A deficiência de Zn no solo causa efeitos indesejáveis na produção agrícola, pois a baixa disponibilidade deste micronutriente para as plantas promove a diminuição da atividade enzimática, além da deficiência deste elemento na alimentação, que pode levar ao estado de subnutrição. Tendo em vista a problemática do Zn no sistema solo-planta e suas variações nos compartimentos do solo, é importante a avaliação de sua fitodisponibilidade e as frações do solo que este elemento está associado. O objetivo deste trabalho foi avaliar a fitodisponibilidade e a compartimentalização de Zn no solo, para as culturas de arroz (Oryza sativa L.) e soja (Glycine max L. Merrill) e avaliar o efeito das doses de Zn sobre a nutrição e exportação deste nutriente pela cultura. Utilizou-se como plantas teste as culturas de arroz e soja para avaliar o efeito das doses de Zn sobre a nutrição e translocação deste nutriente até os grãos. Para tanto, uma amostra de um Latossolo Vermelho, textura argilosa da região de Piracicaba (SP) foi utilizada e ZnCl2 (marcado com 65Zn) como fonte. O experimento foi conduzido em casa de vegetação em DIC, com cinco doses de Zn (0, 1, 2, 4 e 8 mg kg-1 de solo), com quatro repetições. O experimento foi conduzido até a formação de grãos e foi realizada determinação de Zn por Espectrômetria de Absorção Atômica após digestão nitroperclórica e contagem do 65Zn nas partes da planta: parte aérea (PA) e panícula (P), para arroz e PA, vagem (V) e grão (G), para soja. Calculou-se a quantidade de Zn proveniente da fonte (Znpf) nas partes das plantas e o aproveitamento do Zn da fonte pelas culturas (Ap). Nas amostras de solo foram realizadas extrações por DTPA (ZnDTPA) e Mehlich-1 (ZnM1) em duas subamostragens (t1 e t2), antes da semeadura e florescimento, respectivamente. O fracionamento de Zn foi realizado em amostras de t2 nas frações: trocável (ZnTroc); ligado a carbonatos (ZnCarb); a matéria orgânica (ZnMO); a óxidos (ZnOxi) e residual (Znres). Adicionalmente, foi realizada análise do teor pseudo-total de Zn (ZnPST). Os dados obtidos foram submetidos à análise de variância pelo teste-F a 95 % de probabilidade, ajuste das variáveis em função das doses por regressões e teste de média e análises de correlações entre as principais variáveis respostas. O Zn acumulado total na planta se ajustou à regressão linear em função do aumento das doses, entretanto ao analisar as partes separadamente, só houve diferença entre as doses para a variável PA em ambas as culturas. O Znpf total nas plantas apresentou incremento com a adição das doses crescentes de Zn ao solo, entretanto, eu aproveitamento foi baixo, 12 e 8,75 % para arroz e soja, respectivamente. As doses de ZnCl2 adicionadas ao solo, aumentaram a concentração de Zn presente nas frações ZnTroc > ZnMO > ZnCarb, em ordem decrescente. O Zn total acumulado nas plantas de arroz e soja apresentam correlações crescentes para os extratores DTPA e M1 nas duas subamostragens (t1 e t2), em função das doses avaliadas. O Zn extraído pelo DTPA ou M1, apresentaram correlação significativa com o Zn extraído nas frações, na ordem decrescente, ZnTroc > ZnCarb > ZnMO / Zn deficiency in soil causes undesirable effects on agricultural production because the low availability of this micronutrient for plants promotes the decrease in enzymatic activity besides the deficiency of this element in food, which can lead to a state of malnutrition. Considering the problem of Zn in soil-plant system and its variations in soil compartments, it is important to evaluate its bioavailability and forms in soil which this element is associated. The objective of this study was to evaluate Zn bioavailability and compartmentalization in the soil, to the rice (Oryza sativa L.) and soybean (Glycine max L. Merrill) crops and evaluate the effect of Zn levels on nutrition and exportation of this nutrient by the crops. As test plant rice and soybeans were used to evaluate the effect of Zn rates on nutrition and the nutrient translocation to the grains. For this purpose, a sample of an Oxisol (FAO), an clay texture from Piracicaba (SP) region, was used and ZnCl2 (labelled with 65Zn) as a source. The experiment was conducted in a greenhouse in CRD, with five rates of Zn (0, 1, 2, 4 and 8 mg kg-1 soil), with four repetition. The experiment was conducted until the formation of grains and Zn analyzis were performed by Atomic Absorption Spectrophotometery after nitricperchloric digestion and 65Zn counting of parts: shoot (PA) and panicle (P) for rice and PA, beans pods (Pd) and grains (G) for soybeans. The amount of Zn derived from the source (Znpf) was calculated in the plant parts and the recovery of the Zn by the crops (Ap). In the soil samples, extractions were performed by DTPA (ZnDTPA) and Mehlich-1 (ZnM1) methods in two sub samples (t1 and t2) prior to seeding and flowering, respectively. The Zn fractionation was performed on samples of t2 in the fractions: exchangeable (ZnTroc); linked to carbonates (ZnCarb); to organic matter (ZnMO); to oxides (ZnOxi) and residual (Znres). Additionally, analysis of the pseudo-total content of Zn (ZnPST) was performed. Data obtained was subjected to analysis of variance by the F-test at 95% probability, adjusting the variables depending on the rates for regression and average test and analysis of correlations between the main variables. The total cumulative Zn in the plant set to the linear regression in terms of increasing rates, however when analyzing the parts separately, just the PA showed differences between doses, for both crops. The total Znpf increased with the increasing rates, however its recoveries were low, approximately 12% for rice and 8.75 % for soybean. The ZnCl2 rates in soil increased the Zn concentration in the fractions: ZnTroc > ZnMO > ZnCarb, in descending order. The total cumulative Zn in the rice and soybean plants are growing correlations for extractors DTPA and M1 for two sub samples (t1 and t2), depending on the rates evaluated. The Zn extracted by DTPA or M1 were significantly correlated with Zn extracted in fractions in descending order: ZnTroc > ZnCarb > ZnMO

Ce travail est peut être séparé en deux parties. Dans la première, nous rapportons l'étude menée sur un composé modèle d'hydroxyde de Nickel. La caractérisation de ce composé par diffraction X montre qu'il possède une cristallinité supérieure aux hydroxydes de nickel habituellement utilisés. L'observation au microscope électronique à balayage révèle que la poudre est constituée de grains hexagonaux, de dimension supérieure au micromètre, formés de monocristaux, eux aussi hexagonaux, empilés de façon très ordonnée. Les mesures électrochimiques montrent quant à elles que les composés modèles présentent des propriétés redox intéressantes. La morphologie très particulière de ce composé confère à cet hydroxyde de nickel un comportement de type monocristal en spectroscopie Raman. Des mesures in-situ, couplant voltamétrie cyclique et spectroscopie Raman, réalisées sur ce composé modèle, ont donc été mises en place. Les premiers résultats montrent que ces expériences pourraient nous aider à améliorer notre compréhension des mécanismes redox fondamentaux mis en jeu.Dans la deuxième partie, nous étudions le comportement électrochimique d'une électrode de nickel lorsque l'électrolyte (i.e. KOH 7N) est saturé en zinc. Des électrodes de type industriel ont été préparées à partir d'un hydroxyde de Nickel standard et non dopé, puis cyclées en condition galvanostatique. Les échantillons ainsi obtenus ont ensuite été caractérisés par MEB, DRX, IR et EXAFS. Cette dernière technique qui s'est avérée être la plus appropriée pour l'analyse de ces matériaux d'électrodes très hétérogènes nous a ainsi permis d'apporter des réponses pertinentes sur l'insertion du zinc dans la structure cristalline de Ni(OH)2. / This work may be separated in two parts. First, we report the study of a model compound of nickel hydroxide. X-ray diffraction shows that this compound has a better crystallinity than the standard nickel hydroxides used in commercial battery. Scanning Electron Microscopy revealed that the powder of this model hydroxide is composed of hexagonal grains whose dimension is larger than micrometer and who are formed of single-crystals, also hexagonal, stacked in a well ordered way. The electrochemical measurements show that this nickel hydroxide exhibit interesting redox properties. The particular morphology of the compound gives single-crystal type behavior in Raman spectroscopy. Therefore, in-situ measurements combining electrochemical measurements and Raman spectroscopy, performed on a single microscopic hexagonal plate, are proposed. Preliminary results emphasize that this experiment may help us to improve our understanding of the fundamental redox mechanism taking place in nickel hydroxide.Secondly, we study the electrochemical behavior of a nickel electrode in the presence of Zinc in the electrolyte. Industrial-type electrodes were prepared from a standard undoped nickel hydroxide. Then, samples obtained after electrochemical test were characterized by SEM, XRD, IR and EXAFS. The later which turned out to be the most appropriate for the analysis of our electrode materials, allowed us to get deeper insights in the insertion of zinc in the structure of Ni(OH)2.

Les whiskers, filaments métalliques qui poussent sur des surfaces métalliques, sont unproblème très important pour la fiabilité des composants électroniques. Depuis ces dernièresannées, il y a eu un regain d’intérêts industriels dans le domaine de la croissance des whiskers,principalement en raison de la miniaturisation des dispositifs électroniques et des réglementationsenvironnementales interdisant l'utilisation du plomb.Alors que la plupart des recherches concernent les whiskers d'étain, il y a encore peu detravaux sur les whiskers de zinc. Les revêtements d’électrodéposés de zinc sont utilisés commeprotection anticorrosion pour les aciers faiblement alliés dans diverses industries, commel'automobile, l'aéronautique ou l'énergie, ainsi que dans les structures de soutien ou les planchersfaux plafonds dans les centres de données informatiques. Afin d'atténuer, de prévenir et deprédire les défaillances causées par les whiskers de zinc, les mécanismes de sa croissance doiventêtre compris.Grâce à des tests de stockage accéléré et à des observations par microscopie électronique àbalayage (MEB), la cinétique de croissance des whiskers de zinc a été étudiée sur des tôles d'acierau carbone faiblement allié, galvanisé et chromé. Afin de comprendre les mécanismes de lacroissance des whiskers de zinc, la caractérisation quantitative ainsi que les excroissances (densité,volume et vitesse de croissance) ont été reliées aux paramètres suivants: la température, le bainpour l’électrodéposition du zinc, la chromatation, l’épaisseur du substrat d’acier, l’épaisseur durevêtement de zinc ainsi que la contrainte résiduelle.En outre, la microstructure et la cristallographie du revêtement de zinc, des racines deswhiskers ainsi que des whiskers elles-mêmes ont été étudiées par diffraction des électronsrétrodiffusés (EBSD), microscopie électronique à transmission (MET), microanalyse par rayon X(EDX) et le dispositif ASTAR pour l'orientation locale des grains; la préparation des échantillonsa été réalisée à l’aide d’un faisceau d'ions focalisés (FIB). La recristallisation ainsi que lesdislocations dans les whiskers et les excroissances ont été observés; aucun composéintermétallique n’a été observé que ce soit dans les échantillons issus de différents bainsélectrolytes ou encore dans les films / whiskers.Il a été montré que la relaxation de contrainte de compression résiduelle et la croissance deswhiskers sont deux phénomènes différents mais fortement reliés et thermiquement activés.Chacun d'entre eux suit un mécanisme différent; les énergies d'activation apparentes des deuxphénomènes ont été établies, et la diffusion aux joints de grains est proposée comme le principalmécanisme de diffusion pour la croissance des whiskers.Des cinétiques de la croissance des whiskers, à la fois analytique et phénoménologique sontproposées. Une bonne estimation de la croissance des whiskers et de leur vitesse de croissance àdes températures proches des conditions de fonctionnement est obtenue par comparaison avecles données expérimentales. / Whiskers, conductive metallic filaments that grow from metallic surfaces, are a very importantissue for reliability of electronic components. Through recent years, there has been a renewedindustrial interest on whisker growth, mainly due to the miniaturization of electronic devices andthe environmental regulations forbidding the use of lead.While most of the research has been focused on tin whiskers, there is still little reference tozinc whiskers. Electroplated zinc coatings are actually used as anticorrosive protection for lowalloy steels in diverse industries such as automotive, aerospace or energy, as well as for supportstructures or raised-floor tiles in computer data centers. In order to mitigate, prevent and predictthe failures caused by the zinc whiskers, the mechanisms of growth must be understood.By accelerated storage tests and Scanning Electron Microscopy (SEM) observation, kinetics ofgrowth of zinc whiskers was studied on low alloy chromed electroplated carbon steel.Quantitative characterization of both whisker and hillocks (density, volume and growth rate) wasrelated with the parameters temperature, electroplating electrolyte, presence of chrome, steelsubstrate thickness, zinc coating thickness and residual stress, in order to understand themechanisms of growth.Additionally, both microstructure and crystallography of zinc coating, whisker roots and actualwhiskers were studied by Electron Backscatter Diffraction (EBSD), Transmission ElectronMicroscopy (TEM), Energy-dispersive X-ray spectroscopy (EDX) and local grain orientationwith ASTAR setup, using Focused Ion Beam (FIB) for samples preparation. Recrystallization aswell as dislocations were observed in both whiskers and hillocks; no intermetallic compoundswere seen in neither electroplated nor whiskers.It is found that compressive residual stress relaxation and whiskers growth are two differentbut strongly interconnected phenomena both thermally activated, an each of them follows adifferent mechanism; apparent activation energies of the two phenomena are calculated, andgrain boundary diffusion is established as the main diffusion mechanism for whiskers growth.Whiskers growth kinetics, both analytical and phenomenological is proposed. Goodestimation of whiskers growth and whiskers growth rate at temperatures close to operationconditions is obtained when compared with experimental data. / Whiskers, filamentos metálicos que crecen en superficies metálicas, son un problema muyimportante para la fiabilidad de componentes electrónicos. Durante los últimos años, ha habidoun renovado interés industrial en el crecimiento de whiskers, debido principalmente a laminiaturización de dispositivos electrónicos y a las regulaciones ambientales que prohíben lautilización de plomo.La mayoría de las investigaciones se concentran en los whiskers de estaño y hay todavía pocostrabajos sobre los whiskers de zinc. Los recubrimientos de zinc electrodepositado son utilizadoscomo protección anticorrosión para los aceros de baja aleación en diversas industrias, comoautomotriz, aeronáutica o energética, así como en la estructuras de soporte o tejas de techosfalsos en los centros de datos informáticos. Para atenuar, prevenir y predecir las fallas causadaspor los whiskers de zinc, los mecanismos de crecimiento deben ser comprendidos.Gracias a experimentos de almacenamiento de muestras y a observaciones por microscopíaelectrónica de barrido (SEM), la cinética de crecimiento de whiskers de zinc ha sido estudiada enaceros de baja aleación recubiertos de zinc y cromados. Para comprender los mecanismos decrecimiento de whiskers de zinc, la caracterización cuantitativa de whiskers y de protuberancias(densidad, volumen y velocidad de crecimiento) fue relacionada con los parámetros siguientes:temperatura, electrolito usado en la electrodeposición de zinc, cromado, espesor del substrato deacero, espesor del recubrimiento de zinc al igual que el estrés residual.Adicionalmente, microestructura y cristalografía del recubrimiento de zinc, de raíces dewhiskers así como de los propios whiskers fueron estudiadas por medio de la difracción deelectrones por retrodispersión (EBSD), microscopía electrónica de transmisión (TEM),microanálisis por rayos X (EDX) y el dispositivo ASTAR para la orientación local de granos; lapreparación de muestras fue realizada con la ayuda de un haz de iones localizados (FIB). Larecristalización así como las dislocaciones en whiskers y protuberancias fueron observadas;ningún compuesto intermetálico ha sido observado en los recubrimientos ni en los whiskers.Se determinó que la relajación del estrés residual de compresión y el crecimiento de whiskersson dos fenómenos diferentes pero fuertemente interconectados y térmicamente activados. Cadauno de ellos sigue un mecanismo diferente; las energías de activación aparentes de los dosfenómenos han sido establecidas, y la difusión por bordes de grano es propuesta como elprincipal mecanismo de difusión para el crecimiento de whiskers.Cinéticas de crecimiento de whiskers, a la vez analíticas y fenomenológicas son propuestas.Una buena estimación del crecimiento de whiskers y su velocidad de crecimiento a temperaturascercanas a las condiciones de operación es obtenida por comparación con los datosexperimentales.

Corrosion can cause devastating damage to materials, and to protect materials from corrosion is crucial, especially in the aeronautical industry. An electroplated Zinc-Nickel coating provides excellent corrosion protection of steel. Electroplating of ZnNi is a sensitive process which needs frequent and fast feedback controls and adjustments of the process electrolyte. A common process control for electroplating processes is the Hull cell test, which is investigated in this study. The Hull cell test is a lab scaled electroplating unit, which spans a wide range of current densities. It is crucial to establish the relation between process parameters in the Hull cell and the resulting coating characteristics in order to implement it as a process control. The purpose of this study is to establish these relations for the ZnNi electroplating process, and evaluate if the Hull cell test is a suitable process control for this process. How the process parameters; current density, temperature, metal ion concentration, and carbonate contaminations affect the coating characteristics; visual appearance, thickness, composition, surface structure, and phase content has been established. Influence on the coatings were mainly seen at current densities higher and lower than the ones used in production. This demonstrates the strength of the Hull cell test for early detection of process deviations. Coating thickness and composition was measured with X-ray fluorescence. However, the composition values for thin coatings were discovered to be inaccurate, which was avoided by increasing the plating time. Once addressed, the Hull cell test is suitable as a process control for the electroplating process of ZnNi.

O dióxido de manganês (MnO2) é um catalisador eficiente de baixo custo utilizado no cátodo de baterias do tipo metal-ar e células a combustível alcalinas, sendo capaz de promover a redução completa de oxigênio pela rota 4e-. No entanto, o dióxido de manganês é um semicondutor e só pode ser utilizado como material eletródico nos dispositivos mencionados se combinado com algum suporte condutor. O suporte condutor mais utilizado para este fim é o carbono em pó. Entretanto, este material não possui estabilidade suficiente nas condições operacionais das células alcalinas, sendo convertido gradativamente em CO2. Uma das possíveis estratégias para tentar minimizar esta deficiência é incrementar a condutividade eletrônica do óxido puro pela dopagem com alguns cátions metálicos. Sendo assim, este trabalho tem como objetivo geral pesquisar de maneira sistemática o efeito da dopagem de dióxido de manganês com alguns cátions metálicos, como o Bi3+e Ce4+ nas propriedades físico-químicas e eletrocatalíticas deste óxido, visando o uso dos mesmos como em cátodos de baterias recarregáveis do tipo Zn-ar. As análises das características morfológicas dos catalisadores por meio de MEV e TEM mostram que os óxidos de manganês são gerados na forma de nano-bastões de 50 a 100 nm de comprimento. Os óxidos puros e dopados com bismuto e cério apresentam estruturas tetragonais típicas, ocorrendo expansão da célula unitária dos óxidos dopados pela troca de íons manganês pelos correspondentes dopantes na rede cristalina de MnO2. Os resultados eletroquímicos sugerem um aumento de condutividade do óxido dopado que possibilita seu uso sem mistura com carbono. Além disso, observa-se que a RRO é catalisada por um mecanismo que envolve a transferência de 4e- nestes materiais com participação de peróxido como intermediário. O óxido de manganês dopado com Bi apresentou promissor desempenho catalítico para a RDO, o que junto com os demais resultados apresentados para a RRO o qualificou a funcionar como o catalisador bifuncional mais promissor de todos os estudados em baterias do tipo metal-ar. Experimentos realizados em mini baterias do tipo Zn-ar demonstraram a total capacidade do catalisador dopado com bismuto operar como catalisador do eletrodo de ar, resultando num desempenho superior ao de um catalisador convencional de MnO2/C. / Manganese dioxide is at the same time an efficient and low-cost material used as cathode catalyst in the air electrode of metal-air and alkaline fuel cells, capable to promote the complete reduction of oxygen thru the 4e- mechanism. However, manganese dioxide is a semiconductor and can be used as electrodic material in the mentioned devices only combined with a conductor support. High surface area carbon powder is the most commonly used material for such purpose. The problem is that carbon suffers from severe instabilities in the experimental conditions that fuel cells and metal-air batteries operates, being gradually converted into CO2. A possible strategy to overcome or at least minimize the low oxide conductivity is by doping this material with some metallic cations. In this sense, the main purpose of this work was the systematic investigation of the physicochemical and electrocatalytic properties of Bi3+ and Ce4+ doped manganese dioxide materials used as cathode catalysts in the air electrode of alkaline type Zn-air batteries. The morphologic characterization performed SEM and TEM revealed that pure as well cation doped MnO2 are formed as poly dispersed nanorods with 50-100 nm length. Both pure and doped materials presented typical tetragonal structures, although a cell expansion was observed in the doped oxides caused by the exchange of some manganese cations by the doping counter parts. Electrochemical results suggest that a material with increased conductivity results from the doping process, allowing it to operate as air catalyst without the use of a carbon support. Besides, it is observed that the oxygen reduction reaction proceeds thru the 4e- mechanism on the doped oxides involving hydrogen peroxide as intermediate. The Bi doped oxide presented the best performance for the oxygen evolution reaction among all catalysts investigated. This result together with the superior performance for the oxygen reduction reaction presented by this material suggest that Bi doped MnO2 is a potential candidate to operate as an air catalyst of rechargeable alkaline metal-air batteries. Experiments conducted in a mini Zn-air battery using Bi doped MnO2 as air catalyst corroborated this observation.

Sem resumo / Sem abstract

Este trabalho tem como objetivo a obtenção das taxas de sedimentação da plataforma continental e do talude superior, no trecho centro norte do Embaiamento São Paulo (Santos a Cabo Frio), além da verificação do uso do método 210Pb/137Cs, comparados a métodos mais tradicionais como o 14C, para a obtenção destas taxas de sedimentação. Um segundo objetivo é verificar se ocorre a transferência de metais, provenientes da área costeira contígua, para o oceano aberto. Para a realização deste trabalho, foram coletados, em diferentes projetos de pesquisa, 12 testemunhos que foram analisados em função da granulometria e dos teores de CaCO3 e metais (Pb, Cu e Zn). Estes mesmos testemunhos foram submetidos, também, a análise da espectrometria gama para obtenção dos níveis de atividade de 210Pb e 137Cs. A partir da medição destes níveis, após alguns cálculos matemáticos baseados no modelo CIC, puderam ser obtidas as taxas de sedimentação. Os resultados indicaram colunas sedimentares bastante homogêneas, predominantemente siliciclásticas. As taxas de sedimentação obtidas, na ordem de milímetros/ano, são compatíveis com os dados encontrados em outras partes do litoral brasileiro e do mundo, onde o aporte atual de sedimentos não é significativo. Com base nestes dados, pode-se afirmar que o método 210Pb/137Cs é bastante confiável para a obtenção de taxas de sedimentação e identificação dos processos sedimentares atuantes nas áreas costeiras e de plataforma, respeitando-se como limite a isóbata de 100 metros. Em profundidades maiores que esta, a técnica não se mostra um \"proxy\" confiável, pois os dados obtidos foram muito conflitantes, sendo mais recomendado o uso do 14C. Os metais provenientes da zona costeira, aparentemente, não estão alcançando a plataforma continental, mas em alguns pontos isolados, já se nota um aumento em especial do Pb, não atingindo entretanto, os níveis de alerta da resolução CONAMA 344/04. / The objective of the present work is the obtainment of the sedimentation rates of the continental shelf and the upper slope on the central north area from São Paulo Bight (from Santos to Cabo Frio), besides checking the use of the 210Pb/137Cs method when compared to more traditional methods like 14C for obtainment of this sedimentation rates. The second objective is the checking if there is a metal transference deriving from the adjacent coastal area to the open ocean. In this work a total of 12 cores were collected from different research projects and they were analyzed considering the granulometry and CaCO3 and metals (Pb, Cu and Zn) contents. These same samples were also analyzed through gamma spectrometry for obtainment of the activity levels of 210Pb and 137Cs. The sedimentation rates were obtained after mathematical computing based on CIC model. The results indicated rather homogeneous sedimentary columns, predominantly siliciclastics. The obtained sedimentation rates, in a millimeters/year basis, are consistent to the data found in other areas of the Brazilian Coastal and the World Coastal where the actual deposit of sediments is not significant. Based on this data it is possible to state that 210Pb/137Cs method is a really reliable method for obtainment of sedimentation rates and identification of the sedimentary processes occurring on the coastal and shelf areas, respecting 100 meters isobath as the limit. The technique is not a reliable proxy when considering deeper areas as there was much conflict on the resultant data and in this cases, the best recommendation is the use of 14C method. Apparently, the metals deriving from the coastal zone are not reaching the continental shelf, but the growth of Pb can be noticed on some isolated spots although they not reach the warning levels from CONAMA 344/04 resolution

Diese Arbeit untersucht die Möglichkeiten, ortsaufgelöste (2D-) Lumineszenz als eine nicht-invasive Methode zur Charakterisierung des Ethylen-Vinyl-Acetat (EVA) Einkapselungsmaterials in Photovoltaik (PV) Modulen einzusetzen. Im Einzelnen wird gezeigt, dass aus nichtinvasiven Lumineszenzmessungen Aussagen erhalten werden können zu: (i) Auswirkungen der Alterungsbedingungen, Klima und Material, (ii) Nachweis bestimmter Fehlerarten, (iii) Überwachung des Produktionsprozess, (iv) Verbesserung von Lebensdauervorhersagen durch miniaturisierte Multi-Faktor-Alterung und (v) Aussagen über die Materialalterung. (i) Temperatur, UV-Strahlung und Sauerstoff werden als Hauptfaktoren identifiziert, die die Lumineszenz beeinflussen. Beschleunigte Alterung unter UV und Freibewitterung resultieren in ähnlichen Lumineszenzmustern und -Spektren, die sich von denen nach exklusiver thermischer Alterung unterscheiden. (ii) Insbesondere können Risse in Zellen nachgewiesen werden, darüber hinaus gibt es Anhaltspunkte, dass auch Korrosion und Delamination durch Lumineszenz nachweisbar sein könnten. (iii) Lumineszenz ist eine vielversprechende Methode, zerstörungsfrei den Vernetzungsgrad und die Homogenität zu bewerten. (iv) Für wirtschaftliche und effiziente Alterungstests wurde eine Multi-Faktor-Alterungs-Kammer entwickelt und getestet, die die Prüfung der gleichzeitigen Wirkung mehrerer Alterungsfaktoren ermöglicht. (v) Erstmals wird eine Korrelation der EVA-Lumineszenz zu anderen, insbesondere viskoelastischen Materialeigenschaften gezeigt. Es wird geschlossen, dass diffusionsbegrenzte Oxidation (DLO) im EVA zwischen Zelle und Glas eine inhomogene Materialdegradation verursacht. Perspektivisch werden Studien des komplexen Einflusses von Temperatur, UV-und Sauerstoff auf Materialalterung durch 2D-Lumineszenz in Kombination mit Multi-Faktor-Alterung aufgezeigt, ebenso wie die Möglichkeit einer Anwendung zur Bestimmung von apparenten Reaktionsraten aus Lumineszenzintensitätsprofilen. / This work examines the prospects of employing spatially resolved (2D-) luminescence as a non-invasive method for the characterization of the ethylene-vinyl-acetate (EVA) encapsulation material in photovoltaic (PV) modules. It is shown that information can be obtained related to the topics: (i) impact of aging conditions, climate and material, (ii) detection of specific types of failure modes, (iii) use to monitor the production process, (iv) improving service life prediction by miniaturized multi-factor aging and (v) statements about the material aging. (i) Temperature, UV radiation and oxygen are identified as main factors, which influence the luminescence. Accelerated aging under UV and outdoor weathering result in similar luminescence patterns and spectra, different from those after exclusive thermal aging. (ii) Specific failure modes, in particular cracks of the cells, can be detected. In addition, indications exist that corrosion and delamination might be detectable by luminescence. (iii) Luminescence is a promising method that allows non-destructive examination of the degree of crosslinking and the homogeneity in the PV module. (iv) For more economic and efficient aging tests a multi-factor-aging chamber was designed and tested which allows testing the simultaneous action of several aging factors. (v) For the first time, a correlation of EVA-luminescence to others, in particular viscoelastic, material properties, is demonstrated. From the inhomogeneous degradation patterns, it is concluded that diffusion limited oxidation (DLO) in the EVA between glass cell and causes an inhomogeneous material degradation. Interesting prospects emerge, e.g. studies of the complex influence of temperature, UV and oxygen on material aging by 2D-Luminescence using multi-factor-aging. In addition, the evaluation of intensity profiles, for example, regarding apparent reaction rates, is one of many promising applications.

I detta arbete har polerprov framställts för att därefter undersökas med malm- och svepelektronmikroskopi (SEM) med energidispersiv röntgenspektroskopisk analys (EDS). Med dessa metoder har mineralsammansättning, strukturer och texturer identifierats och undersökts. De undersökta proverna kommer från borrkärnor genom malmzonen i Lovisagruvan i Bergslagen, södra Mellansverige. Malmen är en tabulär, silverförande Zn-Pb-sulfidmineralisering.  De kombinerade undersökningarna av polerproven visar att de huvudsakligen består av zinkblände, blyglans, kvarts, mikroklin, granat, amfibol och pyrit, vilka karakteriseras av texturer som visar på omkristallisation, heterogen deformation och lokal remobilisering. De uppvisar småskaliga texturer som sannolikt är direkt relaterade till uppkomsten av s.k. kulmalmstextur. De ingående mineralens inbördes relationer tyder på att blyglans och zinkblände bildades samtidigt och därefter, under regionalmetamorfa förhållanden, tillväxte pyrit och granat som porfyroblaster. Majoriteten av texturerna och strukturerna är sekundära och visar på en kraftig senare överprägling av malmen genom metamorfos och flerfasig deformation under olika tryck- och temperaturförhållanden. / In this project polished sections have been prepared for study by means of ore and scanning electron microscopy (SEM) with energy dispersive x-ray spectroscopy (EDS). The application of these methods allows mineralogy, structures and textures to be characterized. This was done within the EU H2020-funded project X-Mine. The studied samples are from drill cores transecting the ore zone of the Lovisa mine (Lovisagruvan), which is located in Örebro County in the Bergslagen ore province, south central Sweden. Here, a tabular, stratiform silver-bearing Zn-Pb sulphide ore is mined.  Studies of the polished ore sections show that the samples mainly contain sphalerite, galena, quartz, microcline, garnet, amphibole and pyrite, characterized by textures of recrystallisation, heterogeneous deformation and localized remobilization.  The studied samples from the main ore and exhibit textures directly related to the formation off the so-called ball ore. The textural interrelationships of the major minerals indicate that galena and sphalerite formed penecontemporaneously, and then under regional metamorphic conditions, pyrite and garnet formed as porphyroblasts. The majority of the present textures and structures are secondary, representing different stages of metamorphism and deformation under variable P-T-conditions, post-dating original ore formation. / Real-Time Mineral X-Ray Analysis for Efficient and Sustainable Mining, H2020 X-Mine, Projekt-id: 730270

La mucoviscidose est la maladie génétique la plus fréquente dans la population caucasienne. Le genre Scedosporium se situe au deuxième rang parmi les champignons filamenteux isolés des expectorations dans ce contexte. Au niveau pulmonaire, les colonisations/infections entraînent le recrutement de phagocytes qui induisent un stress oxydatif normalement délétère pour les pathogènes. Pour se défendre, ceux-ci ont développé des systèmes antioxydants, notamment diverses enzymes. Ce travail de thèse visait à étudier la réponse au stress oxydatif chez Scedosporium. Tout d’abord, la capacité à germer en présence d’oxydants a été évaluée. Par la suite, trente-trois gènes potentiellement impliqués dans la défense contre le stress oxydatif ont été identifiés. Leur expression en présence d’oxydants et en co-cultures avec des phagocytes suggère un rôle majeur, notamment pour une catalase, une peroxyrédoxine et deux thiorédoxine réductases. Par ailleurs, un mutant défectif pour un gène codant une superoxyde dismutase (SOD) pariétale et spécifique des spores a été produit. L’auranofin, un inhibiteur des thiorédoxine réductases, présente une activité vis-à-vis des Scedosporium et un effet additif avec des triazolés. Un test ELISA a été développé pour le sérodiagnostic des scédosporioses, utilisant une catalase et une Cu/Zn-SOD recombinantes. Ce test sensible et spécifique permet de distinguer les infections à Scedosporium de celles à Aspergillus fumigatus et des colonisations à Scedosporium. Au final, ces résultats indiquent un rôle majeur des enzymes antioxydantes chez Scedosporium, qui pourraient être de véritables facteurs de virulence et donc de nouvelles cibles thérapeutiques. / Cystic fibrosis (CF) is the most common genetic disease in Caucasian populations. The Scedosporium genus ranks the second among the filamentous fungi colonizing the airways of CF patients. In the respiratory tract, colonizations/infections lead to the recruitment of phagocytes which produce an oxidative stress, usually deleterious for pathogens. To defend themselves, pathogens have developed protective antioxidant systems, especially various enzymes. This thesis aimed to study the oxidative stress response in Scedosporium species. First, capacity of several Scedosporium isolates to germinate upon oxidative stress conditions was evaluated. Then, thirty-three genes potentially involved in protection against the oxidative stress were identified. Their overexpression in response to oxidants and in co-cultures with phagocytes suggested a crucial role, especially for one catalase, one peroxiredoxin and the two thioredoxin reductases. A mutant defective for the gene encoding a superoxide dismutase (SOD) anchored to the cell wall and specific for the conidia was produced. Auranofin, a thioredoxin reductase inhibitor, exhibits little anti-Scedosporium activity and an additive effect with triazole drugs. An ELISA was developed for serodiagnosis of scedosporiosis, using recombinant proteins derived from one catalase and a Cu/Zn-SOD. This sensitive and specific assay allows to differentiate Scedosporium infections from Aspergillus fumigatus infections and Scedosporium colonizations. Finally, these results indicate a crucial role of antioxidant enzymes in Scedosporium species, which could therefore be considered as virulence factors and as possible new therapeutic targets.