Made available in DSpace on 2016-12-08T17:19:16Z (GMT). No. of bitstreams: 1 Parte 1.pdf: 86993 bytes, checksum: 84f9ef5ca3d5e4b6abc44c72fe430745 (MD5) Previous issue date: 2012-02-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Epoxy resin / carbon nanotubes (CN) composites are widely used due to the versatile matrix phase and the excellent properties of the reinforcing phase. However, the development of polymer nanocomposites still faces three important challenges: interfacial interaction, dispersion and orientation of the reinforcing phase. This work studied the orientation process of NC by electric field of 100 V/cm, and how this phenomenon changes the properties of these materials. The in situ polymerization method was used to fabricate nanocomposites with multi-walled carbon nanotubes and epoxy resin. We made three sets of nanocomposites, each set contained five concentrations of CN: 0.00, 0.04, 0.08, 0.20 and 0.30 (v/v). In the manufacture of the first set, the samples were not subjected to an electric field during curing, while the second set of samples was prepared under an electric field of 100 V/cm at a frequency of 1 kHz during curing. The third set was prepared under an electric field of 100 V/cm at 60 Hz during curing. Viscosimetry techniques, optical microscopy, scanning electron microscopy, differential scanning calorimetry (DSC) and impedance spectroscopy were used to characterize the dispersion and orientation of carbon nanotubes. The viscosimetry shows that the nanocomposites exhibit a shear thinning behavior for all concentrations studied. However, the viscosity of the material increased considerably with CN concentration, ca. 50% for 0.30% (v/v) NC, difficulting the processing of samples. Optical and electronic microscopies showed that the manufacturing method used to disperse the CN did not provide a homogeneous dispersion. Using the impedance spectroscopy technique it was possible to characterize the orientation of the CN, since the electrical conductivity of all samples submitted to the electric field during curing showed an increase of 2.8 orders of magnitude compared to the set that was not subjected to the electric field. The orientation of the CN decreased the percolation threshold of the samples. Nanocomposite samples not subjected to the electric field during curing (ER) showed a percolation threshold of (0.06 ± 0.02) (v/v), while the set of samples subjected to the electric field (EA) had a percolation threshold (0,010 ± 0,005) (v/v). In these systems the direction of CN showed no dependence on the frequency of the applied electric field during curing, as the electrical conductivity of the samples prepared under the electric field oscillating at 1 kHz and that of the samples prepared at 60 Hz showed similar values. / Compósitos de resinas epoxídicas e nanotubos de carbono (NC) são materiais amplamente estudados para potenciais aplicações funcionais e estruturais, pois a fase matriz polimérica é versátil e a fase reforço apresenta excelentes propriedades. Porém, o desenvolvimento destes nanocompósitos poliméricos ainda enfrenta três desafios para que as propriedades da fase reforço sejam transferidas à matriz: a interação interfacial, a dispersão e a orientação da fase reforço. Nesse trabalho foi estudado o processo de orientação de NC por campo elétrico de 100 V/cm e como esse fenômeno altera as propriedades desses materiais. O método de polimerização ��in situ�� foi usado para fabricar nanocompósitos com nanotubos de carbono de paredes múltiplas e resina epóxi baseada no éter diglicidílico do bisfenol A (DGEBA), tendo em vista o estudo das suas propriedades elétricas. Foram fabricados três conjuntos de nanocompósitos, cada conjunto continha cinco concentrações de NC: 0,00; 0,04; 0,08; 0,20 e 0,30 % (v/v). Na fabricação do primeiro conjunto as amostras não foram submetidas ao campo elétrico durante a cura. Na fabricação do segundo conjunto as amostras foram submetidas a um campo elétrico de 100 V/cm com frequências de 1 kHz durante a cura. Na fabricação do terceiro conjunto as amostras foram submetidas a um campo elétrico de 100 V/cm com frequências de 60 Hz durante a cura. As técnicas de viscosimetria, microscopia ótica, microscopia eletrônica de varredura, calorimetria diferencial de varredura (DSC) e espectroscopia de impedância foram usadas para caracterizar a dispersão e orientação dos nanotubos de carbono. A viscosimetria mostrou que os nanocompósitos apresentam um comportamento pseudoplástico para todas as concentrações estudadas. Contudo, o aumento da concentração de NC aumentou também a viscosidade do material, em cerca de 150 % para 0,30 %(v/v) de NC, dificultando o processamento das amostras. As técnicas de microscopia ótica e eletrônica mostraram que o método de fabricação usado para dispersar os NC não proporcionou uma dispersão homogênea em escala nanométrica. Já com a técnica de espectroscopia de impedância foi possível caracterizar a orientação dos NC, pois a condutividade elétrica do conjunto de amostras submetidas ao campo elétrico durante a cura apresentou um incremento de 2,8 ordens de grandeza quando comparado ao conjunto não submetido ao campo elétrico. A orientação dos NC diminuiu o limiar de percolação das amostras, pois o conjunto de amostras de nanocompósitos não submetidas ao campo elétrico durante a cura apresentou um limiar de percolação de (0,06 ± 0,02) % (v/v). Já o conjunto de amostras de nanocompósitos submetidas ao campo elétrico apresentou um limiar de percolação de (0,010 ± 0,005) % (v/v). Nesse sistema a orientação dos NC não apresentou dependência à frequência do campo elétrico aplicado durante a cura, pois a condutividade elétrica das amostras submetidas ao campo elétrico oscilando a 1 kHz e das amostras submetidas ao campo elétrico oscilando a 60 Hz apresentaram valores similares.

Quel est le point commun entre des propulseurs à effet hall, des sources d'ions et les grandes machines de recherche sur la fusion magnétique ? Ils sont tous composés de plasmas interagissant avec des champs électrique et magnétique orthogonaux, et leurs tailles, sophistications et inaccessibilités rendent leur étude directe compliquée. Cette étude directe peut être menée à bien sur des machines plus simples, comme la colonne de plasma magnétisée Mistral utilisée dans ce travail, qui sont conçues pour l’étude de mécanismes fondamentaux. La tomographie, quant à elle, est couramment utilisée dans les tokamaks et stellarators, mais plus rarement sur des machines de laboratoire. Son intérêt majeur est de pouvoir reconstituer l’évolution temporelle de section 2D de plasma, et ce sans mesure intrusive. Dans le cadre de cette thèse un diagnostic de tomographie a été entièrement conçu, installé, calibré et testé. Les modèles existant de tomographie ont d'abord été adaptés à ce nouveau contexte, pour ensuite développer et valider le code complet d’inversion tomographique associé. Puis, une étude de faisabilité a été réalisée en mettant au point un diagnostic de tomographie utilisant un seul capteur avec un échantillonnage conditionnel sur des modes réguliers. L’attention est alors portée au développement, à la configuration et à l’application du diagnostic complet à 128 voies. Enfin, une étude paramétrique des modes réguliers a fait ressortir l'importance des paramètres de contrôle sur les modes (présence, fréquence et parité), et l'attention qui doit être portée à l'ensemble des paramètres expérimentaux, ainsi que l’évolution de leur forme et le comportement du plasma central. / What do satellites thrusters, ions sources, and fusion devices have in common? They all have plasmas with orthogonal electric and magnetic fields and their size, complexity and accessibility often make them hard to be directly studied. Simpler devices, like the linear magnetised plasma device Mistral used during this work, are conceived in order to understand, predict, and eventually control, some of their fundamental mechanisms. To this purpose, a tomography diagnostic is developed. Tomography is a well known diagnostic in tokamaks and stellarators, but remains seldom used in low temperature plasma studies. Its main advantages are to give access to the temporal evolution of a two-dimensional section of the plasma emissivity, and to be non-intrusive. In the frame of this thesis, a tomography diagnostic has been designed from scratch, implemented, calibrated and tested. The first step consists in the adaptation of existing tomography models in this context, and the full development and validation of the associated numerical code. Then, a proof of concept is conducted with a mono-sensor diagnostic using conditional sampling on coherent rotating modes. Following, the development, configuration, and application of the full 128 channels emission tomography diagnostics on Mistral are reported. New insights to characterise coherent rotating modes, such as the evolution of their shape and the behaviour of the core plasma, are given. Additionally, a parametric study of the rotating modes revealed the complex and intricated effect of control parameters on the modes (existence, frequency, and mode number), and the care that has to be put in monitoring many experimental parameters.

As interações hiperfinas são uma ótima ferramenta para estudar um sítio específico e obter informações importantes sobre o sistema. No presente trabalho analisamos de forma teórica as propriedades eletrônicas, estruturais e hiper nas do Cádmio (Cd) ligado às bases nitrogenadas do DNA. A motivação surgiu da colaboração com o grupo do prof. Artur W. Carbonari do Instituto de Pesquisas Energéticas e Nucleares (IPEN) e que tem como objetivo investigar o DNA e anticorpos de linhagens de camundongos infectados pela cepa Y de Trypanosoma cruzi, protozoário causador da doença de Chagas. A técnica Time Differential Perturbed Angular Correlation (TDPAC) foi utilizada para obter as medidas das interações hiperfinas do DNA. O núcleo de prova das medidas foi o 111Cd. Utilizamos uma abordagem quântica ab initio all-electron, dentro da Teoria do Funcional da Densidade (DFT), através do código computacional CP-PAW que combina o método Projector Augmented Wave (PAW) e a dinâmica molecular quântica de Car-Parrinello (CPMD). Ressaltamos que, até o presente momento, nenhum estudo com esta abordagem teórica e com este código computacional foi realizado para investigar as propriedades hiper nas do Cd ligado as bases nitrogenadas do DNA. / The Hyperfine interactions are good tools to study speci c sites and obtain important information about a given system. In this work we study electronic, structural and hyper ne properties of the Cadmium (Cd) coordinated to the DNA nitrogenous bases. The motivation for this study arose from a collaboration with the group of prof. Arthur W. Carbonari at the Institute of Energy and Nuclear Research (IPEN), which aims to investigate DNA and antibodies to strains of mice infected with the Trypanosoma cruzi, the protozoan that causes Chagas disease. The Time Differential Perturbed Angular Correlation (TDPAC) technique was used to obtain hypefine interactions measurements at a Cd probe bonded to DNA. We use ab initio all-electron calculations, within the Density Functional Theory (DFT) and we use the computer code CP-PAW that combines the Projector Augmented Wave (PAW) method and the Car-Parrinello (CP) quantum molecular dynamics approach to. We emphasize that, until now, no study with this theorectical approach and with this computer code was conducted to investigate the hyper ne properties of the Cd binding to the DNA bases.

Orientador: Marco Antonio Robert Alves / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-09T17:44:13Z (GMT). No. of bitstreams: 1 Tirolli_MarceloNogueira_M.pdf: 2758197 bytes, checksum: 08f6e633be3e083c0e72c41959dd296d (MD5) Previous issue date: 2007 / Resumo: Este trabalho tem como objetivo o estudo do comportamento elétrico de uma ponteira de emissão de campo, modelada na forma de um hemisfério sobre um poste, através de recursos computacionais (simulações). Escolhemos o software comercial Ansys, que utiliza o método dos elementos finitos nas análises dos fenômenos físicos para obtenção do campo elétrico na superfície da ponteira. Em seguida, foi desenvolvido também um programa computacional que realiza o cálculo da corrente de emissão baseado na teoria de emissão de campo de Fowler-Nordheim (F-N). Para calcular a corrente, o programa faz uso dos resultados das simulações do campo elétrico obtidos no software Ansys. Apresentamos também os resultados da influência que as dimensões como o raio de curvatura do hemisfério, a altura da ponteira e a distância entre anodo e catodo exercem sobre o comportamento do campo elétrico, da corrente de emissão e de outras grandezas físicas que envolvem emissão de campo / Abstract: This work aims to study the electrical behavior of a field emission tip, shaped in the form hemisphere on a post, through computational resources (simulations). We chose the Ansys commercial software that uses the finite element methods in the analyses of the physical phenomena to obtain the electric field in the surface of the tip. After that, a computational program was also developed to perform the calculation of emission current based on Fowler-Nordheim (F-N) field emission theory. To calculate the current, the program uses the results of the electric field simulations gotten in Ansys software. We also show the results of influences that dimensions such as the hemisphere curvature radius, the height of the tip and the distance between anode and cathode exert on the behavior of the electric field, emission current and other physical quantities that involve field emission / Mestrado / Eletrônica, Microeletrônica e Optoeletrônica / Mestre em Engenharia Elétrica

A presente dissertação trata da implementação, em um equipamento de eletroforese capilar (CE) com detecção condutométrica sem contato (C4D), de um sistema de controle externo do fluxo eletrosmótico (EOF) via tensão radial externa (Vrad). Através do potencial externo, aplicado diretamente ao capilar, é possível ter o controle do fluxo eletrosmótico de CE, pois, de forma simplificada, esta prática acopla vetorialmente um potencial externo aplicado com o potencial através da solução tampão dentro do capilar. O emprego da técnica possibilitou o aumento de resolução de 2 aminoácidos - Leucina e Isoleucina, cujas mobilidades diferem apenas de 0,12 cm2.V-1.s-1 entre si, em ácido acético 500 mmol.L-1 com pH = 2,55. A estratégia empregada aqui foi a que denominamos de \"coluna capilar infinita\", na qual, com as sucessivas inversões na direção do EOF, conseguimos aprisionar, dentro da coluna capilar, espécies com mobilidade eletroforética menor que a mobilidade do EOF. A literatura descreve que a inversão do EOF se torna mais difícil com o aumento do pH. Foram realizados testes em eletrólitos contendo agentes inversores de fluxo como o CTAB, o CaCl2 e o BaCl2. Ambos os aditivos foram usados em concentrações muito baixas, nas quais foi mantida a direção normal do EOF, sendo que a utilizaçãode tais agentes teve a finalidade apenas de reduzir os grupos silanolatos em soluções de pH acima de 6,0. Tal estratégia proporcionou a reversão do EOF no sistema tampão MES/HIS, cujo pH estava em torno de 6,1. Por fim, a pesquisa gerou uma perspectiva interessante que é a possibilidade de se encontrar combinações de eletrólitos de corrida e surfactantes com o intuito de se estender a faixa de alcance do Vrad para valores altos de pH. / This work presents the implementation, in an equipment for capillary electrophoresis (CE) with contactless conductivity detection (C4D), of a system for external control of the electroosmotic flow (EOF) via external radial voltage (Vrad). Through external potential, directly applied to the capillary, the electroosmotic flow can be controlled, because this practice couples the applied external potential to the zeta potential through the buffer solution within the capillary. The use of the technique allowed the baseline resolution of two amino acids (Leucine and Isoleucine), whose mobilities differ only by 0,12 cm2.V-1.s-1, using acetic acid 500 mmol.L-1 at pH = 2,55 as the running electrolyte. The approach, called \"infinite capillary column\", consists in successive reversals in the direction of the EOF, trapping species within the capillary column with electrophoretic mobility smaller than the EOF mobility. Thus, the two amino acids were retained by a period of approximately 120 minutes in the capillary that was enough to promote the baseline resolution. Previous works describe that the reversion of the EOF becoming more difficult as pH increases. In order to achieve a more effective control of EOF at high pH values (limiting the technique to a narrow performance band), tests were carried out in electrolytes containing flow reversing agents such as CTAB, CaCI2 and BaCI2. These additives were used at very low concentrations, which kept the normal direction of EOF, and the use of such agents had only the purpuse of reducing the density of silanolate groups in solutions of pH above 6,0. This approach allowed the reversion of the EOF using MES/HIS buffer, which pH was 6,1. Finally, this research has generated an interesting perspective about the possibility of finding combinations of electrolytes and surfactants aiming the Vrad range´s extension at high pH values.

Os resultados apresentados neste trabalho estão sistematizados em três partes. Em uma primeira etapa, efetuamos um estudo sistemático do comportamento da estrutura eletrônica em super-redes de deltas em função do período da super-rede e em função da concentração planar de dopantes. Uma nova abordagem, que se baseia no método celular e na solução autoconsistente das equações de Schroedinger e de Poisson, foi desenvolvida e aplicada para super-redes com dopagem planar tipo n em GaAs e em silício. Em ambos os casos, foi observada a transição de um comportamento eletrônico de caráter bi- para tridimensional conforme o período da super- rede diminui. No caso de super-redes de deltas de Si em GaAs foi empreendido o cálculo da energia de corte nos espectros de fotoluminescência de excitação. Uma boa concordância com as medidas experimentais foi obtida. O estudo da estrutura eletrônica para o caso de super-rede de deltas de Sb em Si foi pioneiro. Isto tornou os resultados de nossa investigação teórica de importância fundamental para experimentais e teóricos atuando na 6rea. A concordância entre nossas previsões teóricas e dados experimentais da literatura demonstram a consistência e o poder da abordagem desenvolvida. Em uma segunda etapa, foi efetuado o estudo da distribuição espacial do campo elétrico interno em heteroestruturas contendo camadas tipo \"bulk\", compostas por GaAs e (A1Ga)As. Uma nova abordagem foi desenvolvida para a execuqi3o de cálculos dos perfis de potencial eletrostático e de campo elétrico, sem assumir a ionização total dos dopantes e a não-degenerescência do material. Nosso método transforma a equação de Poisson em uma equação integral que deve ser resolvida autoconsistentemente. Os exemplos numéricos demonstram a aplicabilidade de nossa abordagem a sistemas reais. Perfis do campo elétrico calculados são usados para interpretar os espectros de fotorefletância. Em uma terceira etapa, a teoria geral da fotorefletância de heteroestruturas semicondutoras foi desenvolvida neste trabalho para tornar a interpretação de espectros de fotorefletância precisa e de aplicação eficiente. Um novo metodo de cdculo do coeficiente de reflexgo na presenga de inomogeneidade espacial da funggo dieletrica no interior de cada camada fmeceu um novo patamar de cornpreens20 dos espectros de fotorefletiincia. Este metodo e baseado na construgiio de uma matriz de transferhcia que iraclui as inomogeneidades no interior da camada de um mod0 integral. Portanto, para descrever uma camada de heteroestrutura e preciso ter apenas uma ma& de transferencia. 0s resultados de simulag6es numericas de espectros da fotoreflethcia estilo em uma concordhcia bastante boa com aqueles obtidos atravb de medidas opticas. A eficiencia de nosso metodo o torna aplicavel a simulag6es tip0 \"on-line\". 0s resultados dos metodos anteriores sgo reproduzidos como casos limites de nossa abordagem geral. / The results presented in this work can be displayed along the following three lines. In the first we performed a systematical study of the electronic structure behavior in delta superlattices as a function of superlattice period and sheet doping concentration. A new approach, based on the cellular method and on the selfconsistent solution of Schroedinger and Poisson equations, was developed and applied to superlattices with n-type delta doping in GaAs and silicon. In both cases, a transition from bi- to three- dimensional electronic behavior with the decrease of superlattice period was observed. For Si delta-doping superlattices in GaAs we performed calculations of the energy threshold in the photoluminescence excitation spectra. A good agreement with experimentally measured values was observed. Our investigation of the electronic structure of Sb delta-doping superlattices in Si was a pioneer theoretical study. Due to thls fact, the results of our work are of great importance for experimentalists and theoreticians acting in this area. The agreement between our theoretical predictions and the available experimental data demonstrates the consistency and the power of the developed approach. Along the second line we studied electric field spatial distribution inside of heterosinctures containing bulk layers of GaAs and (A1Ga)As. A new approach was developed to calculate the electrostatic potential and electric field profiles, providing the possibility to take .into account the incomplete ionization of impurities and the degeneracy of the materials. Our method transforms the Poisson equation into an integral equation, which must be solved selfconsistently. Numerical examples show the way to apply our approach to real systems. Internal electric field proiiles, calculated by means of our method are used to interpret photoreflectance spectra. In the third line, a general theory of photoreflectance for semiconductor heterostructures was developed in this work to make the interpretation of fotoreflectance spectra more precise and straightfornard. A new method to calculate the reflection coefficient in the presence of weak spatial inhomogenities of the dielectrical function inside each layer, provided us with a new degree of comprehension of the photoreflectance spectra. This method is based on the construction of a transfer matrix which includes the inhomogenities inside the layer in an integral way. This explains why we need only one matrix to describe one layer of the heterostructure. Results of our numerical simulations are in very good agreement with data of optical measurements. The efficiency of our method makes it suitable for on-line simulations. The results of previous methods emerge from our general approach as limit cases.

A química computacional apresenta a grande vantagem de prover informações fundamentais para espécies moleculares propostas, antes mesmo de sua síntese em laboratório. A Teoria do Funcional da Densidade é bastante utilizada nesta área, produzindo resultados satisfatórios para um grande número de propriedades e sistemas, mas com uma menor demanda por recursos computacionais que métodos mais avançados. Entretanto, o desenvolvimento de funcionais que incluem efeitos relativísticos ainda se encontra num estágio inicial. Em geral, tais efeitos são importantes em compostos de átomos pesados, embora devam ser considerados também em sistemas com átomos mais leves se a propriedade em estudo for particularmente sensível, como é o caso do gradiente de campo elétrico na posição de núcleos em moléculas. Assim, na primeira etapa desta dissertação foi avaliado o desempenho de funcionais comuns de troca-correlação não relativísticos, quando utilizados em conjunto com o formalismo de quatro componentes (tratamento relativístico), no estudo dos gradientes de campo elétrico em núcleos de átomos (índio, antimônio, iodo, lutécio e háfnio) constituindo moléculas diatômicas. Foram investigados funcionais baseados nas aproximações da densidade local e do gradiente generalizado, funcionais híbridos e que incluem correções em termos da atenuação com a distância. Nossos resultados, que estão em acordo com observações da literatura, ressaltam o melhor desempenho de funcionais híbridos e com correções de atenuação para esta propriedade e demonstram a importância do uso do método indireto. Posteriormente, foi feita uma nova parametrização de alguns dos melhores funcionais não relativísticos selecionados na etapa anterior (B3LYP, PBE0 e CAM-B3LYP), dentro do formalismo de quatro componentes, para uso no cálculo destes mesmos gradientes num grupo teste de átomos (cobre, iodo, lantânio e ouro) em moléculas lineares. Nestes casos, os funcionais modificados propostos tiveram um bom desempenho geral e foram particularmente bem sucedidos para cobre e ouro. Finalmente, é possível destacar o funcional híbrido PBE0 e sua modificação, proposta neste estudo, por conta de seu desempenho excelente, tanto para os metais como para os demais elementos que tiveram seus EFGs investigados aqui. / The computational chemistry has the great advantage of providing fundamental information for proposed molecular species even before their synthesis in laboratory. The Density Functional Theory is widely used in this area, producing satisfactory results for a large number of properties and systems, but with a lower demand for computational resources than that of more advanced methods. However, the development of functionals that include relativistic effects is still at an early stage. In general, these effects are important in compounds containing heavy elements, but they must also be considered in systems of lighter atoms if the studied property was particularly sensitive, as occurs for the electric field gradient at the position of nuclei in molecules. Thus, the first step of this dissertation was to evaluate the performance of common non-relativistic exchange-correlation functionals when used in conjunction with the four component formalism (relativistic treatment) in the study of electric field gradients at the nuclei of atoms (indium, antimony, iodine, lutetium and hafnium) forming diatomic molecules. Functionals based on the local density approximation and generalized gradient approximation, hybrid functionals and the ones that include attenuation corrections were investigated. Our results, which are in agreement with observations in the literature, highlight the best performance of hybrid functionals and attenuation corrections for this property and demonstrate the importance of using the indirect approach. Subsequently, there was a new parameterization of some of the best non-relativistic functionals selected in the previous step (B3LYP, PBE0 and CAM - B3LYP) within the four component formalism for calculations of these same gradients in a trial group of atoms (copper, iodine, lanthanum and gold) into linear molecules. In these cases, the modified functionals proposed had a satisfactory overall performance and were particularly successful for copper and gold. Finally, it is possible to mention the excellent performance of the hybrid functional PBE0 and its modification proposed in this study for both metals and the other elements that had their EFGs investigated here.

Cette thèse est consacrée à l’étude de la décharge positive dans les grands intervalles d’air. L’objectif initial est de se doter d’un modèle capable de déterminer la tension U50 ainsi que le facteur d’intervalle k, deux facteurs importants entrant dans le dimensionnement des ouvrages hautes tensions, dans des géométries complexes. Pour ce faire un bilan des modèles de la décharge disponibles dans la littérature a été fait. Notre choix s’est porté sur le modèle de type circuit développé par le groupe du professeur Beroual et appliqué aussi bien à la décharge positive qu’à la décharge négative. Ce modèle est basé sur un schéma électrique équivalent, ses paramètres variant avec le temps en fonction des caractéristiques du canal et de la géométrie de la décharge. La propagation du leader est basée sur un critère lié au calcul du champ à sa tête et où le caractère aléatoire du trajet de la décharge est pris en compte. Comme la plupart des modèles présents dans la littérature, ce modèle ne s’intéresse qu’à l’intervalle de type pointe-plan. Une partie de ce travail a consisté à étendre le domaine d’applicabilité de ce modèle aux intervalles de géométrie complexes. Une étude détaillée de la géométrie pointe-pointe nous a permis de valider notre modèle dans sa capacité à simuler un exemple d’intervalle complexe. De plus, des essais expérimentaux nous ont permis de comparer la valeur de la U50 déterminée à l’aide de notre modèle et celle issue des expériences pour cette géométrie pointe-pointe. Les résultats obtenus sont en bon accord avec une marge d’erreur inférieure à 5%. Au vu du bon accord résultant de la confrontation modèle - expérience de laboratoire et de la grande similarité, grande étincelle - décharge atmosphérique, un modèle de foudre positif a été élaboré. Ce modèle nous a permis d’utiliser pour la première fois le modèle circuit pour modéliser le processus d’attachement de la foudre. Les résultats obtenues permettent de valider la faisabilité de trouver, aux méthodes standards de protection contre la foudre, une alternative numérique basé sur une simulation de la foudre. Une estimation du champ rayonné par le canal du leader a été effectuée. Ce qui ouvre une voie à l’étude de l’interaction de ces champs rayonnés avec les systèmes d’ingénierie. / This thesis is devoted to the study of the positive discharge in large air gaps. The initial goal is to develop a model able to determine the voltage U50 and the k-factor, two important factors involved in the design of high voltage structures in complex geometries. To do this, a review of the discharge models available in the literature was done. We chose the circuit model developed by Professor Beroual’s group and applied to the positive discharge and also to the negative discharge. This model is based on an equivalent circuit diagram, his parameters varying with time according to the leader channel characteristics and the geometry of the discharge. The spread of the leader is based on a criterion related to the calculation of the field at its head and where the randomness of the discharge path is taken into account. As most of models found in the literature, this model applies only to the point-plane type interval. Part of this work was to extend the domain of applicability of this model to complex geometries. A detailed study of the rod-rod gap allowed us to validate our model in its ability to simulate an example of complex geometry. Moreover, experimental tests allowed us to compare the value of the U50 voltage determined using our model and the one from experiments for to this rod-rod geometry. The results are in good agreement with a margin of error of less than 5%. Given the good agreement resulting from the confrontation model - laboratory experience and the great similarity, large spark - atmospheric discharge, a positive lightning model was developed. This model allowed us to use for the first time the circuit model to model the lightning attachment process. The results obtained allow to validate the feasibility to find, to the standard methods of protection against lightning, digital alternative based on a simulation of lightning. An estimate of the field radiated by the leader channel was performed. This opens a way for the study of the interaction of these fields radiated with engineering systems.

La démarche expérimentale menée dans cette thèse a eu comme objectif l'étude de la faisabilité de la séparation électrostatique d'une large gamme de mélanges de matériaux pulvérulents provenant du recyclage des déchets (Al, Cu, ABS, polycarbonate, polystyrène) ou de l'industrie agro-alimentaire (paille, copeaux de bois, semoule). Les recherches se sont focalisées sur des techniques faisant appel à trois mécanismes physiques différents pour la charge des matériaux : la décharge couronne, l'induction électrostatique et l'effet tribo-électrique. Deux nouvelles installations ont été conçues et réalisées, permettent de faciliter la compréhension des phénomènes physiques rencontrés lors de la séparation des particules sous-millimétriques, dont les trajectoires sont difficile à contrôler, en raison des importantes forces aérodynamiques en jeu. La première installation, le séparateur électrostatique multifonctions à électrode-convoyeur, donne la possibilité d'étudier un ou plusieurs des trois mécanismes de charge, en rapport avec les propriétés électriques des matériaux à traiter. La deuxième installation, le séparateur tribo-aéro-électrostatique à électrodes-disques-tournantes, utilise seulement l'effet tribo-électrique pour la charge des matériaux isolants dans un lit fluidisé. Le système de mesures simultanées et continues de la masse et de la charge électrique des produits collectés a facilité l'analyse des phénomènes. Les recherches ont permis de confirmer la séparabilité électrostatique des mélanges de matériaux pulvérulents, en faisant appel à la méthodologie des plans d'expériences pour identifier les facteurs influents et trouver le point de fonctionnement optimal. / The experimental approach undertaken in this thesis was aimed at the study of the feasibility of the electrostatic separation of a wide range mixtures of powdery materials originating from the recycling of waste electric and electronic equipment (Al, Cu, ABS, polycarbonate, polystyrene), or processed in the food industry (straw, wood chips, meal). Researches were focused on techniques using three different physical mechanisms for electrical charging of the materials: corona discharge, electrostatic induction and triboelectric effect. Two new installations have been designed end engineered to facilitate the understanding of the physical phenomena involved in the separation of powdery particles, the trajectories of which are difficult to control, as strongly affected by the aerodynamic forces. The first installation, the belt-type multifunction electrostatic separator, offers the possibility to study one or several of the three charging mechanisms, in relation with the electrical properties of the materials to be processed. The second installation, two-rotating-disks-type tribo-aero-electrostatic separator uses only the triboelectric effect for charging mixtures of insulating materials in a fluidized bed. A system of simultaneous and continuous measurement of mass and electric charge of collected products facilitated the investigation of the physical phenomena. These researches confirm the feasibility of the electrostatic separation of powdery materials, by taking advantage of the design of experiments methodology to identify the influential factors and find the optimum operation conditions.

La compréhension des processus de corrosion est un élément majeur de l’étude de la durabilité des matériaux en environnements agressifs. C’est dans ce cadre que ce travail de thèse se situe. L’objectif est d’apporter un nouvel éclairage sur les processus de corrosion du nickel en milieu aqueux en utilisant la simulation par dynamique moléculaire avec un champ de force réactif « ReaxFF ».Nous nous sommes particulièrement intéressé aux réactions entres les molécules d’eau et les surfaces monocristallines de nickel. Ces résultats ont montré aucune dissociation de l’eau sur les surfaces. Par ailleurs, une adsorption des molécules en bicouche a été constatée, traduisant la polarisation mutuelle entre l’eau et le nickel, ce que confirme le calcul de charges. La surface du métal s’est chargée positivement alors que la première couche d’eau se charge négativement, reproduisant la double couche électrique. L’introduction d’un champ électrique extérieur a conditionné la réaction entre l’eau et le nickel. La présence du champ a permis d’observer les différentes étapes d’oxydation du nickel : l’adsorption des molécules d’eau puis leurs dissociations en OH- et H3O+. La dissolution des atomes de nickel à la surface puis la pénétration de O dans Ni. Ces processus d’oxydation sont répétés au cours du temps pour obtenir le film d’oxyde. L’épaisseur du film d’oxyde dépend linéairement de l’intensité du champ électrique. La cinétique d’oxydation est améliorée pour la surface (110) par rapport aux autres surfaces étudiées. L’étude de l’oxydation d’un bicristal de nickel a montré des processus identique. Par ailleurs, nous avons constaté que les premiers germes d’oxydation se sont produits au niveau des joints de grains et se sont propagés sur toute la surface. L’ensemble de ces résultats est en bon accord avec les observations expérimentales / Understanding of corrosion processes is important for the study of the durability of materials in aggressive environment. The objective is to provide new lights on the corrosion processes of nickel in aqueous condition with molecular dynamics simulation using a reactive force field "ReaxFF."We are particularly interested by the reaction between water molecules and mono-crystalline surfaces of nickel. No dissociation of water was showed on the surfaces. Moreover, an adsorption of molecules in bilayer was observed, reflecting the mutual polarization between water and nickel, which confirms the charge calculation. The metal surface is positively charged and the first water layer charged negatively, reproducing the electrical double layer. The introduction of an external electric field has conditioned the reaction between water and nickel. The presence of the field permits to observe the different stages of nickel corrosion: adsorption of water molecules, their dissociation into OH- and H3O+, the dissolution of the nickel atoms on the surface and the penetration of O in Ni. These oxidation processes are repeated over time to obtain the oxide film. The thickness of the oxide film depends linearly on the electric field intensity. The oxidation kinetics is improved to the surface (110) compared with other orientations studied. All these results are in good agreement with experimental observations