Graphene sheets, one atom thick, two dimensional layers of carbon atoms, have gained enormous importance over the past few years due to their unique attributes - high electronic, thermal conductivities and exceptional mechanical strength. Chemical reduction of graphene oxide (GO) has been considered as a viable route for large scale production of graphene sheets. The reduced graphene oxide (r -GO) sheets although their conductivities are comparatively lower than that of graphene are nevertheless versatile material for applications in thin films and composites. An important consideration in the design of solution processing techniques for the preparation of processable graphene sheets is the dispersibility of GO and r -GO in different solvents, especially aqueous dispersibility. While GO is dispersible in water over a wide range of pH values, r -GO shows poor dispersibility and over a limited range of pH values. Graphene oxide, the oxidized form of graphene, are single atomic layers with lateral dimension that can extend to hundreds of nanometers. The sheets contain a sizable fraction of carbons that are sp3 hybridized and covalently bonded to oxygen in the form of epoxy, carbonyls as well as ionizable hydroxyl and carboxylic functional groups located on the rim of the sheets. The remaining carbons form isolated sp2 graphene like networks. On reduction the oxygen functionalities are removed and the sp2 network partially restored. This thesis focuses on the aqueous dispersibility of GO and r -GO, and describes a strategy to enhance the dispersibility of r -GO by cyclodextrin functionalization. Chapter 1 of the thesis provides a brief review of the synthetic procedures and structure of GO and r -GO while Chapter 2 describes the experimental methods and characterization techniques used in the thesis. The chemistry underlying the aqueous dispersibility of GO and r -GO at different values of pH have been investigated by zeta potential measurements, pH titrations and infrared spectroscopy (Chapter 3). These measurements show that r -GO sheets have ionizable groups with a single pKa value (8.0) while GO sheets have groups that are more acidic (pKa = 4.3), in addition to groups with pKa values of 6.6 and 9.0. Infrared spectroscopy has been used to follow the sequence of ionization events. In both GO and r -GO sheets, it is ionization of the carboxylic groups that is primarily responsible for the build up of charge, but on GO sheets, the presence of phenolic and hydroxyl groups in close proximity to the carboxylic groups lowers the pKa value by stabilizing the carboxylate anion, resulting in superior water dispersibility. Till recently GO was primarily considered only as an easily available precursor for chemical routes to r -GO but it has now been recognized as an interesting material in its own right. Two such attributes that have attracted wide spread attention are the in- trinsic and tunable fluorescence of GO as well as formation of liquid crystalline phases. Aqueous dispersions of GO exhibit strong pH dependent fluorescence in the visible region that originates, in part, from the oxygenated functionalities present. In Chapter 4, the spectral migration on nanosecond timescales of the pH dependent features in the fluores- cence spectra of GO is described. The changes in the steady state fluorescence spectra with pH have been correlated with the sequence of dissociation events that occur in GO dispersions at different values of pH described in Chapter 3, from time resolved emission spectra (TRES) constructed from the wavelength dependent fluorescence decay curves, it is shown that the migration is associated with excited state proton transfer. Both ‘intramolecular’ and ‘intermolecular’ transfers involving the quasimolecular oxygenated aromatic fragments are observed. Aqueous dispersions of GO constitute a distinctive class of 2D-anisotropic colloids with competing interactions - long range electrostatic repulsion, originating from ionized carboxylic groups located on the rim of the sheets and weak dispersive attractive interactions originating from the un-oxidized sp2 graphitic domains. In Chapter 5, it is shown that, colloidal dispersions of GO are intrinsically frustrated, exhibiting a range of arrested or metastable states, encompassing fluid, glass and gels that coexist with liquid crystalline order. These states can be accessed by varying the relative magnitudes of the repulsive and attractive forces by changing the ionic strength of the medium, by addition of salt and/or the concentration of the dispersion. At low salt concentrations, where long range electrostatic repulsions dominates, the formation of a repulsive Wigner glass is observed while at high salt concentrations, when attractive forces dominate, the formation of gels that exhibits a nematic to columnar liquid crystalline transition. These studies highlights how the chemical structure of GO - hydrophilic ionizable groups and hydrophobic graphitic domains coexisting on a single sheet - gives rise to a rich and complex phase diagram. The poor dispersibility of r -GO in aqueous media limits its use in practical applica- tions. To enhance the dispersibility, r -GO sheets have been functionalized by covalently linking -cyclodextrin ( -CD) cavities to the sheets via an amide linkage (Chapter 6). The functionalized -CD: rGO sheets, in contrast to r -GO, are dispersible over a wide range of pH values (2 - 13). Zeta potential measurements indicate that there is more than one factor responsible for the dispersibility. It is shown that planar aromatic molecules adsorbed on the r -GO sheet as well as nonplanar molecules included in the tethered -CD cavities have their fluorescence effectively quenched by the -CD: rGO sheets. The -CD: rGO sheets combine the hydrophobicity associated with r -GO along with the hydrophobicity of the cyclodextrin cavities in a single water dispersible material. Resonance Raman spectroscopy is a powerful analytical tool for detecting and identi- fying analytes, but the associated strong fluorescence background severely limits the use of the technique. In Chapter 7, it is shown that the cyclodextrin functionalized -CD: rGO sheets, described in Chapter 6, provides a versatile platform for resonance Raman detection. Planar aromatic and dye molecules that adsorb on the r -GO graphitic domains and non-planar molecules included within the tethered -CD cavities have their fluorescence effectively quenched. Using the water dispersible -CD: rGO sheets, it is possible to record the resonance Raman spectra of adsorbed and included organic chromophores directly in aqueous media without having to extract or deposit on a substrate. The Raman signal intensities show a linear dependence with the concentration of analyte present in water. This is significant, as it allows for the identification and estimation of organic analytes present in water by resonance Raman spectroscopy.

Esta tesis esta compuesta por tres capítulos. Los dos primeros capítulos estudian los efectos macroeconómicos de una consolidación fiscal y estímulos fiscales cuando la deuda privada es elevada. El tercer capítulo, estudia proyecciones de deuda púbica para el caso español bajo diferentes escenarios macroeconómicos. En el primer capítulo se analiza los efectos macroeconómicos de diferentes planes de consolidación fiscal en los que el gobierno reduce de forma gradual la ratio deuda pública-PIB y el sector privado está altamente endeudado. Lo resultados muestran que en el largo plazo, la consolidación fiscal genera beneficios en términos de output que son mayores en el caso en el que el sector público este altamente endeudado. En el corto plazo, la efectividad de la política fiscal en un escenario de deuda alta, depende del instrumento fiscal utilizado. Finalmente se analiza el bienestar social, encontrando que la política de consolidación fiscal produce una ganancia en términos de bienestar cuando el gasto público o el impuesto al consumo se utilizan como instrumento y este bienestar es mayor en el caso de endeudamiento privado alto. Sin embargo, cuando el instrumento fiscal son los impuestos al trabajo o al capital, se produce una pérdida de bienestar que es amplificada en un escenario de endeudamiento alto. En el segundo capítulo, se estudia como el tamaño de los multiplicadores fiscales depende del nivel de endeudamiento privado. Este artículo contribuye al debate de los efectos de los estímulos fiscales demostrando que el impacto de las políticas fiscales depende del nivel de endeudamiento, considerando el endeudamiento de los hogares y empresas. Finalmente, en el tercer capítulo se examina las proyecciones de deuda para la economía española bajo diferentes escenarios macroeconómicos. Se encuentra que la deuda aumentará hasta un 174% en 2035 si se cumple el escenario macroeconómico que predice la Comisión Europea. En el caso de considerar una subida de impuestos, la deuda disminuye pero lejos de llegar a los niveles pre-COVID.

No description available.

Patterned resistive sheets (PRS) are resistive sheets with periodic patterns which provide further advantages to the functionality of the microbolometer. This study examines the potential of both single- and double-layer designs to achieve spectral selectivity in both broadband and narrowband absorption in the microbolometer's application. First, important design parameters, including rules and processes, are established. These include descriptions of sheet resistance, air gap, material refractive index, thicknesses of dielectric and bolometric layers, mirror, pattern shape and size, and unit cell period. Moreover, interactions among these elements are examined. Second, single-layer designs using dipole and slot PRS are introduced as initial designs for the reduced thermal mass design. Applying holes without changing spectral selectivity are investigated for narrowband application. Moreover, the method to tune the change of spectral selectivity is introduced. Third, newly stacked two-color design is suggested. The out-of-band transmission and reflection characteristics of the dipole and slot PRS are investigated to increase the absorption of each layer. Additionally, different pattern shapes, such as the circular patch and square patch, are investigated for easier fabrication. / text

In this dissertation we investigate the behavior of radially symmetric non-Euclidean plates of thickness t with constant negative Gaussian curvature. We present a complete study of these plates using the Föppl-von Kármán and Kirchhoff reduced theories of elasticity. Motivated by experimental results, we focus on deformations with a periodic profile. For the Föppl-von Kármán model, we prove rigorously that minimizers of the elastic energy converge to saddle shaped isometric immersions. In studying this convergence, we prove rigorous upper and lower bounds for the energy that scale like the thickness t squared. Furthermore, for deformation with n-waves we prove that the lower bound scales like nt² while the upper bound scales like n²t². We also investigate the scaling with thickness of boundary layers where the stretching energy is concentrated with decreasing thickness. For the Kichhoff model, we investigate isometric immersions of disks with constant negative curvature into R³, and the minimizers for the bending energy, i.e. the L² norm of the principal curvatures over the class of W^2,2 isometric immersions. We show the existence of smooth immersions of arbitrarily large geodesic balls in H² into R³. In elucidating the connection between these immersions and the nonexistence/ singularity results of Hilbert and Amsler, we obtain a lower bound for the L^∞ norm of the principal curvatures for such smooth isometric immersions. We also construct piecewise smooth isometric immersions that have a periodic profile, are globally W^2,2, and numerically have lower bending energy than their smooth counterparts. The number of periods in these configurations is set by the condition that the principal curvatures of the surface remain finite and grow approximately exponentially with the radius of the disc.

Ice sheets are among the key controls on global climate and sea level. A detailed understanding of their dynamics is crucial to make accurate predictions of their future mass balance. Ice streams are the dominant negative component in this balance, accounting for up to 90% of the Antarctic ice flux into ice shelves and ultimately into the sea. Despite their importance, our understanding of ice-stream dynamics is far from complete. A range of observations associate ice streams with meltwater. Meltwater lubricates the ice at its bed, allowing it to slide with less internal deformation. It is believed that ice streams may appear due to a localisation feedback between ice flow, basal melting and water pressure in the underlying sediments. This thesis aims to address the instability of ice-stream formation by considering potential feedbacks between the basal boundary and ice flow. Chapter 2 considers ice-flow models, formulating a model that is capable of capturing the leading-order dynamics of both a slow-moving ice sheet and rapidly flowing ice streams. Chapter 3 investigates the consequences of applying different phenomenological sliding laws as the basal boundary condition in this ice-flow model. Chapter 4 presents a model of subglacial water flow below ice sheets, and particularly below ice streams. This provides a more physical representation of processes occurring at the bed. Chapter 5 then investigates the coupled behaviour of the water with the sediment, and Chapter 6 the coupled behaviour of the water with the ice flow. Under some conditions this coupled system gives rise to ice streams due to instability of the internal dynamics.

La dernière période glaciaire est marquée par la présence de deux grandes calottes boréales recouvrant l’actuel Canada et le nord de l’Eurasie. Ces calottes constituent un élément actif du système climatique en interagissant avec les différentes composantes du système Terre. L’objectif de cette thèse est de déterminer par quels mécanismes les changements de circulation atmosphérique lors du dernier cycle glaciaire induisent potentiellement une téléconnexion entre les paléo-calottes de l’hémisphère nord. L’utilisation d’un modèle couplé climat-calotte simplifié m’a permis de tester séparément l’influence de la topographie et de l’albédo des calottes sur les champs de température et de précipitation lors du dernier cycle glaciaire, et de mettre en évidence le rôle de la circulation atmosphérique dans la synergie entre les paléo-calottes de l’hémisphère nord. Pour étudier plus en détail les mécanismes de cette interaction, l’utilisation d’un modèle de circulation générale s’est avérée nécessaire. J’ai tout d’abord effectué une inter-comparaison des modèles ayant participé à l’exercice PMIP3 pour le dernier maximum glaciaire (DMG). Cette inter-comparaison a permis d’illustrer l’impact des conditions glaciaires sur le décalage du courant-jet en Atlantique Nord et d’établir un lien entre ce décalage et les précipitations au sud de l’Europe. Enfin, à l’aide d’expériences idéalisées menées avec le modèle atmosphérique LMDZ, j’ai pu étudier le rôle de chacune des calottes dans les changements de circulation atmosphérique observés auDMG. Cette étude montre en particulier l’influence notable de la calotte nord-américaine sur le bilan de masse de surface de la calotte eurasienne. / The last glacial period is characterized by the presence of two large ice sheets covering Canada and North Eurasia. These ice sheets are a key element of the climatic system by interacting with all the components of the Earth system. The aim of this thesis is to determine by which mechanisms changes in atmospheric circulation may have induced a teleconnexionbetween the Northern hemisphere paleo-ice sheets. The use of a simplified coupled climate-ice sheet model allowed to test separately the influence of the ice-sheet topography and albedo on temperature and precipitation fields throughout the last glacial cycle and to highlight the role of atmospheric circulation within the synergy of past boreal ice sheets.To investigate in more details the underlying mechanisms, the use of a general circulation model was necessary.I therefore carried out an inter-comparisonof the PMIP3 models to examine the GCM responsesto glacial conditions. This work allowed to determinethe role of glacial conditions on the shift of the NorthAtlantic jet stream position and to establish a relationshipbetween this shift and the amount of precipitationover southern Europe. The last part of this thesisis devoted to the respective role of each ice sheeton atmospheric circulation changes observed underglacial conditions. To achieve this, I performed idealizedexperiments with the atmospheric circulationmodel LMDZ. The results highlight the key influenceof the North American ice sheet on the Eurasian icesheet surface mass balance.

Cette thèse se situe dans le domaine de l'électromagnétisme et plus particulièrement, celui de la compatibilité électromagnétique. L'objectif de cette thèse est de proposer une condition d'interface qui évite de mailler les plaques minces conductrices lors d’une modélisation tridimensionnelle. Cette condition permet de prendre en compte de manière précise la réflexion d'une onde ou sa transmission par une plaque conductrice. Elle permet aussi de tenir compte de l'effet de peau de l'effet de peau à l'intérieur de la plaque. Cette condition d'interface est intégrée dans une méthode Galerkin discontinue. La présence des termes de flux dans cette méthode rend facile l'implémentation de cette condition d'interface. Afin de montrer l'intérêt de cette condition dans le cadre de la compatibilité électromagnétique, des configurations d'interaction ondes-Structures sont traitées. Elles ont pour but d'étudier l'efficacité de blindage de diverses cavités bidimensionnelles et tridimensionnelles. / This thesis concerns electromagnetic fields and more particularly electromagnetic compatibility. The aim of this thesis is the modeling an interface condition to avoid the mesh of thin conductive sheets in 3D numerical methods. This interface condition allows to take in account the reflection or the transmission of an incident wave on a conductive sheet. It also takes into account the skin effect in this sheet. This interface condition is integrated in discontinuous Galerkin method. The presence of flux terms is this method makes easy to implement this interface condition. To demonstrate the advantage of this interface condition in electromagnetic compatibility problems, many configurations of interaction wave-Structure are treated. They aim to study the shielding effectiveness of different cavities in two and three dimensions.

Orientador: Mirna Lygia Vieira / Banca: Helmut Troppmair / Banca: Silvia Aparecida Guarnieri Ortigoza / Banca: Renata Barrocas / Resumo: Os espaços de recreação na paisagem urbana são muito significativos para a população local e visitantes, apresentando-se como referências atrativas para um bom aproveitamento do tempo livre, devendo proporcionar qualidade de vida, por exemplo, com funções recreativas, lúdicas, esportivas, entre outras. Esta pesquisa com abordagem perceptiva do ser humano em relação ao espaço recreativo do Lago Azul de Rio Claro, SP, teve por objetivos analisar, descrever e interpretar o papel das lâminas d'água como atração ou repulsão em lugares urbanos. A metodologia aqui utilizada, baseada nos pressupostos de Fisk e Hatry (1983), que fora empregada em diversos espaços de recreação em lugares urbanos nos Estados Unidos, pode revelar as diversas maneiras como são utilizados os centros recreativos pela população, possibilitando aplicar esses conhecimentos acadêmicos na sociedade, proporcionando condições e mudanças na organização do espaço, visando inclusive a qualidade de vida de uma população. Portanto, o poder público local deve estar atento às expectativas de um povo que vive e convive com este lugar, para que este receba melhorias para sua conservação de acordo com os anseios e necessidades de sua população, tornando-se um lugar atrativo em todos os momentos de lazer. / Abstract: The spaces of recreation in the urban landscape are many significant for the visiting and local population presenting itself with attractive references for a good free time utilization should provide quality of life with sporting, playful, recreational functions between others. This research with perceptive approach of a human regarding to the recreational space of Lago Azul from Rio Claro, SP, had for objectives analyze, describe and interpret the water sheets paper as appeal or repulsion in urban places. The methodology here studied, based on the budgets of Fisk and Hatry (1983), that outside employed in diverse recreation spaces in urban places in the United States, can reveal the diverse ways as healthy utilized the recreational centers by the population enabling apply these academic knowledge in the society; providing conditions and changes in the space's organization, aiming at including to the quality of life improvement of any population. Therefore, the local public power should be aware the people's expectations that live and lives together with this place for this receive improvements for its conservation according to the yearnings and needs of its population, becoming an attractive place in all leisure moments. / Mestre

Neste trabalho foram realizados experimentos de soldagem de chapas de Tântalo e Monel 400 com 100 m de espessura. Foram realizadas soldas em um laser de Nd:YAG operando em modo pulsado e em um Laser de Fibra operando em modo contínuo. Em seguida a microestrutura das amostras foram analisadas através de microscopia ótica e foram realizados ensaio de microdureza Vickers. As amostras que apresentaram melhores resultados foram submetidas a ensaios de tração e a ensaios de corrosão. Após análise dos resultados observou-se que a soldagem a laser apresenta muitos benefícios em relação a outros processos convencionais para chapas finas. A soldagem no modo pulsado apresentou maior relação de aspecto se comparado a soldagem em modo contínuo. A soldagem em modo contínuo apresentou uma velocidade de soldagem muito superior ao modo pulsado. Os resultados indicaram que a soldagem no modo pulsado apresenta maior aplicabilidade para chapas finas, devido à necessidade um controle preciso sobre a intensidade aplicada. / This work carried out welding experiments of Tantalum and Monel 400 plates with 100 mm thickness. Welds were made with an Nd: YAG laser operating in a pulsed mode and in a fiber laser operating in continuous mode. Then the microstructure of the samples were analyzed by optical microscopy and were performed Vickers microhardness test. Samples that showed better results were subjected to tensile tests and the corrosion tests. After analysis of the results showed that the laser welding offers many benefits over other conventional processes for thin sheets. The welding in pulsed mode presented in superior aspect ratio compared to welding in continuous mode. The welding in continuous mode showed a much higher welding speed to pulsed mode. The results indicated that the welding in pulsed mode shows more applicability for sheet metal, due the need of a precise control of applied intensity.