Les piles à combustible à membrane échangeuse de protons (PEMFC) permettent de convertir efficacement de l'énergie chimique en électricité. Pour cela l'hydrogène s'oxyde sur une des électrodes de la pile, les protons ainsi créés traversent l'électrolyte (membrane) tandis que les électrons parcourant le circuit extérieur fournissent l'énergie électrique. Tous ces éléments se recombinent à la seconde électrode qui, à l'aide de la réduction de l'oxygène, va former de l'eau. Le rendement n'étant pas parfait, une partie de l'énergie des réactifs est aussi dégradée sous forme de chaleur. Malgré de récents progrès, la commercialisation à grande échelle des piles à combustible est toujours entravée par des problèmes de durabilité, liés notamment à la gestion de l'eau et de la température au sein de ce système. Afin de quantifier le comportement thermique et son effet sur le transport de l'eau, une pile à combustible a été instrumentée, permettant la mesure de la température aux électrodes, des flux de chaleur et d'eau. Les résultats montrent que de forts gradients de température (jusqu'à environ 30 K/mm) peuvent exister pour une pile fonctionnant dans des conditions standard. Il a été observé une nette influence du champ de température dans le cœur de pile sur le transport de l'eau qui se fait vers la partie la plus froide de la pile (généralement les canaux d'alimentation), l'eau traversant les couches de diffusion poreuses sous forme vapeur dans nos conditions expérimentales.

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Piles have been used since prehistoric times in areas with weak subsurface conditions either to reinforce existing ground, create new ground for habitation or trade, and support bridges and buildings. Originally piles were composed of timber and driven with drop hammers using very heavy ram weights. As technology improved so did the materials that piles are composed of as well as the equipment itself. Currently, piling is a multibillion dollar a year industry, thus the need to develop more accurate prediction methods can potentially represent a significant savings in cost, material, and man power. Multiple predictive methods have been developed to estimate developed pile capacity. These range from static theoretical formulae based on geotechnical investigation prior to pile driving even occurring using specific pile and hammer types to semi empirically based dynamic formulae used during actual driving operations to more recently developed computer modeling and signal matching programs which are calibrated with site condition during initial geotechnical investigations or test piling to full scale static load tests where piles are loaded to some predetermined value or failure condition. In this thesis, dynamic formulae are used to predict pile capacity from those installed by drop and diesel hammers and are compared to the results from pile load tests, which are taken as the true measure of developed bearing capacity. The dynamic formulae examined are the Engineering News Record (ENR), Gates, Federal Highway Administration (FHWA) modified Gates, Hiley, and Ontario Ministry of Transportation (MTO) modified Hiley formulae. Methods of investigation include calculating pile capacities from the formulae as they are, omitting the factors of safety, revising the formulae with averaged coefficients and conducting multi regression analysis to solve for one or two coefficients simultaneously and revising the dynamic formula to determine if more accurate bearing capacity prediction are possible. To objectively determine which formulae provide the most accurate bearing capacities, the predicted capacities will be compared to results obtained from static pile load tests and simple statistics on the resulting data set will be calculated including regression analysis, standard deviations, coefficients of variation, coefficients of determination, and correlation values.

Serving as critical gateways for international trade, seaports are pivotal elements in transportation networks. Any disruption in the activities of port infrastructures may lead to significant losses from secondary economic effects, and can hamper the response and recovery efforts following a natural disaster. Particularly poignant examples which revealed the significance of port operations were the 1995 Kobe earthquake and 2010 Haiti earthquake in which liquefaction and lateral spreading of embankments imposed severe damage to both structural and non-structural components of ports. Since container wharf structures are responsible for loading and unloading of cargo, it is essential to understand the performance of these structures during earthquakes. Although previous studies have provided insight into some aspects of the seismic response of wharves, limitations in the modeling of wharf structures and the surrounding soil media have constrained the understanding of various features of the wharf response. This research provides new insights into the seismic behavior of wharves by using new and advanced structure and soil modeling procedures to carry out two and three-dimensional seismic analyses of a pile-supported marginal wharf structure in liquefiable soils. Furthermore, this research investigates the interaction between cranes and wharves and closely assesses the role of wharf-crane interaction on the response of each of these systems. For this purpose, the specific effect of wharf-crane interaction is studied by incorporating advanced models of the crane with sliding/uplift base conditions. To reduce the computational time required for three-dimensional nonlinear dynamic analysis of the wharf in order to be applicable for probabilistic seismic demand analysis, a simplified wharf model and an analysis technique are introduced and verified. In the next step probabilistic seismic demand models (PSDMs) are generated by imposing the wharf models to a suit of ground deformations of the soil embankment and pore water pressure generated for this study through free-field analysis. Convolving PSDMs and the limit states, a set of fragility curves are developed for critical wharf components whose damage induces a disruption in the normal operation of ports. The developed fragility curves provide decision makers with essential tools for maximizing investment in wharf retrofit and fill a major gap in seismic risk assessment of seaports which can be used to assess the regional impact of the damage to wharves during a natural hazard event.

Modification of black cotton soils by chemical admixtures is a common method for stabilizing the swell-shrink tendency of expansive soils. Advantages of chemical stabilization are that they reduce the swell-shrink tendency of the expansive soils and also render the soils less plastic. Among the chemical stabilization methods for expansive soils, lime stabilization is most widely adopted method for improving the swell-shrink characteristics of expansive soils. Lime stabilization of clays in field is achieved by shallow mixing of lime and soil or by deep stabilization technique. Shallow stabilization involves scarifying the soil to the required depth and lime in powder or slurry form is spread and mixed with the soil using a rotovator. The use of lime as deep stabilizer has been mainly restricted to improve the engineering behaviour of soft clays Deep stabilization using lime can be divided in three main groups: lime columns, lime piles and lime slurry injection. Lime columns refer to creation of deep vertical columns of lime stabilized material. Lime piles are usually holes in the ground filled with lime. Lime slurry pressure injection, as the name suggests, involves the introduction of a lime slurry into the ground under pressure. Literature review brings out that lime stabilization of expansive clays in field is mainly performed by mixing of lime and soil up to shallow depths. The use of lime as deep stabilizer has been mainly restricted to improve the engineering behaviour of soft clays. Use of lime in deep stabilization of expansive soils however has not been given due attention. There exists a definite need to examine methods for deep stabilization of expansive soils to prevent the deeper soil layers from causing distress to the structures in response to the seasonal climatic variations. In addition, there exists a need for in-situ soil stabilization using lime in case of distressed structures founded on expansive soil deposits. The physical mixing of lime and soil in shallow stabilization method ensures efficient contact between lime and clay particles of the soil. It however has limitation in terms of application as it is only suited for stabilization of expansive soils to relatively shallow depths. Studies available have not compared the relative efficiency of the lime pile technique and lime-soil mixing method in altering the physico-chemical, index and engineering properties of expansive black cotton soils. To achieve the above objectives laboratory experiments are performed that study: 1. the efficacy of lime piles in stabilizing compacted black cotton soil specimens from Chitradurga District in Karnataka. The efficiency of lime piles in chemically stabilizing the compacted black cotton soil mass was investigated as a function of: a)amount of lime contained in the lime pile b)radial migration of lime from the central lime pile c)migration of lime as a function of soil depth 2. the relative impact of the lime pile technique and lime-soil mixing method in altering the physico-chemical, index and engineering properties of expansive black cotton soil. The organization of this thesis is as follows After the first introductory chapter, a detailed review of literature performed towards highlighting the need to examine stabilization of expansive soils using lime pile technique is brought out in Chapter 2. Chapter 3 presents a detailed experimental programme of the study. 25 mm and 75 mm diameter lime piles were installed in the compacted soil mass to study the influence of amount of lime contained in the lime pile on the soil properties. The amount of quick lime contained in the 25 mm and 75 mm lime piles corresponded to 1 % and 3 % by dry weight of the soil mass respectively. Radial and vertical migration of lime from the central lime pile was examined by sampling soil specimens at different radial distances from the central lime pile and at different depths of soil sample. At a given depth and radial distance, migration of lime was estimated by comparing the exchangeable cation composition, pH and pore salinity of the treated soil with that of the natural (untreated) black cotton soil specimen. Alterations in the soil engineering properties at a given depth and radial distance were evaluated by comparing the index properties, swell potential and unconfined compressive strength of the lime pile treated soil specimen with those of the untreated specimen. To compare the relative efficiency of lime mixing and lime pile technique in altering the swelling behaviour of black cotton soil, batches of black cotton soil specimens were treated with 1 % and 3 % quick lime on dry soil weight basis. The compacted soil-lime mixes were cured at moisture contents of 31-34 % for a period of 10 days. The physico-chemical, index and engineering properties of the 1 % lime mixed specimens are compared with those of the 25 mm lime pile treated specimens. The properties of the 3 % lime mixed soil specimens are compared with those of the 75 mm lime pile treated specimens. Chapter 4 examines the efficacy of lime piles in stabilizing compacted black cotton soil specimens from Chitradurga District in Karnataka. Experimental results showed that controlling the swell potential of deep expansive soil deposits is possible by the lime pile technique. Treatment with lime pile caused migration of dissociated calcium and hydroxyl ions into the surrounding soil mass. In case of 25 mm lime pile, the experimental setup allowed measurement of migration of lime up to three times the lime pile diameter. In case of 75 mm lime pile, the experimental setup allowed measurement of migration of lime up to 1.6 times pile diameter. In both experiments, migration of lime was also uniform through out the soil depth of 280 mm. Migration of calcium and hydroxyl ions increased the pore salinity and pH of the treated soil mass. The increase in pH caused clustering of additional exchangeable calcium ions at the negative clay particle edges. The increased pore salinity and exchangeable calcium ions reduced the diffuse ion layer thickness that in turn suppressed the plasticity index and the swell potential of the compacted expansive soil. The laboratory results hence bring out that lime pile treatment in the field can substantially reduce the swell potential of the soil at least to a radial extent of 2 to 3 times the lime pile diameter. The 75 mm lime pile contained lime content in excess of the initial consumption of lime (ICL) value of the black cotton soil - namely 2.6 %. Laboratory results showed that migration of hydroxyl ions even from the 75 mm pile could not elevate the soil pH to levels required for soil-lime pozzoIonic reactions (pH ≥12). The very low solubility of lime in water (< 1 g/litre) and the impervious nature of the black cotton soil are considered to have impeded efficient interactions between lime and soil in course of treatment of the expansive soil with lime piles. Absence of soil-lime pozzolonic reactions precluded the formation of cementation compounds in the lime pile treated soil specimens. Cementation compounds formed by the soil-lime pozzolonic reactions are responsible for the much higher strengths of lime stabilized soils. Consequently, treatment with 25 mm pile had no impact on the unconfined compressive strength of the black cotton soil. Comparatively, treatment with 75 mm lime pile slightly increased the strength of the treated soil due to increased inter-particle attraction and particle flocculation. Chapter 5 compares the relative efficiency of the lime pile technique and lime-soil mixing method in altering the physico-chemical, index and engineering properties of expansive black cotton soil. Experimental results showed that mixing of soil and lime promote stronger chemical interactions between lime released hydroxyl ions and clay particles than that achieved by diffusion of lime from a central lime pile. The more alkaline pH of the lime mixed soil specimens rendered the clay particle edges more negative. Consequently, more calcium ions were adsorbed at the clay particle edges of the lime mixed soil specimens imparting them higher exchangeable calcium contents than the lime pile treated soil specimens. Also, at 3 % lime addition, the pH of the lime-mixed soil was sufficiently high (in excess of 12) to cause dissolution of silica and alumina from the clay lattice necessary for the formation of cementation compounds. The stronger lime modification reactions plus the lime-soil pozzolonic reactions (applicable for soil treated with lime content greater than ICL value) achieved by the lime mixing technique rendered the expansive soil much less plastic, much less expansive and much stronger than the lime pile treated specimens. The results of the laboratory study hence suggest that if a choice exists in the field between conventional method of spreading-mixing-compacting of soil-lime mixes and treating the ground with lime piles, the former technique should be adopted because of its greater efficacy in stabilizing the expansive soil. Chapter 6 summarizes the findings of the study.

Les générateurs piles à combustibles (PàC) ont des performances qui dépendent fortement des conditions de fonctionnement liées à l'environnement dans lequel ils se trouvent. De plus, le pilotage de ces systèmes demeure délicat en raison du grand nombre de paramètres physiques mis en jeu tels que le profil du courant imposé par la charge, la température du stack, les températures, les pressions, les débits, l'hydratation des gaz... La méthodologie des Plans d'Expériences (PE) permet de définir de manière rationnelle les essais visant à caractériser rapidement et efficacement une PàC. Elle permet de déterminer les paramètres les plus influents sur le comportement de la pile et de mettre en évidence les interactions éventuelles qui lient ces facteurs. D'autre part, la caractérisation du générateur PàC par des PE a pour finalité de prédire le comportement du système vis-à-vis de ses paramètres de fonctionnement et d'envisager ainsi, par la suite, des stratégies de pilotage du système visant à optimiser un critère déterminant tel que la tension, la consommation d'hydrogène, la puissance électrique maximale, voire la durée de vie du stack.<br />Le mémoire est divisé en six chapitres. Après un bref aperçu du fonctionnement d'une PàC et de ses contraintes (premier chapitre), l'auteur donne les éléments essentiels de la méthodologie des PE nécessaires à la compréhension de la suite du travail (deuxième chapitre). Un plan destiné à étudier l'influence des débits et des pressions, côté hydrogène et côté air, sur la puissance maximale de la pile a été réalisé sur une pile PEM 500W utilisée en mode régulation de pression (troisième chapitre). Le plan complet comporte seize essais. Les analyses de la variance pour le plan complet et pour le plan fractionnaire (huit expériences choisies judicieusement parmi les seize réalisées) ont conduit à des résultats sensiblement identiques, à savoir une influence majeure du facteur débit d'air sur le niveau de puissance maximal atteint par la pile étudiée. Les plans et les outils logiciels mis au point ont ensuite été développés et utilisés pour analyser des résultats expérimentaux collectés sur une pile PEM 5kW (chapitre quatre). Les analyses réalisées permettent de cerner clairement et d'exprimer quantitativement, pour différents niveaux de courant de charge, les incidences des paramètres température de stack, pressions et surstoechiométries des gaz réactifs sur les performances de la PàC. Une modélisation statistique de la tension de pile en fonction des paramètres étudiés est mise en œuvre pour optimiser les conditions de fonctionnement de la pile. Le cinquième chapitre est consacré à l'analyse par la Méthode des Surfaces de Réponse (MSR) de résultats expérimentaux issus d'un essai d'endurance d'une PàC 100W ayant fonctionné en régime stationnaire pendant 1000 heures. Cette étude a notamment permis de montrer l'intérêt d'adopter des surstoechiométries variables au cours du temps pour aboutir d'une part à des performances élevées en terme de tension de pile et d'autre part à une diminution de la variabilité des tensions de cellules. Le dernier chapitre montre comment les PE peuvent contribuer à une meilleure compréhension des phénomènes physiques intervenant dans les PàC. Trois domaines sont considérés : les pertes de charge dans les plaques bipolaires distributrices des gaz réactifs, l'impact de l'humidification sur la variation de la résistance interne de la pile et le vieillissement à une température de fonctionnement supérieure à la valeur nominale.<br />L'ensemble des travaux réalisés montre comment la méthode des plans d'expériences peut être un moyen approprié pour caractériser, analyser et améliorer le système complexe que représente un générateur PàC.

Cette thèse en cotutelle résulte de la collaboration entre le laboratoire français GREMI (Orléans) et le groupe australien SP3 (Université National Australienne) sur l'optimisation des piles à combustible par procédé plasma. Mon projet d'étude concerne le développement d'une électrode de pile à combustible constituée d'une nanostructure carbonée imprégnée d'agrégats de catalyseur platine, l'enjeu étant de réduire la quantité de platine tout en conservant de bonnes performances électrochimiques. Durant la première partie passée en France, des électrodes traditionnelles non catalysées ont été imprégnées d'agrégats de platine sur quelques centaines de nanomètres par pulvérisation plasma. Cette méthode a permis de réduire considérablement la charge de platine par rapport à une électrode traditionnelle catalysée chimiquement tout en réduisant légèrement ses performances. La seconde moitié de ma thèse en Australie concerna la croissance d'un support catalytique carboné de grande surface spécifique optimisé pour l'application pile à combustible. Des nanofibres de carbone (CNF) ont donc été déposées sur du papier de carbone recouvert d'une fine couche de nickel en utilisant un procédé CVD (Chemical Vapor Deposition) dans un réacteur plasma Helicon que j'ai conçu et développé. La morphologie des CNF a été caractérisée et optimisée en fonction des paramètres plasmas. Ce tapis de CNF a été imprégné d'agrégats de platine par pulvérisation plasma Helicon. Dans cette nouvelle électrode entièrement réalisée par plasma, le catalyseur dispersé est cette fois réparti sur quelques micromètres ce qui permettra d'augmenter les performances électriques de la pile.

La pile à combustible (PAC) est une technologie maintenant maîtrisée qui permet de convertir efficacement le combustible hydrogène en énergie électrique et thermique avec un faible impact environnemental. L'extension de son utilisation dépend fortement de la qualité de l'interface électronique de puissance qui a pour l'objet d'adapter la pile à la charge. Le travail de recherche présenté dans ce mémoire de Doctorat s'intéresse à la conception d'une interface électronique de puissance pour la pile à combustible pour les trois domaines d'applications : télécommunication, transport et stationnaire. <br />Dans cette objective, l'approche modulaire, qui se base sur l'étude des convertisseurs unitaires et leurs modes de connexion, a été proposée afin de s'adapter à la modularité des stacks de PAC. Des modèles de pertes et de dimensionnement des composants passifs et semi conducteurs ont été construits. La technique de l'entrelacement est introduite afin de résoudre le problème de fort courant et permet d'optimiser le dimensionnement des inductances. Une nouvelle structure nommée double BOOST dual entrelacé (Interleaved Double Dual BOOST – IDD BOOST) a été proposée afin de résoudre les difficultés d'un convertisseur modulaire présentant une tension de sortie élevée et un rapport de tension important. Les stratégies de contrôle – commande multi sources ont été étudié en adaptant aux topologies de l'interface de puissance. Deux prototypes ont été réalisés afin de valider les résultats de prédiction de pertes ainsi que le contrôle commande multi sources.

Cette étude présente une démarche expérimentale originale permettant de sonder la dynamique de l'eau dans les membranes polymères échangeuses d'ions utilisées pour l'application pile à combustible. Grâce à l'utilisation de trois techniques complémentaires, la diffusion des molécules d'eau a été suivie à l'échelle moléculaire (diffusion quasi-élastique des neutrons ; 1 pico s < t < 1 nano s), à l'échelle macroscopique (RMN à gradient de champ pulsé ; 1 milli s < t < 1 s) et à l'échelle dite « intermédiaire » (relaxométrie RMN ; 1 nano s < t < 10 micro sec). Les expériences ont été menées en fonction de la quantité d'eau adsorbée, dans la membrane Nafion® et dans des polyimides sulfonés naphtaléniques. L'analyse des données expérimentales permet de préciser les échelles spatiales des ralentissements de la diffusion dans les deux matériaux, ainsi que de mettre en évidence les aspects structuraux qui permettent à l'eau d'être plus mobile dans le Nafion® que dans les polyimides sulfonés, et ce, quelle que soit la teneur en eau.

The high prevalence of substance use disorders is well-documented among criminal offenders. Drug courts are specialty judicial programs designed to: 1) improve public safety outcomes; 2) reduce criminal recidivism and substance abuse among offenders with substance use disorders; and 3) better utilize scarce criminal justice and treatment resources. Drug courts operate through partnerships between the criminal justice, behavioral health and public health systems. Offenders participate in an intensive regimen of substance abuse treatment and case management while under close judicial supervision. Drug courts' effectiveness in reducing criminal recidivism and drug use has been documented through numerous primary studies as well as meta-analytic reviews. The task remains now to determine the causal mechanisms of drug courts. The current study conducted preliminary activities to develop a measure to assess drug court structures and practices based upon the Ten Key Components of drug courts (NADCP, 1997). The creation and use of such a measure is necessary to the understanding of how drug courts work, why and how best to invest scarce judicial and treatment resources to optimize drug court participant and program outcomes. An iterative process was conducted such that results from previous activities informed subsequent steps in the measurement development process. Participants consisted of a convenience sample of drug court personnel at three local drug courts as well as academic experts in drug courts and measurement. Preliminary measurement development activities included: 1) a comprehensive review of the literature; 2) semi-structured interviews with key stakeholders to inform item development; 3) construction of a draft survey protocol; 4) expert reviews of the draft survey protocol and initial item pool to assess item construct and content validity, response format and clarity; 5) pile sort activity, wherein participants sorted items into piles, one for each measure sub-construct and one `other' pile; 6) exploratory factor analyses based on a joint-proportion matrix derived from pile sort activity data on which items best represent measure sub-constructs; 7) cognitive interviews completed by key stakeholders to review items retained from exploratory factor analyses; and 8) final revisions to the item pool based upon results from cognitive interviews. The item pool developed through the current research will be used as the basis for a future large-scale pilot test to determine the true factor structure underlying the preliminary measure developed. Results of this future research are expected to identify similarities and differences in the underlying factor structure compared to the Ten Key Components.