Commercial granular and fibrous activated carbons have been studied for the removal of heavy metals from aqueous solutions. A wood based activated carbon (AUG WHK) and an activated carbon cloth (KoTHmex TC-66 C) based on polyacrylonitrile fibre as a precursor, were oxidised for different periods of time using nitric acid, ozone and electrochemical methods to introduce various acidic groups at the surface, thereby, enhancing metal binding capacity. Modified samples were subsequently studied for the specific removal of cadmium and mercury ions in solution and compared with the performance of a commercially available weak acid fibrous exchange material (Ecofil-Deco Ltd. K-4). Carbonaceous adsorbents were physically characterised by scanning electron microscopy, surface area and porosimetry (using N2 adsorption at 77K). There was a decrease in BET surface area betweenu ntreateda nd oxidised samples. Acid and electrochemically oxidised samples were completely stable although there was clear evidence of physical damage to ozone-oxidised carbons. Samples were also chemically characterised by pH titration, direct titration, X-ray photoelectron spectroscopy and elemental analysis. A significant increase in oxygen content was obtained after oxidation, which increased the total ion exchange capacity by a factor of approximately 3.3 compared to commercial as-received carbonaceous adsorbents. As the degree of oxidation increased, the point of zero charge was shifted to lower pH values, i. e. from 4.5 to 3.6. (Continues...).

Additive manufacturing provides unmatched control and diversity over structural design of polymeric, ceramic and metallic parts. Nevertheless, until recently, the toolbox of polymeric feedstocks for light based additive manufacturing limited employment of printed parts for applications necessitating high thermomechanical performance. Development of synthetic pathways permitted the first additive manufacturing of high performance poly(amide imides) via ultraviolet assisted direct ink write (UV-DIW) printing. Precursor resins exhibited prerequisite rheology and reactivity for UV-DIW and produced organogels were well-defined and self-supporting. Thermal treatment induced drying and imidization of the precursor organogels to form the desired poly(amide imide) structures. During post-processing the parts displayed linear isotropic shrinkage as low as 26% and exhibited competitive thermomechanical properties. Following expansion of the high performance backbones available for additive manufacturing, simplification of synthetic rigors was undertaken. This investigation facilitated the evolution of the first photocurable and processable small molecule polyimide precursors. These supramolecular carboxylate ammonium nylon salts, coined polysalts, allowed for additive manufacturing of both high performance polyimides and polyetherimides using vat photopolymerization (VP). The use of small molecule precursors over previously investigated polymeric precursors displayed much lower solution viscosities yielding reduction of organic solvent loading, inducing lower overall shrinkage. Polysalts provide a stimulating platform for rapid and facile printing of high performance polyimides in the future. Surveying the excellent carbonization behavior for aromatic polyimides spurred translation of known 2D protocols to post-processing of printed polyimides. Applying pyrolysis methodologies to parts produced using VP and UV-DIW induced efficient carbonization at 1000 °C. Remarkably, the carbonized parts retained structure and did not display cracks or pore formation. Raman spectroscopy indicated production of disordered carbon via the utilized pyrolysis protocol, in line with literature on carbonization of PMDA-ODA polyimide at 1000 °C. Electrical testing indicated production of conductive materials following pyrolysis, with carbonization temperature modulating the performance. The excellent thermal stability, transport properties, and known mechanical performance of carbonaceous materials may enable application of these printed objects in customized electronics and aerospace environments. Exploration of drop-in monomeric units permitted a multi-pronged research program into augmentation of mechanical, rheological and transport properties of high performance polyetherimides (PEIs). Installation of sodium or lithium substituted disulfonated monomers via classical two-step polyimide synthesis afforded two series of sulfonated polyetherimides (sPEI). The sPEIs exhibited robust thermal properties, with high sulfonate mol% inducing Tg > 300 °C. X-ray scattering experiments revealed the development of domains via inclusion of the sulfonate moieties, with low mol% producing larger domain spacing. The larger domains present in the low mol% sPEIs yielded improved ionic liquid uptake within 2 d, yielding improved ionic conductivities at room temperature relative to high mol% samples. The observed conductivities indicated potential of the sPEIs as battery electrolytes, but further ionic liquid incorporation is required for competitive performance. Development of a poly(ethylene glycol) (PEG) bearing macromonomer facilitated synthesis of PEIs and PI graft copolymers. When coupled with 4,4'-(4,4'-isopropylidene-diphenoxy)diphthalic anhydride (BPADA) and meta-phenylene diamine (mPD), the PEG-grafted materials exhibited signs of phase mixing at low mol% incorporation of macromonomer, with a single observable Tg depressed from neat BPADA-mPD. Doping of the PEI-g-PEG with lithium salts allowed for production of polymeric films that displayed good ionic conductivities at room temperatures. Extension of the PEG macromonomer into fully aromatic PIs yielded phase separated materials even at modest loadings, >2.5 mol%. The formed PEG-g-PMDA-ODA contained thermally stable PI main-chains with thermally labile graft chains, which when thermally treated induced facile quantitative PEG removal. Remarkably, the thermally treated materials retained flexibility, even at >60 wt.% PEG removal. Further investigations aim to explore use of novel PEIs in energy storage as well as low density and dielectric materials. / Doctor of Philosophy / High performance polymers enjoy wide use in microelectronics and aerospace industries due to high thermal stability and excellent mechanical performance. However, processing restrictions hinder manufacturing of 3-dimensional objects of many high performance polymers suitable for extreme environments. Additive manufacturing, also known as 3D printing, has garnered attention in both academic and industrial settings over the last four decades due to the unmatched control over part design and internal structure, but the material arsenal for additive manufacturing of polymers lacks options for applications demanding high thermal stability. The first half of this dissertation aimed to promote translation of high performance polymeric chemistries to suitable feedstocks for additive manufacturing. By designing and developing novel chemical pathways, traditional processing limitations were circumvented and high performance polymers, such as poly(amide imides) and polyimides, were successfully processed via light based additive manufacturing. Likewise, by investigating carbonization dynamics of polyimides and expanding current additive manufacturing techniques for processing of fully aromatic polyimides, complex 3D carbonaceous materials were obtained. These carbon objects present extreme thermal stability and electrical conductivity, advantageous for aerospace and electronic industries. Additionally, investigations allowed for development of synthetically facile routes for expanding the available polyimide backbones for additive manufacturing via use of small molecule precursors. The second half of the dissertation explored novel polyetherimide and polyimide reagents for production of functional materials. Harnessing ionic building blocks permitted synthesis of a series of thermally robust polyetherimides displaying promise for energy storage. Similarly, coupling previous literature for ion conduction in solid polymer electrolytes for battery applications with thermally stable and flame resistant polyetherimides enabled synthesis of a series of innovative graft copolymers with good room temperature ionic conductivities. Lastly, pairing of thermally labile polymers with thermally resistant polyimide backbones allowed for development of an exciting platform for obtaining highly insulting and flexible films for electronics applications. Outlined future work aims to probe the formation of pores in the obtained polymer

Yes / In order to evaluate the feasibility of using CO2 as a gasifying agent in the conversion of carbonaceous materials to syngas, gasification characteristics of coal, a suite of waste carbonaceous materials, and their blends were studied by using a thermogravimetric analyser (TGA). The results showed that CO2 gasification of polystyrene completed at 470 °C, which was lower than those of other carbonaceous materials. This behaviour was attributed to the high volatile content coupled with its unique thermal degradation properties. It was found that the initial decomposition temperature of blends decreased with the increasing amount of waste carbonaceous materials in the blends. In this study, results demonstrated that CO2 co-gasification process was enhanced as a direct consequence of interactions between coal and carbonaceous materials in the blends. The intensity and temperature of occurrence of these interactions were influenced by the chemical properties and composition of the carbonaceous materials in the blends. The strongest interactions were observed in coal/polystyrene blend at the devolatilisation stage as indicated by the highest value of Root Mean Square Interaction Index (RMSII), which was due to the highly reactive nature of polystyrene. On the other hand, coal/oat straw blend showed the highest interactions at char gasification stage. The catalytic effect of alkali metals and other minerals in oat straw, such as CaO, K2O, and Fe2O3, contributed to these strong interactions. The overall CO2 gasification of coal was enhanced via the addition of polystyrene and oat straw.

Orientador: Maria Del Pilar Taboada Sotomayor / Co-orientador: Ademar Wong / Banca: Gustavo Troinano Feliciano / Banca: Renata Kelly Mendes Valente / Resumo: Este trabalho descreve a preparação e viabilidade de sensores eletroquímicos à base de nanomateriais carbonáceos e catalisadores biomiméticos da enzima P450, visando à obtenção de sensores sensíveis e seletivos para determinação de tetraciclina. Para tal, inicialmente foram construídos sensores eletroquímicos usando pasta de carbono modificada com 10% (m/m) de MWCNT-COOH (nanotubos de carbono de paredes múltiplas funcionalizados com grupos carboxila) e 10% (m/m) de óxido de grafeno (GO). A Voltametria de pulso diferencial adsortiva com varredura anódica (VPDadVA) permitiu obter melhores resultados em solução tampão fosfato 0,1 mol L-1 (pH 7,0); potencial e tempo de acumulação de 0,2 V e 30 s, respectivamente. Sob estas condições o sensor apresentou uma faixa linear de resposta entre 1,2 x 10-5 e 1,7 x 10-4 mol L-1, sensibilidade de 1,2 x 104 (±1,0x103) μA mol L-1 e limite de detecção de 3,6 x 10-8 mol L-1. Este sensor foi aplicado na determinação de tetraciclina em urina sintética, águas de rio e medicamentos, obtendo-se recuperações com valores próximos a 100% e valores de repetibilidade em termos do desvio padrão relativo (DPR) abaixo de 6%. Na segunda etapa do trabalho, visando à obtenção de um sensor biomimético, além dos materiais nanopartículados, as pastas de carbono foram individualmente modificadas, com 11 compostos organometálicos que mimetizam o sitio ativo da enzima P450. Dentre eles, apenas a bispiridilftalocianinaferro (II), cloreto de 5,10,15,20-tetrafenil-21H,23H-porfirinaferro (III) e 1,2,3,4,8,9,10,11,15, 16,17,18,22,23,24,25-hexadecafluoro-29H,31H-ftalocianinacobalto (II) apresentaram resposta promissora usando voltametria cíclica. Entretanto, quando realizados experimentos de quantificação através de VPDadVA nas condições otimizadas, vi nenhum dos sensores mostrou respostas satisfatórias, apesar dos esforços realizados para conseguir a... / Abstract: This work describes the preparation and feasibility of electrochemical sensors based on carbonaceous nanomaterials and biomimetic catalysts of the P450 enzyme, in order to obtain sensitive and selective sensors for determination of tetracycline. For this, electrochemical sensors were initially constructed using carbon paste modified with 10% (w/w) of MWCNTCOOH (carbon nanotubes multi-walled functionalized with carboxyl groups) and 10% (w/w) of graphene oxide (GO). Differential pulse with adsorptive anodic stripping voltammetry (DPadSAV) provided the best results in phosphate buffer 0.1 mol L-1 (pH 7.0) and accumulation potential and time of 0,2 V and 30 s, respectively. Under these conditions the sensor showed a linear response range between 1.2 x 10-5 and 1.7 x 10-4 mol L-1, sensitivity of 1.2 x 104 (± 1,0 x 103) A mol L-1 and detection limit of 3.6 x 10-8 mol L-1. This sensor has been applied to the determination of tetracycline in synthetic urine, river water and pharmaceutical formulations with recovery values close to 100% and repeatability in terms of relative standard deviation (RSD) below 6%. In the second stage of the work in order to obtain a biomimetic sensor, in addition to the nanoparticulate materials, carbon pastes were individually modified, with 11 organometallic compounds that mimic the active site of P450 enzyme. Among them, only bis(pyridil)phthalocyanine iron (II); 5,10,15,20-tetraphenyl-21H, 23H-porphyrin iron (III) chloride and 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine cobalt (II) showed promising response using cyclic voltammetry. However, when performed experiments by VPD and DPadSAV in optimized conditions, none of the sensors showed satisfactory resposes, despite the efforts made to achieve the quantification of tetracycline. viii Showing that in this case, the these compounds did not improve the sensor response previously obtained... / Mestre

Le carbone est un élément essentiel à la surface de la Terre. Il entre aussi bien dans la composition de certains minéraux (carbonates) que dans les molécules du vivant. Les roches métamorphiques contiennent également des matériaux carbonés (MC) dont l’origine peut être variée. Les MC sous forme solide (matériaux carbonés partiellement ou parfaitement graphitisés) jouent un rôle majeur dans l’évolution pétrologique et géochimique d’une roche enfouie en zone de subduction. Si notre connaissance des MC métamorphiques a largement progressée ces dernières années sur la base d’études naturalistes, expérimentales ou théoriques, il reste de nombreuses questions par exemple autour de la détermination des sources des MC dans les roches métamorphiques. Le rôle des minéralisations en tant que facteur de préservation des MC d’origine biologique (biogénique) est encore mal compris. Nous avons étudié des échantillons naturels (formation Marybank, Nouvelle Zélande) métamorphisés dans le facies schiste bleu et contenant des fossiles végétaux graphitisés et montrant une remarquable préservation morphologique. Nous dressons ainsi un inventaire des processus minéralogiques et chimiques ayant contribué à préserver, ou oblitérer, certaines informations portées par le matériau biologique originel, et plus généralement par le fossile. Pour ce faire, nous avons employé des techniques de caractérisation minéralogiques et géochimiques à haute résolution spatiale des MC fossiles et des minéraux. Nous montrons ainsi que la remarquable préservation morphologique s’accompagne d’une recristallisation avancée de la minéralogie et des MC constituant le fossile. Nous mettons aussi en évidence la présence spectaculaire de nanoparticules de TiO2 dans les MC des fossiles et nous discutons des mécanismes possibles de formation de ces minéralisations exceptionnelles.Il existe des mécanismes complexes, abiotiques, fortement liés aux interactions fluide-roche et permettant la formation de MC graphitiques dans les roches métamorphiques. Ces processus rendent complexe l’étude et l’interprétation des MC dans les roches. Toutefois, ils révèlent le rôle majeur des fluides et des assemblages minéraux dans la dynamique métamorphique du carbone. Nous avons réalisé l’étude détaillée d’un contact entre des serpentinites et des métasédiments (Malaspina, Corse Alpine) au niveau duquel les métasédiments sont décarbonatés. A cause des conditions réductrices imposées par les serpentinites sous-jacentes, le carbone inorganique ainsi libéré précipite sous forme de graphite. Nous employons des méthodes géochimiques, minéralogiques et pétrologiques complémentaires qui permettent de distinguer différentes catégories de matériaux carbonés dans ces roches, mais aussi de proposer un scénario bien contraint de formation abiotique du graphite. Cette étude permet alors de discuter du rôle des gradients redox sur la dynamique du carbone dans une roche métamorphique. L’ensemble de ces travaux sont autant d’exemples qui soulignent certains aspects encore peu explorés du rôle pétrologique fondamental des MC dans les roches métamorphiques. / Carbon is an essential element on the Earth’s surface. It is involved in the formation of certain minerals (carbonates) as well as biomolecules. Metamorphic rocks also contain carbonaceous materials (CM) with various possible origins. Solid CM (partially or completely graphitized CM) play a major role in the petrological and geochemical evolution of a subducted rock. If our knowledge of metamorphic CM increased over the last years based on naturalist, experimental or theoretical studies, many issues remain as to the source of CM in metamorphic rocks for example.The role of mineralization as a factor of preservation of CM of biological origin (biogenic) is still poorly understood. We studied natural samples (Marybank formation, New Zealand) metamorphozed in the blueschist facies and which contain carbonaceous plant fossils that display a remarkable morphological preservation at the microscopic scale. We investigate mineralogical and chemical processes that contributed to preserve, or obliterate, information carried by the original biomaterial, and, more generally, by the fossil. To do so, we have characterized the fossils and the minerals using analytical technics with high special resolution. We show that the remarkable morphological preservation is accompanied by the advanced recristallization of the mineralogy compositing the fossils. We also show the presence of spectacular TiO2 mineral nanocristals in the CM composing the fossils and we discuss about possible mechanisms leading to the formation of these exceptional mineralizations.Complex abiotic processes, intimately linked to fluid-rock interactions, allow the formation of graphitic CM in metamorphic rocks. These processes hinder the study and interpretation of CM in rocks. Nevertheless, they also reveal the major role of fluids and mineral assemblages in the metamorphic dynamics of carbon. We carried a detailed study of a contact between serpentinites and metasediments (Malaspina, Alpine Corsica) that display complete carbonate destabilization. Because of the reduced conditions imposed by the underlying serpentinite, the inorganic carbon released has precipitated and formed graphite. We use geochemical, mineralogical and petrological complementary tools that allow to distinguish different categories of CM in these rocks, and we propose a well constrained scenario for the formation for this abiotic graphite. This study allows discussing the role of redox gradients on the dynamics of carbon in a metamorphic rock.These are all examples stressing the important, and yet poorly explored, petrological role of CM in metamorphic rocks.

Μέχρι σήμερα η επίδραση της αλατότητας στη διεργασία της ρόφησης των οργανικών ρύπων σε στερεούς ροφητές έχει μελετηθεί θεωρώντας ότι η ρόφηση είναι μία γραμμική διεργασία που εξαρτάται από το κλάσμα του οργανικού άνθρακα. Μελέτες της τελευταίας δεκαετίας έχουν αποδείξει ότι η ρόφηση των οργανικών στο περιβάλλον δεν είναι απαραίτητα μία γραμμική διεργασία. Για ιζήματα και εδάφη με σωματιδιακούς ανθρακούχους ρύπους, όπως είναι τα σωματίδια της αιθάλης ή των εξανθρακωμάτων, έχουν παρατηρηθεί ισόθερμες καμπύλες οργανικών ρύπων με μεγάλη έλλειψη γραμμικότητας. Προκαταρκτικές μελέτες έχουν δείξει ότι πράγματι η αλατότητα επηρεάζει τη ρόφηση ανάλογα με το μηχανισμό που παρατηρείται για κάθε είδος ροφητή. Αλλιώς επηρεάζεται η ρόφηση από την αλατότητα, όταν λαμβάνει χώρα στην επιφάνεια του ροφητή, και αλλιώς στους πόρους στο εσωτερικό του ροφητή. Η παρούσα μεταπτυχιακή εργασία περιλαμβάνει πειραματική μελέτη της ισορροπίας της ρόφησης ενός οργανικού ρύπου (του φαινανθρενίου) σε διάφορους ροφητές από το γλυκό και το θαλασσινό νερό. Οι ροφητές περιλαμβάνουν ανθρακούχα σωματίδια και ετερογενή υλικά, όπως γαιάνθρακα, λιγνίτη και θαλάσσια ιζήματα από την περιοχή του Αλιβερίου, του Λαυρίου και του Σαρωνικού κόλπου (Λουτρόπυργος) που έχουν ρυπανθεί από τα παραπάνω ανθρακούχα σωματίδια. Η αλατότητα φαίνεται να επηρεάζει σημαντικά τη ρόφηση του φαινανθρενίου σε σωματίδια λιθάνθρακα όταν τα πειράματα διεξάγονται σε σχετικά χαμηλές συγκεντρώσεις (<200 μg/L). / Until recently sorption of organic compounds onto sediments was believed to be a linear process dependent on the organic carbon fraction content. Non linear sorption and heterogeneous behavior based has been recognized the last decade. Due to salinity, various effects are observed for the different carbonaceous materials on the capacity and also on the degree of nonlinearity. Each material presents a different sorption pattern and various effects due to salinity are observed (e.g. coal sorption isotherm becomes linear in the presence of salinity whereas for lignite no significant difference is observed). In the present work, we study the sorption behavior of phenanthrene onto different sorbents in salt water. Sorbents used include carbonaceous materials, coal, lignite, and marine sediments from Aliveri, Laurio, and Saronikos gulf that are polluted with carbonaceous particles. Salinity seems to affect significantly the sorption of phenanthrene onto coal particles if the experiments are performed at concentrations lower than 200 μg/L.

Made available in DSpace on 2015-08-20T17:10:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-04-24. Added 1 bitstream(s) on 2015-08-20T17:25:48Z : No. of bitstreams: 1 000841964.pdf: 1463703 bytes, checksum: 408f5159b85550b011090a5f648d6c32 (MD5) / Este trabalho descreve a preparação e viabilidade de sensores eletroquímicos à base de nanomateriais carbonáceos e catalisadores biomiméticos da enzima P450, visando à obtenção de sensores sensíveis e seletivos para determinação de tetraciclina. Para tal, inicialmente foram construídos sensores eletroquímicos usando pasta de carbono modificada com 10% (m/m) de MWCNT-COOH (nanotubos de carbono de paredes múltiplas funcionalizados com grupos carboxila) e 10% (m/m) de óxido de grafeno (GO). A Voltametria de pulso diferencial adsortiva com varredura anódica (VPDadVA) permitiu obter melhores resultados em solução tampão fosfato 0,1 mol L-1 (pH 7,0); potencial e tempo de acumulação de 0,2 V e 30 s, respectivamente. Sob estas condições o sensor apresentou uma faixa linear de resposta entre 1,2 x 10-5 e 1,7 x 10-4 mol L-1, sensibilidade de 1,2 x 104 (±1,0x103) μA mol L-1 e limite de detecção de 3,6 x 10-8 mol L-1. Este sensor foi aplicado na determinação de tetraciclina em urina sintética, águas de rio e medicamentos, obtendo-se recuperações com valores próximos a 100% e valores de repetibilidade em termos do desvio padrão relativo (DPR) abaixo de 6%. Na segunda etapa do trabalho, visando à obtenção de um sensor biomimético, além dos materiais nanopartículados, as pastas de carbono foram individualmente modificadas, com 11 compostos organometálicos que mimetizam o sitio ativo da enzima P450. Dentre eles, apenas a bispiridilftalocianinaferro (II), cloreto de 5,10,15,20-tetrafenil-21H,23H-porfirinaferro (III) e 1,2,3,4,8,9,10,11,15, 16,17,18,22,23,24,25-hexadecafluoro-29H,31H-ftalocianinacobalto (II) apresentaram resposta promissora usando voltametria cíclica. Entretanto, quando realizados experimentos de quantificação através de VPDadVA nas condições otimizadas, vi nenhum dos sensores mostrou respostas satisfatórias, apesar dos esforços realizados para conseguir a... / This work describes the preparation and feasibility of electrochemical sensors based on carbonaceous nanomaterials and biomimetic catalysts of the P450 enzyme, in order to obtain sensitive and selective sensors for determination of tetracycline. For this, electrochemical sensors were initially constructed using carbon paste modified with 10% (w/w) of MWCNTCOOH (carbon nanotubes multi-walled functionalized with carboxyl groups) and 10% (w/w) of graphene oxide (GO). Differential pulse with adsorptive anodic stripping voltammetry (DPadSAV) provided the best results in phosphate buffer 0.1 mol L-1 (pH 7.0) and accumulation potential and time of 0,2 V and 30 s, respectively. Under these conditions the sensor showed a linear response range between 1.2 x 10-5 and 1.7 x 10-4 mol L-1, sensitivity of 1.2 x 104 (± 1,0 x 103) A mol L-1 and detection limit of 3.6 x 10-8 mol L-1. This sensor has been applied to the determination of tetracycline in synthetic urine, river water and pharmaceutical formulations with recovery values close to 100% and repeatability in terms of relative standard deviation (RSD) below 6%. In the second stage of the work in order to obtain a biomimetic sensor, in addition to the nanoparticulate materials, carbon pastes were individually modified, with 11 organometallic compounds that mimic the active site of P450 enzyme. Among them, only bis(pyridil)phthalocyanine iron (II); 5,10,15,20-tetraphenyl-21H, 23H-porphyrin iron (III) chloride and 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine cobalt (II) showed promising response using cyclic voltammetry. However, when performed experiments by VPD and DPadSAV in optimized conditions, none of the sensors showed satisfactory resposes, despite the efforts made to achieve the quantification of tetracycline. viii Showing that in this case, the these compounds did not improve the sensor response previously obtained...

Summary Combination of PANI and the cost-effective graphite can obtain composites with good electrochemical performance. For the synthesis method of in-situ polymerization of aniline in presence of GNP, the type and content of oxidant can affect the electrochemical properties of PANI/GNP composites. Besides, the addition of excess dopant can influence the electrochemical properties of a PANI-dominated system. The two eco-friendly reduction ways, namely polymerization of dopamine and adding TA, both produced graphite with good dispersion stability and enhanced interaction with PANI. But the reduction effect of dopamine polymerization was weak, and the non-conductivity of PDA has negative effect on the electrochemical performance of the composites. Using the environmental friendly TA is an effective and facile way to produce cost-effective PANI/graphite composites for supercapacitor purpose. Comparing the two types of graphite, rGO showed lower conductivity and more defects in the carbonaceous structure compared to GNP. In my study, the PANI/(GNP-TA) (1:0.1) composites, which was prepared by using APS as oxidant and without dopant, exhibited the highest capacitive ability. In a three-electrode testing system, the PANI/(GNP-TA) composite showed a high specific capacitance of 351.2 F g-1 at 10 mV s 1. The corresponding two-electrode solid-state supercapacitor device exhibited a promising energy density of 2.3 Wh kg-1 at 0.5 A g-1, which was comparable to the commercially available supercapacitors (around 5 Wh kg-1). But for application the rate capability of the composite needs to be enhanced, in order to maintain the good capacitive performance at high current density.

La pompe de gavage ou pompe à carburant est un organe auxiliaire nécessaire au bon fonctionnement d’un véhicule. Elle permet d’acheminer le carburant du réservoir vers les systèmes d’injections du moteur. Cette pompe, constituée d’un moteur électrique entraînant une turbine, permet la mise en mouvement du carburant. Le passage du courant est assuré entre le stator et le rotor par le biais du contact frottant entre deux balais fixes et un collecteur tournant en composite graphite/polymère, immergé en milieu carburant. Ces travaux ont pour but de contribuer à la compréhension de ce contact glissant électrifié immergé. Un tribomètre spécifique a été développé afin de tester différents couples de matériaux balais-collecteur dans des conditions mécaniques, électriques et physico-chimiques variées, tout en mesurant l’usure, l’effort de frottement et la résistance électrique du double contact. De nouvelles nuances de matériaux carbonés s’adaptant aux contraintes chimiques des nouveaux biocarburants présents sur le marché automobile ont été testées et ont mis en évidence différents comportements tribologiques. L’usure observée est principalement due au passage du courant sous forme d’arcs électriques modifiant ainsi la topographie des surfaces. Deux endommagements distincts sont visibles : le cratère et la bosse dont les volumes augmentent avec l’énergie développée par l’arc et sont reliés à la présence subsurfacique de polymère. A partir de ces conclusions expérimentales, un modèle phénoménologique du comportement à l’usure a été proposé. Il permet d’apporter une aide à la compréhension des mécanismes complexes et nombreux, présents dans le frottement des balais et du collecteur. / The fuel pump, an automotive part, is used to transfer the fuel from the tank to the engine injection systems. This pump consists of an electric motor driving a turbine: this induces the fuel flow. The current flow is realized between the stator and the rotor thanks to the friction of two fixed brushes against a slip ring. All elements are made of graphite/polymer composites and are immersed into fuel. The aim of this work is to contribute to the understanding of immersed electrical sliding contacts. A specific tribometer was developed in order to mimic the fuel pump. It allows simultaneous measurement of friction forces, wear and electrical contact resistance for various mechanical, electrical and physicochemical conditions. New carbonaceous materials, specifically designed for new biofuel, exhibited different tribological behaviour. The wear observed is mainly due to the current flow, electrical arcs in particular, which modifies the surface topography. Two kinds of damage were depicted: craters and bumps whose volume increases with the arc-produced energy as a function of the presence of polymer at the vicinity of the surface. Issued from these experimental results, a phenomenological model of the wear behaviour was proposed. It brings new insights into the complex and numerous mechanisms occurring during the friction of the brushes and commutator.

L’utilisation d’un composite Carbone/Carbone 2D est envisagée pour des pièces de structure, travaillant entre 150 et 400°C, dans l’aéronautique civile. Dans ce domaine de température, la durabilité de ces matériaux n’est pas connue car ils n’ont jamais été développés pour de telles applications. Une première approche a permis de corréler la réactivité chimique des constituants élémentaires (fibres et matrices) à leur état d’organisation structurale. Les vieillissements réalisés sur matériau composite ont ensuite mis en évidence qu’un faible taux d’oxydation pouvait conduire à un abaissement significatif des propriétés mécaniques résiduelles. Les fissures et les décohésions consécutives au procédé d’élaboration conduisent à une oxydation préférentielle du composé le plus réactif et à la ruine prématurée du composite par délaminage. L'évolution des propriétés de ce matériau sur de longues durées est finalement discutée afin d’évaluer sa capacité à remplacer les matériaux métalliques dans des pièces aéronautiques. / A 2D Carbon/Carbon composite is envisaged for structural parts, operating between 150 and 400°C, in civil aircraft. In this temperature range, the durability of these materials remains unknown because they have never been developed for this kind of applications. A first approach allowed us to correlate the chemical reactivity of the elemental constituents (fiber and matrix) to their structural organization. Then, thermal ageing tests performed on the composite material have demonstrated that a low rate of oxidation could be responsible to a significant reduction of residual mechanical properties. Cracks and fiber/matrix debonding resulting to the elaboration process create an extended pathway to a preferential oxidation of the most reactive compound. This latter is followed by a premature failure by delamination. The reduction of the material properties over long periods is finally discussed in order to evaluate its ability to replace metallic materials in aircraft structural parts.