Grâce à leurs propriétés mécaniques et électroniques élevées, les NanoTubes de Carbone (NTC) semblent être les nanocharges idéales pour conférer des propriétés optimum à des matériaux composites, en particulier ceux qui sont élaborés à partir de matrices élastomères. Cependant, pour obtenir une amélioration significative des propriétés une bonne dispersion dans la matrice est nécessaire. La dispersion des NTC dans une matrice élastomère de type EPM est explorée ici en employant un copolymère statistique, le poly(éthylène-stat-acétate de vinyle) (EVA), comme agent dispersant. Les outils classiques de mélange des élastomères, mélangeur interne et mélangeur à cylindres, qui sont des techniques de mélange douces, ont été utilisés dans le cadre de cette étude. Nous avons montré qu’à faible taux de NTC dans la matrice leur dispersion était contrôlée par deux paramètres clés (i) la viscosité de la matrice EPM et (ii) la concentration en EVA. L’augmentation des concentrations de NTC a permis de mettre en évidence que les propriétés rhéologiques et électriques des nanocomposites variaient brusquement à partir de concentrations critiques (seuil de percolation) assez faibles permettant de justifier l’utilisation du système EPM-EVA sélectionné. Nous avons alors préparé un mélange maître EPM-EVA chargé à 20% en NTC possédant de très bonnes propriétés de conductivité. Des mélanges à base d’EPDM chargés par des nanotubes de carbone, du noir de carbone ou le mélange des deux ont également été analysés. Nous avons démontré que la dilution d’un mélange maître permet d’obtenir un élastomère chargé en NTC avec une viscosité Mooney constante et avec un impact fort sur la cinétique de vulcanisation de l’élastomère (accélération de la réaction). Un effet de synergie entre noir de carbone et NTC a été mis en évidence au niveau des propriétés mécaniques mais pas pour les propriétés électriques. / The outstanding properties of Carbon NanoTubes (CNTs) make them ideal candidates for use in nanocomposites, and particularly in those based on rubber matrix. However, to obtain an improvement of the properties, a good degree of dispersion of the CNT in the matrix is crucial. The CNT dispersion in an EPM rubber is investigated here by using a statistical copolymer, the ethylene-stat-vinyl acetate (EVA), as dispersing agent. In this study, we work with the classic methods used for rubber mixing, like an internal mixer and an open two roll mill, which are soft mixing techniques. At low CNT rate in the matrix, the dispersion is controlled by two parameters such as the EPM matrix viscosity and the EVA concentration. The rheological and electrical properties varied abruptly when the CNT concentration is increased in the matrix. The low values obtained for this percolation threshold justify the use of EPM-EVA system. We have prepared an EPM-EVA master batch loaded with 20% of CNT and possessing very good conductive properties. We studied EPDM compound filled with carbon nanotubes, carbon black or the blend of both. We have demonstrated that the dilution of the master batch allows us to obtain a rubber filled with a constant Mooney viscosity but with an important impact on the vulcanization kinetics of elastomers. The synergistic effect between carbon black and carbon nanotubes has been shown on the mechanicals properties but not on the electrical ones.

Les données électromagnétiques imagent des zones du manteau plus conductrice que l’olivine sèche. Il y a peu d’ambiguïté sur le fait qu’un liquide est thermodynamiquement stable et présent au niveau de l’asthénosphère, mais son impact sur la conductivité électrique du manteau reste débattu. Les études pétrologiques réalisées ces 30 dernières années ont montré qu’une péridotite exposée aux conditions the P-T-fO₂ de l’asthénosphère produisait des liquides riches en H₂O and CO₂, mais les conductivités électriques de ces liquides sont mal connues. Pour cette raison, des expériences de conductivité électrique ont été réalisées en piston cylindre sur des liquides riches en H₂O and CO₂. Différentes compositions de liquides ont été explorées, des liquides carbonatés aux basaltes. Les effets de la composition chimique et des volatiles sur ces liquides ont été déterminés. Les mesures de conductivités électriques ont montré que les liquides hydratés et carbonatés sont très conducteurs, et que l’incorporation de basalte décroit la conductivité. Avec ces nouvelles données, un modèle semi-empirique calculant la conductivité en fonction des teneurs en H₂O and CO₂ a été produit. Sur la base de ce modèle et de la conductivité électrique de l’olivine, des profils 1D de conductivité ont été construits. Avec ces profils, l’effet des teneurs en volatiles (partagé entre le liquide et le solide), les fractions de liquides (loi de mélange et interconnexion du liquide) et les différents régimes de température sur la conductivité ont été discutés. Ces calculs ont été considérés en milieu océanique et continental pour différents âges. La conductivité électrique du manteau est donc un outil puissant pour suivre les processus fondamentaux de la fusion du manteau, qui est à son tour étroitement liée aux cycles de H₂O and CO₂ dans le manteau supérieur. / Electromagnetic data images mantle regions more conductive than that of dry olivine. There is no doubt that melt is thermodynamically stable and present in the asthenosphere, but how they can impact on mantle electrical conductivity remains debated. Petrological studies realized some 30 years ago have shown that peridotites exposed at the P-T-fO₂ conditions of the asthenosphere produced H₂O and CO₂ rich-melts, but electrical conductivities of these melts are poorly known. Therefore, electrical conductivity experiments have been performed in piston cylinder on H₂O-CO₂ rich melts. Different melt compositions have been explored, from carbonated melts to basalts. The effects of chemical compositions and volatiles on these melts have been determined. The electrical conductivity measurements have shown that hydrous carbonated melts are very conductive, and the incorporation of basalt decreases the conductivity. With these new data, a semi-empirical law predicting the conductivity as a function of H₂O and CO₂ contents has been produced. Based on this law and the electrical conductivity of olivine, 1D conductivity profiles were constructed. With these profiles, the effect of volatile contents (partitioned between the melt and in the solids), melt fractions (mixing law and interconnection of the melt) and different temperature regimes on conductivity are discussed. These calculations are conducted on oceanic and continental settings with different ages. The electrical conductivities of the mantle is thus a powerful tool to track the fundamental process of mantle partial melting, which is in turn narrowly associated to the cycling of H₂O and CO₂ in the upper mantle.

Orientador: Edson Lazarini / Banca: Marco Eustaquio de Sa / Banca: Roberval Daiton Vieira / Resumo: O molibdênio é essencial no processo de fixação simbiótica do nitrogênio por ser constituinte da enzima nitrogenase. O uso de sementes enriquecidas com molibdênio é uma das formas práticas de fornecimento do nutriente às plantas de soja. Neste contexto, desenvolveu-se o presente trabalho objetivando determinar em diferentes cultivares de soja, a dose de molibdênio a aplicar nos estádios reprodutivos para elevar o teor do mesmo na semente (sementes enriquecidas), bem como possíveis alterações na produtividade e massa das sementes e qualidade fisiológicas destas. O trabalho foi desenvolvido no ano agrícola 2005/06, na Fazenda de Ensino, Pesquisa e Extensão/UNESP - Campus de Ilha Solteira, localizada no município de Selvíria - MS (51º22'W, 20º22'S e altitude 335 m aproximadamente), em um Latossolo Vermelho distrófico típico argiloso. O delineamento experimental utilizado foi o em blocos casualizados, com os tratamentos dispostos em um esquema fatorial 6x2x2 com quatro repetições, ou seja, seis doses de molibdênio (0, 200, 400, 600, 800, 1000 g/ha) aplicadas através de pulverização foliar (dose única aplicada no estádio R5.4 ou parcelada, sendo metade em R3 e metade em R5.4), em dois cultivares de soja (MSOY 7901 e MG/BR 46). As avaliações constaram de: características agronômicas, produtividade, massa de 100 sementes, teor de molibdênio nas sementes, germinação e condutividade elétrica. Pelos resultados obtidos, verificou-se que a produtividade de grãos não é influenciada pela aplicação foliar de doses de molibdênio, em estádios reprodutivos da soja; a massa de 100 sementes responde de forma linear a aplicação de doses crescentes de Mo quando aplicadas em dose única; a cultivar MSOY 7901 apresenta sementes com maior teor de Mo e sendo recomendado a aplicação em dose única; o teor de molibdênio nas sementes tem comportamento... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Molybdenum is essential in the symbiotic fixation process of nitrogen due to its participation on nitrogenase enzyme. The use of seeds enriched with molybdenum is one of the practical forms of supplying the nutrient to the soybean plants. In this context, the present study was developed to determine in different cultivars of soybean, doses of molybdenum applied in the reproductive stage for elevating the Mo seed content (seeds enriched), as well the possible alterations in the productivity, on mass and physiological seed quality. The experiment was conducted in the agricultural year 2005/06, at experimental area belonging to UNESP - Ilha Solteira Campus, located in Selvíria county - MS (51º22'W, 20º22'S and altitude 335 m approximately), in a clayey dystrophic Red Latosol. A randomized block design was used, in a factorial scheme 6x2x2 with four repetitions, or be, six doses of molybdenum (0, 200, 400, 600, 800, 1000 g/ha) applied on the leaves through spraying (unique dose applied in the stadium R5.4 or divided in two applications, being half in R3 and other half in R5.4 stadium), in two cultivars of soybean (MSOY 7901 and MG/BR 46). The evaluations were: agronomic characteristics, productivity, mass of 100 seeds, content of molybdenum in the seeds, germination and electrical conductivity. Through the results obtained, it was verified that the productivity of seeds was not influenced by leaf application of Mo doses, in reproductive stage of the soybean; the mass of 100 seeds fitted to a lineal equation to doses of Mo application when applied in unique dose; the MSOY 7901 cultivar presented seeds with higher Mo content and being recommended the application in unique dose; the Mo content on seeds fitted a quadratic equation as a function... (Complete abstract click electronic access below) / Mestre

Inorganic contaminants, while transported through the bentonite layer, are chemically adsorbed onto the particle surfaces and exhibit a delay in solute breakthrough in hydraulic barriers. Transport of inorganic leachate contaminants through bentonite occurs by advection, diffusion or a combination of these two mechanisms. During the process of chemical solute transport through low permeability bentonite, the amount of cation exchange on the clay particle surface is directly related to the cation exchange capacity (CEC) of montmorillonite and other mineral constituents. The process of diffusion and advection of various inorganic leachate contaminants through bentonite is thoroughly investigated in this study. Diffusion characteristics are of specific interest as they have a prominent effect on the long term properties of bentonite compared to advection. This is mostly true if the hydraulic conductivity of the material is less than 10-8 cm/s and if the thickness of the barrier is small. Chemical reactions in the form of cationic exchange on the clay particle surfaces has been incorporated in the analysis of the diffusion process. Adsorption-desorption (sorption) reactions of chemical compounds that influence the concentrations of inorganic leachates during transport in bentonite clay have been modeled using the Fick's fundamental diffusion theory. Partition coefficients of the solutes in pore space, which affect the retardation factor of various individual ions of chemical solutions, have been investigated during transient diffusion and advection processes. Several objectives have been accomplished during this research study. An evaluation has been carried out of the hydraulic conductivity of bentonite with respect to single species salts and various combinations of electrolyte solutions. Diffusion properties of inorganic leachates through bentonite have been characterized in terms of apparent and effective diffusion coefficients. Time-dependent behavior of the diffusive ions has been analyzed in order to determine the total retention capacity of bentonite before electrical conductivity breakthrough and steady-state chemical stability are reached. An analytical solution of the attenuation of various inorganic ions concentrations through bentonite has been developed. Finally, recommendations were made for landfill liners exposed to highly concentrated inorganic leachates.

Afin de cartographier la structure souterraine des volcans et détecter des ressources géothermiques de haute température, on utilise souvent l’imagerie de résistivité électrique. La résistivité électrique des volcans est affectée par plusieurs facteurs: volume et salinité de l’eau interstitielle, abondance de minéraux conducteurs, température de la roche et présence de magma. Ce travail de thèse tente de contraindre l'interprétation des structures de résistivité électrique autour des volcans actifs, afin de développer des outils innovants pour l'exploration des ressources géothermiques. La contribution des minéraux conducteurs est au cœur de la thèse: conducteurs ioniques solides (minéraux argileux, en particulier la smectite) ou semi-conducteurs électroniques (pyrite, oxydes de fer), mais l’influence de la porosité, de la salinité, de la température et de la présence de magma est aussi étudiée. La thèse utilise le volcan Krafla comme terrain d’étude pour affiner les interprétations des structures de résistivité électriques, du fait de la disponibilité de carottes, de données, de bibliographie et d’infrastructure. La smectite et la pyrite sont formées par altération hydrothermale des roches volcaniques et témoignent ainsi des convections hydrothermales. Les oxydes de fer en revanche sont plutôt formés lors de la cristallisation du magma et sont dissous lors des circulations hydrothermales. La contribution de la smectite à la conductivité électrique de roches volcaniques, saturées en eau à différentes salinités, est d'abord étudiée en laboratoire (à température ambiante) par spectroscopie d’impédance électrique « résistivité complexe ». Des variations non linéaires de la conductivité électrique à 1 kHz avec la salinité sont observées et discutées. La conduction interfoliaire est suggérée comme un mécanisme important par lequel la smectite conduit le courant électrique. L'influence de la pyrite et des oxydes de fer sur les effets de polarisation provoquée est ensuite analysée en utilisant l'angle de phase de l'impédance, qui dépend de la fréquence. Un angle de phase maximal supérieur à 20 mrad est attribué à la pyrite si la roche est conductrice et aux oxydes de fer si la roche est résistive. L'angle de phase maximal augmente d'environ 22 mrad pour chaque pourcent de pyrite ou d'oxyde de fer. Ces résultats de laboratoire en domaine fréquentiel sont appliqués à l’interprétation de tomographies de résistivité complexe sur le terrain en domaine temporel. Smectite, pyrite et oxydes de fer ont pu être identifiés jusqu'à 200 m de profondeur. La température in-situ, plus élevées qu’en laboratoire, semble augmenter la conductivité de la smectite. De manière générale, la tomographie de résistivité complexe est recommandée comme méthode complémentaire aux sondages électromagnétiques pour l'exploration géothermique. / Electromagnetic soundings are widely used to image the underground structure of volcanoes and look for hightemperature geothermal resources. The electrical resistivity of volcanoes is affected by several characteristics of rocks: volume and salinity of pore fluid, abundance of conductive minerals, rock temperature and presence of magma. This thesis aims at improving the interpretation of electrical resistivity structures around active volcanoes, in order to develop innovative tools for the assessment of geothermal resources. I focus on conductive minerals, which can either be solid ionic conductors (clay minerals, in particular smectite) or electronic semi-conductors (pyrite and iron-oxides), but I also investigate the effects of porosity, salinity, temperature and presence of magma. I use Krafla volcano as a laboratory area, where extensive literature, borehole data, core samples, surface soundings and infrastructures are available. Smectite and pyrite are formed upon hydrothermal alteration of volcanic rocks and thus witness hydrothermal convection. On the other hand, iron-oxides are mostly formed during the primary crystallization of magma and dissolved by hydrothermal fluids. The contribution of smectite to the electrical conductivity of volcanic rocks saturated with pore water at different salinity is first investigated in the laboratory (room temperature) by electrical impedance spectroscopy “complex resistivity”. Non-linear variations of the conductivity at 1 kHz with salinity are observed and discussed. Interfoliar conduction is suggested as an important mechanism by which smectite conducts electrical current. The influence of pyrite and iron-oxides on induced polarization effects is then analyzed, using the frequency-dependent phase-angle of the impedance. A maximum phase-angle higher than 20 mrad is attributed to pyrite if the rock is conductive and to ironoxides if the rock is resistive. The maximum phase-angle increases by about 22 mrad for each additional per cent of pyrite or iron-oxide. These laboratory frequency-domain findings are partly upscaled to interpret field time-domain complex resistivity tomography at Krafla: smectite, pyrite and iron-oxides can be identified down to 200 m. The in-situ temperature, higher than in laboratory conditions, appears to significantly increase the conductivity associated to smectite. In general, time-domain complex resistivity measurements are recommended as a complementary method to electromagnetic soundings for geothermal exploration.

Issues of major relevance to the n-type conductivity of Al0.77Ga0.23N associated with Si and O incorporation, their shallow donor or deep donor level behavior, and carrier compensation are elucidated by allying (i) study of Si and O incorporation kinetics at high process temperature and low growth rate, and (ii) electron paramagnetic resonance measurements. The Al0.77Ga0.23N composition correlates to that Al content for which a drastic reduction of the conductivity of AlxGa1−xN is commonly reported. We note the incorporation of carbon, the role of which for the transport properties of AlxGa1−xN has not been widely discussed.

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Total body electrical conductivity (TOBEC) is a noninvasive method for the estimation of lean mass in live subjects. Lipid content can be calculated from the body mass measured and the lean mass estimated from TOBEC. I used live American Kestrels (Falco sparverius) to study the accuracy of this method. TOBEC measurements were compared to actual body content determined by Soxhlet fat extraction using petroleum ether as the solvent. TOBEC estimated 73.7% of the variation in lean mass in a sample of 21 kestrels. The use of restraining devices (Vetrap and cardboard cylinders) altered the TOBEC measurement but only by an average of 1.92% and 0.83%, respectively. TOBEC estimated 83.8% of the variation in lean mass for 21 kestrel carcasses warmed to 39.8oC. No significant difference was found between the slope or elevation of the calibration lines developed using live or dead kestrels. A significant difference was found between measurements taken at two different positions. Body temperature altered the TOBEC measurements by an average of 1.54% (SE = 0.55) for each 10C change over a temperature range of 7.00C (37.3-44.4). The calibration line developed for kestrels was used to estimate lean mass and compute fat mass of migrating kestrels, Sharp-shinned Hawks (Accipiter striatus) and Merlins (Fa/co co/umbarius). The average percent fat mass of kestrels trapped during migration at Cape May, New Jersey, was 6.01 % (SE = 1.92, n = 1 2) for males and 8.51 % (SE = 2.00, n = 13) for females. The difference in lean mass between male and female, and between early, mid-season, and late migrating Sharp-shinned Hawks differed significantly during migration. The fat mass of Sharp-shinned Hawks averaged 5.55% (SE = 0.94, n = 53) for males and 10.92% (SE = 0.80, n = 87) for females. Male Merlins had an average fat mass of 18.05% (SE = 3.35, n = 7) and females averaged 14.19% (SE = 3.15, n = 8).

The present work provides a micromechanics approach based on the generalized self-consistent composite cylinders method as a non-Eshelby approach towards for assessing the impact of carbon nanotubes on the multi-functional nature of nanocom-posites in which they are a constituent. Emphasis is placed on the effective elastic properties as well as electrical and thermal conductivities of nanocomposites con-sisting of randomly oriented single walled carbon nanotubes in epoxy. The effective elastic properties of aligned, as well as clustered and well-dispersed nanotubes in epoxy are discussed in the context of nanotube bundles using both the generalized self-consistent composite cylinders method as well as using computational microme-chanics techniques. In addition, interphase regions are introduced into the composite cylinders assemblages to account for the varying degrees of load transfer between nanotubes and the epoxy as a result of functionalization or lack thereof. Model pre-dictions for randomly oriented nanotubes both with and without interphase regions are compared to measured data from the literature with emphasis placed on assessing the bounds of the effective nanocomposite properties based on the uncertainty in the model input parameters. The generalized self-consistent composite cylinders model is also applied to model the electrical and thermal conductivity of carbon nanotube-epoxy nanocomposites. Recent experimental observations of the electrical conductivity of carbon nanotube polymer composites have identified extremely low percolation limits as well as a per-ceived double percolation behavior. Explanations for the extremely low percolation limit for the electrical conductivity of these nanocomposites have included both the creation of conductive networks of nanotubes within the matrix and quantum effects such as electron hopping or tunneling. Measurements of the thermal conductivity have also shown a strong dependence on nanoscale effects. However, in contrast, these nanoscale effects strongly limit the ability of the nanotubes to increase the thermal conductivity of the nanocomposite due to the formation of an interfacial thermal resistance layer between the nanotubes and the surrounding polymer. As such, emphasis is placed here on the incorporation of nanoscale effects, such as elec-tron hopping and interfacial thermal resistance, into the generalized self-consistent composite cylinder micromechanics model.