Lors de cette thèse, je me suis attaché à améliorer notre connaissance des planètes géantes, depuis notre voisine Jupiter jusqu’aux exoplanètes lointaines : les Jupiter chauds. Grâce aux nouvelles observations gravitationnelles extrêmement fines du satellite Juno, entré en orbite autour de Jupiter en juillet 2016, il est possible d’améliorer significativement les modèles de structure interne de la planète. Cependant, cela ne peut se faire qu’à condition d’avoir une méthode suffisamment précise pour exploiter au maximum les données. J’ai donc étudié la méthode des sphéroides de Maclaurin concentriques et ses limitations. A l’aide des connaissances contemporaines sur les équations d’état, les propriétés diffusives et les transition ou séparation de phase entre l’Hydrogène et l’Hélium, il m’a alors été possible de produire de nouveaux modèles de Jupiter. Arriver à combiner les observations gravitationnelles de Juno et les abondances d’éléments observées par Galiléo n’a pu se faire qu’en décomposant Jupiter en au moins 4 zones, de l’enveloppe externe jusqu’au coeur compact. J’ai montré que la taille de ce coeur compact était dégénérée avec la variation d’entropie à l’intérieur de la planète.La structure interne des Jupiter chauds quant à elle est très dépendante de leur dynamique atmosphérique, qui entraîne une inflation de leur rayon. J’ai étudié les atmosphères de ces planètes à l’aide du modèle de circulation globale de l’Université d’Exeter et d’un code linéaire que j’ai développé, appelé ECLIPS3D. La caractéristique la plus importante de la circulation atmosphérique est la présence d’un jet superrotatif, étendu en latitude.J’ai donc étudié la création de ce jet à l’aide d’arguments théoriques pour s’assurer de sa pertinence physique. L’étude de la solution linéaire dépendante du temps, associée à des arguments numériques sur la convergence de quantité de mouvement par les vents verticaux m’ont permis d’établir une compréhension globale, cohérente de l’accélération de la superrotation dans l’atmosphère de ces planètes.Avec ce travail, j’ai amélioré ma compréhension théorique des planètes géantes et développé des codes qui peuvent être utilisés pour améliorer nos connaissances sur la structure interne et la dynamique atmosphérique des planètes géantes, que ce soit Jupiter, Saturne ou les Jupiter chauds. / Through this thesis, I have been motivated by the will to improve our knowledge of giant planets, from our neigh- bouring Jupiter to the far away worlds across the galaxy: hot Jupiters.With the latest, extremely precise observations of the satellite Juno, new models of the interior of Jupiter can be derived. A precise enough method is required to take full advantage of these outstanding data, and I therefore studied the concentric Maclaurin spheroid method and its limitations.With contemporary understanding on the equations of state, diffusive properties and phase transition/separation of hydrogen and helium, I could then focus on producing new interior models of Jupiter. Combining the gravitational observations of Juno with the elemental observations of Galileo has proven to be a complicated task, which required to decompose the planet into at least four regions from the outer envelope to the inner, compact core. I have shown that the size of the compact core is degenerated with the entropy variation within the planet.Concerning hot Jupiters, I have reminded of the need to understand their atmospheric dynamics to constrain their interior structure, as the wind circulation can lead to an inflation of their radius. Studying numerically their at- mospheric dynamics was performed with the University of Exeter’s global circulation model as well as with the development of a linear solver that I called ECLIPS3D. An important, robust feature is the presence of a broad equatorial superrotation in the atmosphere of these planets.Finally, I have explored the spin up of this superrotation on theoretical grounds, to assess its physical relevance. I have calculated the linear time dependent solution to show the importance of differential drag and radiative damp- ing, and have used numerical simulations to highlight the importance of vertical momentum acceleration. Globally, a coherent picture of the initial spin up of superrotation was obtained.Through this work, I have improved my theoretical understanding of giant planets and developed various codes that can be used to study and improve our knowledge of the interior structure and atmospheric dynamics of giant planets, from Jupiter and Saturn to hot Jupiters.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / As estrelas de nêutrons nascem com altas temperaturas (~ 1011 K) e durante alguns segundos sofrem um rápido resfriamento por emissão de neutrinos. O processo Urca direto é o principal mecanismo para explicar essa perda de energia. O problema do resfriamento das estrelas de nêutrons é um problema de grande interesse porque seu entendimento pode fornecer informações importantes sobre a constituição do interior da estrela. Na literatura existente até o momento, a emissividade de neutrinos é calculada considerando os núcleons como partículas não relativísticas quando considerados todos os níveis de Landau das partículas carregadas. Por outro lado, a emissividade de neutrinos para núcleons relativísticos é calculada considerando somente o primeiro nível de Landau (para campo magnético forte). Para campos magnéticos fracos, onde mais de um nível de Landau é ocupado, é usada a emissividade correspondente à do campo nulo. Neste trabalho aplicamos a teoria de Weinberg-Salan para interações fracas no cálculo da emissividade de neutrinos com e sem campo magnético presente, num cálculo totalmente relativístico para os núcleons e considerando todos os níveis de Landau. Esta é a contribuição original do trabalho. Para descrever a matéria a altas densidades, utilizamos uma teoria relativística de campo médio a temperatura zero que inclui apenas o octeto bariônico e os léptons mais leves. São apresentados os resultados para a emissividade de neutrinos, onde é evidente a ocupação dos diferentes níveis de Landau como função do campo magnético.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / As estrelas de nêutrons nascem com altas temperaturas (~ 1011 K) e durante alguns segundos sofrem um rápido resfriamento por emissão de neutrinos. O processo Urca direto é o principal mecanismo para explicar essa perda de energia. O problema do resfriamento das estrelas de nêutrons é um problema de grande interesse porque seu entendimento pode fornecer informações importantes sobre a constituição do interior da estrela. Na literatura existente até o momento, a emissividade de neutrinos é calculada considerando os núcleons como partículas não relativísticas quando considerados todos os níveis de Landau das partículas carregadas. Por outro lado, a emissividade de neutrinos para núcleons relativísticos é calculada considerando somente o primeiro nível de Landau (para campo magnético forte). Para campos magnéticos fracos, onde mais de um nível de Landau é ocupado, é usada a emissividade correspondente à do campo nulo. Neste trabalho aplicamos a teoria de Weinberg-Salan para interações fracas no cálculo da emissividade de neutrinos com e sem campo magnético presente, num cálculo totalmente relativístico para os núcleons e considerando todos os níveis de Landau. Esta é a contribuição original do trabalho. Para descrever a matéria a altas densidades, utilizamos uma teoria relativística de campo médio a temperatura zero que inclui apenas o octeto bariônico e os léptons mais leves. São apresentados os resultados para a emissividade de neutrinos, onde é evidente a ocupação dos diferentes níveis de Landau como função do campo magnético.

Detailed understanding of the equation of state of light elements such as the hydrogen isotopes in the warm dense matter (WDM) regime is essential for the modeling of the inner structure of many astrophysical objects, in particular Jovian planets as well as inertial confinement fusion (ICF) research. In these systems quantum degeneracy and strong inter-particle forces play an important role making its theoretical description extremely challenging. The Omega laser was used to drive a planar shock wave in cryogenically cooled deuterium creating WDM conditions. We used a set of independent diagnostics to measure the thermodynamic conditions of WDM including velocity interferometry (VISAR), streaked optical pyrometry (SOP) and x-ray Thomson scattering (XRTS). With a narrow-band x-ray backlighter probe at backscattering geometry the spectrally resolved XRTS accessed the boundary of collective and non-collective regimes making our measurement sensitive to both electron temperature and density. This work presents a full set of measurements of the thermodynamic properties for different laser intensity drives creating warm dense deuterium at various degrees of degeneracy and coupling. The measured electron densities and temperatures ranged between 0.2 and 2.15x10²³ cm^−3 and 0.6 − 20 eV respectively. The scattering measurement confirmed the findings from the VISAR and SOP data and together densityfunctional molecular dynamics (DFT-MD) simulations provides a novel self-consistent approach for an accurate characterization of the microscopic structure of WDM. Complementary to the laser compression work, findings from project employing static compression hydrogen with the use of diamond anvil cells is also be presented. The first direct measurement of the local field correction to the Coulomb interactions in degenerate plasma was obtained from inelastic scattering (20 keV probe) at the Diamond Light Source synchrotron facility.

>Magister Scientiae - MSc / We begin by finding a system of differential equations for the background and linearly perturbed variables in the standard, ɅCDM model, using the Einstein Field Equations, and then solving these numerically. Later, we extend this to dynamical dark energy models parameterised by an equation of state, w, and a rest frame speed of sound, cs. We pay special attention to the large-scale behaviour of Δm, the gauge invariant, commoving matter density, since the approximation Δm ≃ δm, where δm is the longitudinal gauge matter density, is more commonly used, but breaks down at large scales. We show how the background is affected by w only, so measurements of perturbations are required to constrain cs. We examine how the accelerated expansion of the universe, caused by dark energy, slows down the growth rate of matter. We then show the matter power spectrum is not in itself useful for constraining dark energy models, but how redshift-space distortions can be used to extract the growth rate from the galaxy power spectrum, and hence how redshift-space power spectra can be used to constrain different dark energy models. We find that on small scales, the growth rate is more dependent on w, while on large scales, it depends more on cs.

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. New phase diagrams created for Hf, Ti and Zr from experimental data. P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled). All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature). Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Orientador: Fernando Antonio Cabral / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-18T13:55:53Z (GMT). No. of bitstreams: 1 Gomes_DanielaCaioAndre_M.pdf: 2263142 bytes, checksum: 6a08300201853fde99cabfc0824e3b26 (MD5) Previous issue date: 2011 / Resumo: Corrigiu-se empiricamente o parâmetro a da equação de estado de Peng-Robinson para o CO2 em função da temperatura e pressão, para que a equação pudesse calcular corretamente a fugacidade do dióxido de carbono em condições supercríticas. Em princípio, o intuito foi verificar se a modelagem termodinâmica com esta correção poderia correlacionar melhor os dados de equilíbrio de fases de sistemas constituídos de dióxido de carbono supercrítico e substâncias de interesse presentes em alimentos. Para testar esta hipótese, os seguintes sistemas bifásicos constituídos de dióxido de carbono supercrítico e componentes graxos foram selecionados da literatura: CO2 ¿ esqualeno, CO2 ¿ ácido oleico, CO2 ¿ tricaprilina, CO2 ¿ éster etílico de EPA, CO2 ¿ éster etílico de DHA, CO2 ¿ alfa-tocoferol, CO2 ¿ alfa-tocoferol, CO2 ¿ trioleína, CO2 ¿ tripalmitina. Tais escolhas são decorrentes do crescente interesse de se recuperar esses componentes minoritários de óleos brutos ou dos subprodutos resultantes do processamento convencional de óleos e gorduras, devido a sua importância na manutenção da saúde humana. Além disso, tem crescido o interesse por produtos naturais isentos de solventes orgânicos indesejáveis. Nesse sentido, os processos de extração com dióxido de carbono supercrítico vêm suprir esta demanda atual, pois é um solvente inerte que não agride o meio ambiente. Os resultados mostraram que as propriedades críticas que são estimadas por métodos de contribuição de grupos influenciaram mais no desempenho da modelagem termodinâmica que a correção do parâmetro a da equação de estado de Peng-Robinson. As maiores correções do parâmetro foram obtidas nas condições de maiores valores de temperatura e menores de pressão. No geral, a correção do parâmetro a não diminuiu o desvio em relação aos valores experimentais quando comparados aos valores obtidos sem a correção do parâmetro. No entanto, em alguns sistemas observou-se que a correção deste parâmetro para as condições de pressões elevadas modificou o comportamento dos valores de solubilidade calculados, produzindo valores mais próximos aos experimentais / Abstract: Corrected empirically the parameter a of the Peng- Robinson equation of state of for CO2 as a function of temperature and pressure, so that the equation could correctly calculate the fugacity of carbon dioxide in supercritical conditions. In principle, the aim was to verify whether the thermodynamic modeling with this correction could better correlate the phase equilibrium data from system consisting of supercritical carbon dioxide and substances of interest in food. To test this hypothesis, the following two-phase systems consisting of supercritical carbon dioxide and fatty components were selected from the literature: CO2 - squalene, CO2 - oleic acid, CO2 - tricaprylin, CO2 - ethyl ester of EPA, CO2 - DHA ethyl ester, CO2 - ?-tocopherol, CO2 - ?-tocopherol, CO2 - triolein, CO2 - tripalmitin. Such choices are the result of growing interest to recover these minor components of crude oils or byproducts resulting from conventional processing of oils and fats, due to its importance in maintaining human health. In addition, interest has grown in natural products free of undesirable organic solvents. In this sense, the processes of extraction with supercritical carbon dioxide come meet this current demand, it is an inert solvent that does not harm the environment. The results showed that the critical properties are estimated by group contribution methods of influence over the performance of thermodynamic modeling that the correction of the parameter to the equation of state of Peng-Robinson. The larger corrections of the parameter were obtained under conditions of higher temperatures and under pressure. In general, the correction of the parameter a does not diminish the deviation from the experimental values when compared to values obtained without the correction parameter. However, in some systems it was observed that the correction of this parameter for the conditions of high pressures changed the behavior of the solubility values calculated, yielding values closer to experimental / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

Les réactions d’oxydation d’hydrocarbures en phase liquide (aussi appelées auto-oxydation) jouent un rôle essentiel dans un grand nombre de procédés de l’industrie pétrochimique car elles assurent la conversion du pétrole en composés chimiques organiques valorisables. Elles régissent également la stabilité à l’oxydation des carburants (vieillissement) et des produits chimiques dérivés du pétrole. Ces réactions d’oxydation en phase liquide relèvent de mécanismes radicalaires en chaîne impliquant des milliers d’espèces et de réactions élémentaires. La modélisation cinétique de tels systèmes reste actuellement un défi car elle nécessite de disposer de données thermodynamiques et cinétiques précises, qui sont rares dans la littérature. Le logiciel EXGAS, développé au LRGP, permet de générer automatiquement des modèles cinétiques détaillés pour des réactions d’oxydation d’hydrocarbures en phase gazeuse. Qu’il s’agisse d’une phase gazeuse ou liquide, les réactions élémentaires mises en jeu sont de même nature et la méthodologie de génération du mécanisme est la même. Pour passer d’un mécanisme en phase gaz à un mécanisme en phase liquide il convient d’adapter les valeurs des constantes d’équilibre et de vitesse (appelées constantes thermocinétiques) des réactions du mécanisme. L’objectif de cette thèse est de proposer une méthode pour corriger les constantes thermocinétiques de la phase gaz pour qu’elles deviennent applicables à la phase liquide. Cette correction fait intervenir une grandeur appelée énergie de GIBBS de solvatation molaire partielle. Une analyse de la définition précise de cette quantité nous a permis de montrer qu’elle s’exprime simplement en fonction d’un coefficient de fugacité et d’une densité molaire. Nous avons ensuite relié cette grandeur à des quantités thermodynamiques mesurables (coefficients d’activité, constantes de HENRY …) et nous nous sommes appuyés sur toutes les données qu’il nous a été possible de trouver dans la littérature pour créer la banque de données expérimentales d’énergies de GIBBS de solvatation molaires partielles la plus complète (intitulée CompSol). Cette banque de données a ensuite servi à valider l’utilisation de l’équation d’état UMR-PRU pour prédire ces énergies. Les bases d’une équation d’état de type SAFT, au paramétrage original, développé dans le cadre de cette thèse, ont été posées. Notre objectif était de simplifier l’estimation des paramètres corps purs de cette équation d’état en proposant une méthode de paramétrage ne nécessitant aucune procédure d’optimisation, claire et reproductible, à partir de données très facilement accessibles dans la littérature. Cette équation a été utilisée pour estimer les énergies de GIBBS de solvatation molaires des corps purs et les énergies de GIBBS de solvatation molaires partielles de systèmes {soluté+solvant}. Enfin, ces méthodes d’estimation des énergies de GIBBS de solvatation molaires partielles ont été combinées au logiciel EXGAS afin de modéliser l’oxydation du n-butane en phase liquide / Liquid phase oxidation of hydrocarbons (also called autoxidation) is central to a large number of processes in the petrochemical industry as it plays a key role in the conversion of petroleum feedstock into valuable organic chemicals. This phenomenon is also crucial in oxidation-stability studies of fuels and its derivatives (aging). These liquid-phase oxidation reactions entail radical mechanisms involving more than thousands of compounds and elementary reactions. Kinetic modelling of these kinds of reactions remains a significant challenge because it requires thermodynamic and kinetic parameters, which are not abundant in literature. The EXGAS software, developed at LRGP, is able to generate these kinds of models but only for oxidation reactions taking place in a gaseous phase. It is assumed that the nature of elementary reactions in the liquid and gaseous phases is the same. The unique need to transfer a kinetic mechanism from a gas phase to a liquid phase is to update kinetic rate constant values and equilibrium constant values (called thermokinetic constants) of mechanism reactions. Therefore, in the framework of this PhD thesis, a new method aimed at applying a correction term to thermokinetic constants of gaseous phases is proposed in order to obtain constants usable to describe liquid-phase mechanisms. This correction involves a quantity called partial molar solvation GIBBS energy. An analysis of the precise definition of this property led us to conclude that it can be simply expressed as a function of fugacity coefficients and liquid molar density. As a result, this property could also be expressed with respect to measurable thermodynamic quantities as activity coefficients or HENRY’s law constants. By combining all the experimental data related to these measurable properties that can be found in the literature, it was possible to develop a comprehensive databank of partial molar solvation GIBBS energies (called the CompSol database). This database was used to validate the use of the UMR-PRU equation of state to predict solvation quantities. Moreover, the bases of a new parameterization for SAFT-type equations of state were laid. It consists in estimating pure-component parameters of SAFT-like equation using a very simple, reproducible and transparent path for non-associating pure components. This equation was used to calculate partial molar GIBBS energy of solvation of pure and mixed solutes. Last, equations of state were combined with EXGAS software to model the oxidation of n-butane in the liquid phase

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