Les générateurs de vapeur des réacteurs à eau pressurisée (REP) sont constitués d'alliage à base nickel. La surface d'échange associée représente environ 75 % de l'aire totale du circuit primaire. Sous l'effet de la corrosion généralisée, des cations nickel sont relâchés dans l'eau de ce circuit. Lorsque ces cations sont exposés au flux neutronique du coeur du réacteur, ils sont activés en éléments radioactifs (58Co). La circulation puis l'incorporation de ces produits de corrosion radioactifs sur les parois du circuit primaire posent alors problème lors des interventions humaines durant les opérations de maintenance.Le but de l'étude présentée ici est de créer par traitement thermomécanique une couche d'oxyde protectrice qui limite fortement le relâchement des cations nickel. L'influence de paramètres tels que la composition de l'atmosphère gazeuse lors du traitement thermique et l'état de surface initial de l'alliage considéré (laminage et rugosité de surface) a été étudiée. Les résultats présentés sont obtenus sur un alliage 690 oxydé à 700 °C sous deux atmosphères gazeuses de pressions partielles en oxygène (P(O2)) différentes.L'étude des cinétiques d'oxydation par analyse thermogravimétrique (ATG), met en avant une cinétique parabolique peu dépendante de la P(O2). Un laminage de 20 % n'affecte pas la cinétique d'oxydation alors qu'un laminage de 40 % et une rugosité de surface plus forte sont responsables d'une prise de masse plus importante. Un marquage à l'or permet de déterminer que la croissance de la couche est majoritairement cationique. L'aspect général de la surface des échantillons oxydés observé par microscopie électronique à balayage (MEB) est similaire quelle que soit la P(O2) : une couche d'oxyde continue d'aspect nanostructuré riche en chrome avec oxydation préférentielle du chrome le long des joints de grains de l'alliage sous-jacent. La spectroscopie de photoélectrons-X (XPS), la spectrométrie à décharge luminescente (SDL) et la diffraction des rayons-X (DRX) mettent en évidence la croissance d'une couche de chromine (Cr2O3) et la présence à l'interface gaz/oxyde de cristallites avec une cristallographie de type spinelle. Pour une faible P(O2) (de 1.10 -6 bar à 5.10 -6 bar) cette partie externe est riche en manganèse (MnCr2O4) alors que des cristallites riches en manganèse, chrome, nickel et en fer viennent s'intégrer dans cette configuration lors d'oxydations sous une P(O2) plus élevée (0,2 bar). L'ensemble des résultats obtenus permet de proposer des conditions de prétraitement sur l'alliage 690. Des échantillons ainsi traités sont testés en milieu primaire simulé et leur relâchement en nickel montre une nette baisse par rapport à des échantillons non traités thermiquement. / Steam generator tubes in pressurized water reactors (PWR) are made of nickel based alloy and represent nearly 75 % of the primary coolant loop surface. Due to generalized corrosion phenomena, nickel cations are released in the primary loop water. After neutron flux exposure in the reactor core, nickel cations can turn into radioactive products, such as 58Co. If carried through the circuit, these radioactive products precipitate and contaminate the loop, making maintenance more difficult.The present study goal is to form a very protective scale on the Alloy 690 surface by a pre-oxidation treatment performed at 700 °C. The impact of different parameters such as oxygen partial pressures of the gaz used during high temperature oxidation (low P(O2)=10 -6 bar or high P(O2)=0.2 bar) and the initial surface state of the sample (cold-worked or surface roughness) is studied. To minimize nickel cation release, the scale obtained must be continuous, homogeneous, rich in chromium and nickel free. The oxidation kinetics, studied using thermogravimetric analysis (TGA), show the existence of parabolic law independent of P(O2). The sample's surface aspect, observed using scanning electron microscopy (SEM), is similar for all P(O2). Top views show a preferential chromium oxidation along the grain boundaries and the formation of a chromium rich oxide scale, confirmed by X-ray photoelectron spectroscopy (XPS) and glow discharge optical emission spectrometry (GDOES); cross sectional views of the material exhibit holes beneath the oxide corresponding with the alloy's grain boundaries. The latter observation and an inert marking test with gold plots suggest a cationic growth of the oxide scale. X-ray diffraction (XRD) indicates the presence of chromia (Cr2O3) for low and high P(O2). For low P(O2), a Mn and Cr spinel is observed near the outer surface. For higher P(O2), a similar spinel layer is made up of Ni, Fe, Mn and Cr.Pretreatment conditions set to be applied on alloy 690 can be proposed thanks to the data collected. Samples, pretreated that way, are tested in simulated primary medium water and their nickel release is clearly cropping compared to non-thermaly-treated samples.

Orientador: Marcelo Fernandes de Oliveira / Banca: Luís Antônio Paulino / Banca: Rafael Villa / Resumo: Na contemporaneidade, as discussões ambientais permeiam a agenda política global. Isso porque as degradações ao meio ambiente possuem impactos que vão além das fronteiras nacionais dos Estados. A interdependência dos países implica em pensar o problema em âmbito transnacional. Entretanto, supomos que a sociedade, com um modelo econômico baseado na ênfase no lucro, não se sensibiliza com a questão ambiental. Nesse contexto, o caso das mudanças climáticas nos comprova que se faz necessária uma articulação que vise a cooperação internacional, pois atitudes isoladas não são suficientes para conter o aquecimento global. Nessa direção, buscamos compreender nesse estudo os motivos que conduziram os países a negociarem um regime internacional do meio ambiente. Em específico, trataremos da criação do Mecanismo de Desenvolvimento Limpo e do estudo empírico da cogeração de energia no setor sucroalcooleiro brasileiro, pois estes vêm sendo apresentados como possíveis alternativas econômicas para a sustentabilidade ambiental e para a mitigação do delicado problema climático que a humanidade terá que enfrentar no século XXI / Abstract: Nowadays, the environment matters take part in the global political agenda. This happens because the environment degenaretion results in impacts that are beyond the state boundaries. The interdependency among the countries incite us necessarily to think about the problem in the internacional ambit. Though, it is supposed that the society based on economical pattern of profit is not sensitive to the enviromental matter. In this context, the climate change issue proves that an articulation focused in the internacional cooperacion is necessary, then isolated attitudes are not enough to hold the global warming. According to this view, this study attempts to comprehend the reasons that led the contries to negociate an internacional regime. Specifically, we deal with the creation of the Clean Development Mecanism and the empirical study of energy cogeneration in sugar and alcohol sector as an economical alternative to sustain the environment and to appease the delicated climate problem that the mankind must face in the twenty-one century / Mestre

A presente Tese tem por objetivo estudar alguns aspectos das interações água-detergente que são importantes para o entendimento das propriedades fisico-químicas da própria micela. além das interações que ocorrem na pseudo-fase micelar. Estas interações foram estudadas utilizando-se duas técnicas: RMN de 1H, para avaliar o efeito de micelas aquosas iônicas, zwitteriônicas e não-iônicas sobre a estrutura da água; e o estudo cinético da hidrólise espontânea de um éster do ácido carbônico, para determinar a reatividade cinética desta água além de, possivelmente, esclarecer alguns aspectos da questão da penetração da água na micela. Foi determinado o efeito da concentração do detergente e a presença de deutério no solvente sobre os deslocamentos químicos dos prótons da água. Foi usada a seguinte série de detergentes: dodecilsulfato de sódio (SOS, aniônico), dodecilbenzenossulfonato de sódio (SDBS, aniônico), perfluoroctanoato de sódio (SPFO, aniônico), cloreto de cetiltrimetilamônio (CTACl, catiônico), éter octilfenil(9,5)polioxietilênico (TX-100) e dodecildimetilamônio-3-propanossulfonato (DDAPS, zwitteriônico). O deslocamento químico dos prótons da água. depende linearmente da concentração de detergente e os coeficientes angulares das retas são sinsíveis à concentração de deutério no solvente. A partir destas correlações foram calculados os fatores de fracionamneto deutério/prótio,φ cujas magnitudes dão uma idéia quantitativa do efeito do detergente sobre a estrutura da água. Para averiguar a origem micelar do fracionamento observado, foram determinados também os fatores de fracionamento para compostos modelos. Estes são constituídos de cadeias carbônicas curtas que não formam agregados mas que possuem os mesmos grupos hidrofílicos dos detergentes. Foram usados os seguintes compostos como modelos: butilsulfato de sódio (modelo para SDS), p-tolouenossulfonato de sódio (modelo para SDBS), perfluorobutirato de sódio (modelo para SPFO) e brometo de butiltrimetilamônio (modelo para CTACl). Os resultados obtidos mostram que estes compostos perturbam pouco a estrutura água e são diminuidores da sua estrutura. Os detergentes, com a excessão de DDAPS e TX-100, claramente aumentam a estrutura da água devido a efeitos eletrorrestritivos. Interações inter e intramoleculares entre os íons do DDAPS resultam numa neutralização interna das cargas e explicam o seu pequeno efeito (aumento) sobre a estrutura do solvente. Nao é fácil oferecer uma explicação simples para a diminuição da estrutura da água na presença de TX-100, pois existe a interferência de fatores cujos efeitos sobre o fracionamento não podem ainda ser avaliados. Entre estes destacamos o enrolamento das cadeias oxietilênicas do detergente. a presença de água fisicamente presa entre estas cadeias e o fato de que a distruibição das moléculas de água entre as unidades de oxietileno não é homogênea. Foram determinadas as constantes de velocidade, os parâmetros de ativação e o efeito isotópico cinético do solvente para a hidrólise independente do pH de carbonato de bis(2,4-dinitrofenila) , na presença de SDS, CTABr, CTACl, TX-100 de cetildimetilamônio-3-propanossulfonato (HDAPS) . O efeito micelar foi analisado em termos da transferência do éster do seio aquoso para água micelar, e do efeito salino acoplado a fatores eletrostáticos das micelas iônicas. Como modelo para o efeito da transferência do meio, a reação foi estudada em misturas de água e acetonitrila. O efeito salino foi avaliado estudando a reação em presença de alguns dos compostos-modelo acima mencionados. Houve mudanças marcantes na entropia e na entalpia de ativação da reação somente em presença de grandes quantidades de acetonitrila no solvente (fração molar de 0,55 a 0,90). O efeito salino foi pequeno. Todos os detergentes, especialmente o SDS, diminuiram velocidade da reação devido a fatores entálpicos desfavoráveis. Para ter uma idéia do sítio da solubilização do éster nas micelas usadas, estudamos o efeito de acetato e decanoato de p-nitrofenila (compostos usados como modelo para CDNF), sobre os deslocamentos químicos dos grupos de cada detergente. Os resultados mostram que o sítio de solubilização destes ésteres não está predominantemente na região da superfície da micela. Os ésteres movimentam-se rapidamente (em relação à escala do tempo da RMN), em todo volume da micela. Efetuamos um cálculo simples mostrando que a penetração da água até os primeiros dois grupos metilênicos pode dar origem a um volume hidratado da micela de mais de 50%. Uma consideração dos parâmetros de ativação, dos resultados de RMN de 1H e do significado do cálculo do volume micelar efetuado, nos levou a concluir que nossos dados cinéticos podem ser explicados sem a necessidade de assumir uma micela extensivamente hidratada, como por exemplo aquela proposta pelo modelo de aglomeração poros (porous cluster model). / Study of micelle-water interactions is relevant to the physical chemistry of the micelle itself, and for a better understanding of the interactions occuring therein. In the present thesis two aspects of these interactions were studied: the effect of the organized assembly on the structure of water at the micellar interface, and on the kinetic reactivity of water as probed by examining the pH-independent (spontaneous) hydrolysis of a carbonate ester. The effect of the following surfactants on the structure of water was studied: sodium dodecylsulphate (SDS, anionic) sodium dodecylbenzene sulphonate (SDBS, anionic), sodium perfluorooctanoate (SPFO, anionic), cetyltrimethylammonium chloride (CTACl, cationic), polyoxyethylene (9.5) octylphenyl ether (TX-100, nonionic), dodecyldimethylammonio-3-propane sulphonate (DDAPS, zwitterionic). The dependence of the chemical shift of the water protons on the surfactant concentration, and on the deuterium content of the solvent was used to calculate the deuterium/protium fractionation factor, φ. The magnitude of the latter (relative to unity, the fractionation factor for bulk water) gives a quantitative idea of the solvent structure perturbation by the micellar pseudophase. In order to ascertain that the observed D/H fractionation is micelle-induced, the fractionation factors for model compounds were also determined. These were short-chain, i.e., non-aggregating compounds bearing the same head-groups as the surfactants. The following model compounds were used: sodium butylsulphate (model for SDS), sodium p-toluenesulphonate (model for SDBS), sodium perfluorobutyrate (model for SPFO) and butyltrimethylammonium bromide (model for CTACl). The following conclusions were drawn from the determined fractionation factors: whereas the short-chain compounds perturb the structure of water only slightly, and are usually water structure breakers, the presence of the micelles clearly enhances the structure of the solvent. Exceptions are zwitterionic DDAPS (marginal structure enhancement) and nonionic TX-100 (water structure decrease). The behavior of the zwitterionic surfactant was explained based on the negligible electrostrictive effect of the micelle due to inter and intramolecular interactions between the head-ions. A simple rationale for the case of TX-100 is not easy because of can complicate such interpretation: the followino factors that coiling of the oxyethylene chains, physical trapping of water between the chains, noneven distribution of the water molecules along the oxyethylene chains. Rate constants, activation parameters, solvent kinetic isotope effect were determined for the pH-independent hydrolysis of 2,4-dintrophenyl carbonate in the presence of SDS, CTABr, CTACl. TX-100 and cetyldimethylammonio-3-propane sulphonate (HDAPS). The micellar effect was analyzed in terms of a transfer Effect, a salt and an electrostatic effect. The first refers to the transfer of the ester form bulk water to \"micellar\" water, and was mimicked by studying the reaction in water-acetonitrile mixtures. Salt effect was evaluated by conducting the hydrolysis in the presence some of the above mentioned short-chain compounds. For the reaction in aqueous acetonitrile the entropy and enthalpy of activation showed sizable changes only at high mole fraction (0.55 to 0.90) of the organic solvent. Salt effect was negligible. The tested detergents, specially SDS, slow the reaction rate due to unfavorable enthalpy. The solubilization site of the ester in the micelles was assesed by 1H NMR. using p-nitrophenyl acetate and decanoate as models. This study showed that the ester in the micelles is not localized at, or very near, to the micelle/water interface, but is rapidly moving (on the NMR time-scale) all over the micellar volume. Analysis of the obtained activation parameters, coupled with the 1H NMR data, and with the result of simple geometric calculation led us to conclude that deep water penetration in the micelle (e.g ., according to the porous cluster model) is not essential to rationalize our data.

O presente trabalho apresenta um estudo sistemático sobre a adsorção e a eletrooxidação do CO sobre eletrodos monocristalinos de platina. A partir da análise das intensidades das bandas integradas e das freqüências do Pt(111)-CO, apresenta-se uma interpretação dos efeitos de acoplamento dipolo-dipolo e de interconversão do COads.. Assim, sobre a Pt(111) os espectros de FTIR in situ mostram que o aumento na razão da intensidade das bandas integradas ACOB/ACOL e nas freqüências do νCOB quando θCO,total diminue é devido à redução do acoplamento dipolo-dipolo entre as moléculas do CO em diferentes sítios e, adicionalmente, à interconversão das formas inclinadas dos COL e COB para a forma do COB. No sentido de explicar esta interconversão, propomos um mechanism baseado nas interações dos orbitais de fronteiras do CO e do metal, associado com a retrodoação de elétrons. Nesse modelo, os deslocamentos das formas inclinadas do COL e do COB em direção à forma do COB são favoráveis provavelmente porque a retrodoação de elétrons, Ptd → CO2π* (LUMO), aumenta quando θCO,total diminui. Experimentos potenciostáticos sugerem que a cinética de nucleação e crescimento é o melhor modelo para descrever a eletrooxidação do CO. Propomos que no potencial de oxidação, ECO oxi. pode existir uma via muito rápida de formação do precursores oxigenados e que este pode lateralmente colidir com as ilhas de CO, impedindo que ocorra a dissipação das ilhas do COads. no potencial de oxidação, ECO oxi.. Apresentamos a evolução do crescimento e da oxidação de sub-monocamada de CO sobre monocristais de platina facetados. Em baixo grau de recobrimento do CO foi observado que a adsorção dessa molécula ocorre sem ocupação preferencial de sítios quinas ou terraças. Assim, sugerimos que a adsorção é um processo randômico e que depois que as moléculas do CO são adsorvidas estas não apresentam apreciáveis deslocamentos a partir de CO-(111) em direção aos sítios CO-(110). Isto significa que depois da adsorção, as moléculas do CO têm um longo tempo de residência ou que apresentam um coeficiente de difusão muito baixo. Mas, para alto grau de recobrimento por CO, os resultados mostram que é possível que laterais interações desempanham importantes papéis na distribuição de ocupação dos sítios e observamos que durante a eletrooxidação, são liberados simultaneamente sítios quinas e sítios terraços. Quanto à pré-oxidação, foi observado que quatro condições experimentais precisam ser satisfeitas para que ela ocorra sobre os monocristais de platina: (i) alto grau de recobrimento por CO; (ii) que a superfície onde oncorre a oxidação do CO tenha defeitos, como sítios quinas (110); (iii) que a camada do CO seja formada sob potenciais mais negativos do que o potencial de carga total zero do metal; (iv) e que exista pequena quantidade de CO dissolvido. As condições (i) e (ii) precisam ser satisfeitas simultaneamente para promover a pré-oxidação do CO; as condições (iii) e (iv) essencialmente contribuem correspondendo à condição (i). Observamos que a magnitude do pre-pico aumenta com o aumento do grau de recobrimento por CO. Então, isto pode ser indicativo que a pré-oxidação não tem relação com a difusão do CO em superfície porque o aumento do grau de recobrimento reduz a probabilidade de difusão em superfície. O modelo de ilhas comprimidas parece ser mais apropriado para descrever a pré-oxidação do CO. / This work presents a systematic study on the CO adsorption and its oxidation at platinum single crystal electrodes. From analysis of integrated band intensity and band frequency position of the Pt(111)-CO interface in acid, it is presented an interpretation of the dipole-dipole coupling effect and surface site inter-conversions of COads.. Thus, on Pt(111), in situ FTIR data show that the increase in both ratio integrated band intensity ACOB/ACOL and frequency of νCOB when θCO,total reduces it is indicative of reduce in dipole-dipole coupling interactions between CO molecules in different surface active sites and a mechanism where the tilted COL and COB in CO pressed adlayer displace or inter-convert in favor of increase of COB concentration. In order to explain that CO interconversion, we propose a mechanism based in frontier molecular orbitals of CO and the orbitals of the metal associated with the electron back bond donation. Thus, the displacement of tilted COL and COB on the surface towards COB is more stable because probably the back bond electron donation, Ptd → CO2π* (LUMO), increase when θCO,total diminishes. Potentiostatic experiments suggest that the nucleation and growth is the better model to describe the CO oxidation. It is proposed here that close to ECO oxi. might there is a fast pathway toward formation of oxygenated species and it might reach the CO islands by side and this hinder the dissipation of COads. islands at ECO oxi.. We report also time evolution studies of low CO adsorption coverage and oxidative stripping on stepped platinum surfaces. In low CO coverage, it was observed that there is no preferential site occupancy for CO adsorption on step or terrace. It is proposed that CO adsorption onto these surfaces is a random process, and after CO adsorption there is no appreciable shift from CO-(111) to CO-(110) sites. This implies that after adsorption, CO molecules either have a very long residence time, or that the diffusion coefficient is much lower than previously thought. But, in high CO coverage, the results show that it is possible that the lateral interaction might play important role in CO site occupancy and it was observed that during the CO electrooxidation the sites released included both terrace (111) and step (110) orientations. Among the CO oxidation a clear CO preoxidation process also occurs. It was observed four experimental conditions which were verified to be fulfilled to promote CO pre-oxidation on platinum single crystal: (i) the CO coverage is should be higher than minimum threshold; (ii) the surface where CO oxidation take place should have defects, such as (110) steps; (ii) the CO monolayer should be formed at potentials below the potential of zero total charge; (iv) and in a small amount of dissolved CO should be present in the electrolyte solution. In both conditions (i) and (ii) are necessary to take place simultaneously to promote CO pre-oxidation, (iii) and (iv) essentially contribute in fulfilling condition (i). It was verified that the magnitude of pre-peak increases with the amount of CO coverage. Thus, this might indicate that the CO pre-oxidation is not having relationship with the CO diffusion on the surface, because the increase of CO coverage diminishes surface diffusion. A picture model of compressed CO islands seems the most to describe CO pre-oxidation.

L'objectif de ce travail a été de comprendre les mécanismes menant à la formation de Nitrure de Gallium monocristallin ( GaN ) sur substrat de silicium par croissance cristalline en configuration Vapeur-Liquide-Solide (VLS), à partir d'une phase liquide de gallium, dans la perspective d'un amélioration ultérieure de la qualité des couches hétéro-épitaxiales de GaN sur silicium destinées aux composants pour l'électronique de puissance.Notre étude s'est concentrée autour de la croissance sur couche-germe 3C-SiC déposée par CVD sur silicium, l'ajout de cette couche intermédiaire permettant d'obtenir des couches de GaN en compression, tout en évitant les interactions chimiques entre le silicium du substrat et le Ga liquide.Une étude expérimentale paramétrique a mis en lumière la sensibilité de la croissance du GaN vis à vis des principaux paramètres de croissance ( température, flux de précurseur azoté ), et en particulier l'influence de ces paramètres sur les proportions des quantités formées des deux polytypes les plus stables du GaN ( 3C-GaN et 2H-GaN ). Nous avons montré, par exemple, qu'une simple variation de 50°C de la température conduit à une variation importante du mode de nitruration des gouttes de gallium, et à un changement radical du polytype majoritaire du GaN formé. Nous avons aussi montré que la croissance cristalline du GaN est très sensible à l'état de surface de la couche-germe CVD de 3C-SiC hétéro-épitaxial. Celle-ci est composée d'une coalescence d'îlots de SiC. Cette morphologie particulière impose sa géométrie quasi-périodique à la distribution des gouttes de gallium et peut favoriser la nucléation du GaN en périphérie des gouttes dans les premiers stades de la croissance.A partir des résultats de cette exploration préliminaire, nous avons pu identifier des conditions de croissance permettant de réaliser une couche quasi-continue de GaN par coalescence de cristallites résultant de la nitruration de gouttes de gallium liquide submicroniques / The aim of this work was to understand the mechanisms that lead to the formation of monocrystalline gallium nitride ( GaN ) on silicon substrate by crystalline growth with the Vapor-Liquid-Solid (VLS) configuration, from a gallium liquid phase, in the perspective of an ulterior improvement of the GaN hetero-epitaxial layers quality on silicon intended for power electronics components. Our study focused on the growth on 3C-SiC seed-layer deposited by CVD on silicon, this layer adding permits to obtain GaN layers in compression with avoiding any interactions between the silicon substrate and the liquid gallium. A parametric experimental study has enlightened the sensitivity of the GaN growth with the growth conditions (the temperature, the flux of the nitrogen precursor) and particularly the influence of the parameters on the ratio of formed quantities of the two most stable GaN polytypes (3C-GaN ou 2H-GaN). We have shown, for example, that a simple variation of 50°C of the temperature permits an important variation of the gallium droplets nitriding mod, and of the GaN preferential polytype. We also showed that the growth of GaN is very sensitive to surface state of the 3C-SiC CVD hetero-epitaxial seed-layer. This one is composed of some SiC coalescing islands. This peculiar morphology imposes its quasi-periodic geometry at the gallium droplet distribution and can favor the GaN nucleation at the droplet periphery during the first stage of the growth. From the results of this preliminary exploration, we were able to identify some growth conditions allowing to obtain an almost continued layer of GaN resulting of the nitriding of submicronic liquid gallium droplets

Les données manquantes sont fréquentes dans les enquêtes et peuvent entraîner d’importantes erreurs d’estimation de paramètres. Ce mémoire méthodologique en sociologie porte sur l’influence des données manquantes sur l’estimation de l’effet d’un programme de prévention. Les deux premières sections exposent les possibilités de biais engendrées par les données manquantes et présentent les approches théoriques permettant de les décrire. La troisième section porte sur les méthodes de traitement des données manquantes. Les méthodes classiques sont décrites ainsi que trois méthodes récentes. La quatrième section contient une présentation de l’Enquête longitudinale et expérimentale de Montréal (ELEM) et une description des données utilisées. La cinquième expose les analyses effectuées, elle contient : la méthode d’analyse de l’effet d’une intervention à partir de données longitudinales, une description approfondie des données manquantes de l’ELEM ainsi qu’un diagnostic des schémas et du mécanisme. La sixième section contient les résultats de l’estimation de l’effet du programme selon différents postulats concernant le mécanisme des données manquantes et selon quatre méthodes : l’analyse des cas complets, le maximum de vraisemblance, la pondération et l’imputation multiple. Ils indiquent (I) que le postulat sur le type de mécanisme MAR des données manquantes semble influencer l’estimation de l’effet du programme et que (II) les estimations obtenues par différentes méthodes d’estimation mènent à des conclusions similaires sur l’effet de l’intervention. / Missing data are common in empirical research and can lead to significant errors in parameters’ estimation. This dissertation in the field of methodological sociology addresses the influence of missing data on the estimation of the impact of a prevention program. The first two sections outline the potential bias caused by missing data and present the theoretical background to describe them. The third section focuses on methods for handling missing data, conventional methods are exposed as well as three recent ones. The fourth section contains a description of the Montreal Longitudinal Experimental Study (MLES) and of the data used. The fifth section presents the analysis performed, it contains: the method for analysing the effect of an intervention from longitudinal data, a detailed description of the missing data of MLES and a diagnosis of patterns and mechanisms. The sixth section contains the results of estimating the effect of the program under different assumptions about the mechanism of missing data and by four methods: complete case analysis, maximum likelihood, weighting and multiple imputation. They indicate (I) that the assumption on the type of MAR mechanism seems to affect the estimate of the program’s impact and, (II) that the estimates obtained using different estimation methods leads to similar conclusions about the intervention’s effect.

Dans ma recherche, je réalise une étude de deux cas cliniques d’enfants, âgés de 9-10 ans qui vivent, l’un dans le non dit de la maladie et l’autre dans le secret de la maladie. Ma problématique est celle-ci : Comment l’enfant infecté vivant dans le non-dit et le secret de la maladie vit cette angoisse de mort dans sa famille ? Comment il se représente sa famille, d’autant plus qu’il vit entre deux cultures. Les outils utilisés sont les dessins, le D 10, les génogrammes et les entretretiens. Je postule, d’une part que selon qu’il sait ou non le nom de sa maladie, l’enfant s’organisera différemment pour se défendre contre cette angoisse de mort. D’autre part, je postule que cette angoisse de mort induit chez ces deux enfants une perturbation de la représentation de la famille. Ce car ces deux enfants, de part leur origine, vivent entre deux cultures et cela génère entre autre des conflits culturels. Mes analyses ont montré, premièrement que l’enfant vivant dans le non dit montre une régression pour se défendre contre l’angoisse de mort. Deuxièmement, l’enfant vivant dans le secret utilise énormément les constructions imaginaires pour se défendre contre l’angoisse de mort. Troisièmement, les conflits familiaux et culturels qui sont présents par le jeu des transmissions, le déni de la maladie et l’omniprésence du secret cristallisent les problèmes. / During my research, I have the conducted a study on two children’s clinical cases, children aged 9-10, one living in a world where no one will speak about the illness and for the other in a world where the illness is a secret. My study is based on the following questions: How is the child infected by the virus, in both cases on the non spoken world and the secret world, living the anguish of death within their families ? How is that translated into the way they live within the family, particularly because they live between two cultures. Tools used are: drawing, D10, genograms and interviews. I propose that, depending whether or not he knows the name of his illness, the child will handle himself differently as he finds a way to defend against the anguish and anxiety of death. I also propose that living with this anguish of death will lead to a disruption in the way they live within their families. Based upon their different origins, the roots of these children living between two cultures, this can already generate differences and cultural conflicts. My analysis shows, first of all that the child living in the unspoken presents a regression in his fight against the anguish of death. Secondly, the child living in the secret builds many imaginary situations in order to fight this worry and anguish of death. Thirdly, the family and cultural conflicts present here by the game of transmissions, the denial of the illness and the omnipresence of the secret, crystallize the problems.

Les données manquantes sont fréquentes dans les enquêtes et peuvent entraîner d’importantes erreurs d’estimation de paramètres. Ce mémoire méthodologique en sociologie porte sur l’influence des données manquantes sur l’estimation de l’effet d’un programme de prévention. Les deux premières sections exposent les possibilités de biais engendrées par les données manquantes et présentent les approches théoriques permettant de les décrire. La troisième section porte sur les méthodes de traitement des données manquantes. Les méthodes classiques sont décrites ainsi que trois méthodes récentes. La quatrième section contient une présentation de l’Enquête longitudinale et expérimentale de Montréal (ELEM) et une description des données utilisées. La cinquième expose les analyses effectuées, elle contient : la méthode d’analyse de l’effet d’une intervention à partir de données longitudinales, une description approfondie des données manquantes de l’ELEM ainsi qu’un diagnostic des schémas et du mécanisme. La sixième section contient les résultats de l’estimation de l’effet du programme selon différents postulats concernant le mécanisme des données manquantes et selon quatre méthodes : l’analyse des cas complets, le maximum de vraisemblance, la pondération et l’imputation multiple. Ils indiquent (I) que le postulat sur le type de mécanisme MAR des données manquantes semble influencer l’estimation de l’effet du programme et que (II) les estimations obtenues par différentes méthodes d’estimation mènent à des conclusions similaires sur l’effet de l’intervention. / Missing data are common in empirical research and can lead to significant errors in parameters’ estimation. This dissertation in the field of methodological sociology addresses the influence of missing data on the estimation of the impact of a prevention program. The first two sections outline the potential bias caused by missing data and present the theoretical background to describe them. The third section focuses on methods for handling missing data, conventional methods are exposed as well as three recent ones. The fourth section contains a description of the Montreal Longitudinal Experimental Study (MLES) and of the data used. The fifth section presents the analysis performed, it contains: the method for analysing the effect of an intervention from longitudinal data, a detailed description of the missing data of MLES and a diagnosis of patterns and mechanisms. The sixth section contains the results of estimating the effect of the program under different assumptions about the mechanism of missing data and by four methods: complete case analysis, maximum likelihood, weighting and multiple imputation. They indicate (I) that the assumption on the type of MAR mechanism seems to affect the estimate of the program’s impact and, (II) that the estimates obtained using different estimation methods leads to similar conclusions about the intervention’s effect.

Molts sistemes mecànics existents tenen un comportament vibratori funcionalment perceptible, que es posa de manifest enfront d'excitacions transitòries. Normalment, les vibracions generades segueixen presents després del transitori (vibracions residuals), i poden provocar efectes negatius en la funció de disseny del mecanisme.El mètode que es proposa en aquesta tesi té com a objectiu principal la síntesi de lleis de moviment per reduir les vibracions residuals. Addicionalment, els senyals generats permeten complir dues condicions definides per l'usuari (anomenats requeriments funcionals). El mètode es fonamenta en la relació existent entre el contingut freqüencial d'un senyal transitori, i la vibració residual generada, segons sigui l'esmorteïment del sistema. Basat en aquesta relació, i aprofitant les propietats de la transformada de Fourier, es proposa la generació de lleis de moviment per convolució temporal de polsos. Aquestes resulten formades per trams concatenats de polinomis algebraics, cosa que facilita la seva implementació en entorns numèrics per mitjà de corbes B-spline. / Many mechanical systems have a vibratory behavior, functionally noticeable, which can be raised when transient excitations happen. Usually, such generated vibrations remain in the system after this transient (residual vibrations), and may imply negative effects in the mechanism's intended function.The method proposed in this thesis has as main objective, the synthesis of excitation signals for mechanical systems in order to reduce residual vibrations. In addition, generated signals are able to achieve two conditions defined by the user related to function of the mechanism (called functional requirements). This method is based on the relationship between the frequency contents of the transient signal and the residual vibration generated, depending on the system damping. From this relation, and taking advantage of the Fourier transform properties, motion laws are generated through the pulses' time convolution. Resultant laws are made up of algebraic polynomial pieces linked together, which makes them very suitable for implementation with numerical calculus through B-spline curves.

Made available in DSpace on 2014-06-11T19:29:47Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-28Bitstream added on 2014-06-13T18:59:33Z : No. of bitstreams: 1 faccin_gm_me_mar.pdf: 1354599 bytes, checksum: 8327460599738c8c2021f924afea272f (MD5) / Na contemporaneidade, as discussões ambientais permeiam a agenda política global. Isso porque as degradações ao meio ambiente possuem impactos que vão além das fronteiras nacionais dos Estados. A interdependência dos países implica em pensar o problema em âmbito transnacional. Entretanto, supomos que a sociedade, com um modelo econômico baseado na ênfase no lucro, não se sensibiliza com a questão ambiental. Nesse contexto, o caso das mudanças climáticas nos comprova que se faz necessária uma articulação que vise a cooperação internacional, pois atitudes isoladas não são suficientes para conter o aquecimento global. Nessa direção, buscamos compreender nesse estudo os motivos que conduziram os países a negociarem um regime internacional do meio ambiente. Em específico, trataremos da criação do Mecanismo de Desenvolvimento Limpo e do estudo empírico da cogeração de energia no setor sucroalcooleiro brasileiro, pois estes vêm sendo apresentados como possíveis alternativas econômicas para a sustentabilidade ambiental e para a mitigação do delicado problema climático que a humanidade terá que enfrentar no século XXI / Nowadays, the environment matters take part in the global political agenda. This happens because the environment degenaretion results in impacts that are beyond the state boundaries. The interdependency among the countries incite us necessarily to think about the problem in the internacional ambit. Though, it is supposed that the society based on economical pattern of profit is not sensitive to the enviromental matter. In this context, the climate change issue proves that an articulation focused in the internacional cooperacion is necessary, then isolated attitudes are not enough to hold the global warming. According to this view, this study attempts to comprehend the reasons that led the contries to negociate an internacional regime. Specifically, we deal with the creation of the Clean Development Mecanism and the empirical study of energy cogeneration in sugar and alcohol sector as an economical alternative to sustain the environment and to appease the delicated climate problem that the mankind must face in the twenty-one century