La stratégie de combustion par auto-inflammation d’une charge homogène en composition s’intègre dans une démarche de réduction des émissions de particules et de NOx, tout en conservant les rendements thermiques élevés des moteurs Diesel classiques. Pour contrôler ce nouveau mode de combustion, une compréhension fine des mécanismes de couplage entre l'aérodynamique et la thermochimie est nécessaire. Des simulations numériques directes d'un écoulement homogène, turbulent, réactif et subissant une compression, ont été effectués. Deux régimes d'auto-inflammation ont ainsi pu être définis. Le premier, dit quasi-homogène, est caractérisé par une auto-inflammation en masse d'un volume important du mélange réactif et s'accompagne de fortes ondes de pression. Dans le second régime, dit localisé, les noyaux s'initient de manière plus sporadique dans l'espace et dans le temps et aucune onde de pression significative n'est générée lors de l'auto-allumage. / Combustion by autoignition of a homogeneous charge aims at reducing particulate matter as well as NOx emissions, while maintaining higher thermal efficiency of conventional diesel engines. To control this new mode of combustion, a fine understanding of the mechanisms of coupling between aerodynamics and thermochemistry is required. Direct Numerical Simulations of a turbulent reactive flow, undergoing a compression, have been performed. This study led to identification of two regimes. The first, known as quasi-homogeneous, is characterized by volumetric autoignition of large zones of the reactive mixture and results in the generation of strong pressure waves, which are potentially dangerous for the structure of engines. In the second regime, called localized, hot spots are initiated more sporadically in space and time, and their topology is such that no significant pressure wave is generated.

Les Jupiters Chauds représentent une classe d’exoplanètes très intéressante à étudier. En effet, ces planètes géantes gazeuses, orbitant très proches de leurs étoiles (typiquement 0.05 UA) reçoivent un ux UV 10 000 fois supérieur à ce que reçoit Jupiter par exemple dans notre Système Solaire. La temprérature atmosphérique, par conséquent très élevée, est comprise entre 1000 et 3000 K. Ces températures élevées, l'importance de la dynamique et la forte irradiation UV font des atmosphères de ces planètes le site d'une chimie unique, n'ayant pas d'équivalent dans le Système Solaire [...]. / Hot Jupiters are a class of exoplanets very interesting to study. Indeed, these giant planets, orbiting very close to their star (typically 0.05 AU), receive a UV ux 10 000 times more intense that the one Jupiter receives in our Solar system. The atmospheric temperature, thus very high, ranges between 1000 and 3000 K. Because of these high temperatures, the important dynamic and strong UV irradiation, the atmospheres of these planets are the site of unique chemistry, having no equivalent in the Solar System [...]

La mort soudaine inattendue (SUDEP) est fréquemment rapportée chez les patients qui souffrent d'épilepsie et compte pour près de 17% des décès dans cette population. Bien que son étiologie soit restée longtemps incertaine, des études menées sur des cas de victimes de SUDEP suggèrent fortement l'implication de l'apnée post-ictale dans la survenue de ce type de décès. Afin d'élucider les mécanismes physiopathologique de la SUDEP, il était nécessaire de mettre en place un modèle animal qui présente à la fois des crise spontanées récurrentes comme dans le syndrome épileptique et des altérations respiratoires. Dans une première partie, nous mettons en évidence la présence d'altérations respiratoires (RAs) chez 30 à 50% des rats qui présentent une épilepsie suite à un état de mal épileptique (SE) induit par l'administration de pilocarpine. Ces RAs, que nous avons assimilées à des apnées, ont été mises en évidence par thermochimie respiratoire et se traduisent par une diminution de la consommation en oxygène, dont la durée peut varier entre 20 secondes et 13 minutes. La présence des RAs est associée à des altérations du système sérotoninergique au niveau du tronc cérébral, où sont concentrés la majorité des groupes de neurones impliqués dans la régulation et dans la modulation de la fonction respiratoire. Nous montrons que de nombreux gènes du système sérotoninergique sont dérégulés lors de la mise en évidence des RAs ; toutefois, seules les altérations touchant le récepteur 5-HT2c semblent être associées au maintien des RAs. Ce résultat est d'autant plus important qu'il avait été montré que la délétion de ce récepteur chez les souris peut conduire à un arrêt respiratoire fatal suite à une crise épileptique, provoquée ou spontanée. Dans une seconde partie, nous montrons que la surface de la zone présentant un hypersignal T2 dans le système limbique ventral des rats épileptiques est prédictive de la présence de RAs. En outre, des différences d'expression du récepteur 5-HT2c similaires à celles qui avaient été observées dans le tronc cérébral sont retrouvées entre les rats épileptiques selon qu'ils présentent ou pas des RAs. Les résultats de cette thèse impliquent donc le récepteur 5-HT2c dans la survenue et/ou le maintien des altérations respiratoires associées à l'épilepsie. Dans le contexte de la SUDEP, nos résultats ouvrent comme première perspective clinique celle de développer des traitements permettant de cibler spécifiquement le récepteur 5-HT2c chez les patients qui présenteraient un risque de survenue de la SUDEP. La seconde perspective clinique serait de pouvoir identifier ces patients à risque à partir de biomarqueurs tels que les anomalies de signal T2 que nous avons identifiées dans la région limbique ventrale qui inclut notamment l'insula, dont il a été montré qu'elle contribue à la modulation de la fonction respiratoire / Pas de résumé anglais

In this dissertation the heat flux prediction capabilities of Residual Distribution (RD) schemes for hypersonic flow fields are investigated. Two canonical configurations are considered: the flat plate and the blunt body (cylinder) problems, with a preference for the last one. Both simple perfect gas and more complex thermo-chemical non-equilibrium (TCNEQ) thermodynamic models have been considered.<p><p>The unexpected results identified early in the investigation lead to a thorough analysis to identify the causes of the unphysical hypersonic heating.<p><p>The first step taken is the assessment of the quality of flow field and heat transfer predictions obtained with RD methods for subsonic configurations. The result is positive, both for flat plate and cylinder configurations, as RD schemes produce accurate flow solutions and heat flux predictions whenever no shock waves are present, irrespective of the gas model employed.<p><p>Subsonic results prove that hypersonic heating anomalies are a consequence of the presence of a shock wave in the domain and/or the way it is handled numerically.<p><p>Regarding hypersonic flows, the carbuncle instability is discarded first as the cause of the erroneous stagnation heating. The anomalies are shown next to be insensitive to the kind and level of dissipation introduced via the (quasi-)positive contribution P to blended B schemes. Additionally, insufficient mesh resolution locally over the region where the shock wave is captured numerically is found to be irrelevant.<p><p>Capturing the bow shock in a manner that total enthalpy is preserved immediately before and after the numerical shock wave is, on the contrary, important for correct heating prediction.<p><p>However, a carefully conceived shock capturing term is, by itself, not sufficient to guarantee correct heating predictions, since the LP scheme employed (be it stand-alone in a shock fitting context or combined into a blended scheme for a shock capturing computation) needs to be immune to spurious recirculations in the stagnation point. <p><p>Once the causes inducing the heating anomalies identified, hypersonic shocked flows in TCNEQ conditions are studied.<p><p>In order to alleviate the computational effort necessary to handle many species non-equilibrium (NEQ) models, the extension of an entropic (or symmetrizing) variables formulation RD to the nS species, two temperature TCNEQ model is accomplished, and the savings in computational time it allows are demonstrated.<p><p>The multi-dimensional generalization of Roe-like linearizations for the TCNEQ model is addressed next: a study on the existence conditions of the linearized state guaranteeing discrete conservation is conducted.<p><p>Finally, the new dissipative terms derived for perfect gas are adapted to work under TCNEQ conditions; the resulting numerical schemes are free of the temperature undershoot and Mach number overshoot problem afflicting standard CRD schemes. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

En rampe de puissance, le combustible nucléaire est soumis à d'importantes contraintes thermiques et mécaniques, et subit une modification profonde de son environnement chimique. Le combustible contraint fortement la gaine, notamment au niveau des zones inter-pastilles, ce qui, associé au relâchement de produits de fission corrosifs, peut conduire à sa rupture par corrosion sous contraintes. Les évolutions simultanées de la mécanique, de la thermique et de la chimie du combustible sont liées, et participent au bon ou mauvais comportement de l'UO2 en rampe de puissance. L'objectif de ce travail est de modéliser à l'échelle d'une pastille de combustible, l'évolution couplée de la chimie, de la thermique et de la mécanique, et de préciser l'impact de ces couplages sur le comportement de l'UO2 en rampe de puissance. La finalité est d'évaluer un terme source en relâchement d'iode pour alimenter les modèles de corrosion sous contraintes dédiés aux études d'Interaction Pastille-Gaine. / Nuclear fuels under power transient undergo high thermal and mechanical stresses, as well as deep chemical modifications. Stresses on the cladding at the inter-pellet plane due to the pellet thermal expansion, associated to the corrosive fission product release, can lead to clad failures, resulting from a stress corrosion cracking mechanism. The thermal, mechanical and chemical properties of the UO2 irradiated fuel are closely dependent and play a major role on the behavior of the material during a power transient. The aim of this work is to model at the pellet scale the chemical, thermal and mechanical coupled changes of the UO2 fuel during a power transient scenario and to evaluate the consequences on the fuel behavior. The final objective is to obtain an evaluation of the iodine release source term to be used in I-SCC modelling codes dedicated to Pellet-Clad-Interaction studies.

Computational chemistry has gained interest as a characterization tool to predict photoluminescence, reactivity and structural properties of organic and transition metal complexes. With the rise of methods including relativity, these studies have been expanded to the accurate modeling of luminescence spectra of complexes with considerable spin-orbit splitting due to heavy metal centers as well as the reaction pathways for these complexes to produce natural products such as hydrogen gas. These advances have led to the synthesis and utility of more effective catalysis as well as the development of more effective organic light emitting diodes (OLEDs) through the incorporation of organometallic complexes as emitters instead of typical organic emitters. In terms of significant scientific advancement presented in this work is in relation to the discovery of significant spin-orbit splitting in a gold(I) alkylphosphine complex, where the splitting results in the states that emit in different colors of the visible region of the electromagnetic spectrum. This work also reveals the discovery both computationally and experimentally, of a genuine polar-covalent bond between two-closed shell metals. This work highlights a complex with an incredibly short gold(I) – copper(I) intermetallic distance leading to a vibrational frequency and dissociation energy that is on par with those of other systems with single-bonded metal centers. Lastly, this work outlines a strategy for the production of hydrogen gas through the use of trinuclear cyclic coinage metal complexes as catalysis to split hydrohalic acids.

Five projects are presented here that use Photoelectron Photoion Coincidence (PEPICO) Spectroscopy to determine high-accuracy thermochemical data on small and intermediate size molecules and radicals that are relevant in modeling combustion and atmospheric processes. Some of the experiments were carried out on the laboratory-based Threshold PEPICO (TPEPICO) apparatus which has the advantage of having a low-temperature inlet system and unlimited measurement time, while most of the projects involved the use of the Imaging PEPICO (iPEPICO) apparatus at the Swiss Light Source, which is capable to determine ionic dissociation energies to sub-kJ/mol accuracy. The iPEPICO on the synchrotron beamline was also useful where measurements required energies in excess of 14 eV. The modeling framework of PEPICO is based on the RRKM statistical theory of dissociation kinetics and statistical energy distributions and models complex dissociation pathways to extract both kinetics and thermochemical data from the experiment. In the first project, we measured the onsets of Br- and I-loss reactions for C 2 H 5 Br and C 2 H 5 I using TPEPICO, respectively. The heats of formations of the two molecules are related through the ethyl cation, which was used in their determination. The second project involved measuring Cl-loss from four S i O j Cl k compounds viz. SCl 2 , S 2 Cl 2 , SOCl 2 , and SO 2 Cl 2 to obtain reliable thermochemistry. The second Cl-loss from S 2 Cl 2 + and SOCl 2 + helped us conclude that assuming three-dimensional translational degrees of freedom yields a more reliable statistical model of product-energy distributions. The third project investigated methanol and its isotopologues to explore the dissociation pathways through the H/D-losses. The 0 K appearance energies were used to determine the accurate heat of formation of CH 2 OH and the proton affinity of formaldehyde. The fourth project explores the dissociation pathways of cis -1-bromopropene, trans -1-bromopropene, 2-bromopropene, 3-bromopropene and bromocyclopropane to find that except for 2-bromopropene, all other isomers dissociate into the allyl cation. To derive accurate thermochemical information on the neutral precursors, a mixed theoretical and experimental thermochemical network was used to determine their 0 K heats of formation. The last project involves measurements on dimethyl disulfide (DMDS) and dimethyl diselenide, which are the simplest models that can be used to study disulfide and diselenide linkages. There are several discrepancies in the thermochemistry of DMDS, whereas ours is the first experimental attempt to study the ionic thermochemistry of dimethyl diselenide experimentally.

Les travaux présentés dans ce manuscrit de doctorat s'inscrivent dans la thématique du stockage inter-saisonnier de l'énergie solaire thermique pour l'habitat et le tertiaire (eau chaude sanitaire et chauffage). Le stockage thermochimique en air humide est une des solutions les plus prometteuses, en particulier avec un réacteur à lit fixe. Le bromure de strontium et l'alun de potassium ont été sélectionnés comme réactifs pour leurs caractéristiques énergétiques lors de réactions d'hydratation et de déshydratation. L'étude est constituée d'avancées théoriques, de nombreuses expérimentations et d'un modèle numérique détaillé. Une étude thermodynamique a démontré l'existence d'une droite de charge qui relie les conditions d'entrée et de sortie de l'air humide au passage du réactif. Les équations régissant les réactions chimiques, les transferts massiques et thermiques et la conservation de la quantité de mouvement ont été établies et un modèle numérique monodimensionnel couplant ces phénomènes a été développé. Des essais sur différents échantillons des deux sels et pour divers conditions opératoires ont été effectués dans le but de comprendre les phénomènes physico-chimiques ainsi que pour valider l'étude théorique et le modèle numérique. / This PhD thesis focuses on seasonal solar thermal energy storage for household applications such as production of heat and domestic hot water. Thermochemical storage was chosen for that purpose. The specific solid/gas reactions with water vapor, also called hydration/dehydration reactions, were used with a multi-scale global approach. The level of the reactor was identified as the critical level of that multi-scale approach. As a consequence, the integrated fixed-bed reactor technology in a moist air open loop system was adopted. A theoretical, experimental and numerical methodology was used for the study where strontium bromide and potassium alum salts were chosen as reactive materials. The corresponding reactions are: + 5 (H2O) ↔ (with Δhr=67.4 kJ/molwater and Δsr=175 J/K.molwater) + 9 (H2O) ↔ < KAl(SO4)2.12H2O > (with Δhr=44.2 kJ/molwater and Δsr=109.8 J/K.molwater) The first salt exhibits very good thermochemical properties. On the other hand, the main advantages of potassium alum are its low cost and the fact that it presents no sanitary risk. More than 30 cycles with 3 different samples of potassium alum and more than 25 cycles with 4 samples of strontium bromide under various stationary and dynamic operating conditions were carried out in order to understand the phenomena. The main experimental results were the following ones: • A very good stability and reproducibility of physical and chemical phenomena was observed for both materials. • A thermal reaction front was also observed. • A thermal hysteresis for both salts was found. • Based on that last observation a theoretical equation named charge-discharge line was developed. Experimental results with both salts validate the charge-discharge line theory. • A correlation between reaction kinetics, temperature rise due to the reaction, power of the reaction and the operating conditions was observed. The criterion for that correlation is the affinity of the reaction. A proportional correlation between affinity and reaction kinetics, temperature rise and power of the reaction was observed. • Spontaneous hydration and over-hydration reactions do not produce any particular difficulties or problems. • Pressure drop through the reactor and evolution of salts volume were also measured. Experimental energy density was measured in the range of 350 kWh/m3 for strontium bromide and 240 kWh/m3 for the potassium alum. • In general, strontium bromide is a very good candidate material for seasonal storage, while potassium alum cannot provide satisfying temperature rise and power. The equations governing those phenomena were also established and used to develop a 1D numerical model with partial differential equations coupling chemical phenomena, mass and thermal transfer phenomena and momentum conservation. Verification, validation and confirmation of this model under a very large range of operating conditions were carried out based on the experimental results of strontium bromide. A total of 19 different test cases were studied in order to validate the numerical model. The effect of humidity, temperature, quantity of reactive material and air flow were studied both for stationary and dynamic conditions. The numerical model was able to provide very satisfying results.