Esta pesquisa foi desenvolvida no laboratório do Centro Internacional de Referência em Reúso de Água (CIRRA), vinculado ao Departamento de Engenharia Hidráulica e Ambiental da Escola Politécnica da Universidade de São Paulo (USP). O projeto de pesquisa teve como objetivo principal a síntese de membranas planas compostas, utilizando o polímero fluoreto de polivinilideno (PVDF), nanopartículas inorgânicas de argila (montmorilonita hidrofílica) e óxido de polietileno (PEO). As membranas foram sintetizadas pelo processo de inversão de fases, utilizando 18% em massa de PVDF, n-metil-pirrolidona como solvente e água como o não solvente. Avaliou-se a influência da introdução de diferentes concentrações de nanopartículas de argila e PEO. As membranas sintetizadas foram submetidas a testes de avaliação de desempenho (permeabilidade, capacidade de separação, potencial de depósitos) e de caracterização (morfologia e características físicas). Os resultados obtidos indicam que a adição de nanopartículas inorgânicas de argila e o formador de poros PEO melhoraram o desempenho e as características físicas das membranas. As membranas Kynar 761 6% argila 0% PEO (K6-0), Kynar 761 0% argila 4% PEO (K0-4) e Kynar 761 6% argila 4% PEO (K6-4) apresentaram as melhores permeabilidades com um aumento, respectivamente, de 520%, 1.250% e 1.100%, em relação à membrana pura. Além disso, observa-se uma melhora de 55%, 60% e 41% na redução do potencial de depósito, respectivamente, para as membranas K6-0, K0-4 e K6-4, quando comparada a membrana de controle. A melhora da permeabilidade e do potencial de depósito das membranas compostas está relacionada à melhoria da hidrofilicidade e da carga superficiail. A morfologia interna das membranas sintetizadas com argila pode ser caracterizada com uma camada superficial com poros conectados verticalmente aos poros em formas de canais da camada intermediária. A camada inferior possui uma morfologia esponjosa com micro-poros. O aumento da quantidade e tamanho dos poros superficiais é proporcional ao aumento da concentração de argila, assim como a diminuição de bloqueios horizontais entre a camada superficial e os poros em formas de canais da camada intermediária. A morfologia interna das membranas sintetizadas com PEO pode ser caracterizada por uma camada superficial densa com poros e uma camada inferior com uma morfologia esponjosa densa com micro-poros. A camada intermediaria tem uma morfologia densa com poros em forma de canais com diâmetros maiores se comprado às membranas sem adição de PEO. A adição de PEO diminui o tamanho médio dos micro-poros, se comparado com as membranas onde apenas argila é adicionada. Foi constatado que a melhoria da permeabilidade está associada à alteração na morfologia interna das membranas compostas. O aumento dos poros superficiais conectados aos poros em forma de canais mais longos e uma camada inferior menor, proporciona uma redução da resistência interna da membrana, devido à formação de caminhos livres, facilitando a passagem da água. Pelas análises de espectrômetro de raios X por dispersão de energia (EDS), foram identificadas nanopartículas de argila dispersas na superfície e na matriz transversal da membrana. Os resultados indicam que a introdução de nanopartículas de argila na solução polimérica é uma técnica de modificação da membrana promissora no melhoramento do desempenho da membrana para o tratamento de água e efluentes. / This research was developed in the International Reference Center for Water Reuse (IRCWR) laboratory inside to the Departamento de Engenharia Hidráulica e Ambiental da Escola Politécnica da Universidade de São Paulo (USP). The main objective of this research is the synthesis of ultrafiltration flat sheet membrane, using polyvinylidene fluoride (PVDF) polymer, clay (montmorillonite hydrophilic) inorganic nanoparticles and polyethylene oxide (PEO). Membranes were synthesized by phase inversion process, using 18% PVDF, mass based, in n-methylpyrrolidone as solvent and water as the non-solvent in the coagulation bath. The influence of different concentrations of clay nanoparticles and PEO was evaluated. Permeability, separation capability, and foulling potential tests were conducted to evaluate membranes performance and morphology analysis and physical characteristics were used for membranes characterization. Results indicated that clay nanoaprticles and PEO addiction can improve membrane permeability and morphology. The Kynar 761 6% clay 0% PEO (K6-0), Kynar 761 0% clay 4% PEO (K0-4) and Kynar 761 6% clay 4% PEO (K6-4) membranes showed the best permeability results, with an increase, respectively of 520%, 1,250% and 1,100%, compared to pure membrane. Furthermore, there is an improvement of 55%, 60% and 41% in the foulling potential reduction, respectively, for K6-0, K0-4 and K6-4 membranes, compared to the control membrane. It was verified that membrane permeability improvement and fouling potential reduction with the addition of clay nanoparticles is related with the improvement of membranes hydrophilicity and surface charge. The internal morphology of the membranes synthesized with clay can be characterized by a surface layer with pores interconnected with finger-like pores in the intermediate layer. The bottom layer has a sponge-like morphology with micro-pores. The increasing number and size of surface pores and also the reduction of horizontal blocks between the surface layer and the finger-like pores in the intermediate layer, is observed with increasing dosage of clay. The internal morphology of the membranes synthesized with PEO can be characterized by a dense surface layer and a bottom layer with dense sponge morphology with micro-pores. The intermediate layer has a dense morphology with finger-like pores with larger diameters if compared to the membranes without addition of PEO. The PEO addition decreases the average size of micro-pores, compared with membranes only clay is added. It was observed that change in composite membranes internal morphology, resulted in the water permeability improvement. The increasing superficial pores connected to longer finger-like pores and a thin bottom layer resulted in an internal pore structure with a lower resistance due to free paths formation, facilitating the flow passage. Using Energy Dispersive X-ray Spectroscopy (EDS) analysis it was possible to observed clay nanoparticles dispersed on membrane surface and in its cross-section matrix. These preliminary results indicate that clay nanoclay addiction in polymeric solution is a promising membrane modification technique for improving membrane performance for water and wastewater treatment.

Foi estudada a enxertia de estireno induzida por radiação gama em filmes de poli(fluoreto de vinilideno) (PVDF) com espessura de 0,125 mm com doses entre 1 e 100 kGy em presença de soluções de estireno/N,Ndimetilformamida (DMF) (1:1, v/v) e estireno/tolueno (1:1, v/v) com taxa de dose de 5 kGy.h-1 por meio do método simultâneo de irradiação sob atmosfera de nitrogênio e em temperatura ambiente, usando raios gama de uma fonte de Co- 60. Depois de enxertados, os polímeros foram sulfonados em soluções de ácido clorossulfônico/1,2-dicloroetano (2 e 10 %). Os filmes foram caracterizados antes e depois de cada modificação com o cálculo do Grau de enxertia, (DOG), espectrometria no infravermelho (FT-IR), microscopia eletrônica de varredura (MEV), calorimetria exploratória diferencial (DSC) e termogravimetria (TG/DTG). Os resultados do grau de enxertia mostraram que a enxertia aumenta com o aumento da dose e varia enormemente de acordo com o solvente utilizado, com enxertias cerca de 20 vezes maiores quando do uso da DMF em relação ao do tolueno. Foi possível confirmar a enxertia do estireno por FT-IR graças ao aparecimento de novos picos característicos e por TG/DTG e DSC por meio das alterações do comportamento térmico dos materiais enxertados/sulfonados. Os materiais sulfonados ainda foram caracterizados por suas capacidades de troca iônica (IEC), que mostraram que tanto os aumentos do grau de enxertia quanto os da concentração do ácido clorossulfônico aumentam o IEC. Os resultados mostraram que é possível obter materiais com capacidades de troca iônica com possibilidade de aplicação como compósitos ionoméricos de metal-polímero. / Gamma-radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses from 1 to 100 kGy in the presence of a styrene/N,N- dimethylformamide (DMF) solution (1:1, v/v) and styrene/toluene (1:1, v/v) at dose rate of 5 kGy h-1 was carried out by simultaneous method under nitrogen atmosphere at room temperature, using gamma rays from a Co-60. After grafting reactions, the polymer was then sulfonated in chlorosulfonic acid/1,2-dichloroethane (2 and 10%) for 3 hours. The films were characterized before and after modification by calculating the degree of grafting (DOG), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). DOG results show that grafting increases with dose, and varies enormously depending on the solvent used, with DOGs about 20 times greater in DMF than in toluene. It was possible to confirm the grafting of styrene by FT-IR due to the appearance of the new characteristic peaks and by the TG and DSC which exhibited changes in the thermal behavior of the grafted/sulfonated material. Sulfonated material was also characterized by ion exchange capacity (IEC) showed that both DOG and sulfonic acid concentration increase IEC values. Results showed that it is possible to obtain materials with ion exchange capacity of possible application as ionic polymer-metal composites.

Tesis por compendio / [ES] El aumento de la esperanza de vida conlleva la aparición de problemas muscoloesqueléticos afectando a la calidad de vida de los pacientes. Las nuevas terapias regenerativas óseas se centran en el uso de las células madre mesenquimales, MSCs, encargadas de la regeneración del tejido in vivo. La inducción de un fenotipo osteogénico prediferenciado in vitro, previo a la implantación de las MSCs, resulta en una mejor capacidad de regeneración del tejido óseo. Habitualmente se han empleado medios de diferenciación osteogénica que contienen dexametasona. Estos métodos son poco eficientes, por lo que el uso de métodos físicos está adquiriendo relevancia. El hueso es un tejido con propiedades piezoeléctricas debido a las fibras de colágeno que forman parte de su matriz extracelular. Este estímulo ha sido relacionado con su capacidad de responder al estrés mecánico y autoregenerarse, donde juegan un papel importante las MSCs. Éstas se encuentran en un entorno electroactivo, y son precisamente estas señales físicas las que pueden influir en su proceso de diferenciación osteogénica pudiendo ser empleadas para su prediferenciación in vitro de forma efectiva. Para comprobar esta hipótesis, en la presente Tesis Doctoral se han diseñado soportes de cultivo piezoeléctricos en 2 y 3 dimensiones basados en el uso del polímero piezoeléctrico polifluoruro de vinilideno (PVDF) combinados con partículas magnetostrictivas de ferrita de cobalto (CFO). Esta combinación permite la estimulación de los soportes de cultivo aplicando un campo magnético con un biorreactor. Este campo magnético genera la deformación del componente magnetostrictivo, que es transmitida a la matriz polimérica, deformándola y generando un campo eléctrico. Ésta última es transmitida a las células cultivadas en estos soportes para estudiar su efecto sobre la diferenciación osteogénica. En el primer capítulo se desarrollaron y caracterizaron membranas electroactivas de PVDF fabricadas por el método de separación de fases inducida por no-solventes. Se empleó etanol como no-solvente, dando lugar a membranas homogéneas altamente porosas. Estas cristalizan en fase g. Se optimizó un recubrimiento basado en la técnica capa a capa (LbL), empleando recombinámeros similares a la elastina (ELRs) que contenían secuencias de adhesión celular RGD. Se estudió la respuesta celular inicial de las MSCs y se comparó con los mismos soportes recubiertos únicamente con fibronectina adsorbida. La presencia de los ELRs es necesaria para promover la adhesión inicial de las MSCs en este tipo de soportes. En el segundo capítulo se combinó el PVDF con CFO, usando agua como no-solvente. Las membranas eran no simétricas, con una superficie lisa, que fue empleada para cultivo celular, con una mayoría en fase b, la más electroactiva. Se recubrieron y caracterizaron las membranas mediante LbL con colágeno tipo I y heparina. Se estudió el comportamiento de las MSCs sobre el LbL, resultando esencial para la proliferación celular en el caso de las membranas PVDF-CFO. En el capítulo tres se desarrollaron films de PVDF y PVDF-CFO cristalizados en presencia del líquido iónico [Bmim][Cl]. La presencia de éste indujo la nucleación del PVDF en fase b. Las MSCs eran capaces de adherirse y proliferar. Se realizaron ensayos de estimulación piezoeléctrica empleando un biorreactor magnético. Las MSCs respondieron a la estimulación incrementado la longitud de sus adhesiones focales, así como reduciendo la vimentina en el citoplasma. Finalmente, se diseñaron soportes de cultivo piezoeléctricos en 3D. Para ello se desarrollaron microesferas de PVDF y PVDF-CFO mediante la técnica de electropulverizado. Las microesferas se encapsularon en hidrogeles de gelatina junto con las MSCs. Se estimularon y tras 7 días, se observó un incremento en la expresión del factor de transcripción RUNX2 en las muestras estimuladas demostrando que la estimulación piezoeléctrica es capaz de activar en mayor medida la diferenciación de las MSCs. / [CA] L'augment de l'esperança de vida comporta l'aparició de problemes muscoloesquelètics afectant la qualitat de vida dels pacients. Les noves teràpies regeneratives òssies es centren en l'ús de les cèl·lules mare mesenquimals, MSCs, encarregades de la regeneració del teixit in vivo. La inducció d'un fenotip osteogènic prediferenciat in vitro, previ a la implantació de les MSCs, resulta en una millor capacitat de regeneració del teixit ossi. Habitualment s'han fet servir mitjans de diferenciació osteogènica que contenen dexametasona. Aquests mètodes són poc eficients, per la qual cosa l'ús de mètodes físics està adquirint rellevància. L'os és un teixit amb propietats piezoelèctriques a causa de les fibres de col·lagen que formen part de la seva matriu extracel·lular. Aquest estímul ha estat relacionat amb la capacitat de respondre a l'estrès mecànic i autoregenerar-se, on juguen un paper important les MSCs. Aquestes es troben en un entorn electroactiu, i són precisament aquests senyals físics els que poden influir en el seu procés de diferenciació osteogènica podent ser emprats per a la seva prediferenciació in vitro de manera efectiva. Per comprovar aquesta hipòtesi, a la present tesi doctoral s'han dissenyat suports de cultiu piezoelèctrics en 2 i 3 dimensions basats en l'ús del polímer piezoelèctric polifluorur de vinilidè (PVDF) combinats amb partícules magnetostrictives de ferrita de cobalt (CFO). Aquesta combinació permet l'estimulació dels suports de cultiu aplicant un camp magnètic amb un bioreactor. Aquest camp magnètic genera la deformació del component magnetostrictiu, que és transmesa a la matriu polimèrica, deformant-la i generant un camp elèctric. Aquesta última és transmesa a les cèl·lules cultivades en aquests suports per estudiar-ne l'efecte sobre la diferenciació osteogènica. En el primer capítol es van desenvolupar i caracteritzar membranes electroactives de PVDF fabricades pel mètode de separació de fases induïda per no solvents. Es va emprar etanol com a no-solvent, donant lloc a membranes homogènies altament poroses. Aquestes cristal·litzen en fase g. S'optimitzà un recobriment basat en la tècnica capa a capa (LbL), emprant recombinàmers similars a l'elastina (ELRs) que contenien seqüències d'adhesió cel·lular RGD. Es va estudiar la resposta cel·lular inicial de les MSCs i es va comparar amb els mateixos suports recoberts únicament amb fibronectina adsorbida. La presència dels ELR és necessària per promoure l'adhesió inicial de les MSCs en aquest tipus de suports. En el segon capítol es va combinar el PVDF amb CFO, usant aigua com a no-solvent. Les membranes eren no simètriques, amb una superfície llisa, que va ser emprada per a cultiu cel·lular, amb una majoria en fase b, la més electroactiva. Es van recobrir i caracteritzar les membranes mitjançant LbL amb col·lagen tipus I i heparina. Es va estudiar el comportament de les MSCs sobre el LbL, resultant essencial per a la proliferació cel·lular en el cas de les membranes PVDF-CFO. Al capítol tres es van desenvolupar films de PVDF i PVDF-CFO cristal·litzats en presència del líquid iònic [Bmim][Cl]. La seva presència va induir la nucleació del PVDF en fase b. Les MSCs eren capaces d'adherir-se i proliferar. Es van realitzar assajos d'estimulació piezoelèctrica emprant un bioreactor magnètic. Les MSCs van respondre a l'estimulació incrementant la longitud de les seves adhesions focals, així com reduint la vimentina al citoplasma. Finalment, es van dissenyar suports de cultiu piezoelèctrics en 3D. Per això es van desenvolupar microesferes de PVDF i PVDF-CFO mitjançant la tècnica d'electropolveritzat. Les microesferes es van encapsular en hidrogels de gelatina juntament amb les MSCs. Es van estimular i després de 7 dies, es va observar un increment en l'expressió del factor de transcripció RUNX2 a les mostres estimulades demostrant que l'estimulació piezoelèctrica és capaç d'activar més la diferenciació de les MSCs. / [EN] Life expectancy increase entails the presence of musculoskeletal disorders producing a substantial impact on patient's quality of life. New bone regenerative therapies are focused on the use of mesenchymal stem cells (MSCs), the main effectors of bone regeneration in vivo. Over the years, it has been demonstrated that the induction of a pre-differentiated phenotype in vitro, before MSCs implantation, results in a better capacity for bone tissue regeneration. For this purpose, biochemical approaches based on the use of osteogenic differentiation medium containing dexamethasone have traditionally been used. These methods are not efficient, which has favoured the use of physical methods as an alternative. Bone is a piezoelectric tissue due to the collagen fibres that conform its extracellular matrix. This stimulus has been related to its ability to respond to mechanical stress and self-regenerate, a process in which MSCs play a key role. MSCs are subjected to an electroactive environment. It is hypothesised that these physical signals may influence their osteogenic differentiation process and be used to effectively pre-differentiate them in vitro. To test this hypothesis, along this Doctoral Thesis, piezoelectric cell culture supports have been designed in 2 and 3 dimensions based on the use of the piezoelectric polymer poly(vinylidene) fluoride (PVDF) combined with magnetostrictive cobalt ferrite oxide (CFO) nanoparticles. This combination allows the stimulation of culture supports by applying a magnetic field with a bioreactor. This magnetic field induces the deformation of the magnetostrictive component, which is transmitted to the polymeric matrix, generating a deformation and producing an electric field, which is transmitted to the MSCs to study its effect on their osteogenic differentiation. In the first chapter, electroactive PVDF membranes manufactured by the non-solvent induced phase separation technique were developed and characterised. Ethanol was used as a non-solvent, which gave rise to highly porous homogeneous membranes crystallised in the g phase. A coating protocol based on the layer-by-layer (LbL) technique, using elastin-like recombinamers (ELRs) containing RGD cell adhesion sequences, was optimised. MSCs' initial cellular response was studied and compared with the membranes coated with adsorbed fibronectin. The presence of the ELRs was necessary to promote MSCs' initial adhesion in this type of support. In the second chapter, PVDF was combined with CFO, using water as a non-solvent. The membranes were not symmetrical, with a smooth surface used for cell culture, with a majority in phase b, the most electroactive. Membranes were coated and characterised by LbL with type I collagen and heparin. The behaviour of MSCs on LbL was studied, essential for cell proliferation in the case of PVDF-CFO membranes. In chapter three, PVDF and PVDF-CFO films crystallised in the presence of the ionic liquid [Bmim][Cl] were developed. The presence of ionic liquid induced PVDF nucleation in the b phase. MSCs were able to adhere and proliferate. Piezoelectric stimulation tests were performed using a magnetic bioreactor. MSCs responded to stimulation by increasing the length of their focal adhesions and reducing vimentin in the cytoplasm. Finally, 3D piezoelectric culture supports were designed. For this, PVDF and PVDF-CFO microspheres were developed using the electrospray technique. The microspheres were encapsulated in gelatin hydrogels together with the MSCs. They were stimulated, and after 7 days, an increase in the expression of the transcription factor RUNX2 was observed in the stimulated samples, demonstrating that piezoelectric stimulation is capable of activating the differentiation of MSCs to a greater extent. / La presente tesis doctoral no podría haberse realizado sin la financiación del Ministerio de Economía y Competitividad a través de la beca para formación de personal investigador BES-2017-080398 y a la Agencia Estatal de Investigación a través de los proyectos PID2019-106000RB-C21 / AEI / 10.13039/501100011033, PID2019-106099RB- C41 y –C43 / AEI / 10.13039/501100011033. / Guillot Ferriols, MT. (2022). Electroactive Environments for Mesenchymal Stem Cells Osteogenic Differentiation [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/191003 / Compendio

<p>    An all-additive manufacturing technique was developed to print piezoelectrically active polymeric materials, primarily poly(vinylidene fluoride) (PVdF), for use in pressure sensors in soft robotics. The research proceeded in three stages. The initial stage used Fused Deposition Modeling (FDM) and electric poling independently to create piezoelectric PVdF pressure sensors. The second stage merged FDM and electric poling processes. The third stage introduced electrospinning to create flexible, high-output piezoelectric PVdF materials, which were combined with three-dimensional (3D) printed soft structures for stretchable pressure sensors.</p> <p>    The main achievement of the research was the development of the Electric Poling-assisted Additive Manufacturing (EPAM) technique, combining electric poling and FDM 3D printing to print piezoelectric materials with custom structures at lower costs. β-phase in semicrystalline PVdF materials is mainly responsible for piezoelectricity. A higher β-phase content results in superior sensor performance. This technique was evaluated by measuring the piezoelectric output voltage of the printed PVdF films, and β-phase content was quantified using Fourier-transform Infrared spectroscopy (FTIR). The developed EPAM technique was combined with Direct Ink Writing (DIW), becoming a hybrid 3D printing technique. This is the first demonstration of applying a hybrid printing technique to print piezoelectric PVdF-based sensors directly. The sensor was constructed using FDM printed PVdF film as the dielectric sandwiched between two parallel DIW printed silver electrodes. The PVdF sensors have both piezoelectric pressure sensing and capacitive temperature sensing functionalities. The application of the capacitive temperature sensor was demonstrated by applying heating-and-cooling cycles while measuring the capacitance as a function of temperature at a constant frequency, showing improved sensitivities at higher frequencies (i.e., 105 Hz) after dielectric polarization.</p> <p>    The third stage of research was motivated by the need for soft piezoelectric pressure sensors for soft robotics. Challenges were twofold: requiring soft piezoelectric materials with high coefficients for excellent sensors and fabrication techniques to incorporate soft materials into designed structures. Inspired by the EPAM technique, a method combining electrospinning and DIW was used to create soft piezoelectric PVdF/thermal plastic polyurethane (TPU) blend microfiber-based pressure sensors. The soft sensor was integrated with an FDM printed soft structure for a stretchable pressure sensor with both piezoelectric sensing and capacitive sensing mechanisms.</p>

Este trabalho descreve a seqüência de fabricação de uma microválvula piezoelétrica posicionada na saída de um microbocal sônico. A técnica usada para fabricar os microbocais foi o jateamento utilizando pó de alumina e o substrato usado foi de vidro. As microválvulas são atuadores fabricados com o polímero poli(fluoreto de vinilideno) (PVDF) que é um material piezoelétrico. Os microbocais têm um formato convergente-divergente com diâmetro na entrada de 1 mm e com diâmetro na garganta em cerca de 240 microns. O atuador foi fabricado no modo bimorfo (duas folhas do polímero coladas com polarização opostas) com dimensões de 3 mm de largura por 6 mm de comprimento. Ambas as folhas do polímero são recobertas por um filme condutor de 200 nm de espessura usados como eletrodos. Aplicando uma voltagem entre os eletrodos uma folha expande enquanto a outra contrai gerando um movimento vertical do atuador. O movimento vertical pode ser maior ou menor dependendo do valor da tensão aplicada. Os dispositivos foram testados usando uma linha de gás, aplicando tensões DC e AC nos eletrodos do atuador. Para controle, também foram realizadas medidas em bocais sem atuadores. No caso onde foram aplicadas tensões DC nos atuadores, a pressão de entrada foi constante de 266 Pa. Aplicando uma tensão de +300 V DC nos eletrodos, o atuador teve um movimento vertical na direção oposta ao do microbocal de 20 microns (movimento de abertura). Neste caso o fluxo de gás medido, quando a razão de pressão entre a entrada e a saída atingiu 0,5, foi de 150 cm3/min. Aplicando uma tensão de -300 V DC (o que significa um movimento vertical de fechamento de 13 microns), o fluxo de gás medido, quando a razão de pressão foi de 0,5, foi de 134 cm3/min. Assim, existe uma faixa de fluxo entre 134 cm3/min e 150 cm3/min que pode ser controlada através do atuador. Em uma das medidas onde se aplicou uma tensão AC (200 V com 5 Hz de freqüência), foi utilizada uma pressão de entrada 13300 Pa. Neste caso, para uma razão de pressão de 0,5, onde o bocal se encontrava blocado, foi observado um fluxo de 847 cm3/min. Considerando que o fluxo do bocal sem atuador, nas mesmas condições de medida foi de 614 cm3/min, concluímos que o dispositivo no modo AC funciona como uma microbomba. A relevância deste trabalho está a utilização do poli(fluoreto vinilideno) (PVDF) na fabricação de um atuador para uso como microválvula. Este material que ainda não havia sido testado para esta finalidade. A fabricação dos microbocais foi feita em um substrato de vidro usando a técnica de jateamento também é inédita. Esta técnica é bastante usada na fabricação de microestruturas na superfície do vidro. Mas nunca tinha sido usada para a fabricação de microbocais que são canais em formato cônico que atravessam o substrato. / This work describes the fabrication and test of a microvalve integrated in a micronozzle. The technique used to fabricate the micronozzles was powder blasting using aluminum oxide powder and glass as substrate. The microvalves are actuators made from PVDF (poli(vinylidene fluoride)), that is a piezoelectric polymer. The micronozzles have convergent-divergent shape with diameter of 1mm at the entrance and throat around 240µm. The actuators were fabricated as a bimorph structure (two piezoelectric sheets were clamped together with opposite polarization) with dimensions 3 mm width and 6 mm length. Both sheets are recovered with a conductive thin film with 200 nm of thickness used as electrodes. Applying voltage between the electrodes one sheet expands while the other contracts and this generate a vertical movement to the entire actuator. If the voltage is changed, this movement can be higher or lower. The devices were tested in a gas line applying DC and AC voltages between the actuator\'s electrodes. Measurements were also realized using a micronozzle without actuator, for control. In the case where DC voltage was applied between the actuators electrodes, the inlet pressure was kept constant in 266 Pa. Applying +300V DC voltage between the electrodes, the actuator moved 20µm vertically in the opposite direction of the micronozzle (it opened). In this case the volume flux rate, for a pressure ratio (outlet / inlet) of 0.5, was 150 cm3/min. Applying -300V DC between the electrodes (that means it closed 13 microns in the micronozzle direction), for a pressure ratio of 0.5, the volume flux rate was 134 cm3/min. With these results, we conclude that it is possible to control the flow through the device in the range between 134 and 150 cm3/min. Flow measurements were also performed applying AC voltage (200V AC with frequency of 5 Hz) between the actuator electrodes and with the inlet pressure kept constant in 13300 Pa. In this case, with a pressure ratio (outlet / inlet) of 0.5, blocking the micronozzle, the flow rate measured was 847 cm3/min. Considering that the flow rate measured for the micronozzle without actuator was 614 cm3/min, in the same measurement conditions, we concluded that the device, in AC mode, was working as a micropump. The relevance of this work was the use of the poly(vinylidene) (PVDF) in the fabrication of the actuators and use it as a microvalve. The micronozzles were fabricated in a glass substrate using the powder blasting technique that was also new.

Este trabalho descreve a seqüência de fabricação de uma microválvula piezoelétrica posicionada na saída de um microbocal sônico. A técnica usada para fabricar os microbocais foi o jateamento utilizando pó de alumina e o substrato usado foi de vidro. As microválvulas são atuadores fabricados com o polímero poli(fluoreto de vinilideno) (PVDF) que é um material piezoelétrico. Os microbocais têm um formato convergente-divergente com diâmetro na entrada de 1 mm e com diâmetro na garganta em cerca de 240 microns. O atuador foi fabricado no modo bimorfo (duas folhas do polímero coladas com polarização opostas) com dimensões de 3 mm de largura por 6 mm de comprimento. Ambas as folhas do polímero são recobertas por um filme condutor de 200 nm de espessura usados como eletrodos. Aplicando uma voltagem entre os eletrodos uma folha expande enquanto a outra contrai gerando um movimento vertical do atuador. O movimento vertical pode ser maior ou menor dependendo do valor da tensão aplicada. Os dispositivos foram testados usando uma linha de gás, aplicando tensões DC e AC nos eletrodos do atuador. Para controle, também foram realizadas medidas em bocais sem atuadores. No caso onde foram aplicadas tensões DC nos atuadores, a pressão de entrada foi constante de 266 Pa. Aplicando uma tensão de +300 V DC nos eletrodos, o atuador teve um movimento vertical na direção oposta ao do microbocal de 20 microns (movimento de abertura). Neste caso o fluxo de gás medido, quando a razão de pressão entre a entrada e a saída atingiu 0,5, foi de 150 cm3/min. Aplicando uma tensão de -300 V DC (o que significa um movimento vertical de fechamento de 13 microns), o fluxo de gás medido, quando a razão de pressão foi de 0,5, foi de 134 cm3/min. Assim, existe uma faixa de fluxo entre 134 cm3/min e 150 cm3/min que pode ser controlada através do atuador. Em uma das medidas onde se aplicou uma tensão AC (200 V com 5 Hz de freqüência), foi utilizada uma pressão de entrada 13300 Pa. Neste caso, para uma razão de pressão de 0,5, onde o bocal se encontrava blocado, foi observado um fluxo de 847 cm3/min. Considerando que o fluxo do bocal sem atuador, nas mesmas condições de medida foi de 614 cm3/min, concluímos que o dispositivo no modo AC funciona como uma microbomba. A relevância deste trabalho está a utilização do poli(fluoreto vinilideno) (PVDF) na fabricação de um atuador para uso como microválvula. Este material que ainda não havia sido testado para esta finalidade. A fabricação dos microbocais foi feita em um substrato de vidro usando a técnica de jateamento também é inédita. Esta técnica é bastante usada na fabricação de microestruturas na superfície do vidro. Mas nunca tinha sido usada para a fabricação de microbocais que são canais em formato cônico que atravessam o substrato. / This work describes the fabrication and test of a microvalve integrated in a micronozzle. The technique used to fabricate the micronozzles was powder blasting using aluminum oxide powder and glass as substrate. The microvalves are actuators made from PVDF (poli(vinylidene fluoride)), that is a piezoelectric polymer. The micronozzles have convergent-divergent shape with diameter of 1mm at the entrance and throat around 240µm. The actuators were fabricated as a bimorph structure (two piezoelectric sheets were clamped together with opposite polarization) with dimensions 3 mm width and 6 mm length. Both sheets are recovered with a conductive thin film with 200 nm of thickness used as electrodes. Applying voltage between the electrodes one sheet expands while the other contracts and this generate a vertical movement to the entire actuator. If the voltage is changed, this movement can be higher or lower. The devices were tested in a gas line applying DC and AC voltages between the actuator\'s electrodes. Measurements were also realized using a micronozzle without actuator, for control. In the case where DC voltage was applied between the actuators electrodes, the inlet pressure was kept constant in 266 Pa. Applying +300V DC voltage between the electrodes, the actuator moved 20µm vertically in the opposite direction of the micronozzle (it opened). In this case the volume flux rate, for a pressure ratio (outlet / inlet) of 0.5, was 150 cm3/min. Applying -300V DC between the electrodes (that means it closed 13 microns in the micronozzle direction), for a pressure ratio of 0.5, the volume flux rate was 134 cm3/min. With these results, we conclude that it is possible to control the flow through the device in the range between 134 and 150 cm3/min. Flow measurements were also performed applying AC voltage (200V AC with frequency of 5 Hz) between the actuator electrodes and with the inlet pressure kept constant in 13300 Pa. In this case, with a pressure ratio (outlet / inlet) of 0.5, blocking the micronozzle, the flow rate measured was 847 cm3/min. Considering that the flow rate measured for the micronozzle without actuator was 614 cm3/min, in the same measurement conditions, we concluded that the device, in AC mode, was working as a micropump. The relevance of this work was the use of the poly(vinylidene) (PVDF) in the fabrication of the actuators and use it as a microvalve. The micronozzles were fabricated in a glass substrate using the powder blasting technique that was also new.

Segmental chain dynamics in polymer blends is a very important topic, not only from a fundamental point of view but also from technological applications. Because of the difficulties in the commercialization of new polymers, industries have turned increasingly towards blending of polymers to optimise their end use (mechanical, rheological) properties. The design of tailor-made materials would be enormously facilitated by the understanding of the blending phenomena at a molecular level. The key question to address is to understand the dynamics of each component of the blend modified by blending? The thesis has systematically studied the effect of multiwalled carbon nanotubes on the chain dynamics, demixing temperature, structural properties and evolution of morphology in a classical miscible polymer blend system (PVDF/PMMA). The thesis comprises of six chapters, Chapter 1 is an introductory chapter that outlines the fundamentals of polymer blends, crystallisation in polymer blends and the basics of dielectric spectroscopy. As one of the rationales of this work is to systematic study whether phase separated in these blends can be used as a tool to develop membrane for water purification. This chapter also gives an overview of the reported studies of ultrafiltration membrane fabrication, factors affecting membrane morphology and flux. In Chapter 2, the materials and methodology used to carry out experiments and the experimental procedures are discussed. Chapter 3 discusses the effect of concentration of PMMA and amine functionalized multiwalled carbon nanotubes (MWNTs) on the crystallisation induced phase separation using FTIR, XRD, POM and shear rheology. Electron microscopy and selective etching confirmed the localisation of MWNTs in the PVDF phase of the blends. Blends with MWNTs facilitated in heterogeneous nucleation manifesting in an increase in crystallisation temperature. The crystallisation induced phase separation in PVDF/PMMA blends was observed to influence the interconnected network of MWNTs in the blends. Chapter 4 discuss the effect of concentration of PMMA and MWNTs on the miscibility and the segmental relaxations was probed in situ by DSC and dielectric relaxation spectroscopy (DRS). The dynamic heterogeneity in the blends as manifested by the presence of an extra relaxation at a higher frequency at or below the crystallisation induced phase separation temperature was also discussed. We found that PVDF/PMMA blend (PVDF ≥ 80 wt%) exhibits three distinct relaxations; αc corresponding to crystalline PVDF, αβ segmental relaxation of PMMA and αm of amorphous miscibility whereas all relaxations overlap and constitute a single broad relaxation in PVDF/PMMA blend (PVDF ≤ 70 wt%). This confirms that there is a certain composition width in this blend wherein three distinct relaxations can be traced. This could due to many reasons like the width of crystal-amorphous interphase in the crystal lamellae, crystal size and morphology is strongly contingent on the concentration of PMMA. Relaxations are not very distinct in presence of MWNTs due to defective spherulites that shift the relaxations towards a higher frequency. Chapter 5 has attempted to tune the microporous morphology of PVDF membranes using crystallisation induced phase separation in PVDF/PMMA blends. As PVDF/PMMA is a melt-miscible blend, the samples were allowed to crystallise and the amorphous PMMA phase, which isolates in the interlamellar or inter-spherulitic regions in the blends, was etched out to generate microporous structures. The pore sizes can be tuned by varying the PMMA concentration in the blends. We observed that 60/40 PVDF/PMMA blends showed larger pores as compared to 90/10 PVDF/PMMA blends. We further modified PVDF membranes by sputtering silver on the surface. The bacterial cell viability was distinctly suppressed (99 %) in silver sputtered membranes. The ICP analysis suggests that slow Ag+ ions release from the sputtered membrane surface assisted in developing antibacterial surface. Our findings open new avenues in designing water filtration membranes and also help in understanding the crystallisation kinetics for tuning pore size in membranes. Chapter 6 summarises the important results of this work. MWNTs act as hetero nucleating agent and specifically interact with PVDF thereby influences the dynamics of PVDF chains. MWNTs can also restrict the amorphous segmental mobility and can influence the intermolecular cooperativity and coupling. The crystallisation induced phase separation in various blends can result in various crystalline morphologies depending on the PVDF concentration. By selectively etching PMMA from the phase-separated blends, microporous morphology can be generated

Ceramics and polymer-ceramic composites associated with high dielectric constants are of both scientific and industrial interest as these could be used in devices such as capacitors, resonators and filters. High dielectric constant facilitates smaller capacitive components, thus offering the opportunity to miniaturize the electronic devices. Hence there is a continued interest on high dielectric constant materials over a wide range of temperatures. Recently, CaCu3Ti4O12 (CCTO) ceramic which has centro-symmetric body centered cubic structure has attracted considerable attention due to its large dielectric constant (ε ~104-105) which is nearly independent of frequency (upto 10 MHz) and low thermal coefficient of permittivity (TCK) over 100-600K temperature range. Apart from the high dielectric ceramics, high dielectric polymer-ceramic composites have also become promising materials for capacitor applications. By combining the advantages of high dielectric ceramics and low leakage behaviour of polymers, one can fabricate new hybrid materials with high dielectric constants, and high breakdown field to achieve high volume efficiency and energy storage density for capacitor applications. The CCTO polycrystalline powders were generally prepared by the conventional solid-solid reaction route with CaCO3, TiO2 and CuO as the starting materials. This method of preparation often requires high temperatures and longer durations. To overcome these difficulties, in the present investigations, an attempt has been made to synthesize CCTO by adopting microwave assisted heating technique and wet chemical synthesis routes. Also the CCTO crystallites (size varying from nano to micrometers) incorporated in the Polyvinyliden fluoride (PVDF) and Polyaniline (PANI) matrix and several composites with high dielectric constants were fabricated and investigated. Further, the high dielectric constant glasses in the system (100-x)TeO2-xCaCu3Ti4O12, (x=0.5 to 3) were fabricated by the conventional melt-quenching technique and their structural and dielectric properties were studied. The results obtained pertaining to these aforementioned investigations are classified as follows. Chapter 1 is intended to give basic information pertaining to the dielectrics and various mechanisms associated with high dielectric constants. Brief exposure to the high dielectric constant materials is also given. The structural aspects of CCTO, various synthetic routes adopted for the synthesis and the origin of the dielectric anomaly in CCTO are elaborated. In addition, basic information about the high dielectric polymer-ceramic composites and glasses are provided. In chapter 2 the various experimental techniques that were employed to synthesize and characterize the materials under investigation were discussed. Chapter 3 reports the synthesis and characterization of CaCu3Ti4O12, (CCTO) powders by microwave assisted heating at 2.45 GHz, 1.1kW. The processing and sintering were carried out at different temperatures for varied durations. The optimum calcination temperature using microwave heating was found to be 950oC for 20 minutes to obtain cubic CCTO powders. This is found to be fast and energy efficient as compared to that of the conventional methods. The structure, morphology and dielectric properties of the CCTO ceramic processed by microwave assisted heating were studied via X-ray diffraction, Scanning electron microscopy (SEM) and impedance analyser. These studies revealed that, the microwave sintered (MS) samples were less porous than that of the conventional ones. Relative density of about 95% was achieved for the MS pellets (1000oC/60min) while for the conventional sintered (CS) pellets (1100oC/2h) it was only 91%. The dielectric constants for the microwave sintered (1000oC/60min) ceramics were found to vary from 11000 to 6950 in the 100 Hz to 100 kHz frequency range. The presence of larger grains (6-10μm) in the MS samples contributed to the higher dielectric constants. Chapter 4 deals with the synthesis of complex oxalate precursor, CaCu3(TiO)4(C2O4)8 • 9H2O, by the wet chemical route. The various trials and the different reaction schemes involved for the preparation of complex oxalate precursor were highlighted. The oxalate precipitate thus obtained was characterized by the wet chemical analyses, X-ray diffraction, FTIR absorption and TG/DTA analyses. The complex oxalate precursor, CaCu3(TiO)4(C2O4 )8.9H2O was subjected to thermal oxidative decomposition and the products of thermal decomposition were investigated employing XRD,TGA, DTA and FTIR techniques. Nanocrystallites of CaCu3Ti4O12 with the size varying from 30-200 nm were obtained at a temperature as low as 680oC. The nanocrystallites of CaCu3Ti4O12 were characterized using Electron Spin Resonance (ESR) and optical reflectance techniques. The selected area electron diffraction (SAED) pattern with the zone axis [012] and spot pattern in electron diffraction (ED) indicate their single-crystalline nature. The optical reflectance and ESR spectra indicate that the Cu (II) coordination changes from distorted octahedra to nearly flattened tetrahedra (squashed) to square planar geometry with increasing heat treatment temperature. The powders derived from the oxalate precursor have excellent sinterability resulting in high density ceramics which exhibited giant dielectric constants upto 40,000 (1 kHz) at 25oC, accompanied by low dielectric loss < 0.07. The effect of calcium content on the dielectric properties of CaxCu3Ti4O12 (x=0.90, 0.97, 1.0, 1.1 and 1.15) derived from the oxalate route was described in Chapter 5. The structural, morphological and dielectric properties of the ceramics were studied using X-ray diffraction, Scanning Electron Microscope along with Energy Dispersive X-ray Analysis (EDX), and Impedance analyzer. The X-ray diffraction patterns obtained for the x= 0.97, 1.0 and 1.1 ceramics could be indexed to a body– centered cubic perovskite related structure associated with the space group Im3. The microstructural studies revealed that the grains are surrounded by exfoliated sheets of Cu-rich phase. The microstructure that is evolved for the Ca0.97 ceramic more or less resembles that of the Ca1.0 ceramic, but the density of such exfoliated sheets of cu-rich phase is lesser for the Ca0.97 ceramic and none for Ca1.1 ceramic. The sintered pellet (x=0.97) was ground and thinned to the required thickness (~ 20nm) and analyzed using Transmission Electron Microscopy (TEM). The current-voltage (I-V) characteristics of the ceramics exhibited non-linear behaviour. The dielectric properties of these suggest that the sample corresponding to the composition x=0.97, has a reduced dielectric loss while retaining its high dielectric constant. Chapter 6 illustrates the results concerning the fabrication and characterization of nanocrystal composites of Polyaniline (PANI) and CaCu3Ti4O12 (CCTO). These were prepared using a simple procedure involving in-situ polymerization of aniline in dil. HCl. The PANI and the PANI-CCTO composites were subjected to X-ray diffraction, Fourier Transform Infrared (FTIR), Thermo gravimetric, Scanning Electron Microscopic (SEM) and Transmission electron microscopic analyses. The FTIR spectra recorded for the composites was similar to that of pure PANI unlike in the case of X-ray diffraction wherein the characteristics of both PANI and CCTO were reflected. The TGA in essence indicated the composites to have better thermal stability than that of pure PANI. The composite corresponding to 50%CCTO-50%PANI exhibited higher dielectric constant (4.6x106 @100Hz). The presence of the nano crystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. The AC conductivity increased slightly upto 2kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers. The value of dielectric constant obtained was higher than that of the other PANI based composites reported in the literature. Chapter 7 deals with the fabrication and characterization of diphasic Poly(vinylidene fluoride) (PVDF)-CCTO composite. The CCTO crystallites (size varying from nano to micrometers) incorporated in the Polyvinylidene fluoride (PVDF) and composites with varying CCTO content were fabricated. The structural, morphological and dielectric properties of the composites were studied using X-ray diffraction, Thermal analysis, Scanning Electron Microscope (SEM), Transmission Electron Microscopic (TEM) and Impedance analyzer. The room temperature dielectric constant as high as 95 at 100Hz has been realized for the composite with 0.55 Vol.fraction of CCTO (micro sized crystallites), which has increased to about 190 at 150oC. Whereas, the PVDF/CCTO nanocrystal composite with 0.13Vol.fraction of CCTO has exhibited higher room temperature dielectric constant (90 at 100Hz). The PVDF/CCTO nanocrystal composite was further investigated for the breakdown strength and electric modulus. The breakdown strength plotted against the dielectric constant evidenced an inverse relationship of breakdown voltage with the dielectric constant. The relaxation processes associated with these composites were attributed to the interfacial polarization or Maxwell-Wagner-Sillars (MWS) effect. Various theoretical models were employed to rationalize the dielectric behavior of these composites. The fabrication and characterization details of optically clear colored glasses in the system (100-x)TeO2-xCaCu3Ti4O12, (x=0.5 to 3 mol%) are reported in Chapter 8. The color varies from olive green to brown as the CaCu3Ti4O12 (CCTO) content increased in TeO2 matrix. The X-ray powder diffraction and differential scanning calorimetric analyses that were carried out on the as-quenched samples confirmed their amorphous and glassy nature respectively. The optical transmittance of the glasses exhibited typical band-pass filter characteristics. The dielectric constant and loss in the 100 Hz-1MHz frequency range were monitored as a function of temperature (323K673K). The dielectric constant and the loss increased as the CCTO content increased in TeO2 at all the frequencies and temperatures under study. Further, the dielectric constant and the loss were found to be frequency independent in the 323-473 K temperature range. The value obtained for the loss at 1MHz was 0.0019 which was typical of low loss materials, and exhibited near constant loss (NCL) contribution to the ac conductivity in the 100Hz-1MHz frequency range. The electrical relaxation was rationalized using the electrical modulus formalism. These glasses are found to be more stable (a feature which may be of considerable interest) as substrates for high frequency circuit elements in conventional semiconductor industries. Thesis ends with summary and conclusions, though each chapter is provided with conclusions and complete list of references.

Le caoutchouc naturel (NR) et le caoutchouc époxydé (ENR) ont constitué la base de cette étude consacrée à l’étude des composites et mélanges de polymères. La présence du groupe époxyde a conduit à une amélioration des propriétés mécaniques de ces formulations en termes de module et de la résistance à la traction. De plus, l’utilisation de la spectroscopie diélectrique a révélé que les ENRs présentent une conductivité plus élevée que le NR à basse fréquence et à haute température. En particulier, le caoutchouc naturel époxidé contenant 50 mol% de groupes époxyde ENR-50 présente des conductivités et permittivités les plus élevées. Par conséquent, ce dernier a été choisi pour préparer des composites polymères en incorporant des particules de titanate de barium (BT) et de noir de carbone (CB). Les résultats montrent que la permittivité et conductivité des composites élaborés augmentent avec le taux d'incorporation de ces charges. Par exemple, les composites BT/ENR-50 atteignent une permittivité élevée 48.7 pour 50 vol% de BT. De plus, les composites CB/ENR-50 présentent un seuil de percolation de 6.3 vol% de CB. Enfin les mélanges à base de poly(fluorure de vinylidène) (PVDF) et d’ENR ont été étudiés. Il a été observé que la morphologie de ces mélanges dépend du degré d’époxydation du caoutchouc naturel et bien entendu de la composition du mélange. Une morphologie co-continue peut être observée dans l’intervalle 40 et 60% en masse d’ENR-50. En outre, les résultats issus d’analyses dynamiques mécanique et diélectrique montrent que ces mélanges présentent une miscibilité partielle. Enfin, des composites à base de ces mélanges binaires PVDF/ENR- 50 contenant BT ont été préparés. L’étude des morphologies a révélé que les particules de BT étaient dispersées dans la phase d’ENR-50 pour le mélange classique. Cependant, les particules de BT sont localisées à l'interface et dans la phase PVDF pour le mélange réticulé dynamiquement. En termes de propriétés, la permittivité plus élevée est obtenue pour le mélange PVDF/ENR 50 (80/20) ayant été réticulé dynamiquement / Natural rubber (NR) and epoxidized natural rubber (ENR) were chosen to study the composites and blends of polymers. The presence of epoxide group caused to improve the mechanical properties in terms of modulus and tensile strength. Furthermore, dielectric spectroscopy revealed that ENR showed conductivity process at low frequency and high temperature. Epoxidized natural rubber containing 50 mol% of epoxide group or ENR-50 exhibited the highest dielectric permittivity and electrical conductivity. Therefore, ENR-50 was then selected to prepare polymer composite filled with barium titanate (BT) and carbon black (CB) particles. The permittivity and conductivity of the composites increased with the volume content of the fillers. The BT/ENR-50 composites reached a high permittivity of 4 8 . 7 for addition of 50 vol% BT. Meanwhile, CB/ENR-50 composite reached percolation threshold at 6. 3 vol% of CB. The phase development and miscibility of poly(vinylidene fluoride) (PVDF)/epoxidixed natural rubber (ENR) blends were then investigated. It was also found that phase structure depended on epoxidation level and blend compositions. The blend exhibited a co-continuous phase morphology in the region of 40 to 60 wt% of ENR-50. Furthermore, the results from dynamic mechanical and dielectric analysis revealed that these blends present a partial miscibility. Finally, the composites based on binary blends of PVDF/ENR-50 containing BT were prepared. The study of the morphologies revealed that BT was dispersed in ENR-50 phase in the case of simple blend. However, the addition of BT after dynamic vulcanization induced localization of BT in PVDF phase and at interface. The highest increment of permittivity can be observed for the composite based on dynamically cured PVDF/ENR-50 (80/20) blend / ศึกษาอิทธิพลของโครงสร้างโมกุลยางธรรมชาติ (NR) และยางธรรมชาติอิพอกไซด์ (ENR) ต่อสมบัติ พบว่าการมีหมู่อิพอกไซด์อยู่ในยาง ENR ทำให้มีการปรับปรุงสมบัติเชิงกล เช่น มอดุลัสและความต้านทานต่อแรงดึง นอกจากนี้สมบัติไดอิเล็กทริกได้แสดงให้เห็นถึงการนำ ไฟฟ้าที่ความถี่ต่ำและอุณหภูมิสูง ยางที่มีหมู่อิพอกไซด์ 50 โมล% (ENR-50) มีค่าการนำไฟฟ้า และค่า permittivity สูงที่สุด ดังนั้นจึงนำยาง ENR-50 ไปใช้ในการเตรียมคอมพอสิตที่ใช้แบเรียม ไททาเนตและเขม่าดำเป็นตัวเติม ซึ่งพบว่าค่า permittivity และค่าการนำไฟฟ้าสูงขึ้นตาม ปริมาณตัวเติมที่ใส่ลงไป ที่ปริมาณ 50%โดยปริมาตรของแบเรียมไททาเนตในยางให้ค่า permittivity สูงถึง 48.7 ในขณะเดียวกันก็พบว่าการเตรียม ENR-50 คอมพอสิตที่ใช้เขม่าดำมี percolation threshold ที่ 6.3 vol% ของเขม่าดำ สำหรับการศึกษาการเปลี่ยนแปลงของสัณฐาน วิทยาและความเข้ากันได้ของพอลิเมอร์เบลนด์ระหว่างพอลิไวนิลลิดีนฟลูออไรด์ (PVDF) กับยาง ENR พบว่า สัณฐานวิทยาของพอลิเมอร์ที่เตรียมได้ขึ้นอยู่กับปริมาณหมู่อิพอกไซด์ในยาง ENR และอัตราส่วนการเบลนด์ อัตราส่วนการเบลนด์ในช่วง 40 ถึง 60% โดยน้ำหนักของยาง ENR- 50 ให้ลักษณะสัณฐานวิทยาแบบวัฏภาคร่วม (co-continuous) นอกจากนี้ผลการทดสอบจาก สมบัติพลวัตเชิงกลและสมบัติไดอิเล็กทริกแสดงให้เห็นถึงความเข้ากันได้บางส่วน (partial miscibility) ท้ายที่สุดนี้ได้เตรียมคอมพอสิตจากพอลิเมอร์เบลนด์ที่เติมแบเรียมไททาเนต สัณฐานวิทยาของคอมโพสิทที่เตรียมได้นั้น พบว่าแบเรียมไททาเนตกระจายตัวในเฟสยางเป็น หลัก อย่างไรก็ตามการเติมแบเรียมไททาเนตหลังจากการวัลคาไนซ์แบบไดนามิกส์ทำให้ แบเรียมไททาเนตกระจายตัวในเฟสพอลิไวนิลลิดีนฟลูออไรด์ (PVDF) และที่ผิวประจัญ (interface) นอกจากนี้คอมพอสิตที่เตรียมจากเทอร์โมพลาสติกวัลคาไนซ์ของ PVDF/ENR 50 ที่ อัตราส่วนการเบลนด์ที่ 80/20 ให้ค่า permittivity ที่สูง

Ce travail de thèse porte sur la compréhension du rôle polyvalent des liquides ioniques (LIs) phosphonium comme agents de nanostructuration et interfaciaux pour la matrice polymère fluorée poly(fluorure de vinylidène-chlorotrifluoroéthylène) (P(VDF-CTFE)). Dans un premier temps, deux LIs phosphonium avec des fonctionnalités différentes générant un encombrement stérique et des fonctions dipolaire additionnelles sont tout d'abord incorporés dans la matrice P(VDF-CTFE) pour préparer des films de polymère additives. La structure de la phase cristalline, la morphologie issue de la dispersion et le comportement de cristallisation sont finement caractérisés dans le but de fournir une compréhension fuie et complète du rôle joué par le LI sur la nanostructuration. Dans un second temps, le rôle d’agent interfacial du LI est étudié avec un LI phosphonium fluoré comprenant un cation combinant trois phényles et une chaîne fluorée courte.Ce LI est utilise pour modifier la surface de l'oxyde de graphène (GO) et de l'oxyde de graphène réduit (rGO) afin de rendre ces nanocharges fonctionnelles et les incorporer dans la matrice P(VDF-CTFE). Ainsi, des films composites de P(VDF-CTFE)/graphène avec différentes teneurs en nanocharges sont préparés et une caractérisation fuie de la structure et des propriétés est entreprise afin de mieux comprendre les mécanisme d’interaction interfaciale et leurs influences sur les films composites, tels que la structure de la phase cristalline, le comportement de cristallisation, la relaxation des chaînes, la morphologie et les propriétés diélectriques finales. / This thesis work deals with an understanding of the versatile roles of phosphonium ionic liquids (ILs) as nanostructuration and interfacial agents for the fluorinated polymer matrix, i.e.,poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)). In this context, two phosphonium ILs with different functionalities in steric hindrance and extra dipolar groups are firstly incorporated in P(VDF-CTFE) matrix to prepare polymer films. The crystalline phase structure, dispersion morphology and crystallization behavior are finely characterized with the goal of providing a full and deep understanding of the versatile and tunable nanostructuration effect of phosphonium ILs. Subsequently, in order to elucidate the mechanism of interfacial influence of IL, a fluorinated phosphonium IL with a cation structure combining three phenyls and a short fluorinated chain is added on the surface of graphene oxide (GO) and reduced graphene oxide (rGO), making them as functional nanofillers to be incorporated into P(VDF-CTFE) matrix. Thus,P(VDF-CTFE)/graphene composite films with different filler contents are prepared in order to investigate the mechanism of interfacial interaction and its influence on the composite films, such as crystalline phase structure, crystallization behavior, chain segmental relaxation behavior, dispersion morphology and the final dielectric properties.