[pt] Este trabalho investiga o impacto de suspensões de grafeno funcionalizado sobre reologia de uma dispersão aquosa de Carbopol. Os derivados de grafeno usados foram óxido de grafeno (GO) e óxido de grafeno amino funcionalizado (AFGO). A variação da concentração e do grau de oxidação do grafeno funcionalizado foram avaliadas e relacionadas à reologia das suspensões. O GO foi produzido a partir da síntese de óxido de grafite pelo método de Hummers modificado, e caracterizado pelas técnicas de DRX, Raman, TGA, FTIR, XPS, TEM e AFM. O GO foi funcionalizado com trietilenotetramina por reação assistida por microondas para produzir AFGO, caracterizado por TGA e XPS. As suspensões foram caracterizadas por experimentos de potencial zeta e testes reológicos de escoamento em estado estacionário e oscilatório. A caracterização do GO mostra que grupos funcionais oxigenados foram incorporados em sua superfície grafítica. O GO oxidado por 96 horas (GO 96 h) apresentou maior distância interplanar e também apresentou menos camadas quando comparado com GO oxidado por 2 horas (GO 2 h). A caracterização do AFGO aponta que grupos aminados foram covalentemente ligados às nanofolhas GO e o GO com maior grau de oxidação produziu AFGO com maior nível de aminação. Todas as nanofolhas sintetizadas são coloidalmente estáveis quando suspensas em meio neutro. Todas as suspensões foram bem modeladas pela equação de Hershel-Bulkley. O aumento da concentração de nanofolhas nas suspensões prejudica a microestrutura do fluido e leva a uma diminuição da viscosidade, tensão de escoamento e elasticidade. O GO 96 h promoveu menor decréscimo na viscosidade, tensão de escoamento e elasticidade do que a suspensão GO 2 h. No caso do AFGO, o maior grau de aminação pode levar a uma queda mais pronunciada nas propriedades reológicas da suspensão. Para a suspensão com maior concentração de GO 96 h, observou-se o aparecimento de histerese em baixas taxas de cisalhamento. Esses resultados mostram que pequenas mudanças na superfície das nanofolhas de grafeno funcionalizado podem influenciar as respostas reológicas de um fluido não newtoniano. / [en] This work investigates the impact of functionalized graphene suspensions on the rheology of a Carbopol aqueous dispersion. The graphene derivatives used were graphene oxide (GO) and amino-functionalized graphene oxide (AFGO). The variation of the functionalized graphene concentration and oxidation was evaluated and related with the suspensions rheology. GO nanosheets were produced from synthesis of graphite oxide by modified Hummers method, and they were characterized by XRD, Raman,TGA, FTIR, XPS, TEM and AFM techniques. The GO was functionalized with triethylenetetramine by microwave assisted reaction to produce the AFGO, which was characterized by TGA and XPS techiniques. The suspensions were characterized by zeta potential experiments and rheological tests through steady-state and oscillatory flow. The GO characterization shows that oxygenated functional groups were incorporated in its graphitical surface. GO oxidized for 96 hours (GO 96 h) showed higher interplanar distance and also presented fewer layers when compared with GO oxidized for 2 hours (GO 2 h). The AFGO characterization points out that aminated groups were covalently attached to the GO nanosheets and the GO with a higher oxidation degree produced an AFGO with higher amination level. All synthesized nanosheets are colloidally stable when suspended at neutral media. All suspensions were well modeled by the Hershel-Bulkley equation. The increase of the nanosheets concentration in the suspensions impairs the level of fluid structure and leads to a decrease in viscosity, yield stress, and elasticity. The GO 96 h promoted a lower decrease in viscosity, yield stress and elasticity than the GO 2 h suspension. In the case of AFGO, the greater amination degree can lead to a more pronounced drop in the suspension rheological properties. For the suspension with a higher concentration of GO 96 h, it was observed the appearance of hysteresis at low shear rates. These results show that small changes in the graphene functionalized nanosheets surface can influence the rheological responses of a non-Newtonian fluid.

Nature develops several materials with remarkable functional properties composed of comparatively simple base substances. Biological materials are often composites, which optime the conformation to their function. On the other hand, synthetic materials are designed a priori, structuring them according to the performance to be achieved. 3D printing manufacturing is the most direct method for specific component production and earmarks the sample with material and geometry designed ad-hoc for a defined purpose, starting from a biomimetic approach to functional structures. The technique has the advantage of being quick, accurate, and with a limited waste of materials. The sample printing occurs through the deposition of material layer by layer. Furthermore, the material is often a composite, which matches the characteristics of components with different geometry and properties, achieving better mechanical and physical performances. This thesis analyses the mechanics of natural and custom-made composites: the spider body and the manufacturing of metallic and non-metallic graphene composites. The spider body is investigated in different sections of the exoskeleton and specifically the fangs. The study involves the mechanical characterization of the single components by the nanoindentation technique, with a special focus on the hardness and Young's modulus. The experimental results were mapped, purposing to present an accurate comparison of the mechanical properties of the spider body. The different stiffness of components is due to the tuning of the same basic material (the cuticle, i.e. mainly composed of chitin) for achieving different mechanical functions, which have improved the animal adaptation to specific evolutive requirements. The synthetic composites, suitable for 3D printing fabrication, are metallic and non-metallic matrices combined with carbon-based fillers. Non-metallic graphene composites are multiscale compounds. Specifically, the material is a blend of acrylonitrile-butadiene-styrene (ABS) matrix and different percentages of micro-carbon fibers (MCF). In the second step, nanoscale filler of carbon nanotubes (CNT) or graphene nanoplatelets (GNP) are added to the base mixture. The production process of composite materials followed a specific protocol for the optimal procedure and the machine parameters, as also foreseen in the literature. This method allowed the control over the percentages of the different materials to be adopted and ensured a homogeneous distribution of fillers in the plastic matrix. Multiscale compounds provide the basic materials for the extrusion of fused filaments, suitable for 3D printing of the samples. The composites were tested in the configuration of compression moulded sheets, as reference tests, and also in the corresponding 3D printed specimens. The addition of the micro-filler inside the ABS matrix caused a notable increment in stiffness and a slight increase in strength, with a significant reduction in deformation at the break. Concurrently, the addition of nanofillers was very effective in improving electrical conductivity compared to pure ABS and micro-composites, even at the lowest filler content. Composites with GNP as a nano-filler had a good impact on the stiffness of the materials, while the electrical conductivity of the composites is favoured by the presence of CNTs. Moreover, the extrusion of the filament and the print of fused filament fabrication led to the creation of voids within the structure, causing a significant loss of mechanical properties and a slight improvement in the electrical conductivity of the multiscale moulded composites. The final aim of this work is the identification of 3D-printed multiscale composites capable of the best matching of mechanical and electrical properties among the different compounds proposed. Since structures with metallic matrix and high mechanical performances are suitable for aerospace and automotive industry applications, metallic graphene composites are studied in the additive manufacturing sector. A comprehensive study of the mechanical and electrical properties of an innovative copper-graphene oxide composite (Cu-GO) was developed in collaboration with Fondazione E. Amaldi, in Rome. An extensive survey campaign on the working conditions was developed, leading to the definition of an optimal protocol of printing parameters for obtaining the samples with the highest density. The composite powders were prepared following two different routes to disperse the nanofiller into Cu matrix and, afterward, were processed by selective laser melting (SLM) technique. Analyses of the morphology, macroscopic and microscopic structure, and degree of oxidation of the printed samples were performed. Samples prepared followed the mechanical mixing procedure showed a better response to the 3D printing process in all tests. The mechanical characterization has instead provided a clear increase in the resistance of the material prepared with the ultrasonicated bath method, despite the greater porosity of specimens. The interesting comparison obtained between samples from different routes highlights the influence of powder preparation and working conditions on the printing results. We hope that the research could be useful to investigate in detail the potential applications suitable for composites in different technological fields and stimulate further comparative analysis.

[pt] Esta pesquisa avaliou a resistência a corrosão de revestimentos de base em resina epóxi, reforçada com 0,1% wt e 0,5% wt de óxido de grafeno reduzido (rGO), aplicado sobre um substrato em aço carbono AISI 1020. Como teste de corrosão foi aplicado testes de imersão em solução com 3,0% wt de NaCl saturadas com CO2, em um vaso de pressão a 70 bar na temperatura de 40 ᵒC, por 528 h. Os revestimentos foram avaliados por teste de aderência (Pull Off), microdureza (Dureza Shore D) e caracterizado por Microscopia Eletrônica de Varredura (MEV) quanto a qualidade de ancoragem do revestimento ao substrato, porosidade e espessura, para a análise de existência de pites na superfície do substrato metálicos foi utilizada microscopia ótica (MO). Os resultados obtidos evidenciaram que os revestimentos nas três condições, como recebido, aditivados com 0,1% wt e 0,5% de rGO tiveram a mesma eficiência na proteção do substrato metálico, todos igualmente, evitaram a formação de pites nas condições de testes propostas. Para adição de 0,1% wt de rGO ocorreu refinamento dos poros e a adição de 0,5% wt promoveu drástica redução da densidade de poros. A adição do rGO não influenciou na Dureza Shore D dos revestimentos. Para pré teste de corrosão, o revestimento com 0,1% wt de rGO obteve maior densidade de poros e menor valor de dureza, seguido pelo 0,0% wt e posterior 0,5% wt de rGO. Para pós testes de corrosão a ordem é invertida. Os resultados pós testes de corrosão indicaram que a porosidade possibilitou a permeação da solução nos revestimentos, e está relacionada com as bolhas e empolamentos, que influenciaram na dureza. A adição de 0,1% wt e 0,5% wt de rGO não influenciou na ancoragem dos revestimentos, obtendo boa acomodação nas irregularidades da superfície metálica do substrato. / [en] This research evaluated the corrosion resistance of an epoxy resin-based coat, reinforced with 0.1 and 0.5 wt% of reduced graphene oxide (rGO), applied to AISI 1020 carbon steel. Immersion tests in aqueous solution with 3.0 wt% NaCl saturated with CO2, in a pressurized cell at 70 bar at 40⁰C, for 528 h. The coating was evaluated by Pull-Off Test, microhardness (Shore D hardness), and Scanning Electron Microscopy (SEM). The quality of the coating anchoring to the substrate, porosity, and thickness was evaluated. The presence of pits on the surface of the metallic substrate was assessed by Optical Microscopy (OM). The results obtained indicated that the addition of rGO contributed to greater corrosion resistance and provided better structural integrity to the coating. The results obtained showed that the coatings under the three conditions, as received and 0.1 and 0.5wt% rGO additions had the same efficiency in protecting the metallic substrate, avoiding pitting. Pore refinement occurred for 0.1wt % rGO, and the addition of 0.5wt% promoted a drastic reduction in pore density. The addition of rGO did not influence on the Shore D Hardness of the coatings. For a precorrosion test, the coating with 0.1wt% of rGO obtained higher pore density and lower hardness value, followed by 0 wt% and later 0.5 wt% of rGO. For the post corrosion test, the order is reversed. The results of the post corrosion test indicated that the porosity allowed the permeation of the solution in the coatings and is related to the bubbles and blistering, which influenced the hardness. The addition of 0.1 and 0.5 wt% or rGO did not affect the coating anchoring, obtaining reasonable accommodation in the irregularities of the substrate metallic surface.

Das Verhalten von durch Graphen oder Graphenoxid (GO) begrenzten Molekülen hat sich, bedingt durch die bemerkenswerten strukturellen und optischen Eigenschaften dieser quasi-zweidimensionalen Materialien, als vielversprechendes Forschungsfeld erwiesen. Die vorliegende Arbeit konzentriert sich auf das Hydrationsverhalten von GO und das Verhalten kleiner, von Graphen begrenzter Moleküle. In dieser Arbeit wurde auf Rasterkraftmikroskopie (SFM) zurückgegriffen, um die GO-Hydration zu untersuchen. Die Ergebnisse zeigen ein graduelles bzw. stufenweises Ansteigen des durchschnittlichen Schichtabstands für relative Luftfeuchtigkeiten (RH) unter halb von 80%, beziehungsweise in flüssigem Wasser. Diese experimentellen Beobachtungen stimmen mit den XRD an vielschichtigem GO in der Literatur überein. Die hier gezeigten Ergebnisse lassen jedoch den angenommenen Einlagerungseffekt, bei der Hydrierung von GO bei geringer RH, außen vor. Stattdessen wird die allmähliche Ausdehnung der kontinuierlichen Einlagerung von Wassermolekülen in den einzelnen GO-Schichten zugeschrieben, während die stufenweise Ausdehnung im komplett in Wasser getauchten Zustand auf das Eindringen einer ganzen Wassermonolage zurückgeführt wird. Andererseits könnte die Grenzfläche zwischen Graphen und dem Substrat ein begrenztes elektrisches Feld aufweisen, das ein weit verbreitetes, auf Ladungstransfer an Grenzflächen zurückzuführendes Phänomen darstellt. Die vorliegende Arbeit behandelt dieses Thema unter Nutzung von Rhodamin 6G (R6G) als Molekül zwischen Graphen und Glimmer, die es begrenzen. Eine Rot-Verschiebung der R6G-Maxima bei geringer RH wird sowohl auf elektrische Felder, die sich auf die Moleküle auswirken, als auch auf mechanische Deformationen der R6G-Struktur an der Grenzschicht zurückgeführt. Die Stärke des elektrischen Feldes wird anhand des Graphen-Raman-Spektrums auf etwa 1 V/nm abgeschätzt. / The behavior of molecules confined by graphene or graphene oxide (GO) has proven to be a promising area of research owing to the remarkable structural and optical properties of these quasi two-dimensional materials. This thesis focuses on the hydration behavior of GO and the behavior of small molecules confined by graphene. In this work, scanning force microscopy (SFM) has been employed to investigate the hydration of GO. The results show a gradual and a step-like increase of the average interlayer distance for relative humidities (RH) below 80% and in liquid water, respectively. These experimental observations are consistent with XRD results on multilayered graphite oxide as reported in the literature. However, the results presented here exclude the postulated interstratification effect, for hydration of GO at low RH. Instead, the gradual expansion is attributed to the continuous incorporation of water molecules into single GO layers, while the step-like expansion when completely immersed in water, is attributed to the insertion of a full monolayer of water. On the other hand, the interface between graphene and its substrate may exhibit a confined electric field, a common phenomenon due to charge transfer at interfaces. In this work, this subject is addressed using Rhodamine 6G (R6G) as a probe molecule confined between graphene and mica. A red shift of the RG6 peaks at low RH is argued to be due to both, electric fields acting on the molecules and mechanical deformation of the R6G structure at the interface. The strength of the field is estimated from the graphene Raman spectra to be on the order of 1 V/nm.

Traditional Lithium-Ion Batteries (LIBs) are a reliable and cost-efficient choice for energy storage. LIBs offer high energy density and low self-discharge. Recent developments in electric-based technologies push for replacing historically used Lead-Acid batteries with LIBs. However, LIBs do not yet meet the demands of modern technology. Silicon and graphene oxide (GO) have been identified as promising replacements to improve anode materials. Graphene oxide has a unique sheet-like structure that provides a mechanically stable, light weight material for LIB anodes. Due to its structure, reduced graphene oxide (rGO) is efficiently conductive and resistive to environmental changes. On the other hand, silicon-based anode materials offer the highest theoretical energy density and a high Li-ion loading capacity of various elements [20]. Silicon-based anodes that have previously been studied demonstrated extreme volumetric expansion over long cycles due to lithiation. Polysiloxane may be an interesting alternative as it is a Si-based material that can retain the high Li-ion loading capacity of Si while lacking the unattractive volumetric expansions of Si. Polymer derived ceramic-decorated graphene oxide anodes have been suggested to increase loading capacity, thermal resistance, power density, and mechanical stability of LIBs. Coupled with mechanically stable graphene oxide, polymer derived ceramic nanoparticle decorated graphene oxide anodes are studied to establish their efficiencies under operating conditions.

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Настоящая работа состоит из 5 глав и посвящена бесферментному электрокаталитическому определению креатинина в слабокислой среде с использованием различных катализаторов, которые представляют из себя комплексы меди с новыми производными 2,2’-бипиридина. В работе приведены аналитические характеристики исследования всех пяти комплексов, трёх выбранных модификаторов и обоснования выбора наилучших веществ для модифицирования стеклоуглеродного электрода в определении концентрации креатинина. Проведено сравнение аналитических характеристик, полученных от метода циклической вольтамперометрии и метода с использованием полевого транзистора с расширенным затвором, и выбран предпочтительный метод анализа. / This work consists of 5 chapters and is devoted to the non-enzymatic electrocatalytic determination of creatinine in a weakly acidic medium using different catalysts, which are copper complexes with new 2,2'-bipyridine derivatives. Analytical characteristics of all five complexes, three selected modifiers and substantiation of the choice of the best substances for modifying the glass carbon electrode in determining creatinine concentration are given in the work. Comparison of the analytical characteristics obtained from the cyclic voltammetry method and the method using a field-effect transistor with an extended gate was carried out and the preferred method of analysis was selected.

[ES] Las pilas de combustible de hidrógeno o bioalcohol son una tecnología prometedora para la generación de energía limpia y eficiente en el intento actual de revertir los severos efectos causados por el cambio climático. No obstante, para lograr generalizar su uso, esta tecnología debe optimizarse. Concretamente, la membrana de intercambio de protones es un componente crucial para mejorar su rendimiento general. Esta línea de investigación, entre otras, está incluida en la mayoría de las actuales líneas estratégicas nacionales y europeas con el objetivo de implantar estos sistemas de producción de energía sostenibles en un futuro próximo. En la presente tesis doctoral se presenta un procedimiento robusto y fiable que permite el diseño de membranas de intercambio de protones mediante la caracterización y análisis de varios materiales poliméricos con la intención de predecir su comportamiento en condiciones operativas. En ese sentido, se analizan cuatro tipos diferentes de microestructuras. En el Capítulo 4 se analizan dos series de membranas basadas en copolímeros en bloque sulfonados de estireno-etileno-butileno-estireno (SEBS). La microestructura se ha ajustado para su idoneidad en aplicaciones de pilas de combustible. Posteriormente, se aplica a las muestras un proceso de sulfonación, fotorreticulación UV e hibridación. En el Capítulo 5 se analiza una serie de membranas de poli(alcohol vinílico) (PVA) convenientemente modificadas para su idoneidad como membranas de intercambio de protones en celdas de combustible de metanol directo (DMFC). El análisis se centra en si la reticulación y la sulfonación mediante el uso de SSA mejoran la estabilidad y aumentan la conducción de protones en la estructura de PVA tal y como se esperaba inicialmente. Además, se evalúa el efecto de la adición de óxido de grafeno (GO) en los espectros dieléctricos y la conductividad protónica. En el Capítulo 6 se analizan dos series de membranas a base de copolímero de poli (epiclorhidrina) (PECH) y poli (epiclorhidrina-co-óxido de etileno) (PECH-co-EO). Ambas membranas están modificadas con unidades de 3,4,5-tris[4-(n-dodecan-1-iloxi)benciloxi]benzoato. El análisis se centra en la capacidad de estas membranas para formar canales, promovidos por la orientación térmica, lo que mejora los mecanismos de transferencia de carga y la conductividad de los protones. En el Capítulo 7 se realiza el análisis de una membrana sintetizada a partir de una red adaptable covalente (CAN). La característica más importante de este tipo de polímeros es la presencia de enlaces reversibles en la estructura que les permite mostrar propiedades físicas como la autoreparación, la soldabilidad y la reciclabilidad. Estas propiedades podrían mejorar el ciclo de vida de las membranas de intercambio protónico. El análisis realizado incluye una evaluación de las dos temperaturas más importantes desde el punto de vista viscoelástico, es decir, la transición vítrea Tg y la temperatura de transición de congelación de la topología Tv, y su impacto en la conductividad protónica. Como resultado de este estudio, se desarrolla una metodología para analizar diversas membranas poliméricas con diferentes microestructuras mediante Análisis Térmico Dieléctrico (DETA). En consecuencia, el estudio de las propiedades dieléctricas, en términos de la permitividad compleja (ε∗), junto con el análisis de la conductividad compleja (σ∗), permite obtener información sobre la dinámica molecular que favorece eficientemente los mecanismos de transferencia de carga. La conductividad protónica (σprot) se estimará a partir de los datos dieléctricos, lo que permitirá evaluar las membranas poliméricas ensayadas para su aplicación como membranas de intercambio protónico. En consecuencia, se puede optimizar el funcionamiento de las membranas de intercambio de protones, y se promueve su implementación masiva. / [CA] Les piles de combustible d'hidrogen o bioalcohol són una tecnologia prometedora per a la generació d'energia neta i eficient en l'intent actual de revertir els severs efectes causats pel canvi climàtic. No obstant això, per a aconseguir generalitzar el seu ús, aquesta tecnologia ha d'optimitzar-se. Concretament, la membrana d'intercanvi de protons és un component crucial per a millorar el seu rendiment general. Aquesta línia d'investigació, entre d'altres, està inclosa en la majoria de les actuals línies estratègiques nacionals i europees amb l'objectiu d'implantar aquests sistemes de producció d'energia sostenibles en un futur pròxim. En la present tesi doctoral es presenta un procediment robust i fiable que permet el disseny de membranes d'intercanvi de protons mitjançant la caracterització i anàlisi de diversos materials polimèrics amb la intenció de predir el seu comportament en condicions operatives. En aqueix sentit, s'analitzen quatre tipus diferents de microestructures. En el Capítol 4 s'analitzen dues sèries de membranes basades en copolímers en bloc sulfonats d'estiré-etilé-butilé-estiré (SEBS). La microestructura s'ha ajustat per a la seua idoneïtat en aplicacions de piles de combustible. Posteriorment, s'aplica a les mostres un procés de sulfonació, fotorreticulació UV i hibridació. En el Capítol 5 s'analitza una sèrie de membranes de poli(alcohol vinílic) (PVA) convenientment modificades per a la seua idoneïtat com a membranes d'intercanvi de protons en cel·les de combustible de metanol directe (DMFC). L'anàlisi se centra en si la reticulació i la sulfonació mitjançant l'ús de SSA milloren l'estabilitat i augmenten la conducció de protons en l'estructura de PVA tal com s'esperava inicialment. A més, s'avalua l'efecte de l'addició d'òxid de grafé (GO) en els espectres dielèctrics i la conductivitat protònica. En el Capítol 6 s'analitzen dues sèries de membranes a base de copolímer de poli (epiclorhidrina) (PECH) i poli (epiclorhidrina-co-òxid d'etilé) (PECH-co-EO). Totes dues membranes estan modificades amb unitats de 3,4,5-tris[4-(n-dodecan-1-iloxi)benciloxi] benzoato. L'anàlisi es centra en la capacitat d'aquestes membranes per a formar canals, promoguts per l'orientació tèrmica, la qual cosa millora els mecanismes de transferència de càrrega i la conductivitat dels protons. En el Capítol 7 es realitza l'anàlisi d'una membrana sintetitzada a partir d'una xarxa adaptable covalent (CA). La característica més important d'aquesta mena de polímers és la presència d'enllaços reversibles en l'estructura que els permet mostrar propietats físiques com l'autoreparació, la soldabilitat i la reciclabilitat. Aquestes propietats podrien millorar el cicle de vida de les membranes d'intercanvi protònic. L'anàlisi realitzada inclou una avaluació de les dues temperatures més importants des del punt de vista viscoelàstic, és a dir, la transició vítria Tg i la temperatura de transició de congelació de la topologia Tv, i el seu impacte en la conductivitat protònica. Com a resultat d'aquest estudi, es desenvolupa una metodologia per a analitzar diverses membranes polimèriques amb diferents microestructures mitjançant Anàlisi Tèrmic Dielèctric (DETA). En conseqüència, l'estudi de les propietats dielèctriques, en termes de la permitivitat complexa (ε∗), juntament amb l'anàlisi de la conductivitat complexa (σ∗), permet obtindre informació sobre la dinàmica molecular que afavoreix eficientment els mecanismes de transferència de càrrega. La conductivitat protònica (σprot) s'estimarà a partir de les dades dielèctriques, la qual cosa permetrà avaluar les membranes polimèriques assajades per a la seua aplicació com a membranes d'intercanvi protònic. En conseqüència, es pot optimitzar el funcionament de les membranes d'intercanvi de protons, i es promou la seua implementació massiva. / [EN] Hydrogen or bioalcohol fuel cells are a promising technology for clean and efficient energy generation in the current attempt to reverse the severe effects caused by climate change. However, in order to achieve its general use, this technology must be optimized. Specifically, the proton exchange membrane is a crucial component to improve your overall performance. This line of research, among others, is included in most of the current national and European strategic lines with the aim of implementing these sustainable energy production systems in the near future. In this doctoral thesis, a robust and reliable procedure is presented that allows the design of proton exchange membranes through the characterization and analysis of various polymeric materials with the intention of predicting their behaviour under operating conditions. In this sense, four different types of microstructures are analysed. In Chapter 4, two series of membranes based on sulfonated block copolymers of styrene-ethylene-butylene-styrene (SEBS) are discussed. The microstructure has been adjusted for its suitability in fuel cell applications. Subsequently, a sulfonation, UV photocrosslinking, and hybridization process are applied to the samples. In Chapter 5, a series of polyvinyl alcohol (PVA) membranes suitably modified for their suitability as proton exchange membranes in direct methanol fuel cells (DMFC) are discussed. The analysis focuses on whether crosslinking and sulfonation using SSA improve stability and increase proton conduction in the PVA structure as initially expected. In addition, the effect of the addition of graphene oxide (GO) on the dielectric spectra, and proton conductivity is evaluated. In Chapter 6 two series of membranes based on copolymers of poly (epichlorohydrin) (PECH) and poly (epichlorohydrin-co-ethylene oxide) (PECH-co-EO) are analysed. Both membranes are modified with 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate units. The analysis focuses on the ability of these membranes to form channels, promoted by thermal orientation, which improves the charge transfer mechanisms and the proton conductivity. In Chapter 7, the analysis of a membrane synthesized from a covalent adaptive network (CAN) is performed. The most important characteristic of this type of polymer is the presence of reversible bonds in the structure that allows them to display physical properties such as self-healing, weldability, and recyclability. These properties could improve the life cycle of proton exchange membranes. The analysis carried out includes an evaluation of the two most important temperatures from the viscoelastic point of view, that is, the glass transition Tg and the freezing transition temperature of the topology Tv, and their impact on the proton conductivity. As a result of this study, a methodology is developed to analyse various polymeric membranes with different microstructures by means of Dielectric Thermal Analysis (DETA). Consequently, the study of the dielectric properties, in terms of the complex permittivity (σ∗), together with the analysis of the complex conductivity (ε∗), allows us to obtain information on the molecular dynamics that efficiently favour the charge transfer mechanisms. The proton conductivity (σprot) will be estimated from the dielectric data, which will allow the evaluation of the tested polymeric membranes for their application as proton exchange membranes. Consequently, the functioning of proton exchange membranes can be optimized, and their massive implementation is promoted. / Pascual José, B. (2023). Design and Characterization of Polymeric Materials for their Application as Electrolytes in Fuel Cells [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/196863

L'objectif de ce travail est de développer et d’étudier une nouvelle classe de fluidesintelligents à base de dispersions colloïdales de carbone, sensibles à un stimulus externe pour desapplications de conversion et stockage d’énergie. Ces stimuli sont de différentes natures : vibrationmécanique, mouvement humain, variation de pression ou écoulement d'un solvant, et peuventaltérer les structures de tels systèmes. Ceci induit une modification de la structure locale desparticules et par conséquent des propriétés diélectriques et électriques. Habituellement, lessuspensions de matériaux carbonés sont étudiées au repos ou séchées. Toutefois, comprendre leurcomportement en flux est essentiel pour de nouvelles applications où ces matériaux sont exploitésdans des conditions dynamiques telle que le stockage d'énergie électrochimique assisté par flux(FAES). Par exemple, les matériaux à base de graphène jouent désormais un rôle important dans lesnouvelles technologies énergétiques. Ils sont utilisés comme additifs conducteurs dans lesassemblages d'électrodes, mais en raison de leur forme anisotrope spécifique, ils permettentégalement d’obtenir des fluides diélectriques sous écoulement.Les cristaux liquides d'oxyde de graphène, en tant que matériau souple électrostrictif, sont étudiéspour la récupération d'énergie mécanique, ainsi que des dispersions de noir de carbone pour lestockage d'énergie.Les propriétés diélectriques et électriques de ces dispersions fluides dans des conditions statiques etdynamiques sont mesurées et analysées. Enfin, l’effet de l’écoulement sur l’orientation et laréorganisation locale des particules et leur comportement diélectrique et électrique sont examinés. / The aim of this work is to develop and study a new class of smart fluids made of colloidalcarbon-based dispersions, which are sensitive to an external stimulus for energy storage orconversion applications. The effect of an external input, such as mechanical vibration, humanmotion, variable pressure, flowing of a solvent, can alter the structures of such systems.Consequently these changes induce modifications of the dielectric and electrical properties. Usually,the suspensions of carbon materials are investigated at rest or dried. However, their flow behavior iscritical when new technologies, which exploit these materials in dynamic conditions such as FAES(Flow-Assisted Electrochemical Energy Storage) are considered. For example, graphene-basedmaterials are now playing a significant role in energy materials. They act as conductive additives inelectrode assemblies, but due to their specific anisotropic shape they also provide a new route toachieve dielectric liquid media.In details, Graphene Oxide liquid crystals as electrostrictive soft material for mechanical energyharvesting and Carbon black dispersions as percolated flowable electrodes for capacitive energystorage are investigated.In particular, the dielectric and electrical properties of these flowable dispersions are studied understatic and dynamic conditions. The effect of the flow-rate on the local orientation and reorganizationof the particles and their related dielectric and electrical behavior are examined.

The objective of my work was to develop HDPE clay nanocomposites for packaging with superior barrier (gas and water) properties by economical processing technique. This work also represents a comparative study of thermoplastic nanocomposites for packaging based on linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and Nylon12. In this study properties and processing of a series of linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and Nylon 12 nanocomposites based on Na-MMT clay and two different aspect ratio grades of kaolinite clay are discussed.