Tesis sobre el tema "Structural kinetic modelling"

Orogenic belts are fundamental features of plate tectonics. The crustal structure of orogens around the world shows a wide range of deformation styles from narrow, asymmetric wedges like the Pyrenees to wide, plateau-like orogens such as the Zagros or the Himalaya. The primary controlling factor on the size and structure of an orogen is the amount of convergence between the colliding plates. However, there are important additional factors providing major controls on the structural development of orogens. Among the potential parameters that can affect the style of deformation are the crustal strength, inherited weaknesses, and the surface processes. These parameters have been studied extensively in the past but their relative importance remains unclear. The aim of this thesis is to improve our understanding of: (1) How surface processes affect mountain building, with a special focus on the relationship between thin-skinned foreland and thick-skinned internal deformation of orogens. (2) How inherited extensional structures affect mountain building. The study was carried out using the Pyrenees as a special reference case. To answer our research questions we have used a wide range of state-of-the-art numerical modelling tools. In paper 1 we present a new method where we couple a structural-kinematic model and a thermo-kinematic model to evaluate the consistency of existing balanced section reconstructions with independent thermochronology data. In papers 2 and 3 we use 2D lithospheric scale thermo-mechanical models with surface process algorithms. Using the above toolset, we demonstrate that syntectonic sedimentation results in longer basement thrust sheets as well as longer thin-skinned thrust sheets and a generally wider orogen. Conversely erosion tends to narrow the wedge and reduce the orogenic loading of the colliding plates, limiting the space available for deposition in the flexural foreland deeps. We also demonstrate that inherited extensional structures play a crucial role in mountain building as they facilitate the migration of deformation into the undeformed basement of the overriding plate. Moreover, a significant amount of lower-crustal/mantle-lithospheric material is preserved at shallow depths only in the presence of extensional inheritance, but significant erosion is needed in order to bring this material to the surface. Our models also show that thin-skinned thrust sheets are generally rooted in the footwall of basement thrusts as they form outward-propagating sequences. As soon as a new basement thrust forms, the thin-skinned sequence situated on top of the new basement thrust-sheet is abandoned in favour of starting a new sequence in the footwall of the new thrust. Regarding our case study, it was possible to reproduce the section restoration using a structural-kinematic model with high accuracy up to the 36-Ma time slice and with limited accuracy up to the 50-Ma time slice. The thermochronometric ages predicted by the thermo-kinematic modelling are generally in good agreement with both the high- and low-temperature thermochronology data available in the Central Pyrenees; hence we conclude that the restoration is to a first order consistent with these datasets. The predicted thermochronological ages approximate the available low-temperature thermochronology data better by taking into account the late-stage burial and re-excavation scenario affecting the southern flank of the Pyrenean wedge presented by Coney et al. (1996), and quantified by Fillon and van der Beek (2012). In conclusion, our model experiments suggest, that extensional inheritance played a prime role in the structural evolution of the Pyrenees, with the major characteristics of the North Pyrenean Unit, including the presence of steep, inverted normal faults, the relative tectonic quiescence of the area after the early inversion and the presence of a lower-crustal body at shallow depth below the unit, best recaptured by our accordion models
Orogenic belts are fundamental features of plate tectonics. The crustal structure of orogens around the world shows a wide range of deformation styles from narrow, asymmetric wedges like the Pyrenees to wide, plateau-like orogens such as the Zagros or the Himalaya. The primary controlling factor on the size and structure of an orogen is the amount of convergence between the colliding plates. However, there are important additional factors providing major controls on the structural development of orogens. Among the potential parameters that can affect the style of deformation are the crustal strength, inherited weaknesses, and the surface processes. These parameters have been studied extensively in the past but their relative importance remains unclear. The aim of this thesis is to improve our understanding of: (1) How surface processes affect mountain building, with a special focus on the relationship between thin-skinned foreland and thick-skinned internal deformation of orogens. (2) How inherited extensional structures affect mountain building. The study was carried out using the Pyrenees as a special reference case. To answer our research questions we have used a wide range of state-of-the-art numerical modelling tools. In paper 1 we present a new method where we couple a structural-kinematic model and a thermo-kinematic model to evaluate the consistency of existing balanced section reconstructions with independent thermochronology data. In papers 2 and 3 we use 2D lithospheric scale thermo-mechanical models with surface process algorithms. Using the above toolset, we demonstrate that syntectonic sedimentation results in longer basement thrust sheets as well as longer thin-skinned thrust sheets and a generally wider orogen. Conversely erosion tends to narrow the wedge and reduce the orogenic loading of the colliding plates, limiting the space available for deposition in the flexural foreland deeps. We also demonstrate that inherited extensional structures play a crucial role in mountain building as they facilitate the migration of deformation into the undeformed basement of the overriding plate. Moreover, a significant amount of lower-crustal/mantle-lithospheric material is preserved at shallow depths only in the presence of extensional inheritance, but significant erosion is needed in order to bring this material to the surface. Our models also show that thin-skinned thrust sheets are generally rooted in the footwall of basement thrusts as they form outward-propagating sequences. As soon as a new basement thrust forms, the thin-skinned sequence situated on top of the new basement thrust-sheet is abandoned in favour of starting a new sequence in the footwall of the new thrust. Regarding our case study, it was possible to reproduce the section restoration using a structural-kinematic model with high accuracy up to the 36-Ma time slice and with limited accuracy up to the 50-Ma time slice. The thermochronometric ages predicted by the thermo-kinematic modelling are generally in good agreement with both the high- and low-temperature thermochronology data available in the Central Pyrenees; hence we conclude that the restoration is to a first order consistent with these datasets. The predicted thermochronological ages approximate the available low-temperature thermochronology data better by taking into account the late-stage burial and re-excavation scenario affecting the southern flank of the Pyrenean wedge presented by Coney et al. (1996), and quantified by Fillon and van der Beek (2012). In conclusion, our model experiments suggest, that extensional inheritance played a prime role in the structural evolution of the Pyrenees, with the major characteristics of the North Pyrenean Unit, including the presence of steep, inverted normal faults, the relative tectonic quiescence of the area after the early inversion and the presence of a lower-crustal body at shallow depth below the unit, best recaptured by our accordion models

In our modern society we are exposed to many natural and synthetic chemicals. The assessment of chemicals with regard to human safety is difficult but nevertheless of high importance. Beside clinical studies, which are restricted to potential pharmaceuticals only, most toxicity data relevant for regulatory decision-making are based on in vivo data. Due to the ban on animal testing of cosmetic ingredients in the European Union, alternative approaches, such as in vitro and in silico tests, have become more prevalent. In this thesis existing non-testing approaches (i.e. studies without additional experiments) have been extended, e.g. QSAR models, and new non-testing approaches, e.g. in vitro data supported structural alert systems, have been created. The main aspect of the thesis depends on the determination of data quality, improving modelling performance and supporting Adverse Outcome Pathways (AOPs) with definitions of structural alerts and physico-chemical properties. Furthermore, there was a clear focus on the transparency of models, i.e. approaches using algorithmic feature selection, machine learning etc. have been avoided. Furthermore structural alert systems have been written in an understandable and transparent manner. Beside the methodological aspects of this work, cosmetically relevant examples of models have been chosen, e.g. skin penetration and hepatic steatosis. Interpretations of models, as well as the possibility of adjustments and extensions, have been discussed thoroughly. As models usually do not depict reality flawlessly, consensus approaches of various non-testing approaches and in vitro tests should be used to support decision-making in the regulatory context. For example within read-across, it is feasible to use supporting information from QSAR models, docking, in vitro tests etc. By applying a variety of models, results should lead to conclusions being more usable/acceptable within toxicology. Within this thesis (and associated publications) novel methodologies on how to assess and employ statistical data quality and how to screen for potential liver toxicants have been described. Furthermore computational tools, such as models for skin permeability and dermal absorption, have been created.

This work is based on an experimental research activity in which direct hydrogenation reaction of biomass-derived compounds was performed to produce gamma-valerolactone (GVL), a relevant organic platform molecule in bio-refinery industry. After defining the best operative, levulinic acid (LA) and its alkyl esters (AL) were tested as starting substrates and a kinetic model was obtained from the data. The kinetic study was the starting point to compare the chemical reactivity of the four chosen substrates in the defined system in order to evaluate their advantages and disadvantages from the reaction point of view and taking into account their implications in a further applicative perspective. Finally, a discussion about a possible correlation between the kinetics and the chemical structures of the different substrates is presented.

Le paraxylène (pX), utilisé dans la fabrication de l'acide téréphtalique pour la production de nylon, est principalement produit par isomérisation de la coupe aromatique C8. Cette dernière est principalement composée des trois isomères du xylènes (para, ortho et méta) et de l'éthylbenzène (EB). L’EB est transformé en xylènes grâce à un catalyseur bifonctionnel comprenant à la fois une fonction acide comme la zéolithe EU-1 et une fonction hydro-déshydrogénante (HD/DHD) comme le platine. L’hydrogénation de l’EB conduit également à la production d’éthylcyclohexane, qui peut subir des réactions non désirées d’ouverture de cycle et de craquage sur la fonction acide du catalyseur. Au cours de ce travail, nous avons cherché à comprendre les facteurs influant sur la sélectivité du catalyseur bifonctionnel en hydroconversion de l’éthylcyclohexane (ECH), et à identifier des phases acides zéolithiques très sélectives. L’effet de paramètres tels que le ratio et la proximité entre sites acides et sites HD/DHD, la localisation des sites acides au sein du réseau zéolithique, et la topologie de ce réseau zéolithique, a été examiné. Des études catalytiques ont été mises en œuvre sur des séries de catalyseurs bifonctionnels à base de zéolithe EU-1, et interprétées à la lueur de calculs ab initio focalisés sur les mécanismes d’isomérisation et d’ouverture de cycle de l’ECH sur la phase acide EU-1. L’intégration de données thermocinétiques déterminées ab initio dans un modèle cinétique en champ moyen a permis de valider l’approche et d’identifier les étapes réactionnelles clés dictant la sélectivité. Un criblage rationnel de structures zéolithes a ensuite été proposé pour identifier les paramètres topologiques influant
The paraxylene (pX), used in the manufacture of terephtalic acid for the production of nylon, is mainly produced by isomerization of the C8 aromatic cut. The latter is mainly composed of the three xylene isomers (para, ortho and meta) and ethylbenzene (EB). EB is converted into xylenes by mean of a bifunctional catalyst comprising both an acid function, such as EU-1 zeolite, and a hydro-dehydrogenating function (HD / DHD), such as platinum. The hydrogenation of EB also leads to the production of ethylcyclohexane, which can undergo undesired ring-opening and cracking reactions on the acid function of the catalyst. In this work, we tried to understand the factors influencing the selectivity of the bifunctional catalyst in the hydroconversion of ethylcyclohexane (ECH), and to identify very selective zeolitic acid phases. The effect of parameters such as the ratio and proximity between acid and HD / DHD sites, the location of acid sites within the zeolite network, and the topology of this zeolite network, was evaluated. Catalytic studies have been carried out over bifunctional catalysts series based on the EU-1 zeolite, and interpreted considering ab initio calculations focused on the isomerization and ring-opening mechanisms of ECH on the EU-1 acid phase. The integration of thermokinetic data (determined by ab initio calculations) in a mean field kinetic model made it possible to validate the approach and to identify the key reaction steps dictating the selectivity. A rational screening of zeolite structures was then proposed to identify the influential topological parameters

Flow mechanisms of compound meandering channels are recognised to be far more complicated than compound straight channels. The compound meandering channels are mainly characterised by the continuous variation of mean and turbulent flow parameters along a meander wavelength; the existence of horizontal shear layer at the bankfull level and the presence of strong helical secondary flow circulations in the streamwise direction. The secondary flow circulations are very important as they govern the advection of flow momentum, distort isovels, and influence bed shear stress, thus producing a complicated and fully three-dimensional turbulent flow structures. A great deal of experiments has been conducted in the past, which explains flow mechanisms, mixing patterns and the behaviour of secondary flow circulations. However, a complete understanding of secondary flow structures still remains far from conclusive mainly because the secondary flow structures are influenced by the host of geometrical and flow parameters, which are yet to be investigated in detail. The three-dimensional Reynolds-averaged Navier-Stokes and continuity equations were solved using a standard Computational Fluid Dynamics solver to predict mean velocity, secondary flow and turbulent kinetic energy. Five different flow cases of various model scales and relative depths were considered. Detailed analyses of the measured and predicted flow variables were carried out to understand mean flow mechanisms and turbulent secondary flow structures in compound meandering channels. The streamwise vorticity equation was used to quantify the complex and three-dimensional behaviour of secondary flow circulations in terms of their generation, development and decay along the half-meander wavelength. The turbulent kinetic energy equation was used to understand energy expense mechanisms of secondary flow circulations. The strengths of secondary flow circulations were calculated and compared for different flow cases considered. The main findings from this research are as follows. The shearing of the main channel flow as the floodplain flow plunges into and over the main channel influences the mean and turbulent flow structures particularly in the crossover region. The horizontal shear layer at the inner bankfull level generates secondary flow circulations. As the depth of flow increases, the point of generation of secondary flow circulations moves downstream. The secondary shear stress significantly contributes towards the generation of streamwise vorticity and the production of turbulent kinetic energy. The rate of turbulence kinetic energy production was found to be higher than the rate of its dissipation in the crossover region, which demonstrates that the turbulence extracts more energy from the mean flu\\' than what is actually dissipated. This also implies that, in the crossover region, the turbulence is always advected downstream by the mean and secondary flows, The strength of geometry induced secondary flow circulation increases with the increase in the relative depth.

Cette thèse est consacrée à l'étude de phénomènes de propagation dans des modèles d’EDP venant de la biologie. On étudie des équations cinétiques inspirées par le déplacement de colonies de bactéries ainsi que des équations de réaction-diffusion importantes en écologie afin de reproduire plusieurs phénomènes de dynamique et d'évolution des populations. La première partie étudie des phénomènes de propagation pour des équations cinétiques. Nous étudions l'existence et la stabilité d'ondes progressives pour des modèles ou la dispersion est donnée par un opérateur hyperbolique et non par une diffusion. Cela fait entrer en jeu un ensemble de vitesses admissibles, et selon cet ensemble, divers résultats sont obtenus. Dans le cas d'un ensemble de vitesses borné, nous construisons des fronts qui se propagent à une vitesse déterminée par une relation de dispersion. Dans le cas d'un ensemble de vitesses non borné, on prouve un phénomène de propagation accélérée dont on précise la loi d'échelle. On adapte ensuite à des équations cinétiques une méthode basée sur les équations de Hamilton-Jacobi pour décrire des phénomènes de propagation. On montre alors comment déterminer un Hamiltonien effectif à partir de l'équation cinétique initiale, et prouvons des théorèmes de convergence.La seconde partie concerne l'étude de modèles de populations structurées en espace et en phénotype. Ces modèles sont importants pour comprendre l'interaction entre invasion et évolution. On y construit d'abord des ondes progressives que l'on étudie qualitativement pour montrer l'impact de la variabilité phénotypique sur la vitesse et la distribution des phénotypes à l'avant du front. On met aussi en place le formalisme Hamilton-Jacobi pour l'étude de la propagation dans ces équations de réaction-diffusion non locales.Deux annexes complètent le travail, l'une étant un travail en cours sur la dispersion cinétique en domaine non-borné, l'autre étant plus numérique et illustre l’introduction
This thesis is devoted to the study of propagation phenomena in PDE models arising from biology. We study kinetic equations coming from the modeling of the movement of colonies of bacteria, but also reaction-diffusion equations which are of great interest in ecology to reproduce several features of dynamics and evolution of populations. The first part studies propagation phenomena for kinetic equations. We study existence and stability of travelling wave solutions for models where the dispersal part is given by an hyperbolic operator rather than by a diffusion. A set of admissible velocities comes into the game and we obtain various types of results depending on this set. In the case of a bounded set of velocities, we construct travelling fronts that propagate according to a speed given by a dispersion relation. When the velocity set is unbounded, we prove an accelerating propagation phenomena, for which we give the spreading rate. Then, we adapt to kinetic equations the Hamilton-Jacobi approach to front propagation. We show how to derive an effective Hamiltonian from the original kinetic equation, and prove some convergence results.The second part is devoted to studying models for populations structured by space and phenotypical trait. These models are important to understand interactions between invasion and evolution. We first construct travelling waves that we study qualitatively to show the influence of the genetical variability on the speed and the distribution of phenotypes at the edge of the front. We also perform the Hamilton-Jacobi approach for these non-local reaction-diffusion equations.Two appendices complete this work, one deals with the study of kinetic dispersal in unbounded domains, the other one being numerical aspects of competition models

Les énergies fossiles jouent un rôle fondamental dans l'économie, la société et la politique. Il existe différentes énergies renouvelables pouvant présenter une alternative telles le solaire, l'éolien, l'hydro-électrique ou encore la biomasse. Parmi ces énergies renouvelables, la biomasse est la seule source de carbone pouvant être utilisée pour la production de carburants, produits chimiques ou matériaux. Parmi les produits chimiques issus de la biomasse, la production de molécules plateformes comme l'acide lévulinique (AL) et ses esters est une voie attractive. Ces molécules peuvent être obtenues par solvolyse de la cellulose ou hémicellulose. L’hydrogénation de ces molécules plateformes conduit à la production de γ-valerolactone (GVL) qui peut aussi être considéré comme une molécule plateforme. Pour favoriser le passage à l'échelle industrielle et trouver les conditions opératoires optimales vis-à-vis de la sécurité et des coûts de production, les questions suivantes doivent être répondues : - Quel est le risque thermique de cette réaction d' hydrogénation? ; - Quel réactif doit-on utiliser : AL ou ses esters? ; - Afin de favoriser l’intégration énergétique, comment mesurer les enthalpies de réactions? Dans un premier temps l'évaluation des risques thermiques pour l' hydrogénation de l’acide lévulinique en GVL catalysée par Ru/C dans l'eau a été effectuée. Un modèle cinétique simple incluant un bilan énergétique en condition pseudo-adiabatique a été développé pour estimer les constantes cinétiques et les paramètres de risque thermique. Par cette étude, il a été possible de déterminer des conditions opératoires sûres pour ce système afin de prévenir les emballements thermiques. Dans un deuxième temps, une approche structure-réactivité a été effectuée en utilisant le concept de relation linéaire de l’énergie libre, à savoir l’équation de Taft. Cette équation a été utilisée pour l'hydrogénation de l'acide lévulinique et de ses esters en GVL catalysée par Ru/C. Le GVL a été utilisé comme solvant pour solubiliser les différents réactifs : AL, lévulinate de méthyle (LM), d'éthyle (LE) et de n-butyle (LB). Il a été démontré que la première étape cinétique, à savoir l'hydrogénation de LA, LM, LE ou LB en leurs intermédiaires et la cinétique de la deuxième étape, à savoir la cyclisation suivent l'équation de Taft. Les effets polaires et stériques ont été évalués et il a été montré que l'effet polaire gouverne ces étapes réactionnelles. La dernière partie de cette thèse consiste à estimer les enthalpies de réaction par calorimétrie. L'estimation de ces constantes thermodynamiques peut s'avérer complexe parce que le GVL est utilisé comme solvant et qu'il n'y a pas d'informations sur les intermédiaires. L’hydrogénation du lévulinate de méthyle a été sélectionnée pour cette étude. Une méthode utilisant les données calorimétriques et analyse chimique a permis d’évaluer l'enthalpie réactionnelle globale et les enthalpies des 2 réactions consécutives. Il a été montré que l'enthalpie globale a une valeur de -51.5 kJ/mol de GVL produits montrant que le système est dans sa globalité exothermique. L’enthalpie d'hydrogénation a été estimée à -58-66 kJ/mol de LM consommé et celle de cyclisation à +7,16 kJ/mol de GVL produits
Fossil energy plays a fondamental role in the economy, society and politics. Till now, different renewable energy are explored to be an alternative for energy supply, such as wind, solar, hydro­ and biomass energy. Among these renewable energy, biomass is regarded as the organic carbon source which can be applied for production of fuels, chemicals or materials. Among the bio-based chemicals, production of platform molecules such as levulinic acid (LA) and its esters is one of attractive way for biomass valorization. LA and its esters can be obtained through hydrolysis and alcoholysis of cellulose or hemicellulose. By further hydrogenation, γ-valerolactone (GVL) is produced and it is also regarded as a platform molecule for further upgrading to biofuels and chemicals with wide application. To scale-up the hydrogenation reaction and to find the optimum operating conditions towards safety and cost, the following questions must be answered : - What is the thermal risk of this reaction? ; - Which starting materials to choose (LA or esters)? ; - For a better energy integration of this process, how to measure the reaction enthalpies? Herein, at first, thermal risk assessment for hydrogenation of LA to GVL catalyzed by Ru/C in water was performed. A simplified kinetic model including energy balance under near-adiabatic conditions was developed to estimate the kinetic constants and thermal risk parameters of this reaction system. Through this thermal risk assessment, it was possible to know the safe operation conditions for this reaction system, i.e., preventing the risk of thermal runaway. Secondly, a structure-reactivity approach was carried out using the concept of Linear Free Energy Relationships (LFER). i.e., Taft equation. The Taft equation (LFER) was applied to hydrogenation of LA and its corresponding esters to GVL catalyzed over Ru/C. GVL was used as a solvent to allow the solubility of the different reactants, namely, LA, methyl levulinate (ML), ethyl levulinate (EL) and n-butyl levulinate (BL). It was demonstrated that the kinetics of the first step, i.e., hydrogenation of LA, ML, EL or BL to the corresponding intermediates and the kinetics of the second step, i.e., ring-closure follow Taft equation. The polar and steric effect of the substituents were evaluated, and it is shown that polar effect governs the kinetics of both reaction steps. Thirdly, the estimation of reaction enthalpies by calorimetry experiments was done. The estimation of such thermodynamic constants by using different thermodynamic models can be hazardous, because in this study GVL was used as a solvent and there are no data concerning the intermediates. Hydrogenation of methyl levulinate (ML) to GVL catalyzed over Ru/C was selected for this study. A method which links calorimetry measurement with composition analysis was developed to determine the reaction enthalpies of the overall reaction and two consecutive steps. It was found that the overall reaction enthalpy was -51.5 kJ/mol of GVL produced, which indicates that the reaction for production of GVL from ML is exothermic. The reaction enthalpy for the first hydrogenation step was calculated to be -58.66 kJ/mol of ML consumed, and for the reaction enthalpy for the second ring-closure step was calculated to be +7.16 kJ/mol of GVL produced

Les sociétés modernes ont besoin de moteurs à combustion interne plus propres et plus efficaces. Cette contrainte entraîne une évolution significative des systèmes de combustion et de la formulation de carburants. L’adéquation moteur-carburant est l’élément clé à optimiser pour atteindre cet objectif. Parmi les paramètres en jeu, la réactivité du carburant est une caractéristique de premier ordre. C’est l’une des raisons en lien avec l’utilisation des additifs. Ils permettent au carburant d’améliorer l’ensemble de ses propriétés notamment vis-à-vis de la combustion. Cependant, le choix et l’utilisation des additifs se heurte encore à un manque de compréhension de leur mécanisme d’action. Dans ce contexte, cette thèse vise à mieux comprendre l’effet chimique des additifs sur la réactivité dans la phase gazeuse. Trois additifs, dont un booster de cétane, un booster d’octane et un antioxydant sont considérés : le 2-ethylhexyl nitrate (EHN), le ferrocène et le 2,4 xylénol respectivement. L’effet chimique de ces additifs sur la réactivité d’un carburant modèle contenant 35 % de n-heptane et 65 % de toluène en volume a fait l’objet d’une étude expérimentale et numérique. Des expériences ont été menées à l’aide de trois équipements : un tube de choc, une machine de compression rapide et un brûleur à flamme plate. L’utilisation de ces équipements permet d’explorer la variation de la réactivité dans des conditions variables représentatives du fonctionnement des moteurs. En parallèle, un modèle cinétique détaillé a été élaboré en s’appuyant sur des données récentes de la littérature. L’accord satisfaisant entre les expériences et les simulations permet de proposer des hypothèses quant à l’effet chimique des additifs
Modern societies require cleaner and more efficient internal combustion engines. This constraint has involved a significant evolution in the combustion systems and fuel formulation. Engine-fuel adequacy is the key item to be optimized to achieve this goal. Among adjustable parameters, the reactivity of the fuel is the most important characteristic to be considered. This leads to an increasing use of additives that allows fuel to meet various combustion requirements. However, the design and the use of additives still faces a lack of comprehension regarding their effect. In this context, this thesis aims to better understand the chemical effect of additives on the fuel gas-phase reactivity. Three additives including a cetane booster, an octane booster, and a free radical scavenger are considered: 2-ethylhexyl nitrate, ferrocene, and 2,4-xylenol, respectively. The chemical effect of these additives on the reactivity of a surrogate fuel containing 35% n-heptane and 65% toluene by volume was experimentally and numerically investigated. Experiments were conducted in three devices: a shock tube, a rapid compression machine, and a heat flux burner. The use of these experimental devices allows to explore the reactivity over a wide range of engine-relevant conditions. For simulations, a detailed kinetic model was developed based on recent literature data. The satisfactory agreement between experiments and simulations enables to propose several hypothesis regarding the chemical effect of the additives

Les Grès d’Annot préservés dans les chaînes subalpines méridionales sont des turbidites riches en sable déposées dans le basin d’avant pays alpin durant l’Eocène supérieur et l’Oligocène inférieur. La sédimentologie et la stratigraphie de ce système turbiditique ont déjà été étudiées, mais le contexte structural reste mal connu. Cette thèse est consacrée à l’étude tectonique des Grès d’Annot, combinant un travail de terrain et l’utilisation d’outils de modélisation géométrique en 3D (gOcad) et cinématique (Trishear), centrés sur les sous-bassins d’Annot, du Grand Coyer et de Sanguinière. L’objectif est d’étudier l’héritage et l’évolution structural du bassin turbiditique et de le replacer dans le contexte régional du SE de la France. Les résultats indiquent que le remplissage du bassin périalpin précoce (Eocène et Oligocène) est bien plus complexe qu’une simple migration de la sédimentation (Grès d’Annot) et de la déformation vers l’avant pays. Ils révèlent des interactions entre tectonique et sédimentation à différentes échelles. A l’échelle de l’avant-pays, une coupe équilibrée illustre le contrôle primordial de la marge passive salifère préexistante sur la structure de la chaîne plissée. Le sel triasique constitue un décollement basal régional, qui de par sa faiblesse, a accommodé une déformation alpine précoce d’une large zone de l’avant-pays dès l’Éocène moyen et supérieur. Les variations de stratigraphie mécanique des séries mésozoïques sont à l’origine d’un changement de style structural : lors de la compression, plusieurs niveaux de décollement actifs se développent dans la partie orientale où les séries sont plus argileuses et plus fines. Ceci induit, en surface, une géométrie de bassin complexe avec des plis de longueurs d’ondes différentes et des migrations de charnière au cours de la sédimentation turbiditique. L’héritage structural du bassin d’avant-pays, jusqu’alors sous-estimé, est le résultat de l’ouverture de la Téthys alpine et d’une déformation précoce régionale exprimée par des plis d’axe E-W qui débute dès le Crétacé supérieur et s’accentue durant l’Éocène moyen. Des résultats préliminaires de thermochronologie (datations U-Th/He sur zircons détritiques de grès moyens à grossiers ou de granodiorites présentes dans les coulées de débris du dépocentre de Sanguinière) suggèrent une exhumation des reliefs à l’origine du matériel détritique liée à cette déformation crétacée. L’étude structurale détaillée de la série des Grès d’Annot et de son substratum dans les sous-bassins d’Annot et du Grand Coyer permet de définir en 3D les connections entre les dépocentres et de proposer une évolution structurale de ceux-ci à l’échelle du bassin. Les paléocourants montrent un parallélisme avec la direction des plis majeurs, indiquant un confinement alors que des directions divergentes à proximité des structures tectoniques plus mineures ou transverses suggèrent que ces dernières interagissent avec les écoulements. Les turbidites se déposent parallèlement dans plusieurs synclinaux alpins, actifs en alternance ou en même temps. A l’échelle des dépocentres, la modélisation géométrique 3D du dépocentre d’Annot en utilisant gOcad permet d’identifier les structures héritées et de démontrer la contemporanéité du plissement alpin et des dépôts turbiditiques. La migration de l’onlap des dépôts de grès et la variation des pendages à l’intérieur des membres turbiditiques sont associées à une migration du dépocentre. Cette géométrie est liée à une migration de la charnière synclinale qui favorise une tendance des dépôts à migrer latéralement plutôt qu’à s’empiler.D’un point de vue sédimentologique et stratigraphique, les Grès d’Annot sont connus pour être un bon analogue des réservoirs des grands fonds de type « riches en sable », situés sur les marges passives en aval de deltas
The Annot Sandstone, exposed in the southern sub-alpine chains, consists of sand-rich turbidites deposited in the Tertiary Alpine foreland basin (Upper Eocene – Lower Oligocene Annot Sandstone basin). While the sedimentology and stratigraphy of this turbidite system have been largely described and discussed, its structural framework remains unconstrained. This thesis presents a study of the tectonics of the Annot Sandstone basin based on field surveys and 3D geometrical (gOcad) and kinematic modelling (Trishear), focusing in particular on the Annot, Grand Coyer and Sanguinière sub-basins. Objectives were to determine the structural evolution of the sub-basins, including the role of inherited features, and to use these data to better constrain the alpine tectonic history of SE France.Infill of the early alpine foreland basin is more complex than a simple foreland migration of sedimentation and deformation. Results reveal complex interactions of tectonics and sedimentation at different scales during deposition of the Annot Sandstone.•At the foreland scale, a balanced cross-section illustrates the critical control by the pre-existing salt-based passive margin architecture on the structure of the fold and thrust belt. Triassic evaporates regionally acted as a weak basal detachment, accommodating an early alpine deformation phase of the whole foreland from the Middle to Upper Eocene. Variations in mechanical stratigraphy within the Mesozoic sediments generated a change in structural style. For example, the eastern region is characterized by a thinner, shalier Mesozoic succession, leading to several active detachments during alpine compression. Multiple fold wavelengths and synsedimentary rolling hinges generated by these active detachments led to complex depocentres. The previously under-estimated structural heritage of the foreland basin derived from rifting and spreading of the Alpine Tethys and from an early regional deformation responsible for E-W trending folds, which began in the Late Cretaceous and increased during the Middle Eocene. Preliminary thermochronology results (U-Th/He datings on detrital zircons of medium to coarse sandstone blocks and granodiorite blocks from debris flows of the Sanguiniere depocentre) suggest an exhumation of source areas during this Cretaceous deformation.•A detailed study of structures within the Annot and Grand Coyer sub-basins and their Cretaceous substrate revealed connected depocentres evolving in 3D at the basin scale. Paleocurrent directions are mainly parallel to the main alpine fold axes recording structural confinement, while some diverging directions indicate flow interaction with minor or oblique tectonic features. Turbidites were deposited along the axis into several alpine synclines, which were simultaneously or successively active.•Concerning the depocentre infill, 3D geometrical modelling of the Annot depocentre (using gOcad) was used to identify inherited structures and to constrain alpine fold activity during turbidite deposition. The onlap migration and the specific stacking and dip pattern within turbidite members (laterally rather than vertically stacked deposits) record depocentre migration linked with a rolling synclinal hinge. Due to its sedimentology and its stratigraphy, the Annot Sandstone is well-known as an analogue for sand-rich reservoirs deposited at delta toes in deep-water passive margins. This study reveals that, structurally, it is also a good example of axially-sourced turbidite depocentres developed on a multi-detachement fold and thrust belt

Les pièces situées dans des zones chaudes/tièdes (300-400°C) de l'avion sont actuellement en titane (mât moteur) ou en composite à matrice époxy (plenum). Comment pourrait-on diminuer la masse de ces pièces tout en évitant leur dégradation à hautes températures de fonctionnement ? Le projet TACT (Technologie pour Aérostructures composites Tièdes), porté par Nimitech Innovation® (Groupe LAUAK), propose une solution innovante consistant à mettre en oeuvre par voie RTM des pièces structurales tièdes à base de renfort en fibres de carbone (FC) et de matrice Cyanate ester (CE). Le choix de la matrice thermodurcissable CE est justifié par son caractère thermostable, c'est-à-dire sa capacité d'opérer en continu à de hautes températures de fonctionnement (avec une température de transition vitreuse Tg>300°C). Par ailleurs, elle possède la facilité de mise en oeuvre des époxydes du fait qu'elle s'adapte généralement bien aux paramètres du procédé RTM. Toutefois, l'exothermie élevée de la matrice CE lors de la réticulation implique un gradient de température dans la pièce composite et peut ainsi engendrer des problèmes de surchauffe. Les travaux scientifiques menés dans le cadre de cette thèse se focalisent sur la problématique de surchauffe de la résine pendant le processus de polymérisation très exothermique dans le moule RTM. L'objectif serait ainsi de maîtriser le cycle de cuisson du composite afin d'éviter tout problème d'emballement ou de dégradation pendant la réticulation de la matrice. Dès lors, la thèse s'organise de la manière suivante : dans un premier temps, le comportement thermocinétique de la matrice CE (pure et catalysée) est analysé pendant l'étape de réticulation, et ceci dans l'optique de contribuer à l'optimisation de cycle de cuisson lors de la mise en oeuvre du composite FC/CE par procédé RTM. Ensuite, les propriétés thermiques (capacité calorifique, conductivité, diffusivité) en fonction du degré d'avancement de la résine CE sont menés afin d'évaluer le gradient thermique régi par l'équation de la chaleur permettant de maîtriser la cuisson de la résine dans l'épaisseur. Par ailleurs, la vitrification de la matrice CE est étudiée par le suivi de la température de transition vitreuse Tg en fonction de la température et du taux d'avancement à l'aide de différents techniques de mesure (DSC, DMA, TMA). Enfin, une modélisation de la vitrification à l'aide du modèle Di-Benedetto permettra l'estimation de la température de la transition vitreuse Tg ∞ pour le réseau tridimentionnel entièrement réticulé
Aeronautical parts which operate in high temperature area (300-400°C) are currently made of titanium (aircraft pylon) or composite materials based on epoxy matrix (plenum). In which extent the weight of these pieces could be reduced as well as avoiding their degradation when operating at these working temperature ranges? TACT project (Technologie pour Aérostructures composites Tièdes), overseen by Nimitech Innovation® (Groupe LAUAK), suggests an innovative solution based on the development of high performance composites parts reinforced by carbon fibers (CF) and cyanate ester matrix (CE) through RTM process. The CE resin belongs to the class of high-performance thermosetting polymers and is mainly chosen in this project due to its thermal stability when operating at high temperatures (with a glass transition Tg>300°C), as well as epoxy-like processability. However, the cross-linking reaction exhibits highly exothermic process, resulting in non-linear increase in internal temperature, which may cause a temperature overshoot. The scientific work carried out within this thesis focuses on the problem of overheating of the resin during the highly exothermic polymerization process in the RTM mold. The objective would thus be to control the curing cycle of the composite in order to avoid problems of runaway or degradation during the crosslinking of the matrix. Hence, the thesis is organized as follows: firstly, thermokinetic behavior of CE resin is analyzed during the crosslinking process in order to optimize the curing cycle. Secondly, thermal properties (heat capacity, conductivity, diffusivity) are identified as a function of the conversion degree in order to evaluate the thermal gradient covered by the heat equation making it possible to control the curing along the thickness of the composite. Moreover, the vitrification of the cyanate ester matrix is studied by monitoring the glass transition temperature Tg as a function of the temperature and conversion degree using different methods (DSC, DMA, TMA). Finally, Di-Benedetto model, a vitrification model, is chosen in order to identify the glass transition temperature Tg∞ of a full crosslinked resin

Computational tools allow the simulation of biological processes giving results which can be used to build computational/experimental approaches for the study of cellular processes dynamics. In my Doctoral Thesis I described and applied calculation methods for the quantitative analysis of the dynamics of different cellular processes. The first chapter describes the mathematical and computational methods then used in the applications described in the following chapters: the first part describes the detailed kinetic models based on ordinary differential equations (ODEs) and the topographic and stoichiometric models to simulate the cellular metabolism of microorganisms. Particular attention is given to the application of an hybrid method: the structural kinetic modelling (SKM). The second part describes some computational methods proposed in literature for the time-series images analysis obtained with confocal microscopy on living cells. Calculation methods described allow the automated detection and tracking of microtubules comets. The second chapter describes my research activities in the application of the quantitative methods to the analysis of metabolic pathways in microorganisms. The application of ODEs and SKM methods are described and through computational simulations the output variation in kinetic parameters are analyzed respect to the perturbations in the input kinetic parameters. The parameter estimation is described through the comparison between experimental and simulation data and a method to build a difference index of kinetic parameters is suggested for build a computational/experimental approach to the analysis of cellular metabolism of microorganisms. The third chapter describes my research activities on the analysis of images obtained from confocal microscopy. Applications of computational methods for detection and tracking of microtubules comets are described. Microtubules dynamics are determined through the analysis of the growing of the microtubules plus ends by the study of EB3 protein made fluorescently by translational fusion with GFP. These methods have been applied to the study of the effects of the inactivation of the Citron kinase protein on the microtubules dynamics and on the angle of the mitotic spindle.

Gli strumenti di calcolo permettono la simulazione al calcolatore di processi biologici fornendo risultati che possono essere utilizzati per la costruzione di approcci computazionali/sperimentali per lo studio della dinamica dei processi cellulari. Nella mia Tesi di Dottorato ho descritto ed applicato metodi di calcolo per l’analisi quantitativa della dinamica di diversi processi cellulari. Il primo capitolo descrive i metodi matematici e computazionali utilizzati poi nelle applicazioni descritte nei capitoli successivi: la prima parte descrive i modelli cinetici dettagliati basati su equazioni differenziali ordinarie (ODEs) ed i modelli topografici e stechiometrici per simulare il metabolismo cellulare di microrganismi. Particolare attenzione è data all’applicazione di un metodo ibrido proposto in letteratura: lo Structural kinetic modeling (SKM). La seconda parte descrive alcuni metodi computazionali proposti in letteratura per l’analisi di serie di immagini su cellule viventi ottenute con la tecnologia della microscopia confocale. Sono descritti i metodi di calcolo che permettono il riconoscimento e la tracciatura automatica di comete di microtubuli. Il secondo capitolo descrive la ricerca che ho svolto con l’applicazione dei metodi quantitativi all’analisi dei percorsi metabolici cellulari di microrganismi. Si descrivono le applicazioni del metodo ODEs ed SKM e tramite simulazioni al calcolatore si analizzano le variazioni nell’output dei parametri cinetici considerando perturbazioni nell’input. Si descrive la stima di parametri attraverso il paragone tra dati sperimentali e simulati e si propone un metodo di costruzione di un indice di differenza parametrica che possa essere utile nella costruzione di un approccio computazionale/sperimentale all’analisi del metabolismo cellulare di microrganismi. Il terzo capitolo descrive la ricerca che ho svolto sull’analisi di immagini da microscopia confocale. Si descrivono le applicazioni dei metodi computazionali di rilevazione e tracciatura applicati allo studio della dinamica dei microtubuli, determinata a partire dall'analisi della crescita delle estremità positive grazie allo studio della proteina EB3, resa fluorescente mediante fusione traduzionale con GFP. Tali metodiche sono state applicate allo studio degli effetti dell'inattivazione della proteina Citron kinase sulla dinamica dei microtubuli e sull'angolo del fuso mitotico.
Computational tools allow the simulation of biological processes giving results which can be used to build computational/experimental approaches for the study of cellular processes dynamics. In my Doctoral Thesis I described and applied calculation methods for the quantitative analysis of the dynamics of different cellular processes. The first chapter describes the mathematical and computational methods then used in the applications described in the following chapters: the first part describes the detailed kinetic models based on ordinary differential equations (ODEs) and the topographic and stoichiometric models to simulate the cellular metabolism of microorganisms. Particular attention is given to the application of an hybrid method: the structural kinetic modelling (SKM). The second part describes some computational methods proposed in literature for the time-series images analysis obtained with confocal microscopy on living cells. Calculation methods described allow the automated detection and tracking of microtubules comets. The second chapter describes my research activities in the application of the quantitative methods to the analysis of metabolic pathways in microorganisms. The application of ODEs and SKM methods are described and through computational simulations the output variation in kinetic parameters are analyzed respect to the perturbations in the input kinetic parameters. The parameter estimation is described through the comparison between experimental and simulation data and a method to build a difference index of kinetic parameters is suggested for build a computational/experimental approach to the analysis of cellular metabolism of microorganisms. The third chapter describes my research activities on the analysis of images obtained from confocal microscopy. Applications of computational methods for detection and tracking of microtubules comets are described. Microtubules dynamics are determined through the analysis of the growing of the microtubules plus ends by the study of EB3 protein made fluorescently by translational fusion with GFP. These methods have been applied to the study of the effects of the inactivation of the Citron kinase protein on the microtubules dynamics and on the angle of the mitotic spindle.