Neste trabalho são apresentados os valores do primeiro coeficiente de Townsend de ionização, α, para o isobutano puro, obtidos com uma câmara de placas paralelas de anodo resistivo no intervalo de campo elétrico reduzido de 140 Td a 230 Td. O método empregado baseia-se em uma nova versão da técnica de Townsend pulsada, onde a ionização primária é produzida pela incidência de um feixe de laser pulsado de nitrogênio em um eletrodo (catodo) de alumínio. O anodo de vidro de alta resistividade (ρ = 2 x 1012Ω.cm) protege o detector contra descargas disruptivas. Para validação inicial do método, a comparação entre as correntes elétricas medidas nos regimes de ionização e de avalanche foi usada na determinação dos valores de α no nitrogênio, gás amplamente estudado com dados bem estabelecidos na literatura. Esta técnica foi estendida com sucesso para obtenção do parâmetro α para o isobutano puro. A presença de efeitos relativos à carga espacial, recombinação e à queda ôhmica através do anodo resistivo foi investigada mediante variação da taxa de repetição do feixe de laser, de sua intensidade e do campo elétrico aplicado. Destes processos secundários, somente a queda ôhmica mostrou-se relevante e os valores de campo elétrico reduzido foram corrigidos para este efeito. Os primeiros coeficientes de Townsend obtidos são compatíveis, dentro do erro experimental, com os determinados com o programa Magboltz 2 versões 7.1 e 8.6. / In this work are presented data of Townsend first ionization coefficient, α, in pure isobutane, obtained with a parallel plate chamber of resistive anode, for the reduced electric field range of 140 Td up to 230 Td. The adopted method is based on a new version of the Pulsed Townsend Technique, where the primary ionization is produced by the incidence of nitrogen pulsed laser beam in an aluminum electrode (cathode). The glass anode of high resistivity (ρ = 2 x 1012 Ω.cm) protects the detector against sparks. To validate the method, the α values were determined by comparing the ionization and avalanche electric currents in nitrogen, gas widely studied with well-established data in literature. This technique was successfully extended to obtain α parameters in pure isobutane. The presence of effects related to spatial charge, recombination and ohmic drop across the resistive anode was investigated by varying laser pulse repetition rate, its intensity and applied electric field. Of these secondary processes, only the ohmic drop was relevant and the reduced electric field values were corrected for it. The first Townsend coefficients obtained are compatible, within the experimental errors, with those determined with Magboltz 2 program versions 7.1 e 8.6.

Neste trabalho são apresentados os valores do primeiro coeficiente de Townsend de ionização, α, para o isobutano puro, obtidos com uma câmara de placas paralelas de anodo resistivo no intervalo de campo elétrico reduzido de 140 Td a 230 Td. O método empregado baseia-se em uma nova versão da técnica de Townsend pulsada, onde a ionização primária é produzida pela incidência de um feixe de laser pulsado de nitrogênio em um eletrodo (catodo) de alumínio. O anodo de vidro de alta resistividade (ρ = 2 x 1012Ω.cm) protege o detector contra descargas disruptivas. Para validação inicial do método, a comparação entre as correntes elétricas medidas nos regimes de ionização e de avalanche foi usada na determinação dos valores de α no nitrogênio, gás amplamente estudado com dados bem estabelecidos na literatura. Esta técnica foi estendida com sucesso para obtenção do parâmetro α para o isobutano puro. A presença de efeitos relativos à carga espacial, recombinação e à queda ôhmica através do anodo resistivo foi investigada mediante variação da taxa de repetição do feixe de laser, de sua intensidade e do campo elétrico aplicado. Destes processos secundários, somente a queda ôhmica mostrou-se relevante e os valores de campo elétrico reduzido foram corrigidos para este efeito. Os primeiros coeficientes de Townsend obtidos são compatíveis, dentro do erro experimental, com os determinados com o programa Magboltz 2 versões 7.1 e 8.6. / In this work are presented data of Townsend first ionization coefficient, α, in pure isobutane, obtained with a parallel plate chamber of resistive anode, for the reduced electric field range of 140 Td up to 230 Td. The adopted method is based on a new version of the Pulsed Townsend Technique, where the primary ionization is produced by the incidence of nitrogen pulsed laser beam in an aluminum electrode (cathode). The glass anode of high resistivity (ρ = 2 x 1012 Ω.cm) protects the detector against sparks. To validate the method, the α values were determined by comparing the ionization and avalanche electric currents in nitrogen, gas widely studied with well-established data in literature. This technique was successfully extended to obtain α parameters in pure isobutane. The presence of effects related to spatial charge, recombination and ohmic drop across the resistive anode was investigated by varying laser pulse repetition rate, its intensity and applied electric field. Of these secondary processes, only the ohmic drop was relevant and the reduced electric field values were corrected for it. The first Townsend coefficients obtained are compatible, within the experimental errors, with those determined with Magboltz 2 program versions 7.1 e 8.6.

Le gaz électrogénéré dans les réacteurs électrochimiques est un phénomène à la fois électrochimique et hydrodynamique. La chute ohmique dans la solution électrolyte est l'un des paramètres importants à évaluer pour l'optimisation des réacteurs électrochimiques. Elle est due à la résistance de la solution, donc, à sa conductivité électrique et la distance entre les deux électrodes. Pour réduire la consommation énergétique de la cellule de réduction électrolytique de particules d'hématite en fer métallique, on a étudié la conception des anodes, sièges de la production des bulles d'oxygène, dans deux cellules équivalentes d'électrolyse d'eau dans un milieu alcalin. Les résultats ont montré que seulement 25% de l'anode est réellement active et que le taux de rétention augmente le long de l'anode et les bulles atteignent leur vitesse terminale dès 50% de la hauteur de l'anode. Ceci nous a permis de formuler des recommandations qui permettent d'avoir les meilleures conditions de désengagement des bulles électrogénérées, pour une consommation énergétique plus faible du procédé électrochimique / Electrogenerated gas in electrochemical reactors is considered as an electrochemical and hydrodynamic phenomenon. The ohmic drop in the electrolyte solution is one of important parameter to evaluate for the optimization design of electrochemical reactors. It is due to the resistance of the solution, therefore, its electrical conductivity and of the distance between the two electrodes. To reduce the energy consumption of the electrolytic reduction cell of hematite particles to metallic iron, we studied the design of anode, the location of oxygen bubbles production, in two equivalent cells for water electrolysis in an alkali media. The results showed that the gas hold up increases along the anode and only 25% of the initial anode height is actually active. Moreover the bubbles reach their terminal velocity after 50% of the initial anode height. This allowed us to formulate recommendations that allow the best conditions of bubbles electrogenerated disengagement and low energy consumption

Cette étude porte sur la compréhension des mécanismes de la corrosion par piqûres susceptible d’affecter les aciers au carbone prévus pour le stockage des déchets radioactifs. Des modèles de transport/réaction ont été développés pour simuler, par la méthode des éléments finis, la propagation d’une piqûre à la surface du fer en milieu chloruré. Pour les modèles conservatifs, la piqûre est activée par un potentiel imposé au métal. A partir de différentes études paramétriques (géométrie, environnement…), les simulations ont permis d’identifier les facteurs critiques responsables d’un accroissement ou d’une inhibition de la vitesse de corrosion localisée. Par ailleurs, les essais sur des électrodes occluses, dites « lead-in-pencil », confirment que le confinement favorise la précipitation d’un film salin en fond de piqûre. Enfin, la simulation de situations de couplage entre la piqûre et la surface cathodique externe a permis de décrire l’évolution réaliste de la vitesse de corrosion localisée en milieu aéré et en potentiel libre. L’analyse des résultats de ces trois axes démontre que la chute ohmique dans la piqûre est le facteur contrôlant sa progression. Dans la majorité des cas, toute augmentation de cette chute ohmique (due à la précipitation, au confinement ou à l’augmentation du rapport des surfaces cathodique/anodique), conduit à une vitesse de corrosion plus rapide des surfaces externes. Ce phénomène est qualifié « d’évasement ». La croissance en profondeur, pour une vitesse d’oxydation dépendante du pH, reste à confirmer. Pour simuler le comportement à long terme du fer vis-à-vis de la piqûration, dans les conditions de stockage, les nouveaux modèles devront reposer sur la détermination plus précise de l’environnement et des lois de dissolution et de précipitation / This study deals with the understanding of the mechanisms of pitting corrosion susceptible to occur on carbon steel selected for high level nuclear waste containers. Transport/reaction models have been developed in order to simulate, by finite element method, the propagation of a pit on iron in chlorinated medium. For conservative models, pit is activated by imposing a potential on metal. Thanks to different parametric studies (geometry, environment…) simulations have permitted to classify, by severity order, the factors responsible of the increase or the inhibition of the localized corrosion rate. Otherwise, experiments on occluded (called « lead-in-pencil ») electrodes confirm that confinement favors the formation of a salt film at the bottom of the pit. Finally, the simulation of galvanic coupling between the pit and the surrounding cathodic surface has permitted to describe the realistic evolution of the localized corrosion rate in aerated medium and for free corroding conditions. The analysis of the results from these three ways of investigation has demonstrated that the ohmic drop inside the pit is the most important factor controlling his growing. In most study cases, any increase of this ohmic drop (due to precipitation, confinement or augmentation of the cathodic /anodic surfaces ratio), leads to a faster corrosion rate of the surrounding surface. This phenomenon is called “opening” of the pit. The progression at the pit bottom for a pH-dependant oxidation rate is still to confirm. In order to simulate the long term behavior of iron during pitting, in storage application, new models require a more accurate determination of the environment conditions, dissolution and precipitation laws