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Measuring with high precision the electrical resistance of highly ordered natural graphite samples from a Brazil mine, we have identified a transition at ∼350 K with ∼40 K transition width. The steplike change in temperature of the resistance, its magnetic irreversibility and time dependence after a field change, consistent with trapped flux and flux creep, and the partial magnetic flux expulsion obtained by magnetization measurements, suggest the existence of granular superconductivity below 350 K. The zero-field virgin state can only be reached again after zero field cooling the sample from above the transition. Paradoxically, the extraordinarily high transition temperature we found for this and several other graphite samples is the reason why this transition remained undetected so far. The existence of well ordered rhombohedral graphite phase in all measured samples has been proved by x-rays diffraction measurements, suggesting its interfaces with the Bernal phase as a possible origin for the high-temperature superconductivity, as theoretical studies predicted. The localization of the granular superconductivity at these two dimensional interfaces prevents the observation of a zero resistance state or of a full Meissner state.

Une pile à combustible microbiennes (PCM) est un dispositif capable de produire de l’énergie électrique à partir d’énergie chimique grâce à l’activité catalytique des bactéries en présence de combustibles organiques. Ces travaux de thèse ont eu pour objectif la synthèse des nouveaux matériaux d’anode et de cathode qui pourraient constituer des alternatives aux matériaux à base de platine. Coté anode, nous avons synthétisé des matériaux par précipitation chimique sur du graphite en poudre à partir de mélanges contenant des ions ferreux et sulfures. Les caractérisations physicochimiques ont montré la formation de composés soufrés (mackinawite, polysulfures et soufre élémentaire) qui se transforment en produits soufrés plus oxydés en présence d’air. La formation de vivianite a été confirmée dans le cas d’un excès d’ions ferreux par rapport aux ions sulfures. Les analyses électrochimiques montrent que ces matériaux ont un comportement réversible avec des densités de courant d’oxydation élevées à bas potentiel. Coté cathode, nous avons choisi la synthèse par voie électrochimique d’un film de MnOx sur substrat d’acier inoxydable. Les caractérisations physicochimiques ont démontré la formation de la birnessite. Les analyses électrochimiques montrent que la réduction de ce matériau conduit à des courants cathodiques significatifs mais avec une réversibilité limitée, même en présence d’air. La réalisation de prototypes de PCM dans lesquels l’anode à base de composés soufrés est immergée dans une solution de terreau et la cathode à base de MnOx est au contact de l’air, a permis d’obtenir des puissances instantanées maximales de l’ordre de 12 W.m-3 et 1,8 W.m-2, et des densités de courant de l’ordre de 25 A.m-3 et 3,8 A.m-2. Un travail d’optimisation du fonctionnement de PCM a été réalisé. Ainsi, l’augmentation de la conductivité de la solution anodique et la diminution de quantité de sédiment dans la solution de terreau a permis d’améliorer la réponse électrochimique du matériau anodique et d’obtenir des puissances instantanées maximales de l’ordre de 17,5 W.m-3 et 2,7 W.m-2, et des densités de courant de l’ordre de 60 A.m-3 et 9,2 A.m-2. Le facteur limitant reste toujours le comportement électrochimique du film de MnOx. / A microbial fuel cell (MFC) is a device allowing the production of electric power from chemical energy thanks to the catalytic activity of bacteria in presence of organic fuel. These works aimed the synthesis of new anode and cathode materials which could be an alternative to platinum materials. On the anode side, we synthesized the materials by chemical precipitation on powder graphite from mixtures containing ferrous and sulfide ions. Physicochemical characterizations showed the formation of sulfur compounds (mackinawite, polysulfide and elementary sulfur) which transform into sulfur products more oxidized in presence of air. Formation of vivianite was confirmed in the case of an excess of ferrous ions in relation to sulfide ions. Electrochemical analysis shows that these materials have a reversible behavior with high current densities at low voltage. On the cathode side, we chose electrochemical synthesis of an MnOx film on stainless steel substrate. Physicochemical characterizations showed birnessite formation. Electrochemical analysis show that the reduction of this material Leeds to significative cathodic currents but with a limited reversibility, even in presence of air. The realization of MFC prototypes in which the sulfur compounds-based anode is submerged in compost solution and the MnOx-based cathode is in contact with air, allowed the getting of maximum instantaneous powers on the order of 12 W.m-3 and 1,8 W.m-2, and current densities on the order of 25 A.m-3 et 3,8 A.m-2. An optimization work of the MFC functioning has been done. So, the conductivity increase of the anodic solution and the decrease of sediment quantity in the compost solution allowed the improvement of the electrochemical response of the anodic material and to obtain maximal instantaneous powers on the order of 17,5 W.m-3 and 2,7 W.m-2, and current densities on the order of 60 A.m-3 et 9,2 A.m-2. The limiting factor remains the electrochemical behavior of the MnOx film.

New methods to fabricate nanometer sized structures will be a major driving force in transforming nanoscience to nanotechnology. There are numerous examples of the incorporation of nanoscale structures or materials enhancing the functionality of a device. Graphitic carbon is a widely used material in electroanalysis due to a number of advantageous properties such as wide potential window, low cost, mechanical stability, and applicability to many common redox systems. In this thesis, the fabrication of nanometer sized graphitic carbon structures is described. These structures were fabricated by using a combination of electron-beam lithography (EBL) and pyrolysis. EBL allows for the precise control of shape, size and location of these carbon nanostructures. The structure and electrochemical reactivity of thin films of the pyrolyzed material is initially examined. The methodology to fabricate nanosized carbon structures and the structural and electrical characterization of the nanostructure is presented. The nanometer sized carbon structures fabricated in this work are being applied as nanoelectrodes. For nanoband structures, we observe a limiting current plateau which is characteristic of radial diffusion to cylindrical ultramicroelectrodes. Their voltammetric behaviour shows good agreement with classical theoretical predictions. Both carbon film and nanoband electrodes have been used as substrates for metal electrodeposition. The size and morphology of the deposited Au particles depends greatly on the substrate. On the nanoband electrodes, the Au particles exhibit a multi-branched or dendridic morphology. Their size and surface area are much larger than those electrodeposited on the carbon film electrode under the same conditions. The surface enhanced Raman spectroscopy (SERS) properties of the gold deposited on the nanobands was studied. A high enhancement in Raman intensity for a molecular layer on the nanoband supported gold is observed.

Small graphite-moderated and gas-cooled reactors have been around since the beginning of the atomic age. Though their existence in the past has been associated with nuclear weapons programs, they are capable of being used in civilian power programs. The simpler design constraints associated with this type of reactor would make them ideal for developing nations to bolster their electricity generation and help promote a greater standard of living in those nations. However, the same benefits that make this type of reactor desirable also make it suspicious to the international community as a possible means to shorten that state?s nuclear latency. If a safeguards approach could be developed for a fuel cycle featuring one of these reactors, it would ease the tension surrounding their existence and possibly lead to an increased latency through engineered barriers. The development of this safeguards approach follows a six step procedure. First, the fuel cycle was analyzed for the types of facilities found in it and how nuclear material flows between facilities. The goals of the safeguards system were established next, using the normal IAEA standards for the non-detection and false alarm probabilities. The 5 MWe Reactor was modeled for both plutonium production and maximum power capacity. Each facility was analyzed for material throughput and the processes that occur in each facility were researched. Through those processes, diversion pathways were developed to test the proposed safeguards system. Finally, each facility was divided into material balance areas and a traditional nuclear material accountancy system was set up to meet the established safeguards goals for the facility. The DPRK weapons program is a great example of the type of fuel cycle that is the problem. The three major facilities in the fuel cycle, the Fuel Fabrication Facility, the 5 MWe Reactor, and the Radiochemical Laboratory, can achieve the two goals of safeguards using traditional methods. Each facility can be adequately safeguarded using methods and practices that are relatively inexpensive and can obtain material balance periods close to the timeliness limits set forth by the IAEA. The Fuel Fabrication Facility can be safeguarded at both its current needed capacity and its full design capacity using inexpensive measurements. The material balance period needed for both capacities are reasonable. For the 5 MWe reactor, plutonium production is simulated to be 6.7 kg per year and is on the high side of estimates. The Radiochemical Laboratory can also be safeguarded at its current capacity. In fact, the timeliness goal for the facility dictates what the material balance period must be for the chosen set of detectors which make it very reasonable.

The amount and morphology of the graphite phase largely controls the resulting properties of cast iron. For instance, in flake graphite cast irons the mechanical properties are low while the thermal conductivity is high. This is in contrast with spheroidal graphite cast irons where the mechanical properties are high and the thermal conductivity is low. These differences are due to the different graphite morphologies and must be accounted for in the design work and material selection of cast iron components. In this work the influence of the graphite phase on the elastic and plastic deformation behaviour of cast irons has been studied. The material grades studied originate from castings for marine diesel engine piston rings with different chemical analyses. Two groups of pearlitic cast iron materials were studied; one with differences in graphite morphology and one with grey irons that differed in graphite content. For these different material grades the mechanical properties were correlated to microstructural parameters. In addition to standard uniaxial tensile tests, acoustic emission measurements were used for the study of deformation. When studying the modulus of elasticity of the cast iron it was found that the modulus of elasticity of the inherent graphite phase depends on the roundness of the graphite particles and is due to the strong anisotropy of the graphite phase. A linear correlation between nodularity and the modulus of elasticity of the graphite phase was derived. This correlation made it possible to account for the anisotropy of the graphite phase in the model used. By applying the linear function when modelling the effective modulus of elasticity, a high accuracy between experimental and theoretical values was achieved. Another factor affecting the elastic response when subjecting a cast iron component to tensile load was found to be the plastic deformation that actually occurs at very low strains for all of the studied cast iron grades. It was observed that the plastic deformation in the low strain elastic region, quantified by using acoustic emission measurements, increased linearly with decreasing modulus of elasticity. These measurements showed that the amount of plastic deformation in the elastic region was largely controlled by the graphite morphology. It was concluded that as the roundness of the graphite particles increases, the plastic deformation activity in the elastic region decreases. The plastic deformation activity continued linearly into the pronounced plastic region of the tensile tests. A decrease in roundness or increase in graphite fraction resulted in an increase of the amount of plastic deformation and the strain hardening exponent. A dependence between strength coefficient and graphite fraction was observed. Models for the flow curves for pearlitic cast irons were developed and shown to accurately reproduce the observed experimental curves. The surveys performed and conclusions from this thesis will be helpful in the design of new cast iron materials.

This thesis proposes a modified structure model for graphite oxide (GO), an important precursor in graphene chemistry, develops a new strategy to convert GO back to graphene-like structure, and demonstrates its possible applications in both water purification and supercapacitor technologies. GO, a nontraditional compound first obtained from graphite oxidation over 150 years ago, is now becoming an important player in the production of graphene-based materials, which has high technological relevance. GO structure and reduction have been vigorously investigated, but its precise chemical structure still remains obscure, and the complete restoration of the sp2 carbon lattice has not yet been achieved. In our work, solid state 13C NMR (MAS) analysis offered a piece of evidence for five or six-membered ring lactol structure existing in GO that had never been assigned before, leading to a modified Lerf-Klinowski model for GO. A three-step reduction strategy, involving sodium borohydride (NaBH4), sulfuric acid, and high temperature thermal annealing, described in the thesis, successfully reduced GO back to chemically converted graphene (CCG) with the lowest heteroatom abundance among all those previously reported. In addition to the chemical significance of graphene/CCG production, GO and its derivatives were used as novel adsorbents in water purification. GO-coated sand showed higher retention than ordinary sand for both Rhodamine B and mercuric ion (Hg2+) contaminants in water. Further functionalization of GO with thiophenol resulted in better adsorption capacity toward Hg2+ than that of activated carbon. In addition, free-standing films of GO were treated and reduced with a CO2 laser beam into different conductive reduced GO (RGO) patterns, and directly used as supercapacitor devices which showed good cyclic stability and energy storage capacities comparable to that of existing thin film ultracapacitors. GO turned out to be a solid electrolyte with anisotropic proton conductivity similar to Nafion, while the large amount of trapped water in GO played an important role.

Small graphite-moderated and gas-cooled reactors have been around since the beginning of the atomic age. Though their existence in the past has been associated with nuclear weapons programs, they are capable of being used in civilian power programs. The simpler design constraints associated with this type of reactor would make them ideal for developing nations to bolster their electricity generation and help promote a greater standard of living in those nations. However, the same benefits that make this type of reactor desirable also make it suspicious to the international community as a possible means to shorten that state?s nuclear latency. If a safeguards approach could be developed for a fuel cycle featuring one of these reactors, it would ease the tension surrounding their existence and possibly lead to an increased latency through engineered barriers. The development of this safeguards approach follows a six step procedure. First, the fuel cycle was analyzed for the types of facilities found in it and how nuclear material flows between facilities. The goals of the safeguards system were established next, using the normal IAEA standards for the non-detection and false alarm probabilities. The 5 MWe Reactor was modeled for both plutonium production and maximum power capacity. Each facility was analyzed for material throughput and the processes that occur in each facility were researched. Through those processes, diversion pathways were developed to test the proposed safeguards system. Finally, each facility was divided into material balance areas and a traditional nuclear material accountancy system was set up to meet the established safeguards goals for the facility. The DPRK weapons program is a great example of the type of fuel cycle that is the problem. The three major facilities in the fuel cycle, the Fuel Fabrication Facility, the 5 MWe Reactor, and the Radiochemical Laboratory, can achieve the two goals of safeguards using traditional methods. Each facility can be adequately safeguarded using methods and practices that are relatively inexpensive and can obtain material balance periods close to the timeliness limits set forth by the IAEA. The Fuel Fabrication Facility can be safeguarded at both its current needed capacity and its full design capacity using inexpensive measurements. The material balance period needed for both capacities are reasonable. For the 5 MWe reactor, plutonium production is simulated to be 6.7 kg per year and is on the high side of estimates. The Radiochemical Laboratory can also be safeguarded at its current capacity. In fact, the timeliness goal for the facility dictates what the material balance period must be for the chosen set of detectors which make it very reasonable.

The carbonaceous material possesses many kinds of structures and extensive applicability. For example, they are used for lithium battery and fuel cell electrode, printer¡¦s carbon powder, and for the reinforcement of tire. The carbon nanotube and carbon nanocapsule are the novel carbonaceous materials. Their unique property and applicability have attracted a lot of investigation. In this research, we attempt to understand the relationship between the structures and chemical properties of the carbonaceous material. Graphite is an ideal model for this study, and the temperature-programmed desorption method is applied in this investigation. XRD and TEM are also used to support the results of TPD method. Four kinds of exploration molecules are chosen. They are benzene-like molecules, cyclohexane-like molecules, long chain molecules and alcohol-like molecules, respectively. We attempt to find out the differences of the interaction between graphite and various kinds of molecules. The benzene-like molecules with alkyl branch are strongly adsorbed on graphite. The adsorption of long chain molecules on graphite is the next. There are more than one kind of adsorption site on graphite available for 1,3-hexadiene and alcohol-like molecules adsorption. The adsorption behavior of 1,3-hexadiene and alcohol molecules are more complicated. Although the desorption activation energy for different molecules on graphite with different coverages are different. The difference in the desorption activation energy are negligible. The tendency of change is similar for the same kind of molecules. The adsorbed molecules can also diffuse into graphite¡¦s interlayer structure. The interlayer distance of graphite can be changed by the diffusion process of the adsorbed molecules. The desorption activation energies may change when graphite¡¦s pore size changes or functional groups exist on graphite surface. The changes of the activation energy caused by the change of graphite¡¦s pore size or by the surface functional groups are more prominent than the changes induced by the coverage difference of adsorbed molecules on graphite.

Thesis (Ph. D.)--University of Missouri-Columbia, 1999. / Typescript. Vita. Includes bibliographical references (leaves 304-307). Also available on the Internet.