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The effect of different electron acceptors on substrate degradation was studied in pure and mixed cultures of various hydrogenotrophic homoacetogenic, methanogenic, sulfate-reducing, fumarate-reducing and nitrate-ammonifying bacteria. Two different species of these bacteria which during organic substrate degradation produce and consume hydrogen, were cocultured on a substrate which was utilized only by one of them. Hydrogen, which was excreted as intermediate by the first strain (and reoxidized in pure culture), could, depending on the hydrogen acceptor present, also be used by the second organism, resulting in interspecies hydrogen transfer. The efficiency of H2 transfer was similar when methanol, lactate or fructose were used as organic substrate, although the free energy changes of fermentative H2 formation of these substrates are considerably different. In coculture experiments nitrate or fumarate>sulfate> CO2/CH4>sulfur or CO2/acetate were the preferred electron acceptors, and an increasing percentage of H2 was transferred to that bacterium which was able to utilize the preferred electron acceptor. In pure culture the threshold values for hydrogen oxidation decreased in the same order from ≤1,100 ppm for homoacetogenic bacteria to about 0.03 ppm for nitrate or fumarate reducing bacteria. The determined H2-threshold values as well as the percentage of H2 transfer in cocultures were related to the Gibbs free energy change of the respective hydrogen oxidizing reaction.

No English abstract, Ce travail concerne l'étude de l'évolution au cours du dégazage à chaud d'une poudre d'alliage d'aluminium X7091 concernant 6.3% de zinc, 2.2% de magnésium et 1.6% de cuivre. En l'absence de traitement thermique et gazeux, l'alliage X7091 est recouvert d'une couche d'oxydes hydratés qui assure un rôle protecteur vis-à-vis de l'oxydation et de la sublimation des éléments alliés. La stabilité de cette couche est essentiellement fixée par sa teneur en eau de constitution, elle-même fonction des conditions de température et de pression. Pour une perte en eau critique de 0,1% en masse, il y a précipitation d'une nouvelle phase oxydée à travers laquelle le zinc et le magnésium sont susceptibles de diffuser. Dès lors, il y a compétition entre le phénomène de sublimation et celui d'oxydation. La nature de l'atmosphère gazeuse environnante est alors déterminante sur le type de processus mis en jeu. En présence d'oxygène ou de vapeur d'eau, l'oxydation du magnésium devient importante et la couche de magnésie formée assure à nouveau un effet protecteur vis-à-vis du départ du zinc. La mise au point d'un modèle représentant l'évolution des couches superficielles et son application aux résultats expérimentaux conduit à la détermination des valeurs des coefficients de diffusion de l'eau dans la couche d'oxydes et du magnésium dans l'oxyde. Les informations obtenues sont exploitables à l'échelon industriel. Elles ont permis la détermination des conditions optimales de dégazage de l'alliage X7091 et par suite la fabrication de pièces mécaniques saines aux côtes finies.

No english abstract, Nous avons présenté au cours de ce travail une méthode de dosage de l'hydrogène dans les matériaux en couches minces par la réaction nucléaire la réaction ¹H(¹⁵N, α γ)¹²C. Les caractéristiques analytiques essentielles de cette méthode sont sa sélectivité (pratiquement aucune interférence) sa sensibilité élevée en surface (

Many of the nitrogen containing polymers produce HCN when involved in fires. Various methods of HCN determination in fire gases are reviewed. The methods discussed are colorimetric tubes, specific ion electrode, wet chemical analysis and gas chromatography. Two common problems in HCN determination are concentration decrease by absorption and interferring reactions. Authors recommend that at least two different methods be employed in order to avoid errors caused by interference and absorption., Reprinted from: Journal of Combustion Toxicology, v. 3, November 1976, p. 363-370. ISSN: 0362-1669

Nous avons étudié l'effet Stark linéaire des états de Rydberg de faible | m_l | et observé une quasi-dégénéréscence des séries | m_l | = 0, 1 et 2 du sodium et | m_l | = 0, 1 du lithium. Nous avons expliqué théoriquement ce comportement non-hydrogénoïde assez inattendu. A partir d'atomes de lithium dans un état de Rydberg de faible | m_l |, nous avons préparé des atomes circulaires (| m_l | = l = n-1) et nous avons observé pour la première fois une transition induite par une onde submillimétrique entre deux états de Rydberg circulaires. Cette expérience est un premier pas vers la mesure de la constante de Rydberg en unité de fréquence. Nous avons mis en évidence un comportement dynamique spécifique des atomes circulaires dans un champ électrique faible (~1V/cm) de direction variable.

SPOROMUSA ACIDOVORANS sp. nov. was isolated from a pilot fermenter inoculated with effluent sample from the alcohol distillation industry. The isolate was a Gram-negative, motile, curved, spore-forming rod. The DNA base composition was 42 % G+C. The temperature range for growth was 20 to 40°C, with an optimum at 35°C ; growth occurred within a pH range of 5.4 to 7.5, with an optimum at pH 6.5. Growth substrates included methanol, H2-CO2, formate, fructose, ribose, fumarate, succinate and glycerol. Yeast extract was required for growth. The organism performed the homoacetogenic reaction. (Résumé d'auteur)

No English abstract, La cinétique de perméation de l'hydrogène gazeux à travers une feuille mince de palladium a été mesurée par spectrométrie de masse. Il a été constaté un phénomène d'affaiblissement des cinétiques de perméation lorsque le métal est soumis à des expositions successives au gaz. L'origine de ce phénomène est liée à une modification de l'état énergétique de la surface du palladium comme le prouvent des expériences de thermodésorption ainsi qu'une simulation numérique sur ordinateur. Cette variation d'énergie a pu être corrélée à la présence de certaines impuretés (Carbone, Oxygène et Soufre) à la surface du métal qui a été analysé par spectrométrie AUGER. Par ailleurs, des expériences de microcalorimétrie et de thermogravimétrie ont pu mettre en évidence l'existence d'une réaction chimique irréversible à la surface du palladium en présence d'hydrogène pur. Cette réaction semble liée aux quantités de soufre fixé sur le solide ainsi qu'à la présence d'oxygène dans l'atmosphère résiduelle.

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In recent years at the many hydro-electric stations erected on the Dnieper, the Volga and the Kama, emissions of combustible gases were detected in the concrete foundations of the structures, during the second and third year after the filling of the reservoirs. In the gas formation, methane and nitrogen predominate and more rarely, hydrogen. This phenomenon had not been investigated. In this article the results of research into the occurrence of gas in the foundations of the Kama hydro-electric station are explained, also some information is given on the chemical composition of the gases at the V.I. Lenin hydro-electric station on the Dnieper, the V.I. Lenin hydro-electric station on the Volga, and the 22nd KPSS Convention station on the Volga, where the author became acquainted with the phenomenon under natural conditions.

No english abstract, Dans l'optique de la séparation de l'hydrogène pour les piles à combustibles, nous avons étudié successivement le transfert des gaz à travers les membranes poreuses, non-poreuses et élastiques. Nos membranes en caoutchouc minces et étirées ont réussi à concilier sélectivité et perméabilité. L'étirement, sous forme sphérique de ces membranes, permet de déterminer, en une seule opération, les variations continues de perméabilité et de contrainte appliquée à la membrane. Afin d'améliorer les vitesses de transfert des gaz dissous à travers les membranes, nous avons étudié d'une part le transport physique de ces gaz, d'autre part celui accompagné de réactions chimiques à travers les membranes. Nous avons adopté trois méthodes de mesure des flux de gaz : En régime stationnaire, en régime d'évolution, avec écoulement de la phase liquide dans de longs conduits. Ces méthodes nous ont permis de déterminer la perméabilité globale du système et de montrer que cette perméabilité ainsi que l'épaisseur de la couche-limite de diffusion équivalente sont indépendantes du gradient de pression. Nous avons montré que l'efficacité du transport (dans le cas d'une réaction chimique lors du passage du gaz dans le liquide) est amélioré par l'augmentation des vitesses de retour à l 'équilibre chimique grâce à un catalyseur tel que l'anhydrase carbonique. Dans le cas particulier des membranes oxygénatrices de sang, nous avons réduit la barrière de l'oxygène en le faisant traverser sans forme d'eau oxygénée et en le régénérant grâce à la catalase fixée au niveau de l'interface membrane-solution à oxygéner. Afin de mesurer les concentrations en métabolites, nous avons transposé les réactions enzymatiques obtenues en solution, en réactions uniquement localisées au niveau d'une électrode, grâce à l'emploi d'enzymes fixées. Ces modèles de capteurs utilisent des enzymes capables de transformer les concentrations intéressant certains phénomènes physiologiques en produits sensibles aux électrodes de mesure. Ils offrent ainsi la possibilité de mesure in vivo en continu et permettent des contrôles et des régulations à distance.

International audience; RESUME-Afin de dimensionner un système énergétique par hybridation directe d'une pile à combustible avec une batterie pour une application aéronautique, un modèle électrique équivalent de cette hybridation a été développé. Le dimensionnement optimal de ce système est réalisé par un algorithme combinatoire pour, d'une part, répondre aux besoins de la mission et, d'autre part, minimiser sa masse. La mise en oeuvre d'un modèle électrique équivalent de l'hybridation à partir de modèles statiques des composants permet de réduire son temps de résolution. Pour s'assurer de la validité du modèle statique de l'hybridation, il est comparé avec un modèle dynamique. Plusieurs technologies de batteries, Nickel Cadmium (NiCd) ou Lithium-ion (Li-ion), sont proposées afin d'étudier les avantages et les inconvénients de chaque batterie utilisée lors de cette hybridation. Les caractéristiques de la batterie apparaissent déterminantes dans le dimensionnement des éléments du système. La préchauffe de la pile, assurée par la batterie, contraint également sa taille.

The rationalization of elementary processes at surfaces is of prime importance for numerous natural and technological areas. From a fundamental pointof view, the way the energy concomitant to any chemical reaction is distributed among the desorbing molecules degrees-of-freedom and the surface is far frombeing fully pictured. In this work, quasiclassical molecular dynamics (QCT)simulations have been carried out to investigate this issue for the recombination ofH2 and N2 resulting from atomic adsorbate abstraction by atom scattering off theW(100) and W(110) covered surfaces, these processes being of relevance inplasma-wall interactions. Potential energy surfaces, built from density functional(DFT) theory calculations, have been used to simulate, within the framework ofclassical dynamics (including semi-classical corrections), the subpicosecond Eley-Rideal and Hot-Atom processes. The implementation of effective models to accountfor energy dissipation to surface phonons and electron-hole pair excitations, have allowed to rationalize the non-adidabatic dynamics of atom abstraction at metalsurfaces.; La rationalisation des processus chimiques élémentaires aux surfacesest d'intérêt primordial pour de nombreux phénomènes naturels ou d'intérêttechnologique. D'un point de vue fondamental, la façon dont l'énergie, concomitanteà toute réaction chimique, est distribuée parmi les degrés de liberté des moléculesformées et/ou transférée à la surface est loin d'être systématisée. Dans ce travail,des simulations, reposant sur la méthode des trajectoires quasi-classiques (QCT),sont réalisées pour examiner cette problématique lors de recombinaisons demolécules d'hydrogène (H2) et d'azote (N2) résultant de l'abstraction d'atomesadsorbés via collision par un atome provenant de la phase gazeuse sur des surfacesde Tungstène - W(100) et W(110) - à taux de couverture non nul. Ces processussont ici étudiés pour leur intérêt en physique des interactions plasma-paroi. Dessurfaces d'énergie potentielle, construites à partir de calculs de structure électroniquebasés sur la théorie de la fonctionnelle densité (DFT), sont utilisées pour simuler,dans le cadre de la mécanique classique - incluant les corrections semi-classiquespertinentes - les processus ultrarapides dit de "Eley-Rideal" et par "atomes-chauds"(sub-picoseconde). La mise en place de modèle effectifs, pour tenir compte de ladissipation de l'énergie aux phonons de la surface et aux excitations électroniques(paires électron-trou), permet de rationaliser la dynamique non-adiabatique del'abstraction atomique aux surfaces métalliques.

HTSE field (High Temperature Steam Electrolysis) is moving from the research phase to development phase. It?s now necessary to prove and to possibly improve the technology competitiveness. Therefore we need a tool able to allow communication between hydrogen producers and electrolysis cell stack designers. Designers seek where their efforts have to focus, for example by searching what are the operating best conditions for HTSE (voltage, temperature). On the contrary, the producer wants to choose the most suitable stack for its needs and under the best conditions: hydrogen has to be produced at the lowest price. Two main constraints have been identified to reach this objective: the tool has to be inserted into a process simulation software and needs to be representative of the cell and stack used technology. These constraints are antagonistic. Making an object model in a process simulation usually involves a highly simplified representation of it. To meet these constraints, we have built a model chain starting from the electrode models and leading to a representative model of the HTSE technology used process. Work and added value of this thesis mainly concern a global and local energy optimization approach. Our model allows at each scale an appropriate analysis of the main phenomena occurring in each object and a quantification of the energy and economic impacts of the technology used. This approach leads to a tool able to achieve the technical and economic optimization of a HTSE production unit., L'examen de la filière EVHT (Electrolyse de Vapeur d'eau à Haute Température) montre qu'elle est en train de passer de la phase de recherche à la phase de développement. Il devient maintenant nécessaire de prouver et si possible d'améliorer la compétitivité de cette technologie. Pour cela nous avons fait ressortir le besoin de posséder un outil capable de faire le lien entre les producteurs d'hydrogène, propriétaires d'usine, et les fabricants d'empilements de cellules d'électrolyse. Pour répondre à cet objectif principal, deux contraintes fortes sont identifiées : être insérable dans un schéma usine (logiciel de simulation de procédé), et être représentatif de la technologie de cellule et du stack utilisée. La modélisation d'un objet dans un logiciel de simulation de procédé implique généralement une représentation très simplifiée de celui-ci. Pour pouvoir satisfaire ces contraintes, nous avons bâti une chaîne de modèles partant des modèles d'électrodes et aboutissant finalement à une modélisation de procédé représentative de la technologie EVHT utilisée. Le travail et la valeur ajoutée de cette thèse sont focalisés sur cette démarche d'optimisation énergétique globale et locale, qui permet, à chaque échelle, une analyse adaptée des phénomènes principaux se déroulant dans chaque objet et le chiffrage de l'impact énergétique et économique de la technologie utilisée. Cette démarche permet d'aboutir à un outil capable de réaliser une optimisation technico-économique poussée sur une unité de production EVHT

14 th International Symposium on Metal-Hydrogen Systems, MANCHESTER, ROYAUME-UNI, 20-/07/2014 - 25/07/2014; This study proposes the thermal management of the hydrogen 'metal-hydride' storage system. The thermal topic is the main problem of the interaction between this kind of tanks and the fuel cell. A state of the art concerning the coupling between hydride storage and various types of fuel cells (low and high temperature) is given with the perspectives of our study.

The actualization of a hydrogen economy requires cost-effective and environmentally benign solutions to hydrogen production. Chemical energy in the form of hydrogen is more interesting than electricity to satisfy our ever-increasing energy demand because it can be stored more easily. Photoelectrochemical (PEC) water splitting is a carbon-neutral process which converts solar energy into chemical energy (hydrogen) using a light-absorbing semiconducting material to generate the necessary photovoltage to split water into hydrogen and oxygen. So far, record efficiencies in solar-to-hydrogen conversion have been achieved using p-type semiconductors, but only with very expensive materials. However, the spread of this technology relies on the development of semiconductor electrodes made of cheap and abundant elements that are stable in water for a reasonable long time. The semiconductors investigated in this thesis are p-type copper based oxides. Hydrogen production is measured by the photocurrent of water reduction at the semiconductor surface. In the first chapter a roundup of the basics of photoelectrochemical hydrogen generation is presented. In Chapter 2, ternary oxides presenting the delafossite crystal structure are explored, a class of materials that is expected to be stable in water under reducing conditions and that has never been studied for PEC photocathodes. The main achievements of this thesis are presented in Chapters 3-6. It is shown that CU2O, a semiconductor notoriously unstable in aqueous solutions yet a very efficient light absorber, can be stabilized against photocathodic degradation and thus used for water reduction. A preliminary optimization study is carried out to understand the synthetic parameters that control the photoactivity of cuprous oxide obtained by electrodeposition. The deposition current density, temperature and bath pH are changed to find the conditions where photoactivity is optimized. They most photoactive films are then characterized in terms of their optical and electrical properties, which are relevant to the photon-to-electron conversion efficiency (Chapter 3). The surface protection technique consists in the growth of ultrathin oxide layers (about 10-20 nm) by atomic layer deposition (ALD) on the CU2O electrodes (Chapter 4). This powerful technique enables a uniform and continuous coverage of a substrate and a control of the thickness at the atomic scale. Therefore, the passivation technique developed in this thesis can be applied to CU2O morphologies much more complex than those employed in this study and most probably to other semiconductors as well. Photocurrents up to 7.6 mA cm-2 are achieved using CU2O electrodes protected with amorphous Al-doped ZnO and TiCh. and decorated with a Pt catalyst. This photocurrent equals half of the maximum photocurrent possible for C112O and is the highest photocurrent ever measured for an oxide-based photoelectrode for PEC water splitting under AM 1.5 illumination. Further improvements to extend the performance over longer timescales and improve the overall photocathode stability are presented in Chapter 5. The concept of surface passivation against reductive decomposition of a semiconductor is proved for water splitting and important progresses are made in optimizing and understanding the key parameters for preserving the photoactivity of the material under operation. Particularly, the studies presented in Chapter 5 focus on the protective layers, exploring the relationship between the electrical properties of the ALD layers and their chemical stability in different electrolytes and after different temperature treatments. Although some decay in the hydrogen evolution over time is still observed, the last results on the protected electrodes show conversion efficiencies of 60% of the initial value after 10 hours of testing at the standard potential of hydrogen evolution, while for the unprotected electrodes the efficiency drops to 0% after a few minutes.

The question of storing energy in France has become of primary importance since the launch of a road map from the government which places in pole position this topic among seven major milestones to be challenged in the context of the development of innovative technology in the country. The European objective to reach 20% of renewables in the energy market, from which a large part would come from wind and solar power generation, raises several issues regarding the capacity of the grid to manage the various intermittent energy sources in line with the variability of the public demand and offer. These uncertainties are highly influenced by unpredictable weather and economic fluctuations. To facilitate the large-scale integration of variable renewable electricity sources in grids, massive energy storage is needed. In that case, electric energy storage techniques involving the use of underground are often under consideration as they offer a large storage capacity volume with a adapted potential of confining and the space required for the implantation. Among the panel of massive storage technologies, one can find (i) the Underground Pumped Hydro-Storage (UPHS) which are an adaptation of classical Pumped Hydro Storage system often connected with dam constructions, (ii) the compressed air storage (CAES) and (iii) the hydrogen storage from conversion of electricity into H2 and O2 by electrolysis. UPHS concept is based on using the potential energy between two water reservoirs positioned at different heights. Favorable natural locations like mountainous areas or cliffs are spatially limited given the geography of the territory. This concept could be extended with the integration of one of these reservoirs in an underground cavities (specifically mined or reuse of preexisting mines) to increase opportunities on the national territory. Massive storage based on compression and relaxation of air (CAES) requires high volume and confining pressure around the storage that exists naturally in the underground and which increases with depth. However, the move to an interesting efficiency requires that the heat generated during compression can be stored and used during expansion. This storage can be also underground. H2 underground storage is part of the "Power to gas" concept which allows for converting electricity into a gas available for either electrical or gas grid. Each of these techniques requires the selection of appropriate geological formations which contains specific characteristics in agreement with several criteria under consideration when choosing electric energy storage methods for application (lifetime, life cycle, discharge rate, environmental impact, public acceptance ...). We propose in this paper a preliminary review of the potential massive electric energy storage capacities in France of using specific geological formations (salt, basement) and the various physical phenomena linked to the couple geology/technology. Several approaches and methodologies developed formerly with other applications (geothermal, CO2 storage, heat storage ...) will be used to investigate rock mechanical integrity, geochemical and thermal environmental impacts associated to these innovative technologies.

Print ISBN: 978-1-4673-2247-8 INSPEC Accession Number: 13225540; International audience; Fuel cell vehicles (FCV) are characterized by the utilization on the same electric bus of an hydrogen fuel cell (FC) stack as a primary energy source and a storage element like batteries as energy storage system. In our project, the fuel cell is a Polymer Electrolyte Membrane (PEM), which is well adapted for transport field applications. A lithium rechargeable battery, more specifically a LiFePO4, is used to supplement the FC over the driving cycle. According to the requirements of the drive cycle of the vehicle, a 20 kW PEM FC system and a 5 kWh LiFePO4 battery are considered here. To define the power supplied by the source and the energy storage system, an energy management system (EMS) is used. A power split strategy is implemented in the EMS in order to obtain an optimal behaviour for the vehicle in terms of hydrogen consumption and considering the constraints of the system (FC and battery dynamics). Due to the non linear FC dynamics, a non linear control is applied which results in a simplification of the optimization problem.

As an alternative solution to fossil fuels, hydrogen is may be the most advanced technology. However, its large scale development is today harshly hindered by the issues it encounters, its storage being certainly the most significant. Various storage methods are under investigation but solid storage as in sodium borohydride NaBH4 appears to be convenient with regard to its storage capacities, safety and cost. The hydrogen stored in NaBH4 can be released by hydrolysis at ambient temperature. The hydrolysis reaction leads to the formation of 4 hydrogen molecules and borates: ( ) (2 ) ( ) ( ) 4 ( ) 4 2 2 2 2 NaBH ++ x H O l → NaBO . xH O + H gThe efficiency of this reaction suffers from two problems. First, slow kinetics of hydrogen release is observed for this reaction. Second, the “hydration” of NaBO2 is detrimental to the storage capacities of the system NaBH4-H2O. Indeed, the higher the pseudo-hydration degree (i.e. x), the lower the gravimetric hydrogen storage capacity. Both issues are the topics we have studied in the present work. Hydrogen release can be accelerated by using a cobalt catalyst. Hence, we focused on various cobalt-based catalysts. A reference catalyst was first chosen, and then tested and compared to lab-prepared cobalt nanoparticles and other cobalt-based materials (oxide, hydroxide and carbonate). The Langmuir-Hinshelwood kinetic model well captured the kinetics of the hydrolysis reaction. Accordingly, a reaction mechanism based on the adsorptions of both BH4 - and H2O on the catalyst surface has been proposed. The adsorptions are expected to occur on specific surface sites which nature has been discussed. The gravimetric hydrogen storage capacity of NaBH4-H2O can be increased by decreasing the pseudo-hydration degree (i.e. x) of the borates. However, this implies that the thermodynamics of the NaBO2•xH2O compounds are well known as they are crucial for favouring the formation of water-free borates. Borates were then synthesized and characterized in terms of crystallographic structure, pseudo-hydration degree and thermal stability. In this context, a new sodium borate has been synthesized: Na3[B3O4(OH)4] or NaBO2•2/3H2O. Besides, we studied the liquid+solid, liquid+vapor and solid+solid equilibria that permitted to set the binary phase diagram NaBO2-H2O at atmospheric pressure; Le contexte environnemental (réchauffement climatique) et économique (épuisement des ressources en énergies fossiles) entraîne une nécessaire mutation du paysage énergétique mondial. L’hydrogène est présenté comme un vecteur d’énergie propre pouvant, par l’intermédiaire d’une pile à combustible, fournir de l’électricité pour diverses applications (nomade, portable, automobile et stationnaire). Cependant, son développement reste tributaire de son mode de stockage. Parmi les composés présentant de bonnes capacités de stockage, le borohydrure de sodium NaBH4 se distingue puisqu’il permet aussi un dégagement contrôlé de l’hydrogène d’après la réaction d’hydrolyse suivante : ( ) (2 ) ( ) ( ) 4 ( ) 4 2 2 2 2 NaBH ++ x H O l→NaBO . xH O + H g Il constitue ainsi une solution sûre et facile d’utilisation, et est donc envisageable pour des applications grand public. La thèse avait pour objectif l’approfondissement des connaissances relatives à la réaction catalysée d’hydrolyse du borohydrure de sodium selon deux axes principaux: la catalyse de la réaction et l’étude des produits d’hydrolyse. Concernant le premier axe, notre objectif était de mieux comprendre et d’améliorer la cinétique de la réaction d’hydrolyse, les catalyseurs étudiés étant à base de cobalt. Un catalyseur « modèle » a été utilisé et comparé à des nanoparticules métalliques synthétisées et d’autres espèces chimiques à base de cobalt (oxyde, hydroxyle et carbonate). Le modèle cinétique de Langmuir-Hinshelwood a permis de décrire la cinétique de l’hydrolyse. Un mécanisme réactionnel basé sur les adsorptions en surface du catalyseur de BH4 - et de H2O a été proposé. Enfin, la nature des sites actifs en surface a été discutée. En ce qui concerne le second axe de la thèse, nous avions deux objectifs : identifier les phases formées en fonction des conditions expérimentales et approfondir les connaissances thermodynamiques du système binaire NaBO2-H2O pour définir les différents équilibres se formant à l’issu de la réaction d’hydrolyse. Pour ce faire, les borates ont d’abord été synthétisés, puis caractérisés en termes de structure cristallographique et de stabilité en température. C’est ainsi qu’un nouveau borate de sodium, Na3[B3O4(OH)4] ou NaBO2•2/3H2O, a été obtenu. D’autre part, l’étude des équilibres liquide+solide, solide+solide et liquide+vapeur nous a permis d’établir le diagramme binaire NaBO2-H2O à pression atmosphérique.

International audience; Afin de dimensionner un système énergétique par hybridation directe d'une pile à combustible avec une batterie pour une application aéronautique, un modèle électrique équivalent de cette hybridation a été développé. Le dimensionnement optimal de ce système est réalisé par un algorithme combinatoire pour, d'une part, répondre aux besoins de la mission et, d'autre part, minimiser sa masse. La mise en oeuvre d'un modèle électrique équivalent de l'hybridation à partir de modèles statiques des composants permet de réduire son temps de résolution. Pour s'assurer de la validité du modèle statique de l'hybridation, il est comparé avec un modèle dynamique. Plusieurs technologies de batteries, Nickel Cadmium (NiCd) ou Lithium-ion (Li-ion), sont proposées afin d'étudier les avantages et les inconvénients de chaque batterie utilisée lors de cette hybridation. Les caractéristiques de la batterie apparaissent déterminantes dans le dimensionnement des éléments du système. La préchauffe de la pile, assurée par la batterie, contraint également sa taille.

Le but de la présente étude était d'étudier l'impact de la variation des niveaux d'eau d'un marais d'eau douce (Baie Saint-François, Québec) sur l'évolution des concentrations et des flux d'hydrogène, monoxyde de carbone, méthane et dioxyde de carbone. Une approche originale impliquant l'association d'un gradient de concentration de ces composés sur un profil vertical de 1,5 m au transfert de flux turbulent micrométéorologique fut utilisée pour la détermination des flux. L'étude démontre qu'une hausse du niveau d'eau d'un bassin versant alimentant une zone humide influence les flux de méthane, de monoxyde de carbone d'hydrogène et de dioxyde de carbone. En conditions submergées, le marais émettait du méthane et du monoxyde de carbone et consommait moins d'hydrogène troposphérique. Ainsi, cette étude démontre que des mesures in situ peuvent servir à inférer des scénarios d'impacts possibles des changements climatiques et des variations des niveaux d'eau sur les émissions des gaz à effets de serre dans l'écosystème du fleuve Saint-Laurent., Wetlands are known for their great biodiversity and the important carbon reservoir that they represent. Moreover, in the global warming context, these ecosystems represent net sources or sinks for different greenhouse gases depending of their conditions. For instance, flooded conditions favour methane production whereas they prevent hydrogen and carbon monoxide soil consumption. Baie Saint-François is a freshwater wetland that opens onto Lake Saint-Pierre (St. Lawrence River) where water levels are subject to important fluctuations due to natural processes and human activities (hydroelectricity and navigation). This study was done in order to assess the impact of the Lake Saint-Pierre water level variations on the tropospheric methane, carbon monoxide, hydrogen and carbon dioxide dynamics over the wetland. Knowledge of these dynamics should provide indications about the possible effects of the decreasing or increasing water level associated with the global warming on the production or consumption of these trace gases.Studies were carried out between June and August 2003 in Baie Saint-François where soil was subjected to successions of flooded and dry conditions. Water and carbon dioxide fluxes were obtained with a Bowen ratio micrometeorological station including a high frequency single infrared gas analyser. Hydrogen, carbon monoxide and methane fluxes were estimated with the modified Bowen method, their vertical concentration gradients (1.5 m) were measured over the plant canopy. The Bowen Ratio station was equipped with different probes to measure parameters such as net radiations, soil heat fluxes and vertical temperature gradients. The turbulent transfer coefficient (k) obtained every 20 min was assumed equal for heat, water vapour and trace gases. Hence, fluxes calculations were done by the multiplication of the turbulent transfer coefficients with the vertical concentration gradients of hydrogen, carbon monoxide and methane.The instrument used to detect hydrogen, carbon monoxide and methane was a RGA5. This analyser has two detectors: the reductive gas detector (RGD) for hydrogen and carbon monoxide and a flame ionisation detector (FID) for methane. The RGD contains an HgO bed wherein oxygen reacts with reductive gases resulting in Hg° releases detectable by differential UV absorbance. Chemicals were detected continuously in 10 min cycles with an analytical reproducibility of ±0.2, 0.3 and 2% for hydrogen, carbon monoxide and methane. Generally, vertical concentration gradients measured were greater than these limits. A calibration gas containing hydrogen, carbon monoxide and methane at 4940, 1000 and 1000 ppbv respectively in nitrogen was analysed daily to verify calibration. To ensure data integrity, linearity of the instrument was assayed by several dilutions of the standard gas and the integration of the curves gave a correction factor for hydrogen (18%) and carbon monoxide (13%). An intercomparison with NOAA (National Oceanic and Atmospheric Administration) was done to corroborate these correction factors.Background carbon monoxide, methane and carbon dioxide levels were in agreement with literature values. However, hydrogen was low, as observed by other investigators in summertime, since this season is related to minimal concentrations. Methane followed a diurnal cycle where maximum levels were observed during nighttime. In wet conditions, these nocturnal peaks reached occasionally 4000 ppbv and could be explained by specific production mechanisms and diurnal changes of vertical mixing in the boundary layer. Sensitivity of the processes responsible for methane and carbon monoxide cycling was seen between July 21st and 26th where a rain episode (total precipitation of 33.2 mm) increased their background concentrations. It seems that this precipitation was enough to favour methanogenesis and inhibit tropospheric CO and CH4 consumptions by a reduction of the diffusion of these chemicals into the soil.Our results demonstrated that four to eleven days following a variation of the Lake Saint-Pierre water level, a change in the tropospheric hydrogen, carbon monoxide and methane concentrations was observed. This lag might be explained by the distance between the lake and the research station (about 1.5 km) and the required time for the adaptation of soil microorganisms to the disruption of their environment. The concentration variations of these chemicals resulted from the inhibition of the processes responsible for their consumption or the activation of the processes accountable for their production.In June, the wetland was flooded and the CO2 median flux was -56.5 g m-2 d-1. Fluxes increased significantly (Mann-Whitney, α=0.01) in July to 5.30 g m-2 d-1, possibly due to dry conditions. Indeed, absence of water favours the activity of soil aerobic microorganisms which might produce more carbon dioxide than the quantity used by plants during photosynthesis.Methane was produced in June where the median flux was 54 mg m-2 d-1. These emissions were caused by the presence of water which maintained anaerobic conditions in the sediments, a suitable environment for methanogenic microorganisms. July was characterised by dry conditions, which generated aerobic environments in soils, an unfavourable microniche for methanogens. Therefore, methane median fluxes decreased significantly (Mann-Whitney, α=0.05) to 0.011 mg m-2 d-1 in July. In August, before the end of the investigation period, water levels had increased but methane fluxes were not significantly higher than in July. Moreover, in this period, methane concentrations tended to increase, showing that after an augmentation of the Lake Saint-Pierre water level, Baie Saint-François flooding area could represent a methane source.During summer 2003, Baie Saint-François acted as a net source of carbon monoxide. In June, the median flux was 21 µg m-2 d-1 due to presence of water which inhibited consumption by soil. Emissions were significantly (Mann-Whitney, α=0.05) lower in July (15 µg m-2 d-1) due to the absence of water, which represented a suitable environment for microorganisms consuming tropospheric carbon monoxide. In August, the median carbon monoxide flux attained 65 µg m-2 d-1 due to an increase of the Lake Saint-Pierre water level. Net carbon monoxide emissions observed in wet and dry conditions might be due to the high organic content in soil and water in addition to the presence of plants since all of these are subjected to photooxidation, generating this pollutant. Therefore, an increase of the Lake Saint-Pierre water level is associated with an augmentation of tropospheric carbon monoxide due to the inhibition of the processes responsible of its consumption.A decline in the water level might result in the activation of the soil microorganisms (or abiotic hydrogenases) able to consume tropospheric hydrogen. At the beginning of the campaign (June), the median hydrogen flux was weak (-1.37 g m-2 d-1) due to the presence of water. However, a net soil consumption was seen in July, where the median hydrogen flux decreased to -125 g m-2 d-1. The Lake Saint-Pierre water level increase observed in August was associated with a significant (Mann-Whitney, α=0.05) augmentation of the hydrogen median flux to 299 g m-2 d-1. Consequently, a rise in the Lake Saint-Pierre water levels induced an inhibition of the processes responsible of the tropospheric hydrogen consumption.This study illustrated that the water level fluctuations of the Lake Saint-Pierre have an impact on the H2, CO, CH4 and CO2 dynamics over the surrounding wetlands. When the Lake Saint-Pierre water level decreased, the wetlands acted as a carbon monoxide and carbon dioxide source, but as a consumer of tropospheric hydrogen and a minor source of methane.

The increase of components density in advanced microelectronics is practically dictated by the device size and the achievable pitch between the devices. Scaling down dimensions of devices and progress in the circuit design allowed following Moore's law during more than 40 years. Today the traditional scaling has reached limits when physical phenomena inherent to the nanoscale generate as many challenges and issues as the gain in performance compared to previous device generation. This work proposes another alternative to overcome the difficulty of traditional scaling and still continue to increase the integration density and with improved device performances: the vertical stacking of devices or the completion of the planar integration with an in-volume, vertical integration of multiple channels and other structures. In contrast with many other works, we investigated stacking of channel on bulk silicon substrates which will avoid the higher costs of engineered substrates like SOI. This thesis reports on the development of strategies to fabricate advanced multilevel 3D structures in bulk silicon, and their integration as stacked transistor channels. We propose some credible alternatives for the design, fabrication and characterization of a Field Effect Transistor exploiting vertically stacked channels. We investigate two main technologies: (i) silicon transformation during a high temperature annealing in hydrogen ambient, and, (ii) profile engineered trenches. We propose several design and process optimization to be able to fabricate stacked silicon structures (membranes, nanowires, Fins) that could be used as suspended transistor channels. Two original fabrication processes are presented, enabling the manufacturing of bulk silicon transistors with a matrix of stacked channels. We successfully validate the fabrication process of two level suspended Fin channel transistor. Double-stacks of nanowires stacks (promoting a new concept of stacking the stacks) are also demonstrated morphologically. Some of the fabricated structures are electrically characterized, demonstrating basic functionally of a MOSFET but also some difficult control of parasitic transistor effect. We have tried to eliminate such effects by a special design of the source and drain pads in a second integration process. The transfer, Id-Vg, and output, Id-Vd, characteristics of fabricated devices always show a transistor behavior and the extracted mobility values for n-type transistors tend to confirm that the conduction in the suspended channels dominates over the sidewall or bottom parasitic transistor. However, the presence of a parasitic transistor remains important and its elimination needs further efforts. The demonstrated 3D silicon structures in this work show the possibility to sculpture and integrate stacked channels in bulk silicon for making MOSFETs with multiple suspended channels, potentially with independently control of these channels. The morphological work carried out can also find novel applications in other silicon applications areas, like photonics, micro fluidics and Micro-Electro-Mechanical-Systems.