio (PdNP) e de platina (PtNP), mostraram-se versáteis nas mais diversas condições, quer sejam condições supercríticas, presença ou não de água, presença e natureza da base e diferentes doadores de hidrogênio. Em dióxido de carbono, dois regimes reacionais foram avaliados: dióxido de carbono subcrítico, onde o gás atua como agente expansor da fase líquida ao se dissolver nela permitindo que a reação ocorra em uma fase líquida rica em gás hidrogênio; e dióxido de carbono supercrítico, sistema onde a temperatura influencia fortemente a reação e a pressão tende a ter efeito negativo sobre a velocidade de reação, devido a efeitos de diluição e de competição das moléculas do gás com as moléculas dos reagentes. A condição reacional ótima foi determinada para o regime supercrítico e dados cinéticos foram obtidos para os regimes sub- e supercrítico. / The catalytic hydrodechlorination reaction (HDC) of polychlorinated biphenyls (PCB) was studied in several reactional systems: organic solvents, supercritical carbon dioxide, presence and nature of additives (bases and co-solvents), in temperatures of 25 °C to 100 °C and pressures of 1 bar to 250 bar. The reagents used were: a model compound, 2,4-dichlorobiphenyl, commercial mixtures of PCB (Aroclor, Ascarel) and other halogenated compounds (chlorobenzenes and bromochlorobenzene). The catalysts evaluated, palladium supported in activated carbon (Pd/C), palladium supported in mesoporous silica (Pd/SiO2), palladium ferromagnetic nanoparticles (FFSiNH2Pd), and hollow palladium ((PdNP) and platinum (PtNP) nanoparticles, showed to be versatile in several conditions, either supercritical conditions, presence or not of water, nature of the base, and different hydrogen donors. In carbon dioxide, two reaction regimes were evaluated: subcritical carbon dioxide, where the gas acts as an expansion agent of the liquid phase when it dissolves in it, allowing that the reaction happens in a liquid phase rich in hydrogen; and supercritical carbon dioxide, a system where the temperature has a strong influence over the reaction and the pressure has a negative effect on the rate of the reaction, due to dilution and the competition of gas molecules with the reagents molecules for the catalyst. The optimal reaction condition was determined for the supercritical regime and kinetic data were obtained for both the sub and supercritical regimes.