Esta tese envolveu a síntese de 11 precursores poliméricos inéditos, derivados de bifenilos e terfenilos, substituídos por grupos receptores e doadores de elétrons, por meio de reações de acoplamento de Suzuki. Tais precursores foram convertidos aos respectivos polímeros, poli(p-xilileno)s e poli(p-fenileno vinileno)s, via redução catódica, conduzindo a um total de 11 polímeros, sendo dez deles inéditos. Os polímeros obtidos foram caracterizados por métodos espectroscópicos (UV-VIS, IV, RMN), análises térmicas, SEC e medidas de condutividade elétrica pós-dopagem. Um dos polímeros foi empregado na construção de dispositivos metal/polímero/metal (\"sanduíche\"), que permitiram a determinação da mobilidade dos portadores de carga, bem como da altura de barreira para injeção de elétrons na junção metal/polímero. / The synthesis via Suzuki coupling reaction of 11 new biphenylenic and terphenylenic polymer precursors, substituted by long-chain electron donating or withdrawing groups, is described. The electrochemical reduction of these precursors led to the corresponding poly(p-xylylene)s and poly(p-phenylene vinylene)s. Ten out of the 11 generated polymers have been never described before. AII the polymers were fully characterised by spectroscopic (UV-VIS, IR, NMR) and thermal analyses, as well as by SEC and electrical conductivity measurements of iodine-doped specimens. The positive charge carrier mobility and the barrier height for electron injection (metal/polymer) could be determined through I x V investigations of sandwich devices (metal/polymer/metal) for one of the polymers.

Die Copolymerisation wurde mit dem Ziel untersucht, polymere Materialien zu synthetisieren, die die individuellen Eigenschaften der entsprechenden Homopolymere kombinieren. Die Dissertation konzentrierte sich auf die Elektrosynthese und Charakterisierung von leitfähigen Copolymerfilmen auf Basis von Pyrrol- und Thiophenderivaten. Mit einer Reihe von elektrochemischen, spektroskopischen und mikroskopischen Untersuchungsmethoden (Zyklovoltammetrie, elektrochemische Impedanz-spektroskopie, photoelektrochemische Spektroskopie, Elektrospray- Ionisations-Massenspektroskopie, Festkörper- NMR, Raman-Spektroskopie, Thermoanalyse und Rasterelektronenmikroskopie) wurde die Bildung echter Copolymere von Pyrrol mit Bithiophen und von 3-Methylthiophen mit Ethyl-3-thiophenazetat nachgewiesen. Die analytischen Ergebnisse bestätigen, dass Random- Copolymere und keine Block-Copolymere gebildet wurden. Die elektronischen und strukturellen Eigenschaften der Copolymerfilme liegen zwischen denen der jeweiligen Homopolymere und sind abhängig von der Copolymerzusammensetzung. Insbesondere die Halbleiterparameter der Copolymerfilme von Pyrrol mit Bithiophen wie Flachband-Potential, Bandlücken-Energie und Ladungsträgerdichte verschieben sich von denen des reinen Polypyrrols bis zum Polybithiophen, wenn der Gehalt an Bithiophen im Copolymerfilm vergrößert wird. Diese Parameter sind einstellbar durch Variation des Monomerverhältnisses oder des Polymerisationspotentials. Außerdem konnten die strukturellen und elektronischen Eigenschaften des funktionalisierten Polymers Ethyl-3-thiophenazetat durch Copolymerisation mit 3-Methylthiophen deutlich verbessert werden. Die synthetisierten leitfähigen Copolymerfilme können in der Sensorik Anwendung finden. / The copolymerization has been studied as a new strategy to synthesize polymer materials by combining interesting properties of the respective homopolymers. In this dissertation, the work focused on the electrosynthesis and characterization of conducting copolymer films based on pyrrole and thiophene derivatives. A variety of electrochemical, spectroscopic and microscopic techniques such as cyclic voltammetry, electrochemical impedance and photoelectrochemical spectroscopy, electrospray ionization mass spectroscopy, solid state NMR and Raman spectroscopy, thermal analysis and scanning electron microscopy supported the formation of true copolymers of pyrrole with bithiophene and 3-methylthiophene with ethyl-3-thiophene acetate. The analytical results exhibited that random copolymers were produced rather than block copolymers. The electronic and structural characteristics of the copolymer films were intermediate between those of the respective homopolymers and they were dependent on the copolymer composition. In particular, the semiconducting parameters of the copolymer films of pyrrole and bithiophene such as flat band potential, band gap energy and charge carrier density shifted from those of polypyrrole to polybithiophene with increasing bithiophene content of the copolymer films. Such parameters were controlled precisely by alternating either the monomer ratio or the polymerization potential. In addition, the morphological and electronic properties of the functionalized polymers of ethyl-3-thiophene acetate were increased significantly by copolymerization with 3-methylthiophene. The obtained conducting copolymer films were able to be applied in the field of sensoric.

Tesis por compendio / [ES] La funcionalización de tejidos permite dotar a estos de nuevas propiedades que no poseen de forma inherente. Por su parte, el grafeno presenta excelentes características en cuanto a conductividad térmica y eléctrica, resistencia y flexibilidad. En esta tesis se evalúa la aplicación de grafeno sobre diferentes sustratos textiles para obtener tejidos capaces de conducir la electricidad y responder a estímulos térmicos, bien disipando el calor o bien transformando una corriente eléctrica en un incremento de temperatura en su superficie. Para ello, se aplica grafeno empleando diferentes métodos recubrimiento con rasqueta e impregnación sobre tejidos de celulosa y de poliéster. En primer lugar, destaca la influencia que ejerce la estructura del tejido sobre la resistencia eléctrica del recubrimiento, dando como resultado que aquellos tejidos con mayor coeficiente de ligadura son los que mejores resultados presentan al tener una superficie más homogénea en la que se deposita el recubrimiento. Asimismo, se halla que la incorporación de materiales de cambio de fase en el recubrimiento con grafeno permite una mayor disipación de calor cuando se calienta el tejido. Además, se consigue calefactar las muestras empleadas utilizando diferentes voltajes eléctricos lo que, a su vez, sirve para evaluar los defectos del recubrimiento analizando las imágenes termográficas. Entre otros hallazgos relevantes también cabe destacar la influencia que ejerce la humedad del sustrato sobre la resistencia eléctrica del grafeno y la importancia del curado térmico de las resinas para asegurar una buena solidez a los lavados. / [CA] La funcionalización de teixits permet dotar a aquests de noves propietats que no posseeixen de manera inherent. Per part seua, el grafé presenta excel·lents propietats quant a conductivitat tèrmica i elèctrica, resistència i flexibilitat. En aquesta tesi s'avalua l'aplicació de grafé sobre diferents substrats tèxtils per a obtindre teixits capaços de conduir l'electricitat i respondre a estímuls tèrmics, bé dissipant la calor o bé transformant un corrent elèctric en un increment de temperatura en la seua superfície. Per a això, s'aplica grafé emprant recobriment amb rasqueta i estampat sobre teixits de cel·lulosa i de polièster. En primer lloc, destaca la influència que exerceix l'estructura del teixit sobre la resistència elèctrica del recobriment, obtenint que aquells teixits amb major coeficient de lligadura són els que millors resultats presenten en tindre una superfície més homogènia en la qual es deposita el recobriment. Així mateix, es troba que la incorporació de materials de canvi de fase en el recobriment amb grafé permet una major dissipació de calor quan es calfa el teixit. A més, s'aconsegueix calefactar les mostres emprades utilitzant diferents voltatges elèctrics el que, al seu torn, serveix per a avaluar els defectes del recobriment analitzant les imatges termogràfiques. Entre altres troballes rellevants també cal destacar la influència que exerceix la humitat del substrat sobre la resistència del grafé i la importància del curat tèrmic de les resines per a assegurar una bona solidesa a les rentades. / [EN] Fabrics functionalization provides them with new properties that they do not inherently possess. Furthermore, graphene has excellent characteristics in terms of thermal and electrical conductivity, resistance, and flexibility. In this thesis, the application of graphene on different textile substrates is evaluated to obtain fabrics capable of conducting electricity and responding to thermal stimuli, either by dissipating heat or by transforming an electrical current into an increase in surface temperature. For this purpose, graphene is applied using knife-coating and screen-printing on cellulose and polyester fabrics. First of all, it is worth highlighting the influence exerted by the structure of the fabric on the electrical resistance of the coating, obtaining that those fabrics with the highest interlacing coefficient are the ones that present the best results as they have a more homogeneous surface on which the coating is deposited. Also, it is found that the incorporation of phase change materials in the coating containing graphene allows for greater heat dissipation when the fabric is heated. In addition, it is possible to heat the samples using different electrical voltages, which also serves to evaluate the defects of the coating by analyzing the thermographic images. Among other relevant findings, it is also worth highlighting the influence that substrate humidity exerts on the resistance of graphene and the importance of thermal curing of the resins to ensure good washing fastness. / Ruiz Calleja, TR. (2021). Funcionalización de textiles mediante la aplicación de grafeno [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/179634 / TESIS / Compendio

No description available.

Organic coatings are extensively used as protective coatings in several industries including the automotive and aircraft industries. The last few years have witnessed an increased interest in improving not only the mechanical properties but also the corrosion protection properties of organic coatings. Among the currently investigated methods of improving the performance of organic coatings is the incorporation of additives in the organic paint matrix. Vapor grown carbon nanofibers (VGCNFs) are a class of carbon fibers that are produced by catalytic dehydrogenation of a hydrocarbon at high temperatures. Depending on the method of synthesis and the post-treatment processes, the diameter of the VGCNFs is normally in the 10-300 nm range. The small size, light weight, high aspect ratio, and unique physical, thermal, mechanical, and electrical properties of VGCNF make it an ideal reinforcing filler in polymer matrix nanocomposites to enhance the mechanical properties of the pure polymeric material in high performance applications in several industries such as the automotive, aircraft, battery, sensors, catalysis, electronics, and sports industries. The main objective of the current investigation was to study the corrosion protection offered by the incorporation of VGCNFs into a commercial alkyd paint matrix applied to the surface of mild steel coupons. The corrosion protection was investigated by immersing samples in air saturated 3% NaCl solution (artificial seawater). The samples were studied by electrochemical impedance spectroscopy (EIS) along with other measurements, including electrochemical (open circuit potential, cyclic voltammetry), chemical (salt spray test), electrical conductivity, and surface analysis (SEM, AFM, optical profilometry, and nanoindentation). The study involved the investigation of the effect of the weight percent (wt %) of the VGCNF as well as the coating film thickness on the corrosion protection performance of the coated steel samples when exposed to the corrosive electrolyte. By way of contrast, the EIS behavior of steel coupons coated with a paint coating incorporating different weight percents of powdered silicon carbide (SiC) particles was also studied. The EIS spectra were used to calculated and graph several corrosion parameters for the investigated systems. At the end, the studied coatings were ranked in order of their anticorrosive properties.

Ces travaux de recherche s'inscrivent dans le développement de nouveaux catalyseurs pour les piles à combustible de type PEMFC. L'objectif est d'améliorer le transfert de charges et de matières au sein des électrodes afin d'améliorer la durabilité des matériaux. Nous avons développé des catalyseurs qui permettent la transposition de la phénoménologie du point triple à l'échelle moléculaire. Le greffage de polymères conducteurs protoniques à la surface de nanoparticules de platine a été réalisé afin d'obtenir des complexes catalytiques nano-composites, comportant le catalyseur au platine, un conducteur protonique et un conducteur électronique. L'ensemble des matériaux issus de cette première étape ont été caractérisé en demi-cellule électrochimique afin de déterminer les catalyseurs les plus actifs et les plus sélectifs. Les matériaux les plus prometteurs ont enfin été testés en mono-cellule PEMFC de 5 cm² et 25 cm² afin de déterminer d'une part les performances in situ et d'autre part la durabilité des matériaux. Les électrodes nano-composites, formulées sans Nafion®, ont des caractéristiques équivalentes aux systèmes commerciaux. En effet, elles fournissent une densité de puissance maximale de 1 W.cm-2 et une durabilité de 20 µV.h-1 sur 300 h. Ces électrodes formulées sans composé fluoré permettent le recyclage du platine par pyrolyse. / This research work is within the scope of new catalysts for PEM fuel cells. The objective is to decrease the platinum amount in the electrode and to promote mass and electronic transfers, in order to improve the durability of the systems. We developed catalysts that enable the implementation of the phenomenology of the triple phase boundary at the molecular scale. The fieldwork concerns the grafting of proton conducting polymers (PSS) on the platinum nanoparticles surface in order to obtain nanocomposite catalysts. All synthetized materials are characterized in electrochemical half-cell, in order to determine the most active and the most selective catalyst. Then, the best catalytic complexes are tested in PEMFC 5 cm² and 25 cm² single-cell to determine in situ performance and materials durability. The properties of the nanocomposites electrodes formulated without Nafion®, are equivalent to commercial systems. Indeed, they provide a maximum power density of 1 W.cm-2 and a durability of 20 µV.h-1 during 300 h. These electrodes formulated without fluorinated compound allow platinum recycling by pyrolysis.

Thesis presents synthesis and study of thiophene monomers, oligomers and polymers. The new series of thieno[3,4-b]pyrazine copolymers based on 3-dodecylthiophene and pyrazine monomers were prepared by oxidative polymerization with FeCl3. The effective synthetic method for preparation of 3-alkylthiophenes and thiophene oligomers was developed by optimizing of Kumada cross-couplig. The mentioned method could be realized for multikilos scale with possibility of transfer to pilot plant production. The second part of thesis focuses on synthesis and study of new thiophene compounds, which consist of both 2,3-diazo-1,3-butadiene bridge with two terminal chromophores and two thiophene units linked together via -position by pyrazine or hydrazine bridge. Finally, the new type of regular alternating copolymer consists of 2,2´:5´,2´´-terthiophene-5,5´-dicarboxylic acid (TEDA) and polyethyleneoxide (PEO) was prepared. Formation of polymer nano-subunits as separated phases in solid state was confirmed by TEM.

<p>Multifunctional additive manufacturing has the immense potential of addressing present needs within structural health monitoring by enabling a new additive manufacturing paradigm that redefines what a sensor is, or what sensors should resemble. To achieve this, the properties of printed components must be precisely tailored to meet structure specific and application specific requirements. However due to the limited number of commercially available multifunctional filaments, this research investigates the in-house creation of adaptable piezoresistive multifunctional filaments and their potential within structural health monitoring applications based upon their characterized piezoresistive responses. To do so, a rigid polylactic acid based-filament and a flexible thermoplastic polyurethane based-filament were modified to impart piezoresistive properties using carbon nanofibers. The filaments were produced using different mixing techniques, nanoparticle concentrations, and optimally selected manufacturing parameters from a design of experiments approach. The resulting filaments exhibited consistent resistivity values which were found to be less variable under specific mixing techniques than commercially available multifunctional filaments. This improved consistency was found to be a key factor which held back currently available piezoresistive filaments from fulfilling needs within structural health monitoring. To demonstrate the ability to meet these needs, the piezoresistive responses of three dog-bone shaped sensor sizes were measured under monotonic and cyclic loading conditions for the optimally manufactured filaments. The characterized piezoresistive responses demonstrated high strain sensitivities under both tensile and compressive loads. These piezoresistive sensors demonstrated the greatest sensitivity in tension, where all three sensor sizes exhibited gauge factors over 30. Cyclic loading supported these results and further demonstrated the accuracy and reliability of the printed sensors within SHM applications.</p>