Thesis (Ph. D.)--Florida State University, 2006. / Advisor: James S. Brooks, Florida State University, College of Arts and Sciences, Dept. of Physics. Title and description from dissertation home page (viewed Sept. 20, 2006). Document formatted into pages; contains xiii, 106 pages. Includes bibliographical references.

Thesis (M. Eng.)(Chemical Engineering)--University of Pretoria, 2006. / Accompanied by a CD-ROM containing Matlab programs. Includes bibliographical references. Available on the Internet via the World Wide Web.

Thesis (Ph.D.)(Chemistry)--University of Pretoria, 2007. / Includes summary. Includes bibliographical references. Available on the Internet via the World Wide Web.

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

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1994. / Vita. Abstract. Includes bibliographical references (leaves 222-230). Also available via the Internet.

Increased public awareness, stricter legislation standards, and environmental and health effects associated with water pollution are driving the development of improved wastewater treatment techniques. In order to meet these challenges, a novel and cost effective process has been developed at the University of Manchester to treat water contaminated with dissolved organics by exploiting a combination of adsorption and electrochemical regeneration. Adsorption of organics takes place on the surface of a non-porous and highly electrically conductive graphite adsorbent, followed by anodic electrochemical regeneration leading to oxidation of the adsorbed organic contaminants. The mechanism of degradation of adsorbed organics during electrochemical regeneration is particularly important from the point of view of the breakdown products. Ideally, complete oxidation of the adsorbed organics to CO2 and H2O should occur, but it is also possible that intermediate by-products may be formed. These breakdown products could be released into the water, be released as gases during the regeneration process or may remain adsorbed on the surface of the adsorbent. Information about the breakdown products is an important requirement for the commercial application of the process. This PhD project focused on an investigation of the formation of intermediate oxidation products released into the water (liquid phase) and with the regeneration gases. Phenol was chosen as a model pollutant and a graphite intercalation compound (GIC) adsorbent, Nyex®1000 (Arvia® Technology Ltd) was used. The main oxidation products formed during both batch and continuous adsorption with electrochemical regeneration were 1,4-benzoquinone, maleic acid, oxalic acid, 4-chlorophenol and 2,4-dichlorphenol. These compounds were detected in small concentrations compared to the overall concentration of the phenol removed. Two mechanisms of organic oxidation during electrochemical regeneration of the GIC adsorbents were identified. The first was the complete oxidation of the adsorbed species on the surface of the adsorbent and the second involved the indirect electrochemical oxidation of organics in solution. Breakdown products were found to be formed due the indirect oxidation of organics in solution. The formation of (chlorinated and non-chlorinated) breakdown products was found to be dependant on current density, pH, initial concentration, chloride content and the electrolyte used in the cathode compartment. The concentrations of chlorinated breakdown products can be minimized by using low current density, low initial concentrations, a chloride-free environment and/or treating the water over a number of adsorptions and regeneration cycles. On the other hand, non-chlorinated breakdown products can be minimized by applying higher current density and treating the solution over several cycles of adsorption and regeneration. Therefore, selection of optimum conditions is important to reduce the formation of undesirable breakdown products. The formation of free chlorine during batch electrochemical regeneration was also investigated under a range of operating conditions including the initial concentration of chloride ions, current density and pH. The outcomes of this study have important implications in optimising the conditions for the formation of chlorinated breakdown products and in exploring the role of electrochlorination for water disinfection. Analysis of the regeneration gases has revealed that the main components of the gases generated during the electrochemical regeneration of GIC adsorbents were CO2 and H2O. A preliminary mass balance has suggested that about 60% of the adsorbed phenol was oxidised completely to CO2. However, further work is needed to determine the fate of the remaining phenol. The surface characterization of the GIC adsorbent during adsorption and electrochemical regeneration was carried out using surface techniques including Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Energy dispersive X-ray spectroscopy (EDS) and Boehm titration. FTIR and Raman spectroscopy were found to be unsuitable for determining the concentration changes at the surface of the adsorbent during adsorption and regeneration. However, Boehm titration has shown that the GIC adsorbent has phenolic, carboxylic and lactonic groups. The concentrations of phenolic groups were found to be higher after phenol adsorption and to decrease during electrochemical regeneration. The results of EDS analysis gave results which were consistent with these observations. Another important aspect of this PhD project was to explore the potential application of adsorption and electrochemical regeneration using GIC adsorbents to water disinfection. A model microorganism E. coli was selected for adsorption and electrochemical regeneration studies under a range of experimental conditions. This study has provided evidence that the process of adsorption and electrochemical regeneration using GIC adsorbents can be used for disinfection of water. Disinfection of water was found to be a combination of two processes: the adsorption of microorganisms followed by their deactivation on the surface; and electrochemical disinfection in solution due to indirect oxidation. The possible disinfection mechanisms involved in these processes include electrochlorination, pH changes and deactivation by direct oxidation of microorganisms. Scanning electron microscopy was found to be a useful tool for investigating changes in surface morphology of microorganisms during adsorption and electrochemical regeneration. The disinfection of a variety of bacteria, fungi and yeasts was tested and evaluated. However, disinfection of protozoa including C. parvum was not demonstrated successfully. It was also demonstrated that the process of adsorption with electrochemical regeneration using GIC adsorbents can be used to simultaneously remove organics and to disinfect microorganisms.

Cette étude s’inscrit dans le cadre de la recherche de nouveaux matériaux anodiques à forte capacité pour accumulateurs à ion lithium. Il y est décrit, la synthèse de systèmes graphite-étain obtenus par réduction, en présence de graphite à des taux variables, des chlorures d’étain SnCl2 et SnCl4, par les hydrures alcalins NaH et LiH activés par un alcoolate. Les nanomatériaux préparés présentent des capacités réversibles stables en cyclage, assez proches de celles calculées à partir des teneurs en métal déterminées par analyse élémentaire. Cependant, on peut noter des différences importantes entre les valeurs et l’évolution en cyclage des capacités irréversibles selon l’hydrure ou le mélange d’hydrure utilisé(s). Avec l’hydrure de sodium NaH, la capacité irréversible, très élevée au premier cycle, s’annule pratiquement dès le deuxième cycle ; avec l’hydrure de lithium LiH, cette capacité irréversible, bien que plus faible au premier cycle, donne une valeur résiduelle récurrente aux cycles suivants. Il a finalement été montré que l’utilisation du mélange des deux hydrures NaH/LiH permet de préserver les avantages des deux systèmes précédents et d’obtenir des matériaux combinant de manière synergique leurs propriétés. / This study is devoted to the development of new anodic materials with high capacities for lithium-ion batteries. The synthesis of graphite-tin systems obtained by reduction, in the presence of graphite at various rates, of the tin Chlorides SnCl2 and SnCl4, by the alkoxide-activated alkaline hydrides ( sodium hydride or lithium hydride) is described. The nanomaterials prepared have stable reversible capacities in cycling, close to those calculated from the amounts of metal given by elemental analysis. However, important differences between the values and the evolution in cycling of the irreversible capacities depending on the hydride or the mixture of hydride used were observed. With sodium hydride, the irreversible capacity, very high during the first cycle, is practically cancelled at the second cycle; with lithium hydride, this irreversible capacity, although lower to the first cycle, gives a recurring residual value at the following cycles. The use of the NaH/LiH allowed to preserve the advantages of the two preceding systems and to synergistically combine their properties.

Once current nuclear reactor operation ceases in the U.K. there will be an estimated 99,000 tonnes of irradiated nuclear graphite waste which may account for up to 30% of any future UK geological ILW disposal facility [1]. In order to make informed decisions of how best to dispose of such large volumes of irradiated graphite (I-graphite) within the UK nuclear programme, it is necessary to understand the nature and migration of isotopes present within the graphite structure. I-graphite has a combination of short and long term isotopes such as 14C, 3H and 36Cl, how these behave prior to and during disposal is of great concern to scientific and regulatory bodies when evaluating present decommissioning options. Various proposed decontamination and immobilisation treatments within the EU Euroatom FP7 CARBOWASTE program have been explored [2, 3]. Experiments have been carried out on UK irradiated British Experimental Pile Zero and Magnox Wylfa graphite in order to remove isotopic content prior to long term storage and to assess the long term leachability of isotopes. Several leaching conditions have been developed to remove 3H and 14C from the irradiated graphite using oxidising and various acidic environments and show mobility of 3H and 14C. Leaching analysis obtained from this research and differences observed under varying leaching conditions will be discussed. Thermal analysis of the samples pre and post leaching has been performed to quantify and validate the 14C and 3H inventory. Finally the research objectives address differences in leachability in the graphite to that of structural and operational variation of the material. Techniques including X-ray Tomography, Scanning Electron Microscopy, Autoradiography and Raman spectroscopy have been examined and show a significant differences in microstructure, isotope distribution and location depending of irradiation history, temperature and graphite source. Ultimately the suitability of the developed chemical treatments will be discussed as whether chemical treatment is a viable option prior to irradiated graphite long term disposal.

The relationship between surface energy and precipitated graphite form in Fe-C alloys was examined in this thesis.Surface tension and contact angle data were obtained using the sessile drop technique. Carbon saturated, puron iron crucibles were melted on pyrolytic graphite, the effect of time, temperature (1500-1600°C) and additions of Ni, Mn, S or Ce being examined. The graphite form was established by metallographic examination. An average ƔLV of 1152 dynes/cm was determined for the Fe-C alloys (4.6% C) at approximately 1300°C, the average contact angle being 128°. No significant change occurred with additions of Ni ( 0.85%) and Mn ( 1.65%). Additions of S lowered the surface energy and increased the equilibrium contact angle. Ce additions had a similar effect although a direct comparison with the Fe-C alloys could not be made as different temperatures were used. However, the interfacial energy difference apparently increased with increasing Ce content, implying an adsorption of Ce to the graphite-melt interface. The change from the flake to the nodular form was accomplished in several transition stages, the interfacial energy differences being small, indicating a marked dependence on the solidification and growth conditions. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

La méthode solide-liquide en milieu alliage fondu à base de lithium a permis ces dernières années la synthèse de plusieurs composés d'intercalation du graphite (CIG) insérés à coeur au sein des systèmes graphite-lithium-alcalino-terreux. Dans le cadre de cette thèse, cette méthode de synthèse a été étendue aux systèmes graphite-lithium-lanthanoïde, avec une difficulté supplémentaire qui est la méconnaissance des diagrammes de phases binaires lithium-lanthanoïde dont les données sont capitales pour déterminer les domaines de température et de composition chimique des alliages susceptibles de conduire à des CIG. L'immersion de plaquettes de pyrographite dans certains alliages lithium-europium judicieusement choisis a mené à un composé binaire EuC6 ainsi qu'à un composé ternaire graphite-lithium-europium de premier stade.La cinétique de formation de EuC6 a été suivie par diffraction des rayons X ex situ afin de comprendre les différentes étapes de la réaction et d'identifier les phases intermédiaires menant au composé final thermodynamiquement stable. Ce mécanisme révèle un processus réactionnel plus « coopératif » que celui menant au composé CaC6 et a été décrit par une succession d'étapes contribuant à l'insertion à coeur de l'europium.La composition élémentaire du composé ternaire a été déterminée grâce à une analyse par faisceau d'ions qui a permis de doser simultanément les trois éléments lithium, carbone et europium. Le résultat de cette analyse a conduit à la formule chimique Li0,25Eu1,95C6. EuC6 a également été étudié par microsonde nucléaire, le rapport atomique C/Eu de 6 a ainsi notamment pu être confirmé.Des études structurales ont été menées pour les composés binaires et ternaires. D'une part, il a été possible d'effectuer la résolution structurale complète du binaire EuC6, qui cristallise dans une maille hexagonale de groupe d'espace P63/mmc. D'autre part pour le ternaire Li0,25Eu1,95C6, la séquence d'empilement poly-couche selon l'axe c du feuillet inséré a été modélisée, par combinaison des données structurales avec les informations issues de l'analyse par faisceau d'ions.Les composés d'intercalation du graphite sont des solides de basse dimensionnalité qui se prêtent idéalement à l'étude des relations structure-propriétés. Ainsi dans le système graphite-lithium-calcium, le caractère supraconducteur des composés CaC6 et Li3Ca2C6 a été étudié par spectroscopie de spin de muon ([mu]SR). Pour le système graphite-lithium-europium, des mesures magnétiques réalisées préalablement à ce travail ont été poursuivies et complétées par des analyses [mu]SR (pour Li0,25Eu1,95C6 et EuC6) ainsi que par spectrométrie Mössbauer de 151Eu (pour Li0,25Eu1,95C6) à basse température. / The molten alloy solid-liquid method containing lithium has recently enabled the synthesis of several bulk graphite intercalation compounds (GICs) in graphite-lithium-alkaline earth metal systems. As part of this thesis, this synthesis method was extended to graphite-lithium-lanthanide systems, with an additional difficulty which is the lack of knowledge of lithium-lanthanide binary phase diagrams whose data are crucial for determining the temperature range and chemical composition of alloys that may lead to GICs.The immersion of pyrographite platelets in some europium-lithium alloys wisely chosen led to a binary EuC6 compound as well as a graphite-lithium-europium first stage ternary compound.Kinetics study of EuC6 compound was followed by ex situ X-ray diffraction in order to understand the different reaction steps and identify intermediate phases leading to the thermodynamically stable final compound. This mechanism revealed a reaction process more "cooperative" than that leading to CaC6 binary compound and was described by a succession of steps that contribute to the bulk insertion of europium.The elementary composition of the ternary compound was determined by ions beam analysis allowing the simultaneous quantification of the three elements lithium, carbon and europium. The refinement of these analyses led to the chemical formula Li0,25Eu1,95C6 for the ternary compound. EuC6 has also been studied by nuclear microprobe analysis, and especially the C/Eu atomic ratio equal to 6 has been confirmed.Structural studies have been undertaken for binary and ternary compounds. On one hand, it was possible to fully resolve the three-dimensional structure of the binary EuC6, which crystallizes in a hexagonal unit cell with P63/mmc space group. On the other hand, the c axis stacking sequence of the poly-layered intercalated sheet of the ternary compound was modeled by combining structural data with information from the ions beam analysis. The graphite intercalation compounds are low-dimensional solids that are ideal for the study of structure-properties relations. Thus in graphite-lithium-calcium system, superconducting character has been studied for CaC6 and Li3Ca2C6 compounds by muons spin spectroscopy ([mu]SR). For the graphite-lithium-europium system, previous magnetic measurements have been continued and supplemented by [mu]SR analysis (for Li0,25Eu1,95C6 and EuC6) and by low temperature 151Eu Mössbauer spectroscopy (for Li0,25Eu1,95C6).