Background: Nutritional deficiencies are frequent in celiac disease (CeD), and one of the most common is zinc (Zn) deficiency. Supplements are often prescribed to treat Zn deficiency; however, they have been associated with adverse events and reduced absorption of other minerals. Data collected in our clinic showed that 38% of CeD patients would opt for a diet to improve Zn, however, such a diet may be challenging due to food interactions with phytic acid, which blocks Zn absorption. Therefore, the feasibility and efficacy of a Zn-optimized diet compared to supplementation is unknown. Aims: To assess the feasibility of the protocol and collect data on estimated effect sizes for secondary outcomes to plan a properly powered randomized controlled trial (RCT). Methods: We conducted an open-label, pilot RCT. CeD patients were randomized to Zn supplementation (Zn gluconate 25mg) or a Zn-optimized diet for 3 months and followed up with a 3-month pragmatic approach. We evaluated enrollment rates and adherence to both interventions. Plasma and urine Zn, stool samples, and questionnaires were collected pre- and post-intervention. Results: We enrolled 28 participants and 16 of them have completed the study. Interim analysis shows an enrollment fraction of 26% (i.e. 28/108 eligible participants), and a dropout rate of 17.9%. Eighty-two % of participants allocated to the Zn-supplement intervention and 50% in the dietary intervention were compliant at 3 months. Based on the effect size for normalization of plasma Zn at 3 months, 142 participants are required for an adequately powered RCT in the future. There were no significant differences in gastrointestinal or extra-intestinal symptoms, quality of life, anxiety and depression or adverse events between interventions. Conclusion: Based on this preliminary analysis, recruitment of participants will take 6 months longer than expected. Assessment of reasons for diet non-adherence will allow implementation of strategies to improve feasibility. / Thesis / Master of Science in Medical Sciences (MSMS)

The complex refractive index is reported at room temperature for CdxZn1_xO thin film alloys for Cd composition up to 0.16. The CdxZn1_xO epilayers were grown by molecular-beam epitaxy on smooth ZnO/GaN/sapphire lattice templates. Transmission spectra were recorded by spectrophotometry in the 350-800nm wavelength range. The refractive index and extinction coefficient were derived by an evolutionary algorithm, which optimizes the Sellmeier and Forouhi-Bloomer dispersion models by a least-squares fitting to the experimental data.

Le but de cette thèse était d’étudier la dynamique de croissance par pulvérisation par plasma RF magnétron des couches minces à base d’oxyde de zinc destinées à des applications électroniques, optoélectroniques et photoniques de pointe. Dans ce contexte, nous avons mis au point plusieurs diagnostics permettant de caractériser les espèces neutres et chargées dans ce type de plasmas, notamment la sonde électrostatique, la spectroscopie optique d’émission et d’absorption, ainsi que la spectrométrie de masse. Par la suite, nous avons tenté de corréler certaines caractéristiques physiques de croissance des couches de ZnO, en particulier la vitesse de dépôt, aux propriétés fondamentales du plasma. Nos résultats ont montré que l’éjection d’atomes de Zn, In et O au cours de la pulvérisation RF magnétron de cibles de Zn, ZnO et In2O3 n’influence que très peu la densité d’ions positifs (et donc la densité d’électrons en supposant la quasi-neutralité) ainsi que la fonction de distribution en énergie des électrons (populations de basse et haute énergie). Cependant, le rapport entre la densité d’atomes d’argon métastables (3P2) sur la densité électronique décroît lorsque la densité d’atomes de Zn augmente, un effet pouvant être attribué à l’ionisation des atomes de Zn par effet Penning. De plus, dans les conditions opératoires étudiées (plasmas de basse pression, < 100 mTorr), la thermalisation des atomes pulvérisés par collisions avec les atomes en phase gazeuse demeure incomplète. Nous avons montré que l’une des conséquences de ce résultat est la présence d’ions Zn+ suprathermiques près du substrat. Finalement, nous avons corrélé la quantité d’atomes de Zn pulvérisés déterminée par spectroscopie d’émission avec la vitesse de dépôt d’une couche mince de ZnO mesurée par ellipsométrie spectroscopique. Ces travaux ont permis de mettre en évidence que ce sont majoritairement les atomes de Zn (et non les espèces excitées et/ou ioniques) qui gouvernent la dynamique de croissance par pulvérisation RF magnétron des couches minces de ZnO. / The goal of this thesis was to study the growth dynamics of zinc oxide based thin films by RF magnetron sputtering plasmas for advanced electronic, optoelectronic, and photonic applications. In this context, we have developed several diagnostics to characterize neutral and charged species in such plasmas, in particular electrostatic probe, optical emission and absorption spectroscopy, as well as plasma sampling mass spectrometry. Afterward, we have tried to correlate specific physical characteristics of as-grown ZnO thin films, in particular the deposition rate, to fundamental plasma properties. Our results have shown that the ejection of Zn, In and O atoms during the RF magnetron sputtering of Zn, ZnO and In2O3 targets does not significantly influence the number density of positive ions (and thus the electron density assuming quasi-neutrality) as well as the electron energy distribution function (populations of low and high energy). However, the ratio of the number density of metastable argon atoms (3P2) to the electron density decreases with increasing concentration Zn atoms; a feature that can be ascribed to Penning ionization of RF sputtered Zn atoms. Furthermore, over the range operating conditions examined in this study (low-pressure plasmas), the thermalization of sputtered atoms by collisions with atoms in the gas phase remains incomplete. We have shown that one of the consequences of this result is the presence of suprathermic Zn+ ions near the target. Finally, we have correlated the quantity of sputtered Zn atoms determined by optical emission spectroscopy with the deposition rate of ZnO thin films measured by spectroscopic ellipsometry. This set of data lead us to the conclusion that mainly Zn atoms (and not excited and/or ionic Zn species) govern the growth dynamic of ZnO-based thin films during magnetron sputtering in argon RF plasmas.

Les gisements de sulfures massifs encaissés dans les massifs hercyniens marocains des Jebilets et Guemassa sont de type (VMS) déformés et métamorphisés. Il manque toutefois une évaluation de la contribution de cette déformation à leur structuration actuelle, et l’éventuel impact de celle-ci sur le plan économique et en termes d’exploration. Par conséquent, cette contribution vise principalement à définir le contexte structural de ces minéralisations, en vue d’en déduire un modèle structural relatif au VMS de Hajjar.Le VMS de Hajjar, appartenant au domaine des Guemassa (Meseta occidentale). Il est encaissé dans des terrains d’origine volcanosédimentaire composés de pélites, de grès et de lentilles et barres calcaires intrudés par des sills et dykes felsique et basique. Les principaux corps volcaniques correspondent aux dômes rhyolitiquesLe gisement de Hajjar est composé de 3 corps minéralisés : le corps principal (CP), le corps Nord-Est (CNE) et les corps ouest et extrême ouest descenderie (CWD, CEWD). Le gisement de Hajjar est affecté par un seul plan XY d’aplatissement subvertical de directions N0 à N45. L’encaissant et les corps sulfurés présentent les mêmes assemblages métamorphiques silicatés, qui présentent soit une texture granoblastique « statique » lorsque la déformation est faible, soit des caractéristiques prés à syn-tectoniques lorsque la schistosité est fortement exprimée. La texture, les formes des biotites et d'andalousites (± cordiérite suspectée) sont typiques du métamorphisme de contact HT / BP des faciès de cornéennes. L'assemblage syntectonique est composé de quartz + chlorite + micas blancs (± calcite), et remplace partiellement les anciennes biotites et andalousites. Les données de surface du bloc N'Fis montrent la présence d'un seul plan XY subvertical orienté N130. Les biotites du métamorphisme de contact sont allongées parallèlement à la schistosité. L’ensemble des données indiquent que le VMS de Hajjar et le bloc N'Fis sont affectés par une seule schistosité qui est synchrone d’un métamorphisme de contact de HT / BP. La virgation importante de la schistosité des affleurements d'Imarine au VMS de Hajjar est dû à une importante zone de cisaillement - transpressive de direction ENE-WSW. Près de la mine Hajjar, une telle zone de cisaillement à l’échelle régionale est reconnue pour la première fois, et constitue une caractéristique structurale-clé du district de Hajjar.La minéralisation de Hajjar est fortement déformée et métamorphisée. Elle est affectée par le plissement, la schistosité et la mylonitisation dans un contexte cisaillant. Les structures minéralisées stratiformes sous forme de rubans riches en pyrrhotite précèdent clairement la déformation et le métamorphisme de contact. D’autres structures minéralisés riche en (Zn, Cu, Pb) présentent un rubanement tectonique issu de la remobilisation par fluide de la minéralisation précoce Le stade précoce est caractérisé par la précipitation de la pyrrhotite, pyrite, arsénopyrite, sphalérite et la galène, alors que le stade syncinématique constitue l’événement concentrateur majeur caractérisé par la dissolution et la recristallisation de la paragenèse précoce avec un enrichissement en Zn, Cu. Le stade tardif post-cinématique est responsable la néoformation de sulfures, à savoir la chalcopyrite, la pyrite et quelques traces de sphalérite.Nous avons mis en évidence un épaississement tectonique dans les zones de charnières. Le métamorphisme pré à syntectonique favorise le comportement ductile et la recristallisation des sulfures (Po, Cpy et Sph). Les veines triangulaires polymétalliques à l'extrémité des lentilles de sulfures massifs sont le témoin d'une remobilisation hydrothermale assistée par un fluide pendant la déformation. L’ensemble de nos études débouche sur la proposition d’un modèle 3D tectonométamorphique pour le VMS des Guemassa et des propositions pour rechercher des extensions de la minéralisation. / The massive sulphide deposits hosted in the Moroccan Hercynian massifs of Jebilets and Guemassa are Volcanogenic Massive Sulfide (SMV), deformed and metamorphosed. However, an assessment of the contribution of this deformation to their current structure and the eventual impact on the economy and in terms of exploration is missing. Therefore, this contribution aims mainly to define the structural context of these mineralizations, in order to deduce a structural model relating to Hajjar's VMS.The VMS of Hajjar, belonging to the domain of Guemassa (Western Meseta). It is hosted in volcanosedimentary terrain composed of pelites, sandstones and lentils and limestone bars intruded by felic and basic sills and dykes. The main volcanic bodies correspond to the rhyolitic plugs.The Hajjar deposit is composed of 3 mineralized bodies: main body (CP); north-eastern body (CNE); western body (CWD) and extreme western body(CEWD.). The Hajjar deposit is affected by a single XY plane of subvertical flattening of directions N0 to N45. The host rock and sulphide bodies have the same silicate metamorphic assemblages, which exhibit either a "static" granoblastic texture when the strain is low or pre to syn-tectonic features when the foliation is strongly expressed. The texture shapes, and aggregates of the biotite and andalousite (± suspected cordierite) are typical of HT/LP “contact” metamorphism in the hornfels facies. The syn-tectonic assemblage is composed of quartz + chlorite + white micas (± calcite) and partially replaced the former biotite and andalousite blasts. The data from the N’Fis block show the occurrence of a single sub-vertical XY plane oriented N130. The biotites of contact metamorphism are elongated parallel to the foliation. These data imply that the Hajjar MSD and the N’Fis block are affected by a single foliation which encompasses a HT/LP contact metamorphism. The significant inflexion of foliation from Imarine outcrops to Hajjar VMS is due to major right-lateral ENE-trending transpressive shear zone at Hajjar. Near the Hajjar mine, such a regional shear zone is recognized for the first time, and is a structural key feature of the Hajjar district.The mineralization of Hajjar is strongly deformed and metamorphosed. It is affected by folding, foliation and mylonitic bands within a regional scale shear zone. Structures such as pyrrhotite-rich ribbons clearly pre-date the deformation and the HT/LP contact metamorphism. The early stage is characterized by the precipitation of pyrrhotite, pyrite, arsenopyrite, sphalerite, and galena, whereas the synkinematic stage constitutes major concentrator event characterized by the dissolution and recrystallization of early paragenesis with enrichment in Zn, Cu. The late post-kinematic stage is responsible for the neoformation of sulphides, namely chalcopyrite, pyrite and some traces of sphalerite.We have demonstrated a tectonic thickening within the fold hinge zone. pre-syntectonic metamorphism favors ductile behavior and sulfide recrystallization (Po, Cpy, and Sph). The polymetallic veins argue for hydrothermal fluid-assisted remobilization during deformation. All of our studies lead to the proposal of a 3D tectono-metamorphic model for the VMS of Guemassa and proposals to search extensions of the mineralization.

Ces dernières années, les besoins en électronique de puissance s’orientent vers la miniaturisation globale des cartes électroniques, parallèlement à une augmentation des puissances de travail. C’est dans ce contexte que s’inscrivent les travaux de cette thèse, principalement axée sur l’élaboration, l’amélioration des performances et l’intégration de composants passifs (inductances, transformateurs…) en électronique de puissance.Les matériaux choisis pour remplir les fonctions magnétiques de ces composants dans leurs conditions de travail sont les ferrites NixZn1-xFe2O4 (0<x<1). Du cuivre est ajouté pour diminuer la température de frittage, de plus de 1200 °C à moins de 950°C, permettant le cofrittage avec un métal conducteur, et du cobalt pour diminuer les pertes totales en puissance du ferrite formé. La formulation finale devient alors (NixZnyCuz)1-εCoεFe2-δO4 (x+y+z=1). Enfin, de l’oxyde de bismuth Bi2O3 est ajouté comme fondant pour abaisser encore la température de frittage et éviter les problèmes de diffusion.Après une étude bibliographique, les travaux se sont orientés selon différents axes. Il s’agissait tout d’abord d’optimiser la formulation du ferrite pour élaborer des échantillons aux propriétés électromagnétiques et physicochimiques ciblées. Cet axe de travail regroupe de nombreuses études sur la formulation des ferrites Ni-Zn-Cu-Co, parmi lesquelles les principales sont l’étude de l’influence de la stœchiométrie en fer, du rapport Ni/Zn dans la formulation et du procédé d’ajout de cobalt selon son taux. Ces travaux ont permis de mettre en évidence qu’un léger défaut de fer maîtrisé (~Fe1,98) pouvait améliorer les propriétés et les performances de ces ferrites. L’étude de l’influence du rapport Ni/Zn a permis la réalisation de ferrites à perméabilités très faibles, de 40 à 135, et aux bonnes performances en puissance. Les résultats de cette étude ont été publiés dans le Journal of the Japan Society of Powder and Metallurgy. Tout au long de la thèse, l’élaboration d’échantillons céramiques, base incontournable de chaque étude, a été réalisé au laboratoire, comme la plupart des tests et caractérisations. Ces derniers peuvent être microstructuraux et physicochimiques (DRX, MEB, BET, ATD/ATG…), ou électromagnétiques (mesures d’aimantation, de perméabilité, de pertes en puissances, etc…).La finalité de ces travaux étant l’intégration de puissance, cette dernière représente le second axe majeur, et regroupe également de nombreuses études, parmi lesquelles les principales sont les études des influences du bobinage sur les pertes d’un composant de type inductance et de l’entrefer (espacement amagnétique au sein du circuit magnétique), classiquement utilisé pour diminuer la perméabilité apparente, non sans conséquence sur les performances en puissance. Une campagne de mesures de pertes totales a également été réalisée dans l’objectif de dégager des lois comportementales sur la variation de ces pertes en puissance et en fréquence.Tous ces travaux et leurs résultats sur le matériau ferrite, son utilisation en électronique de puissance, et une bonne maîtrise du procédé d’élaboration (notamment multicouche), ont permis la réalisation de microcomposants passifs intégrables, aux propriétés ciblées et aux très bonnes performances (pertes diminuées d’un facteur 6 à 10 par rapport au commerce). / In recent years, power electronics needs are moving towards the global miniaturization of electronic boards, and an increase of the working powers. The works performed during this thesis, mostly oriented on the elaboration, the performances improvement and the integration of passive components (inductors, transformers…) in power electronics, are inscribed in this context.The materials chosen to perform the magnetic functions of those components in their work conditions are the NixZn1-xFe2O4 (0<x<1) ferrites. Copper is added to reduce the firing temperature, from more than 1200 °C to less than 950 °C, allowing cofiring with a conducting metal, and cobalt is added to reduce the power core losses of the sintered ferrite. The final formulation then becomes (NixZnyCuz)1-εCoεFe2-δO4 (x+y+z=1). Finally, bismuth oxide Bi2O3 is added as a sintering aid to lower even more the sintering temperature and avoid diffusion problems.After a bibliographic study, the works were oriented along different axes. Firstly, the ferrite formulation was optimized to elaborate samples with targeted electromagnetic and physicochemical properties. This working axis gathers numerous studies on the Ni-Zn-Cu-Co ferrites formulation, among which the main ones are the study of the influence of iron stoichiometry, the Ni-Zn ratio in the formulation and the cobalt adding process and level. These studies have shown that a light and controlled iron deficiency (~Fe1,98) could improve the properties and the performances of these ferrites. The study of the influence of the Ni/Zn ratio allowed the production of very low permeability ferrites, from 40 to 135, with good power performances. Its results were published in the Journal of the Japan Society of Powder and Metallurgy. Throughout this thesis, the elaboration of ceramic samples, the essential basis of every study, was undertaken at the laboratory, as most of the tests and characterizations. These can be microstructural and physicochemical (XRD, SEM, BET, TDA/TGA…), or electromagnetic (magnetization and permeability measurements, power losses…).The final purpose of this work is power integration, and it represents the second main axis. It also gathers many studies, among which the main ones are the study of the influence of the winding on the losses of an inductor-type component and the influence of the air gap, commonly used to reduce the apparent permeability, not without consequences on the power performances. A total losses measurement campaign has also been undertaken in order to bring out behavioral laws on core losses variation according to induction and frequency.All this work and the results on the ferrite material, his power electronic application, and a good control of the elaboration process (multilayer especially), allowed the production of passive micro-components for integration, with targeted properties and very high performances (core losses reduced by 6 to 10 relative to commercial materials).

As altas concentrações de aerossol fino e ultrafino observadas na atmosfera de áreas urbanas possuem um importante papel no clima local e global, devido sua interação com a radiação solar e também pela característica de formação dos núcleos de condensação de nuvens (CCN). Essas altas concentrações de partículas são responsáveis pela poluição do ar, atualmente considerada como o principal problema ambiental para a saúde pública no mundo, sendo relacionada ao câncer, doenças respiratórias, cardiovasculares e o mal de Alzheimer. Nesse contexto, o presente trabalho almejou a caracterização e discriminação de fontes poluentes para o aerossol atmosférico da cidade de São Paulo, utilizando os isótopos de Pb, Zn e Cu simultaneamente. Além disso, nesse estudo também foi realizada a avaliação do efeito das fontes locais e remotas para a ativação do CCN na atmosfera dessa região. São Paulo é a maior cidade da Região Metropolitana de São Paulo (RMSP), que por sua vez é a maior megacidade da América do Sul, e está entre as dez maiores do mundo. Amostras de aerossol urbano foram coletadas no inverno de 2013 e verão de 2014 na cidade de São Paulo. Ao mesmo tempo foram coletadas, em São Paulo e Cubatão, amostras de fontes poluentes importantes para a RMSP, como aquelas relacionadas ao tráfego veicular (combustíveis, pneu, poeira de rua e aerossol de túnel), construção civil (cimento) e à área industrial de Cubatão (aerossol). Adicionalmente, foram medidas no inverno de 2014 a concentrações de CCN, a distribuição por tamanho e a concentração em número das partículas. As determinações das composições isotópicas de Pb, Zn e Cu foram realizadas com um novo procedimento analítico, desenvolvido para a separação sequencial e purificação desses elementos, a partir de uma mesma solubilização de amostra, seguida pelas análises por espectrometria de massas empregando MC-ICP-MS e TIMS. A validação da exatidão e precisão desse procedimento foi realizada pela análise de amostras de materiais de referência, aerossol e fontes poluentes. Com base nos dados isotópicos das fontes poluentes, o tráfego veicular foi diferenciado da área industrial de Cubatão utilizando as assinaturas isotópicas de Pb dessas fontes, que demonstraram grande reprodutibilidade quando comparadas com estudos anteriores. Adicionalmente, as assinaturas isotópicas da poeira de rua e dos pneus foram discriminadas das emissões veiculares em um diagrama \'delta\'66ZnJMC vs 206Pb/207Pb. As assinaturas isotópicas de Zn e Cu da poeira de rua, emissões veiculares e cimento foram discriminadas em um diagrama \'delta\'65CuNIST vs \'delta\'66ZnJMC. As contribuições das fontes para as composições isotópicas de Pb e Zn, determinadas no aerossol da cidade de São Paulo, foram quantificadas utilizando modelos de mistura ternária. Nesses modelos o tráfego veicular (57 a 66%) foi predominante, seguido pela fonte não-caracterizada (25 a 32%), que mostrou uma assinatura isotópica de Pb e Zn específica observada nas duas campanhas. A área industrial de Cubatão apresentou contribuições de 11 a 17%, enquanto a poeira de rua contribuiu em até 18% para as assinaturas de Pb e Zn no aerossol. No inverno de 2014, o tráfego veicular local, o sal marinho e a queima de biomassa foram identificadas nas amostras de aerossol por análises de PMF, trajetórias de massas de ar e pelo sistema lidar. Também foram observados eventos de formação de aerossol secundário em 35% dos dias de medição. A ativação de CCN foi menor durante o dia em relação ao período noturno, sendo esse padrão associado principalmente as emissões do tráfego veicular local. Comparando os dias com contribuições das fontes remotas, pôde-se concluir que o material particulado proveniente do tráfego veicular durante o dia mostrou o maior efeito nos parâmetros de ativação de CCN em comparação com as fontes remotas de sal marinho e queima de biomassa. / Fine and ultrafine aerosol particles in high concentrations found in the atmosphere of urban areas, play an important role in local and global climate through interaction with solar radiation and cloud condensation nuclei (CCN) formation. These high concentrations of particles are related to the air pollution, which is the major environmental problem to the public health in the world, related with cancer, cardiovascular, respiratory and Alzheimer diseases. In this context, this study reports the simultaneous use of Pb, Zn and Cu to characterize and discriminate pollutant sources of the atmospheric aerosol from São Paulo City and evaluate the effect of local and remote sources to CCN activation in the atmosphere of this area. São Paulo is the main city of Metropolitan Area of São Paulo (MASP), which is the largest megacity in South America and rank among the ten most populous in the world. Urban aerosol samples were collected during winter of 2013 and summer of 2014 in the São Paulo city. At the same time, samples of the main pollutant sources of MASP, were sampled in São Paulo and Cubatão, such as vehicular traffic (fuels, tyres, road dust and tunnel aerosol), construction (cement) and aerosol from Cubatão industrial area. In addition, CCN concentrations, particle number concentrations and size distributions were measured during the winter of 2014 in the same sampling site. The Pb, Zn and Cu isotopic composition were determined by a new analytical procedure, developed to sequential separation of these elements, using a unique sample dissolution, followed by mass spectrometry analysis by MC-ICP-MS and TIMS. Analytical procedure validation of Accuracy and precision was carried with reference materials, aerosol and pollutant source samples. Based on isotopic data obtained on the pollutant sources, vehicular traffic was differentiated from Cubatão industrial area, using Pb isotopic fingerprints of this sources, which showed long term reproducibility when compared with previous studies. In addition, road dust and tyre isotopic signatures were discriminated from vehicular emissions in a \'delta\'66ZnJMC vs 206Pb/207Pb four isotope plot. Interestingly, Zn and Cu isotopic fingerprints of road dust, vehicular emission and cement was distinguished in a \'delta\'65CuNIST vs \'delta\'66ZnJMC four isotope plot. In order to quantify contributions of sources to Pb and Zn isotopic compositions determined in aerosol from São Paulo city, ternary mixing models were performed. In these models, vehicular traffic accounted to the main contribution (57 to 66%), followed by non-characterized source (25 to 32%), with a specific Pb and Zn isotopic signature identified in aerosol during the two campaigns. Cubatão industrial area showed contributions of 11 to 17%, whereas road dust contributed 18% to Pb and Zn isotopes in aerosol. In the winter of 2014, local vehicular traffic, sea salt and biomass burning were identified in aerosol by PMF, air masses trajectories and lidar analysis. Some new particle formation (NPF) events were identified on 35% of the sampling days. CCN activation was lower during the daytime compared to nightime periods, a pattern that was found to be associated mainly with local road-traffic emissions. Comparing the days with remote sources events, we concluded that particulate matter from local vehicular emissions during the daytime have a greater effect on CCN activation parameters than that from sea salt and biomass burning remote sources.

The effect of individual additions of calcium oxide (CaO), Gd, Nd and Y was investigated on the microstructure, mechanical properties and corrosion resistance of the as-cast ZK40 alloy. The microstructural features were analised using optical, scanning and transmission electron microscopy, X-ray diffraction and Scanning Kelvin Atomic Probe Force Microscopy. The compressive and tensile behaviours of the as-cast alloys at room temperature were investigated. Electrochemical Impedance Spectroscopy, hydrogen evolution and weight loss under immersion in 0.5 wt.% NaCl solution were used to evaluate the corrosion behaviour. The results of the mechanical and corrosion tests were correlated with the microstructures. The 2 wt.% Gd addition enhanced the ductility, while the Nd addition resulted in deterioration in mechanical properties. The addition of 2 wt.% Gd and 1 wt.% Y resulted in the improvement of the ductility. The addition of CaO did not affect the mechanical properties while the 2 wt.% Nd deteriorate it. The 1 wt.% Y addition enhanced the ductility. The CaO addition did not caused enhancement in mechanical properties. The corrosion behaviour was enhanced with the addition of CaO and Gd. The modification of ZK40 with Gd opens up new perspectives in the development of Mg-Zn based alloys. / O efeito da adição individual de óxido de cálcio (CaO), Gd, Nd e Y foi investigado na microestrutura, propriedades mecânicas e resistência à corrosão de ligas ZK40 fundidas. As características microestruturais foram analisadas via microscopia óptica, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, difração de Raios-X e \"Scanning Kelvin Atomic Probe Force Microscopy\". O comportamento à compressão e à tração das ligas à temperatura ambiente foi investigado. Espectroscopia eletroquímica de impedância, evolução de hidrogênio e ensaios de imersão em solução de 0.5% em peso de NaCl foram utilizados para avaliar a resistência à corrosão. Os resultados dos ensaios mecânicos e corrosão foram relacionados com a microestrutura. A adição de 2% em peso de Gd melhorou a ductilidade, ao passo que a adição de Nd resultou na piora das propriedades mecânicas. A adição de 2% em peso de Gd e 1% em peso de Y resultou na melhora da ductilidade. A adição de 1% em peso de Y causou uma melhora na ductilidade e a adição de CaO não teve impacto benéfico nas propriedades mecânicas. A resistência à corrosão foi melhorada com a adição de CaO e Gd. A modificação da liga ZK40 com a adição de Gd abre novas perspectivas no desenvolvimento de ligas Mg-Zn.

O cinturão Fíngoè é uma unidade tectônica do Supercontinente Gondwana Oeste composta por rochas supracrustais formadas há aproximadamente 1.33 Ga. Essas rochas são portadoras de mineralizações de Au, Cu, Zn, Pb e Fe. Com cerca de 150 km de comprimento, e orientado WSW-ENE, este cinturão estende-se desde o Monte Atchiza a oeste até cerca de 30 km para leste da vila de Fíngoè no norte de Moçambique e consiste de uma extensa variedade de rochas metassedimentares e metavulcânicas. O cinturão Fíngoè apresenta especialização metalogenética para Au e Cu, que já foram explotados no passado em diversos locais. Muitos destes registros estão associados com magnetita e malaquita. Atualmente trabalhos de prospecção e pesquisa mineral têm sido realizados pela empresa de mineração African Queen Mines Ltda, através do projeto denominado de King Solomons, localizado na parte central do mesmo. A geologia da área abrangida pelo prospecto Mankombiti, mostra uma predominância de rochas carbonáticas, granitos e gabros. As rochas carbonáticas são consideradas importantes na gênese de depósitos tipo skarn e depósitos de substituição de metais de base e Au devido à sua natureza fortemente reativa. Os dados geocronológicos realizados neste trabalho indicaram uma idade precisa para a rocha intrusiva granítica associada à mineralização de 1079,1 ± 8,2 Ma, que poderia ser a idade da formação do skarn e consequentemente desta mineralização. Entretanto a idade obtida para o processo de alteração hidrotermal que afetou o gabro, na ordem de 657 ± 36 Ma e a idade modelo Pb-Pb sugerida pelo modelo de Stacey e Kramers (1975) para a calcopirita da mineralização principal de 725 Ma, sugerem que a mineralização, do prospecto Mankombiti é neoproterozóica. Para melhor entendimento dos processos que estiveram envolvidos na formação deste depósito skarn, duas hipóteses são consideradas: (i) poderia ser admitida a presença de corpos graníticos intrusivos em 700 Ma, situados em profundidade, que não foram ainda caracterizados, como responsáveis pela fonte de calor necessária, (ii) pode ser admitida ocorrência de um evento distensional em 700 Ma que produziria um adelgaçamento da litosfera e a consequente ascensão da astenosfera, produzindo uma elevação do fluxo térmico gerando os fluidos mineralizantes necessários. / The Fíngoè belt is a tectonic unit of West Gondwana Supercontinent, comprised of supracrustal rocks formed at approximately 1.33 Ga. These rocks are carriers of Au, Cu, Zn, Pb and Fe mineralization. With about 150 km long and oriented WSW- ENE, this belt extends from west of the Atchiza Mount to about 30 km east of the Fíngoè village in the north Mozambique, and consists of an extensive variety of metasedimentary and metavolcanic rocks. The Fíngoè metallogenic belt provides specialization for Au and Cu, which have been exploited in the past in various locations. Many of these records are associated with magnetite and malachite. Currently, the prospecting and mineral exploration have been conducted by the African Queen Mines Ltd mining company, through a project called the King Solomons, located in the central part of it. The geology of the studied area shows a predominance of carbonate rocks, granites and gabbros. The carbonate rocks are considered important in the genesis of the skarn deposits type and deposits of replacement for base metals and Au due to its highly reactive nature. The geochronological data performed in this work indicate a precise age of the 1079.1 ± 8.2 Ma for the intrusive granitic rock associated with mineralization, which could be interpreted as the age of the skarn and consequently of the mineralization. However the age obtained for the hydrothermal alteration that affected the gabbro at about 657 ± 36 Ma and the Pb-Pb model age suggested by the model of Stacey and Kramers (1975) for primary chalcopyrite mineralization at 725 Ma, suggesting that the mineralization of the Mankombiti prospectus was developed during the Neoproterozoic time. For understanding the processes that were involved in the skarn-type mineralization processes, two hypotheses are here considered: (i) could be admitted the presence of i ntrusive granitic rocks at 700 Ma, situated in depth, which have not yet been characterized, as responsible for the heat source required, (ii) may be admitted occurrence of an extensional event at 700 Ma to produce a thinning of the lithosphere and the uplift of the asthenosphere, producing high thermal flows generating the mineralization fluids.

Made available in DSpace on 2017-07-24T19:37:52Z (GMT). No. of bitstreams: 1 Ariana Rodrigues.pdf: 4102019 bytes, checksum: 823cb458ebe2eea53b3ba0d11aed9880 (MD5) Previous issue date: 2012-03-06 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / The increasing pathogenic bacteria resistance to antibiotics has led to the development of new alternatives to replace them. The Photodynamic Antimicrobial Chemotherapy (PACT) is one of the alternatives recently researched. Several associations between photosensitizer (PS) and light sources are used to inactivate different micro-organisms. The porphyrin derivatives have interesting features and are amongst the most investigated compounds in PACT, showing promising results. The light-emitting diode (LED) source presents advantages, since this device has been shown efficient against bacteria and is economically feasible. The present study investigated the photodynamic activity of different porphyrin derivatives/LED systems for application in PACT. The following porphyrin derivatives were used: 5,10,15,20-tetrakis(2,6-difluor-5-sulfonatophenyl) sodium porphyrinate, Na4[H2(TDFSPP)], 5,10,15,20-tetrakis(2,6-difluor-5-sulfonatophenyl) zinc (II) sodium porphyrinate, Na4[Zn(TDFSPP)]) and 5,10,15,20-tetrakis(4-sulfonatophenyl) manganese (III) sodium porphyrinate, Na4[Mn(TSPP)]. LED systems were used in different emission bands: orange, red, green and blue. The photodynamic activity of PS/LED systems were analyzed through the photobleaching test, photoxidation of bovine serum albumin (BSA) protein, uric acid and microbiological assay with ATCC and hospital Staphylococcus aureus strains. The results showed no significant photobleaching of porphyrin derivatives using LED as a light source. The PS/LED systems led to oxidation of the BSA protein and uric acid, except for the derivative Na4[Mn(TSPP)]. The photoxidation constant rate for Na4[H2(TDFSPP)]/green and blue LED, Na4[Zn(TDFSPP)]/green and blue LED systems, were close to the constant rate for drugs with application in photodynamic therapy (PDT). The uric acid test result indicated that compounds are capable of generating singlet oxygen. The Na4[H2(TDFSPP)]/blue LED system had a higher photodynamic activity against ATCC and hospital S. aureus strains. The results demonstrated that the systems under study present potential to be used in PDT and PACT. / A crescente resistência de bactérias patogênicas a antibióticos levou ao desenvolvimento de novas alternativas que possam substituí-los. Uma das alternativas investigadas atualmente é a quimioterapia fotodinâmica antimicrobiana (PACT). Várias associações entre fotossensibilizadores (FS) e fontes de luz são utilizadas para inativar diferentes micro-organismos, comprovando a eficiência dessa terapia. Os derivados porfirínicos apresentam características interessantes para aplicação em PACT e estão entre os compostos mais investigados, apresentando resultados promissores. O uso de LED como fonte de luz apresenta vantagens, uma vez que esse dispositivo tem mostrado bons resultados na eliminação de bactérias e é economicamente mais viável. Assim, no presente estudo, investigou-se a atividade fotodinâmica de diferentes sistemas derivados porfirínicos/LEDs para possível aplicação em PACT. Para isso, utilizou-se os seguintes derivados porfirínicos: 5,10,15,20-tetrakis (2,6-difluoro-5-sulfonatofenil) porfirinato de sódio, Na4[H2(TDFSPP)], 5,10,15,20-tetrakis (2,6-difluoro-5-sulfonatofenil) zinco (II) porfirinato de sódio, Na4[Zn(TDFSPP)], e 5,10,15,20-tetrakis (4-sulfonatofenil) manganês (III) porfirinato de sódio, Na4[Mn(TSPP)]. A irradiação dos compostos foi feita utilizando-se sistemas de LED com diferentes faixas de emissão: alaranjado, vermelho, verde e azul. A atividade fotodinâmica dos sistemas FS/LED foi avaliada por meio dos testes de fotobranqueamento, foto-oxidação da proteína BSA, ácido úrico e de ensaio microbiológico, utilizando-se a bactéria Staphylococcus aureus de origem ATCC e hospitalar. Os resultados mostraram que os derivados porfirínicos não sofreram fotobranqueamento quando associados aos diferentes LEDs. Os sistemas FS/LED levaram à oxidação da proteína BSA e à degradação da molécula de ácido úrico, exceto para o derivado Na4[Mn(TSPP)]. As constantes de foto-oxidação obtidas para os sistemas Na4[H2(TDFSPP)]/LED verde e azul; Na4[Zn(TDFSPP)]/LED verde e azul, ficaram próximas aos valores obtidos para fármacos com aplicação em Terapia Fotodinâmica (TFD). Os resultados do teste do ácido úrico para esses mesmos sistemas indicaram que eles são capazes de gerar oxigênio singlete. O sistema Na4[H2(TDFSPP)]/LED azul apresentou maior atividade fotodinâmica sobre as cepas de S. aureus ATCC e hospitalar. Assim, os resultados demonstram que os sistemas investigados apresentam potencial para aplicação em TFD e PACT.

Η παρούσα διπλωματική εργασία εστιάζει στη μελέτη των πετρωμάτων που φιλοξενούν τη μεταλλοφορία ψευδαργύρου, αργύρου και μολύβδου στην ευρύτερη περιοχή των Μολάων Λακωνίας. Οι κύριοι σχηματισμοί που εντοπίζονται στην υπό μελέτη περιοχή είναι η ενότητα της Άρνας και τα στρώματα του Τυρού. Σκοπός της εργασίας αυτής είναι η πετρογραφική και γεωχημική μελέτη των δύο προαναφερθέντων σχηματισμών, ώστε να καταστούν κατανοητές οι συνθήκες σχηματισμού. Πραγματοποιήθηκαν 9 χημικές αναλύσεις σε ηφαιστειακά πετρώματα των στρωμάτων του Τυρού για κύρια στοιχεία, ιχνοστοιχεία και σπάνιες γαίες, παράλληλα μελετήθηκαν και 15 πετρογραφικές λεπτές τομές των ηφαιστειτών αυτών. Τα δεδομένα συμπληρώθηκαν με 14 χημικές αναλύσεις κύριων στοιχείων και 9 χημικές αναλύσεις ιχνοστοιχείων των πετρωμάτων της ενότητας της Άρνας από βιβλιογραφική πηγή. Τα ηφαιστειακά πετρώματα των στρωμάτων του Τυρού αποτελούν ηφαιστείτες με εύρος συστάσεων από ανδεσιτικό βασάλτη έως δακίτη. Φέρουν ασβεσταλκαλικό χαρακτήρα με ελαφρά θολεϊτική τάση. Επίσης, προβάλλονται στα πεδία των θολεϊτών ηφαιστειακού τόξου, καθώς και σε ζώνη καταβύθισης των λιθοσφαιρικών πλακών. Ορισμένα εκ των δειγμάτων έχουν μεταμορφωθεί σε πρασινοσχιστολιθική φάση, ενώ στην πλειοψηφία των φέρουν έντονη εξαλλοίωση. Τα πετρώματα της ενότητας της Άρνας αποτελούν μεταηφαιστειακά πετρώματα βασαλτικής σύστασης. Φέρουν σαφή θολεϊτικό χαρακτήρα και προβάλλονται στο πεδίο των βασαλτών μεσωκεάνιας ράχης. / This thesis focuses on the study of the rocks that host the metalliferous of zinc, silver and lead in the wider area of Molai, Laconia. The main formations, which are spotted in the under study area, are the section of Arna Units and the Tyros Beds. The purpose of this work is the petrographic and geochemical study of the two formations mentioned above, so that the conditions of the formation become comprehensible. Nine chemical analysis were carried out in volcanic rocks of Tyros Beds for main elements, trace elements and rare earth elements, while at the same time fifteen petrographic thin sections of those volcanic rocks were studied. The data was complete with fourteen chemical analysis of main elements and nine chemical analysis of trace elements of the Arna Units from a bibliographical source. The volcanic rocks of Tyros Beds are volcanic rocks with amplitude of composition from andesitic basalt to dacite. They have calc-alcaline nature with a slight tholeitic tendency. Also, they are displayed / projected in the fields of the volcanic arc’s tholeites as well as in the zone of the lithospheric plates’ submersion. Some of the samples have been transformed into a greenschist phase, while the majority has an intense alteration. The rocks of Arna Units are metavolcanic rocks with basaltic composition. They have a clear tholeitic nature and they are displayed in the field of the basalts of the mid ocean ridge.