The major hurdle in the development of transdermal route as a versatile drug delivery method is the formidable transport barrier provided by the stratum corneum. Despite decades of research to overcome the stratum corneum barrier, limited success has been achieved. The objectives of this research were to develop and characterize two different strategies to overcome the stratum corneum barrier for transdermal delivery of biopharmaceuticals and vaccines. In the first strategy, coated microneedles (sharp-tipped, micron-sized structures) were developed to enable delivery of drugs directly into the skin by bypassing the stratum corneum barrier. In the second strategy, instead of bypassing the barrier, microdermabrasion was used to selectively abrade stratum corneum with sharp microparticles for topical drug application. Coated microneedles For developing painless microneedles, the first detailed study was performed to characterize the effect of microneedle geometry on pain caused by microneedle insertions in human volunteers. This study demonstrated that microneedles are significantly less painful than a 26-gage hypodermic needle and that decreasing microneedle length and numbers reduces pain. Next, the first in-depth study of microneedle coating methods and formulations was performed to (i) develop a novel micron-scale dip-coating process, (ii) test the breadth of compounds that can be coated onto microneedles, and (iii) develop a rational basis to design novel coating formulations based on the physics of dip-coating. Finally, a plasmid DNA-vaccine was coated onto microneedles to immunize mice, to provide the first evidence that microneedle-based skin immunization can generate a robust in vivo antigen-specific cytotoxic-T-lymphocyte response using similar, or lower, DNA doses on microneedles as when using the gene gun or intramuscular injection. Microdermabrasion We demonstrated for the first time that microdermabrasion in monkeys and humans can selectively, yet completely remove the stratum corneum layer. Using a mobile mode of microdermabrasion, an increase in the number of treatment passes led to greater tissue removal. Furthermore, topical application of Modified Vaccinia Ankara virus after microdermabrasion induced virus-specific antibodies in monkeys. In conclusion, both coated microneedles and microdermabrasion were developed to enable delivery of biomolecules into the skin, indicating their potential for transdermal delivery of a wide range of biopharmaceuticals and vaccines.

Avec le développement de l’éolien, les prescriptions techniques de raccordement de cette technologie obligeront le maintient de sa connexion lors d’incidents sur la tension du réseau électrique. L’enjeu pour le gestionnaire du réseau est de pouvoir utiliser tous les générateurs pour garantir la stabilité du système électrique.A partir d’un modèle dynamique d’une éolienne à base de Machine Asynchrone à Double Alimentation (MADA), une commande vectorielle améliorée a été proposée en prenant en compte la dynamique du flux statorique engendrée par la chute de tension. Les performances supérieures en terme de maintient de la production ont été établies par comparaison avec la méthode de commande classique. Son domaine d’utilisation a été également déterminé.Pendant les creux de tension importants, une protection matérielle (crowbar) est implémentée avec un contrôle de la démagnétisation de la MADA. En outre, de la puissance réactive peut être produite à la fois par la MADA et par le convertisseur connecté au réseau électrique au cours de la défaillance du réseau.Un contrôle vectoriel à hystérésis des courants pour les deux convertisseurs électroniques multiniveaux est proposé et évalué pour améliorer la réponse dynamique de ces convertisseurs et pour réduire les effets des variations des paramètres sur les performances de la commande. Selon la durée du défaut, des objectifs différents de contrôle doivent être réalisés en priorité pour empêcher des surintensités rotoriques et pour fournir de la puissance réactive. Une reconfiguration complète du dispositif de commande de cette éolienne est détaillée pour renforcer le maintient de la production éolienne lors de défaillances / With the massive development of wind energy, the technical requirements for connecting this technology will require the improvement of the fault ride-through capability of grid-connected wind turbines. The task for the grid system operator is to use all generators to ensure the stability of the electrical system.From a dynamic model of a Doubly Fed Induction Generator (DFIG) based wind generator, an improved vector control has been proposed by taking into account the dynamics of the magnetic flux, which are generated by the voltage dip. The higher performances have been established by comparison with the conventional control method. The operation domain was also determined.During serious voltage dips, a hysteresis control scheme of the active Crowbar is proposed to protect the system within a demagnetization method of the DFIG. Moreover, additional reactive power can be produced both by the MADA and the grid-side converter in order to support the electric network during the grid fault.A space vector hysteresis current control strategy of both three-level converters is proposed to improve the dynamic response of the system and to reduce the parameter variation effects on the control performanceDepending on the grid fault duration, different control objectives have to be achieved with priority to restrain the rotor over-current or to supply reactive power. Then the reconfiguration scheme of the control strategies of high power DFIG wind turbine system is proposed to enhance the fault ride-through capability of the DFIG system. With this specific methodology, the DFIG can stay connected and can supply maximal reactive current during voltage dips to help voltage recovery

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-16T11:47:56Z No. of bitstreams: 1 FABIANA MEDEIROS DO NASCIMENTO SILVA - TESE (PPGEQ) 2017.pdf: 6622967 bytes, checksum: bfed827814b744a5e9e9e565d28f0682 (MD5) / Made available in DSpace on 2018-08-16T11:47:56Z (GMT). No. of bitstreams: 1 FABIANA MEDEIROS DO NASCIMENTO SILVA - TESE (PPGEQ) 2017.pdf: 6622967 bytes, checksum: bfed827814b744a5e9e9e565d28f0682 (MD5) Previous issue date: 2017 / Capes / O presente trabalho tem como objetivo geral sintetizar as membranas zeolíticas (Mordenita/α-alumina), utilizando os métodos de síntese hidrotérmica, crescimento secundário: dip-coating e transporte em fase vapor, para serem avaliadas no processo de separação emulsão óleo/água. Dentro deste contexto foram avaliados alguns parâmetros, destacando-se, a influência do tempo de cristalização na síntese da zeólita mordenita, a influência do precursor (sulfato de alumínio e gibsita) na síntese da membrana zeolítica, influência dos métodos de síntese das membranas zeolíticas e os testes de permeação de água e o processo de separação emulsão óleo/água. A síntese da zeólita mordenita foi realizada utilizando o método hidrotérmico a 170°C, com tempos de cristalização de 24, 36, 48, 72, 96 e 120 horas, a fim de avaliar a cristalinidade da zeólita, e selecionar o melhor tempo para a síntese das membranas zeolíticas. Os suportes cerâmicos α-alumina foram preparados a partir da decomposição dos precursores sulfato de alumínio a 1000°C e gibsita a 1200ºC por 2 horas, e conformados, compactados e sinterizados a 1300ºC por 2h, e então submetidos às técnicas de caracterização: Difratometria de raios X (DRX), Adsorção Física de Nitrogênio, Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Fluorescência de raios X por Energia Dispersiva (FRX-ED) e Termogravimétrica/Térmica Diferencial (TG/DTA). As membranas zeolíticas foram sintetizadas pelos métodos de síntese hidrotérmica, crescimento secundário: dip-coating e transporte em fase vapor a 170°C por 72h e caracterizadas por DRX e MEV. Os suportes cerâmicos e as membranas zeolíticas foram avaliadas em testes de permeação de água e no sistema de separação emulsão óleo/água de um efluente sintético, utilizando um processo de separação por membrana (PSM). Os ensaios foram realizados nas condições de concentração inicial da emulsão 100 mg.L-1, temperatura de 25 °C e pressão de 2,5 bar, permitindo avaliar a permeabilidade e a seletividade a partir da variação da concentração do permeado em (mg.L-1) e da percentagem de rejeição ao óleo (%R). A partir dos resultados obtidos para a síntese dos materiais, pode-se observar a efetiva formação da zeólita mordenita em fase pura e cristalina. Os precursores foram decompostos de maneira satisfatória obtendo a fase α-alumina. A manutenção da fase α-alumina pós-produção dos suportes cerâmicos foi confirmada após caracterização. De acordo com os resultados exibidos pelas análises de DRX e MEV as membranas zeolíticas MZMOR/α-alumina apresentaram uma distribuição homogênea e uniforme dos cristais zeolíticos correspondentes à fase mordenita, sem a presença de impurezas, livres de defeitos e sem fissuras, confirmando a formação da estrutura da membrana zeolítica pelos três métodos de síntese, utilizados neste trabalho. A zeólita mordenita se mostrou excelente em relação à adesão e formação da camada zeolítica sobre o suporte cerâmico α-alumina. A partir da avaliação da permeabilidade e seletividade nos testes de separação da emulsão óleo/água, pode-se concluir que a inserção da zeólita mordenita aos suportes cerâmicos melhorou o processo de separação da emulsão óleo/água. Em termos de eficiência no processo de separação, considera-se que a membrana zeolítica MZMOR/α – Al2O3 (SHGB) foi a que apresentou melhor relação entre fluxo e capacidade seletiva, mostrando a eficácia da utilização das membranas zeolíticas. Todas as membranas zeolíticas sintetizadas e avaliadas mostraram-se promissoras. / The objective of the present work is to synthesize zeolite membranes (Mordenite/α-alumina) using hydrothermal synthesis, secondary growth: dip-coating and vapor-phase transport, to be evaluated in the oil/water emulsion separation process. The influence of the crystallization time on the synthesis of the mordenite zeolite, the influence of the precursor (aluminum sulphate and gibsite) on the synthesis of the zeolite membrane, influence of the synthesis methods of the zeolite membranes and the water permeation tests and the oil/water emulsion separation process. The synthesis of the mordenite zeolite was performed using the hydrothermal method at 170°C, with crystallization times of 24, 36, 48, 72, 96 and 120 hours, in order to evaluate the crystallinity of the zeolite, and to select the best time for the synthesis of zeolite membranes. The α-alumina ceramic supports were prepared from the decomposition of the aluminum sulfate precursors at 1000°C and gibsite at 1200°C for 2 hours, and conformed, compacted and sintered at 1300°C for 2h, and then submitted to the characterization techniques: (XRD), Nitrogen Physical Adsorption, Scanning Electron Microscopy (SEM), X-ray Fluorescence Spectroscopy (FRX-ED) and Thermogravimetric/Differential Thermal (TG/DTA). The zeolite membranes were synthesized by hydrothermal synthesis, secondary growth: dip-coating and vapor-phase transport at 170°C for 72 hours and characterized by XRD and SEM. Ceramic supports and zeolite membranes were evaluated in water permeation tests and in the oil/water emulsion separation system of a synthetic effluent using a membrane separation process. The tests were carried out under the conditions of initial concentration of the emulsion 100 mg.L-1, temperature of 25°C and pressure of 2,5 bar, allowing to evaluate the permeability and the selectivity from the variation of the permeate concentration in (mg. L-1) and the percentage of oil rejection (% R). From the results obtained for the synthesis of the materials, it is possible to observe the effective formation of zeolite mordenite in pure and crystalline phase. The precursors were satisfactorily decomposed to give the α-alumina phase. The maintenance of the post-production α-alumina phase of the ceramic supports was confirmed after characterization. The MZMOR/α-alumina zeolite membranes presented a homogeneous and uniform distribution of the zeolite crystals corresponding to the mordenite phase, without the presence of impurities, free of defects and without cracks, confirming the formation of the structure of the zeolite membrane by the three methods of synthesis, used in this work. The mordenite zeolite showed excellent adhesion and formation of the zeolitic layer on the ceramic support α-alumina. From the evaluation of the permeability and selectivity in the oil/water emulsion separation tests, it can be concluded that the insertion of the mordenite zeolite to the ceramic supports improved the separation process of the oil/water emulsion. In terms of efficiency in the separation process, the zeolite membrane MZMOR/α-Al2O3(SHGB) was considered to have the best relationship between flow and selectivity, showing the efficacy of zeolite membranes. All zeolite membranes synthesized and evaluated were promising.

Le travail de thèse porte sur les méthodes de synthèse de nanostructures de dioxyde de titane et de leurs études physicochimiques afin de préciser les corrélations entre la morphologie, le dopage métallique, les caractéristiques structurales avec l'efficacité photocatalytique. Le grand intérêt pour les nanomatériaux TiO2 réside dans la mise au point de nouvelles sources d'énergie ou la conservation de l’environnement par des processus photocatalytiques. Cependant, la limitation principale de TiO2 est du au large gap électronique (eV ~3,2) du polymorphe Anatase. Ainsi, un des objectifs importants pour l'amélioration de l’efficacité des nanomatériaux TiO2 est d'augmenter leur photoactivité en décalantla création de paires d'électron-trou de l’UV à la gamme du visible. D'ailleurs, on a montré que l'utilisation de nanostructures 1D de TiO2 (nanotubes) a amélioré la collection de charges, en favorisant leur transport dans les structures 1D, qui par conséquent réduit au minimum la recombinaison et prolonge les durées de vie des électrons.La première partie de ce travail est dédiée à la synthèse des nanopoudres TiO2 dopées par des ions métalliques (Ag, Cu, Eu) préparés par sol-gel. Même avec différents éléments de dopage qui apparemment peuvent adopter le même état de valence (2+) (Cu2+, Ag2+, Eu2+), différents comportements ont été démontrés pour l'incorporation efficace de ces ions dans la structure de TiO2. L'anomalie entre les rayons ioniques des différents éléments utilisés module le rapport du dopage substitutionnel. Ceci est en effet réalisé pour Cu2+ mais dans moins d'ampleur pour Ag2+ tandis que les ions d'europium forment une ségrégation de phase Eu2Ti2O7. La dégradation de colorants de bleu de méthylène (MB) a étéaméliorée légèrement avec les échantillons dopés Ag. La raison a été attribuée aux clusters métalliques Ag qui ont été en effet mis en évidence à travers leur bande d’absorption plasmonique. La deuxième partie porte sur des couches minces de TiO2 dopés (Cu, Ag, et Eu) qui ont été élaborés par sol-gel et spin-coating et dipcoating. Les paramètres optimaux ont été obtenus pour réaliser les films cristallins mais présentant une organisation mésoporeuse qui dépend également du processus de dopage. Des études de Photocatalyse ont été également réalisées et l'efficacité des films ont été comparées en fonction des éléments dopants. La troisième partie de la thèse est liée à la modification morphologique des nanoparticules pour former des nanotubes à l'aide de la méthode hydrothermale sous pression contrôlée. Un plan d'expérience basé sur la méthode Taguchi a été utilisé pour la détermination des paramètres optimaux.Les nanotubes TiO2 augmentent la surface spécifique en comparaison avec les nanoparticules. La dégradation de bleu deméthylène par les nanotubes a montré une efficacité photocatalytique plus élevée qu’avec les nanopoudres TiO2 pures etdopés Ag. / The thesis work is focused on the synthesis methods of titanium dioxide nanostructures and their physico-chemical studies in order to point out the correlations between the morphology, metal doping, structural features with the photocatalytic efficiency. The great interest on TiO2 nanomaterials deals with new sources of energy or in the environment preservation through the photocatalytic properties. However, the main limitations is due to the wide band gap (~3.2 eV) of the anatase polymorph. Thus, a major objective for improvement of the performance of TiO2 nanomaterials is to increase theirphotoactivity by shifting the onset of the electron-hole pairs creation from UV to the visible range. Moreover, it was found that using onedimensional (1-D) TiO2 (nanotubes) improved the charge collection by 1D nanostructures which consequently minimizes the recombination and prolongate the electron lifetimes. The first part of this work is focused on the synthesis of TiO2 nanopowders doped with metallic ions (Ag, Cu, Eu) prepared by Solgel. Even with different doping elements which apparently can adopt the same valence state (2+) such as (Cu2+, Ag2+,Eu2+), different behaviors were demonstrated for the effective incorporation of these ions in the host structure of TiO2. The discrepancy between ionic radii of the different used elements modulates the ratio of the substitutional doping. This is indeed achieved for Cu2+ but in less extent for Ag2+ while Europium ions form segregated phase as Eu2Ti2O7. The experiments on the degradation of methylene blue (MB)dyes have shown slight improvement with Ag-doped samples. The reason was tentatively attributed to the Ag clusters which were indeed demonstrated through their plasmon optical band. The second part of the work concerns thin films of TiO2 doped (Cu, Ag, and Eu) which were elaborated by spin coating and dip coating. The optimal parameters were obtained to achieve crystalline films but presenting mesoporous organisation which also depends on the doping process. Photocatalysis investigations were also realized and the efficiency of the films compared as function of the doping elements.The third part of the thesis is related to the morphological modification from nanoparticles to nanotubes by using the hydrothermal method with controlled pressure. An experimental design based on Taguchi Method was employed for the determination of the optimal parameters. TiO2 nanotubes increase the surface area in comparison with TiO2nanoparticles. TiO2 nanotubes were tested for the methylene blue degradation and show a higher photocatalytic efficiency than TiO2 nanopowders and TIO2 doped with Ag.

Made available in DSpace on 2016-12-08T17:19:30Z (GMT). No. of bitstreams: 1 elementos pre-textuaus.pdf: 86552 bytes, checksum: b4f9afc7367b0456da6227d06b49d099 (MD5) Previous issue date: 2007-06-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Blackeart malleable iron samples were galvanized using twenty different zinc bath compositions. Each bath was made with different concentration and combinations of bismuth, nickel, tin and aluminium. These additions aim not only to substitute lead, a hazardous element to the environment, but also to reduce coating thickness, usually higher than established by standards due to the great reactivity between cast iron and zinc bath. Additional studies were made to check the corrosion resistance and to check the maintenance or intensity of the coating s brightness. When using just bismuth and nickel additions to the zinc bath, it wasn t observed a considerable coating thickness reduction, but bismuth influenced bath fluidity, favoring better zinc draining and formation of more compacted and defined zinc-iron compounds. It was observed that bismuth decreased the coating s corrosion resistance, while nickel can increase the corrosion resistance when the bath has small bismuth concentrations. Tin addictions reduced the coating thickness when used together with bismuth and nickel addictions. However, tin did not only reduce the corrosion resistance, but also decreased the coating s brightness. Highest aluminium concentrations reduced the coating s thickness considerably when compared to the coating s thickness of the samples galvanized in the other baths. Aluminium also increased corrosion resistance when compared to the coatings of the samples galvanized in baths containing bismuth, nickel and tin. However excessive coating thickness reduction, caused by highest aluminium addictions to the bath, reduced corrosion resistance. Highest aluminium addictions were totally favorable to the coating s brightness. The combination of bismuth, nickel, tin and aluminium were effective on coating thickness reduction and some of these combinations also provided greater rust resistance and shinier coatings. Hence, the chemical elements added weren t detrimental to the environment and they are good alternatives to substitute lead in the hot-dip galvanizing process. / Amostras de ferro fundido maleável preto foram galvanizadas em vinte diferentes banhos de zinco, cada qual composto por concentrações e combinações variadas de bismuto, níquel, estanho e alumínio. Além de substituir o chumbo, um elemento tóxico e nocivo ao meio ambiente, objetiva-se com estas adições a redução da espessura do revestimento galvanizado, normalmente em excesso ao estabelecido em norma devido à grande reatividade dos ferros fundidos com o banho de zinco. Estudos adicionais foram realizados para a verificação da resistência à corrosão e para a verificação da manutenção ou intensificação do brilho dos revestimentos. Utilizando adições somente de bismuto e níquel ao banho de zinco não foi observada uma redução considerável da espessura do revestimento, mas o bismuto influenciou na fluidez do banho favorecendo o melhor escorrimento do zinco e a formação de fases zinco-ferro mais compactas e definidas. Observou-se que o bismuto diminuiu a resistência à corrosão dos revestimentos, mas o níquel pode aumentar a resistência à corrosão quando se têm adições menores de bismuto ao banho. Adições de estanho reduziram a espessura de camada quando utilizadas em conjunto com adições de bismuto e níquel, mas o estanho foi prejudicial à resistência à corrosão além de diminuir o brilho dos revestimentos. O alumínio em concentrações mais elevadas tornou as espessuras dos revestimentos consideravelmente menores quando comparadas às espessuras dos revestimentos galvanizados nos outros banhos estudados. O alumínio ainda aumentou a resistência à corrosão dos revestimentos em relação aos revestimentos galvanizados nos banhos contendo bismuto, níquel e estanho. Contudo a redução excessiva da espessura da camada, proporcionada por adições maiores de alumínio, fez com que a resistência à corrosão diminuísse novamente. Adições de maiores teores de alumínio foram totalmente favoráveis ao aumento do brilho dos revestimentos. A combinação de elementos químicos como o bismuto, níquel, estanho e alumínio mostrou-se efetiva na redução da espessura de camada, sendo que algumas destas combinações também proporcionaram maiores valores de resistência à corrosão e revestimentos com brilhos mais intensos. Além disso, os elementos químicos adicionados não são nocivos ao meio ambiente, sendo boas alternativas para substituir o chumbo na galvanização por imersão a quente. Palavras-chave: galvanização por imersão a quente, espessura de camada, resistência à corrosão, compostos intermetálicos zinco-ferro.

Made available in DSpace on 2014-07-29T14:52:09Z (GMT). No. of bitstreams: 1 Tese thannya nascimento.pdf: 3166640 bytes, checksum: 0a9faeb659c9594423ee5e7f8b495662 (MD5) Previous issue date: 2009-01-22 / The goal of this study was to evaluate the genetic structure and the spatial pattern of intra and interpopulational gene flow of Dipteryx alata Vogel, based on nuclear and chloroplastidial microsatellite markers. Primers were developed based on sequencing of random fragments from a shotgun genomic library for detection of microsatellite regions. 12 microsatellites regions were obtained from 688 sequences, which allowed the construction of pairs of primers. These regions are composed of motifs with two to six nucleotides, ranging from 136 to 380 base pairs. This shows that the random sequencing strategy from shotgun libraries is interesting because it allows the achievement of primers for repetitive regions with different motifs. Two of these loci (Da_E06 e Da_E12) were polymorphic with three alleles each. He estimation for these loci showed satisfactory values (0.2946 and 0.2879, respectively), considering the number of alleles. Also, we used a transferred primer from the species Phaseolus vulgaris (BM164) for D. alata. Moreover, other two chloroplastidials microsatellite primers were used for molecular analyses of georeferenced subpopulations, totalizing 775 plants distributed over the natural occurrence area of Cerrado. 210 of these plants were collected and georeferenced one by one along the margins of the Araguaia River in the states of Mato-Grosso (RAMT) and Goiás (RAGO) for spatial distribution of genetic variability in local scale analysis. The relationship between estimations of genetic diversity parameters with patterns of potential distribution of species was evaluated. This was used to test the hypothesis that the genetic variability of D. alata populations is distributed according to the central-periphery model. D. alata subpopulations showed considerable high levels of genetic variability that was significantly structured among subpopulations and well structured in space, both for nuclear and chloroplastidial data. The estimation of the apparent cross-fertilization rate (ta = 1.0575) indicates that the species is allogamous. Estimations of migration rates by pollen and by seeds were lower than one, indicating that seed dispersal contributes more effectively for total gene flow. Estimates of the genetic diversity parameters from the Araguaia River population showed similar values between both margins. The estimation of the apparent cross-fertilization rate (0.9434) indicated that the Araguaia River is not a physical barrier to effective gene flow. The effective size of the neighborhood, i.e., the mean number of individuals in an area where panmixia occurs was 85.64 and 22.99 for nuclear and chloroplastidial data, respectively, indicating that seed dispersal is more restricted. The correlogram generated with chloroplastidial data presented a cline pattern of variance more evident than with nuclear data, suggesting that the presence of spatial genetic structure is being more influenced by seed dispersal. We observed that the genetic parameters do not follow a classical central-periphery model, because peripheral population (according to geographical distribution of sampling locations) tended to demonstrate higher values for these estimations, mainly the South and Western subpopulations. The relationship found between the fixation index (f) with human impact indicated that the subpopulations evaluated can be affected by fragmentation process and land use, probably caused by the recent human colonization in Cerrado biome. / O objetivo geral deste estudo foi avaliar a estrutura genética e o padrão espacial do fluxo gênico intra e interpopulacional de Dipteryx alata Vogel, com base em marcadores microssatélites nucleares e cloroplastidiais. Foi utilizada uma estratégia de desenvolvimento de iniciadores que se baseia no seqüenciamento aleatório de fragmentos provenientes de uma biblioteca genômica shotgun para a detecção de regiões microssatélites, em barueiro. Das 668 sequências obtidas, foram encontradas 12 regiões microssatélites que possibilitaram a construção dos pares de iniciadores. Estas regiões são compostas por motivos com dois a seis nucleotídeos, que variam entre 136 a 380 pb. Isto mostra que a estratégia de sequenciamento aleatório a partir de bibliotecas shotgun é interessante por possibilitar a obtenção de iniciadores para regiões repetitivas com diferentes motivos. Dois destes locos (Da_E06 e Da_E12) foram polimórficos, apresentando três alelos cada. As estimativas de He para estes locos apresentaram valores satisfatórios, considerando o número de alelos, e foram iguais a 0,2946 e 0,2879, respectivamente. Isto indica que os iniciadores desenvolvidos e padronizados com sucesso neste trabalho podem ser utilizados para estudos genético-populacionais. Juntamente com estes dois iniciadores desenvolvidos, foi utilizado outro transferido da espécie Phaseolus vulgaris (BM164) para D. alata, além de outros dois iniciadores microssatélites cloroplastidiais para análises moleculares de 23 subpopulações georeferenciadas, totalizando 775 plantas, distribuídas ao longo da área de ocorrência natural do Cerrado. Destas plantas, 210 foram coletadas e georreferenciadas uma a uma, ao longo das margens do alto rio Araguaia nos estados de Mato-Grosso (RAMT) e Goiás (RAGO), para análises de distribuição espacial da variabilidade genética em escala local. Para testar a hipótese de que a variabilidade genética das subpopulações de D. alata se distribui conforme o modelo central-periférico, foram avaliadas as relações entre as estimativas de parâmetro genético de diversidade com os padrões de distribuição potencial da espécie. Foi observado que as subpopulações de D. alata apresentam consideráveis níveis de variabilidade genética que se encontra significativamente estruturada entre as subpopulações, tanto para os dados nucleares quanto para os cloroplastidiais, apresentando-se também estruturada no espaço. A estimativa da taxa de fecundação cruzada aparente (ta = 1,0575) indica que a espécie seja alógama. As estimativas das razões de migração via pólen e via semente foram menores do que 1, o que indica que a dispersão de sementes contribui mais efetivamente para o fluxo gênico total em escala regional. As estimativas dos parâmetros genéticos de diversidade referentes à população contígua ao Rio Araguaia mostraram valores semelhantes entre as margens do rio. A estimativa da taxa de fecundação cruzada aparente (0,9434) confirma a reprodução por alogamia no barueiro. O baixo nível de diferenciação entre as subpopulações das duas margens do rio indica que o rio Araguaia não confere uma barreira física efetiva ao fluxo gênico. O tamanho efetivo de vizinhança, ou seja, o número médio de indivíduos numa área onde ocorre panmixia, para os dados nucleares e cloroplastidiais foi igual a 85,64 e 22,99, respectivamente, indicando que a dispersão de sementes é mais restrita em escala local. O correlograma gerado a partir dos dados cloroplastidiais apresenta um padrão clinal de variação mais evidente do que o proveniente dos dados nucleares, o que sugere que a presença da estrutura genética espacial deve estar sendo mais influenciada pelo padrão de dispersão da semente. Foi observado que parâmetros genéticos estimados para D. alata não se enquadram no clássico modelo central-periférico, pois as populações tidas como periféricas (de acordo com a distribuição geográfica dos pontos de coleta) tendem a exibir maiores valores para estas estimativas, com destaque para as as subpopulações das bordas Sul e Oeste do bioma. A relação encontrada entre os valores estimados para o índice de fixação intrapopulacional (f) com o impacto humano indica que as subpopulações estudadas podem estar sofrendo as conseqüências dos processos de fragmentação e uso da terra na variabilidade genética, causado provavelmente pelo recente processo de ocupação do Cerrado.

O processo industrial não-contínuo de zincagem por imersão a quente (ZIQ) pode ocasionar a contaminação superficial do aço-carbono zincado por imersão a quente (AZIQ) com resíduos de cloreto. Estes resíduos, se não forem efetivamente eliminados, podem influenciar negativamente no desempenho dos esquemas de pintura dos sistemas dúplex (zincagem mais pintura). Sabe-se que no processo de ZIQ, a cromatização é amplamente utilizada, entretanto, o efeito que este pós-tratamento exerce no desempenho dos esquemas de pintura ainda não é bem estabelecido. Neste contexto, este trabalho teve como objetivos: I - verificar o grau de contaminação no AZIQ com sal de cloreto devido ao próprio processo de ZIQ; II - verificar os efeitos da contaminação com sal de cloreto e da cromatização do processo ZIQ no desempenho de tintas aplicadas sobre o AZIQ; e III – determinar pré-tratamentos para pintura adequados para o bom desempenho das tintas aplicadas sobre o AZIQ. A metodologia adotada para alcançar o objetivo I envolveu a zincagem de chapas de aço-carbono em diferentes prestadores de serviço de ZIQ, em diferentes condições. Estas chapas zincadas foram analisadas por microanálise química qualitativa por espectrometria de dispersão de energia (EDS) em microscópio eletrônico de varredura (MEV) e pela determinação dos teores de cloreto superficiais, por método de extração com água em ebulição. A partir dos resultados obtidos para se alcançar o objetivo I, foi possível definir as condições no processo de ZIQ que potencialmente causam maior contaminação da superfície do AZIQ com sal de cloreto. Assim, para se alcançar os objetivos II e III, chapas de aço-carbono foram zincadas naquelas condições de máxima contaminação com sal de cloreto e parte delas foi submetida ao pós-tratamento de cromatização. Em seguida, uma grande parte destas chapas zincadas (cromatizadas ou não) foi submetida aos pré-tratamentos para pintura de desengraxe com solvente orgânico, de hidrojateamento a alta pressão, de jateamento abrasivo ligeiro e de ação mecânica com esponja abrasiva e água quente. Finalmente, as chapas zincadas, incluindo as não submetidas aos pré-tratamentos, foram pintadas com uma demão de tinta de aderência mais uma demão de tinta de acabamento. As chapas zincadas e pintadas foram submetidas a ensaios acelerados (imersão em água destilada e exposição em câmara de umidade saturada) e não-acelerados de corrosão (exposição em estação de corrosão atmosférica) e avaliadas por meio dos ensaios tradicionais de acompanhamento de desempenho (grau de empolamento e ensaios de aderência de tinta) e eletroquímicos (medida de potencial de circuito aberto, curva de polarização e espectroscopia de impedância eletroquímica – E.I.E.). Algumas chapas zincadas, antes da pintura, foram submetidas aos ensaios de caracterização física (exame microestrutural e morfológico em MEV e rugosidade superficial), química microanálise por EDS, difração de raios X e teor de cloreto superficial pelo método de extração com água em ebulição) e eletroquímica. Os resultados obtidos, neste estudo, permitiram verificar que a aplicação adicional de sal cloreto de amônio sólido durante o processo de ZIQ tende a aumentar o grau de contaminação superficial do AZIQ com cloreto e, as etapas de resfriamento e/ou de cromatização do processo também contribuem para esta contaminação. No geral, o desempenho do AZIQ cromatizado teve desempenho inferior em relação ao não-cromatizados. O hidrojateamento a alta pressão e a lavagem com água e ação mecânica foram os prétratamentos que proporcionaram os melhores desempenhos dos esquemas de pintura. / The batch galvanizing process (BGP) can lead to surface contamination of hot-dip galvanized steel (HDGS) with chloride residues. If these residues are not effectively eliminated, they can influence negatively on the performance of duplex systems (galvanizing plus painting). It is known that the chromate quenching is widely used in the BGP, however the effect of this post-treatment on the performance of duplex systems is not well established yet. In this sense, this work aimed: I – to verify the contamination degree of HDGS with chloride salt due to the BGP itself; II – to verify the effects of the chloride salt contamination and chromate quenching on the performance of paints applied on HDGS; and III – to determine the suitable surface preparation for painting in order for obtaining a good paint performance applied on HDGS. The adopted methodology to achieve goal I involved the galvanizing of steel plates in different service renderings with BGP, in different conditions. These HDGS plates were submitted to the qualitative energy dispersive microanalyses (EDS) in scanning electron microscopy (SEM) and to the determination of superficial chloride contents by the boiling water extraction method. From the obtained results, the conditions in the BGP that potentially lead to greater surface contamination of HDGS with chloride salt were determined. Thus, to achieve goals II and III, steel plates were galvanized under the maximum chloride salt contamination condition and part of them were submitted to chromate quenching. After that, a great part of these HDGS plates (chromated or non chromated quenching) was submitted to the surface preparations for painting through organic solvent cleaning, high pressure hydroblasting, sweep blasting and handled scrub cleaning with an abrasive sponge and hot distilled water. Finally, the HDGS plates, including those not submitted to the surface preparations for painting, were painted with one coat of primer plus one coat of finishing paint. The HDGS painted plates were submitted to accelerated (distilled water immersion and humidity chamber exposure) and non accelerated (atmospheric exposure) corrosion tests and their performance were verified by means of traditional tests (degree of blistering and paint adhesion) and electrochemical measurements (open circuit potential, polarization curve and electrochemical impedance spectroscopy – E.I.S.). Before painting, some HDGS plates were submitted to tests for physical (microstructural and morphological analyses in MEV and surface roughness), chemical (EDS, X-ray diffraction and superficial chloride contents by the boiling water extraction method) and electrochemical characterization. The obtained results allowed verifying that the additional application of solid ammonium chloride salt during the BGP tends to increase the degree of superficial chloride contamination of the HDGS and, the water and/or chromate quenching also contribute for this contamination. In general, the chromated HDGS presented worst performances. The high pressure hydroblasting and the handled scrub cleaning with an abrasive sponge and hot distilled water were the surface preparations for painting that provided the best performances of paint systems.

Cette thèse traite de la reconstruction d'hypersurfaces au sein de champs de normales en dimension quelconque et trouve des applications dans l’analyse des empreintes digitales (lignes dermiques), des images satellites météorologiques (lieux de turbulence) et astrophysiques (bras de galaxies) ainsi que dans l’analyse stratigraphique des images sismiques (horizons). Les méthodes développées s’appuient sur la minimisation d’une équation aux dérivées partielles non linéaire reliant une hypersurface au pendage déduit d’un champ de normales. Elles prennent en compte des contraintes diverses telles que des points de passages, des frontières, des bornes et des discontinuités. La contribution principale de la thèse réside dans l’introduction d’un changement d’espace du pendage qui permet de reconstruire aussi bien des hypersurfaces exprimées sous des formes implicites dans les repères de définition des champs de normales que des horizons sismiques de manière rapide et interactive. Deux schémas de reconstruction d’horizons sismiques unidimensionnels présentant une discontinuité d’amplitude et de lieu inconnus sont également proposés. / This thesis deals with the reconstruction of hypersurfaces from a finite-dimensional normal vector field. Application scopes can be found in the analysis of fingerprints (epidermal ridges), meteorological images (eddies and cyclones), astrophysical images (galaxy arms) and in the stratigraphic analysis of seismic images (horizons). The hypersurfaces are obtained by solving a non-linear partial derivative equation relied on the local dip deduced from a normal vector field. Several constraints such as boundaries, bounds, points belonging to the hypersurface or discontinuities can be considered.The major contribution of this thesis consists in a local dip transformation which allows to reconstruct implicit hypersurfaces as well as seismic horizons by a fast and interactive method. Two schemes dedicated to the reconstruction of discontinuous one-dimensional seismic horizons are also proposed when the discontinuity location and jump are unknown.

A l'échelle de plusieurs dizaines de millions d'années, un système de subduction implique de grandes déformations de la plaque plongeante assimilée un solide viscoélastique, et du manteau supérieur assimilé à un fluide newtonien. L'objectif de ce travail est de développer une stratégie de couplage solide-fluide appliquée à l'étude de l'interaction lithosphère-asthénosphère. Cette stratégie est basée sur l'utilisation de maillages non-conformes aux interfaces et d'une méthode de domaines fictifs (MDF) pour la résolution du problème fluide. Pour l'efficience des modèles 3D, nous employons une formulation simplifiée de la méthode de domaines fictifs par multiplicateurs de Lagrange. La MDF développée est validée par des comparaisons avec des solutions analytiques qui montrent que la méthode est d'ordre 1. La stratégie de couplage est également validée par la comparaison avec d'autres méthodes de couplage solide-fluide. Une première étude est ensuite menée pour analyser l'influence de certains paramètres rhéologiques et cinématiques sur la dynamique d'une subduction contrôlée par les vitesses des plaques. Cette étude, en 2D, concerne plus spécifiquement le mécanisme de plissement périodique du slab lorsque celui-ci est ancré à 660 km de profondeur. Ce mécanisme induit des variations de pendage du slab générant des variations de l'état de contrainte de la plaque chevauchante. Un intérêt particulier est porté sur l'influence de la viscosité du manteau sur les plissements. Dans ce cadre, nous réalisons une application à la subduction andine. / Over the time scale of tens of millions of years, a subduction system involves large deformations of tectonics plates, as one plate sinks into the Earth's mantle. The aim of this work was to develop a soli-fluid coupling method applied to the lithosphere-asthenosphere interaction in the context of subduction zones. Plates were assumed to behave as viscoelastic bodies, while the upper mantle was assimilated to a newtonian fluid. The method developped here is based on the use of non-matching interface meshes and a fictitious domain method (FDM) for the fluid problem. To optimize the computational efficiency of 3D model, we used a simplified version of the Lagrange multipliers fictitious domain method. The developped FDM has been benchmarked with analytical solutions and we showed that this FDM is a first-order method. The coupling method has also been compared to other fluid-solid coupling methods using matching interfaces meshes. A first two-dimensional study was performed in order to evaluate the influence of some rheological and kinematic parameters on the dynamics of a subduction controlled by the velocity of the plates. This study aimed at investigating cyclic slab folding over a rigid 660 km depth transition zone. This folding mechanism induces variations in slab dip that generate variations in the stress state of the overriding plate. We focussed on the influence of the upper mantle viscosity on slab folding. We also applied this model to the Andean subduction zone. Several studies have determined a cyclic variation of the South-American tectonic regime (period of 30-40~Myrs) which may have been related to the slab dip evolution.

The rise in the world population can be correlated with an increase in energy need. Fossil fuels are not going to able to cover this need in energy because not only are they limited, they also have a negative effect on the environment. A reason the more to switch renewable energy. One of the most popular renewable energy source is solar energy. The organic solar cell could be a low-cost, light-weight and flexible option for photovoltaics. This thesis will discuss the morphology of the active layer of an organic solar cell. The polymer poly(9,9-dioctylfluorenyl-2,7-diyl) and the fullerene derivate [6,6]-phenyl C61-butyric acid methyl ester were used as model components for the active layer. These two components were processed in different solvents, different ratios, different total concentrations and were either dip- or spin-coated on glass substrates. These samples were analyzed with atomic force microscopy, steady state and time resolved fluorescence and UV/Vis spectroscopy. The analysis show that the morphology of the films processed in chloroform and tetrahydrofuran would react very similar in α-phase and β-phase by dip- and spin-coated samples. Xylene would react the opposite as tetrahydrofuran and chloroform while ethylbenzene would react little with different samples. / De stijging in wereldpopulatie kan gelinkt worden met een stijging in energieverbruik. Het is niet aan te raden om fossiele brandstoffen te gebruiken voor deze energiestijging want niet alleen zijn ze beperkt aanwezig op aarde ook zijn ze niet goed voor het milieu. Een reden te meer om naar duurzame energie over te schakelen. Één van de meeste populaire energiebronnen is zonne-energie. Hierbij zou de organische zonnecel een goedkope, lichte en flexibele optie zijn. Deze thesis zal de morfologie van de actieve laag van een zonnecel bespreken. Het polymeer poly(9,9-dioctylfluorenyl-2,7-diyl) en het fullereen derivaat [6,6]-fenyl C61-butylzuur waren de twee model componenten voor de actieve laag. Deze twee componenten werden in verschillende oplosmiddelen, verschillende verhoudingen en verschillende totaal concentraties bereidt en werden vervolgens gedipcoated of gespincoated op glazen substraten. De stalen werden vervolgens geanalyseerd door atomic force microscopy, steady state en time resolved fluorescence en UV/Vis spectroscopy. De analyse toont dat de morfologie van de films bereidt in chloroform en tetrahydrofuraan gelijkaardig reageren in α- fase en β-fase bij gedipt- en gespincoaten stalen. Terwijl xyleen net omgekeerd reageert als chloroform en tetrahydrofuraan. Bij ethylbenzeen zou de fases maar heel weinig veranderen bij de verschillende stalen.