Um dos métodos mais utilizados para proteção contra a corrosão de aços comuns consiste na proteção catódica com revestimentos metálicos eletroquimicamente mais ativos, que estes. Os revestimentos de zinco são os mais usados para este tipo de proteção. De forma a protegerem o substrato, estes revestimentos devem atuar como anodos de sacrifício, sofrendo corrosão e transformando o substrato de aço em catodo. Todavia, não é de interesse, que o revestimento de zinco apresente altas taxas de corrosão de forma que a proteção contra a corrosão conferida ao aço seja duradoura. Uma das formas mais empregadas para reduzir a velocidade de corrosão do revestimento de zinco é por meio de tratamentos da superfície, por exemplo, por tratamentos de conversão. Os tratamentos de conversão mais eficientes são os que utilizam e geram rejeitos, que contêm íons de cromo hexavalente. Todavia, estes íons são carcinogênicos e tóxicos e, dessa forma, os processos que os utilizam em alguma etapa do tratamento, vêm sofrendo crescentes restrições, já sendo proibidos em países com leis ambientais mais rígidas. Esta é a razão para o crescente interesse e grande investimento em pesquisa tratamentos, que possam resultar em revestimentos com potencialidade para substituir, de forma eficiente e efetiva o uso do cromo hexavalente. Este foi o objetivo do presente trabalho. Neste estudo, foi investigado o efeito de tratamentos, que resultam em camadas de conversão na presença de ácido oxálico e na proteção contra a corrosão da superfície do zinco. Camadas de conversão foram obtidas por imersão de amostras de zinco em soluções de ácido oxálico (ácido etanodióico) com diferentes concentrações. Todas as soluções de tratamento apresentaram elevada acidez e resultaram em ataque da superfície de zinco com formação de revestimento de conversão com diferentes características. Ensaios preliminares de névoa salina foram então realizados para investigar a proteção conferida pelo sistema revestimento de conversão-verniz contra a corrosão do substrato de zinco. Estes ensaios foram decisivos para a escolha da faixa de concentração do banho de conversão com maior potencial para formação de revestimentos de conversão protetores. Os resultados deste ensaio e os de espectroscopia de impedância eletroquímica mostraram que tratamentos em soluções com composição superiores a 10-1 M de ácido oxálico resultaram em camadas muito defeituosas, nas quais o ataque localizado do substrato metálico é favorecido, sendo obtidas impedâncias menores que a superfície do zinco sem qualquer tratamento. Os resultados de XPS mostraram, que os revestimentos de conversão formados em soluções de ácido oxálico na faixa de 10-3 M a 10-1 M são compostos de oxalato de zinco e produtos de corrosão do zinco, especificamente ZnO, Zn (OH)2, e ZnCO3. Já a concentração de 10-1 M de ácido oxálico foi a, que produziu os resultados mais promissores com a formação de um revestimento, que conferiu proteção mais duradoura à superfície do zinco entre os obtidos. As espessuras médias das camadas de conversão de oxalato de zinco formadas em soluções com 10-1 M e 1 M de ácido oxálico, estimadas por FIB, foram respectivamente 600 nm e 300 nm, o que mostra que a concentração de 1 M de ácido causou intenso ataque corrosivo da superfície, enquanto a camada formada em meio com 10-1 M permitiu a deposição de camada mais espessa e mais protetora contra a corrosão do substrato. Os resultados de XPS indicaram a degradação da camada de oxalato de zinco com o tempo de ensaio, porém o ataque desta ao longo do ensaio de corrosão, resulta na formação de simonkolleite, identificada por difração de raios X, para períodos mais longos do ensaio de corrosão, no caso do revestimento formado em solução com 10-1 M em comparação a 1M. A simonkolleite atua por efeito barreira bloqueando os defeitos/porosidade da camada. O crescente acúmulo destes produtos de corrosão com a continuidade do processo corrosivo e a aderência destes ao substrato metálico foi indicada para superfície tratada em solução com 10-1 M de ácido oxálico. Finalmente, foi proposto um modelo para interação entre o revestimento de conversão de oxalato de zinco e os produtos de corrosão em que a retenção dos produtos de corrosão na superfície faz com, que a camada na superfície se torne mais espessa e mais compacta com o tempo de exposição ao ensaio de corrosão. Estas observações explicam o aumento de impedância observado com o tempo de ensaio nesta condição. Os resultados obtidos permitiram concluir, que o revestimento de conversão de oxalato de zinco formado em solução com 10-1 M de ácido oxálico resulta em proteção efetiva do substrato metálico além de apresentar boa aderência com camada de verniz. Estes resultados indicam potencialidade deste tratamento como preparação de superfícies de zinco, que serão recobertas com revestimentos orgânicos (tintas, vernizes ou lacas). / One of the most used methods for protection of common steels is the cathodic protection by galvanic coupling with metallic coatings electrochemically more active than these. Zinc coatings are the most commonly used for this type of protection. In order to protect the metallic substrate, these coatings must act as sacrificial anodes, corroding themselves and converting the steel substrate into cathode. However, it is not appropriate that the zinc coating presents high corrosion rates, so that the corrosion protection conferred to the steel is long-lasting. One of the most commonly employed methods of reducing the corrosion rate of zinc coatings is by surface treatments, such as, conversion treatments. The most efficient conversion treatments to date are those that use hexavalent chromium ions or generate residues containing these ions. However, hexavalent chromium is carcinogenic and toxic and, therefore, the processes that involve their use at some stage of the treatment, are under increasing restrictions, and have already been prohibited in developed countries. This is the reason for the growing interest and great investment in research studies in search for treatments that may result in coatings with the potential to efficiently and effectively replace the use of hexavalent chromium. This was the objective of the present study. In this study, the effect of treatments in oxalic acid solutions that resulted in conversion layers on the corrosion protection of zinc surface has been investigated. Conversion layers were obtained by immersion of zinc samples in solutions of oxalic acid (ethanedioic acid) with different concentrations. All the treatment solutions presented high acidity and resulted in attack of zinc surface and formation of conversion coatings of different characteristics. A layer of varnish was applied and preliminary salt spray tests were then carried out to investigate the corrosion protection provided by the system conversion coating -varnish to the zinc substrate. These tests were decisive for the choice of the conversion bath composition range with greater potentialities for the formation of protective conversion coatings. The results of the salt spray test and of electrochemical impedance spectroscopy (EIS) showed that treatments in solutions with compositions greater than 10-1 M of oxalic acid resulted in very defective conversion layers in which the localized attack of the metallic substrate is favored, and lower impedances than the zinc surface without any treatment were obtained for surfaces treated in these solution. The XPS results showed that conversion coatings formed in oxalic acid solutions in the range of 10-3 M to 10-1 M are composed of zinc oxalate and zinc corrosion products, specifically ZnO, Zn (OH)2, and ZnCO3. The concentration related to the most promising results was 10-1 M and in this solution, the coating formed that promoted the longer lasting protection of the zinc surface among those obtained. The average thicknesses of the zinc oxalate conversion layers formed in solutions with 10-1 M and 1 M of oxalic acid, estimated by FIB, were respectively 600 nm and 300 nm. This result showed that in 1 M of oxalic acid an intense corrosive attack of the zinc surface occurred, while the layer formed in 10-1 M was thicker and more protective against substrate corrosion. The XPS results indicated degradation of the zinc oxalate layer formed in 10-1 M solution with time of exposure to the test solution, but for the protection of the coating lasted for longer periods, comparatively to that formed in 1M solution, once the attack of the first film resulted in formation of simonkolleite, which was identified by X-ray diffraction. Simonkolleite acts by barrier effect blocking defects / porosity in the conversion layer. The increasing accumulation of corrosion products with test time and their adhesion to the metallic substrate was indicated for surface treated in solution with 10-1 M of oxalic acid. Finally, a model has been proposed for the interaction between the zinc oxalate conversion coating and the corrosion products in which the retention of these products on the surface is promoted by the conversion coating and the surface layer becomes thicker and more compact with time of exposure. These observations explain the increased impedance observed with the test time associated to this coating. The obtained results allowed concluding that the conversion coating of zinc oxalate formed in solution with 10-1 M of oxalic acid results in effective protection of the metallic substrate besides promoting good adhesion with a layer of varnish. These results indicate the potential of this treatment as preparation of zinc surfaces that will be covered with organic coatings (paints, varnishes or lacquers).

Les conditions sévères de fonctionnement des réacteurs du futur, Génération-IV, -haute température et fortes irradiations-nécessitent le développement de matériaux adaptés. Les aciers ODS (Oxide Dispersion Strengthened) sont des candidats très compétitifs pour le gainage du combustible en raison de leurs excellentes propriétés de gonflement et de fluage. Ces atouts majeurs sont induits par la fine dispersion de nanoparticules d’oxydes (Y, O, Ti) obtenue par co-broyage de poudres de la matrice et d’oxyde dont les conditions sont à optimiser pour maitriser la distribution en taille et composition de ces nanoparticules. Dans l’objectif de mieux comprendre le mécanisme de formation de ces nanoparticules à l’échelle atomique, la présente thèse met à profit l’utilisation de la spectroscopie d’annihilation de positons (PAS) et de la spectrométrie de masse d’ions secondaires pour étudier l’interaction des défauts lacunaires avec des solutés Y, O et Ti et évaluer leur rôle dans la formation des nanoparticules. Les irradiations avec des ions He ont été effectuées pour révéler les propriétés des défauts lacunaires et les implantations d’Y, Ti, O ont été réalisées pour étudier les interactions de ces éléments Y, Ti, O avec les lacunes dans la matrice de fer. La distribution des défauts en profondeur indique la présence de défauts lacunaires avec une taille plus petite dans la région où la concentration d’Y, Ti, O est la plus élevée. Cet effet est plus prononcé pour O, Y et Ti respectivement. Il est expliqué par la formation de V-X (X=O, Y, Ti) complexes qui réduisent la probabilité de la mobilité et d’agglomération des défauts lacunaires. Les recuits des échantillons implantés Y et O révèlent que des complexes O-lacune sont mobiles à température ambiante, et que l’yttrium ne diffuse pas jusqu’à 550°C alors que des complexes Y-lacunes sont encore détectés comme cela est attendu par des résultats théoriques. Un modèle des premières étapes de la nucléation des nanoparticules est proposé en utilisant les résultats obtenus dans cette thèse. / The severe operating conditions of the future nuclear reactor, Generation-IV, -high temperature and high irradiation damage-, require the adapted materials development. Oxide-dispersion strengthened (ODS) alloy is one of the most potential candidates expected to be used for fuel cladding material because of their outstanding swelling and creep properties. Their excellent properties are induced by the fine dispersion of oxide nanoparticles (Y, O, Ti), obtained by mechanical alloying of steel and oxide powders and which has to be better mastered. But the atomic scale clustering mechanism of these nanoparticles is not yet cleared. In this context, the present thesis using positron annihilation spectroscopy (PAS) and secondary ion mass spectrometry (SIMS) sheds light on the interaction of vacancy defects with Y, O and Ti solutes to better understand their roles in the nanoparticles formation. The He irradiations have been performed to reveal the vacancy defects properties and Y, Ti, O implantations realized to study the Y, Ti, O-vacancy interactions in bcc Fe matrix. In all cases, the defects depth distribution shows a lower size of vacancy defects in the region where the concentration of the incident ions Y, Ti and O is the highest. This effect of the ions on the damage formation is more pronounced for respectively O, Y and Ti. It is explained by the formation of V-X (X=O, Y, Ti) complexes which reduce the mobility and agglomeration probability of the vacancy defects. The annealing of the Y and O implanted samples reveals that some O-vacancy complexes are mobile at room temperature and Y doesn’t diffuse up to 550°C whilst Y-vacancy complexes remain as it is expected from theory. A model of the first steps of the ODS nanoparticles nucleation is proposed by using the results obtained in this thesis.

Submitted by Ricardo Cedraz Duque Moliterno (ricardo.moliterno@uefs.br) on 2016-04-06T23:39:59Z No. of bitstreams: 1 Disserta??o Alirio- RGV.pdf: 1134374 bytes, checksum: c5cada877e2f1b7066d7296503b7a9a8 (MD5) / Made available in DSpace on 2016-04-06T23:39:59Z (GMT). No. of bitstreams: 1 Disserta??o Alirio- RGV.pdf: 1134374 bytes, checksum: c5cada877e2f1b7066d7296503b7a9a8 (MD5) Previous issue date: 2016-02-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The aims of this study were to evaluate the adaptability and stability of 14 yellow passion fruit plant hybrids and to estimate the genetic components of variance and average via mixed models (REML/BLUP), estimate the phenotypic, genotypic and environmental correlations between passion fruit characteristics in three environments. The selection of genotypes was based on methods of adaptability, as produced by the harmonic mean of genetic values (MHVG); of stability, as produced by the relative performance of genetic values (PRVG); and on a joint selection for both adaptability and stability, as produced by the harmonic mean of the relative performance of the genetic values (MHPRVG). The genetic correlations were estimated (rG), phenotypic (rF) and environment (rE) for each environment. The following traits were evaluated: fruit number (FN); total cumulative productivity (TCP); fruit mass (FM); fruit length (FL); fruit diameter (FD); peel mass (PM); peel thickness (PT); pulp mass (PUM); juice yield (JY); soluble solids (SS); titratable acidity (TA); and SS/TA (RATIO). The estimates for heritability and the genetic gains in the evaluated environments were found to have good perspectives for the selection of superior genotypes, except for traits TCP, SS, and JY. There was a marked effect from the genotype x environment interaction (GxE) for most traits, except for FL, JY, SS, TA, and SS/TA. The most stable and adaptable hybrids in the evaluated environments were BRS Gigante Amarelo (BRS Yellow Giant), HFOP-09, H09-09, GP09-02, GP09-03, and BRS Sol do Cerrado (BRS Sun of Cerrado). In 88.88% of cases the estimates of genotypic correlations were higher than phenotypic in the three environments. In Len??is genotypic correlations between FN x FM, FD, PT, PM, PUM, SS and TA, differed from the other environments. In Dom Basil?o and Rio de Contas to TCP correlated positively with FM, FL, FD and PM. In all environments the selection of fruits with higher FM facilitating higher LF, FD, PM and PUM and the selection of the oval thinner peel fruit shape. In general, for correlations between traits of agronomic importance, such as FN x TCP, SS; FM x FD, PM, PUM, RATIO; FD x FM, PUM, RATIO; FL/FD x PT e FM x RATIO showed the same behavior in the three evaluation environments, except for characteristics FN x FM, FD, PT, PM, PUM e TA in Lenc?is. / Os objetivos deste trabalho foram avaliar a adaptabilidade e estabilidade de 14 h?bridos de maracujazeiro-amarelo, estimar os componentes gen?ticos de vari?ncia e de m?dia via modelos mistos (REML/BLUP), estabelecer as correla??es fenot?picas, genot?picas e ambientais entre caracter?sticas do fruto de maracujazeiro em tr?s ambientes. Foram avaliados 14 gen?tipos de maracujazeiro nos ambientes de Dom Bas?lio-BA, Rio de Contas-BA e Len??is-BA, utilizando o delineamento experimental em blocos casualizados completos, com tr?s repeti??es e nove plantas por parcela. A sele??o gen?tipos baseou-se nos m?todos da adaptabilidade dada pela m?dia harm?nica dos valores gen?ticos (MHVG), estabilidade pela performance relativa dos valores gen?ticos (PRVG) e sele??o conjunta para adaptabilidade e estabilidade dada pela m?dia harm?nica da performance relativa dos valores gen?ticos (MHPRVG). Foram estimadas as correla??o genot?pica (rG), fenot?pica (rF) e de ambiente (rE) para cada ambiente. Foram avaliados os caracteres, n?mero de frutos (NF); produtividade total acumulada (PR); massa do fruto (MF); comprimento de frutos (CF); di?metro do fruto (DF); rela??o CF/DF; massa da casca (MC); espessura de casca (EC); massa da polpa (MP); rendimento de suco (RE); s?lidos sol?veis (SS); acidez titul?vel (AT) e RATIO (SS/AT). As estimativas de herdabilidade e os ganhos gen?ticos nos ambientes avaliados apresentaram boas perspectivas para sele??o de gen?tipos superiores. Houve efeito pronunciado da intera??o GxE para a maioria dos caracteres, exceto CF, RE, SS, AT e SS/AT. De acordo com o crit?rio MHPRVG os h?bridos mais est?veis e adapt?veis nos ambientes de avalia??o foram o BRS Gigante Amarelo, HFOP-09, H09-09, GP09-02, GP09-03 e BRS Sol do Cerrado. Em 88,88% dos casos as estimativas das correla??es genot?picas foram maiores do que as fenot?picas nos tr?s ambientes. Em len??is as correla??es genot?picas foram negativas entre NF x MF, DF, EC, MC, MP, SS e AT, divergindo dos demais ambientes. Nos ambientes de Dom Bas?lio e Rio de Contas a PR correlacionou se positivamente com MF, CF, DF e MC. Em todos os ambientes a sele??o de frutos com maiores MF proporcionar? maiores CF, DF, PC e PP e pela sele??o do formato de frutos ovais menor espessura de casca. De modo geral, para as correla??es entre caracter?sticas de import?ncia agron?mica, como NF x PR, SS; MF x DF, MC, MP, RATIO; DF x MC, MP, RATIO; CF/DF x EC e MC x RATIO apresentaram o mesmo comportamento nos tr?s ambientes de avalia??o, exceto para caracter?sticas NF x MF, DF, EC, MC, MP e AT em Len??is.

This thesis studies possible methods of semiconductor sample measurement by SIMS, with emphasis on testing different measurement parameters and sample preparation. Part of this master thesis deals with the design of a modified sample holder compatible with the used ToF-SIMS$^{5}$ instrument, IONTOF company, which is capable of tilting the sample by defined angle. This holder enables sample preparation in the main chamber of the instrument without the need of transferring the sample between instruments, which limits the probability of sample contamination. This sample holder was tested by ion machining of TIGBT sample edge and by imaging of a crater edge, created in previous measurement. Edge termination structures prepared by different techniques were measured on the TIGBT samples. Further measurements with the goal of optimizing the depth resolution for thin layers were done on Molybdenum-Silicon-multilayer X-Ray Mirror. Part of the measurements was focused on comparing depth profiles measured at low temperatures. For these measurements the samples with Indium multilayers in GaN substrate were used.

Afin d'optimiser les performances des circuits intégrés, l’industrie de la micro et nanotechnologie mène d'intenses recherches sur la miniaturisation à l'échelle sub-22nm de leurs principaux constituants que sont les transistors MOS. La réduction de la taille de grille atteint néanmoins des limites qui rendent problématique le contrôle du canal. L'une des approches les plus prometteuses pour contourner ce dilemme et ainsi poursuivre la miniaturisation des futurs nœuds technologiques, consiste au développement des transistors d’architectures 3D (Trigate ou FinFET). La mise au point de telles structures requiert une caractérisation de plus en plus fine, surtout à une étape clé de leur élaboration, qui est celle du dopage par implantation ionique. Du fait des faibles profondeurs implantées, l'analyse par diffusion d'ions de moyenne énergie (MEIS) est tout à fait adaptée pour quantifier les implants et évaluer la conformité du dopage grâce à sa bonne résolution en profondeur (0.25 nm). Néanmoins, les dimensions de la sonde (0.5 × 1 mm2) étant très supérieures à celles des motifs, il nous a fallu développer un protocole d’analyse propre à de telles architectures. Les échantillons étudiés dans le cadre de cette thèse sont des systèmes modèles. Ils sont constitués de réseaux de lignes de silicium (Si) 3D, formées par gravure lithographique par faisceaux d’électrons (e-beam) sur des plaques 300 mm de types silicium sur isolant (SOI). Le dopage a été réalisé à une énergie de 3 keV par implantions conventionnelle (ou beam line) et immersion plasma (PIII).L’analyse des spectres MEIS des implants insérés dans chaque facette des motifs a été possible grâce aux simulations 3D types Monte-Carlo effectuées avec le logiciel PowerMEIS. Nous avons ainsi développé une nouvelle méthode adaptée à la caractérisation du dopage 3D. Les mesures ont montré que, contrairement à la méthode PIII, la dose implantée par la méthode conventionnelle correspond à celle visée. Cependant la distribution des dopants introduits au sein des nanostructures par les deux méthodes de dopage n’est pas uniforme. Dans les échantillons implantés par PIII, on a observé une importante concentration des dopants aux sommets des motifs et un faible dopage des flancs. Ceci étant moins marqué dans celui implanté par la méthode conventionnelle. En corrélant les techniques de Microscopie Electronique en Transmission (MET), d’analyses par rayons x synchrotron et MEIS, nous avons également pu déterminer les dimensions des zones implantées ainsi que celles des zones cristallines dans les réseaux de lignes gravées.L'exploitation de la technique MEIS en mode canalisation a permis une évaluation complète des couches non gravées. L’investigation des endommagements post – dopage dans les régions cristallines non implantées ont été menées toujours avec la même technique MEIS. Les résultats ont révélé une importante influence de la méthode d’implantation et la température sur les défauts et les déformations dans le cristal. L’origine des anomalies au sein des échantillons a ainsi été identifiée en corrélant les mesures MEIS et celles par spectrométrie de masse des ions secondaires en temps de vol (ToF-SIMS). / With the aim of optimizing the performances of integrated circuits (ICs), the nanotechnology industry is carrying out intense research activities on the miniaturization at the sub-22 nm scale of their main constituents: the MOS transistors. Nevertheless, the shrinking of the gate size has reached the limits that make the control of the channel problematic. One of the most promising approaches to circumvent this dilemma and thus further the miniaturization of the future technological nodes, is the development of transistors of 3D architecture (Trigate or FinFET). The elaboration of such nanostructures requires increasingly fine characterization tools precisely at a key stage of their fabrication, namely the ion implantation doping. Given the ultra-shallow implantation depths, the medium energy ion scattering (MEIS) analysis technique is suitable for quantifying the implants and evaluating the doping conformity thanks to its good depth resolution (0.25 nm). However, the dimensions of the beam (0.5×1 mm2) being by far larger than those of the patterns, we had to develop an analysis protocol dedicated to such architectures. The samples studied in the framework of this thesis are considered as model systems. They are constituted of 3D silicon (Si) Fin – shaped line gratings, etched on the 300 mm wafers of silicon on insulator (SOI) types by using the electron beam (e-beam) lithography. The doping has been carried out at an energy of 3 keV by using the conventional (or beam line) and plasma immersion ion implantation (PIII) methods.The analyses s of the MEIS spectra of the dopants implanted into each part of the patterns were possible thanks to the 3D Monte-Carlo simulations performed with the PowerMEIS software. We have thus developed a new method suitable for the characterization of the 3D doping. The measurements have shown that, contrarily to the PIII method, the dose implanted by the conventional method is as targeted. However, the distribution of the dopants inserted within the nanostructures by using the two doping methods is not uniform. In the PIII implanted samples, a large dopants' focusing at the tops of the patterns and low sidewalls' doping have been observed. This is less marked in the one implanted by the conventional method. By correlating the Transmission Electron Microscopy (TEM), synchrotron x – ray analyses and MEIS, we have also determined the dimensions of the implanted and crystal areas of the line gratings.The exploitation of the MEIS technique in channeling mode has permitted the full assessment of the impacts of the implantation in the non-etched layers. The investigations of the crystal qualities in the non-implanted areas were carried out with the same technique. The results show that the temperature conditions have a considerable influence on the defects and lattice deformations. The origin of the anomalies in the samples has thus been identified by correlating the MEIS and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) measurements.

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