No description available.

Dans le cadre de cette thèse, nous avons cherché à mieux comprendre le comportement des éléments traces – et notamment des éléments légers Li et B – lors des processus de dégazage magmatique par une approche géochimique, basée sur l'analyse de produits volcaniques naturels (laves, gaz, aérosols volcaniques) de deux volcans aux styles éruptifs très contrastés, le Piton de la Fournaise (Réunion) et le Lascar (Chili). Dans un premier temps, cette étude s'est intéressée au rôle des transferts de gaz dans le déclenchement des éruptions majeures et aux échelles de temps impliquées. L'étude des compositions en éléments traces des laves récentes (1998-2008) du Piton de la Fournaise nous a notamment permis d'identifier des anomalies transitoires en éléments volatils (p.e., Li, Cu, B, Tl, Bi, Cd) en début de l'éruption majeure d'avril 2007. La cinétique de fractionnement par diffusion des éléments explique les anomalies observées. Les courts laps de temps nécessaires pour fractionner par diffusion Li par rapport à Cd (minutes à quelques heures) et Bi par rapport à Cd (quelques heures à deux jours) soutiennent l'idée que les magmas ont subi des variations rapides de pression quelques jours avant l'effondrement du cratère du Dolomieu. Dans un second temps, ce travail de thèse a porté sur le dégazage passif du volcan Lascar. Le panache volcanique dilué a été échantillonné au cours de 3 missions d'échantillonnage, menées entre 2009 et 2012, et caractérisé en termes de gaz acides (SO2, HCl, HF) et d’éléments traces. Au cours de ces missions, des mesures de flux de SO2 par DOAS ont également été réalisées. Les données mettent en évidence deux sources principales qui contribuent à l'activité de dégazage observée en surface: un réservoir magmatique profond et un système hydrothermal superficiel. Les contributions des deux sources varient dans le temps en réponse aux changements de l'activité volcanique. Cette évolution temporelle a été démontrée non seulement avec des traceurs répandus comme le SO2 et HCl, mais aussi avec des éléments traces à la fois volatils et très mobiles tel que le B. Pour la détermination des teneurs en B de nos échantillons, nous avons développé une méthode de dosage très précise par dilution isotopique. Appliquées aux laves du Piton de la Fournaise, cette technique nous a permis d'estimer les quantités de B perdues lors des processus de dégazage magmatique (ϵB compris entre 10 et 30%) ainsi que leur dépendance aux conditions de dégazage (continu en système ouvert, processus pré-, syn- et post-éruptifs). Appliquées aux aérosols du Lascar, elle nous a permis de montrer que la volatilité du B est favorisée lors des processus hydrothermaux (interactions gaz-eau, gaz-roche). Enfin, appliquées à des enclaves de péridotites, cette technique nous a permis d'apporter des contraintes nouvelles sur le comportement du B dans le manteau terrestre et d'estimer la teneur en B du manteau primitif (0,26 ± 0,04 ppm). / This study is aimed at better understanding the behavior of trace elements – and notably those of light elements such as Li and B – during magma degassing processes. For this purpose, we used a geochemical approach based on the analysis of fresh lavas and volcanic aerosols from Piton de la Fournaise (Réunion) and Lascar (Chile) volcanoes, respectively. Firstly, this thesis work focused on the role of gas transfers in triggering major eruptions and the time scales involved. Trace element analyses of recent lavas (1998-2008) of Piton de la Fournaise reveal anomalous abundances of volatile elements (e.g., Li, Cu, B, Tl, Bi, Cd) a few days prior to the April 2007 summit collapse. The kinetic (diffusive) fractionation of elements accounts for the observed anomalies. The short time-scales required to fractionate Li from Cd diffusively (minutes to hours) and Cd from Bi (few hours to two days) support the idea that the magmas underwent rapid pressure variations a few days before the summit collapse.Secondly, this study concentrated on the quiescent degassing activity of Lascar volcano. Both major gaseous species and trace element enrichment in gas and aerosols collected in the sustained plume over the period 2009 to 2012 suggest the involvement of two main degassing sources with contrasted geochemical signatures: a deep magmatic reservoir and a shallow hydrothermal system. Contributions from these two dominant sources vary with time in response to changes in volcanic activity. This temporal evolution has been shown not only by well-known tracers such as SO2 and HCl, but also by a trace element both volatile and highly fluid-mobile such as B. To determine the bulk boron concentration of our samples, we have developed a robust low-blank method based on isotope dilution ICP-MS. Applied to lavas of Piton de la Fournaise, this technique allowed us to quantify the amount of B lost during magma degassing (10-30%) and its dependency on degassing conditions. Applied to aerosols of Lascar, it enabled us to show that B volatility is enhanced during hydrothermal processes (gas-water, gas-rock interactions). Finally, applied to fertile peridotite xenoliths, it led us to establish new constraints on the behavior of B during mantle processes and estimate a primitive mantle B content of 0.26 ± 0.04 ppm.

La Zone des Andes Volcaniques Centrales (ZAVC) est la province magmatique la plus active système des Andes qui produit une grande variété de magmas, dont la composition s’étale des basaltes aux magmas calco-alcalins et aux shoshonites, et de structures volcaniques. Un des problèmes importants dans l’étude des systèmes volcaniques est la compréhension des processus qui contrôlent l’origine, la nature, et l’évolution des volatils au cours de l’ascension du magma. Les études menées sur les volcans de la ZAVC ont porté essentiellement sur la caractérisation des sources primaires et la contamination des magmas lors de leur ascension vers la surface. Peu d’études ont porté sur le problème du dégazage comme outil pour caractériser les processus magmatiques et la composition des gaz présents dans les systèmes volcaniques. L’objectif de cette étude et de déterminer les conditions magmatiques des systèmes actifs des volcans Irruputuncu et Lastarria par l’analyse des inclusions vitreuses dans les minéraux (plagioclases et pyroxènes). Les résultats montrent que les inclusions pour ces deux volcans ont une composition plus différenciée que la roche totale, ce qui suggère que la composition du verre représente un liquide résiduel transitoire, produit au cours d’une cristallisation fractionnée, lors de l’évolution du liquide et/ou du mélange avec un autre magma. Ce processus s’est produit à faible profondeur lors des dernières phases magmatiques. Il faut noter que toutes les inclusions vitreuses des produits des Andes centrales et du sud et de quelques arcs volcaniques ont des compositions plus évoluées que la roche totale et qu’il existe un enrichissement d’éléments comme Si, Na et K. L’interaction entre les minéraux et la riche totale indique la présence d’une zone de mush sous le système volcanique, mis en évidence par les minéraux en déséquilibre avec le liquide. Ainsi, lorsque le magma migre vers le haut (stocké dans des sills) il interagit avec la zone de mush et la résorption des minéraux permet d’incorporer des cristaux exotiques. En contrepartie, le magma en déséquilibre conduit à des cristaux de même origine. Les conditions pré-éruptives de pression, de température et de fugacité d’oxygène déterminées à partir des inclusions des produits d’Irruputuncu et de Lastarria sont de1.9-11.7 kbar, 810-970 °C et NNO+3, et sont semblables à celles observées pour d’autres volcans dans les Andes centrales au Nord du Chili. Les teneurs en volatils sont de 0-1500 ppm pour le Fluor, 10-3300 ppm pour Cl, 10-1600 ppm pour S, et 0-5 poids% pour H2O. Ces grandes gammes de pression, température et teneurs en volatil reflètent la variabilité des conditions de stockage des magmas et de capture des inclusions vitreuses dans les minéraux hôtes. Ceci a pu se produire à différentes profondeurs (6.3 à 15.2 km à Irruputuncu et 9.5 à 18 km au Lastarria) et dans des zones à différents degrés de refroidissement. De plus, la teneur en Soufre décroît inversement avec la pression et la température, et est lié directement à la fugacité d’oxygène. La teneur en volatile est semblable à celle d’autres systèmes volcaniques, ce qui suggère que la faible teneur en Soufre dans les inclusions témoigne de la séparation de cette phase en conséquence du refroidissement et de la cristallisation fractionnée d’un magma andésitique avant le mélange. Ces résultats montrent que les conditions magmatiques des volcans du nord du Chili et de la Bolivie sont similaires, probablement à cause du contexte tectonique et des processus magmatiques (mélanges et cristallisation fractionnée), des zones de stockage et des interactions entre magmas et fluides hydrothermaux identiques. Cependant, les volcans basaltiques présentent d’autres caractéristiques, ce qui indique que chaque système volcanique répond à des conditions dynamiques et tectoniques spécifiques. / The Central Volcanic Andes Zone (CVAZ) is the most active magmatic province in the Andean system, resulting in a wide variety of magmas, ranging from basalts to calc-alkaline and shoshonites dacites, and a variety of volcanic structures. One of the important problems in the study of volcanic manifestations is the understanding of the processes controlling the origin, nature and evolution of volatiles during ascent of magma. Studies conducted in the volcanoes of the ZVAC have focused primarily on the characterization of the primary source and contamination of magma as this rise to the surface. Few studies have addressed the problem of outgassing as a source of characterization of magmatic processes and the current composition of magma degassing which is present in the active volcanic systems. The objective of this research is to determine the magmatic conditions of Irruputuncu and Lastarria active volcanic systems, through the analysis of melt inclusions in minerals (plagioclases and pyroxenes). The results indicate that melt inclusions-hosted plagioclase and pyroxene both volcanoes have a more acid composition than whole rock, we suggest that glass compositions represent residual transitory melt that is found in the magma, like product of a fractional crystallization, to the evolution of the melt and/or mixing of magma. This process ocurr to shallow depth, which represents the lasts phases magmatic. It should be noted that in all the vitreous inclusions of the Central Andes, South and some island arcs, it is observed that the composition of the inclusions tends to be relatively more evolved than whole rock; it is suggest that slight enrichement of elements such as Si, Na and K occur at the between melt and minerals. Meanwhile, the interaction between minerals and whole rock indicate the presence of zone mush under each volcanic system, this is evidenced in large part by crystals in disequilibrium with the melt. Therefore, when that magma ascends (stored sills structure) interacts with the mush zone, reabsorption the minerals incorporating exotic crystals. On the other hand, when the magma is in equilibrium generate cognate crystals. The conditions of pressure, temperature and oxygen fugacity determined from the melt inclusions for pre-eruptive magmatic conditions in Irruputuncu and Lastarria systems vary between 1.9 to 11.7 kbar, 810-970 °C and NNO+3, similar to those observed in other volcanoes in the Central Andes of northern Chile. Otherwise, range of volatiles content varies in 0-1500 ppm F, 10-3300 ppm Cl, 10-1600 ppm S, 0-5 %wt H2O; this wide range of variation in the values of pressure, temperature and concentration of volatile, reflecting the variability of magma storage conditions during entrapping vitreous inclusions in the host crystal. This could at different depths (6.3 to 15.2 km Irruputuncu volcano and 9.5 to 18 km Lastarria volcano) and in areas with different degrees of cooling structures represented by sills. Moreover, the S content decrease with increase pressure and temperature, and is related directly with the fugacity of oxygen. The volatile content is similar in various volcanic systems, this suggest that the low S content in melt inclusions represent the separation of this phase as a results of cooling and fraccionate crystallization of a andesitic magma before of mixing. It appears that the magmatic conditions in the volcanoes of northern Chile and Bolivia have similar characteristic, due to the geotectonic context of this zone, resulting varied magmatic process, such as magma mixing, evolved fraccionate crystallization (rhyolitic magma), accumulation of magma in shallow areas, interaction between magmatic and hydrothermal fluids. However, basaltic volcanoes present differents characterics, which indicate that each volcanis system respond to a dynamic of geotectonic conditions and interaction with the environment. / La Zona Volcánica de los Andes Centrales (ZVAC) es la provincia magmática más activa en el sistema Andino, originando una gran diversidad de magmas, cuya composición varía de basaltos a dacitas con tendencia calcoalcalina a shoshonitica, y una gran variedad de estructuras volcánicas. Uno de los problemas importantes en el estudio de las manifestaciones volcánicas es la comprensión de los procesos que controlan el origen, naturaleza y evolución de los volátiles durante el ascenso del magma. Los estudios que se han realizado en los volcanes de la ZVAC se han concentrado fundamentalmente en la caracterización de la fuente primaria y la contaminación del magma a medida que estos ascienden a la superficie. Pocos estudios han abordado el problema de la desgasificación como fuente de caracterización de los procesos magmáticos y de la composición actual del magma en desgasificación que está presente en los sistemas volcánicos activos. El objetivo de esta investigación es determinar las condiciones magmáticas de los sistemas volcánicos activos Irruputuncu y Lastarria, a través del análisis de inclusiones vítreas en minerales (plagioclasas y piroxenos). Los resultados geoquímicos indican que las inclusiones hospedadas en los cristales de plagioclasa y piroxeno de los volcanes Irruputuncu y Lastarria tienen una composición química más ácida que la roca total, por lo que sugiere que la composición química del vidrio atrapado en los fenocristales representa el líquido residual transitorio que se alberga en el magma, producto de un ciclo de cristalización fraccionada, a la evolución del fundido y/o mezcla de magma. Este proceso ocurre a profundidades relativamente someras, donde se albergan las últimas fases del magma. Cabe destacar que en todas las inclusiones vítreas de los volcanes de los Andes Centrales, Sur y en algunos de arcos de islas, se observa que la composición de las inclusiones tiende a ser relativamente más evolucionada que la roca total; se sugiere que en el borde o límite donde interactúan el fundido y el cristal ocurre un leve enriquecimiento de elementos como el Si, Na y K. Por su parte, los estudios realizados entre MI-mineral y minerales-roca total indican la presencia de una zona mush bajo cada sistema volcánico, esto se evidencia en gran parte por cristales que no están en equilibrio con el fundido. Por lo tanto, cuando el magma asciende (almacenado en estructuras de sills) interactúa con la zona mush, que reabsorbe los minerales e incorporándolos como cristales. Por otra parte, cuando los magmas se equilibran forman cristales cognatos. Las condiciones de presión, temperatura y fugacidad de oxígeno determinadas a partir de las inclusiones vítreas, para las condiciones magmáticas en los sistemas Irruputuncu y Lastarria, varían entre los 1,9 a 11,7 kbar, 810 a 970°C y NNO+3, rangos similares a los observados en otros volcanes de los Andes Centrales del Norte de Chile. Por otra parte, el rango del contenido de volátiles varía entre 0-1500 ppm F, 10-3300 ppm Cl, 10-1600 ppm S, 0-6 %wt H2O; este amplio rango de variación en los valores de presión, temperatura y concentración de volátiles, reflejan la variabilidad de las condiciones de almacenamiento del magma durante el atrapamiento de las inclusiones vítreas en el cristal huésped. Esto ocurriría a diferentes profundidades (6,3 a 15,2 km para el volcán Irruputuncu y 9,5 a 18 km para el volcán Lastarria) y en zonas con distinto grados de enfriamiento, representados por estructuras de sills. Cabe destacar que el contenido de S disminuye con el aumento de la presión y temperatura, y se relaciona directamente a la fugacidad del oxígeno. (...)

The present thesis was to study non-metallic inclusions during vacuum degassing in ladle treatment. Emphasize was mostly given to liquid CaO-Al2O3 inclusions. A series of industrial experiments were carried out at Uddeholm Tooling AB, Hagfors, Sweden. To gain an insight into the industrial findings, laboratory investigations were also performed. Large number of steel samples were collected and examined. Liquid calcium aluminate inclusions with low SiO2 and high SiO2 were often found with spinel inclusions before vacuum degassing. Laboratory experiments showed that spinel would react with the dissolved Ca in the liquid steel forming calcium aluminate inclusions. This laboratory results agreed with the industrial observation that spinel phase was quite often found in the center of the calcium aluminate phase. After vacuum degassing, most of the inclusions were calcium aluminate liquid inclusions. When dissolved Al level was low, 2 types of liquid calcium aluminate inclusions with considerably different SiO2 contents were found to coexist even at the end of the process. In view of the lack of the thermodynamic data for SiO2 activities in the low silica region, thermodynamic measurements were conducted in the CaO-Al2O3-SiO2-MgO system. The experimental results could reasonably explain the coexistence of the two types of the liquid oxide inclusions. While the total number of inclusions decreased during vacuum degassing, the number of bigger inclusions (>11.3 μm) increased generally in used ladles. This finding was in accordance with the previous studies, wherein, ladle glaze was found to be responsible for the supply of bigger inclusions. The behaviors of several types of inclusions in liquid steel were examined using a laser scanning confocal microscope (LSCM). While alumina inclusions tended to impact on each other, agglomerate and grow very quickly, none of the other types of inclusions, such as spinel and calcium aluminate was observed to agglomerate. The results of LSCM study agreed well with the industrial observation. Examination on a huge number of inclusions did not show any indication of impact and physical growth of the inclusions, except the alumina inclusions. The removal of inclusions around open-eye in a gas-stirred ladle was experimentally studied by a cold model with oil and water. Most of the simulated inclusions were brought up to the oil phase by gas-water plume. Inclusion removal into oil layer took place when the inclusions passed through the sphere-bed of the oil layer around the open-eye. A calculation showed that the contribution of metal-gas plume in inclusion removal was much larger than that of buoyancy mechanism. The results of the industrial experiments revealed that the inclusions distribution strongly depended on stirring condition. When a ladle was stirred by both gas and induction, inclusion removal near slag layer was significant. / QC 20100803

Massive sulfide deposits in the Noranda mining camp, northwestern Québec, are mainly associated with extensive footwall alteration defined by intense chloritization and sericitization. However, Fe-carbonate alteration also occurs in proximity to some deposits. To test the exploration significance of carbonate alteration in the camp, two areas of intense carbonate alteration were examined, around the small Delbridge deposit and near the new Pinkos occurrence in the Cyprus Rhyolite. Between 1969 and 1971, the Delbridge deposit produced 370,000 t of ore grading 9.6% Zn, 0.61% Cu, 110 g/t Ag, and 2.1 g/t Au. Recent drilling at the new Pinkos occurrence intersected 2.64 m of massive to semi-massive sulfides grading 8.1% Zn and 18.2 g/t Ag. Alteration mapping has shown that the distribution of Fe-carbonates can be used to identify vertically extensive zones of hydrothermal upflow at both properties. At Delbridge, intense Fe-carbonate alteration in brecciated rhyolite defines a pipe-like upflow zone that extends vertically for up to 300 m within the stratigraphic footwall of the massive sulfides and 100 m into the hanging wall. The location of known massive sulfide mineralization coincides with the intersection of the alteration pipe and a favorable horizon marked by the occurrence of fine-grained volcaniclastic rocks. At Pinkos, a similar zone of Fe-carbonate alteration occurs in outcrops of coherent rhyolite. Fe-carbonate alteration is most intensely developed along polygonal cooling fractures in massive rhyolite and decreases in intensity towards the centers of the columns. Fe-carbonate stringers and locally abundant matrix carbonate occur in fragmental rocks at the stratigraphic top of the coherent rhyolite flows and are most intense at the location of sulfide-bearing outcrops that mark the known mineralized horizon. Whereas Fe-carbonate alteration defines the central part of the hydrothermal upflow zones at both properties, disseminated pyrite occurs at the margins and is widespread outside the main upflow zones. This may indicate that Fe-carbonate in the main upflow zones formed at the expense of earlier disseminated sulfides. Replacement of pyrite by synvolcanic Fe-carbonate alteration at Delbridge and Pinkos can probably be attributed to a relatively high concentration of dissolved CO2, possibly of magmatic origin, in the main-stage ore-forming fluids.

Massive sulfide deposits in the Noranda mining camp, northwestern Québec, are mainly associated with extensive footwall alteration defined by intense chloritization and sericitization. However, Fe-carbonate alteration also occurs in proximity to some deposits. To test the exploration significance of carbonate alteration in the camp, two areas of intense carbonate alteration were examined, around the small Delbridge deposit and near the new Pinkos occurrence in the Cyprus Rhyolite. Between 1969 and 1971, the Delbridge deposit produced 370,000 t of ore grading 9.6% Zn, 0.61% Cu, 110 g/t Ag, and 2.1 g/t Au. Recent drilling at the new Pinkos occurrence intersected 2.64 m of massive to semi-massive sulfides grading 8.1% Zn and 18.2 g/t Ag. Alteration mapping has shown that the distribution of Fe-carbonates can be used to identify vertically extensive zones of hydrothermal upflow at both properties. At Delbridge, intense Fe-carbonate alteration in brecciated rhyolite defines a pipe-like upflow zone that extends vertically for up to 300 m within the stratigraphic footwall of the massive sulfides and 100 m into the hanging wall. The location of known massive sulfide mineralization coincides with the intersection of the alteration pipe and a favorable horizon marked by the occurrence of fine-grained volcaniclastic rocks. At Pinkos, a similar zone of Fe-carbonate alteration occurs in outcrops of coherent rhyolite. Fe-carbonate alteration is most intensely developed along polygonal cooling fractures in massive rhyolite and decreases in intensity towards the centers of the columns. Fe-carbonate stringers and locally abundant matrix carbonate occur in fragmental rocks at the stratigraphic top of the coherent rhyolite flows and are most intense at the location of sulfide-bearing outcrops that mark the known mineralized horizon. Whereas Fe-carbonate alteration defines the central part of the hydrothermal upflow zones at both properties, disseminated pyrite occurs at the margins and is widespread outside the main upflow zones. This may indicate that Fe-carbonate in the main upflow zones formed at the expense of earlier disseminated sulfides. Replacement of pyrite by synvolcanic Fe-carbonate alteration at Delbridge and Pinkos can probably be attributed to a relatively high concentration of dissolved CO2, possibly of magmatic origin, in the main-stage ore-forming fluids.

Massive sulfide deposits in the Noranda mining camp, northwestern Québec, are mainly associated with extensive footwall alteration defined by intense chloritization and sericitization. However, Fe-carbonate alteration also occurs in proximity to some deposits. To test the exploration significance of carbonate alteration in the camp, two areas of intense carbonate alteration were examined, around the small Delbridge deposit and near the new Pinkos occurrence in the Cyprus Rhyolite. Between 1969 and 1971, the Delbridge deposit produced 370,000 t of ore grading 9.6% Zn, 0.61% Cu, 110 g/t Ag, and 2.1 g/t Au. Recent drilling at the new Pinkos occurrence intersected 2.64 m of massive to semi-massive sulfides grading 8.1% Zn and 18.2 g/t Ag. Alteration mapping has shown that the distribution of Fe-carbonates can be used to identify vertically extensive zones of hydrothermal upflow at both properties. At Delbridge, intense Fe-carbonate alteration in brecciated rhyolite defines a pipe-like upflow zone that extends vertically for up to 300 m within the stratigraphic footwall of the massive sulfides and 100 m into the hanging wall. The location of known massive sulfide mineralization coincides with the intersection of the alteration pipe and a favorable horizon marked by the occurrence of fine-grained volcaniclastic rocks. At Pinkos, a similar zone of Fe-carbonate alteration occurs in outcrops of coherent rhyolite. Fe-carbonate alteration is most intensely developed along polygonal cooling fractures in massive rhyolite and decreases in intensity towards the centers of the columns. Fe-carbonate stringers and locally abundant matrix carbonate occur in fragmental rocks at the stratigraphic top of the coherent rhyolite flows and are most intense at the location of sulfide-bearing outcrops that mark the known mineralized horizon. Whereas Fe-carbonate alteration defines the central part of the hydrothermal upflow zones at both properties, disseminated pyrite occurs at the margins and is widespread outside the main upflow zones. This may indicate that Fe-carbonate in the main upflow zones formed at the expense of earlier disseminated sulfides. Replacement of pyrite by synvolcanic Fe-carbonate alteration at Delbridge and Pinkos can probably be attributed to a relatively high concentration of dissolved CO2, possibly of magmatic origin, in the main-stage ore-forming fluids.

La croissance de la phase vésiculée, moteur de l'éruption, est contrôlée par les processus de diffusion qui permettent la migration des gaz (et notamment des gaz rares) dans les bulles. On utilise la haute volatilité des gaz rares comme traceur géochimique de l'évolution d'une phase gazeuse sans interaction chimique. Ainsi, documenter précisément les mécanismes de diffusion des différents gaz rares (He, Ne, Ar) lors de l'éruption (c'est-à-dire en fonction de la chute de température et de pression du système), permet de quantifier les phénomènes de fractionnement de la phase gazeuse. La compréhension des processus de fractionnements cinétiques, permet dès lors de prédire le temps nécessaire pour atteindre une certaine quantité de gaz rares dans une bulle (située au sein d'un système magmatique), lors de l'éjection des laves. Pour cela, la compréhension de l'influence de la température et de la structure du réseau silicaté sur les coefficients de diffusion est nécessaire. Cependant, la compréhension physique des processus de diffusion ainsi que l'évolution des coefficients de diffusion en fonction de la température, n'est pas suffisante pour dériver des temps caractéristiques d'une éruption volcanique de type Plinian. La complexité symptomatique de tels systèmes, nécessite une résolution numérique des équations de diffusion prenant en compte la dépendance des coefficients de diffusion à la température. Plusieurs verres synthétiques et naturels de composition basaltique ont été fabriqués dans le but de déterminer la vitesse de diffusion des gaz rares. Les données de diffusivités expérimentales mesurées sur ces systèmes, depuis l'état vitreux de basse température (T = 423 K) jusqu'à des températures sur-liquidus (T = 1823 K), documentent nos connaissances des processus physiques de diffusion dans ces milieux. Un modèle numérique intègre ces données et permet de suivre en continue la variation des coefficients de diffusion lors de la trempe d'une lave. On a pu ainsi montré : - La relation particulière entre la structure du milieu diffusif et les espèces diffusantes. La quantité de formateurs de réseaux (SiO2) et de modificateurs (CaO - MgO - etc.), joue sur la connectivité des chemins de diffusions de chaque gaz rare, avec un effet antagoniste entre l'ouverture globale du réseau et la connexion des tétraèdres de la structure. - La présence de comportements non-arrheniens des gaz rares proches de la Tg, due à la relaxation du réseau silicate. - L'importance des données expérimentales dans l'étude des mécanismes de dégazage des magmas basaltiques. En effet, les études précédentes utilisent des extrapolations des coefficients de diffusions, mesurés dans le verre pour extrapoler les diffusivités dans le liquide silicaté. Nos données montrent que le fractionnement cinétique des gaz rares pendant le dégazage de lave basaltique, est surestimé par ces extrapolations basées sur les vitesses de diffusions aux basses températures (T << Tg) / Noble gas geochemistry is an important tool for constraining the history of the volatile phase during magmatic eruptions. Degassing processes control the gas flux from liquid to bubble, leading to solubility- or kinetic-control of the fractionation mechanisms. Noble gases have no chemical interactions at magmatic conditions and are therefore well adapted to tracing gas fractionation mechanisms during the evolution of the gas phase. Well constrained diffusion coefficients, and their dependence on temperature, of several noble gases are critical for estimating the timescale of a plinian eruption, for example. During the quench phase of the lava ejected in the plume, atmospheric noble gases will diffuse through the liquid/glass shell surrounding gas bubbles. Diffusion of these atmospheric gases determine the gas content measured in the eruption products, which are therefore a function of the timescale of the eruption, the initial and final temperatures, the glass/liquid shell thickness and the cooling rate of the magma. Therefore, it should be possible to calculate plinian eruption timescales from noble gas fractionation patterns trapped in pumice. However, in order to perform the diffusion calculations, it is first necessary to model the diffusive system: a numerical resolution of the diffusion equations for hollow sphere geometry is required as there are no analytical solutions (for complex thermal histories such as for a plinian ash column). In order to constrain the diffusion mechanisms (He, Ne and Ar) in silicate glasses and liquids, several synthetic basaltic glasses were produced. Diffusion coefficients were measured from low temperatures (423 K) to the Tg (glass transition temperature) of the system (1005 K). These experiments allowed us to investigate the physical processes that limit diffusion in glassy media: He, Ne and Ar diffusion in silicate glasses show non-Arrhenian behavior as the Tg is approached thought to be due to structural relaxation of the silicate network itself. Complementary diffusion experiments (on He and Ar) at super-liquidus conditions (1673 K and 1823 K) provide important information on the temperature dependency of He/Ar fractionation in silicate liquids. These diffusion measurements required that a new experimental protocol was developed in order to investigate noble gas diffusivities in silicate melts. The results show that relative He and Ar diffusion (i.e. DHe/DAr) decreases with temperature, from 165 at temperatures close to the Tg to 3.2 at high (>1823K) temperature. The measured coefficient diffusions are incorporated to a numerical model of the diffusion equations for a hollow sphere geometry that were developed as a MatLab code as part of this thesis work. This enabled us to determine the likely timescales of plinian eruptions from existing noble gas measurements. These results also have important implications for mechanisms of degassing in basaltic magmas: previous work used diffusivities measured on glasses in order to extrapolate to noble gas diffusivities at magmatic temperatures. Our measurements show that kinetic fractionation of noble gases during degassing of basaltic magmas has likely been overstated because noble gas diffusion in the glass cannot be extrapolated to the liquid state

Increasing demands regarding performance, safety and environmental compatibility of hydraulic mobile machines in combination with rising cost pressures create a growing need for specialized optimization of hydraulic systems; particularly with regard to hydraulic reservoirs. In addition to the secondary function of cooling the oil, two main functions of the hydraulic reservoir are oil storage and de-aeration of the hydraulic oil. While designing hydraulic reservoirs regarding oil storage is quite simple, the design regarding de-aeration can be quite difficult. The author presents an approach to a system optimization of hydraulic reservoirs which combines experimental and numerical techniques to resolve some challenges facing hydraulic tank design. Specialized numerical tools are used in order to characterize the de-aeration performance of hydraulic tanks. Further the simulation of heat transfer is used to study the cooling function of hydraulic tank systems with particular attention to plastic tank solutions. To accompany the numerical tools, experimental test rigs have been built up to validate the simulation results and to provide additional insight into the design and optimization of hydraulic tanks which will be presented as well.

The control of non-metallic inclusions is very important for the improvement of performance during the application of tool steel. This present study was performed to see the effect of changing of some process parameters during the vacuum degassing of the melt and how these changing parameters affects the characteristics of inclusions in tool steel. The main parameters that were changed during the vacuum degassing were the change of induction stirring, argon flow rate from both the plug 1 and 2 and different ladle ages for different heat. Electrolytic extraction method was used to observe the morphology and characteristics of inclusions as a 3 dimensional view in tool steel. Four lollipop samples from four different heats were used for the experiment and all the samples were after vacuum (AV) degassing. In this study four different types of inclusions were found and they are classified as type 1, 2, 3 and 4. Of them type 1 inclusion was the major one with mostly spherical shaped. This study shows that among the three parameters, induction stirring has the biggest effect for the total number of inclusions per volume in the sample than the other two parameters Heat 4A showed the lowest number of inclusions per volume comparing with the other heats. The main reason behind this can be said that the induction stirring was the lowest comparing with the other heats with moderate argon flow and ladle age of 12. Extreme value analysis was used in this study to predict the probability of getting largest size inclusions in a certain volume of the metal. For the prediction of the largest inclusion size, both the electrolytic extraction (3D) and cross-sectional (2D) method was used. Later in this study comparison was done to determine the accuracy of both the methods and it is concluded that for the type 1 inclusions electrolytic extraction method shows almost similar trend with cross-sectional method and electrolytic extraction method shows better accuracy for the prediction of largest size inclusions than the cross-sectional method. Electrolytic Extraction method is also applicable for the prediction of largest size inclusions for multiple types of inclusions.