La transition d’un comportement séismique/instable à un comportement aséismique/stable est observée dans la partie en aval des zones sismogéniques (12-15 km de profondeur). Cette transition est supposée être contrôlée par l’activation de la plasticité de basse température du quartz à ~350°C. À cause de la grande profondeur à laquelle cette transition a lieu, le seul moyen pour étudier les processus physiques qui agissent en ces contestés, est l’étude des anciens prismes d’accrétion exhumés actuellement dans des chaines de montagnes. Le mélange tectonique de Hyuga et l’unité de Morotsuka appartiennent au prisme fossile de Shimanto et sont des unités metasédimentaires déformées à des températures peu inférieures ou égales à la limite fragile/ductile (~250 et ~340°C respectivement). Les résultats des observations de microstructures en microscopie optique et en microscopie électronique à balayage (diffraction des électrons rétrodiffusés) confirment que 1) la pression dissolution et une intense microfracturation sont les mécanismes de déformation principaux du quartz dans le mélange de Hyuga et localement l’activation de la plasticité du quartz est aussi observée; 2) dans l’unité de Morotsuka la recristallisation dynamique du quartz est pleinement active. Ces considérations indiquent que la température n’est pas le seul paramètre qui control l’activation de la plasticité du quartz, et laisse supposer la participation de l’effet adoucissant de l’eau. Avec le but de mieux comprendre le rôle de l’eau sur la rhéologie quartz, des expériences en Presse Griggs ont été menées, le matériel du départ étant de porphyroclasts de quartz (immergés dans une matrice sec) à la fois très riches en eau (provenant du mélange tectonique de Hyuga) et secs (quartz du Brésil). Ces expériences montrent l’effet très adoucissant de l’eau, qui à parité de conditions de déformation, favorise la migration de joint des grains dans le quartz de Hyuga tandis que le quartz du Brésil reste indéformé à exceptions de ses bordures extérieures. L’eau « en excès » est expulsée dans la matrice pour le quartz de Hyuga et stockée dans des bandes de cisaillement C’; l’eau incorporée par le quartz de Brésil n’est pas suffisantes pour favoriser la recristallisation dynamique. / The trasition from instable seismic to stable aseismic behaviour is observed in at the lower limit of the seismogenic zones in subduction zones (12-15 km). This transition is supposed to be controlled by the onset of quartz low grade plasticity at about 350°C. Due to inaccessibility of these geodynamic contests, the only way to study the physical processes acting at these depth are exhumed accretionary prisms exposed in mountain chains. The Hyuga tectonic mélange and the Foliated Morotsuka are metasedimentary units constituting the Shimanto accretionary prism (Japan). They were deformed at temperatures of ~250°C and ~340°C respectively, so slightly lower or equal to the temperature transition. Results by optical microscopy and EBSD reveal that 1) quartz deformation mechanisms active in Hyuga Tectonic Mélange are pressure solution and microfracturation accompanied by local quartz low grade plasticity; 2) dynamic recrystallization is totally active in quartz of the Foliated Morotsuka. These considerations allow to consider the role of water in triggering quartz plasticity especially in such water-rich contest as subduction zones. With the aim to better understand the role played by water on quartz rheology, we deformed high hydrated (from Hyuga unit) and dry (classic Brazil) quartz porphyroclasts within a quartz matrix, with the Griggs apparatus. These experiments show the weakening water effect on quartz strength. At the same deformation conditions, the high hydrated Hyuga quartz show recrystallization by grain boundary migration while the dry Brazil porphyroclasts are mostly undeformed, at exception of the outer recrystallized rims. The exceeding water expulsed from Hyuga quartz is stored in C’ shear bands in the matrix; water absorbed by dry Brazil porphyroclasts is not enough to promote dynamic recrystallization.

Thermal waters in Karlovy Vary are characterized by carbonate sedimentation in places of their emergence. These sediments contain radium. Radium bond in every type of sinter (aragonite, calcite) has been investigated experimentally by acid sinter dissolution. It has been found out, that radium can join dissoluble fraction in both sinter types . The original hypothesis that radium can bond only aragonite-type of sinter has been refuted. Additional experiments have been processed using synthetic radiobarite. Present radium in radiobarite can be partly dissoluted using acids. If radium was incorporated in radiobarite (it is known from locality Vřídlo in Karlovy Vary and elsewhere) then maybe it would be partly dissoluted in experiments.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2016-10-05T18:21:53Z No. of bitstreams: 1 2016 - Jo?o Pedro Chalfun Haouche Meneses.pdf: 6719960 bytes, checksum: ac9a27b5731b19e4693f71fae09adefe (MD5) / Made available in DSpace on 2016-10-05T18:21:53Z (GMT). No. of bitstreams: 1 2016 - Jo?o Pedro Chalfun Haouche Meneses.pdf: 6719960 bytes, checksum: ac9a27b5731b19e4693f71fae09adefe (MD5) Previous issue date: 2016-01-25 / Petrobras / The drilling of wells in salt layers faces major challenges in Brazil?s oil industry. Drilling in such layers requires the development of new technologies and operational procedures to make the process economically viable. One of the main problems is the dissolution of the salt layers in water-based drilling fluids. An uncontrolled dissolution presents a potential risk for the operation and can cause abrupt changes in the properties of the fluids. The main objective of this work was to study the effects of the dissolution of sodium chloride particles in non-Newtonian fluids containing xanthan gum. The study was divided into three parts, rheological experiments, kinetics experiments in a mixing tank and a mathematical modeling. The rheological experiments aimed at studies of the effect of the addition of saline particles on the rheology of non-Newtonian fluids, the effect of the concentration of suspended particles in the rheology of saturated fluids and the effect of the size of suspended particles in the rheology of saturated fluids. The Einstein equation was used to calculate the apparent viscosity of saturated fluids, taking into account the effect of the concentration of salt particles in suspension. The experiments in the mixing tank aimed at the study of the kinetics of dissolution with time in different operating conditions. Fluids were prepared using different concentrations of xanthan gum and different initial concentrations of sodium chloride. The effects of the viscosifier concentration and the initial concentration gradient were evaluated. A phenomenological model was used to represent the dissolution process, which provides the variation of the concentration of the fluid, the variation of the volume fraction of solids, the variation of the particles mean diameter and the variation of the interfacial mass transfer area as a function of time. In the rheology studies, it was verified that the addition of sodium chloride to the non-Newtonian fluid, in the studied conditions, increased the apparent viscosity of the solution. The increase of the concentration of suspended sodium chloride particles increased the apparent viscosity of the suspensions. The increase of the size of the suspended particles decreased the apparent viscosity of the suspension. Statistical tests were made in order to evaluate the statistical relevance of the performed studies. In the kinetics study, the convective mass transfer coefficient was estimated and simulations were made for the other variables of the process. The estimations showed that the xanthan gum concentration in the fluid and the initial sodium chloride concentration in the fluid affect the mass transfer coefficient. The average relative error observed for the simulations was 2,2%. / A perfura??o de po?os em camadas salinas enfrenta grandes desafios na ind?stria de petr?leo do Brasil. A perfura??o em tais camadas exige o desenvolvimento de novas tecnologias e procedimentos operacionais para tornar a perfura??o economicamente vi?vel. Um dos principais problemas enfrentados ? a dissolu??o das camadas de sais em fluidos de perfura??o base ?gua. Uma dissolu??o descontrolada apresenta um risco em potencial para a opera??o, podendo causar mudan?as bruscas nas propriedades dos fluidos. Este trabalho teve como principal objetivo estudar os efeitos da dissolu??o de part?culas de cloreto de s?dio em fluidos n?o-Newtonianos contendo goma xantana. O estudo foi dividido em tr?s partes, experimentos reol?gicos, experimentos de cin?tica em um tanque de mistura e modelagem matem?tica. Os experimentos reol?gicos tiveram como objetivo os estudos do efeito da adi??o de part?culas salinas na reologia de fluidos n?o-Newtonianos, do efeito da concentra??o de part?culas suspensas na reologia de fluidos saturados e do efeito do tamanho das part?culas suspensas na reologia de fluidos saturados. A equa??o de Einstein foi utilizada para calcular a viscosidade aparente dos fluidos saturados levando em conta o efeito da concentra??o de part?culas salinas em suspens?o. Os experimentos no tanque de mistura tiveram como objetivo o estudo da cin?tica de dissolu??o com o tempo em diferentes condi??es operacionais. Foram preparados fluidos com diferentes concentra??es de goma xantana e diferentes concentra??es iniciais de cloreto de s?dio. Foi analisado o efeito da concentra??o do viscosificante na cin?tica de dissolu??o bem como o efeito do gradiente de concentra??o inicial. Um modelo fenomenol?gico foi utilizado para representar o processo de dissolu??o, o qual prev? as varia??es da concentra??o do fluido, a varia??o da fra??o volum?trica de s?lidos, a varia??o do di?metro m?dio das part?culas e a varia??o da ?rea interfacial de transfer?ncia de massa em fun??o do tempo. Nos estudos de reologia, verificou-se que a adi??o de cloreto de s?dio ao fluido n?o-Newtoniano, nas condi??es estudadas, aumentou a viscosidade aparente da solu??o. O aumento da concentra??o de part?culas suspensas de cloreto de s?dio provocou um aumento na viscosidade aparente das suspens?es. O aumento do tamanho das part?culas suspensas de cloreto de s?dio diminuiu a viscosidade aparente da suspens?o. Testes estat?sticos foram feitos para analisar a relev?ncia estat?stica dos estudos realizados. No estudo da cin?tica, o coeficiente convectivo de transfer?ncia de massa foi estimado e simula??es foram feitas para as demais vari?veis do processo. As estima??es mostraram que a concentra??o de goma xantana no fluido e a concentra??o inicial de cloreto de s?dio no fluido influenciam o coeficiente de transfer?ncia de massa. O erro relativo m?dio simula??es observado para as simula??es foi de 2,2%.

Nesta investigação será analisada a reconfiguração político-territorial do Vice-Reino do Novo Reino de Granada, no final do século XVIII e nas duas primeiras décadas do século XIX. Em primeiro lugar, examinar-se-á a organização político-territorial do Vice-Reino, estabelecida pela monarquia espanhola. Em segundo lugar, analisar-se-á a formação de juntas de governo, congressos, Estados provinciais e confederações, que, após a dissolução da monarquia, em 1808, foram legitimadas por meio de atas, constituições de tipo moderno e guerras. Esses acontecimentos modificaram a organização política e territorial do antigo Vice-Reino, entre 1809 e 1816. / This research analyzes the political and territorial reconfiguration of the Viceroyalty of New Kingdom of Granada, in the late eighteenth century and the first two decades of the nineteenth century. In the first place, the political and territorial organization of the Viceroyalty established by the Spanish monarchy will be examined. Secondly, the formation of governments juntas, congress, provincial States and confederations after the dissolution of the monarchy in 1808 will to be analyzed, as well as how they were legitimated by actas, constitutions of modern type and wars that changed political and territorial organization of the former Viceroyalty, between 1809 and 1816.

The Merriam-Webster Dictionary (2018) defines heartbreak as “crushing grief, anguish or distress.” Heartbreak can lead to biological, psychological and social responses and consequences. Heartbreak from the dissolution of a romantic relationship is a form of disenfranchised grief, which is defined as the griever’s belief that society does not recognize their source of grief as legitimate (Doka, 1989). The literature shows that talking about grief helps those who experience it (Fisher & Archer, 2008). Hence, the present study sought to provide a consensus of the best practices that marriage and family therapists have utilized to help broken-hearted clients. I employed a modification of the Delphi technique, a research method which seeks to reach consensus on a topic through group communication between experts in the subject area discussed (Hsu & Sandford, 2007) in order to gather data about best practices from marriage and family therapists on how they have helped their broken-hearted clients. This study consisted of a total of 20 experts, who are licensed marriage and family therapists. The findings suggest that the disenfranchisement of the grief resulting from the dissolution of a romantic relationship is closely associated with the symptom of sadness experienced by the broken-hearted. In addition, the way in which MFTs can help the disenfranchised griever is by providing an empathic presence in sessions, generating historical conversations through the use of a genogram, involving family members in the therapeutic process and having future oriented conversations. The results of this study have illustrated a plethora of techniques and best practices that have reportedly proven successful in helping the broken-hearted client.

The effects of system pressure on the performance stability of flow-through capacitive deionization (CDI) cells was investigated. Initial data showed that the highly porous carbon electrodes possessed air/oxygen in the micropores, and the increased system pressure boosts the gases solubility in saline solution and carries them out of the cell in the effluent. Upon applying a potential difference to the electrodes, capacitive-based ion adsorption occurs in competition with faradaic reactions that consume oxygen. Through the addition of backpressure, the rate of degradation decreases, allowing the cell to maintain its salt adsorption capacity (SAC) longer. The removal of oxygen from the pore space of the electrodes makes it no longer immediately accessible to faradaic reactions, thus hindering the rate of reactions and giving the competing ion adsorption an advantage that is progressively seen throughout the life of the cell. A quick calculation shows that the energy penalty to power the pump is fairly insignificant, especially in comparison to the cost of replacing the electrodes in the cell. Thus, operating at elevated pressures is shown to be cost effective for continuous operation through the reduced electrode replenishment costs.

High self-monitors choose as friends skilled activity partners, whereas low self-monitors select friends who are similar in attitude and values. We hypothesized that (a) as self-monitoring increased, individuals would identify the loss of shared interest as the cause for dissolving a former friendship and (b) as self-monitoring decreased, individuals would identify the loss of shared attitudes and values as the cause for dissolving a former friendship. One-hundred sixty one (82 males, 79 females) participants were recruited from MTurk. Participants were prompted with a forced choice measure to identify one of two reasons why a past close friendship dissolved. For one response participants could identify a loss of shared activities, for the other a loss of shared values. Participants then completed the 25-item Self-Monitoring Scale. For exploratory purposes, participants then completed a measure of the strategies they used to terminate that relationship of a best friend. Our results were consistent with our predictions, as self-monitoring appeared to influence the cause of dissolution in former close friendships. Additionally, as self-monitoring tendencies increased, participants were more likely to report using cost escalation, manipulation, distant/mediated communication, and de-escalation as strategies for ending a friendship. Explanations for these findings and suggestions for future research are discussed.

Afin d'assurer le confinement de déchets radioactifs en milieu géologique profond, il est envisagé d'utiliser des matériaux argileux de site et des bentonites. Leur stabilité en présence de fer métal, constituant des conteneurs de déchets, est étudiée. Ces études démontrent que la réactivité de tels matériaux est principalement portée par les smectites dioctaédriques et les kaolinites qu'ils contiennent. En revanche, la présence de sulfures inhibe la réaction Fe(0)-argiles. La nature du produit de réaction dépend de la quantité de fer métal disponible. A pH basique, par contact physique avec les agents oxydants de la smectite (H+, OH- et Fe3+), le Fe(0) est corrodé. Cette réaction est favorisée par les hétérogénéités des surfaces latérales de la smectite, qui altérée définit un micro-domaine à l'intérieur duquel nucléent des serpentines-Fe si l'apport en fer est suffisant. De telles néoformations entrainent une diminution des propriétés de confinement de la barrière argileuse.

Les nuages sont des éléments essentiels de notre atmosphère qui agissent à la fois sur le bilan radiatif terrestre et sur sa capacité oxydante en transformant chimiquement une grande variété d'espèces solubles. Ces nuages se forment par la condensation de vapeur d'eau sur des particules d'aérosols, appelés noyaux de condensation. La fraction soluble de ces particules conditionne l'hygroscopie des particules et détermine ainsi la taille des gouttes du nuage. Ce paramètre est déterminant pour définir les propriétés optiques des nuages. De plus, la dissolution des particules est la source primaire en phase aqueuse de différentes espèces dont les métaux de transition. Ces éléments sont impliqués dans divers processus d'oxydoréduction et en particuliers dans les processus responsables de la formation des pluies acides. Il est par conséquent très important de connaître, de manière fiable, les processus aboutissant à la solubilisation de l'aérosol dans les gouttes d'eau nuageuses. Le principal objectif de ce travail a donc été de développer un outil expérimental puis une approche de modélisation afin de comprendre et de simuler la dissolution des particules piégées dans une phase nuageuse liquide. Dans un premier temps, ce travail a consisté à mettre en oeuvre un dispositif expérimental, comportant un réacteur de dissolution en circuit ouvert, qui permet de suivre la cinétique de dissolution dans des conditions proches des conditions nuageuses. Cet outil expérimental a ensuite été utilisé pour une caractérisation systématique des différents facteurs d'influence recensés jusqu'alors sur la dissolution, c'est à dire le pH, la nature des aérosols, leur degré d'altération... mais également sur des facteurs jusqu'alors non expérimentés que sont la force ionique, la nature des acides et les cycles d'évapocondensation nuageuse. Les expériences de dissolution menées sous ces différentes conditions nuageuses ont permis de mettre en avant et de quantifier l'effet important des ions H+ et OH- sur la dissolution, ainsi que du degré de solubilisation de la particule. Ces observations ont ensuite été utilisées pour l'élaboration d'un mécanisme de dissolution des particules en phase aqueuse. Une quantification de ce mécanisme a enfin été réalisée en paramétrisant les principaux facteurs impliqués dans la dissolution. La comparaison des résultats calculés et expérimentaux montre une assez bonne adéquation, validant la paramétrisation effectuée. Finalement ce travail permet d'apporter des informations qualitatives et surtout quantitatives des interactions entre l'eau et les particules d'aérosols qui étaient encore manquantes et montrent notamment l'importance du processus de dissolution pour comprendre le rôle des aérosols dans l'implication climatique et chimique des nuages.

Cette thèse traite, dans une première partie, de la propagation unidimensionnelle de fronts de réactions exothermiques, à différentes échelles de description. Dans une approche macroscopique, la quantité de chaleur dégagée par la réaction vient coupler l'équation de convection-réaction-diffusion et les équations de l'hydrodynamique. Ce travail montre l'existence d'un domaine interdit de vitesses de propagation pour un front d'onde chimique stationnaire. Il met en évidence une transition entre une propagation principalement déterminée par les processus de réaction-diffusion, pour de faibles chaleurs de réaction, et une propagation principalement déterminée par les équations de l'hydrodynamique et l'équation d'état du fluide, pour une quantité de chaleur plus importante. Cette bifurcation est illustrée dans les cas d'un gaz parfait et d'un fl uide de van der Waals. La simulation microscopique de la dynamique des particules par la méthode 'Direct Simulation Monte Carlo' (DSMC) permet de retrouver ces résultats pour un gaz dilué. Dans une seconde partie, cette thèse développe un modèle de précipitation d'aiguilles de gypse à partir de grains d'hémihydrate de sulfate de calcium ainsi qu'un algorithme de simulation de la prise du plâtre à une échelle submicrométrique. Les résultats de simulation sont comparés à ceux issus d'une approche déterministe et d'une approche stochastique par une équation maîtresse. En dégageant un ensemble de paramètres ajustables et interprétables physiquement, le modèle permet de proposer une explication de l'effet d'un traitement industriel con dentiel améliorant la cinétique de formation et la morphologie du matériau final.