Les pompes sèches primaires dédiées aux procédés de fabrication en microélectronique sont soumises à des environnements très corrosifs de plus en plus oxydants et halogénés (Cl2, F2 et O2). Or pour des raisons mécaniques et économiques, les parties fonctionnelles des pompes sont usinées dans la fonte à graphite sphéroïdale EN-GJS-500-7. La fonte est alors protégée par un dépôt de nickel-phosphore (NiP) chimique. Cette thèse, reprend des études classiques sur la cinétique et le mécanisme de nickelage d'une part, et sur l'optimisation des propriétés mécaniques et la résistance à la corrosion des couches de NiP d'autre part. Cependant, le caractère innovant de ce travail repose sur la réalisation de couches NiP sur un substrat en fonte à graphite sphéroïdale.L'étude de la cinétique de nickelage et la caractérisation morphologique des revêtements en fonction du temps de dépôt a montré l'influence de la nature chimique du substrat. Les sphères de graphite affleurantes à la surface du substrat n'étant pas catalyseur du nickel chimique, provoque des défauts dans le revêtement, dommageables pour la conformité du dépôt. Il a été montré qu'une polarisation cathodique de la surface du substrat pouvait, dans les premiers instants du dépôt, amorcer le nickelage à l'aplomb des sphères de graphite.Une relation entre la microstructure des dépôts en fonction des traitements thermiques subis et des propriétés mécaniques des couches de NiP a été mise une évidence. Les dépôts NiP amorphes présentent une faible dureté et un comportement ductile tandis que les dépôts cristallisés possèdent une dureté élevée et un comportement fragile. Ces dépôts ont une bonne tenue à la corrosion en milieux halogéné lorsqu'ils sont intacts. Actuellement, au niveau industriel, les dépôts les plus fragiles sont choisis, bien qu'ils présentent une résistance à la corrosion plus faible : en effet, la durée de vie des pompes est alors supérieure car les effets de grippage sont atténués.Mots-clés : nickel chimique, résistance à la corrosion, fonte à graphite sphéroïdale, caractérisation physico-chimique, couches minces, durabilité mécanique / Primary dry pumps dedicated to manufacturing processes in microelectronics are subjected to highly corrosive environments that are increasingly oxidizing and halogenous (Cl2, F2 and O2). However, for mechanical and economic reasons, the functional parts of the pumps are machined in EN-GJS-500-7 spheroidal graphite cast iron. The cast iron is consequently protected by a nickel-phosphorus chemical deposit. This thesis is based on classical studies on the kinetics and the nickel-plating mechanism on the one hand, and on the optimization of the mechanical properties and corrosion resistance of the NiP layers on the other hand. The innovative nature of this work is based on the production of NiP layers on a spheroidal graphite cast iron substrate.The study of the kinetics of nickel-plating as well as the morphological characterization of coatings as a function of the deposit time showed the influence of the chemical nature of the substrate. The flush graphite spheres on the surface of the substrate being not a catalyst for the chemical nickel, they can cause defects in the coating and a loss of compliance. It has been shown that a cathodic polarization of the surface of the substrate, in the first moments of the deposit, could initiate the nickel-plating right on the graphite spheres.A relationship exists between the microstructure of the deposits as a function of the thermal treatments undergone and the mechanical properties of the NiP layers. The amorphous NiP deposits have a low hardness and a ductile behavior while crystallized deposits have a high hardness and a brittle behavior. These deposits have a good resistance to corrosion in halogenated environments when they are intact. Actually, at the industrial level, the most brittle deposits are chosen, although they have a lower corrosion résistance: indeed, the service life of the pumps is higher because the seizing effect are minimized.Keywords: electroless nickel, resistance to corrosion, spheroidal graphite cast iron, physicochemical characterization, thin layers, mechanical durability

Orientadores: Iakov Veniaminovitch Kopelevitch, George Gershon Kleiman / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-11T13:15:15Z (GMT). No. of bitstreams: 1 MedinaPantoja_JuanCarlos_D.pdf: 3933664 bytes, checksum: 33f9dc730779c11f8c3d83b7ee0e56b4 (MD5) Previous issue date: 2007 / Resumo: Esta tese é o resultado da investigação das propriedades elétricas e magnéticas de dois semimetais: bismuto (Bi) policristalino romboédrico e grafite pirolítica altamente orientada (HOPG). Inicialmente nós discutimos o efeito Hall no limite quântico, que acontece em amostras de grafite HOPG com certo grau de desordem e onde a desordem é reduzida. Em particular, a resistência Hall R xy (B) exibe platôs em amostras HOPG menos desordenadas que possuem uma característica quase-bidimensional e uma forte anisotropia. Em amostras com maior desordem é observada a ocorrência de picos em lugar de platôs, evidenciando, experimentalmente, a predição de T. Ando. A condutância Hall reduzida Rxy (v) G0xy . fornece uma evidencia experimental para a coexistência de ambos os tipos de férmions de Dirac, normais e sem massa. Este resultado revela que o efeito Hall quântico inteiro e semi-inteiro tomam lugar simultaneamente na amostra HOPG. Nós encontramos as transições metal¿isolante (MIT) e isolante¿metal (IMT) induzidas por campo magnético em amostras de bismuto (Bi), quando o campo é aplicado paralelo ao eixo-c cristalográfico e observamos que estas transições têm enormes semelhanças com o MIT e IMT achados em HOPG e amostras monocristalinas Kish. As análises destes resultados experimentais sugerem que estas transições devem estar associadas à transição entre o estado metal de Bose (líquido não superfluido de pares de Cooper) e isolante excitônico. O aumento do momento diamagnético em bismuto e sua supressão próxima do campo crítico do MIT evidenciam a existência de correlações supercondutoras (metal de Bose) e excitônicas. Nós reportamos a observação experimental do efeito Hall anômalo Hall (AHE) em amostras de bismuto e de grafite HOPG. Os resultados indicam que este AHE pode ser compreendido, autoconsistentemente, através de modelos de pareamento excitônico induzido pelo campo magnético, possivelmente, devido ao surgimento de ferromagnetismo / Abstract: This thesis is the result of the investigation of the electric and magnetic properties of two semimetals: highly oriented pyrolitic graphite (HOPG) and polycrystalline bismuth (Bi), rhomboedral. Initially we discuss the Hall effect in the quantum limit that occurs in HOPG samples with a certain degree of disorder and with reduced disorder. In particular, the Hall resistance R xy (B) exhibits plateaus in less disordered HOPG samples, which present characteristic quasi-bidimensional and strongly anisotropic. In more disordered samples there occur peaks instead of plateaus, experimentally evidencing the T. Ando's prediction. The reduced Hall conductance G xy (v)/ G 0xy gives evidence experimental for the coexistence of both massless and massive Dirac fermions. This result reveals that the integer- and semi-integer QHE take place simultaneously in HOPG samples. We observed magnetic field induced metal-insulator (MIT) and insulator-metal (IMT) transitions, when this field is in the crystallographic c-axis direction, and observed that these transitions are very similar to the MIT and IMT observed in HOPG and monocrystalline samples (Kish). The analysis of the experimental results suggests that these transitions must be associated with the transition from the Bose metal state (a non superfluid liquid of Cooper pairs) to the excitonic insulator. The increase of the diamagnetic momentum in bismuth and its suppression in the vicinity of the critical field of the MIT evidences the existence of superconducting (Bose metal) and excitonic correlations. We report the experimental observation of the anomalous Hall effect (AHE) in HOPG samples. This AHE may be autoconsistently understood by means of magnetic field induced excitonic pairing models, possibly, due to the onset of ferromagnetism / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Les applications des nanoparticules métalliques nécessitent des assemblées monodisperses et stables sur un substrat tel que le graphène ou le graphite. Le graphène épitaxié sur métal (GEM) est étudié, car il facilite l'auto-organisation des adsorbats. La différence entre les mailles du graphène et du métal conduit à un effet de moiré contenant certaines régions favorables de l'adsorption. Ce travail est consacré surtout aux systèmes Ru-C et Pt-C où nous nous sommes intéressé au substrat du GEM nu, des agrégats y etant deposés et des agrégats métalliques sur graphite. Les potentiels d'ordre de liason permettent de mener des études en dynamique moléculaire sur des systèmes de taille réaliste à température finie. Dans le cas du système Pt-C une paramétrisation est disponible dans la littérature. Cependant, pour le système du Ru-C une paramétrisation sur la base de données DFT était nécessaire. Ce modèle atomistique néglige les forces de dispersion importantes pour des milieux étendus. Basé sur les modèles de Grimme, nous avons développé une description implicite tenant compte de la structure du substrat et son extension semi-infinie. De plus les effets d'écrantage importants pour des milieux métalliques sont pris en compte. Basé sur ce champ de force nous montrons des propriétés des adsorbats sur des substrats carbonés où nous évaluons le modèle de forces de dispersion. Grâce à des simulations de dynamique moléculaire, la stabilité des adsorbats et du graphène a été étudié dans le contexte de la dynamique vibrationnelle et de diffusion. En accord avec les expériences, la mobilité des adsorbats sur graphite s'avère élevée en comparaison avec des adsorbats sur GEM / Applications of metal nanoparticles require monodisperse and stable assemblies on a substrate such as graphene or graphite. Epitaxial graphene on metal (GOM) has attracted research interest because it contributes to the self-organisation of adsorbates. The difference in the lattice constants of graphene and metal leads to a moiré that contains certain regions that are favorable for adsorption. This work is mainly concerned with the Ru-C and Pt-C systems where we were interested in the bare substrate of GOM, adsorbates deposited thereon and metal clusters on graphite. Bond order potentials allow to carry out molecular dynamics studies for systems of realistic size and at finite temperature. In the case of the Pt-C, a parametrization is available in the literature. However, for Ru-C systems a custom parametrization effort based on data from electronic structure calculations was necessary. This atomistic model neglects long ranged dispersion forces that are important for adsorption phenomena on extended substrates. Based on the Grimme models, we developed an implicit description that takes the layered structure and the semi-infinite extension of the substrate into account. Also, screening effects that are important for metal materials are taken into account. Based on this force field, we show results concerning the properties of adsorbates on carbon substrates while evaluating the dispersion model. With the help of molecular dynamics simulations, the stability of adsorbates and graphene has been studied in the context of vibrational and diffusion dynamics. In agreement with experiments, the mobility of the adsorbates on graphite is high in comparison with adsorbates on GOM

Le démantèlement des réacteurs nucléaires de première génération UNGG (Uranium Naturel Graphite Gaz) génèrera en France environ 23 000 tonnes de déchets de graphites irradiés. Les principaux radionucléides présents dans ces déchets sont des produits d’activation tels que le 14C, le 36Cl et le 3H. Les deux premiers sont dimensionnants pour le stockage, le 14C (T =5730 ans) essentiellement en raison de son inventaire initial important et le 36Cl du fait de sa longue période (302 000 ans). Le scénario de référence envisagé pour la gestion de ces déchets de faible activité à vie longue est le stockage mais une décontamination préalable plus ou moins poussée a également été envisagée. De ce fait, la connaissance de la localisation et la spéciation de ces radionucléides dans le graphite irradié est un prérequis indispensable pour l’optimisation d’un procédé de traitement et l’évaluation de la sûreté du stockage. L’objectif de cette thèse CIFRE, réalisée en partenariat avec EDF, est de mettre en oeuvre des études expérimentales permettant, dans une première partie, de simuler et d’évaluer l’impact de la température, de l’irradiation et de la corrosion radiolytique du graphite sur le comportement migratoire du 14C en réacteur et sur les modifications structurales qui en découlent. Les données ainsi acquises servent d’appui à la deuxième partie de ce travail consacrée à l’étude d’un procédé de décontamination thermique du graphite en présence de vapeur d’eau. Ce travail est mené par implantation de l’isotope stable 13C permettant de simuler la présence de l’isotope radioactif 14C. L’utilisation de différentes natures de graphite de référence tels qu’un graphite vierge de qualité nucléaire, un graphite modèle HOPG bien ordonné de structure lamellaire et un graphite de structure nanoporeuse de type SLX 50 broyé permet de simuler les différents états de structure rencontrés dans un graphite irradié par des neutrons. L’étude d’échantillons inactifs permet ainsi de s’affranchir des contraintes liées à l’étude d’échantillons radioactifs et de réaliser des études paramétriques du comportement migratoire de l’espèce implantée, difficiles à mettre en oeuvre sur du graphite irradié. La première partie de ce travail consiste en l’étude des effets couplés et découplés de la température et de l’irradiation ionique (simulant l’irradiation neutronique) sur le comportement migratoire du 13C. Les résultats obtenus montrent que, dans la gamme de températures du graphite en réacteur (200 - 500 °C), le 13C est stable quel que soit l’état de l’endommagement de la structure du graphite. D’une manière générale, l’irradiation et la température ont des effets antagonistes. L’irradiation induit une déstructuration du graphite compensée par les effets de recuit conduisant à la réorganisation de la structure dont le degré dépend de l’état initial. Ainsi, en fonction de la localisation du graphite au sein du modérateur, son état de structure sera contrasté selon qu’il aura été irradié dans les zones chaudes à haut flux neutronique ou dans les zones à bas flux et plus froides. Cependant, dans tous les cas, le 14C aura été stabilisé. La deuxième partie concerne l’étude du procédé de décontamination thermique en présence de vapeur d’eau qui a été réalisée sur un dispositif de thermogravimétrie couplé à un générateur de vapeur d’eau. L’influence de la température (700 °C et 900 °C) et de l’humidité relative (50 % HR et 90 % HR) a été testée à un débit de gaz humide fixe de 50 mL/min sur les différents échantillons de référence. L’utilisation d’eau marquée avec de l’18O a permis de tracer la migration des espèces oxydantes dans le graphite. Ainsi, l’efficacité du procédé a été mise en évidence permettant une élimination préférentielle par gazéification des zones les plus nanoporeuses qui sont à priori également les plus concentrées en 14C / The decommissioning of French gas cooled nuclear reactors (UNGG) will generate around 23000 tons of irradiated graphite waste containing radionuclides such as 14C, 36Cl. Both might be dose determining at the outlet, 14C as major contributor to the radioactive dose and 36Cl due to its mobility in the clay repository. The reference management for this Low-Level Long-Lived Waste (LLW-LL) is disposal but its partial decontamination has also been foreseen. Therefore, information on inventory, location and speciation of the radionuclides in the irradiated graphite are mandatory for optimizing the decontamination process and to get reliable insights on the behavior of the radionuclides in the repository. This thesis supported by EDF aims in a first part at studying the impact of temperature, graphite irradiation and radiolytic corrosion on the behavior of 14C and following structure modification. Then, the acquired data are used to support the second part devoted to study 14C decontamination by steam reforming. 13C implantation is used to simulate the presence of 14C. The experiments are carried out on different reference samples such as virgin nuclear graphite, a model and ordered lamellar HOPG graphite and a nanoporous graphite SLX 50 that allow simulating the different structural states of a neutron irradiated graphite. The first part investigates the coupled and decoupled effects of ion irradiation (used to simulate neutron irradiation) on 13C migration. The results show that, at reactor temperatures of 200 - 500 °C, 13C remains stable whatever the graphite structural disorder level. Irradiation and temperature have antagonist effects: irradiation disorders graphite whereas temperature has an annealing effect leading to a reordering of the graphite structure at a level depending on its initial one. Thus, according to graphite position in the moderator this will lead to structure contrasts depending on whether it has been irradiated at high neutron flux and high temperature or low neutron flux and colder temperature. However, 14C is stabilized in the graphite structure in all cases. The second part is devoted the study of 14C steam reforming using a thermogravimetric analyzer coupled to a steam generator. The reference samples were analyzed at temperatures of 700 °C and 900 °C and relative humidities of 50 % and 90 % at a constant humid gas rate of 50 mL/min. 18O labelled water was used to follow the migration of the oxidizing species into graphite. Accordingly, the tests put in evidence the preferential gasification of nanoporous graphite that should also be the richest in 14C. Moreover, the addition of Ni to graphite before steam reforming proved to be very efficient but the gasification was very important and needs adjusting Ni impregnation

Composite materials are multifunctional materials having unique mechanical and physical properties that can be tailored to meet the requirements of a particular application. Aluminium based Metal Matrix Composites (MMC) always draw the attention of researchers due to its unique characteristics such as better strength to weight ratio, low wear rate and lower thermal expansion coefficient. There are various methods for manufacturing of MMC that can be grouped into two major categories: (a) Solid sate method such as powder metallurgy, co-extrusion and (b) Liquid state method such as stir casting. All of these methods for production of composites have their own advantages and disadvantages. Porosity, and poor wettabilty of dispersoids with matrix are few common problems in solid state route. Formations of undesirable phases, and segregation of dispersoids are common problems in liquid state processing route. Friction Stir Processing (FSP) technique, a derivative technique of Friction Stir Welding (FSW) has emerged as a major solid state technique to produce composites. However, there are several challenges associated with it. Most of the past work has been on limited volume of material. Researchers have tried to combine FSP technique with powder metallurgy technique to overcome aforementioned challenges associated with these techniques. Where on one hand, powder metallurgy ensures the uniform dispersion of dispersoids in the matrix, on the other hand FSP on sintered billet removes the pores and other defects. The combination of these two techniques leads to a more controlled and uniform properties. However, at the same time, it can be noted that the combination of these processes is tedious and time consuming. In this study, an attempt is made to achieve bulk dispersion of a second phase into an aluminium matrix using FSP technique. A 5 mm thickness composite is attempted in this work. To achieve this objective proper and uniform mixing of the particles is required. To achieve this, new tools and processing steps are to be designed and analyzed for a better understanding of material flow around the tool pin and the effect of different tool pin geometries on the material flow. Keeping this objective, a detailed study is carried out on material flow during FSW process using aluminium as base metal. A marker material technique is employed to understand the material flow. A strip of copper is selected as the marker material. Material flow can be qualitatively predicted during the process by observing the distribution of marker material in the weld nugget. Three different kinds of tools, each with an additional feature are designed for this purpose (a) Plain frustum shape pin (b) threaded frustum shape pin and, (c) Triflute pin . The material flow due to the plain pin tool can be considered as primary flow during the FSP. Three different kinds of flow zones are observed in the weld nugget in the case of plain tool. It is found that higher numbers of geometrical features (threads and flutes) not only enhance the material flow but also lead to the additional flow currents and more thorough and uniform mixing. A closer study of the weld nugget revealed that the copper marker particles and the matrix were diffusion bonded. Based on the reaction time available and temperature in the weld nugget a diffusion layer thickness of 4 nm is expected between copper and aluminium. However, the diffusion layer thickness was found to be 3.5 μm, which is nearly three orders of magnitude higher. This can be attributed to the enhancement of diffusion due to simultaneous application of strain and temperature. As copper is soluble in the aluminium, an insoluble marker material tin was used for study of flow in the weld nugget. However, the effect of insolubility and lower melting point had some unexpected effect on the processing loads. The normal load during steady state tool traverse in conventional butt-welding is found to be around 2.7 KN while it attains an average value of 14.7 KN when a thin strip of tin is sandwiched between these plates. However, a drop in the torque of around 13.12 NM is observed when tin was sandwiched between the plates as compared to the case when no insert was present. On closer examination of the flow behavior, it is seen that the tin melted, squeezed out and formed a lubricious layer between the tool and the work piece. This reduced the torque significantly and a concomitant drop in temperature was observed. The interaction between the tool and the colder aluminium work piece would thus result in much larger normal and transverse load Based on the expected and unexpected results of flow pattern in the weld nugget, a new FSP tool and processing steps were developed to manufacture MMC. Tungsten, which is the highest melting point metal is chosen as the dispersing phase. Further, as tungsten has high melting point, the kinetics of intermetallics formation would be low for the given FSP processing time at the processing temperature. This would lead to tungsten acting as a more ductile strengthening particle, which is expected to should give some unique characteristics to the MMC. Tungsten powder with an average diameter of 414 nm was dispersed in aluminum matrix with three different proportions after optimizing all the process parameters. It is noted that the mechanical properties are significantly influenced as the tungsten content in the matrix increases. In practice, MMC shows relatively low ductility compared to the parent metal. However in this case the composite exhibited even better ductility than the as received aluminium plates (rolled sheets). The composite showed around 129 MPa of yield strength along with 21% ductility when tungsten content is 3.8 at.%. It is also found that the reaction between aluminum and tungsten occurs during the processing and form the Al12W intermetallic phase. Though the formation of this intermetallic phase was unlikely due to the low temperature and short time available during the process, the reaction kinetics between aluminium and tungsten would have been enhanced due to the simultaneous application of strain and temperature. Given that the metal-metal, tungsten-aluminium composite produced by FSP had unique properties and also formed intermetallics, a study on incorporation of a highly insoluble material, graphite was carried out. Further graphite with its own unique properties and very low wettability with aluminium could possibly impart completely different properties to the system. Past work on graphite aluminium composites produced by other methods did not show promise. As FSP imposes high strains at relatively high flow stresses on the processed material, it was seen that the graphite got sheared to form multi-layer graphene composites with the aluminium. The graphene sheets are formed by mechanical exfoliation of graphite particles during its incorporation in the matrix. The formation of graphene was confirmed after separating the graphite from the processed zone and TEM studies of the composite. It is seen that most of the graphite got converted into multilayer graphene. This aluminium-graphene composite exhibited enhanced ductility and UTS. As received aluminium plates exhibited only 11% ductility and around 100 MPa of UTS while this composite exhibited around 26 % ductility and 147 MPa of UTS. However, there is only a slight improvement in yield strength of this composite.

Cette thèse vise à étudier les nanoparticules d'or (NPOs) comme radio sensibilisateur et nano catalyseur afin d'améliorer la production d'espèces réactives de l'oxygène (EROS) et à fournir un aperçu de l'effet protecteur potentiel des acides aminés de base contre les effets des rayonnements ionisants afin d'étudier le mécanisme de dommages de l'ADN. En outre, il vise à améliorer notre connaissance des effets directs et indirects sur l'ADN plasmatique qui est une cible importante et sensible lors de l'étude des effets des rayonnements ionisants. Cette étude nécessite à la fois Ia bonne distribution et le contrôle de l'ADN déposé sur graphite HOPG. Nous avons procédé à la préparation de films (couches nanométriques à l’échelle) faite d'un complexe d'ADN avec des amines, ainsi que les acides aminés basiques. Nous avons caractérisé le déposé sec par microscopie a force atomique et par XPS. Nous avons montré que les couches contenant des acides aminés basiques sont très denses et que la protection contre les dommages de l'ADN après re-dissolution dans l'eau est très efficace. Ensuite, nous avons déposé l'ADN plasmatique à sec soul sur des feuilles minces de mylar et d'exposé ces films à un faisceau de protons à différentes énergies, Nous avons montré que, dans le value de pic de Bragg d'énergie a protons énergies inferieure a 500 keV il y a un rendement Cleve de protons a endommagé l'ADN. L'effet indirect a donc été étudié en exposant l'ADN plasmatique en solution aqueuse par rayons X ultra-mous. Nous avons procédé a de telles expériences en utilisant 100 lit de solution d'ADN plasmatique avec et sans différentes concentrations de 2-amino-2-hydroxymethyl-propane-1,3-diol, (Tris) et l'arginine (Arg) à température ambiante et sous agitation. Une très bonne procédure expérimentale. Nous avons montré que les rendements pour les pauses ADN simples brins ont permis au ratio indirect des effets directs à déterminer à 96% en bon accord avec la valeur de 97% découlant d’une étude basée sur l’irradiation aux rayons gamma de solutions congelées de l’ADN plasmatique. Nous analysons nos résultats et nous suggérons que les produits secondaires de Arginine réagissent avec les radicaux OH pour produire des effets secondaires; notamment en raison du fait que, contrairement au Tris, Arg est capable de liaison à l'ADN à l'extérieur et également à l'intérieur de la double hélice. Nous avons exposé également l'ADN de plasmide en solution aqueuse et complexe aux deux autres acides aminés basiques (lysine et histidine) par rayons X ultra-mous. Nous avons constaté que la présence de ces acides aminés augmente également la détérioration de l'ADN et suggère que les acides aminés sont donc également susceptibles de produire des effets secondaires. Enfin, nous avons étudié Ie rôle de nanoparticules d'or (NPO) dans le renforcement de la sensibilisation de la radio de l'ADN. En utilisant de nouveaux protocoles expérimentaux, nous avons fini à interpréter l'interaction du (NPOs) avec ionisation rayonnement dans des solutions aqueuses oxygénées. Pour obtenir une meilleure compréhension des mécanismes de sensibilisation de radio par NPOs, nous avons utilisé une variété de espèces détritivores, spécifiques et réactives d'oxygène et l'ADN plasmatique comme sonde afin de favoriser les voies donnees et de determiner laquelle d'entre elles est la plus efficace dans l'ADN dommageable. Cette étude a démontré pour la première fois que les NPOs contribuent en permanence à l'amélioration de la production de OH en utilisant un stock potentiel maintenu sous la forme d'HO2 • / 02 • - et H202 produits de radiolyse de l'eau primaire. Nous avons montre en effet que H202 peut réagir avec NPOs pour produire • OH radicaux. / This thesis aims at studying the gold nanoparticles (GNPs) as radiosensitizer and nanocatalyst in order to enhance the generation of reactive oxygen species (ROSs) and at providing insight into the potential protective effect of basic amino acids against ionizing radiation effects in order to study the mechanism of DNA damage. Also, it aims at improving our knowledge of direct and indirect effect on plasmid DNA which is an important and sensible target when studying ionizing radiation effects. This study required both the good distribution and control of the DNA deposited on HOPG (Highly Ordered Pyrolytic Graphite). We carried out the preparation of films (nanometer scaled layers) made of complex of DNA with diamines as wel as basic amino acids. We have characterized dry deposited by AFM (Atomic Force Microscopy) and by XPS (X-ray photoelectron spectroscopy). We have shown that the layers containing basic amino acids are very dense and that the protection against DNA damage after re-dissolution in water is very effective. Then, we have deposited dry plasmid DNA alone on thin mylar foils and exposed those films to a proton beam at various energies. We have shown that in the Bragg-peak energy range i.e. at proton energies lower than 500 keV there is a high efficiency of protons to damage DNA. The indirec effect was thus studied by exposing plasmid DNA in aqueous solution by (USX). We carried out such experiments by using 100 pit of plasmid DNA solution with and without different concentrations of 2-Amino-2-hydroxymethyl-propane-1,3-diol (Tris) and arginine (Arg) at ambient temperature and under stirring. A very good agreement was found with the rare data dealing with DNA plasmid exposed to Al Ka photons at low temperature (T < 277 K), which therefore validated the experimental procedure. We showed that the yields for DNA single strand breaks determined enabled the ratio of indirect to direct effects to be determined at 96.2%; in good agreement with the value of 97.7% stemming from a study based on y-ray irradiation of frozen solutions of plasmid DNA. We analyze our results and suggest that secondary products of Arginine react with OH radicals to produce side effects; notably due to the fact that contrary to Tris, Arg is capable of binding DNA outside but also inside the double-helix. We exposed also the plasmid DNA in aqueous solution and complexed to the two other basic amino acids (histidine and lysine) by USX. We found that the presence of tilos amino acids also increases DNA damage and suggest that those amino acids are therefore also prone to produce side effects. Lastly, we studied the role of Gold Nano Particles (GNPs) in enhancing DNA radio sensitization. By using new experimental protocols, we achieved to interpret the interaction of GNPs with ionization radiation in oxygenated aqueous solutions. To get better insight into the mechanisms of radiosensitization by GNPs, we used a variety of specific reactive oxygen species scavengers and plasmid DNA as a probe in order to favor given pathways and to determine which of them is the most effective in damaging DNA. This study has demonstrated for the first time that the GNPs contribute permanently to the enhancement of ■OH production by using a potential stock kept under the form of 1102•/02•- and H202 primary water radiolysis products. We showed indeed that H202 ca react with GNPs to produce •0H radicals.

Les propriétés exceptionnelles des nanotubes de carbone (CNT) attirent de nombreux industriels dans les domaines de la microélectronique, des matériaux ou de la nanomédecine. Néanmoins, le risque sanitaire lié à ce nanomatériau reste encore mal compris. Des profils toxicologiques différents, dépendant des caractéristiques physico-Chimiques des CNT, ont été mis en évidence. Une approche « safer by design » est proposée, afin d’identifier les paramètres pouvant, dès la conception des CNT, pour limiter le risque sanitaire. Dans ce contexte, cette thèse avait pour objectif d’étudier l’impact sur la réponse in vitro d’une lignée de macrophages murins (RAW 264.7) de deux traitements de post-Production de CNT : la fonctionnalisation acide et le recuit haute température.Les groupements acides en surface des CNT fonctionnalisés ont entrainé une augmentation de la réponse pro-Inflammatoire sans influencer significativement la cytotoxicité. D’un autre côté, la fonctionnalisation acide, principalement par l’élimination des impuretés métalliques, a permis de diminuer le stress oxydant. Les CNT recuits à haute température étaient à l’origine d’une réponse pro-Inflammatoire plus importante que les CNT bruts, confirmant lasensibilité de cette réponse biologique à la chimie de surface. En revanche, le recuit n’a pas diminué significativement le stress oxydant malgré la purification des CNT, suggérant l’importance des défauts de structure sur cette réponse biologique. La fonctionnalisation acide de nano-Graphite et de noir de carbone a eu un impact similaire à celle des CNT sur l’activité biologique des macrophages. La comparaison de ces trois nanomatériaux fonctionnalisés semble s’accorder avec le paradigme mettant en exergue la toxicité spécifique des fibres et des plaquettes. Enfin, afin de compléter ces résultats, des études exploratoires sur les interférences entre les tests de toxicité et les CNT, ainsi que sur le stress oxydant, ont été conduites. / Due to their exceptional properties, carbon nanotubes (CNT) have aroused a huge interest among in industrial fields such as microelectronics, material science and nanomedicine. Nevertheless, the health impacts of this nanomaterial still remain not well understood. The first toxicological studies pointed out that there is no unique response regarding the healthimpact of the CNT, but different toxicological profiles according to their various physicochemical properties. A safer by design approach is thus proposed to identify the parameters decreasing from their production the CNT biological impacts. In this context, this work aimed at studying the impact on the in vitro response from a macrophage cell line (RAW 264.7) of two post-Production treatments: acid functionalization and high temperature annealing.Surface acid groups from functionalized CNT enhanced the pro-Inflammatory response although the cytotoxicity remained stable. On the other hand, acid functionalization, through the elimination of metallic impurities, significantly decreased the oxidative stress. Annealed CNT increased the pro-Inflammatory response compared to the pristine CNT. It thus confirmed the sensitivity of this response for the changes in surface chemistry. However, the high temperature annealing did not influence the oxidative stress, despite of the CNT purification. It suggested that structural defects are also of importance for this response. Besides, the acid functionalization of nano-Graphite and carbon black displayed trends in the macrophage response similar to the acid functionalization of CNT. The comparison of these three carbon-Based nanomaterials seemed to conform to the fibre and platelets paradigm. Eventually, exploratory studies have also been conducted on the interferences between CNT and the toxicity assays, and on the oxidative stress.

This thesis deals with lithiation of negative electrode li-ion batteries. In this thesis is used several electrode materials: carbon, FeCl3, lithiated carbon electrodes and silicon carbide. Reduction of irreversible capacity lithium-ion batteries leads to increased capacity and also we can use new materials as a positive electrode. Thesis deals with the differences in the properties of materials using lithiation and their use in practice

Electroconductive composites are modern materials that are commonly used in many industries such as the construction industry among others. For example these materials can be useful as sensors for monitoring changes in constructions. The aim of this thesis is the research of electrically conductive silicate composite based on secondary raw materials. The design of this composite is based on the development of its own mixtures and experimental verification of the effect of the structure. The introduction part consists of a detailed analysis of 15 materials. Samples of the 5 fine and 2 coarse electrically conductive fillers were tested. Composite with filler Condufit C4 was selected as representative for type of fine fillers. Composite with filler Supragraphite C300 was selected as representative for type of coarse fillers. The selection of the composites was based on the impedance of the fabricated composites with these fillers. Subsequently, the individual components of the primary mixture were substituted. The cement was replaced by high-temperature fly ash in the amount of 20, 30, and 40 %, the aggregate of a similar fraction was replaced by steel sawdust, and the primary electrically conductive fillers were replaced by secondary ones in the amount of 30 and 50 %. All proposed replacements reduced the impedance of the composite. The most effective replacement for impedance reduction was replacement with waste graphite (up to 92 % reduction), which also slightly improved the mechanical properties of the composite. The result of this thesis is an optimized electrically conductive composite based on secondary raw materials with a fine type of filler with 30 % replacement by waste graphite "odpad vysavač"which achieves an impedance of 5 ohms. The partial goal of this thesis is a verification of the influence of moisture on the impedance of composites. Results are significantly affected by moisture when using the coarse type of filler, when using the fine type are not.

The electronic market is continually moving towards higher power densities. As a result, the demand on the cooling is increasing. Focus has to be put on the whole thermal management chain, from the component to be cooled to the ambient. Thermal interface materials are used to efficiently transfer heat between two mating surfaces or in some cases across larger gaps. There are several different thermal interface materials with various application areas, advantages and disadvantages. This study aimed to evaluate thermal and mechanical properties of graphite sheets and graphite gap pads. The work was done in cooperation with Ericsson AB. A test rig based on the ASTM D5470 standard was used to measure the thermal resistance and thermal conductivity of the materials at different pressures. It was found that several graphite sheets and gap pads performed better than the materials used in Ericsson’s products today. According to the tests, the thermal resistance could be reduced by about 50 % for the graphite sheets and 90 % for the graphite gap pads. That was also verified by placing the materials in a radio unit and comparing the results with a reference test. Both thermal values and mechanical values were better than for the reference materials. However, the long term reliability of graphite gap pads could be an issue and needs to be examined further. / Elektronikbranschen rör sig mot högre elektriska effektertätheter, det vill säga högre effekt per volymenhet. Som en följd av detta ökar också efterfrågan på god kylning. Kylningen måste hanteras på alla nivåer, från komponenten som ska kylas, ända ut till omgivningen. Termiska interface material (TIM) används för att förbättra värmeöverföringen mellan två ytor i kontakt med varandra eller för att leda värmen över större gap. Det finns flera olika TIM med olika tillämpningsområden, fördelar och nackdelar. Denna studie gick ut på att utvärdera termiska och mekaniska egenskaper hos grafitfilmer och så kallade ”graphite gap pads” då de används som TIM. Projektet gjordes i sammarbete med Ericsson AB. En testuppställning baserat på ASTM D5470-standarden användes för att utvärdera värmeledningsförmågan och den termiska resistansen hos de olika materialen vid olika trycknivåer. Resultaten visade att flera grafitfilmer och ”gap pads” presterade bättre än materialen som används Ericssons produkter idag. Enligt testerna skulle den termiska resistansen kunna minskas med 50 % för grafitfilmerna och 90 % för ”gap padsen”. Materialens fördelaktiga egenskaper verifierades i en radioenhet där temperaturerna kunde sänkas i jämförelse med ett referenstest med standard-TIM. De nya materialen var mjukare än referensmaterialen och skulle därför inte orsaka några mekaniska problem vid användning.  Den långsiktiga tillförlitligheten för grafitbaserade ”gap pads” måste dock undersökas vidare eftersom de elektriskt ledande materialen skulle kunna skapa kortslutningar på kretskorten.