This thesis presents a research project in the field of oxygen system fire safety relating to the heterogeneous burning of iron in normal gravity and reduced gravity. Fires involving metallic components in oxygen systems often occur, with devastating and costly results, motivating continued research to improve the safety of these devices through a better understanding of the burning phenomena. Metallic materials typically burn in the liquid phase, referred to as heterogeneous burning. A review of the literature indicates that there is a need to improve the overall understanding of heterogeneous burning and better understand the factors that influence metal flammability in normal gravity and reduced gravity. Melting rates for metals burning in reduced gravity have been shown to be higher than those observed under similar conditions in normal gravity, indicating that there is a need for further insight into heterogeneous burning, especially in regard to the rate-limiting mechanism. The objective of the current research is to determine the cause of the higher melting rates observed for metals burning in reduced gravity to (a) identify the rate-limiting mechanism during heterogeneous burning and thus contribute to an improved fundamental understanding of the system, and (b) contribute to improved oxygen system fire safety for both ground-based and space-based applications. In support of the work, a 2-s duration ground-based drop tower reduced-gravity facility was commissioned and a reduced-gravity metals combustion test system was designed, constructed, commissioned and utilised. These experimental systems were used to conduct tests involving burning 3.2-mm diameter cylindrical iron rods in high-pressure oxygen in normal gravity and reduced gravity. Experimental results demonstrate that at the onset of reduced gravity, the burning liquid droplet rapidly attains a spherical shape and engulfs the solid rod, and that this is associated with a rapid increase in the observed melting rate. This link between the geometry of the solid/liquid interface and melting rate during heterogeneous burning is of particular interest in the current research. Heat transfer analysis was performed and shows that a proportional relationship exists between the surface area of the solid/liquid interface and the observed melting rate. This is confirmed through detailed microanalysis of quenched samples that shows excellent agreement between the proportional change in interfacial surface area and the observed melting rate. Thus, it is concluded that the increased melting rates observed for metals burning in reduced gravity are due to altered interfacial geometry, which increases the contact area for heat transfer between the liquid and solid phases. This leads to the conclusion that heat transfer across the solid/liquid interface is the rate-limiting mechanism for melting and burning, limited by the interfacial surface area. This is a fundamental result that applies in normal gravity and reduced gravity and clarifies that oxygen availability, as postulated in the literature, is not rate limiting. It is also established that, except for geometric changes at the solid/liquid interface, the heterogeneous burning phenomenon is the same at each gravity level. A conceptual framework for understanding and discussing the many factors that influence heterogeneous burning is proposed, which is relevant to the study of burning metals and to oxygen system fire safety in both normal-gravity and reduced-gravity applications.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-07-01T15:05:14Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Souza_Tese_2015_09_22.pdf: 8187999 bytes, checksum: 664629aed28d692dce410fefbfe793dc (MD5) / Made available in DSpace on 2016-07-01T15:05:14Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Souza_Tese_2015_09_22.pdf: 8187999 bytes, checksum: 664629aed28d692dce410fefbfe793dc (MD5) Previous issue date: 2015-09-22 / Anp / Sob certas hipóteses simplificadoras, o modelo matemático que descreve o escoamento de água e óleo em reservatórios de petróleo pode ser representado por um sistema não linear de Equações Diferenciais Parciais composto por uma equação elíptica de pressão (fluxo) e uma equação hiperbólica de saturação (transporte). Devido a complexidades na modelagem de ambientes deposicionais, nos quais são incluídos camadas inclinadas, canais, falhas e poços inclinados, há uma dificuldade de se construir um modelo que represente adequadamente certas características dos reservatórios, especialmente quando malhas estruturadas são usadas (cartesianas ou corner point). Além disso, a modelagem do escoamento multifásico nessas estruturas geológicas incluem descontinuidades na variável e instabilidades no escoamento, associadas à elevadas razões de mobilidade e efeitos de orientação de malha. Isso representa um grande desafio do ponto de vista numérico. No presente trabalho, uma formulação fundamentada no Método de Volumes Finitos é estudada e proposta para discretizar as equações elíptica de pressão e hiperbólica de saturação. Para resolver a equação de pressão três formulações robustas, com aproximação dos fluxos por múltiplos pontos são estudadas. Essas formulações são abeis para lidar com tensores de permeabilidade completos e malhas poligonais arbitrárias, sendo portanto uma generalização de métodos mais tradicionais com aproximação do fluxo por apenas dois pontos. A discretização da equação de saturação é feita com duas abordagens com característica multidimensional. Em uma abordagem mais convencional, os fluxos numéricos são extrapolados diretamente nas superfícies de controle por uma aproximação de alta resolução no espaço (2ª a 4ª ordem) usando uma estratégia do tipo MUSCL. Uma estratégia baseada na Técnica de Mínimos Quadrados é usada para a reconstrução polinomial. Em uma segunda abordagem, uma variação de uma esquema numérico Verdadeiramente Multidimensional é proposto. Esse esquema diminui o efeito de orientação de malha, especialmente para malhas ortogonais, mesmo embora alguma falta de robustez possa ser observada pra malhas excessivamente distorcidas. Nesse tipo de formulação, os fluxos numéricos são calculados de uma forma multidimensional. Consiste em uma combinação convexa de valores de saturação ou fluxo fracionário, seguindo a orientação do escoamento através do domínio computacional. No entanto, a maioria dos esquemas numéricos achados na literatura tem aproximação apenas de primeira ordem no espaço e requer uma solução implícita de sistemas algébricos locais. Adicionalmente, no presente texto, uma forma modificada desses esquemas “Verdadeiramente” Multidimensionais é proposta em um contexto centrado na célula. Nesse caso, os fluxos numéricos multidimensionais são calculados explicitamente usando aproximações de alta ordem no espaço. Para o esquema proposto, a robustez e o caráter multidimensional também leva em conta a distorção da malha por meio de uma ponderação adaptativa. Essa ponderação regula a característica multidimensional da formulação de acordo com a distorção da malha. Claramente, os efeitos de orientação de malha são reduzidos. A supressão de oscilações espúrias, típicas de aproximações de alta ordem, são obtidas usando, pela primeira vez no contexto de simulação de reservatórios, uma estratégia de limitação multidimensional ou Multidimensional Limiting Process (MLP). Essa estratégia garante soluções monótonas e podem ser usadas em qualquer malha poligonal, sendo naturalmente aplicada em aproximações de ordem arbitrária. Por fim, de modo a garantir soluções convergentes, mesmo para problemas tipicamente não convexos, associados ao modelo de Buckley-Leverett, uma estratégia robusta de correção de entropia é empregada. O desempenho dessas formulações é verificado com a solução de problemas relevantes achados na literatura. / Under certain simplifying assumptions, the problem that describes the fluid flow of oil and water in heterogeneous and anisotropic petroleum reservoir can be described by a system of non-linear partial differential equations that comprises an elliptic pressure equation (flow) and a hyperbolic saturation equation (transport). Due to the modeling of complex depositional environments, including inclined laminated layers, channels, fractures, faults and the geometrical modeling of deviated wells, it is difficult to properly build and handle the Reservoir Characterization Process (RCM), particularly by using structured meshes (cartesian or corner point), which is the current standard in petroleum reservoir simulators. Besides, the multiphase flow in such geological structures includes the proper modeling of water saturation shocks and flow instabilities associated to high mobility ratios and Grid Orientation Effects (GOE), posing a great challenge from a numerical point of view. In this work, a Full Finite Volume Formulation is studied and proposed to discretize both, the elliptic pressure and the hyperbolic saturation equations. To solve the pressure equation, we study and use three robust Multipoint Flux Approximation Methods (MPFA) that are able to deal with full permeability tensors and arbitrary polygonal meshes, making it relatively easy to handle complex geological structures, inclined wells and mesh adaptivity in a natural way. To discretize the saturation equation, two different multidimensional approaches are employed. In a more conventional approach, the numerical fluxes are extrapolated directly on the control surfaces for a higher resolution approximation in space (2nd to 4th order) by a MUSCL (Monotone Upstream Centered Scheme for Conservation Laws) procedure. A least squares based strategy is employed for the polynomial reconstruction. In a second approach, a variation of a “Truly” Multidimensional Finite Volume method is proposed. This scheme diminishes GOE, especially for orthogonal grids, even though some lack of robustness can be observed for extremely distorted meshes. In this type of scheme, the numerical flux is computed in each control surface in a multidimensional way, by a convex combination of the saturation or the fractional flow values, following the approximate wave orientation throughout the computational domain. However, the majority of the schemes found in literature is only first order accurate in space and demand the implicit solution of local conservation problems. In the present text, a Modified Truly Multidimensional Finite Volume Method (MTM-FVM) is proposed in a cell centered context. The truly multidimensional numerical fluxes are explicitly computed using higher order accuracy in space. For the proposed scheme, the robustness and the multidimensional character of the aforementioned MTM-FVM explicitly takes into account the angular distortion of the computational mesh by means of an adaptive weight, that tunes the multidimensional character of the formulation according to the grid distortion, clearly diminishing GOE. The suppression of the spurious oscillations, typical from higher order schemes, is achieved by using for the first time in the context of reservoir simulation a Multidimensional Limiting Process (MLP). The MLP strategy formally guarantees monotone solutions and can be used with any polygonal mesh and arbitrary orders of approximation. Finally, in order to guarantee physically meaningful solutions, a robust “entropy fix” strategy is employed. This produces convergent solutions even for the typical non-convex flux functions that are associated to the Buckley-Leverett problem. The performance of the proposed full finite volume formulation is verified by solving some relevant benchmark problems.

Contrairement aux idées reçues, le sol est une ressource naturelle non renouvelable menacée. La réhabilitation des friches industrielles polluées aux HAP, toxiques et persistants, représente donc un enjeu majeur. Les techniques traditionnelles ne sont pas toujours très appropriées, c’est pourquoi ce travail vise à étudier la pertinence de l’oxydation chimique in situ, habituellement utilisé pour le traitement de nappes contaminées par des polluants moins récalcitrants (COHV, BTEX). Il s’inscrit dans le cadre du projet OXYSOL (ANR-PRECODD) destiné à construire une filière complète de traitement in situ et de refonctionnalisation. Ce travail a consisté à étudier et optimiser ces performances en travaillant avec la terre d’une ancienne cokerie. Ensuite, l’objectif a été de mettre en évidence les principaux paramètres limitants en utilisant différentes terres polluées contrastées. Tout d’abord, les expériences en systèmes fermés ont conduit à sélectionner les deux oxydants les plus adaptés: le réactif de Fenton et le persulfate activé. Ensuite, l’oxydation a été étudiée en systèmes ouverts de l’échelle du laboratoire à l’échelle pilote afin d’optimiser les conditions d’injection. Les résultats obtenus, comparables à ceux en systèmes fermés, ont mis en évidence le caractère très limitant de la faible disponibilité des HAP ainsi que l’existence d’une fraction impossible à atteindre (taux d’abattement inférieur à 50%). Enfin, les derniers résultats ont corroboré la relation entre l’âge de la pollution, la disponibilité des HAP et les performances de l’oxydation chimique. Par ailleurs, ils ont permis d’expliquer et hiérarchiser les effets limitants de différents paramètres (disponibilité des HAP, teneur en carbone organique, en carbonate, pH, structure des HAP et mode d’injection) en fonction de l’oxydant utilisé. Les recherches effectuées soulignent l’importance d’étudier les performances de l’oxydation chimique directement avec la terre prélevée sur le site pollué. / Contrary to general belief, soil is a threatened nonrenewable natural resource. Consequently, the restoration of brownfields contaminated with PAHs, that are toxic and persistent contaminants, is a major challenge. Usual techniques are not always appropriate, so the aim of this work is to study the relevance of in situ chemical oxidation (ISCO), usually used for groundwater treatment contaminated with less recalcitrant pollutants (CVOCs, BTEX). It is a part of OXYSOL project aiming at the conception of a global treatment pathway including in situ remediation and soil construction. This work was to study and optimize oxidation efficiency with the soil of a former coking plant. Then, objective was to highlight main limiting factors using different contrasting soils. First, experiments were run in batch systems to select both most suitable oxidants: Fenton's reagent and activated persulfate. Then oxidation was performed in flow systems from the bench to the pilot scale in order to optimize injection parameters. Results, comparable to those obtained in batch systems, showed that oxidation efficiency was strongly limited because of low PAHs availability and highlighted presence of unavailable PAHs (degradation ratio lower than 50%). The last results confirmed the relationship between pollution aging, PAHs availability and chemical oxidation performance. Moreover, they help to understand and compare the influence of different limiting factors (PAHs availability, organic carbon content, carbonate content, pH, PAHs structure and injection method) depending on the oxidant. The research underlined the need to investigate chemical oxidation performance with soil samples collected from contaminated sites and not with spiked soils.

Le procédé sol-gel permet la réalisation de matériaux optiquement performants et la possibilité d’intégrer diverses molécules dans ces systèmes ouvre les portes à des applications dans de nombreux domaines. Nous nous sommes intéressés en particulier à la réalisation de matériaux sol-gel monolithiques, fortement dopés avec des molécules actives, dans le cadre de la réalisation de limiteurs optiques performants dans le visible et dans l’infrarouge.La mise au point de procédés et de matrices sol-gel compatibles avec divers types de chromophores a tout d’abord été effectuée. Une investigation des paramètres expérimentaux et de la nature des précurseurs influençant la microstructure des matériaux a été réalisée, ainsi que la mise au point de méthodes de gélification accélérée capables de piéger efficacement les chromophores dans les matrices sol-gel même à de très hautes concentrations.Le dopage des matrices obtenues avec différents chromophores pour la limitation optique dans le visible et dans l’infrarouge s’en est suivi, avec une étude de l’impact des matrices sur les propriétés optiques des dopants. L’évaluation des performances en limitation a révélé les performances exceptionnelles des systèmes étudiés dans le visible, et des résultats prometteurs pour l’infrarouge.Enfin, la synthèse de nanoparticules d’or isotropes et anisotropes et leur incorporation dans les matériaux préparés a permis de mettre en évidence des effets d’exaltation importants sur les propriétés non-linéaires des chromophores au sein des matrices sol-gel et permettent d’améliorer les performances en limitation de manière considérable. / Sol-gel chemistry is a potent approach for the realization of optical materials, and enables chromophores incorporation in materials making the soft process a gateway for many applications. In this work, we focused on monolithic sol-gel materials, heavily doped with optically active chromophores for the realization of solid-sate optical power limiting devices in the visible and near-infrared range.The elaboration and optimization of compatibles sol-gel matrices with those chromophores was the first step. An investigation of the different synthesis parameters and the nature of the precursors on the materials nanostructure were done, together with the creation of high speed gelation processes to enable the incorporation of very high chromophores contents.Using these approaches, the preparation of highly doped materials for optical power limiting in the visible and the near infrared range was successful, and the impact of the matrices on chromophores properties was studied. Evaluation of optical limiting properties of these materials revealed exceptional performance in the visible range and promising results for the NIR range.Finally, isotropic and anisotropic gold spheres were prepared and incorporated inside the materials. The resulting composites showed enhancements of the non-linear properties of the chromophores inside the matrix, and dramatic improvement of the optical power limiting efficiency was achieved.

The Diploma Thesis deals with an implementation of the new method for an assessment of a cloning efficiency of the cancer stem cells separated by a high speed cell sorter. The cell-sowing on the microtitration plates was performed by the flow cytometry method in a combination with the high speed cell sorter. In the first part of the Diploma Thesis the new method was introduced and tested on the selected cell lines. The obtained results were compared with the results of the limiting dilution assay within four cell lines. As for the second part of my Diploma Thesis, the method was practically applied to analysis of the cloning capacity of two subpopulations of cE2 cells based on the expressions of characteristic markers of stem and cancer stem cells - CD44 and CD 133. Based on the findings, the new method can be introduced as an approved proceeding for the cloning capacity assessment of cancer stem cells in other workplaces that possess analogical device equipment.

La microspectroscopie Raman confocale apparait comme un outil à fort potentiel pour l'analyse in vivo de la peau, avec des applications innovantes en dermatologie et cosmétologie. Cette technique biophotonique permet d'accéder à des informations moléculaires très spécifiques d'un échantillon ; et ceci de façon totalement non destructive et sans aucun marquage ni préparation particulière. Les travaux référencés ont porté sur la caractérisation des constituants cutanés, l'évaluation du taux d'hydratation, le suivi de la perméation d'actif ou encore le diagnostic des lésions tumorales de la peau. Ces études ont été réalisées avec des configurations instrumentales très diverses. En vue de la conception d'une nouvelle micro-sonde Raman confocale, cette thèse a permis d'établir un cahier des charges précis ; les paramètres instrumentaux ont été définis et leurs effets sur la qualité des enregistrements Raman (fluorescence parasite, rapport signal sur bruit, atténuation du signal en profondeur) ont été évalués. En particulier, l'effet de la longueur d'onde d'excitation, paramètre clé en spectroscopie Raman, a été analysé. Dans nos expérimentations, la répétabilité et la variabilité du signal Raman ont également été prises en compte. Dans le but d'évaluer l'approche Raman pour l'analyse de la perméation cutanée d'actif, la diffusion cutanée de deux molécules (caféine et resvératrol) appliquées en faibles concentrations a été suivie sur un microspectromètre Raman confocal avec des paramètres d'acquisition similaires à ceux définis pour la micro-sonde. Nous avons montré la possibilité d'enregistrer des cinétiques de diffusion, et également mis en évidence des points limitatifs spécifiques de ces études expérimentales. / Confocal Raman microspectroscopy seems to be a tool with strong potential for in vivo skin analyses, and for innovative applications in dermatology and cosmetology fields. This biophotonic technique allows access to very specific molecular information non-destructively and without any particular skin labeling or sample preparation. The referenced work focused on the characterization of the cutaneous constituents, the evaluation of the rate of skin hydration, the monitoring of active ingredient permeation or diagnosis of tumoral skin lesions. These studies were performed with a variety of instrumental configurations. In view of the design of a new confocal Raman micro-probe, this thesis has established a registry of precise specifications; the instrumental parameters were defined, and their effects on the quality of the Raman records (parasite fluorescence, signal to noise ratio, signal attenuation in depth) were evaluated. In particular, the impact of the excitation wavelength, a key parameter in Raman spectroscopy, was analyzed. In our experiments, the reproducibility and the variability of the Raman signal were also considered. In order to evaluate the Raman approach for the analysis of cutaneous permeation of active ingredients, the cutaneous diffusion of two molecules (caffeine and resveratrol) applied in low concentrations were monitored by confocal Raman microspectroscopy using the acquisition parameters defined for the micro-probe. We have demonstrated the possibility of recording diffusion kinetics and at the same time unraveled specific limitations of these experimental studies.

L’étude du frottement dans les contacts lubrifiés fortement chargés est un sujet complexe. En effet, le frottement dépend fortement du comportement rhéologique du lubrifiant dans le centre du contact et, celui-ci n'est pas bien connu à pression et taux de cisaillement élevé. Diverses méthodes expérimentales ont été développées pour expliquer le comportement plateau dans les courbes de frottement, associé à l’existence d’une contrainte limite de cisaillement, mais aucune d'elles n'a fourni une image complète des mécanismes réels impliqués. Dans la continuité de ces efforts, des études sont présentées dans ce mémoire. Le premier défi dans ce travail est d'effectuer des mesures de frottement dans des conditions isothermes nominales, ce qui signifie que même si des effets thermiques doivent se produire dans toute mesure de frottement, il est possible de les minimiser et de rendre les résultats insensibles à une faible dissipation d'énergie dans le volume expérimental d'intérêt. La minimisation de l’échauffement du lubrifiant aide à se focaliser sur l’origine mécanique de la contrainte limite de cisaillement et de mieux caractériser sa dépendance à la pression et à la température. C'est pourquoi, tout d'abord, une série d'expériences a été réalisée sur deux lubrifiants, un diester pur (benzyl benzoate) et une huile minérale de turbine (Shell T9) avec des vitesses d'entraînement variables. Cela nous permet d'abord d'observer directement l'influence des effets thermiques sur les valeurs de la contrainte limite de cisaillement et ensuite, de déterminer les conditions expérimentales qui limitent ces effets tout en assurant un régime en film complet. Le deuxième objectif est de caractériser le comportement en frottement des lubrifiants sous conditions isothermes nominales et sur une large gamme de pression (jusqu'à 3 GPa) et de température (jusqu’à 80°C) afin d'établir un nouveau modèle découplé permettant de décrire la dépendance à la température et à la pression de la contrainte limite sous fortes charges. Enfin, l'étude se focalise sur la compréhension du comportement microscopique des lubrifiants dans des conditions extrêmes de cisaillement et de pression. Des mesures in situ de spectroscopie Raman et Brillouin ont été également effectuées sous conditions statiques, afin d'étudier le changement de phase du lubrifiant. / Friction in highly loaded lubricated contacts is a complex issue. Indeed, it highly depends on the lubricant rheological behaviour in the Hertzian region, which is not well known under such high pressure and high shear stress. Various experimental methods have been developed to explain the plateau-like behaviour in friction curves referred to as the limiting shear stress (LSS), but none of them provided a full picture of the real mechanisms involved. In a continuation of these efforts, some investigations are presented in this manuscript. The first challenge in this work is to carry out friction measurements under nominal isothermal conditions, meaning that even if thermal effects must occur in any friction measurement, it is possible to minimize them and to make the results almost insensitive to a weak energy dissipation within the experimental volume of interest. Minimizing shear heating of the lubricant help us to focus on the mechanical origin of the LSS and to better characterize its dependence to pressure and temperature. That’s why, first of all, a series of experiments was performed on two lubricants, a pure diester fluid (benzyl benzoate), and a commercial turbine mineral oil (Shell T9) with varying entrainment velocities. This allow us first to directly observe the influence of the lubricant shear heating on the LSS values and then to determine the experimental conditions which limit this thermal effect while ensuring a full film regime. The second objective is to characterize the frictional behavior of both lubricants under nominal isothermal conditions and over a wide range of pressure (up to 3 GPa) and temperature (up to 80°C) in order to establish a new uncoupled model to describe the temperature and pressure dependence of the limiting shear stress under highly loaded conditions. Finally, the study focuses on the understanding of the microscopic behavior of lubricants under extreme shear and pressure conditions. In situ Raman and Brillouin spectroscopy investigations were also conducted under static conditions, in order to study the lubricant phase changes under various pressure and temperature conditions.

Le changement des pratiques agricoles et surtout pastorales dans les Pyrénées Centrales a entraîné une colonisation des terres par le frêne (Fraxinus excelsior L.) en constituant des peuplements denses et fréquents dans le paysage pyrénéen. Ce travail est centré sur l'étude de la répartition actuelle et future de ces peuplements qu'on appelle "des accrus" et sur leur potentialité de croissance en relation avec les facteurs qui peuvent être limitants dans la perspective d'une valorisation économique de ces accrus. L'étude de la croissance a été réalisée à trois niveaux : la croissance en hauteur en fonction de la fertilité, et la croissance en diamètre en fonction du climat et de la compétition. Pour ce dernier facteur, la croissance a été étudiée sur des peuplements en place (sans intervention) et suites à deux modalités d'éclaircie. La détection des accrus de frêne au stade perchis avec les outils de télédétection n'est pas réalisable et nécessiterait d'importants investissements et adaptations pour devenir utilisables. La présence des accrus de frêne est surtout modulée par la topographie et l'utilisation du sol. En ce qui concerne la croissance en diamètre de ces accrus, elle est modulée par la vigueur des arbres, la compétition et le climat. Ce sont surtout les températures maximales d'avril et les températures minimales de septembre ou d'août qui influencent la croissance en surface de cerne. Le frêne réagit dès la première année à l'éclaircie, d'autant plus fortement et durablement que le peuplement est plus jeune. L'effet de la nutrition minérale sur la classification des accrus étudiés, selon leur croissance en hauteur, n'est pas évident. L'ensemble des résultats obtenus dans ce travail constitue un outil pour aider à gérer les accrus de frêne dans la zone étudiée surtout dans un objectif économique. / The changes of pastoral management practices in the Central Pyrenees are at the origin of the colonization process of grasslands by the ash (Fraxinus excelsior L.). This colonization process leads to the establishment of very dense and frequent patches of ashes in the Pyrenean landscape. The research is focused on the study of the current and future distribution of these forest patches resulting of the extension of ash trees by natural seeding called "the accrues" and on their potentiality of growth in relation to the nutritional factors which can be limiting from the point of view of an economic valorization of these new forest patches. The study of the tree growth was carried out on different levels: growth in height according to the fertility, and growth in diameter according to the climate and the competition. For this last factor, the growth was studied on in situ tree settlements without intervention and with two levels of thinning. The recognition of ash patches patterns within the mountain landscape was not possible using the traditional tools of remote sensing (SPOT) and should have require new technologies such as LIDAR or multispectral aero data which were out of reach during the PhD work. Exploratory field work has shown that at the landscape level, the presence of ash patches is a function of the topography and the land use history. With regard to the diameter growth of these increased, it is modulated by the strength of the trees, the level of competition and the climate. The maximum temperatures of April and the minimal temperatures of September or August influence the growth on the surface of tree ring. The ash reacts to the first year to thinning, especially for recent settlements and young trees. The effect of the mineral nutrition on the tree growth in height is not significant. The results on spatial pattern dynamics and the references on ash growth in a wide range of soil conditions obtained during this work constitutes a tool to help to manage ash patches within the studied area mainly with an economic point of view.

Différentes techniques de chromatographie liquide des polymères ont été étudiées selon leur principe d’élution et le comportement conformationnel des polymères suscité au sein de la phase stationnaire. De part leur capacité à caractériser des copolymères à blocs, la Chromatographie Liquide aux Conditions Critiques (LC CC) et la Chromatographie Liquide aux Conditions Limites de Désorption (LC LCD) ont été utilisées pour déterminer la composition chimique de copolymères à blocs à base de poly(oxyde d’éthylène) et de polystyrène. La LC LCD s’est distinguée par sa capacité à séparer de manière efficace les copolymères à blocs de leurs homopolymères parents. Cette méthode chromatographique a ensuite été optimisée afin d’être appliquée à une plus large gamme de masses molaires. / Several advanced techniques of liquid chromatography of polymers were studied according to their elution principle and the conformational behaviour of polymers along the stationary phase. Because of their potential to characterize block copolymers, Liquid Chromatography under Critical Conditions (LC CC) and Liquid Chromatography under Limiting Conditions of Desorption (LC LCD) were employed to determine the chemical composition of Poly(ethylene oxide) and Polystyrene based block copolymers. Interestingly, LC LCD was proved to be particularly efficiently to separate block copolymers from both their parent homopolymers. LC LCD method was then optimized to extend the applicable molar masses ranges.

This thesis concerns quadratic response properties and their application to properties in Jablonski diagrams such as resonant two-photon absorption and excited state absorption. Our main interest lies in optical power limiting applications, and in this context, molecules containing heavy metal atoms prove superior. Therefore, we are interested in how relativity affects these properties, and in order to assess this, a four-component relativistic framework is adopted. To properly address the molecular properties of interest, both relativistic effects and electron correlation need to be accounted for. These two properties are not additive, and, therefore, correlation needs to be incorporated into the four-component framework. We present the implementation of quadratic response properties at the four-component density functional level of theory. For second-harmonic generation, we have, with numerical examples, demonstrated that correlation and relativity are indeed not additive and that the inclusion of noncollinear magnetization is of little importance. We report that both electron correlation as well as relativity strongly affect results for second-harmonic generation. For example, relativity alone reduces the µβ-response signal by 62% and 75% for meta- and ortho-bromobenzene, respectively, and enhances the same response by 17% and 21% for meta- and ortho-iodobenzene, respectively. In the four-component framework, we present the implementations of single and double residues of the quadratic response function, which allows for the evaluation of resonant two-photon absorption cross sections and excited state properties. Using these tools, we discuss different levels of approximation to the relativistic Hamiltonian and we demonstrate that for two-photon absorption, a proper treatment of relativistic effects qualitatively alters the spectrum. For example, already for an element as light as neon, significant differences are seen between the relativistic and nonrelativistic spectra as triplet transitions acquire substantial absorption cross sections in the former case. Finally, quantum mechanics in conjunction with electrodynamics is applied to determine clamping levels in macroscopic samples. The microscopic properties of the optically active chromophores are determined by response theory, and then, electrodynamics is used to describe the interactions between the chromophores and incident laser pulses. Using this approach a series of molecules have been investigated and their performances have been compared and ranked in order to find novel materials for optical power limiting applications.