La technologie supercondensateur a fait l'objet d'un grand intérêt ces dernières années. Cependant, tandis qu'une grande attention a été donnée aux électrodes, aux électrolytes et aux électrolytes de polymère gélifiée, peu d'études ont été centrées sur l'amélioration des séparateurs macroporeux. Dans le cadre du projet SEPBATT/DURAMAT, les séparateurs macroporeux à base de poly(fluorure de vinylidène) (PVdF) ont été préparés par inversion de phase, pour les supercondensateurs. Nos membranes présentent également une bonne stabilité thermique, en revanche leurs propriétés mécaniques sont significativement plus faibles que celles des membranes commerciales. De plus le séparateur PVdF de porosité 80% rempli par l'électrolyte à base d'AN atteint, à 25°C, 18mS/cm, tandis que dans les mêmes conditions mais avec le séparateur commercial en cellulose, la conductivité n'atteint que 10 mS/cm. Ce travail a été complété par l'étude de techniques de renforcement (addition de composites, réticulation par l'irradiation) appliquées aux membranes précédemment préparées, pour augmenter leur tenue mécanique. Ces membranes ont montré un renforcement des propriétés mécaniques sans nuire aux propriétés de conduction ionique (15 mS/cm). / Abstract In recent years a strong interest has been devoted to supercapacitor technology. However, while great attention has been paid to electrodes, electrolytes and gel polymer electrolytes, only few reports have been dedicated to macroporous separators. Hereby, in the frame of project SEPBATT/DURAMAT, macroporous poly(vinylidene fluoride) (PVdF) based separators were prepared by phase inversion technique for applications of supercapacitors. Their mechanical properties are relatively lower than those of commercial membranes nevertheless such membranes exhibit good thermal stability. Whereas commercial cellulose based separators filled with tetraethyl ammonium tetrafluoroborate + CH3CN electrolyte show 10 mS/cm (at 25°C), our PVdF macroporous separators exhibit significantly higher conductivity (18 mS/cm) under the same conditions. This study was completed with application of reinforcement techniques (addition of composites, crosslinking by irradiation) on to previously prepared membranes in order to increase their mechanical strength. Reinforced membranes showed good high mechanical strength whereas the ionic conductivity is almost maintained (15mS/cm).

Les travaux de cette thèse portent sur la caractérisation du polymères piézoélectriques de PVDF et celles de ses composites avec un alliage à mémoire de forme, pour des applications de récupération l'énergie thermique. Tout d'abord, une discussion est donnée sur les avancées actuelles des technologies de récupération d'énergie ainsi que leurs intérêts économiques. Des valeurs typiques de l'énergie pouvant être générée sont estimées, ainsi que des énergies nécessaires pour certaines applications.Une attention particulière est accordée aux principes de fonctionnement des matériaux pyroélectriques et piézoélectriques. Le PVDF et l'alliage à mémoire de forme NiTiCu sont également introduits.Des techniques de caractérisation adaptées sont introduites pour par voie direct caractériser le PVDF en tant que générateur de charges électriques, et son aptitude à la récolte de l'énergie thermique. Puisque le PVDF est un matériau très souple, la flexion à quatre points, la flexion sur tube, et la machine de traction sont utilisés pour étudier sa réponse piézoélectriques directe en mode quasi-statique, ainsi que les changements de propriétés piézoélectriques sous contrainte. Des mesures d'auto-décharge sous différents champs électriques appliqués, températures et contraintes sont effectuées pour étudier la stabilité du matériau.Un concept de récupération d'énergie utilisant des composites de matériaux fonctionnels de familles différentes est introduit. Ici, le couplage entre un matériau piézo-/pyroélectrique et un alliage à mémoire de forme est proposé. Le voltage pyroélectrique simple est combiné avec un voltage piézoélectrique induit par la transformation de phase de l'alliage à mémoire de forme, pour augmenter l'énergie totale générée par le système en chauffant. Une preuve de concept est présentée d'abord pour un matériau semi-flexible basé sur une céramique PZT, et ensuite pour le PVDF qui est entièrement flexible.Enfin, un circuit de gestion d'énergie a été conçu et intégré au récupérateur d'énergie en PVDF. Les hauts pics de tension générés lors du chauffage or refroidissement sont abaissés par un convertisseur de type buck à deux étages jusqu'au une tension de sortie utile stable. L'énergie de sortie est utilisée pour alimenter une carte d'émission sans fil. Ainsi, une chaîne complète de génération d'énergie, exploitant des variations de température et allant jusqu'au l'émission de données représentatives de l'événement thermique survenu est présentée.Les résultats de ces travaux concernent un large spectre d'applications potentiels, particulièrement les capteurs autonomes sans fil, et des objets de l'Internet of Things, avec une flexibilité mécanique élevée, une épaisseur réduite et de faible coût de maintenance. / This work deals with the characterization of piezoelectric polymers PVDF and its composites with shape memory alloys, for thermal energy harvesting applications. First, we discuss current advancements on energy harvesting technologies as well as their economical interests. Typical values of energy that can be generated are given together with energies typically needed for applications.Particular attention is given to the functioning principles of pyroelectric and piezoelectric materials. PVDF and shape memory alloy NiTiCu are also introduced.Custom characterization techniques are introduced to characterize PVDF piezoelectric properties relevant to generator applications and to evaluate its suitability for thermal energy harvesting. Since PVDF is a very flexible material, four-point bending, tube bending and a tensile machine experiments are used to study its piezoelectric response in quasi-static mode, as well as changes in piezoelectric properties with increased strain. Self-discharge measurements under various applied electric fields, temperatures and strains are performed to study the stability of material.A concept of composite energy harvesting, utilizing two materials of different families, is introduced. Here, we propose the coupling of piezo-/pyroelectric material and shape memory alloy. The pure pyroelectric voltage is combined with generated piezoelectric voltage, induced by shape memory alloy transformation, to increase the total energy generated by the system during heating. The proof of concept is shown first for ceramic PZT-based semi-flexible material and then for fully flexible PVDF.Finally, a power management circuit was designed and integrated with the PVDF energy harvester. High generated voltage peaks at heating are lowered by a two-step buck converter to a useful stable output voltage. Output energy are used to power a wireless emission card. Thus, a complete power generation chain from temperature variations to data emission is presented.The results of this work concern a wide range of applications, especially modern autonomous wireless sensors and Internet of Things objects, with low profile, high mechanical flexibility and low maintenance costs.

Les processus de lavage, et plus particulièrement l'utilisation de solutions chlorées, peuvent engendrer une dégradation prématurée des membranes de filtration d'eau. Alors que le marché des technologies membranaires en PVDF est en pleine expansion, peu de travaux portent sur l'étude de leur dégradation sur le long terme. Dans ce contexte, la thèse a porté sur l'étude du vieillissement de membranes de filtration commercialisées en PVDF. Les échantillons sont immergés dans une solution d'hypochlorite de sodium et l'effet du pH sur leur dégradation est approfondi. Les propriétés mécaniques, d'hydrophilie, les performances hydrauliques ainsi que la porosité sont étudiées. L'évolution des propriétés est mise en relation avec la structure chimique étudiée à différentes échelles : moléculaire, macromoléculaire et supramoléculaire. Cette approche n'a à ce jour jamais été utilisée dans le cas des membranes fibres creuses en PVDF. Les analyses en chromatographie d'exclusion stérique révèlent les modifications les plus importantes. La dégradation du PVDF des membranes se traduit par un phénomène prédominant de coupures de la chaîne principale du PVDF accompagné, dans une moindre mesure, d'un phénomène de réticulation. Les principales modifications sont constatées à des pHs inférieurs à 10 révélant la possible action conjointe des radicaux OH•, ClO• et Cl•. Le vieillissement d'une membrane PVDF additivée montre à la fois une dégradation du PVDF et une élimination des additifs. Alors que la membrane sans additif conserve une stabilité de ses propriétés, l'élimination des additifs entraine une évolution de la porosité et une propension au colmatage plus importante. Cependant, les membranes PVDF conservent des propriétés d'utilisation acceptables au regard des conditions extrêmes de vieillissement étudiées. / The cleaning processes, especially the use of chlorine solutions, may cause the untimely degradation of the water filtration membranes. While the market for PVDF membrane-based treatment technologies is rapidly expending, only few works deal with the study of their ageing on a long-term basis. In this context, this project focuses on the study of the ageing of two PVDF filtration membranes. Samples are immersed in a sodium hypochlorite solution and the effect of the chlorine solution pH is investigated. The properties of the membranes are characterized throughout the study by tensile tests, hydrophilicity, hydraulic performances and porosity analysis. The evolution of properties is related to the chemical structure of the membranes at a molecular, a macromolecular and a supramolecular scale. Until now, this approach has never been used in the case of PVDF membranes under chlorine conditions. The size exclusion chromatography analyses revealed the most important modifications. The degradation occurs mainly by chain scissions of the PVDF and crosslinking phenomenon in lesser extent. The main modifications occurred at pH less than 10 proving the joint action of OH•, ClO• and Cl• radicals. The ageing of the PVDF membrane containing additives showed at the same time the PVDF degradation and the elimination of the additives. Whereas the properties of the additive-free PVDF membrane were preserved, the elimination of additives led to a modification of the porosity and an increased fouling. However, even if the PVDF degradation is proved, the using properties of the PVDF membranes remain acceptable taking into consideration extreme conditions of ageing studied.

Le développement des énergies renouvelables peut non seulement compenser le manque d'énergie fossile à l'avenir, mais aussi sauver notre planète en réduisant la pollution par les émissions de CO2. Les matériaux piézoélectriques ont la capacité de convertir les mouvements mécaniques environnementaux en énergie électrique. Dans le cadre de cette thèse, deux types de matériaux piézoélectriques ont été étudiés pour la récupération d’énergie : les nanofils de ZnO et les microfibres de PVDF-TrFE. L’objectif ultime de cette thèse est de réaliser les dispositifs de la récupération d’énergie à faible coût pour rendre les capteurs autonomes.Au cours de la dernière décennie, les nanofils de ZnO ont suscité un grand intérêt dans le domaine de la recherche en raison de leurs multifonctionnalités avec un grand potentiel d’applications dans les différents domaines (récupération d’énergie par effet piézoélectrique et photovoltaïque, capteurs biologiques & chimiques, dépollution de l’eau & de l’air par effet photocatalytique, …). Le PVDF-TrFE est un polymère attrayant dans les applications de la récupération d'énergie en raison de ses propriétés piézoélectriques, son faible coût et sa grande flexibilité mécanique.Dans ce travail, deux méthodes de synthèse ont été employées pour obtenir les micro- & nanomatériaux piézoélectriques : Hydrothermale pour les réseaux verticaux des nanofils de ZnO et Electrospinning pour les microfibres de PVDF-TrFE. Les conditions de synthèse ont été optimisées afin d’obtenir les échantillons adéquats aux applications envisagées. Ensuite, deux types de dispositifs de la récupération d’énergie ont été fabriqués. Dans un premier temps, nous avons conçu des microgénérateurs (MGs) à base des microfibres de PVDF-TrFE déposées sur le substrat Kapton. Ces MGs flexibles basés sur l’effet piézoélectrique direct permettant la conversion de l’énergie mécanique en énergie électrique à basse fréquence de l’ordre d’hertz. Le second type de nanogénérateurs (NGs) est basé sur des nanofils verticaux de ZnO sur le substrat en silicium. Les tests de la récupération d’énergie ont été réalisés dans une gamme de fréquences de quelques centaines d’hertz pour l’application aéronautique / Development of renewable energy can not only compensate for the lack of fossil energy in the future, but also save our planet by reducing CO2 emission pollution. Piezoelectric materials have the ability to convert environmental mechanical movements into electrical energy. In this thesis, two types of piezoelectric materials have been studied for energy harvesting: ZnO nanowires and PVDF-TrFE microfibers. The ultimate goal of this thesis is to realize the low cost energy harvesting devices for self-powered sensors.Over the past decade, ZnO nanowires had attracted a great interest in the research field due to their multifunctionality with a great potential in the various applications (energy harvesting by piezoelectric and photovoltaic effect, bio & chemical sensors, water & air purification by photocatalytic effect ...). PVDF-TrFE is also an attractive polymer in energy harvesting due to its piezoelectric properties, high mechanical flexibility, and also for its low cost.In this work, two synthesis methods have been used to obtain the piezoelectric micro- & nanomaterials: Hydrothermal for the ZnO nanowire arrays and Electrospinning for the PVDF-TrFE microfibers. The synthesis conditions have been optimized in order to obtain the suitable samples for the applications. Then, two types of energy harvesting devices were manufactured. First, we realized the microgenerators (MGs) based on the PVDF-TrFE microfibers deposited on the Kapton substrate. These flexible MGs based on the direct piezoelectric effect allowing the conversion of mechanical energy into electrical energy at low frequency of the order of hertz. The second type of nanogenerators (NGs) is based on ZnO nanowire array on the silicon substrate. The energy harvesting tests were carried out in a frequency range of a few hundred hertz for the aeronautical application

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.

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.

Idag är de flesta kemiska industrier försedda med system för nivåreglering. Dessa system syftar till att kontrollera vätskenivån i en behållare, trots störningar i form av smuts och skum. För denna process finns olika modeller av nivågivare på marknaden, men de flesta är antingen dyra eller kräver mycket rengöring och underhåll. Denna studie syftar till att undersöka om det är möjligt att mäta vätskenivån i en behållare som kan produceras till låg kostnad, och har en tillräcklig precision för att kunna användas som ett larm för att skydda doppvärmaren mot överhettning. Därför har ett konceptprov av kapacitiva nivågivare utförts där två varianter av kapacitiva nivågivare, etsad och tråd, har konstruerats och verifierats. Etsade varianter innefattar ett kopparlaminat med konfiguration av två fingerelektroder som rullats i ett PVDF-rör. Trådvarianten består av en partvinnad teflontråd som dragits på ett PVDF-rör. I både varianter varieras kapacitans med vattennivån beroende av avståndet mellan fingerelektroder i den etsade varianten och avståndet mellan teflontrådar i trådvarianten. Kapacitansen har beräknats för avståndet mellan fingerelektroder och mellan teflontrådar i form av en urladdningstid korrelerad med vattennivån. För denna process används en generatorkrets för fyrkantsvåg som byggts på en PCB. Resultatet av nivåmätning med båda varianter blev inte det önskade, men nivåmätningsfelet ligger inom ett acceptabelt intervall. Intervallet ligger mellan [+0,80,-0,52] för den etsade varianten och mellan [+1,02,-1,10] för trådvarianten. Det visar att den etsade varianten ger ett mindre nivåmätningsfel än trådvarianten. Nivåmätningsfelet kan minimeras genom att välja en lämpligare krets. / Today, most chemical industries have systems for level control. These systems aim to control the fluid level in a tank, despite dirt and foam disturbances. For this process there are different models of level sensors on the market, but most are either expensive or require a lot of cleaning and maintenance. This study aims to investigate whether it is possible to measure the level of fluid in a tank which can be produced at low cost and has sufficient precision to be used as an alarm to protect the immersion heaters from overheating. Therefore, a conceptual level of capacitive level sensors has been performed in which two variants of capacitive level sensors, etch and wire have been designed and verified. Etched variants include a copper-laminate with two finger electrode configurations rolled in a PVDF tube. The wire variant consists of a twisted Teflon wire drawn on a PVDF pipe. In both variations, capacitance with the water level varies depending on the distance between finger electrodes in the etched variant and the distance between the Teflon wires in the wire variant. The capacitance has been calculated for the distance between finger electrodes and between Teflon threads in the form of a discharge time correlated with the water level. For this process, a square wave generator circuit is built on a PCB. The result of level measurement with both variants did not get the desired, but the level measurement error is within an acceptable range. The interval is between [+ 0.80, -0.52] for the etched variant and between [+ 1.02, -1.10] for the wire variant. It shows that the etched variant gives a smaller level measurement error than the wire variant. The level measurement error can be minimized by selecting a more appropriate circuit.

A busca por tecnologias cada vez mais eficazes no tratamento de águas e efluentes fez com que o desenvolvimento de membranas desempenhasse um papel importante nos processos de separação. A nanofiltração apresenta-se como uma tecnologia promissora para remoção de sais multivalentes em soluções aquosas. O preparo de membranas poliméricas pela técnica de inversão de fases permite a obtenção de estruturas distintas. Neste estudo avaliou-se o uso de diferentes não-solventes no preparo de membranas de poli(fluoreto de vinilideno) pelo método de inversão de fases, quanto às características estruturais e propriedades funcionais. Foram utilizados como não-solventes: água destilada, solução de dodecil sulfato de sódio e etanol/água, resultando nas membranas denominadas MT1, MT2 e MT3, respectivamente. O uso de um surfactante aniônico, como o dodecil sulfato de sódio, no preparo de membranas de poli(fluoreto de vinilideno) apresenta-se como uma inovação tecnológica. O uso de diferentes não-solventes alterou a taxa de precipitação do polímero, o que ocasionou alterações na estrutura química, morfológica, cristalina e nas propriedades de transporte das membranas. Análises de microscopia eletrônica de varredura e porosimetria de deslocamento líquido-líquido mostraram a obtenção de estruturas assimétricas, com poros na ordem de 1-2 nm para as membranas MT1 e MT2, e estrutura simétrica, com alta porosidade, para a membrana MT3. A análise de espectroscopia de infravermelho com transformada de Fourier mostrou a presença das fases cristalina α e β nas três membranas e no polímero. Análise termogravimétrica realizada em atmosfera inerte apresentou massa residual em torno de 20-30 % referente ao material carbonáceo, o qual foi eliminado com a utilização de atmosfera oxidante na análise. Os valores de cristalinidade aparente, do polímero e das membranas, apresentaram grandes variações quando determinados pela técnica de calorimetria exploratória diferencial, porém quando determinados a partir dos difratogramas obtidos pela técnica de difração de raios X, a variação foi pequena, apresentando valores em torno de 47%. A avaliação da composição química da superfície das membranas, por espectroscopia de fotoelétrons induzidos por raio X, mostrou que houve variação na quantidade de ligações C-F quando diferentes não-solventes foram utilizados. Essas variações contribuíram para alterações na hidrofobicidade das membranas. As membranas MT1 e MT2 apresentaram características hidrofílicas, com ângulo de contato em torno de 70°, e a membrana MT3 apresentou característica hidrofóbica, com ângulo de contato em torno de 142°. A maior hidrofobicidade da membrana MT3 é resultante da rugosidade superficial e da maior composição relativa de ligações C-F na superfície desta membrana. Ensaios de permeação realizados até a pressão de 20 bar mostraram que a membrana MT2 sofreu maior efeito de compactação e apresentou menor fluxo de permeado. Os ensaios realizados com soluções de cloreto de sódio, de cálcio e férrico mostraram diferentes eficiências de retenção. Para as membranas MT1 e MT2 a retenção de sais mono e divalentes foi praticamente igual, em torno de 5%. Para a solução de cloreto férrico, a retenção apresentou valores médios em torno de 16% e 27% para as membranas MT1 e MT2, respectivamente. Em função do tamanho de poros apresentados e da pressão transmembrana aplicada nos ensaios de permeação, as membranas MT1 e MT2 podem ser utilizadas em processos de nanofiltração. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-03T19:42:35Z No. of bitstreams: 1 Dissertacao Monica Beatriz Thurmer.pdf: 13606935 bytes, checksum: 4fd6cc5e74e44b43096cb2a30daf32e2 (MD5) / Made available in DSpace on 2014-06-03T19:42:35Z (GMT). No. of bitstreams: 1 Dissertacao Monica Beatriz Thurmer.pdf: 13606935 bytes, checksum: 4fd6cc5e74e44b43096cb2a30daf32e2 (MD5) / The search for increasingly efficient technologies in water and effluent treatment made the development of membranes take on an important role in separation processes. The nanofiltration is presented as a promising technology for removal of multivalent salt in aqueous solution. The polymeric membranes preparation by phase inversion technique allows the obtaining of different structures. This study evaluated the use of different nonsolvents in the poly(vinylidene fluoride) membrane preparation, by phase inversion method, on the structural characteristics and functional properties. Were used as nonsolvents: distilled water, solution of sodium dodecyl sulfate and ethanol/water, resulting in the membranes called MT1, MT2 and MT3, respectively. Use of an anionic surfactant, like as sodium dodecyl sulfate, in the preparation of poly(vinylidene fluoride) membranes is presented as a technological innovation. The use of different non-solvents changed the rate of polymer precipitation which caused changes in chemical, morphology and crystalline structures, and transport properties of the membranes. Scanning electron microscopy and liquid-liquid displacement porosimetry analysis showed asymmetric structures, with pores on the order of 1-2 nm for the MT1 and MT2 membrane, and symmetrical structure, with a high porosity for MT3 membrane. The analysis by Fourier transform infrared spectroscopy showed the presence of α and β crystalline phases in the three membranes and in the polymer. Thermogravimetric analysis carried out in an inert atmosphere showed residual mass around 20-30% from the carbonaceous material, which was eliminated with the use of an oxidizing atmosphere in the analysis. The values of apparent crystallinity of the polymer and the membranes showed large variations, by differential scanning calorimetry technique, but when determined from the diffractograms obtained by X-ray diffraction technique, the variation was small, showed values around 47%. The evaluates of the membranes chemical surface composition by X-ray photoelectron spectroscopy showed that there was variation in the amount of C-F bonds, where different non-solvents were used. These variations contributed to changes in membranes hydrophobicity. The MT1 and MT2 membranes showed hydrophilic characteristics with contact angle around 70°, and the MT3 membrane showed hydrophobicity characteristics with contact angle around 142°. The highest hydrofobicity of the MT3 membrane is result of the surface roughness and the relative composition of CF bonds on this membrane surface. Permeation tests performed until a pressure of 20 bar, it was found that the MT2 membrane has a greater effect compression and showed a lower permeate flux. Tests conducted with solutions of sodium, calcium and ferric chloride showed different retention efficiencies. For MT1 and MT2 membranes the retention of mono and divalent salts was practically equal, around 5%. For the solution of ferric chloride, the retention showed medium values around 16% and 27% for the MT1 and MT2 membranes, respectively. Due to the pore size presented and transmembrane pressure applied on permeation tests, the MT1 and MT2 membranes may be used in nanofiltration processes.