La membrane conductrice protonique constitue un rouage essentiel du fonctionnement des piles à combustible PEMFC. Les travaux de recherche présentés dans ce document consistent à développer une membrane non perfluorée basée sur une technologie nanocomposite hybride susceptible d’être produite à faible coût. Cette membrane est composée d’une matrice poly(VDF-co-HFP) dans laquelle sont dispersées des nanoparticules de silice fonctionnalisée par de l’acide poly(styrène sulfonique) (PSSA). Ce travail a porté sur l’étude de la mise en oeuvre de la membrane afin d’obtenir une membrane homogène et dense avec des caractéristiques physico-chimiques et électrochimiques intéressantes. Les performances en pile après rodage à 60 °C sont extrêmement satisfaisantes avec un gain en densité de puissance de 40 % à 0,7 V par rapport au Nafion® NRE211. Les études de durabilité de la membrane ont mis en évidence un phénomène d’élution de la silice fonctionnalisée ayant pour conséquence un fort déclin de tension. Différentes stratégies de modification de la membrane ont été proposées pour améliorer la stabilité de la membrane. Les plus intéressantes consistent à modifier la morphologie de la matrice (grades de PVDF plus rigides ou réticulation du poly(VDF-co-HFP) par irradiation) pour mieux confiner les charges ou à greffer la silice fonctionnalisée sur la matrice. Cette dernière stratégie conduit à une diminution par trois du gonflement et par 2,5 de la vitesse de déclin à 80°C. / The proton conductive membrane is an essential part of the operation of PEMFC. This document presents the development of a non-perfluorinated membrane based on a hybrid nanocomposite technology likely to be produced at low cost. This membrane is composed of a poly(VDF-co-HFP) matrix in which are dispersed poly(styrene sulphonic acid) (PSSA) functionalized silica nanoparticles. This work focuses on the study of the implementation of the membrane to obtain a homogeneous and dense membrane with good physicochemical and electrochemical characteristics. Fuel cell performances after running at 60 °C are extremely satisfactory with a gain, compared to Nafion NRE211, of 40% for the power density at 0.7 V. However, the durability studies showed an elution phenomenon of the functionalized silica particles which results in a high voltage decline. Different membrane modification strategies have been proposed to improve the stability of the membrane. The most interesting involve modifying the morphology of the matrix (more rigid grades of PVDF or poly(VDF-co-HFP) crosslinking by radiation) to better confine the particles or grafting functionalized silica to the matrix. This last strategy leads to a threefold decrease of the swelling and 2.5 factor of the decay rate at 80 °C.

Grâce à leurs excellentes propriétés mécaniques, électriques et chimiques, les dispositifs organiques électroniques à base de polymères conducteurs peuvent résoudre l’incompatibilité entre les modules électroniques rigides en silicone et les exigences des tissus mous qui constituent l’environnement biologique. Les avancées en matière de semiconducteurs organiques et en microélectronique ont donné naissance à la bioélectronique. Cette discipline emploie des capteurs à des fins diagnostiques, telles que la détection des métabolites ou la mesure d’un potentiel d’action neuronal, et des actionneurs à des fins thérapeutiques, comme l’application locale d’un traitement à l’intérieur même du corps, ou la stimulation cérébrale profonde afin de guérir un trouble neurologique. En bioélectronique, l’utilisation de matériaux organiques, tels que le polymère conducteur poly(3,4-éthylènedioxythiophène) polystyrène sulfonate de sodium (PEDOT:PSS) a permis de développer des composants électroniques biomédicaux de qualité exceptionnelle, comme par exemple le transistor organique électrochimique (OECT), qui ont été testés in vitro et in vivo. Ce manuscrit explique en détail la fabrication, la fonctionnalisation et la caractérisation du OECT à base de PEDOT:PSS. Afin de pouvoir intégrer ce capteur à des systèmes de mesure biomédicaux déjà établis, l’OECT est intégré à des circuits simples, tels qu’un amplificateur de tension ou un pont de Wheatstone. Ces circuits sont mis à l’épreuve de la pratique clinique, dans le cas de mesures électrocardiographiques, ou de détection de métabolites dans des cellules cancéreuses. Cela permet d’apprécier à la fois leur applicabilité, et leurs limites. / Due to their outstanding mechanical, electrical and chemical properties, organic electronic devices based on conducting polymers can bridge the gap between the rigid silicon based read-out electronics and the soft biological environment and will have a huge impact on the medical healthcare sector. The recent advances in the field of organic semiconductors and microelectronics gave rise to a new discipline termed bioelectronics. This discipline deals with sensors for diagnostic purposes, ranging from metabolite detection and DNA recognition all the way to single neuronal firing events, and actuators for therapeutic purposes, through for example active local drug delivery inside the body or deep brain stimulation to cure neurological disorder. The use of organic materials such as the conducting polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) in the field of bioelectronics has brought about a variety of outstanding electronic biomedical devices, such as the organic electrochemical transistor (OECT), that have been implemented for both in vitro and in vivo applications. The present manuscript gives a detailed explanation of the fabrication, functionalization and characterization of OECTs based on PEDOT:PSS. To be able to intercept this sensor element with traditional biomedical recording systems, the OECT is implemented into simple circuit layouts such as a voltage amplifier or a Wheatstone bridge. These sensor circuits are then applied to real-life biomedical challenges, such as electrocardiographic recordings or metabolite detection in tumor cell cultures, to demonstrate their applicability as well as their limitations.

O presente trabalho tem como objetivo analisar as propriedades mecânicas, térmicas, termo dinâmico-mecânicas e morfológicas de compósitos preparados com poliestireno expandido reciclado e pó de madeira. Compósitos com diferentes teores de agente compatibilizante e diferentes teores de pó de madeira foram desenvolvidos em extrusora dupla rosca co-rotante e moldados por injeção. Os resultados obtidos demonstram que o compatibilizante com maior quantidade de anidrido maleico, menor massa molar ponderal média e utilizado em quantidade igual a 2% em massa gerou compósitos com melhores propriedades mecânicas. A melhora na adesão interfacial também foi observada através da análise termo dinâmico-mecânica. Verificou-se aumento no módulo de armazenamento, redução na altura do pico de tan δ e também menor valor do fator de adesão, associado com a maior adesão na região da interface. Para os compósitos desenvolvidos com diferentes teores de pó de madeira a densidade obtida foi semelhante a densidade teórica indicando estar de acordo com a regra das misturas. A utilização de compatibilizante reduziu o teor de vazios dos compósitos. Os resultados obtidos nos ensaios de flexão demonstraram que o módulo de flexão aumenta com a quantidade de carga e também se aproxima do comportamento previsto pela regra das misturas, entretanto os compósitos sem compatibilizante apresentaram redução na resistência a flexão com o aumento do teor de pó de madeira. No ensaio de impacto observou-se redução da resistência ao impacto com a adição de carga, porém os compósitos com compatibilizante apresentaram resultados superiores aos compósitos sem compatibilizante para todos os teores de pó de madeira. Observou-se aumento no módulo de armazenamento, no módulo de perda e também na efetividade do reforço com a adição de pó de madeira. Ocorreu redução na largura e também na altura do pico de tan δ conforme a adição das partículas de madeira, contudo os compósitos com compatibilizante apresentaram redução mais acentuada devido à melhora na adesão interfacial. O modelo teórico para predizer o comportamento do módulo de armazenamento demonstrou proximidade com os valores experimentais para baixos teores de carga. Para tan δ o modelo teórico se mostrou inadequado. As micrografias dos compósitos sem compatibilizante indicaram arrancamento e a presença de vazios entre o pó de madeira e a matriz, entretanto os compósitos com compatibilizante demonstraram maior recobrimento das partículas de madeira pela matriz. A estabilidade térmica dos compósitos com compatibilizante foi reduzida para todos os teores de pó de madeira quando comparada aos compósitos sem compatibilizante. / The present work aims to analyze the mechanical, thermal, dynamicalmechanical thermal properties and morphology of composites based on recycled polystyrene and wood flour. Composites with different types and levels of coupling agent and also with different levels of wood flour were developed in a co-rotating twin-screw extruder and injection molded. The results show that the coupling agent with higher amount of maleic anhydride, lower weight average molecular weight and used in to 2% by weight produced composites with better mechanical properties. The improvement in interfacial adhesion was also observed by dynamical-mechanical thermal analysis. An increase in the storage modulus, decrease in peak height and also lower value of adhesion factor, was observed due to the improved on interfacial adhesion. For the composites developed with different levels of wood flour density obtained was similar to theoretical density indicating that in accordance with the rule of mixtures. The use of coupling agent reduced the concentration of voids in the composites. The flexural modulus increases with the amount of wood flour and also approaches the behavior predicted by the rule of mixtures, however the composites without coupling agent showed reduction in flexural strength. The impact strength decreases with the addition of wood flour, but the composites with coupling agent showed better results than the composite without coupling agent for all levels of wood flour. There was an increase in the storage modulus, loss modulus and also the efficiency of filler with the addition of wood flour. There was a reduction in width and also in peak height of tan δ as the addition of wood particles, composite with coupling agent demonstrated greater reduction due to improved on interfacial adhesion. The theoretical model to predict the behavior of the storage modulus showed proximity with the experimental values for low levels of filler. Theoretical model for tan δ proved inadequate. The micrographs of composites without coupling agent indicated the presence of pulled-out traces and gaps between the wood flour and matrix, however the composites with coupling agent show the strong bonding and good wetting of the fillers by the matrix. The thermal stability of composites with coupling agent was reduced for all levels of wood flour when compared to composites without coupling agent.

A sinterização a laser (SL), uma das tecnologias de manufatura aditiva (MA), se mostra de grande interesse devido a uma série de características, mas, principalmente, devido a sua capacidade de processar uma ampla gama de materiais em pó, a qual amplia possibilidades de pesquisa e desenvolvimento no campo do Design. Neste trabalho, sob o prisma da MA, tem-se por objetivo realizar a sinterização a laser em um equipamento de gravação e corte a laser convencional, sem pré-aquecimento do material. No desenvolvimento do estudo, foi utilizado um equipamento galvanométrico a laser para a realização de experimentos de sinterização de poliestireno em pó (PS 200). Os ensaios de caracterização desse material polimérico amorfo, constataram o diâmetro médio dos grãos de 54,3 μm em formato irregular. Para viabilizar o processo proposto, investigaram-se os parâmetros de processo para a SL, valendo-se de um dispositivo de controle da altura da mesa de trabalho. A melhor amostra (geometria circular) foi construída com potência 20 W, velocidade de varredura de 200 m/min e distância entre linhas de varredura do feixe laser de 0,1 mm. Esse último parâmetro, é relacionado ao diâmetro do foco do feixe laser, o qual foi estimado pelos ensaios em 0,3 mm. Com isso, foi calculada a densidade de energia transferida para o material, conhecida como Número de Andrew (An), em 0,06 J/mm² Análises visuais, macroscópicas e microscópicas, antes e depois da sinterização de uma camada (2D) e de camadas empilhadas (3D), além de sua digitalização tridimensional, foram realizadas. As amostras apresentaram deformação no plano x-y (elipticidade), no eixo z (empenamento) e grande porosidade. Nos ensaios de empilhamento de camadas foi determinada, para os parâmetros utilizados, a espessura de camada de 0,15 mm. Posteriormente, foi construído um modelo 3D com 100 camadas, o qual apresentou um acabamento liso na maior parte de sua lateral, porém, foram observadas estrias verticais ao longo da sua altura, as quais foram consideradas como característica do processo (devido à inércia dos espelhos galvanométricos). Por fim, esses parâmetros foram validados em um ensaio valendo-se de uma forma orgânica (face humana) em escala 1:4. O fator crítico foi o empenamento, o qual prejudica a distribuição de novas camadas de pó, mas pôde ser contornado com espessuras de camada de alturas superiores a esse empenamento. Assim, considera-se que para a viabilização prática do processo de sinterização proposto, em equipamentos de corte e gravação a laser convencionais, torna-se importante o desenvolvimento de um dispositivo de distribuição de pó automatizado, o qual permitiria a construção de modelos 3D de maior tamanho e complexidade. / Laser sintering (SL), one of the additive manufacturing (MA) technologies, is of great interest due to a number of characteristics, but mainly due to its ability to process a wide range of powder materials, which offers possibilities for research and development in the Design’s field. In this work, under the prism of the MA, the goal is to perform laser sintering in a conventional laser engraving and cutting equipment, without preheating the material. In the development of the study, a galvanometric laser equipment was used to perform powder polystyrene (PS 200) sintering experiments. The characterization tests of this amorphous polymer material showed the average grain diameter of 54.3 μm in irregular shape. In order to make the proposed process feasible, the process parameters for the SL were investigated, using a device to control the height of the workbench. The best sample (circular geometry) was built with 20 W power, laser scan speed of 200 m/min and distance between scanned lines of 0.1 mm. This last parameter is related to the diameter of the laser beam waist, which was estimated by the tests in 0.3 mm Thus, the energy density transferred to the material, known as Andrew's Number (An), was calculated at 0.06 J/mm². Macroscopic and microscopic visual analysis, before and after the sintering of a two-dimensional layer (2D) and of stacked layers (3D), in addition to its 3D scanning, were performed. The samples displayed deformation in the x-y plane (ellipticity), at the z-axis (warpage) and high porosity. In the layer stacking tests, the layer thickness of 0.15 mm was determined for the parameters used. Next, a 3D model with 100 layers was sintered, which presented a smooth finish in most of its lateral, however, vertical streaks were observed along its height, which were considered as characteristic of the process (due to the inertia of the galvanometric mirrors). Finally, these parameters were validated in an assay using an organic form (human face) in a 1: 4 scale. The critical factor was the warpage, which impairs the distribution of new layers of powder, but could be worked around with layer thicknesses of heights higher than this warpage. Thus, it is considered that for the practical feasibility of the proposed sintering process in conventional laser cutting and engraving machine, it is important to develop an automated powder distribution device, which would allow the construction of greater size and complexity 3D models.

Orientador: Alexandre Luiz Souto [Unesp] Borges / Resumo: Este estudo visou sintetizar e caracterizar mantas não tecidas de nanofibras (NFs) do acrilonitrila butadieno estireno (ABS), poliamida 6 (PA6) e poliestireno (PS), e avaliar sua capacidade de ser utilizada como reforço no polimetilmetacrilato (PMMA). O ABS foi dissolvido em diclorometano e acetona, a PA6 pelo 1,1,1,3,3,3-hexafluoro-2-propanol e o PS pela dimetilformamida, em uma concentração definida em estudo piloto. Após determinados os melhores parâmetros de eletrofiação (tensão contínua, razão de fluxo e distância agulha/anteparo) as amostras de cada grupo foram analisadas em microscopia eletrônica de varredura, análise de molhabilidade, análise de difratometria de raios X, espectroscopia de infravermelho por transformada de Fourier, diâmetro das fibras e resistência a tração. As NFs produzidas foram incluídas na área de tração dos corpos de prova em resina acrílica ativada termicamente (RAAT) conforme ISO1567, perfazendo 4 grupos (n=20), 1 controle (Grupo 1) e 3 experimentais (Grupo 2, RAAT+NF/ABS; Grupo 2, RAAT+NF/PA6; Grupo 4, RAAT+NF/PS), para ensaio de flexão três pontos para analisar suas propriedades mecânicas, como: módulos de elasticidade e resistência a flexão. De acordo com os testes de caracterização, as mantas se apresentaram hidrofóbicas, não houve mudança de sua estrutura polimérica, concluindo-se então que a técnica da eletrofiação foi promissora na síntese de mantas de NFs. A variação dos parâmetros afetou diretamente a morfologia, resultando em fibras u... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study aimed to synthesize and characterize non-woven blankets of acrylonitrile butadiene styrene (ABS), polyamide 6 (PA6) and polystyrene (PS) nanofibers (NFs), and to evaluate their ability to be used as reinforcement in polymethyl methacrylate (PMMA). ABS was dissolved in dichloromethane and acetone, PA6 by 1,1,1,3,3,3- hexafluoro-2-propanol and PS by dimethylformamide at a concentration defined in a pilot study. After determining the best electrospun parameters (continuous voltage, flow rate and needle/shield distance) the samples from each group were analyzed by scanning electron microscopy, wettability analysis, X-ray diffraction analysis, Fourier transform infrared spectroscopy, fiber diameter and tensile strength. The NFs produced were included in the tensile area of the thermally activated acrylic resin (RAAT) specimens according to ISO1567, making up 4 groups (n = 20), 1 control (Group 1) and 3 experimental (Group 2, RAAT+NF/ABS; Group 3, RAAT+NF/PA6 and Group 4 (RAAT+NF/PS), for three point bending test to analyze their mechanical properties, as: modules of elasticity and flexural strength. According to the characterization tests, the blankets were hydrophobic, there was no change in their polymeric structure, concluding that the electrospinning technique was promising in the synthesis of NFs blankets. The parameters variation affected directly in the morphology, resulting in uniform, bulky and without defects (beads) NFs blankets. The Groups 3 and 4 (NF/PA6+RA... (Complete abstract click electronic access below) / Mestre

The diploma thesis deals with the proposal of a new guesthouse with a restaurant. The building is located in a slightly sloping terrain in the cadastral area of the village Vlasatice Brno-venkov in the South Moravian Region in the Czech Republic. The ground-plan shape of the building is mostly rectangular with folded facade parts. It is a partially basement building, to a lesser extent, recessed below ground level with three above-ground floors. The pension has a total of 22 rooms with a total capacity of 46 persons for short-term accommodation. Four rooms on the first floor are designed as wheelchair accessible. For the proper operation of the pension there is a reception on the first floor and an office with the appropriate meeting room on the second floor. One-storey part of the building consists of a restaurant with a capacity of 76 persons, which is designed as a frame skeleton with intensive vegetation single-skin flat roof. The preparation and meals and service of the restaurant is ensured by the kitchen together with its operations and respective warehouses located on the first floor. The basement is used primarily for the operation of the guesthouse, which is located air-conditioning engine room, utility room, workshop or warehouse. The building is for the most part bricked and the peripheral, internal bearing or partition walls are made of polished ceramic blocks porotherm. External walls are insulated with contact insulation system ETICS of gray EPS polystyrene. The glazed Schüco façade is used as the shell of the skeleton structure. The construction of the ceiling is composed of filigree ceiling panels and a singlelayer flat roof with a slope of 3% is used for roofing the building. The thesis contains project documentation for the realization of the construction.

The study deals with interactions of polyelectrolytes polystyrene sulfonate and hyaluronic acid with nitrogenic amphiphilic substances, represented by lysine and albumine. To study the interactions pH-metry, conductance, viscositic and turbidity measurement, DLS and reometry were used. All mixtures of different concentrations were measured and the data were compered with data obtained from measurement of samples with amphiphilic sumstances without polyelectrolytes. Observed interactions occured in the aminoacid concentrations between 0 to 20 mmoldm-3, then the PSS interaction groups were fully bonded by lysine and no more interactions were recognized. The same behaviour were observed in albumine solutions with concentration under 2 gdm-3.

This thesis is focused on investigation of phospholipid-hyaluronan system. First, appropriate method for preparation of bulk solution of phospholipid/lipid and suitable fluorescence probe were chosen. Sonification was selected as a method for preparation of bulk solution and pyrene was chosen as a fluorescence probe. From the group of phospholipids lecithin was selected. Next to phospholipid, lipid with no phosphate group (DPTAP) was utilized for comparison, alternatively a mixture of lipid (DPTAP) and phospholipid (DPPC). Instead of hyaluronan another polyelectrolytes (sodium polystyrene sulfonate, sodium alginate) were used too. Measurements were performed in water environment and in phosphate buffer saline (PBS). All investigation was accomplished by fluorescence spectroscopy and dynamic light scattering.

The aim of this thesis is to evaluate the possibility of introducing Full Mold technology in specific conditions of production in foundry environment. The emphasis is placed on the least possible intervention with to established manufacturing process. The work also aims, through the comparison of the specific test castings, to map the weaknesses of this technology in the company and create possible optimization or complete removal of this weaknesses.

Orientador: Paulo César Lodi / Resumo: Esse trabalho avaliou as propriedades do poliestireno expandido (EPS) para verificar a viabilidade e emprego deste em obras geotécnicas. Foram estudadas as propriedades mecânicas e hidráulicas do material, por meio de ensaios de resistência ao cisalhamento direto, compressão triaxial, compressão uniaxial simples e cíclica, absorção de água, permeabilidade e empuxo conforme as normas vigentes e métodos utilizados pela literatura corrente. Utilizou-se uma gama variada de massas específicas de EPS (10, 15, 20, 25 e 30 kg/m3), incluindo duas recicladas (10 e 12,5 kg/m³). Os principais resultados mostram que os parâmetros de resistência ao cisalhamento direto apresentam variações crescentes conforme aumenta-se a massa específica, assim como os valores de resistência à compressão simples e cíclica. O mesmo é valido para o módulo de elasticidade, que também aumenta com a massa específica. As amostras de baixa massa específica apresentaram um significante intercepto coesivo, enquanto que as maiores possuem elevada parcela de ângulo de atrito. Os parâmetros de absorção de água tendem a diminuir com o aumento da massa específica e todas apresentaram valores muito proximos de permeabilidade. Além disso, valor de 20 kg/m³ é um valor de transição da massa específica com relação ao comportamento das amostras. / Abstract: This work evaluated the properties of expanded polystyrene (EPS) to verify its feasibility and use in geotechnical works. The mechanical and hydraulic properties of the material were studied by tests of direct shear strength, triaxial, simple and cyclic uniaxial compression, water absorption, permeability and thrust according to current standards and methods used in the current literature. A wide range of specific masses (10, 15, 20, 25 and 30 kg/m³) were used, including two recycled (10 and 12.5 kg/m³). The main results show that the direct shear strength parameters show increasing variations as the specific mass increases, as well as the simple and cyclic compressive strength values. The same is true for the modulus of elasticity, which also increases with the specific mass. The samples of low specific mass presented a significant cohesive intercept, while the larger ones had a high proportion of friction angle. Water absorption parameters tend to decrease with increasing specific mass and all presented very close permeability values. In addition, a value of 20 kg/m³ is a specific mass transition value with respect to sample behavior. / Mestre