Eletrodos compósitos a base de grafite e resina poliuretana de origem vegetal foram preparados e avaliados quanto ao seu desempenho em relação à determinação voltamétrica e amperométrica de hidroquinona, paracetamol e atenolol. Os eletrodos foram preparados sob pressões diferentes em prensa hidráulica, demonstrando que quanto maior a pressão, maior a corrente medida para uma mesma solução, até um valor limite. O ferricianeto de potássio foi usado como sonda eletroquímica para testes de desempenho do eletrodo em voltametria de onda quadrada (SWV) e por análise em fluxo (FIA), com detecção amperométrica com o eletrodo compósito 60% (grafite, m/m) como eletrodo de trabalho. A hidroquinona (HQ) foi determinada em SWV e FIA, com limites de detecção (LD) da ordem de 283 nmol L-1 e 100 mol L-1, respectivamente. A determinação de HQ em reveladores fotográficos forneceu resultados que concordam com o método de comparação em cromatografia líquida de alta eficiência (HPLC) com 95% de confiança. Determinação de paracetamol (APAP) em voltametria de pulso diferencial (DPV), eletrodo de disco rotatório (RDE), FIA e cronoamperometria levaram a limites de detecção de 3,9; 2,6; 18,9 e 6,7 mol L-1, respectivamente, usando o eletrodo compósito 60% (grafite, m/m). O APAP foi determinado em formulações farmacêuticas comerciais, com o compósito, em DPV e FIA, com resultados concordantes com HPLC, com 95% de confiança. Estudos também foram feitos na determinação de atenolol (ATN) em DPV e FIA, com limites de detecção de 3,2 e 18,1 mol L-1, respectivamente, usando o eletrodo compósito 60% (grafite, m/m). Em formulações farmacêuticas foi possível determinar o ATN em concordância com resultados de HPLC. Houve interferência de ácido ascórbico no APAP e furosemida e propanolol no caso do ATN. Entretanto, os concomitantes presentes em formulações farmacêuticas não interferiram e procedimentos de adição de padrão permitiram obter resultados satisfatórios em DPV. Em FIA não foi necessário fazer adição de padrão. Apenas o ATN se adsorve na superfície do eletrodo, usando DPV, mas foi possível determiná-lo sem necessidade de renovação de superfície entre medidas sucessivas, inclusive em fluxo. Em todos os casos o compósito foi mais sensível que o carbono vítreo, talvez pela presença de grupos funcionais no polímero. / Composite electrodes from graphite and vegetal polyurethane resin were prepared and evaluated in relation to their performance in voltammetric and amperometric determination of hydroquinone (HQ), acetaminophen (APAP) and atenolol (ATN). The electrodes were cured under different pressures in an hydraulic press showing that as higher the pressure, higher the current measured for a same solution, until a limiting value. Potassium ferricyanide was used as an electrochemical probe to test the performance of the electrode in square wave voltammetry (SWV) and as a rotating disc electrode (RDE). The HQ was determined using SWV and FIA, with amperometric detection at the composite electrode as a working electrode. Limits of detection (LD) of 283 nmol L-1 and 100 mol L-1 were obtained in SWV and FIA, respectively. The determination of HQ in photographic developers showed results that agreed a comparison method based on of high performance liquid chromatography (HPLC) with 95% of confidence. The APAP was determined in differential pulse voltammetry (DPV), RDE, FIA and chronoamperommetry, with LD 3.9, 2.6, 18.9 and 6.7 mol L-1, respectively, using the graphite-PU 60 % (graphite, w/w) composite electrode. The procedure was applied in the determination of APAP in commercial pharmaceutical formulations, at the composite in DPV and FIA with results that agreed with HPLC at 95% confidence level. The ATN was also determined using DPV and FIA, with LD of 3.2 and 18.1 mol L-1, respectively. In pharmaceutical formulations it was possible to determine the ATN in agreement with results of HPLC. Interference of ascorbic acid in the APAP and furosemide and propanolol using ATN determinations were observed. However, the concomitants present in pharmaceutical formulation did not interfere and standard addition procedures permitted to obtain satisfactory results in DPV. In FIA, standard addition was not necessary, being the analytes determined on the bases of analytical curves. Only ATN adsorved in the surface of the electrode using DPV, but it was possible to determine it without necessity of surface renovation between successive measurements, including in FIA. In all cases, the composite was more sensitive than glassy carbon (GC), probably due to the presence of functional groups in the polymer and/ or because of the active area of the composite.

A modificação e/ou a funcionalização de eletrodos têm por objetivos o desenvolvimento de métodos eficazes para a preparação de eletrodos quimicamente modificados (EQMs) que possam aliar melhorias em sua sensibilidade, seletividade e reatividade em relação aos eletrodos base. Entretanto, a estabilidade e a reprodutibilidade dos EQMs quanto ao processo de lixiviação dos modificadores precisam ser melhorados para que se possam obter eletrodos mais robustos com longo tempo de análise. Uma das possibilidades para se obter eletrodos mais estáveis é por meio de uma ligação estável do tipo covalente entre o eletrodo base e o modificador. Desta forma este trabalho tem por objetivo a funcionalização da grafite por meio de uma reação covalente entre os modificadores cloreto de 4-nitrobenzoíla (4-NB), cloreto de 3,4-dihidroxibenzoíla (3,4-DHB) e do cloreto de 2,2?-bipiridina 4,4?-dicarbonílico (2,2-BP) por meio de uma reação de acilação de Friedel-Crafts assistida por radiação de microondas. O material de síntese foi caracterizado por voltametria cíclica, espectroscopia de infravermelho, curvas termogravimétricas e térmicas diferenciais e espectroscopia de impedância eletroquímica em comparação com a mistura física entre a grafite e os modificadores. Além disso, realizou-se uma generalização da síntese de Friedel-Crafts para outros substratos carboníferos eletródicos como os nanotubos e as fibras de carbono, além de algumas aplicações dos materiais funcionalizados, como exemplos, a grafite funcionalizada e as fibras de carbono funcionalizadas com o derivado bipiridínico (GFT-2,2BP e CNF-2,2BP), por meio de uma ligação entre as bipiridinas funcionalizadas covalentemente nos materiais carboníferos e alguns complexos de rutênio tais como [Ru(bpy)2(OH2)2](PF6)2, [RuCl2(PPh3)3] e do precursor RuCl3.3H2O em eletrooxidações de compostos orgânicos. Para a grafite funcionalizada com nitro derivado (GFT-4NB), realizou-se a eletrooxidação de NADH sobre o potencial redox da hidroxilamina/nitroso. Os resultados dos experimentos de EIS demonstram que a grafite funcionalizada possui uma maior resistência que o material obtido por mistura física. Isto seria esperado já que a formação da ligação covalente afeta a deslocalização de elétrons pi. Finalmente esta metodologia seria uma plataforma geral para a preparação de grafite covalentemente modificada com derivados cujas moléculas possui aplicações de interesse. Assim, o material obtido por este método pode ser usado em aplicações como em eletrodos de pasta de carbono, eletrodos impressos, filmes finos e nanocompósitos e mesmo como um catalisador em reações químicas. Desde que a resposta eletroquímica é muito sensível ao eletrólito, este trabalho abriu uma larga variedade de estudos para entender a interação desses materiais no meio aquoso e orgânico. / Modification and/or functionalization of eletrodic materials have been investigated in order to improve the application of chemically modified electrode (CME) regards on their sensitivity, selectivity and reactivity comparing with unmodified substrate. However, the stability and reproducibility of these CME are one of the most important goals to achieve mainly regarding on the lixiviation of the modifier molecule. Quimisorption is one way to obtain very stable modified materials, since the redox mediator is attached to the substrate by covalent bound. Still it is very important to study the stability and chemical reactivity of these materials. The aim of this work is to synthesize graphite, carbon nanotube and carbon fiber with 4-nitrobenzoíl chloride (4-NB), 3,4-dihidroxibenzoíl chloride (3,4-DHB) and 2,2-bipyridine- 4,4-dicarbonil chloride (2,2-BP) in Friedel-Crafts condition mediated by microwave radiation. The materials were characterized by cyclic voltammetry (CV), using carbon paste electrode (CPE), infrared spectroscopy (IR), thermo gravimetric (TG) and differential thermal analysis (DTA) and electrochemical impedance spectroscopy (EIS). All of the synthesized graphite derivatives were compared with the respective physical mixtures. Moreover, graphite derivatives with bipyridine were used as a ligand in the synthesis with [Ru(bpy)2(OH2)2](PF6)2, [RuCl2(PPh3)3] and RuCl3.3H2O. These products were used as electrocatalysts to oxidize alcohols in comparison with the complex incorporated in graphite. Graphite obtained from 4-NB reaction was employed to oxidize NADH in the redox potential of hydroxylamine/nitroso derived. Results from EIS measurements have show that graphite functionalized has higher resistance than the material obtained by physical mixture. This would be expected since the covalent bound would affect a pi electron dislocation. In conclusion, this methodology would be a general platform to prepare graphite and derivatives covalently bounded to molecules that have interesting application. In addition, it\'s been shown that the catalytic property of the respective function organic hasn\'s changed after reaction with carbon substrate. Thus the material obtained by this method could be used in applications such as carbon paste electrodes, finger print electrodes, thin films and nanocomposites and even as a catalyst in chemical reaction. Since the electrochemical response is very sensitive regards on the electrolyte, this work opened a wide range of studies to understand the interaction of these materials in aqueous and organic medium.

This thesis supports the Master of Fine Arts exhibition at the Slocumb Galleries in Ball Hall at East Tennessee State University, from February 23rd through February 27th 2009. The exhibition is comprised of eight graphite drawings, one ink drawing, eight vinyl prints, two hundred sixty lenticular prints, over fifty digital inkjet prints, and one video installation. The exhibition presents the artist's exploration into using drawings and prints as installation as they relate to quantum physics and universal scale. Subjects discussed, on a project-by-project basis, include thought, ideas, methods, influences, and process by which the work in the exhibition was achieved.

L'objectif de ce travail a été de proposer une méthode permettant d'augmenter la résistance à l'oxydation et à la corrosion par Si liquide des creusets de graphite utilisés dans la purification de Si métallurgique pour obtenir Si de qualité photovoltaïque. La Thèse est constituée de deux parties. Dans la première partie, nous étudions les interactions capillaires (mouillage, infiltration, réactivité) Si/graphite, et l'effet de ces interactions sur la pollution de Si et sur l'intégrité mécanique du graphite. Dans la deuxième partie nous mettons au point un traitement de siliciuration du graphite et nous montrons que ce traitement confère au graphite une résistance remarquable à l'oxydation à haute température

Etude structural de l'arrangement d'espèces insérées dans le graphite par EXAFS. Cette technique, parfaitement adaptée à l'étude de composés non cristallins, permet d'obtenir des informations structurales locales autour d'un atome donné. L'étude réalisée sur les CIG : MCl₂ (M = Ni, Co) a permis de révéler la présence d'une distorsion des octaèdres MCl⁶ au sein du réseau graphitique. La structure du composé d'intercalation de SnF₄ a été déterminée par diffraction X, EXAFS et spectroscopie Mössbauer. Une transition de phase au voisinage de 150 K a été mise en évidence. Enfin, de nouveaux GIG à base de fluorures de chrome et de vanadium ont été synthétisés et ont fait l'objet d'une étude par spectroscopie d'absorption X (EXAFS + XANES).

<p>Reliable ways of storing energy are crucial to support our modern way of life; lithium-ion batteries provide an attractive solution. The constant demand for higher energy density, thinner, lighter and even more mechanically flexible batteries has motivated research into new battery materials. Some of these will be explored in this thesis.</p><p>The main focus is placed on the development of new anode materials for lithium-ion batteries and the assessment of their electrochemical and structural characteristics. The materials investigated are: natural Swedish graphite, SnB₂O₄ glass and intermetallics such as: Cu₆Sn₅, InSb, Cu₂Sb, MnSb and Mn₂Sb. Their performances are investigated by a combination of electrochemical, <i>in si</i>tu X-ray diffraction and Mössbauer spectroscopy techniques, with an emphasis on the structural transformations that occur during lithiation.</p><p>The intermetallic materials exhibit a lithium insertion/metal extrusion mechanism. The reversibility of these reactions is facilitated by the strong structural relationships between the parent compounds and their lithiated counterparts. Lithiation of a majority of the intermetallics in this work proceeds via an intermediate ternary phase. The intermetallic electrodes provide high volumetric capacities and operate at slightly higher voltages vs. Li/Li⁺ than graphite. This latter feature forms the basis for a safer system.</p><p>Jet-milling of natural Swedish graphite results in decreased particle and crystallite size, leading to improved performance; the capacity is close to the theoretical capacity of graphite. Jet-milled graphite also shows an enhanced ability to withstand high charging rates.</p>

Reliable ways of storing energy are crucial to support our modern way of life; lithium-ion batteries provide an attractive solution. The constant demand for higher energy density, thinner, lighter and even more mechanically flexible batteries has motivated research into new battery materials. Some of these will be explored in this thesis. The main focus is placed on the development of new anode materials for lithium-ion batteries and the assessment of their electrochemical and structural characteristics. The materials investigated are: natural Swedish graphite, SnB2O4 glass and intermetallics such as: Cu6Sn5, InSb, Cu2Sb, MnSb and Mn2Sb. Their performances are investigated by a combination of electrochemical, in situ X-ray diffraction and Mössbauer spectroscopy techniques, with an emphasis on the structural transformations that occur during lithiation. The intermetallic materials exhibit a lithium insertion/metal extrusion mechanism. The reversibility of these reactions is facilitated by the strong structural relationships between the parent compounds and their lithiated counterparts. Lithiation of a majority of the intermetallics in this work proceeds via an intermediate ternary phase. The intermetallic electrodes provide high volumetric capacities and operate at slightly higher voltages vs. Li/Li+ than graphite. This latter feature forms the basis for a safer system. Jet-milling of natural Swedish graphite results in decreased particle and crystallite size, leading to improved performance; the capacity is close to the theoretical capacity of graphite. Jet-milled graphite also shows an enhanced ability to withstand high charging rates.

High temperature synthesis of nanocrystals in non-polar solvents typically produces materials with narrow size distribution and high yields. However, the mechanism leading to the preservation of monodispersity on depletion of monomers is not understood, for example, in the case of iron oxide nanoparticles. In our study, it was found that oleic acid, a surfactant added to the mixture of iron precursor and solvent, gradually decomposed to release carbon monoxide at 320°C. This strong reducing gaseous product had a substantial impact on the size distribution of nanocrystals produced. The reduced forms of iron oxide catalyzed the disproportionation of carbon monoxide resulting in a graphitic carbon deposit on the surface of nanoparticles. The graphite coating inhibited further growth of particles and prevented Ostwald ripening. Graphite presence was demonstrated by Raman spectroscopy and Fourier transform infrared spectroscopy. It was found that the amount of graphite deposited on the surface of nanocrystals increased with time at 320°C. Quantitative data regarding the carbon content was obtained by thermo gravimetric analysis and energy dispersive spectrometry. The surface activity of the nanocrystals was shown to be affected by the carbon coating in applications such as arsenic removal.

This thesis investigates the chemistry of graphene from its basic synthesis to further modulation of its structure, geometry and surface chemical functional groups. A series of wet chemistry and dry chemistry experiments were performed. The wet chemistry includes the diazonium salt functionalization, graphene oxidation and reduction, nanotube unzipping chemistry, graphite intercalation and exfoliation. The dry chemistry includes chemical vapor deposition and solid carbon source synthesis of graphene, the control of domain size and stacking order, graphene hydrogenation and lithographically patterned graphene superlattices. With all these chemical approaches, graphene's electrical and optical properties, solubility in organic solvents, crystallography, and chemical reactivity were carefully investigated and discussed. In addition to the fundamental chemistry of graphene, the bio- and environmental impact of this new material was also taken into consideration and investigated.

La propriété de graphite des lacs Guéret et Guinécourt est localisée à environ 300 km au nord-nord-ouest de la ville de Baie-Comeau. Cette propriété se situe dans le Terrane de Gagnon, dans la région Parautochtone de la Province de Grenville. Ce secteur n'est pas étranger à l'exploration minière. En effet, dans les années 1950, plusieurs travaux furent menés, le but de ceux-ci étant de définir le potentiel en formations de fer apparentées à celles du Groupe de Knob Lake comme celles trouvées à Fermont, Labrador City, Schefferville et Gagnon. Puis au début des années 2000, après un hiatus de quarante années, de grandes quantités de graphite furent mises au jour par les compagnies Exploration Esbec, Quinto Technology Inc. et SOQUEM Inc.. On dénombre trois types de graphite dans la région, soit du graphite macrocristallin, du graphite microcristallin et du graphite en veine. La minéralisation graphiteuse est contrôlée par la Formation de Menihek du Groupe de Knob Lake et confinée dans celle-ci. Les trois types de graphite ont une distribution particulière à l'intérieur de la Formation de Menihek. Le graphite macrocristallin est associé à un schiste quartzo-feldspathique tandis que le graphite microcristallin et celui en veine sont associés à un méta-mudstone graphiteux. Le contrôle stratigraphique du graphite s'observe tant au niveau local qu'au niveau régional, soit entre les lacs Guinécourt au Québec et Wabush Lake au Labrador. L'étude de la répatition des gisements de graphite en comparaison avec les types de formations de fer de la Formation de Sokoman a permis l'élaboration d'un outil d'exploration. Cet outil est minéralurgique et met en compte la dichotomie existante entre le graphite et l'hématite. Cette dichotomie montre que la minéralisation graphiteuse est absente lorsqu'il y a présence d'hématite primaire. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Graphite, Hématite, Dichotomie, Formations de fer, Province de Grenville, Terrane de Gagnon, Groupe de Knob Lake.