Os polímeros condutores intrínsecos são materiais isolantes ou semicondutores que, quando submetidos a um processo de dopagem, passam a apresentar condutividade próxima à metálica. Dentre os polímeros condutores sintetizados mais estudados está a poli(anilina), (PANI), que apesar de ter sido sintetizada pela primeira vez há aproximadamente 150 anos, continua sendo objeto de estudo de muitos grupos de pesquisa por todo o mundo até hoje. Apesar das características atrativas da PANI (facilidade de preparação e dopagem, estabilidade química e baixo custo), ela é categorizada como um material insolúvel e infusível em condições normais, o que dificulta sua processabilidade e aplicabilidade. Em vista dessas características indesejáveis, muitos derivados da PANI, tais como PANIs substituídas, copolímeros e blendas, são preparados em busca de novos materiais mais solúveis e processáveis. A obtenção do PPSA, um copolímero alternado da PANI e do PPS, mostrou-se atraente devido à possibilidade desse material poder apresentar as propriedades desejáveis de ambos os homopolímeros, juntamente com uma maior solubilidade. Nesta tese, apresentar-se-á a preparação desse polímero bem como sua respectiva caracterização espectroscópica e térmica e a determinação da massa molecular pela técnica de espalhamento de luz. Um estudo do comportamento eletroquímico por voltametria cíclica combinada com técnicas \"in situ\": espectroscopia Raman Ressonante, UV-Visível e por microbalança eletroquímica a cristal de quartzo também será mostrado. / The intrinsic conducting polymers are insulating or semi-conducting materials that show conductivities similar to metals when submitted to a doping process. Polyaniline (PANI), synthesized for the first time 150 years ago, is still the subject of research of many groups in the world, being one of the most studied conductive polymers. Besides its attractive properties (easy synthesise and doping, chemical stability and low cost), PANI is an insoluble and infusible material in normal conditions, what makes its processability and applicability very difficult. In order to overcome these difficulties, many PANI derivatives, such as substituted PANIs, copolymers and blends have been prepared, searching for more soluble materials and processible. PPSA, an alternate copolymer of PANI and PPS, is an attractive alternative because this material can show interesting properties of both homopolymers, together with a higher solubility. In this thesis it will be shown the preparation of this copolymer, as well as its spectroscopic and thermal characterization, and the determination of its molar mass by light scattering. The electrochemical behavior, studied by cyclic voltammetry combined with \"in situ\" techniques such as Raman resonant spectroscopy, UV-VIS and electrochemical quartz crystal microbalance, will also be shown.

Numerous publications are available on the structure and properties correlation of fibers spun from polymers with flexible chains such as polyethylene terephthalate (PET), nylon, polypropylene. Also considerable amount of work is reported in fibers spun from rigid rod polymers like poly(p-phenylene terephthalamide) due to their value in high performance fibers category. However, very limited literature is available on the structure-properties relationship in fibers manufactured from poly(phenylene sulfide) (PPS), a high performance polymer which possesses chain flexibility between above two classes of polymers. A few researchers have studied crystallization kinetics and the fibers by extruding the polymer using capillary rheometers. However, there is a lack of in-depth study of conversion of PPS into fibers through melt spinning and further enhancement of properties by drawing and annealing experiments. The purpose of the present research was to fill this void by systematically studying the fiber manufacture from PPS polymers. Four variances of proprietary Fortron® linear PPS resins differing in MW were analyzed for their characteristics such as molecular weight (MW) and MW distribution (MWD) using gel permeation chromatography (GPC), rheological properties using melt flow indexer (MFI) and capillary extrusion rheometer, and crystallization kinetics using differential scanning calorimetry (DSC). The fibers were spun on a pilot melt spinning facility, using a multi-hole spinneret, under different processing conditions. As-spun fibers were drawn and annealed subsequently by varying draw-annealing conditions. Thorough characterization of the as-spun and drawn-annealed fibers was carried out using various analytical techniques such as tensile testing, DSC, polarized light optical microscopy (POM), wide angle X-ray scattering (WAXS), and small angle X-ray scattering (SAXS). Relationship between polymer characteristics, process conditions and structure-properties in the fibers was analysed statistically. A strong correlationship between polymer molecular weight, processing conditions during melt spinning and draw-annealing, processing behavior during melt spinning and drawing, fiber tensile properties and fiber morphology is reported herein. Interaction effects of material and process variables in evolving fiber structure and properties are also discussed. Through optimal combination of material and process variables, PPS fibers of tenacity close to six gpd were obtained. With the help of several characterization tools listed earlier, melting behavior of PPS polymers and fibers is decoded, and probable structural model of high tenacity PPS fibers is proposed.

Os polímeros condutores intrínsecos são materiais isolantes ou semicondutores que, quando submetidos a um processo de dopagem, passam a apresentar condutividade próxima à metálica. Dentre os polímeros condutores sintetizados mais estudados está a poli(anilina), (PANI), que apesar de ter sido sintetizada pela primeira vez há aproximadamente 150 anos, continua sendo objeto de estudo de muitos grupos de pesquisa por todo o mundo até hoje. Apesar das características atrativas da PANI (facilidade de preparação e dopagem, estabilidade química e baixo custo), ela é categorizada como um material insolúvel e infusível em condições normais, o que dificulta sua processabilidade e aplicabilidade. Em vista dessas características indesejáveis, muitos derivados da PANI, tais como PANIs substituídas, copolímeros e blendas, são preparados em busca de novos materiais mais solúveis e processáveis. A obtenção do PPSA, um copolímero alternado da PANI e do PPS, mostrou-se atraente devido à possibilidade desse material poder apresentar as propriedades desejáveis de ambos os homopolímeros, juntamente com uma maior solubilidade. Nesta tese, apresentar-se-á a preparação desse polímero bem como sua respectiva caracterização espectroscópica e térmica e a determinação da massa molecular pela técnica de espalhamento de luz. Um estudo do comportamento eletroquímico por voltametria cíclica combinada com técnicas \"in situ\": espectroscopia Raman Ressonante, UV-Visível e por microbalança eletroquímica a cristal de quartzo também será mostrado. / The intrinsic conducting polymers are insulating or semi-conducting materials that show conductivities similar to metals when submitted to a doping process. Polyaniline (PANI), synthesized for the first time 150 years ago, is still the subject of research of many groups in the world, being one of the most studied conductive polymers. Besides its attractive properties (easy synthesise and doping, chemical stability and low cost), PANI is an insoluble and infusible material in normal conditions, what makes its processability and applicability very difficult. In order to overcome these difficulties, many PANI derivatives, such as substituted PANIs, copolymers and blends have been prepared, searching for more soluble materials and processible. PPSA, an alternate copolymer of PANI and PPS, is an attractive alternative because this material can show interesting properties of both homopolymers, together with a higher solubility. In this thesis it will be shown the preparation of this copolymer, as well as its spectroscopic and thermal characterization, and the determination of its molar mass by light scattering. The electrochemical behavior, studied by cyclic voltammetry combined with \"in situ\" techniques such as Raman resonant spectroscopy, UV-VIS and electrochemical quartz crystal microbalance, will also be shown.

Poly(phenylene sulfide) (PPS), an engineering thermoplastic with excellent mechanical, thermal, and chemical properties, was gelled for the first time using 1,3-diphenylacetone (DPA) as the gelation solvent in a thermally induced phase separation (TIPS) process. PPS was dissolved in DPA at high temperatures to form a homogeneous solution. The solution was cooled, initiating phase separation and eventually forming a solidified PPS network around DPA-rich domains. Evacuation of DPA from the gel network creates monolithic PPS aerogels, one of few physically crosslinked polymer aerogel systems comprised of a high-performance thermoplastic. In this work, specific properties of PPS aerogels were controlled through the manipulation of various processing parameters, such as polymer concentration, post-process annealing conditions, mode of manufacturing (casting versus additive manufacturing), dissolution temperature, and drying method. The ultimate goal was to elucidate key process-morphology-property relationships in PPS aerogels, to ultimately improve aerogel performance and applicability. The phase diagram of PPS/DPA was first elucidated to determine the phase separation mechanism of the system, which guides all future processing decisions. The phase diagram indicated that the system undergoes solid-liquid phase separation, typical for solutions with relatively favorable polymer-solvent interactions. This assignment was validated by the calculation of the Flory-Huggins interaction parameter through two independent methods - Hansen solubility parameters and fitting melting point depression data. The influence of polymer composition on PPS aerogel properties was then characterized. As polymer concentration increased, aerogel density and mechanical properties increases, and porosity decreased. The particular morphology of PPS aerogels from DPA was that of a fibrillar network, where these axialitic (pre-spherulitic) fibrils are comprised of stacks of PPS crystalline lamellae, as suggested by x-ray scattering and electron microscopy. These interconnected microstructures responded more favorably to compressive load than similar globular PEEK aerogels, highlighting the importance of aerogel microstructure on its mechanical response. Upon solvent extraction, PPS aerogels were annealed in air environments to improve their mechanical behavior. Annealing did not dramatically shrink the aerogels, nor did it appear to affect the micron-scale morphology of PPS aerogels as observed by electron microscopy. The resistance to densification of PPS aerogels was mainly a product of their interconnected fibrillar morphologies, aided by subtle microstructural changes that occurred upon annealing. Exposure to a high temperature oxidative environment (160 – 240 oC) increased the degree of crystallinity of the aerogels, and also promoted chemical crosslinking within the amorphous PPS regions, both of which may have helped to prevent severe densification. With enhanced physical and chemical crosslinking, annealed PPS aerogels displayed improved compressive properties over unannealed analogues. Additionally, the thermal conductivity of both annealed and unannealed aerogel specimens was below that of air (~ 0.026 W/mK) and did not display a dependence on polymer composition nor on annealing condition. Generally, these experiments demonstrate that annealing PPS aerogels improved their mechanical performance without negatively affecting their inherent fibrillar morphology, low density, or low thermal conductivity. To fabricate aerogels with geometric flexibility and hierarchical porosity, PPS/DPA solutions were printed through material extrusion (MEX) and TIPS using a custom-built heated extruder. In this process, solid solvated gels were first re-dissolved in a heated extruder and solutions were deposited in a layer-wise fashion onto a room-temperature substrate. The large temperature gradient between nozzle and substrate rapidly initiated phase separation, solidified the deposited layers and formed a printed part. Subsequent solvent exchange and drying created printed PPS aerogels. The morphology of printed aerogels was compositionally-dependent, where the high extrusion temperature required to dissolve highly-concentrated inks (50 wt % PPS) also destroyed self-nuclei in solution, yielding printed aerogels with spherulitic microstructures. In contrast, aerogels printed from 30 wt % solutions were deposited at lower temperatures and demonstrated fibrillar microstructures, similar to those observed in 30 wt % cast aerogel analogues. Despite these microstructural differences, all printed aerogels demonstrated densities, porosities, and crystallinities similar to their cast aerogel counterparts. However, printed aerogel mechanical properties were microstructurally-dependent, and the spherulitic 50 wt % aerogels were much more brittle compared to the fibrillar cast 50 wt % analogues. This work introduces a widely-applicable framework for printing polymer aerogels using MEX and TIPS. Intrigued by the compositional morphological dependence of the printed PPS aerogels, the dissolution temperature (Tdis), and thus the self-nuclei content, of cast PPS/DPA solutions was systematically varied to understand its influence on aerogel morphology and properties. As Tdis increased, the length and diameter of axialites increased while aerogel density and porosity were relatively unaffected. Thus, the isolated influence of axialite dimensions (analogous to pore size and pore concentration) on aerogel properties could be studied independent of density. At low relative densities (below 0.3, aerogels of 10 – 30 wt %), compressive modulus and offset yield strength tended to decrease with Tdis, due to an increase in axialite length (akin to pore size) and number of axialites (akin to number of pores). At higher relative densities (above 0.3, 40 and 50 wt %), axialitic aerogels were so dense that changes in pore dimensions did not result in systematic changes in mechanical response. All spherulitic aerogels fabricated at the highest Tdis¬ demonstrated reduced mechanical properties due to poor interspherulitic connectivity. The thermal conductivity of all aerogels increased with polymer composition but demonstrated no clear trend with Tdis. A model for thermal conductivity was used to deconvolute calculated conductivity into solid, gaseous, and radiative components to help rationalize the measured conductivity data. This work demonstrates the importance of nucleation density control in TIPS aerogel fabrication, especially at low polymer concentrations. The specific method used to dry an aerogel generally has a great influence on its microstructure and density. Vacuum or ambient drying is the most industrially-attractive technique due to low cost and low energy usage; however, it is typically the most destructive process due to high capillary forces acting on the delicate aerogel microstructure. Three drying methods, vacuum drying, freeze drying, and supercritical CO2 drying, were used to evacuate PPS gels fabricated at three PPS concentrations (10, 15, and 20 wt %). Almost all aerogel specimens displayed excellent resilience against shrinkage as a function of the drying method, besides the 10 wt % vacuum dried sample which shrunk almost 40%. While the micron-scale aerogel morphology captured by electron microscopy appeared to be unaffected by the drying method, other properties such as aerogel surface area, mesoporous volume, and mechanical properties were effectively functions of the degree of aerogel shrinkage. Aerogel thermal conductivity was low for all samples, and in particular, vacuum dried aerogels demonstrated slightly lower conductivities than other ambiently-dried aerogel systems such as silica and carbon. In general, vacuum drying appears to be industrially viable for PPS aerogels at concentrations above 10 wt %. / Doctor of Philosophy / Polymer aerogels are nanoporous solid networks of low density. These materials are used in applications such as thermal insulation, absorbance/filtration, drug delivery, biomedical scaffolds, solid state batteries, and others. One method of creating polymeric aerogels is through thermally induced phase separation (TIPS), where a polymer is first dissolved in a high boiling point solvent at a high temperature. Next, the solution is cooled, inducing phase separation and gelation. Extraction of the gelation solvent transforms the solvated gel into an aerogel. To create polymeric aerogels with good properties and wide-ranging applicability, one should use a high-performance polymer. In this work, aerogels are for the first time made from poly(phenylene sulfide) (PPS), an engineering thermoplastic with good mechanical properties, thermal stability, and chemical resistance. PPS aerogels are fabricated using TIPS over a wide compositional range, and their microstructures, physical properties, thermal properties, and compressive properties are fully characterized. To further enhance aerogel performance, the fabrication process can be optimized to precisely control the aerogel morphology and thus the resulting properties. The influence of processing variables such as the polymer concentration, the post-fabrication aerogel annealing conditions, the method of manufacturing (traditional casting versus additive manufacturing), the dissolution temperature (temperature at which the polymer dissolves in solution prior to gelation), and the drying method on the aerogel behavior is investigated. Generally, results suggest that understanding critical process-morphology-property relationships allows for precise control over the nature of PPS aerogels.