Submitted by Ary Cera Zanetta Neto Zanetta (ary.zanetta@brasil-capital.com) on 2014-08-19T19:21:54Z No. of bitstreams: 1 Efeitos de Choques Globais na Economia Brasileira_ Uma Análise a Partir do GVAR.pdf: 1085836 bytes, checksum: 25e953aa352fed09b5b828362226aab9 (MD5) / Rejected by JOANA MARTORINI (joana.martorini@fgv.br), reason: A ficha catalográfica não está valida, por gentileza aguardar o envio da ficha correta pala biblioteca digital. on 2014-08-19T19:29:14Z (GMT) / Submitted by Ary Cera Zanetta Neto Zanetta (ary.zanetta@brasil-capital.com) on 2014-08-19T20:33:33Z No. of bitstreams: 1 Efeitos de Choques Globais na Economia Brasileira_ Uma Análise a Partir do GVAR.pdf: 1085836 bytes, checksum: 25e953aa352fed09b5b828362226aab9 (MD5) / Approved for entry into archive by JOANA MARTORINI (joana.martorini@fgv.br) on 2014-08-20T16:30:59Z (GMT) No. of bitstreams: 1 Efeitos de Choques Globais na Economia Brasileira_ Uma Análise a Partir do GVAR.pdf: 1085836 bytes, checksum: 25e953aa352fed09b5b828362226aab9 (MD5) / Made available in DSpace on 2014-08-20T19:02:31Z (GMT). No. of bitstreams: 1 Efeitos de Choques Globais na Economia Brasileira_ Uma Análise a Partir do GVAR.pdf: 1085836 bytes, checksum: 25e953aa352fed09b5b828362226aab9 (MD5) Previous issue date: 2014-08-05 / O objetivo deste estudo é avaliar a propagação de choques econômicos de alguns países sobre o crescimento econômico brasileiro, com principal destaque para China, Estados Unidos da América (EUA) e Argentina, que são os principais parceiros comerciais do Brasil. O aumento do comércio com a China tornou o Brasil muito mais vulnerável a choques no PIB chinês e menos vulnerável, do que no passado recente, a choques no PIB americano, enquanto que a influência da Argentina manteve-se estável. Foi aplicada a metodologia Vetor Autorregressivo Global (Global Var – GVAR), introduzida por Pesaran, Schuermann e Weiner (2004), Garratt, Lee, Pesaran e Shin (2006) e Dées, Di Mauro, Pesaran e Smith (2007), para analisar os canais de comércio e a transmissão de choques entre o resto do mundo e o Brasil. Usando dados trimestrais a partir de 1990 até o final de 2013, foi possível constatar que o aumento da relevância da economia Chinesa na balança comercial Brasileira exerce pressão sobre o crescimento econômico do Brasil. Em suma, a China tornou-se mais relevante para o crescimento econômico do Brasil do que os EUA e a Argentina. / The objective of this study is to evaluate the impact of variations in the Gross Domestic Product (GDP) of countries and economic blocks over Brazilian economic growth, with emphasis on China, United States of America (USA) and Argentina, which are the main commercial partners of Brazil. The increase in trading with China has made Brazil more vulnerable to shocks in Chinese GDP and less vulnerable, than in the recent past, to shocks in American GDP, and stability in the case of Argentina. It has been applied the methodology Global Vector Autorregressive (Global Var – GVAR), introduced, explained and expanded by Pesaran, Schuermann and Weiner (2004), Garratt, Lee, Pesaran and Shin (2006) and Dées, Di Mauro, Pesaran and Smith (2007) to analyze the trading channels and the transmission of shocks between the rest of the world and Brazil (specially with China, USA and Argentina). Using a sample from the first quarter of 1990 to the third quarter of 2013 it is possible to see that the increase of relevance of the Chinese economy on the Brazil trade balance increased the relevance of the Chinese economy over the Brazilian economy. Therefore, the conclusions of this work indicate a considerable vulnerability of the Brazilian economy to the Chinese economic cycle and, in a lower degree than in the past, to the American and Argentinian economies.

Submitted by Alexandre Otomo de Almeida (otomo.almeida@gmail.com) on 2017-03-04T15:15:48Z No. of bitstreams: 1 Dissertacao_vf2.pdf: 906019 bytes, checksum: 389d53353d9269653e591405747ca68f (MD5) / Rejected by Renata de Souza Nascimento (renata.souza@fgv.br), reason: Alexandre, boa noite Para que possamos aceitar seu trabalho, por gentileza, realizar os ajustes de acordo com as normas a ABNT: Diminuir os espaços entre as frases do título. A apresentação ocorreu em 2017. Alterar São Paulo 2016, para São Paulo 2017. Na contra capa e folha de assinaturas, em campo de conhecimento deverá colocar sua área: Economia. Em seguida, submeter novamente o arquivo. att on 2017-03-07T00:11:09Z (GMT) / Submitted by Alexandre Otomo de Almeida (otomo.almeida@gmail.com) on 2017-03-07T02:06:07Z No. of bitstreams: 1 Dissertacao_vf2.pdf: 905969 bytes, checksum: ddcaca60b92b7d4a93c6ae17626d4f8a (MD5) / Approved for entry into archive by Renata de Souza Nascimento (renata.souza@fgv.br) on 2017-03-08T23:41:02Z (GMT) No. of bitstreams: 1 Dissertacao_vf2.pdf: 905969 bytes, checksum: ddcaca60b92b7d4a93c6ae17626d4f8a (MD5) / Made available in DSpace on 2017-03-09T13:17:42Z (GMT). No. of bitstreams: 1 Dissertacao_vf2.pdf: 905969 bytes, checksum: ddcaca60b92b7d4a93c6ae17626d4f8a (MD5) Previous issue date: 2017-02-09 / This paper consists of a study over the impact of interest rates and maturities of loans for electronics and home appliances in Brazil, designed for consumers with credit constraints. Using micro data on loans of one of the largest retailers in the Brazilian market, some econometric models were built using conditional and nested logit approach, in order to estimate elasticities of loan demand with respect to the interest rate, the maturity of the loan and the terms value. Moreover, marginal substitution rates were also estimated between those attributes to evaluate consumer’s propensity to choose different combinations of loan conditions. Given the number of different product categories sold by this retailer, two of the most important were selected. The results suggest that the interest rate, the payment terms and the loan maturity are important factors on consumer decision. Loan demand is leveraged by loan’s smaller interest rates and payment terms. However, there is a material marginal substitution rate between payment terms and loan maturity or interest rate. This means that consumers are highly prone to change from loans with higher payment terms to others with lower ones, even if they face higher interest rates and longer terms to maturity. Results also suggest that consumers are not really aware of the real value paid for these products. / O trabalho tem por objetivo o estudo do impacto da taxa de juros e dos prazos de financiamento sobre a demanda de eletroeletrônicos no Brasil para os públicos com restrição de acesso a crédito. Utilizando dados de vendas por meio de crédito direto ao consumidor (CDC) de um grande varejista brasileiro, foram construídos modelos logit condicional e aninhado para dimensionamento das elasticidades da demanda às taxas de juros, aos prazos de parcelamento e ao valor das parcelas. Além disso, foram dimensionadas as subsequentes taxas marginais de substituição entre os atributos dos planos de financiamento oferecidos aos clientes, para avaliar a propensão à troca de condições de planos de financiamento pelos consumidores. Dada a extensão das categorias de produtos existentes no varejista em questão, foram selecionadas duas categorias de alta representatividade no resultado de vendas. Para as duas categorias selecionadas, foi constatado que a taxa de juros é fator importante na decisão de compra, bem como o número e valor das parcelas. A demanda se mostrou positivamente impactada por taxas de juros menores, bem como por valores de parcela menores. No entanto, os consumidores se mostraram altamente dispostos à substituição de planos com prazos de financiamento e taxas de juros menores por planos com valores menores das parcelas. Por fim, foi constatado que os consumidores têm baixa consciência do valor real pago pelos produtos comprados.

Submitted by Pedro Ricardo Bernardino de Freitas (pedro.rbf@gmail.com) on 2011-12-08T18:35:16Z No. of bitstreams: 1 Dissertacao_Pedro_R_B_Freitas.pdf: 6802890 bytes, checksum: 70d840d6a8a31071b5ccdcb01e41463e (MD5) / Approved for entry into archive by Vitor Souza (vitor.souza@fgv.br) on 2011-12-15T16:45:18Z (GMT) No. of bitstreams: 1 Dissertacao_Pedro_R_B_Freitas.pdf: 6802890 bytes, checksum: 70d840d6a8a31071b5ccdcb01e41463e (MD5) / Made available in DSpace on 2011-12-27T12:32:40Z (GMT). No. of bitstreams: 1 Dissertacao_Pedro_R_B_Freitas.pdf: 6802890 bytes, checksum: 70d840d6a8a31071b5ccdcb01e41463e (MD5) Previous issue date: 2011-08-29 / O trabalho utiliza conceitos da economia do bem estar e a elasticidade da renda tributável para analisar o custo social das reações comportamentais dos contribuintes do imposto de renda sobre as pessoas físicas no Brasil, em resposta a uma mudança de política tributária. A elasticidade da renda tributável despertou grande atenção recente, motivada pela perspectiva de estimar em conjunto todas as reações comportamentais a uma mudança no sistema tributário através de um único parâmetro, mensurando custos de eficiência e de bem estar suportados pela economia de forma relativamente simples. O trabalho aborda a utilização de medidas de variação de bem estar para avaliar mudanças na política tributária e faz uma resenha da literatura sobre a elasticidade da renda tributável, conceitos, características, vantagens e limitações. Um modelo de preferências é especificado para exemplificar a dimensão das reações à tributação e os custos de eficiência envolvidos, e discutir a viabilidade do emprego da elasticidade da renda tributável como parâmetro estrutural. / This study aims to analyse the social cost and behavioural responses due the taxation of earned income in Brazil using welfare concepts and the elasticity of taxable income with respect to the net of tax rate. The elasticity of taxable income has deserved great attemption and is a main issue in public economics research agenda. Under some conditions, it holds the perspectives of measuring efficiency costs of income taxation from a wide array of behavioural responses just estimating one single parameter. The study introduces the use of welfare changes measures for tax policy evaluation and reviews the concepts about elasticity of taxable income, its characteristics, advantages and limitations of use. We develop a model in which we show the dimension of responsiveness of taxpayers. Based on this model, we estimate the efficiency cost and excess burden of income taxation and discuss the use of elasticity of taxable income as a structural parameter.

La problématique suivie dans ce travail est la détermination des propriétés effectives, élastiques et conductivité, de matériaux poreux hétérogènes tels que des roches, les roches oolithiques en particulier, en relation avec leur microstructure. Le cadre théorique adopté est celui de l’homogénéisation des milieux hétérogènes aléatoires et on suit les approches par tenseurs d’Eshelby. Ces approches sont basées sur la résolution des problèmes d’Eshelby : le problème de l’inclusion (premier problème) et le problème de l’inhomogénéité (second problème) isolées dans un milieu infini. La solution de ces problèmes de référence est analytique, en élasticité linéaire isotrope et en diffusion linéaire stationnaire, dans le cas d’inhomogénéités 2D ou 3D de type ellipsoïde. Elle conduit à la définition de tenseurs caractérisant les interactions entre l’inclusion/inhomogénéité et le milieu environnant. On utilise dans ce travail les tenseurs de contribution relatifs à une inhomogénéité isolée, définis par Kachanov et Sevostianov 2013, contributions à la souplesse (élasticité) et à la résistivité (conductivité). Ces tenseurs au cœur des méthodes d’homogénéisation de type EMA (Effective Medium Approximation), et en particulier les schémas NIA (Non Interaction Approximation), Mori Tanaka et Maxwell. Ce travail est centré sur la caractérisation des paramètres géométriques microstructuraux dont l’influence sur les propriétés effectives est majeure. On étudie en particulier les effets de forme des inhomogénéités, la nouveauté est l’aspect 3D. Les observations microstructurales de roches oolithiques, dont le calcaire de référence de Lavoux, mettent en évidence des hétérogénéités de forme 3D et concave. En particulier les matériaux de remplissage inter-oolithes, pores ou calcite syntaxiale. Ces formes peuvent être observées sur d’autres matériaux hétérogènes et ont été peu étudiées dans le cadre micromécanique. Cela nécessite de considérer des formes non ellipsoïdales et de résoudre numériquement les problèmes d’Eshelby. Le cœur de ce travail est consacré à la détermination des tenseurs de contribution d’inhomogénéités 3D convexes ou concaves de type supersphère (à symétrie cubique) ou supersphéroïde (à symétrie de révolution). Le premier problème d’Eshelby a été résolu, dans le cas de la supersphère, par intégration numérique de la fonction de Green exacte (solution de Kelvin dans le cas isotrope) sur la surface de l’inclusion. Des modélisations 3D aux éléments finis ont permis de résoudre le second problème d’Eshelby et d’obtenir les tenseurs de contribution à la souplesse et à la résistivité pour les superphère et supersphéroïde. Sur la base des résultats numériques, des relations analytiques simplifiées ont été proposées pour les tenseurs de contribution sous forme de fonctions des paramètres élastiques des constituants et du paramètre adimensionnel p caractérisant la concavité. Un résultat important, dans le cas de la superphère et dans le domaine concave, est l’identification d’un même paramètre géométrique pour les tenseurs de contribution à la souplesse et à la résistivité. Les résultats numériques et théoriques obtenus sont appliqués à deux problèmes : l’estimation de la conductivité thermique effective de roches calcaires oolithiques d’une part et l’étude de l’extension des relations dites de substitution définies par Kachanov et Sevostianov 2007 au cas non ellipsoïdal d’autre part. Pour le premier problème, un modèle micromécanique de type Maxwell, à deux échelles a permis de retrouver les résultats expérimentaux disponibles dans la littérature, en en particulier l’influence de la porosité sur la conductivité thermique effective dans les cas sec et humide. Dans le cas du second problème, les résultats obtenus ont permis de montrer que la validité de relations de substitution est restreinte, dans le cas non ellipsoïdal et en considérant une forme d’inhomogénéité de type supersphère, au domaine convexe seulement / Focusing on the effect of shape factor on the overall effective properties of heterogeneous materials, the 1st and the 2nd Eshelby problem related to 3-D non-ellipsoidal inhomogeneities with a specific application to oolitic rocks have been discussed in the current work. Particular attention is focused on concaves shapes such as supersphere and superspheroid. For rocks, they may represent pores or solid mineral materials embbeded in the surrounding rock matrix. In the 1st Eshelby problem, Eshelby tensor interrelates the resulting strain about inclusion and eigenstrain that would have been experienced inside the inclusion without any external contraire. Calculations of this tensor for superspherical pores– both concave and convex shapes – are performed numerically. Results are given by an integration of derivation of Green’s tensor over volume of the inclusion. Comparisons with the results of Onaka (2001) for convex superspheres show that the performed calculations have an accuracy better than 1%. The current calculations have been done to complete his results. In the 2nd Eshelby problem, property contribution tensors that characterizes the contribution of an individual inhomogeneity on the overall physical properties have been numerically calculated by using Finite Element Method (FEM). Property contribution tensors of 3D non ellipsoidal inhomogeneities, such as supersphere and superspheroid, have been obtained. Simplified analytical relations have been derived for both compliance contribution tensor and resistivity contribution tensor. Property contribution tensors have been used to estimate effective elastic properties and effective conductivity of random heterogeneous materials, in the framework of Non-Interaction Approximation, Mori-Tanaka scheme and Maxwell scheme. Two applications in the field of geomechanics and geophysics have been done. The first application concerns the evaluation of the effective thermal conductivity of oolitic rocks is performed to complete the work of Sevostianov and Giraud (2013) for effective elastic properties. A two step homogenization model has been developed by considering two distinct classes of pores: microporosity (intra oolitic porosity) and meso porosity (inter oolitic porosity). Maxwell homogenization scheme formulated in terms of resistivity contribution tensor has been used for the transition from meso to macroscale. Concave inter oolitic pores of superspherical shape have been taken into account by using resistivity contribution tensor obtained thanks to FEM modelling. Two limiting cases have been considered: ‘dry case’ (air saturated pores) and ‘wet case’ (water liquid saturated pores). Comparisons with experimental data show that variations of effective thermal conductivity with porosity in the most sensitive case of air saturated porosity are correctly reproduced. Applicability of the replacement relations, initially derived by Sevostianov and Kachanov (2007) for ellipsoidal inhomogeneities, to non-ellipsoidal ones has been investigated. It it the second application of newly obtained results on property contribution tensors. We have considered 3D inhomogeneities of superspherical shape. From the results, it has been seen that these relations are valid only in the convex domain, with an accuracy better than 10%. Replacement relations can not be used in the concave domain for such particular 3D shape

Dans ce mémoire, des méthodes spectrales basées sur la transformée de Fourier rapide ("fast Fourier transform" en anglais notée "FFT") sont développées pour résoudre les équations de champs et d’évolution des densités de dislocations polarisées ou géométriquement nécessaires dans la théorie de la mécanique des champs de dislocations ("Field Dislocations Mechanics" en anglais et notée "FDM") et de son extension phénoménologique et mésoscopique ("Phenomenological Mesoscopic Field Dislocations Mechanics" en anglais et notée "PMFDM"). Dans un premier temps, une approche spectrale a été développée pour résoudre les équations élasto-statiques de la FDM pour la détermination des champs mécaniques locaux provenant des densités de dislocations polarisées et des hétérogénéités élastiques présentes dans les matériaux de microstructure supposée périodique et au comportement élastique linéaire. Les champs élastiques sont calculés de façon précise et sans oscillation numérique même lorsque les densités de dislocations sont concentrées sur un seul pixel (pour les problèmes à deux dimensions) ou sur un seul voxel (pour les problèmes à trois dimensions). Ces résultats sont obtenus grâce à l’application de formules de différenciation spatiale pour les dérivées premières et secondes dans l’espace de Fourier basées sur des schémas à différences finies combinées à la transformée de Fourier discrète. Les résultats obtenus portent sur la détermination précise des champs élastiques des dislocations individuelles de types vis et coin, et des champs élastiques d’interaction entre des inclusions de géométries variées et différentes distributions de densités de dislocations telles que les dipôles ou les boucles de dislocations dans un matériau composite biphasé et des microstructures tridimensionnelles. Dans un second temps, une approche spectrale a été développée pour résoudre de façon rapide et stable l’équation d’évolution spatio-temporelle des densités de dislocations dans la théorie FDM. Cette équation aux dérivées partielles, de nature hyperbolique, requiert une méthode spectrale avec des filtres passe-bas afin de contrôler à la fois les fortes oscillations inhérentes aux approches FFT et les instabilités numériques liées à la nature hyperbolique de l’équation de transport. La validation de cette approche a été effectuée par des comparaisons avec les solutions exactes et les méthodes éléments finis dans le cadre de la simulation des phénomènes physiques d’annihilation ou d’extension/annihilation de boucles de dislocations. En dernier lieu, une technique numérique pour la résolution des équations de la PMFDM est développée dans le cadre d’une formulation FFT pour un comportement élasto-visco-plastique avec la prise en compte de la contribution des dislocations géométriquement nécessaires et statistiquement stockées ainsi que des conditions de saut de la distorsion plastique aux interfaces de type joint de grains ou joint de phases. Cette technique est par la suite appliquée à la simulation de la déformation plastique de structures modèles telles que des microstructures périodiques à canaux et des polycristaux métalliques / Fast Fourier transform (FFT)-based methods are developed to solve both the elasto-static equations of the Field Dislocation Mechanics (FDM) theory and the dislocation density transport equation of polarized or geometrically necessary dislocation (GND) densities for FDM and its mesoscopic extension, i.e. the Phenomenological Mesoscopic Field Dislocations Mechanics (PMFDM). First, a numerical spectral approach is developed to solve the elasto-static FDM equations in periodic media for the determination of local mechanical fields arising from the presence of both polarized dislocation densities and elastic heterogeneities for linear elastic materials. The elastic fields are calculated in an accurate fashion and without numerical oscillation, even when the dislocation density is restricted to a single pixel (for two-dimensional problems) or a single voxel (for three-dimensional problems). These results are obtained by applying the differentiation rules for first and second derivatives based on finite difference schemes together with the discrete Fourier transform. The results show that the calculated elastic fields with the present spectral method are accurate for different cases considering individual screw and edge dislocations, the interactions between inhomogeneities of various geometries/elastic properties and different distributions of dislocation densities (dislocation dipoles, polygonal loops in two-phase composite materials). Second, a numerical spectral approach is developed to solve in a fast, stable and accurate fashion, the hyperbolic-type dislocation density transport equation governing the spatial-temporal evolution of dislocations in the FDM theory. Low-pass spectral filters are employed to control both the high frequency oscillations inherent to the Fourier method and the fast-growing numerical instabilities resulting from the hyperbolic nature of the equation. The method is assessed with numerical comparisons with exact solutions and finite element simulations in the case of the simulation of annihilation of dislocation dipoles and the expansion/annihilation of dislocation loops. Finally, a numerical technique for solving the PMFDM equations in a crystal plasticity elasto-viscoplastic FFT formulation is proposed by taking into account both the time evolutions of GND and SSD (statistically stored dislocations) densities as well as the jump condition for plastic distortion at material discontinuity interfaces such as grain or phase boundaries. Then, this numerical technique is applied to the simulation of the plastic deformation of model microstructures like channel-type two-phase composite materials and of polycrystalline metals

To develop a project sizing concrete pavement is necessary to know the mechanical properties and the different treatment processes of material to be used. This study aimed to analyze the mechanical properties such as flexural strenght, compressive strength, indirect tensile strength and static modulus of concrete paving. The three types of concrete were studied: An actual reference (typically used in paving, one with the addition of polypropylene fibers (common practice for floors), and a high strength concrete used to rapidly release the traffic. Different methods of curing were applied: chemical cure with and without the use of wet burlap bags (widely applied in pavements) and curing in a moist chamber (as recommended by standard). This evaluation of the mechanical properties for the concrete studied in different curing methods applied, showed that the microstructure of concrete is significantly interfering with the results, especially in cured concrete to track conditions (chemical cure without and with the placement of burlap sacks). Where factors such as the absorption and reabsorption of water evaporation to cement hydration, cracking the interface folder / aggregate, ambient conditions related to temperature and humidity, are interfering with the tensile strength in bending, compressive strength, indirect tensile strength and particularly in the static modulus and still, from the results obtained in this study and those reported by other authors who studied a high-strength concrete, it is possible to verify that there are particularities still unknown about the behavior of high strength concrete. / Para o desenvolvimento de um projeto de dimensionamento de pavimentos de concreto é necessário conhecer as propriedades mecânicas e os diferentes processos de tratamento do material a ser utilizado. Este trabalho teve por objetivo analisar as propriedades mecânicas, tais como, resistência à tração na flexão, resistência à compressão axial, resistência à tração por compressão diametral e módulo de elasticidade estático em concretos para pavimentação. Foram estudados os três tipos de concretos: um concreto referência, (tipicamente empregado em pavimentação, outro com a adição de fibras de polipropileno (prática comum em pavimentos) e um concreto de alta resistência, utilizado para rápida liberação ao tráfego. Diferentes métodos de cura foram aplicados: cura química com e sem a utilização de sacos de aniagem úmidos (largamente aplicados em pavimentos) e cura em câmara úmida (conforme preconizado por norma). A avalição das propriedades mecânicas para os concretos estudados, nos diferentes métodos de cura aplicados, mostrou que a microestrutura dos concretos, está interferindo de forma significativa nos resultados obtidos, principalmente nos concretos curados para condições de pista (cura química sem e com a colocação de sacos de aniagem), onde fatores como a absorção e reabsorção da água de evaporação para hidratação do cimento, a fissuração da interface pasta/agregado, as condições ambientes relacionadas à temperatura e umidade, estejam interferindo na resistência à tração na flexão, resistência à compressão axial, resistência à tração por compressão diametral e principalmente no módulo de elasticidade estático e ainda, a partir dos resultados obtidos na presente pesquisa e daqueles apresentados por outros autores que estudaram um concreto de alta resistência, é possível verificar que existem particularidades ainda desconhecidas sobre o comportamento do concreto de alta resistência.

Les microgels sont des particules colloïdales de polymère réticulé gonflées par un solvant. Déformables et poreuses, elles peuvent changer d’état de gonflement lors de l’application d’un stimulus. Ce travail de thèse a pour but de développer de nouveaux concepts tirant profit des propriétés stimulables et de la déformabilité intrinsèque des microgels tout en approfondissant les connaissances sur le comportement de ces objets en solution et aux interfaces. Les microgels de poly(N-alkylacrylamide) sont utilisés comme modèles. Dans un premier temps, notre travail a porté sur l’étude d’un nouveau type de microgels électrochimiluminescents grâce à l’incorporation d’un complexe métallique de ruthénium dans la matrice polymère. A la transition de phase, ces microgels présentent une exaltation de l’intensité ECL jusqu’à 2 ordres de grandeur, en lien avec la distance entre les sites redox. Le concept est ensuite transposé à des microgels sensibles aux saccharides et à des systèmes comportant deux luminophores, un donneur ECL et un accepteur d’énergie pouvant donner lieu à un transfert d’énergie par résonance. La deuxième partie de la thèse est consacrée à l’adsorption de microgels à une interface liquide-liquide plane, en vue de mieux comprendre l’origine de la stabilité des émulsions stabilisées par ce genre d’objets. De façon analogue aux protéines flexibles, les microgels changent de conformation à l’interface, passant d’un état étendu à un état comprimé, à l’origine de variations de l’élasticité interfaciale. Les microgels ainsi adsorbés sont fonctionnalisés de façon régiosélective dans l’eau et permettent de produire des microgels non symétriques, dits Janus, susceptibles de s’auto-assembler. / Microgels are colloidal particles made of cross-linked polymer swollen by a solvent. Soft and porous, they can adapt their swelling degree in response to a stimulus. The main objective of this work is to develop new concepts taking advantage of microgels’ stimuli-responsive properties and intrinsicsoftness while deepening understanding of their properties in solution and at interfaces. Poly(Nalkylacrylamide) microgels are used as a model. Initially our work focused on the study of a new type of electrochemiluminescent (ECL) microgels thanks to the incorporation of a ruthenium complex in the polymer matrix. At the volume phase transition, these microgels exhibit an amplification of the ECL intensity up to 2 orders of magnitude, related to the decrease of the distance between redox sites. This concept is then transposed to saccharides-sensitive microgels and systems bearing two luminophores, an ECL donor and an energy acceptor in order to give rise to resonance energy transfer. The second part of this manuscript is devoted to adsorption of microgels at a planar liquid-liquid interface, to improve knowledge on the origin of the stability of emulsions stabilized by such objects. Such as flexible proteins, microgels can change their conformation at the interface, from an extended to a compressed state, causing variation in the interfacial elasticity. When microgels are adsorbed they can also be functionalized regioselectively in water to produce non-symmetrical microgels, called Janus, able to self-assemble.

[pt] No mundo inteiro o Setor Elétrico têm passado por mudanças radicais. A principal meta desse processo de restruturação foi promover a competição nos segmentos de geração, distribuição e comercialização energia elétrica e a participação de agentes privados no processo de produção. Essa reestruturação está baseada em uma otimização centralizada e nas seguintes premissas: Geradores ofertam sua produção em um Mercado Atacadista de Energia - MAE . Os agentes privados são livres para decidir sobre a construção de novas usinas e para competir por contratos de energia vendas com empresas distribuidoras e clientes individuais.O novo ambiente competitivo permite, no entanto, que em cenários de preços spots elevados as empresas Distribuidoras de energia elétrica possam vender as diferenças entre os valores de demanda contratados e consumidos. A possibilidade de retração de carga por meio de negociações com clientes pode resultar em sobras de energia que poderão ser vendidas diretamente no Mercado Spot. Por outro lado, a reação dos Geradores através de instrumentos financeiros adequados (como contratos bilaterais, contratos futuros e de opção) ou de políticas operacionais (via Operador do Sistema) podem resultar em um -jogo- de estratégias no MAE. Esta tese investiga alguns conceitos, metodologias e ferramentas computacionais desenvolvidas para a operação e comercialização da energia elétrica envolvendo análise de riscos e instrumentos financeiros. O problema de gerenciamento e retração forçada da demanda (elasticidade forçada) é decomposto em dois subproblemas:Subproblema de operação: usando programação dinâmica dual estocástica . Subproblema de análise de riscos: usando a teoria da utilidade O modelo proposto é avaliado através de um estudo de caso considerando os dados do sistema interligado Sul-Sudeste, para o qual são simuladas ações de retração da demanda. / [en] Electricity utilities all over the world have been undergoing radical changes in their market and its regulatory structure. A basic trend in this restructuring process has been to promote competition in generation, distribution/retailing segments and participation of private agents in the energy production process. This restructuring is based on centralized optimization, by market-oriented approaches: Generators bid prices for their energy in a Wholesale Energy Market - WEM. Instead of following an expansion schedule produced by a central planning agency, private agents are free to decide about the construction of generator units and to compete for energy sales contracts with utilities and individual customers.The competitive environment permits, however, which in high spot prices scenarios the electric utilities sell some differences between bilateral contract and real consumption. The possibility of load retraction by means of negotiations with clients would result in surplus generation which could be sold directly to the spot market. On the other hand, the reaction of the Generators via financial means (such as bilateral contracts, forward contracts and option prices) or operational policies from System Operator can result in a WEM -gaming-. This thesis investigates some conceptual issues, methodologies and computational tools developed to operation and commercialization of the electrical energy considering risk analysis and financial instruments. The demand side and retraction management problem is decomposed in two sub-problems: Operation sub-problem: uses stochastic dual dynamic programming (SDDP)tools Risk analysis sub-problem: uses utility theoryThe approach will be illustrated with a case study with data taken from the Brazilian system, where the demand side management is simulated and the numerical results are presented.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aim of this study was to evaluate the flexural strength, elastic modulus, mass changes and surface roughness of two cobalt-chromium alloys, before and after immersions in four cleaning solutions and distilled water (as control). Co-Cr alloys (Co-Cr®, Dentsply-DeguDent Industria e Comércio, São Paulo, Brasil; and GM 800+®, Dentaurum GmbH & Co KG, Ispringen, Alemanha) were investigated. Fifty bar specimens (25 x 3 x 0,5 mm) for the flexural test, 50 quadrangular specimens (10 x 10 x 1 mm) for mass changes evaluation and 35 cylindrical specimens (10 x 1 mm) for surface roughness measurements were obtained by casting. They were polished by abrasive paper (#240 to #2500) and diamond polishing paste (3μm). Specimens were randomly divided into 5 groups according the following cleaning, solutions: pure white vinegar, 0.2% peracetic acid, sodium perborate - Corega Tabs®, 0.37% sodium hypochlorite and the control, distilled water. Surface roughness (Ra parameter) was analyzed using a profilometer (Mitutoyo SJ 410, Mitutoyo Corp, Kanagawa, Japan) before and after 5, 20 e 90 immersions (10 min each). Ra changes (ΔRa5, ΔRa20 e ΔRa90) were calculated for the different intervals. Qualitative surface analyses were performed by Scanning Electron Microscope (JSM 6360 SEM, JEOL). Both alloys, immersed in pure white vinegar, 0.2% peracetic acid, sodium perborate - Corega Tabs®, 0.37% sodium hypochlorite had similar roughness changes after 90 immersions (ΔRa from -0,012 to 0,022 μm). There was a significant surface roughening in hypochlorite (ΔRa90= 0,064 μm for CoCr®; and ΔRa90 = 0,592 μm for GM 800+). The number of immersions influenced on the roughness changes only in hypochlorite and there were greater changes in the GM 800+ alloy. After 90 immersions, GM 800+ alloy showed mass lost in the hypochlorite solution (-0,3%). This alloy presented higher flexural strength after 90 immersions in SH (σF= 1516 MPa in hypochlorite; 1366 MPa in control). However, there were no elastic modulus changes. CoCr® alloy did not present differences in the σF or in elastic modulus in any solution. The only solution that damaged the alloy surface was 0.37% sodium hypochlorite. / O objetivo deste trabalho foi avaliar a rugosidade superficial,o percentual de variação de massa, a resistência flexural e o módulo de elasticidade de duas ligas de Cobalto-Cromo após submetidas à imersões em quatro soluções limpadoras e água (controle). Foram utilizadas as ligas Co-Cr® DeguDent (Dentsply-DeguDent Industria e Comércio, São Paulo, Brasil) e Remanium® GM 800+ (Dentaurum GmbH & Co KG, Ispringen, Alemanha). De cada liga fundiu-se cinquenta corpos de prova, 50 cilíndricos (10 x 1 mm) para a análise da rugosidade, 50 quadrangulares (10 x 10 x 1 mm) para avaliação da variação de massa e em formato retangular (25 x 2,5 x 0,75 mm) para o teste flexão 3 pontos. O polimento se deu por seqüencia de lixas (#400 a 2500) e pasta diamantada (3μm). A distribuição aleatória foi em 5 grupos, conforme os agentes de limpeza: vinagre branco puro, ácido peracético 0,2% , perborato de sódio (Corega Tabs®), hipoclorito de sódio 0,37% e o controle: água destilada. Foram realizadas avaliações da rugosidade superficial (Parâmetro Ra) através de rugosímetro (Mitutoyo SJ 410, Mitutoyo Corp, Kanagawa, Japan) antes e após 5, 20 e 90 ciclos de imersão de 10 minutos. As alterações de Ra (ΔRa5, ΔRa20 e ΔRa90) foram calculadas entre os diferentes interrupções. Análise complementar da superfície foi realizada em imagens obtidas por microscopia eletrônica de varredura (JSM 6360 SEM, JEOL Ltd., Tokyo, Japan). A pesagens dos corpos de prova para cálculo da variação de massa se deu após 5 e 90 imersões, utilizando-se de balança eletrônica analítica com sensibilidade de 0,0001 g (FA 2004, Coleman E. P. L. Com. e Imp. Ltda. Santo André, São Paulo). Os ensaios de flexão a 3 pontos para determinação da resistência flexural (σF) e do módulo de elasticidade foram realizados após 90 imersões. Os dados obtitos foram analisados quanto a normalidade e testes de comparação entre médias foram aplicados conforme o tipo de distribuição. As duas ligas, imersas nas soluções vinagre puro, ácido peracético, corega tabs® apresentaram comportamento semelhante em relação as alterações de rugosidade superficial (Ra), quando comparadas ao controle, após 90 imersões (ΔRa entre -0,012 e 0,022 μm). Aumento da rugosidade significativo ocorreu na solução de hipoclorito (ΔRa90= 0,064 μm (CoCr®) e 0,592 μm (GM 800+). O número de imersões influenciou na variação de rugosidade, apenas para a solução de hipoclorito, sendo que as maiores variações ocorreram na liga GM 800+. Após 90 imersões a liga GM 800+ demonstrou perda de massa na solução de hipoclorito (-0,3%). Ocorrendo para essa liga aumento da resistência flexural (σF= 1516 MPa em hipoclorito; 1366 MPa no controle) após 90 imersões, sem modificação de seu módulo de elasticidade. A liga CoCr® não apresentou diferenças na σF ou no módulo de elasticidade nas diferentes soluções. A única solução que causou dano à superfície das ligas foi o hipoclorito de sódio 0,37%.

O Tungstato de Zircônio (ZrW2O8) é um material que exibe Expansão Térmica Negativa (ETN), isotrópica em um amplo intervalo de temperatura (0,3 a 1050 K). Apesar de amplamente estudado, existem controvérsias acerca dos mecanismos microscópicos responsáveis por este comportamento. A fase cúbica deste composto, denominada a-ZrW2O8, já foi motivo de estudo através de simulações computacionais utilizando Potenciais Interatômicos (PI) e Dinâmica de Rede na Aproximação Quasi-Harmônica (DRQH). Nos dois PI distintos propostos na literatura conseguiu-se reproduzir a ETN da a-ZrW2O8, mas não a dependência com a temperatura do tensor de elasticidade. É partindo desta observação que este trabalho pretende avaliar o desempenho de PI existentes e de novos PI em simulações computacionais visando a descrição da dependência com a temperatura do tensor de elasticidade da a-ZrW2O8 entre 0 e 300 K. Utilizaram-se dados experimentais, tais como posições atômicas, parâmetros de rede e o tensor de elasticidade da a-ZrW2O8 em temperaturas entre 0 e 300 K e, em outra série de cálculos, a hipersuperfície de energia ab initio no limite atérmico para obter os parâmetros dos PI. Diferentes estratégias foram empregadas na busca pelos parâmetros dos PI incluindo minimização em linha, Newton-Raphson/BFGS e Algoritmo Genético (AG). Concluiu-se que não é possível descrever as propriedades estruturais e elásticas da a-ZrW2O8 em função da temperatura com PI simples e que esta incapacidade não está relacionada a qualquer limitação da DRQH ou dos parâmetros dos PI, mas à forma analítica dos PI empregados. Isto sugere que se deve ter cautela na interpretação de resultados obtidos com estes potencias já disponíveis na literatura. Como alternativas para a solução deste problema, pode-se considerar o uso de redes neurais para a representação da hipersuperfície de energia ab initio, o uso de PI mais sofisticados que levam em consideração a vizinhança atômica (bond order potentials) e, também, cálculo ab initio a T > 0, este último a um custo computacional muito mais elevado. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-05-28T17:16:32Z No. of bitstreams: 1 Dissertacao Emiliano Chemello.pdf: 1343523 bytes, checksum: 46461698a2b6139def916307ab93478f (MD5) / Made available in DSpace on 2014-05-28T17:16:32Z (GMT). No. of bitstreams: 1 Dissertacao Emiliano Chemello.pdf: 1343523 bytes, checksum: 46461698a2b6139def916307ab93478f (MD5) / Zirconium tungstate (ZrW2O8) is a material that exhibits negative thermal expansion (NTE), over a wide temperature range (0.3 at 1050 K). Although thoroughly studied, controversies still remain concerning the microscopic mechanisms responsible for this behavior. The cubic phase of this compound, denominated a-ZrW2O8, was already the subject of study through computer simulations using interatomic potentials (IP) and lattice dynamics in quasiharmonic approximation (LDQH). In two different IPs proposed in the literature succeeded in reproducing the a-ZrW2O8 NTE, but not the dependence with temperature of the elasticity tensor. Starting from this observation, this work intends to evaluate of existent IPs and same proposed new IPs in computer simulations aiming the calculation of the tensor of elasticity for a-ZrW2O8 between 0 and 300 K. Experimental data (such as atomic positions, lattice parameters and the tensor of elasticity of a-ZrW2O8 at 0 and 300 K) and, in another series of calculations, the ab initio energy hypersurface in the athermic limit, were used to obtain the parameters of the IPs. Different strategies were used in the search for the parameters of IP, including line minimization, Newton-Raphson/BFGS and genetic algorithm (GA). At the end of an exhaustive search we were led to conclude that it is not possible to describe the structure and elastic properties of a-ZrW2O8 as a function of temperature with simple IPs and that this incapacity is not related the any limitation of LDQH or of the parameters of the IPs, but instead to the analytical form of the tested IPs. This suggests that same results obtained with IPs already available in the literature may be unreliable. As alternatives for the solution of this problem, it can be considered the use of a neural network for the representation of the ab initio energy hypersurface, the use of more sophisticated IPs than take into account the atomic neighborhood (bond order potentials) and even (with a computational cost much higher) ab initio calculations at T > 0.