In der vorliegenden Arbeit werden verschiedene Methoden zur Bestimmung von Sintertemperaturen für Brennstoffaschen vorgestellt und verglichen, mit dem Ziel die Agglomerationsneigung von Aschen zu charakterisieren. Es wurden Untersuchungen an drei ausgewählten Kohleaschen unter inerten, oxidierenden und reduzierenden Bedingungen durchgeführt. Die Methoden Erhitzungsmikroskopie (ASV), Hochtemperatur-Röntgendiffraktometrie (HT-RDA), Thermogravimetrische Differenz-kalorimetrie (TG-DSC), Thermodynamische Gleichgewichtsberechnungen (GGW), Elektrochemische Impedanzspektroskopie (EIS), Untersuchung der Schereigenschaften (SV) und die Bestimmung der Kaltdruckfestigkeit (KDF) wurden angewendet. Die Kombination der Untersuchungen ließ eine umfangreiche analytische Charakterisierung der Sintervorgänge zu. Unter der Berücksichtigung einer guten Vergleichbarkeit hinsichtlich der ermittelten Sintertemperaturen, stellt die EIS eine Alternative zur etablierten aber zeitaufwändigen Bestimmung der KDF dar. In Abhängigkeit von der Aschezusammensetzung, der Korngröße und der Gasatmosphäre, ist bereits ab einer Temperatur von 650 °C eine Agglomeration von Aschepartikeln möglich.

La sédimentation des suspensions aqueuses de particules minérales microniques, polydisperses et concentrées a été analysée à l’aide du Turbiscan MA 2000 fondé sur la diffusion multiple de la lumière, en vue d’établir la procédure qui permet de déceler la présence d’une morphologie fractale, puis de déduire les règles de comportements des suspensions fractales par la modélisation avec les réseaux de neurones. Le domaine des interactions interparticulaires physicochimiques (0 à 10% volumique en solide) a été privilégié.La méthodologie de détermination de la structure multifractale des agglomérats et de la suspension a été proposée. La modification structurale des agglomérats qui est à l’origine de comportements non linéaires des suspensions et qui dépend des propriétés cohésives des particules primaires, est interprétée par la variation de la mobilité électrophorétique des particules en suspension. Une approche d’estimation de ces modifications structurales par les réseaux de neurones, à travers la dimension fractale, a été présentée. Les limites du modèle à assimiler ces comportements particuliers ont été expliquées comme résultant du faible nombre d’exemples et de la grande variabilité des mesures aux faibles fractions volumiques en solide. / The sedimentation of aqueous suspensions of micron-sized mineral particles, polydisperses and concentrated, was analyzed using the Turbiscan MA 2000 based on the multiple light scattering in order to establish the procedure to detect the presence of a fractal morphology, and then to deduce the set of laws of fractal behavior of suspensions by modeling with neural networks. The methodology for determining the multifractal structure of agglomerates and the suspension was proposed. The structural modifications of the agglomerates at the origin of the nonlinear behavior of suspensions and which depends on cohesive properties of primary particles, is interpreted by the change of the electrophoretic mobility of suspended particles. The estimation by neural networks of these structural changes, through the fractal dimension has been presented. The limits of the model to learn these specific behaviors have been explained as resulting from the low number of examples and the great variability in the measurements at low volume fractions of solid.

This thesis examines the role of rock avalanches in tectonically active terrains including the effects of the deposits on glacier behaviour and their contribution to moraine formation. The chronologies of mountain glacier fluctuations, based on moraine ages, are widely used to infer regional climate change and are often correlated globally. In actively uplifting mountain ranges rock avalanches that travel onto the ablation zone of a glacier can reduce ice-surface melting by insulating the ice. This can cause buried ice to thicken due to slower ablation and can significantly alter the overall glacier mass balance. This glacier response to supraglacial rock avalanche deposits can confound apparent climatic signals extracted from moraine chronologies. This thesis investigates the processes through which rock avalanche deposits may affect glaciers and develops a new technique to identify the presence of rock avalanche debris in glacial moraines. From laboratory experiments on the effects of debris on ice ablation it is demonstrated that the rate of underlying ice ablation is controlled by diurnal cyclicity and is amplified at high altitude and in lower latitudes. The relatively low permeability of rock avalanche sediment in comparison with non-rock avalanche supraglacial debris cover contributes to the suppression of ablation, at least partly because it greatly reduces the advection of heat from rain water to the underlying ice. The laboratory findings are supplemented by field investigations of two recent rock avalanche deposits on glaciers in the Southern Alps of New Zealand. This work demonstrates that the rock avalanche deposits are very thick (10 m at Aoraki/Mt. Cook and 7m at Mt. Beatrice) and almost stopped the ablation of the overlying ice. This resulted in the formation of an ice-platform more than 30 m high. This led to a reduction of the existing negative mass balance of the affected Tasman and Hooker Glaciers. There was little noticeable alteration of the overall glacial regime due to the small scale of the debris covered area (4 and 1% of the ablation zones for the Tasman and Hooker Glaciers, respectively) but there is a significant contribution to supraglacial debris, which is passively transported toward the terminus. A conceptual model of the response of mountain valley glaciers to emplacement of extensive rock avalanche debris on the ablation zone has been proposed for the effect of this type of debris on terminal moraine formation based on enhanced ‘dumping’ of supraglacial sediments. A new technique has been developed to distinguish rock-avalanche-derived sediment from sediment of glacial origin, based on the sedimentary characteristics of the finest fraction. Examination of rock avalanche sediment under the Scanning Electron Microscope showed that finer particles tend to form strong clumps, which comprise many smaller (down to nanometre-scale) clasts, named here ‘agglomerates’. These agglomerates are present in the fine fraction of all examined rock avalanche deposits and absent in known non-rock-avalanche-derived glacial sediments. The agglomerates are characteristics of sediment produced under the high-stress conditions of rock avalanche emplacement and contrast with lower-stress process sub- and en-glacial environments. It is demonstrated that these agglomerates are present in some moraines in the Southern Alps of New Zealand that have been attributed to climate fluctuation. Consequently, this technique has the potential to resolve long-standing arguments about the role of rock avalanches in moraine formation, and to enhance the use of moraines in palaeoclimatological studies.

Le travail de thèse présenté ici apporte des éléments de compréhension sur l'influence de la gestion de l'eau et de la gestion thermique d'une PEMFC sur ses performances électriques. Un modèle bidimensionnel représentant les transferts de matière et de chaleur dans l'épaisseur d'une cellule élémentaire et le long des canaux d'alimentation est mis en place. Une partie spécifique de l'étude concerne la modélisation microscopique des agglomérats réactionnels et l'influence de l'eau présente dans ces zones actives sur les performances électriques locales et globales de la pile. Dans l'optique de réaliser un modèle pouvant s'intégrer à un système de contrôle, les transports couplés de l'eau liquide et vapeur, de la chaleur et des charges sont résolus analytiquement. Quelles que soient les conditions de fonctionnement, le modèle permet de calculer quel est l'état interne de la pile en terme d'hydratation, de production de courant et de chaleur. Le diagnostic de l'état interne de la pile en fonction des conditions opératoires permet de connaître précisément comment adapter les paramètres d'alimentation de la pile pour obtenir des performances électriques optimales. Les distributions locales d'eau, de courant et de température sont présentées en fonction de la stratégie d'alimentation en gaz de la pile et de l'orientation du circuit de régulation thermique. Une partie consacrée au diagnostic de fonctionnement d'une pile illustre en quoi l'utilisation du modèle et la connaissance de l'état interne de la pile apporte des informations primordiales lors de l'utilisation d'une pile à combustible / The present work contributes to the understanding of water management and thermal management of a PEM fuel cell influences on the electrical performances. A bidimensional model representing mass and heat transfer in the cell thickness and along distribution channels is done. A specific part of the study concerns a microscopic representation of reactive agglomerates. This part presents the impact of the liquid water presence on local and global current densities. In te vein of integrating this model in a total fuel cell control system, simplifications have been done and coupled mass, heat and charge transfers are solved analytically. For any operating condition, the model gives a complete view of the hydric, thermal and electric inner situation of the cell. This diagnosis of the inner state of the cell leads to find the operating conditions giving to the optimal electric performances. Water, current and temperature distributions are presenting for different gas feeding strategies and different thermal management configurations. A specific part is dedicated to illustrate how this local diagnosis of the cell state can be used to estimate its global electric performances

In der vorliegenden Arbeit werden verschiedene Methoden zur Bestimmung von Sintertemperaturen für Brennstoffaschen vorgestellt und verglichen, mit dem Ziel die Agglomerationsneigung von Aschen zu charakterisieren. Es wurden Untersuchungen an drei ausgewählten Kohleaschen unter inerten, oxidierenden und reduzierenden Bedingungen durchgeführt. Die Methoden Erhitzungsmikroskopie (ASV), Hochtemperatur-Röntgendiffraktometrie (HT-RDA), Thermogravimetrische Differenz-kalorimetrie (TG-DSC), Thermodynamische Gleichgewichtsberechnungen (GGW), Elektrochemische Impedanzspektroskopie (EIS), Untersuchung der Schereigenschaften (SV) und die Bestimmung der Kaltdruckfestigkeit (KDF) wurden angewendet. Die Kombination der Untersuchungen ließ eine umfangreiche analytische Charakterisierung der Sintervorgänge zu. Unter der Berücksichtigung einer guten Vergleichbarkeit hinsichtlich der ermittelten Sintertemperaturen, stellt die EIS eine Alternative zur etablierten aber zeitaufwändigen Bestimmung der KDF dar. In Abhängigkeit von der Aschezusammensetzung, der Korngröße und der Gasatmosphäre, ist bereits ab einer Temperatur von 650 °C eine Agglomeration von Aschepartikeln möglich.

[pt] Uma das características mais relevantes nos aglomerados de minério de ferro é a sua porosidade, que impacta fortemente no desempenho desses materiais nos processos siderúrgicos. O desempenho é diretamente dependente da existência de uma rede porosa que permite o fluxo de gases pelo interior desses aglomerados sem comprometer sua integridade física. Neste trabalho, amostras de diferentes tipos de aglomerados de minério de ferro foram caracterizadas com o auxílio de técnicas de microtomografia computadorizada de raios X (microCT), processamento digital de imagens e modelagem de rede de poros (PNM). Com isso, a influência da microestrutura desses aglomerados na variação da sua porosidade e permeabilidade foi avaliada. O uso de microCT permitiu uma visualização 3D da estrutura dos aglomerados, permitindo realizar uma análise da estrutura interna das amostras para a discriminação do espaço poroso. O pixel size ideal foi estipulado por meio de diversas capturas com resoluções diferentes. A PNM foi utilizada para realizar a simulação da permeabilidade absoluta das amostras, correlacionando com a porosidade, conectividade dos poros e diâmetro de poros e conexões. Foi realizada uma variação de mais ou menos 5 tons de cinza nos limiares de segmentação para estipular a sensibilidade do impacto desse parâmetro nos resultados da modelagem. Os dois aglomerados apresentaram porosidade parecida, em torno de 20 por cento. Os resultados para piores resoluções apresentaram uma inconsistência, em muitos casos não possuindo sequer permeabilidade. As imagens adquiridas com um tamanho de voxel de 2 micrômetros resultaram em cálculos consistentes de permeabilidade, em torno de 0,4 a 2,4 mD para os briquetes e 0,03 a 1,6 mD para as pelotas, sugerindo que os briquetes são levemente mais permeáveis. A variação do limiar de segmentação dos poros teve forte impacto nos resultados das modelagens, influenciando diretamente no valor do cálculo da permeabilidade absoluta. / [en] One of the most relevant features of iron ore agglomerates is their porosity, which strongly impacts the performance of these materials in steelmaking processes. Performance is directly dependent on the existence of a porous network that allows gas flow through the interior of these agglomerates without compromising their physical integrity. This study characterized samples of different iron ore agglomerates using X-ray microcomputed tomography (microCT), digital image processing, and pore network modeling (PNM). The influence of the microstructure of these agglomerates on the variation of their porosity and permeability was evaluated. MicroCT enabled a 3D visualization of the agglomerate structure, allowing for an analysis of the internal structure of the samples to discriminate the porous space. The ideal pixel size was determined through various captures at different resolutions. PNM was used to simulate the absolute permeability of the samples, correlating it with porosity, pore connectivity, and pore and connection diameter. A variation of more or less 5 gray tones in the segmentation thresholds was performed to determine the sensitivity of this parameter s impact on the modeling results. The two agglomerates had similar porosity of around 20 percent. The results for lower resolutions showed inconsistency, with many cases lacking permeability altogether. Images acquired with a pixel size of 2 micrometers resulted in consistent permeability calculations, ranging from 0.4 to 2.4 mD for briquettes and 0.03 to 1.6 mD for pellets, indicating that briquettes are slightly more permeable. The variation of pore segmentation threshold had a strong impact on the modeling results, directly influencing the value of the absolute permeability calculation.