No description available.

No description available.

The work in this thesis addresses the improvement of electrocatalyst performance in hydrogen PEM fuel cells. An agglomerate model for a catalyst layer was coupled with a one dimensional macroscale model in order to investigate the fuel cell performance. The model focuses on the agglomerate scale and the characteristic length in this study was 0.4 µm. The model was validated successfully with the experimental data. Based on the analysis of variance method at a 99% confidence level, the variation in the average fuel cell voltage was significantly sensitive to that in the volume fraction of electrolyte in an agglomerate. The effect of changing electrolyte film thickness was observed to have a significant impact only in the mass transport limited region, whereas the effect of changing agglomerate radius was found over the entire range of current density. An analysis comparing the effect of agglomerate shape at a constant platinum loading, a constant characteristic length and assuming the semi-finite structure was suitable for this study. Sphere, cylinder and slab agglomerate geometries were considered. The behaviour of the utilisation effectiveness was discovered to be strongly affected by the agglomerate shape. The improvement in the utilisation effectiveness was non-linear with current density. The advantage of the slab geometry in distributing reactant through the agglomerate volume was reduced and consequently the increase in utilisation effectiveness for slab-like agglomerates diminishes in the high current density region. At 0.85 Acm−2, the maximum improvement of the catalyst utilisation effectiveness in slab was 27.8% based on the performance in sphere. The improvement in fuel cell maximum power density achieved using slab-like agglomerate was limited to around 3%. The improvement in the overall fuel cell performance by changing the agglomerate shape was not significant. To achieve significant improvements in fuel cell performance will require changes to other features of the catalyst layer.

The thesis is focussed on the performance of the fuel cell and the design of the cell for operation with natural gas and renewable fuels, e.g. biogas or gasified biomass. The performance is one of the important issues for the development and commercialisation of fuel cell stacks. In order to operate fuel cell on renewable fuels, without preceding reforming of the fuel, a high temperature fuel cell is needed, i.e. a solid oxide fuel cell (SOFC) or a molten carbonate fuel cell (MCFC). At present, the latter fuel cell type is much more mature when regarding the technical aspects than is the solid oxide fuel cell. The German company MTU has up to date installed about thirty MCFC plants, mainly in Europe and the USA but also in Japan. Moreover the European Commission has decided that the use of renewable fuels must increase at the expense of fossil fuels. This decision is one step towards a smaller dependence on fossil energy sources and limited emissions of greenhouse gases. The objective of this work is to better understand the factors that influence the cell performance: to determine the kinetic parameters of the hydrogen oxidation and the carbon monoxide oxidation and to get more information about the reaction mechanism, even when dealing with gases of low hydrogen content. The latter is of special importance when operating the cells on biogas or gasified biomass. These fuels also contain higher concentrations of carbon monoxide and carbon dioxide. It was found that the hydrogen mechanism proposed by Jewulski and Suski describes the anode performance even at lower concentrations of hydrogen, i.e. gases corresponding to gasified biomass. Furthermore, the carbon monoxide reaction will only slightly influence the anode performance but if the rate of the shift reaction is small the influence of direct oxidation of carbon monoxide will increase. Experimental investigations have shown that mass transfer limitations in the gas phase exist. By mathematical modelling it was found that the current collector has a larger affect on the concentration gradients than the porous electrode. The concentrations gradients in the current collector are caused by the shift reaction that mainly takes place at the electrode. However, if the gas corresponds to equilibrium at the current collector the profiles will become almost uniform. Furthermore the influence of wetting properties, the pore structure and pore size distribution have also been investigated in this thesis. The outcome of this thesis may be used for electrode development and design, as well as for input to reliable cell and stack models for system simulations. / QC 20101008

The greening of air transport is the driver for developing technologies to reduce the environmental impact of aviation with the aim of halving the amount of carbon dioxide (COଶ) emitted by air transport, cutting specific emissions of nitrogen oxides (NO୶) by 80% and halving perceived noise by the year 2020. Fuel Cells (FC) play an important role in the new power generation field as inherently clean, efficient and reliable source of power especially when comparing with the traditional fossil-fuel based technologies. The project investigates the feasibility of using an electric hybrid system consisting of a fuel cell and battery to power a small model aircraft (PiperCub J3). In order to meet the desired power requirements at different phases of flight efficiently, a simulation model of the complete system was first developed, consisting of a Proton Exchange Membrane hybrid fuel cell system, 6DoF aircraft model and neural network based controller. The system was then integrated in one simulation environment to run in real-time and finally was also tested in hardware-in-the-loop with real-time control. The control strategy developed is based on a neural network model identification technique; specifically Model Reference Control (MRC), since neural network is well suited to nonlinear systems. To meet the power demands at different phases of flight, the controller controls the battery current and rate of charging/discharging. Three case studies were used to validate and assess the performance of the hybrid system: battery fully charged (high SOC), worst case scenario and taking into account the external factors such as wind speeds and wind direction. In addition, the performance of the Artificial Neural Network Controller was compared to that of a Fuzzy Logic controller. In all cases the fuel cell act as the main power source for the PiperCub J3 aircraft. The tests were carried-out in both simulation and hardware-in-the-loop.

Depuis plusieurs années, de nouvelles méthodologies basées sur l’utilisation du champ électrique pour agir ou caractériser les cellules ou les tissus cellulaires génèrent de nombreuses avancées et apportent des nouvelles promesses dans les laboratoires de recherche et dans l'industrie : diagnostic de cancer, ElectroChimioThérapie (insertion d’un médicament en perméabilisant les membranes des cellules), thérapie génique (insertion d’un gène thérapeutique), immunothérapie (vaccins anti-tumoraux obtenus par électrofusion de cellules dendritiques et cellules cancéreuses pour réactiver le système immunitaire).L’application d’ impulsions électriques à des cellules ou dans des tissus cellulaires induit un changement sur leurs propriétés, en particulier sur leurs membranes qui deviennent transitoirement perméables, laissant temporairement le passage aux ions et macro-molécules. Les phénomènes induits lors d’une perméabilisation par application de champ électrique ont été partiellement caractérisés en microscopie epi-fluorescence. Pour effectuer un suivi en temps réel de la dynamique du processus de l’électroperméabilisation, une voie prometteuse consiste à caractériser électriquement l’échantillon. Dans cet objectif, mon travail de thèse consiste à mettre en oeuvre le suivi en temps réel de l’évolution des caractéristiques électriques sur une large bande de fréquences d’un tissu cellulaire ou d’une cellule isolée, avant, pendant et après la sollicitation par un champ électrique pulsé.Dans le cadre de ma thèse un modèle du système biologique et de son environnement a été élaboré, afin de mieux décrire des phénomènes observés expérimentalement: effet des sollicitations électriques sur la viabilité cellulaire, sur la perméabilité de la membrane externe, effets induits sur les composés intracellulaires, dynamique de fusion membranaire. Le degré de perméabilisation de l’objet biologique (cellule ou tissu) dépend de manière fortement non-linéaire de nombreux paramètres, ce qui rend complexe l’élaboration de ce modèle et son interprétation. La détection de ce niveau de perméabilisation est effectuée en temps réel (mesure du niveau de perméabilisation avant, pendant et après l’application de l’impulsion électrique). In fine cette approche devrait permettre d’optimiser le taux de perméabilisation cellulaire en fonction de l’application considérée. Ce système de contrôle individuel du niveau de perméabilisation cellulaire pourrait à terme être parallélisé massivement sur une puce dédiée à l’électroporation d’un grand nombre de cellules. Afin d’avoir une vision multi-échelle des effets, l’étude a été menée sur plusieurs modèles expérimentaux: qui vont du tissu (échelle millimétrique) à la cellule unique, en passant par les échelles intermédiaires (caractérisation de spéroides cellulaires).Dans ces deux derniers cas (sphéroide, cellule unique) l’objet biologique est isolé dans une biopuce microfluidique équipée d’électrodes de mesure et d’application du champ (échelle micrométrique).Les micro-dispositifs que j’ai réalisé pour caractériser en temps réel la perméabilisation de cellules, intègrent une géométrie spécifique d’électrodes, ainsi que d'un réseau de canaux microfluidiques pour contrôler le débit de cellules Le degré de miniaturisation de ces puces permet de travailler au niveau de la cellule unique, et appliquer des champs électriques de forte amplitude, de forte fréquence, localisés spatialement. / The increasing interest for new methodologies based on the use of the electric field to characterize the cells or tissue cells and generate brought promising development in research laboratories and industry: cancer diagnosis, electrochemotherapy (insertion of a drug after cell membranes permeabilization), gene therapy (insertion of a therapeutic gene), immunotherapy (anti-tumor vaccines obtained by electrofusion of dendritic cells and cancer cells to activate the immune system).The application of electrical pulses to cells or cell tissues induces a change in their properties, in particular on their membranes which become transiently permeable, and temporarily allow the passage of ions and macromolecules. Effect linked to the permeabilization phenomenon have been partially characterized by epi-fluorescence microscopy. Nevertheless, in order to perform the real-time monitoring of the electroporation process and know its dynamics, the electrical sample characterization is employed. Thus the aim of this work is to implement a real-time monitoring of dielectrical characteristics changes, on a wide frequency range, of a cellular tissue or a single cell, before, during and after the pulsed electric field application.As part of my thesis a model of the biological system has been developed to better describe the phenomena observed experimentally: effect of electrical stress on cell viability, on the permeability of the outer membrane, induced effects on the intracellular compounds, dynamics of membrane fusion.The degree of permeabilization of the biological sample (cells or tissues) is non linearly dependent of several parameters, which makes complicated the development of the model and its interpretation.The detection of a specific level of permeabilization is done in real time (measure of the level of permeabilization before, during and after the electric pulses application). This cell permeabilization level control could eventually be parallelized on a chip dedicated to the electroporation of a large number of cells. The latter can be used to optimize the electric pulses parameters in order to reach the desired permeabilization level. In order to have a multi-scale overview of the phenomenon, the study was performed on different size-level: from the tissue level (millimeter scale) to the single cell model through the intermediate scales (cell spéroides characterization).In the latter two cases (spheroid, single cell) the biological sample is isolated in a microfluidic biochip where the electric field solicitation are applied (micrometer scale).The microdevice designed and fabricated during this work, allows the real time characterization of the cell permeabilization. Furthermore the miniaturization of the system is crucial to work at the level of the single cell, and make possible the application of electrical fields of high amplitude, high frequency and spatially localized.

Ziel dieser Arbeit ist es, eine simulationsbasierte Untersuchung des Betriebs eines PEM-Brennstoffzellensystems mit besonderem Fokus auf den Wasserhaushalt zu ermöglichen. In PEM-Brennstoffzellen sind die Wechselwirkungen in Bezug auf den Feuchtehaushalt z.B. von Transportmechanismen, Degradation und Leistung abhängig. Im PEM-Brennstoffzellensystem werden die Wechselwirkungen der Feuchte durch eine mögliche Rezirkulation und/oder eine passive Befeuchtung der Kathode erweitert, Um diese Abhängigkeiten korrekt darzustellen, wurde ein PEM-Brennstoffzellen Stack-Modell entwickelt, das einerseits einen hohen Grad an Detailtreue und andererseits hohe Anforderungen an die Laufzeit erfüllt, um akzeptable Simulationszeiten für Brennstoffzellensystemsimulationen zu ermöglichen. Der Kern des Modells ist eine neuartige 2-D + 1-D Struktur, die flächenspezifische Bedingungen, wie z.B. trockene Kathodeneinlass- und feuchte Kathodenauslassbedingungen in Abhängigkeit von Gleich- oder Gegenstromstrukturen, löst. Um diesen Anforderungen an die Laufzeit gerecht zu werden, wurde ein numerischer Löser entwickelt, der speziell an die Struktur und den Inhalt angepasst ist. Das Brennstoffzellenmodell und dessen Möglichkeiten zur Integration in eine Systemsimulation werden in dieser Arbeit vorgestellt. / The aim of this work is to enable simulation based investigation of the operation of a PEM fuel cell system, with the special focus on its water management. For PEM fuel cells their multi-level interaction regarding humidity is characteristic depending e.g. on transport mechanisms, degradation and performance. In the PEM fuel cell system, the interaction of the humidity is further enhanced by a possible recirculation and passive humidification systems of the cathode. In order to display these dependencies correctly, a PEM fuel cell stack model has been developed, which on the one hand meets high degree of resulting details and on the other hand meets high requirements concerning its runtime, to enable acceptable simulation times for fuel cell system simulations. The core of the model is a novel 2-D + 1-D structure that resolves area specific conditions, such as dry cathode inlet and wet cathode outlet conditions in dependence of co- or counter flow fields. To meet those requirements regarding its runtime a numerical solver has been developed that is specially adapted to the structure and content. The fuel cell model as well as its possibilities with respect to the integration in system simulation is presented in this work.

Le développement de cancer entraîne une dérégulation du métabolisme du cuivre (Cu) qui a notamment été étudiée par analyse de la composition isotopique naturelle du Cu. Les cellules tumorales hépatiques sont enrichies en isotopes lourds du Cu par rapport aux cellules péri-tumorales. Le but de cette thèse est d'identifier les mécanismes responsables de cette différence, en utilisant la levure Saccharomyces cerevisiae dont les mécanismes de réduction et d'import du Cu sont proches de ceux de l'Homme. En mutant les gènes codants pour les importateurs ou les réductases du Cu, j’ai montré que son import protéique génère un enrichissement intracellulaire en isotopes légers du Cu, qui est modulé par l'activité des réductases. Une modélisation numérique m’a permis de montrer que le flux de Cu par les importateurs haute-affinité Ctr est linéairement et négativement corrélé à la composition isotopique du Cu. Ce flux étant modulé par la capacité de réduction membranaire du Cu, j’ai pu lier l'enrichissement en isotopes lourds du Cu des cellules hépatiques tumorales à une diminution de l'activité des réductases membranaires. Par ailleurs, pour un même fond génétique, j'ai mis en évidence une corrélation entre un moindre enrichissement en isotopes légers du Cu et une résistance accrue à un médicament anticancéreux, le cisplatine. De plus, le traitement au cisplatine entraîne un enrichissement des cellules en isotopes lourds du Cu d'autant plus petit que la souche est résistante au cisplatine. Ainsi, ces résultats montrent que la mesure de la composition isotopique du Cu avant et après traitement au cisplatine pourrait permettre de suivre l'apparition d’une chimiorésistance chez les malades, caractérisée par un enrichissement en isotopes lourds du Cu dans les tumeurs, ce qui ouvre la voie au développement d'un nouveau biomarqueur non-invasif de l'apparition d'une résistance au cisplatine. / Cancer development leads to Cu metabolism disregulation which were especially studied by the natural copper (Cu) isotopic composition. Hepatocellular carcinoma (hCC) are enriched in heavy Cu isotopes compared to peri-tumoral cells. The goal of this thesis is to identify the mechanism responsible for this difference. I used the yeast Saccharomyces cerevisiae where Cu reduction and Cu import mechanism are close to the human. By mutating the genes coding for Cu reductases or Cu importers, I showed that protein Cu import generate an intracellular light Cu enrichment which is modulated by Cu reductases activity. With a numerical modelisation I calculated that the Cu flux through high-affinity Cu importers is linearly and negatively correlated to the natural Cu isotopic composition. This flux is modulated by the cell reduction ability. Therefore, I have linked the heavy Cu isotopes enrichment in hCC to a lower reductases activity. Besides, for a same genetic background, I observed a correlation between a lower light Cu enrichment and an higher resistance to a anti-tumoral drug, the cisplatin. Moreover, I observed that cisplatin treatment leads to an enrichment in heavy Cu isotopes which is lower for resistant to cisplatin strains. Those results shown that the Cu isotopes measurement in tumors before and after the cisplatin treatment might be used to trace the chemoresistance apparition in patient with cancer which is characaterize by a tumoral heavy Cu isotopes enrichment. This results might pave the way to the development of a new prognosis biomarker of the cisplatin resistance apparition.