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Characterization, Mechanism and Kinetics of Phase-separation of Mixed Langmuir-Blodgett FilmsQaqish, Shatha Eid 16 April 2009
The phase separation of mixed Langmuir-Blodgett (LB) monolayers was investigated using a combination of atomic force microscopy (AFM), X-ray photoelectron emission microscopy (X-PEEM) and confocal fluorescent microscopy measurements. Shapes of phase-separated domains that formed on solid substrate surfaces depended on a competition between line tension and dipole-dipole interactions. In the mixed LB film of arachidic acid (C19H39COOH) (C20) and perfluorotetradecanoic acid (C13F27COOH) (F14), the components phase separated into elevated hexagonal domains of C20 surrounded by a continuous domain primarily consisting of F14. The underlying molecular arrangement of C20 was found to be an oblique packing. The domains in this system grew via Ostwald ripening and the kinetics of their growth was modeled by twodimensional LifshitzSlyozov equation. In the stearic acid (C17H35COOH) (C18) and F14 mixed films, the C18 domains formed a linear pattern where the F14 molecules filled the areas in between the lines occupied by C18. For the mixed film of palmitic acid (C15H31COOH) (C16) and perfluorooctadecanoic acid (C17F35COOH) (F18), the surfactants phaseseparated into elevated hexagonal domains with hairy extensions radiating from them. These domains were composed of F18 and surrounded by C16. Ostwald ripening was found to be the mechanism of domain growth. Phase separation was controlled by different forces such as line tension and dipole interactions, as well as the diffusion of the molecules, solubility of the surfactant in the sub-phase, temperature and surface pressure. Simple mechanisms regarding phase separation and pattern formation were discussed in these mixed systems. It was observed that all fatty acid / F14 systems in this study were immiscible at all molar fractions examined. The fatty acid / F18 systems were immiscible at short chains of fatty acids (myristic acid (C13H27COOH) C14, C16, C18), whereas at longer fatty acid chains (C20, C22 behenic acid (C21H43COOH)) the components of the mixed system became miscible. When perfluorocarboxylic acid chain combined with fatty acids, the domains changed from large hexagonal domains into narrow lines as the fatty acid chain decreased in length.
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Characterization, Mechanism and Kinetics of Phase-separation of Mixed Langmuir-Blodgett FilmsQaqish, Shatha Eid 16 April 2009 (has links)
The phase separation of mixed Langmuir-Blodgett (LB) monolayers was investigated using a combination of atomic force microscopy (AFM), X-ray photoelectron emission microscopy (X-PEEM) and confocal fluorescent microscopy measurements. Shapes of phase-separated domains that formed on solid substrate surfaces depended on a competition between line tension and dipole-dipole interactions. In the mixed LB film of arachidic acid (C19H39COOH) (C20) and perfluorotetradecanoic acid (C13F27COOH) (F14), the components phase separated into elevated hexagonal domains of C20 surrounded by a continuous domain primarily consisting of F14. The underlying molecular arrangement of C20 was found to be an oblique packing. The domains in this system grew via Ostwald ripening and the kinetics of their growth was modeled by twodimensional LifshitzSlyozov equation. In the stearic acid (C17H35COOH) (C18) and F14 mixed films, the C18 domains formed a linear pattern where the F14 molecules filled the areas in between the lines occupied by C18. For the mixed film of palmitic acid (C15H31COOH) (C16) and perfluorooctadecanoic acid (C17F35COOH) (F18), the surfactants phaseseparated into elevated hexagonal domains with hairy extensions radiating from them. These domains were composed of F18 and surrounded by C16. Ostwald ripening was found to be the mechanism of domain growth. Phase separation was controlled by different forces such as line tension and dipole interactions, as well as the diffusion of the molecules, solubility of the surfactant in the sub-phase, temperature and surface pressure. Simple mechanisms regarding phase separation and pattern formation were discussed in these mixed systems. It was observed that all fatty acid / F14 systems in this study were immiscible at all molar fractions examined. The fatty acid / F18 systems were immiscible at short chains of fatty acids (myristic acid (C13H27COOH) C14, C16, C18), whereas at longer fatty acid chains (C20, C22 behenic acid (C21H43COOH)) the components of the mixed system became miscible. When perfluorocarboxylic acid chain combined with fatty acids, the domains changed from large hexagonal domains into narrow lines as the fatty acid chain decreased in length.
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Etude pétro-chronologique de la chaîne des Longmen Shan (Tibet oriental) : héritage géologique et implications pour la géodynamique actuelle / A petro-chronological study of the Longmen Shan thrust belt (eastern Tibet) : geological inheritance and implication for the present geodynamicsAiraghi, Laura 27 October 2017 (has links)
Un des enjeux majeurs en Sciences de la Terre est la compréhension des mécanismes de déformation de la lithosphère continentale dans des zones de convergence. Le plateau Tibétain constitue un laboratoire naturel idéal pour l'étude des processus crustaux profonds actifs dans ces contextes, du fait de sa superficie et de son altitude remarquables. Le soulèvement et l'épaississement de la croûte Tibétaine ont été classiquement attribués aux effets de la collision Inde-Asie Tertiaire. Cependant, cette interprétation a été récemment mise en question par une série d’observations géologiques et géophysiques non concordantes, à différents endroits du plateau.L'objectif de cette thèse est de quantifier l’importance de l’héritage géologique dans la déformation à long-terme et à court-terme d’une chaîne active, en déchiffrant les différentes étapes de la structuration des Longmen Shan, la bordure la plus énigmatique du plateau Tibétain. Dans la chaîne des Longmen Shan la croûte Tibétaine est très épaissie (>60 km) et l'activité tectonique est localisée le long des failles d’échelle lithosphérique, comme démontré par les séismes de Wenchuan 2008 (Mw 7.9) et de Lushan 2013 (Mw 6.6). Un fort gradient topographique est présent, bien que les taux de convergence mesurés par GPS soient très faibles (<3 mm/an). Ces caractéristiques ne sont pas explicables par un modèle unique de déformation crustale, ce qui suggère une forte contribution de l'héritage géologique acquis avant la collision Inde-Asie dans la structure actuelle de la chaîne.Une étude pétro-chronologique qui combine des observations microstructurales avec la cartographie chimique des minéraux majeurs et accessoires, la modélisation thermodynamique et la datation in-situ par méthode 40Ar/39Ar et U-Pb/Th sur mica et allanite a été appliquée aux roches métamorphique à l’affleurement de chaque côté des faille majeures. L’analyse haute résolution montre que les minéraux métamorphiques dans la matrice des sédiments à grenat provenant des unités internes de la chaîne préservent dans leur composition le témoignage de différentes étapes du métamorphisme. Ceci s’explique par un rééquilibrage chimique incomplet en raison de la variabilité des fluides disponibles au cours du métamorphisme. Les différentes étapes du métamorphisme sont aussi enregistrées dans le signal 40Ar/39Ar des micas et dans la composition des minéraux accessoires.La compréhension des processus pétrologiques à petite échelle a été intégrée aux observations de terrain afin de quantifier l’épaississement de la croûte Tibétaine au Mésozoïque (> 30 km) et de mettre en évidence un saut métamorphique >150°C à travers les failles majeures, hérité de la tectonique Mésozoïque. Si les unités internes de la chaîne ont été fortement déformées, découplées du socle cristallin et métamorphisées à T ~580-600°C (P ~11 kbar), les unités externes apparaissent moins déformées et épaissies (T< 400°C, P< 5 kbar). Une exhumation partielle du socle depuis c. 20 km de profondeur a été également documentée à 120-140 Ma et reliée à un évènement tectonique méconnu auparavant.Cette thèse a ainsi permis de quantifier la durée et les conditions qui caractérisent les différentes étapes de la maturation de la chaîne: les unités internes atteignent la relaxation thermique 40 Ma après le début de la propagation du prisme orogénique. Le socle est réactivé 40 Ma plus tard, lorsqu’il atteint des conditions thermiques proches de celles de sa couverture sédimentaire. L’héritage géologique Mésozoïque contrôle fortement l’état thermique et rhéologique de la croûte supérieure au moment de la réactivation Cénozoïque ainsi que la structure actuelle de la chaîne.L’étude petro-chronologique de différents segments de la chaîne a aussi mis en évidence une segmentation métamorphique héritée du Mésozoïque qui correspond à la segmentation actuelle des failles. Ceci suggère que des structures héritées pourraient en partie contrôler la localisation des séismes récents. / One of the major challenges in Earth Sciences is understanding how the continental lithosphere deforms in convergent settings, according to which timescales. For its elevation and extension the Tibetan plateau is an ideal natural laboratory for the study of deep crustal processes in active convergent settings. The rise and thickening of the Tibetan plateau has generally been related to the only collision between the Eurasian and Indian plates during the Cenozoic. However, this interpretation has been recently put into question by apparently contrasting geophysical and geological features observed at different locations on the plateau.The aim of this PhD is to quantify the importance of the geological inheritance in the long-term and short-term deformation of an active thrust belt, focusing on the Longmen Shan orogen, the most enigmatic border of the Tibetan plateau. In the Longmen Shan (eastern Tibet) the Tibetan crust is over thickened (>60 km), the tectonic activity is localized along lithospheric faults -as demonstrated by the occurrence of the Mw 7.9 Wenchuan (2008) and Mw 6.6 Lushan (2013) earthquakes- and a high topography survives despite low convergence rates measured by GPS (<3 mm/yr). These observations are hardly reconcilable in a unique model of crustal deformation, suggesting a contribution of the geological inheritance from the geological history preceding the India-Asia collision.A petro-chronological approach that combines microstructural observations, compositional mapping of major and accessory mineral phases, thermodynamic modelling, in-situ 40Ar/39Ar dating, Ar diffusion modelling and in-situ U/Pb-Th allanite dating was applied to metamorphic rocks on each side of the major faults that strike parallel to the belt. This high-resolution study shows that in garnet-bearing rocks of the internal units of the belt matrix minerals record different stages of the metamorphic path in their composition. This is due to an incomplete chemical re-equilibration explained by a variable fluid availability during metamorphism. Different stages of metamorphism and fluid-assisted reactions sequences are also recorded in the 40Ar/39Ar signal of micas and in the composition and textures of the accessory phases.The understanding of petrological processes at the small scale was combined with field observations to quantify the Mesozoic thickness of the Tibetan crust at > 30 km and to unravel a metamorphic jump of greater than 150°C across the major faults, inherited from the Mesozoic tectonics. While internal units of the belt were strongly deformed, decoupled from the basement and metamorphosed at T ~ 580-600°C (P ~11 kbar), external units were less deformed and experienced lower temperatures conditions (T < 400°C, P < 5 kbar). The partial exhumation of the crystalline basement from c. 20 km depth along the major fault (in both internal and external units) occurred at c. 120-140 Ma during a previously poorly documented tectonic event.The multi-method approach applied on a wide geographical area and on a large time interval enabled to quantify the rates and conditions of the different stages of the maturation of the belt; internal units reached the thermal relaxation at ~600°C 40 Ma after the beginning of the propagation of the orogenic load. The basement was re-activated 40 Ma later, at similar thermal conditions than its sedimentary cover. The Mesozoic geological inheritance is therefore a key element in the present structure of the belt and strongly controlled the rheological and structural state of the upper crust at the moment of the Cenozoic re-activation.The petro-chronological study of different segments of the belt showed an along-strike metamorphic segmentation of the Longmen Shan inherited from the Mesozoic. This segmentation corresponds to the present fault segmentation, underlying the potential role of inherited structure in controlling the geographic distribution of the recent earthquakes.
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