La gestion des déchets produits par l’industrie nucléaire est un enjeu majeur de nos sociétés. En France, l’Agence nationale pour la gestion des déchets radioactifs (Andra), est chargée de la mise en œuvre du projet Cigéo, centre industriel de stockage géologique, un concept de stockage profond en milieu argileux des déchets radioactifs HA et MAVL. Dans ce concept, le verre a été choisi comme matrice de confinement pour les déchets radioactifs de haute activité et la prédiction du comportement du colis de déchet sur le long terme est l’un des éléments essentiels de sureté. Afin d’identifier les mécanismes d’altération du verre en présence de fer issu du conteneur de stockage, différents systèmes verre/fer/argilite ont été altérés dans des conditions proches du probable site de stockage géologique. Un couplage de techniques de caractérisation post-mortem de l’échelle micro à nanométrique a permis de caractériser les systèmes et d’identifier les silicates de fer qui se forment dans la couche d’altération du verre SON68 et dans les produits de corrosion du fer. A 50°C, les smectites dioctaédriques de FeIII (assimilées à de la nontronite) se forment préférentiellement, tandis que des serpentines trioctaédriques riches en FeII (greenalite, berthierine) ne sont détectées que pour une température de 90°C. Ces phyllosilicates nanométriques ont un impact macroscopique sur l’altération du verre nucléaire. En effet les interactions silicium/fer entretiennent l’altération du verre et retardent l’atteinte du régime d’altération en vitesse résiduelle. / Management of waste generated by the nuclear industry is a major challenge for our societies. In France, the French national radioactive waste management agency (Andra) is responsible for the implementation of the Cigéo project, an industrial geological storage center planning to use deep storage in clay medium for high level and intermediate-level long lived waste. Glass has been chosen in this project as a containment matrix for high-level radioactive waste. Understanding the long-term expected evolution of the waste package's behavior is critical for safety purposes.In order to identify the alteration mechanisms of the glass in the presence of iron from the storage container, different glass/iron/argillite systems have been altered under conditions close to those in the probable geological storage site. A coupling of post-mortem characterization techniques from the micrometric to nanometric scale allowed to characterize the systems and to identify the iron silicates formed in the glass alteration layer of the SON68 glass and in the iron corrosion products. At 50°C dioctahedral smectites of FeIII (assimilated to nontronite) are preferentially formed, while FeII-rich trioctaedric serpentines (greenalite, berthierine) are detected only at a temperature of 90°C.These nanometric phyllosilicates have a macroscopic impact on the alteration of nuclear glass. Indeed silicon/iron interactions maintain the alteration of the glass and delay the achievement of the residual rate in its alteration regime.

Les bactéries jouent un rôle important dans le fonctionnement des sols et participent activement à l'altération des silicates. L'altération des silicates contrôle en partie la lixiviation d'éléments minéraux majeurs essentiels en solution (maintien de la fertilité des sols). Cependant, si les principaux processus d'altération des silicates sont bien connus en milieu aérobie (acidolyse et complexolyse), cette fonction d'altération bactérienne des silicates n'a jamais été utilisée comme indicateur biologique de la fertilité des sols. Le premier objectif de ce travail de thèse a donc été d'identifier les processus d'altération de 2 micas par des bactéries hétérotrophes en utilisant un modèle d'altération empirique basé sur l'activité des protons et ligands pour identifier et étudier les interactions entre les bactéries et les minéraux. Le traçage des processus d'altération par les isotopes stables du Mg a également été testé. Le second objectif a été de corréler la fonction d'altération de communautés bactériennes aux conditions naturelles rencontrées dans différents sols. Ce travail confirme que l'oxydation partielle du glucose en acides organiques est le mécanisme prédominant par lequel les bactéries amplifient la lixiviation d'éléments en condition aérobie lors de l'altération de la biotite et de la phlogopite, surtout pour des pH proches de la neutralité. Le modèle empirique utilisé a été adapté pour permettre de comparer les taux de libération initiaux du fer lors de l'altération abiotique et bactérienne de micas afin d'identifier les 2 processus majeurs impliqués. Cette approche a permis de mettre en évidence des phénotypes d'altération en fonction du métabolisme, la compétence des souches bactériennes utilisées et des conditions expérimentales. L'étude menée avec les isotopes stables du Mg comme traceurs d'altération n'a pas montré de fractionnements signant chaque processus. L'utilisation du modèle a ensuite permis de montrer que le potentiel d'altération des silicates par les communautés bactériennes dépend de leur origine et en particulier des teneurs en MO et en nutriments des horizons de sols échantillonnés. Deux stratégies d'altération des silicates par ces communautés ont été mises en évidence : (1) les communautés bactériennes isolées des horizons riches en nutriments libèrent peu d'acides organiques, mais très complexants (stratégie K), (2) les communautés isolées d'horizons pauvres en nutriments libèrent beaucoup d'acides organiques peu complexant (stratégie r). L'approche interdisciplinaire proposée dans ce travail permet d'identifier et de caractériser les processus d'altération de phyllosilicates par des bactéries et offre un outil d'identification fonctionnel prometteur pour évaluer la qualité des sols / The bacteria play an important role in soil functioning and are also involved to the weathering of silicate minerals. The silicate weathering controlled the leaching of essential major mineral elements in solution, essential to maintaining soil fertility. However, although the main weathering processes of silicates are well known in aerobic (the proton- and ligand-promoted dissolution), this function of bacterial weathering of silicate minerals has never been used as a biological indicator of soil fertility. The first aim of this work was therefore to identify the process of weathering in two phyllosilicates by heterotrophic bacteria, using an empirical model of silicates weathering based on the activity of protons and ligands to identify and study the interactions between bacteria and minerals. Tracing of weathering processes by isotopic approach using stable isotopes of Mg has also been tested. The second aim was to correlate the “silicate weathering” function of bacterial communities of various soils in field conditions. This study confirms that the partial oxidation of glucose to organic acids is the predominant mechanism by which bacteria accelerate the leaching of elements under aerobic conditions during the weathering of biotite and phlogopite especially at pH close to neutrality. The empirical model used has been adapted to compare the initial release rate of iron in bacterial and abiotic weathering of micas to identify the two major processes involved. This approach highlighted the identification of phenotypes according to the metabolism and the competence of the bacterial strains used. The study with stable isotopes of Mg as tracers of weathering showed no fractionation during the proton- and ligand-promoted dissolution. Using the model in the second part of this work showed that the silicate weathering potential by microbial communities depends on their origin and in particular the contents of OM and nutrients of soil horizons sampled. Two strategies of silicate weathering in these communities have been identified: (1) the bacterial communities isolated from nutrient-rich horizons released few organic acids, but very chelating (strategy K), (2) communities isolated from nutrient-poor horizons release many low chelating organic acids (strategy r). The interdisciplinary approach proposed in this work to identify and characterize the weathering of phyllosilicates by soil heterotrophic bacteria or communities in different environments. It provides a original and promising tool for identifying functional to evaluate the quality of natural soils

Les approches macroscopiques (cinétique chimique) et microscopiques (spectroscopie EXAFS polarisée) ont été couplées dans le but de caractériser les mécanismes moléculaires de fixation de cations divalents (Co, Zn) sur l' hectorite, une smectite magnésienne, et sur le quartz. À pH = 6,5, haute force ionique, et pour un rapport Zn/hectoritc de - 50 umol/g, une adsorption spécifique de Co et Zn a lieu. Cette adsorption n' atteint pas l'équilibre avant plusieurs heures, et coïncide avec une libération initiale accrue de protons et de Mg en solution, puis une inhibition à long terme (t >= 48 h) de la cinétique de dissolution de l' hectorite. Co et Zn adsorbés forment des complexes de surface mononucléaires en continuité structurale de la couche octaédrique des feuillets d' hectorite. À basse force ionique, Co et Zn sont initialement adsorbés par échange cationique. Cette réaction atteint l'équilibre en moins de 5 min. Ces cations forment initialement des complexes de sphère externe sur les sites d'échange, puis ils migrent progressivement vers les sites de bordure des feuillets, où ils forment des complexes de surface similaires à ceux formés à haute force ionique. Le mécanisme et l'amplitude de l'adsorption de Zn sur l'hectorite à pH 7,3, à haute force ionique et pour un rapport Zn/hectorite de 1480 umol/g, dépend de la concentration en silice dissoute [Si) . La quantité de Zn adsorbé est limitée pour [Si) ~ 30-60 umoI/L, et Zn forme des polymères de petite taille (2-3 octaèdres) en continuité structurale de la couche octaédrique de l'hectorite. La quantité de Zn adsorbé est beaucoup plus importante pour [Si) ~ 540 umoI/L; cette adsorption est corrélée à une adsorption de Si, et correspond à la nucléation de phyllosilicates TOT zincifères en épitaxie dans le plan ab des feuillets. Une analyse approfondie de spectres EXAFS de Co adsorbé sur le quartz révèle que cet élément polymérise sous forme de couches d'octaèdres liées à des couches de tétraèdres de Si, pour former des phyllosilicates cobaltifères. Le mécanisme de cette néoformation est discuté.

Ce travail de thèse a appréhendé les mécanismes de stockage/libération, d’un point de vue élémentaire et isotopique, du calcium (Ca) et du strontium (Sr) sur ou dans des phases minérales communes des sols (minéraux primaires, minéraux argileux, oxy-hydroxydes, carbonate pédogénétiques). Une méthode de mesure robuste du δ88Sr a dû être développée et validée par la mesure de matériaux de références internationaux, pour la plupart jamais mesuré dans la littérature. Les résultats montrent que l’adsorption du Ca sur des minéraux phyllosilicatés génère un fractionnement isotopique par prélèvement préférentiel de l’isotope léger (40Ca) dans nos conditions expérimentales lorsque les minéraux possèdent une charge structurale et une surface spécifique importante et/ou un espace interfoliaire ouvert à l’adsorption de cations hydratés. Une étude sur des rhizolithes en milieu naturel a mis en avant que l’utilisation des isotopes du Ca et du Sr permet un traçage de source et de mécanismes efficaces dans les thématiques touchant au stockage de ces deux éléments dans les sols. / This PhD thesis examined the mechanisms of storage and release, from and elementary and isotopically point of view, of calcium (Ca) and strontium (Sr) onto or into mineral phases commonly encountered within soils (primary minerals, clay minerals, oxy-hydroxides, pedogenic carbonate). A robust δ88Sr measurements method had to be developed in the laboratory and validated by the measurement of international reference materials, mostly never measured in the literature. The results of this work show that Ca adsorption onto phyllosilicate minerals generates a quantifiable isotopic fractionation by preferential uptake of the light isotope (40Ca) under our experimental conditions when the minerals have a significant structural charge and specific surface area and/or an interlayer space open to hydrated cations adsorption. A study on rhizoliths in natural environment has also highlighted that the combination of Ca and Sr isotopes allows an effective tracing of sources and mechanisms in the problematic related to the storage of these two elements within soils.

Com o objetivo de avaliar os efeitos da interação entre o silício (Si) e o fósforo (P) na planta e no solo, foram realizados três experimentos. No primeiro experimento, avaliou-se o efeito de duas fontes de Si (wollastonita e filossilicato) em diferentes doses (0 a 250 mg dm-3) sobre o aproveitamento do P do superfosfato triplo marcado com o radioisótopo 32P. Utilizouse o arroz (Oryza sativa) como planta teste. Neste primeiro experimento, as duas fontes de Si promoveram incremento na quantidade do elemento nas plantas, porém tiveram comportamento diferente quanto à produção de matéria seca da parte aérea e de P acumulado, tendo apenas o filossilicato promovido ganhos para estas variáveis. Constatou-se que o maior acúmulo do P pela planta em relação ao tratamento controle (sem Si) foi devido à maior absorção do nutriente do solo e não do fertilizante, sendo baixo o aproveitamento do superfosfato triplo pelas plantas para as duas fontes de Si. No entanto, a wollastonita liberou maiores quantidades de Si no solo em relação ao filossilicato. No segundo experimento foram avaliadas as formas de aplicação (em sulco ou misturado ao solo) de Si e P no aproveitamento do P do superfosfato triplo pelo arroz. Aplicou-se uma dose de Si (125 mg dm-3) intermediária daquelas utilizadas no primeiro experimento para ambas as fontes de Si, wollastonita e filossilicato, e a mesma dose de P (53 mg dm-3). De acordo com os resultados desse experimento, as duas fontes de Si apresentaram respostas similares, não havendo diferença para nenhuma variável analisada. No terceiro experimento foi realizado um teste de incubação (sem planta), no qual se aplicou as mesmas doses de Si do primeiro experimento (0 a 250 mg dm-3) e a mesma dose de P (53 mg dm-3), a fim de avaliar o comportamento da liberação de Si pelas fontes wollastonita e filossilicato em função do tempo, entre 0 a 90 dias. Foram realizadas coletas mensais de amostras do solo. Verificou-se que ambas as fontes de Si apresentaram a maior liberação deste elemento no solo próximo aos 60 dias após a aplicação. O teor de P no solo, no terceiro experimento (de incubação do solo), apesar de ter sido aplicado em uma única dose, comportou-se de maneira similar ao Si, tendo aumentado com o passar do tempo e obtendo valor máximo próximo de dois meses após a aplicação. Nos três experimentos, verificou-se que apesar do extrator ácido acético indicar maior teor de Si no solo, o extrator cloreto de cálcio obteve dados mais coerentes quando comparado com o Si acumulado na parte aérea das plantas de arroz. Dessa forma, a utilização do Si pode constituir um componente útil para o manejo da adubação, tendo em vista que houve interação positiva com o P, que é um dos nutrientes mais limitantes nos solos brasileiros. / With the aim of evaluating the effects of the interaction between the silicon (Si) and phosphorus (P) in plant and soil, three experiments were carried. In the first experiment, the effect of two sources of Si (wollastonite and phyllosilicate) at different doses (0-250 mg dm- 3) on P recovery from triple superphosphate labeled with the radioisotope 32P was evaluated. We used the rice (Oryza sativa) as a test plant. In this first experiment, the two sources of Si promoted increase in the amount of the element in plants, but have different behavior regarding the production of dry matter of shoots and P uptake, with only the phyllosilicate promoted gains for these variables. It was found that the greater accumulation of P by the plant compared to the control treatment (without Si) was due to higher absorption of nutrients from the soil and fertilizer, and low utilization of the triple superphosphate by plants to the two sources of Si However, wollastonite released higher amounts of Si in the soil in relation to the phyllosilicate. In the second experiment the application forms (in groove or mixed with soil) of Si and P in P recovery from triple superphosphate for rice were evaluated. Applied a dose of Si (125 mg dm-3) intermediate from those used in the first experiment for both sources of Si, wollastonite and phyllosilicate, and the same dose of P (53 mg dm-3). According to the results of this experiment, the two sources of Si showed similar responses, with no differences for any variable analyzed. In the third experiment a test incubation (no plant) in which applied the same doses of Si in the first experiment (0 to 250 mg dm-3) and the same dose of P (53 mg dm-3) was performed to order to evaluate the behavior of the wollastonite for Si sources and phyllosilicate a function of time, between 0-90 days. Monthly collections of soil samples were taken. It was found that both sources of Si had the highest soil release in the next 60 days after application. The content of P in the third experiment (incubation ground), although it has been applied in a single dose, behaved similarly, and increased with the passage of time and getting maximum near two months the application. In three experiments, we found that despite the extractor acetic acid indicate higher Si content in the soil, the extractor calcium chloride obtained more consistent data when compared with the Si accumulated in shoots of rice plants. Thus, the use of Si can be a useful for fertilization management component, considering that there was a positive interaction with P, which is one of the most limiting nutrients in Brazilian soils.

Com o objetivo de avaliar os efeitos da interação entre o silício (Si) e o fósforo (P) na planta e no solo, foram realizados três experimentos. No primeiro experimento, avaliou-se o efeito de duas fontes de Si (wollastonita e filossilicato) em diferentes doses (0 a 250 mg dm-3) sobre o aproveitamento do P do superfosfato triplo marcado com o radioisótopo 32P. Utilizouse o arroz (Oryza sativa) como planta teste. Neste primeiro experimento, as duas fontes de Si promoveram incremento na quantidade do elemento nas plantas, porém tiveram comportamento diferente quanto à produção de matéria seca da parte aérea e de P acumulado, tendo apenas o filossilicato promovido ganhos para estas variáveis. Constatou-se que o maior acúmulo do P pela planta em relação ao tratamento controle (sem Si) foi devido à maior absorção do nutriente do solo e não do fertilizante, sendo baixo o aproveitamento do superfosfato triplo pelas plantas para as duas fontes de Si. No entanto, a wollastonita liberou maiores quantidades de Si no solo em relação ao filossilicato. No segundo experimento foram avaliadas as formas de aplicação (em sulco ou misturado ao solo) de Si e P no aproveitamento do P do superfosfato triplo pelo arroz. Aplicou-se uma dose de Si (125 mg dm-3) intermediária daquelas utilizadas no primeiro experimento para ambas as fontes de Si, wollastonita e filossilicato, e a mesma dose de P (53 mg dm-3). De acordo com os resultados desse experimento, as duas fontes de Si apresentaram respostas similares, não havendo diferença para nenhuma variável analisada. No terceiro experimento foi realizado um teste de incubação (sem planta), no qual se aplicou as mesmas doses de Si do primeiro experimento (0 a 250 mg dm-3) e a mesma dose de P (53 mg dm-3), a fim de avaliar o comportamento da liberação de Si pelas fontes wollastonita e filossilicato em função do tempo, entre 0 a 90 dias. Foram realizadas coletas mensais de amostras do solo. Verificou-se que ambas as fontes de Si apresentaram a maior liberação deste elemento no solo próximo aos 60 dias após a aplicação. O teor de P no solo, no terceiro experimento (de incubação do solo), apesar de ter sido aplicado em uma única dose, comportou-se de maneira similar ao Si, tendo aumentado com o passar do tempo e obtendo valor máximo próximo de dois meses após a aplicação. Nos três experimentos, verificou-se que apesar do extrator ácido acético indicar maior teor de Si no solo, o extrator cloreto de cálcio obteve dados mais coerentes quando comparado com o Si acumulado na parte aérea das plantas de arroz. Dessa forma, a utilização do Si pode constituir um componente útil para o manejo da adubação, tendo em vista que houve interação positiva com o P, que é um dos nutrientes mais limitantes nos solos brasileiros. / With the aim of evaluating the effects of the interaction between the silicon (Si) and phosphorus (P) in plant and soil, three experiments were carried. In the first experiment, the effect of two sources of Si (wollastonite and phyllosilicate) at different doses (0-250 mg dm- 3) on P recovery from triple superphosphate labeled with the radioisotope 32P was evaluated. We used the rice (Oryza sativa) as a test plant. In this first experiment, the two sources of Si promoted increase in the amount of the element in plants, but have different behavior regarding the production of dry matter of shoots and P uptake, with only the phyllosilicate promoted gains for these variables. It was found that the greater accumulation of P by the plant compared to the control treatment (without Si) was due to higher absorption of nutrients from the soil and fertilizer, and low utilization of the triple superphosphate by plants to the two sources of Si However, wollastonite released higher amounts of Si in the soil in relation to the phyllosilicate. In the second experiment the application forms (in groove or mixed with soil) of Si and P in P recovery from triple superphosphate for rice were evaluated. Applied a dose of Si (125 mg dm-3) intermediate from those used in the first experiment for both sources of Si, wollastonite and phyllosilicate, and the same dose of P (53 mg dm-3). According to the results of this experiment, the two sources of Si showed similar responses, with no differences for any variable analyzed. In the third experiment a test incubation (no plant) in which applied the same doses of Si in the first experiment (0 to 250 mg dm-3) and the same dose of P (53 mg dm-3) was performed to order to evaluate the behavior of the wollastonite for Si sources and phyllosilicate a function of time, between 0-90 days. Monthly collections of soil samples were taken. It was found that both sources of Si had the highest soil release in the next 60 days after application. The content of P in the third experiment (incubation ground), although it has been applied in a single dose, behaved similarly, and increased with the passage of time and getting maximum near two months the application. In three experiments, we found that despite the extractor acetic acid indicate higher Si content in the soil, the extractor calcium chloride obtained more consistent data when compared with the Si accumulated in shoots of rice plants. Thus, the use of Si can be a useful for fertilization management component, considering that there was a positive interaction with P, which is one of the most limiting nutrients in Brazilian soils.

L'anisotropie des propriétés physiques macroscopiques d'un échantillon polycristallin ne peut être observée que si les cristallites de cet échantillon sont préférentiellement orientés. <br />L'intérêt de l'analyse quantitative des orientations préférentielles (QTA) a joué un rôle primordial dans le passé, et encore aujourd'hui, par exemple pour optimiser les propriétés mécaniques d'alliages métalliques, pour comprendre les déformations mises en jeu dans certains phénomènes géophysiques ou pour limiter les pertes de matière lors de procédés industriels.<br /><br /><br /> Récemment, l'élaboration de matériaux aux propriétés physiques très anisotropes a relancé un intérêt croissant pour l'analyse texturale. C'est le cas pour les ferro et piézo-électriques, les supraconducteurs, les conducteurs ioniques, les matériaux composites, les polymères ... L'utilisation de la diffraction (rayons X, neutrons et électrons) a aujourd'hui largement remplacé les anciennes méthodes pétrographiques (principalement microscopies optiques en lumière polarisée), qualitatives et souvent incomplètes: <br /><br /><br /> - pour le calcul de certaines propriétés physiques macroscopiques, conséquences de tenseurs anisotropes (propriétés mécaniques, propagation anisotrope des ondes acoustiques, propriétés magnétiques), qui peuvent être modélisées en introduisant des données de QTA.<br /><br /><br /> - pour comprendre la corrélation qui existe entre les tenseurs microscopiques et leur répercutions macroscopique dans des échantillons polycristallins texturés (piézo et ferroélectricité ...)<br /><br /><br /> - pour déterminer les modes de croissance (épitaxie ...), donc optimiser l'élaboration.<br /><br /><br /> La limite de certaines techniques d'investigation structurale a aussi pu être repoussée grâce à l'incorporation des informations de QTA. Par exemple: <br /><br /><br /> - en EXAFS, grâce à l'emploi combiné de l'EXAFS polarisé et de la QTA, pour atteindre des paramètres structuraux particuliers<br /><br /><br /> - en couplant les analyses Rietveld et WIMV pour l'analyse combinée structure-texture-contraintes <br /><br /><br /> - en analyse de texture elle-même, en utilisant les méthodes du profil complet pour l'étude de la texture de composés partiellement cristallisés ou turbostratiques,<br /><br /><br /> Ces approches sont décrites dans ce travail.

L'objectif de la thèse est de créer une collection de roches et minéraux analogues pour calibrer et tester les futurs (et existants) instruments de vol, en accord avec la géologie de Mars afin de préparer les futures missions in situ (MSL-2011 et ExoMars-2018). Les échantillons sont caractérisés avec des instruments de laboratoire (microscope, Raman, IR, DRX, MEB, microsonde électronique, et ICP-MS), mais aussi avec des instruments de vol en développement (Mössbauer MIMOS II, les spectromètres ExoMars Raman et IR (MicroOmega)). L'ensemble des échantillons sont décrits sur une base de données en ligne à l'adresse : www.isar.cnrs-orleans.fr. Une partie de cette thèse est dédiée au développement d'un instrument de cathodoluminescence, qui peut être adapté au spatial. L'étude des processus d'altération des basaltes sur Terre montrant des similarités avec les processus de surface et de subsurface présent sur Mars, permet d'aider à mieux comprendre et interpréter les objets sur Mars. Pour cela, et pour compléter la collection, des basaltes altérés dans des conditions hydrothermales et acides ont été collecté dans la mine de Skouriotissa à Chypre. L'évolution minéralogique des basaltes à travers les différents facies d'altération a été étudiée. Parce que les basaltes terrestres sont plus pauvres en Fe et Mg que les basaltes martiens, deux basaltes artificiels ont été synthétisé. Ces deux échantillons sont différents en terme de refroidissement (~110°C/h et trempé). On note que le basalte refroidi lentement montre des textures spinifex similaires aux komatiites. Si ce type de basalte est présent sur Mars, et altéré en présence d'eau, ceci peut avoir d'importantes implications exobiologiques.

Submitted by Jesiel Ferreira Gomes (jesielgomes@ufcg.edu.br) on 2018-04-19T18:12:18Z No. of bitstreams: 1 MATHEUS AMADOR NICCHIO – DISSERTAÇÃO (PPGEPM) 2017.pdf: 3849783 bytes, checksum: 788d0c6e30dc2784af843fcbd619289a (MD5) / Made available in DSpace on 2018-04-19T18:12:18Z (GMT). No. of bitstreams: 1 MATHEUS AMADOR NICCHIO – DISSERTAÇÃO (PPGEPM) 2017.pdf: 3849783 bytes, checksum: 788d0c6e30dc2784af843fcbd619289a (MD5) Previous issue date: 2017-02 / Neste trabalho nós identificamos a origem de argilominerais e a evolução microestrutural de bandas de deformação filossilicáticas em rochas porosas ausentes de matriz, de composição arcoseana lítica, de baixo grau de litificação. Adicionalmente, estimamos a influência nas propriedades petrofísicas exercidas pelos diferentes estágios evolutivos da deformação e as comparamos com rocha não deformada e em bandas de deformação com clay smearing. Nós estudamos bandas de deformação presentes em zonas de dano de clusters bem desenvolvidos em afloramento fortemente deformado por falhas transtensivas de direções principais NE-SW e NW-SE. A identificação da composição do material de preenchimento de bandas de deformação foi realizada através da análise química pontual. Os processos deformacionais foram identificados através de análise microestrutural, utilizando como critério de identificação o tipo de banda e o teor de argilominerais presentes no núcleo da deformação. Os estágios evolutivos das estruturas foram identificados através da análise dos padrões microestruturais tais como foliação S-C e feições sigmoidais em zonas ricas em argila. As análises petrofísicas foram realizadas através de medições laboratoriais em plugues de rochas. As análises químicas realizadas no núcleo das bandas de deformação e nos minerais do arcabouço indicaram a adição de óxidos de ferro como único componente distinto dos encontrados no arcabouço original da rocha, indicando a autigênese de argilominerais,com percolação de fluidos aquosos em ambiente oxidante. As características microestruturais indicaram a presença de mais de um estágio evolutivo, iniciando-se pelo processo de catáclase. A continuação do cisalhamento e a autigênese de argilominerais no núcleo da banda ocasionaram em estiramento de zonas mais concentradas em argilominerais, chegando a um estágio final, onde ocorre a presença de foliação do tipo S-C marcada pela orientação de argilominerais autigênicos. As análises petrofísicas indicaram redução de até 2 ordens de grandeza na permeabilidade em amostras com bandas de deformação filossilicaticas autigênicas em comparação à rocha não deformada, não havendo mudanças significativas em diferentes estágios evolutivos após a formação de argilominerais. Já bandas de deformação com clay smearing apresentaram redução de cerca de 3 ordens de grandeza, apresentando um potencial selante superior ao das bandas filossilicáticas por autigênese. / In this work we describe the genetic processes and the microstructural evolution of phyllosilicate deformation bands developed in poorly lithified, high porosity lithic arkosean rocks with no clay matrix. Additionally, we estimate the influence on the petrophysical properties exerted by the different evolutionary stages of the deformation and compare them with non-deformed rock and deformation bands with clay smearing. We studied deformation bands present in damage zones of well developed clusters in strongly deformed outcrop, affected by transtensive faults of the main NE-SW and NW-SE directions. The deformation bands filling material were identified by punctual chemical analysis. The deformation processes were identified through microstructural analysis, using as identification criterion the type of deformation band and the clay minerals content in deformation band nucleous. The evolutionary stages of the structures were identified through analysis of microstructural patterns such as S-C foliation and sigmoidal features in clay-rich areas. The petrophysical analyzes were performed through laboratory measurements on rock plugs. Chemical analyzes were carried out in the core of the deformation bands and the minerals of the framework indicated the addition of iron oxides as the only component distinct from those found in the original rock structure, indicating clay authigenesis, with percolation of aqueous fluids in an oxidizing environment. The microstructural characteristics indicated the presence of more than one evolutionary stage, beginning with cataclasis. The continuation of shear and the clay minerals authigenesis in the deformation band nucleus resulted in stretching of areas with high clay concentration, reaching a final stage, where S-C type foliation marked by the orientation of autigenic clays occurs. The petrophysical analysis indicated reduction of up to 2 orders of magnitude in the permeability in samples with autigenic phyllosilicate deformation bands in comparison to the non-deformed rock, showing no significant changes in different evolutionary stages after the formation of clay minerals. Deformation bands with clay smearing presented a reduction of about 3 orders of magnitude, presenting a sealant potential superior to that of the phyllosilicate deformation bands by authigenesis.

La limitation de perméation des gaz aux bordes de l’encapsulation des photovoltaïques organiques flexibles a été adressée par l’identification des chemins de perméation du vapeur d’eau et par la formulation des nanocomposites adhésives. Une version modifiée du test de calcium optique a été développée pour identifier l’importance des chemins de perméation différents présent dans l’encapsulation des modules photovoltaïques organiques flexibles. Les nanoparticules des phyllosilicates et les nanoparticules des zéolithes ont été dispersées dedans les formulations des adhésifs différents incluant les adhésifs acryliques sensibles à pression et les adhésifs UV réticulables. Les propriétés mécaniques, optiques, et barrières de vapeur d’eau des nanocomposites ont été caractérisés en plus de leur photo-stabilité sous irradiation UV. Les nanocomposites ont été également utilisés pour encapsuler les cellules photovoltaïques organiques et la stabilité des dispositifs a été évaluer sous les conditions de vieillissement accélérés d’humidité et température. / In order to address the issue of lateral water and oxygen permeation through the sides of the encapsulation and into flexible organic photovoltaic (OPV) devices, the water vapor permeation pathways were identified and several adhesive nanocomposites formulated and tested to limit these pathways. To identify the relative importance of the various water vapor permeation pathways present in the encapsulation of flexible OPV devices, a modified version of the optical calcium test was developed. Passive nanoparticles (phyllosilicates) and active nanoparticles (zeolites) were both evaluated dispersed in UV curing acrylate adhesives and acrylic block copolymer pressure sensitive adhesives. The nanocomposites were characterized for their mechanical and optical properties as well as their water vapor permeation and UV photostability. The adhesives were also used to encapsulate OPV devices and tested in accelerated humidity aging.