A corrosão é um processo eletroquímico espontâneo e, sabendo que diversos metais estão sujeitos a este fenômeno, a sua deterioração é inevitável, o que impõe à comunidade científica desafios para retardar tal efeito. A literatura sobre o tema aponta como uma das ações mais recorrentes para alcançar esse retardo a aplicação superficial de películas poliméricas, dentre as quais destaca-se o desenvolvimento de revestimentos inteligentes. A incorporação na tinta de formadores de filmes encapsulados confere ao revestimento a característica de autorreparação, e a escolha de silanos como agentes reticulantes se destaca positivamente, uma vez que o filme gerado pela molécula apresenta caráter hidrofóbico. Nesse contexto, o objetivo deste estudo é verificar, primeiro, a melhor condição de reticulação do silano na presença de radiação ultravioleta e, segundo, se a adição de microcápsulas de poli(ureia-formaldeído-melamina) contendo metacriloxissilano em uma tinta epóxi base solvente confere a este revestimento proteção contra a corrosão, pelo efeito de autorreparação. Para isso, estudou-se a cinética de polimerização do formador de filme e o seu encapsulamento em microcápsulas de poli(ureia-formaldeído-melamina). Determinada a melhor condição de encapsulamento, corpos de prova de aço carbono foram pintados com a tinta contendo as microcápsulas produzidas. O efeito de autorreparação - desencadeado pela ruptura das microcápsulas ao se provocar um defeito mecânico no revestimento - foi comprovado pelas técnicas de espectroscopia de impedância eletroquímica (EIE), técnica de varredura por eletrodo vibratório (SVET) e por ensaio acelerado de corrosão em câmara de névoa salina. / Corrosion is a spontaneous electrochemical process and, knowing that several metals are subjected to this phenomenon, its deterioration is inevitable, which imposes challenges for scientific community to delay this effect. The literature on this subject points out, as one of the most recurrent actions to achieve this delay, the superficial application of polymer films, which stands out the development of smart coatings with self-healing properties. The incorporation of encapsulated film formers gives to coatings the self-healing ability, and the choice of silanes as film-forming agent stands out positively since the film has a hydrophobic character. In this context, the aims of this study are, firstly, verify the best crosslinking condition of silane induced by UV light and, secondly, investigate whether the addition of poly(urea-formaldehyde-melamine) microcapsules containing methacryloxysilane into the solvent-based epoxy coating brings protection to this coating against corrosion by self-healing effect. For this purpose, the polymerization kinetics of the film former by ultraviolet radiation and their encapsulation in poly(urea-formaldehyde-melamine) microcapsules were studied. Given the best encapsulation condition, carbon steel panels were coated with the self-healing paint. The self-healing effect - triggered by the rupture of the microcapsules caused by an induced mechanical defect in the coating - was demonstrated by techniques as electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) and by accelerated corrosion tests in salt spray chamber.

L’enjeu actuel pour les industriels de l’aéronautique est de diminuer la consommation en carburant et/ou d’augmenter le rendement des avions. A terme, Safran souhaite remplacer les aubes de turbine, actuellement en superalliage, par des aubes en matériau composite tissé de type SiC/SiBC. Il est alors important de prévoir leurs durées de vie. Ce travail a donc consisté à développer un modèle de durée de vie pour ces composites autocicatrisants. Ces matériaux tissés sont constitués de fibres Nicalon, d’une interphase de pyrocarbone et d’une matrice autocicatrisante multicouche (B4C, SiC et SiBC). La particularité de ces composites est l’oxydation de chaque constituant du matériau en fonction de l’environnement (température, atmosphère sèche ou humide). Le modèle de durée de vie développé offre un compromis entre des temps de calcul réduits, malgré la prise en compte de phénomènes physico-chimiques complexes, et une prévision de la durée de vie suffisamment précise. L’approche retenue est un couplage entre un modèle d'endommagement mécanique et un modèle physico-chimique. Un modèle de durée de vie uniaxial a été proposé afin de justifier les différents couplages nécessaires entre les parties mécanique et physico-chimique mais également pour optimiser les algorithmes de résolution. Ce modèle a permis d’identifier les coefficients pour deux nuances de matériaux. Afin de réaliser des essais de structures, un modèle de durée de vie multiaxial a été proposé et implanté dans le code de calcul ZéBuLoN. Un protocole d’identification a également été proposé dans ce travail même si les essais de caractérisation jusqu’ici réalisés ne sont pas suffisants pour identifier complètement le modèle 3D sur ces matériaux. / The current challenge for the aerospace industry is to decrease the fuel consumption and/or to increase the performance of planes. In the future, Safran Group wishes to replace the turbine blades, currently in superalloy, with woven composite SiC/SiBC material blades. Therefore, it is important to predict their life time. This work involved developing a life time model of these self-healing composites. These woven materials are made up of Nicalon fibers, and an interphase of pyrocarbone and a self-healing matrix (B4C, SIC and SiBC). The particularity of these composites is the oxidation of every constituent of the material depending on the environment (temperature, dry or wet atmosphere). The developed life time model offers a compromise between reduced calculating time, in spite considering complex physico-chemical phenomena, and an accurate enough prediction of the life time. The approach chosen is a coupling between a mechanical damage model and a physico-chemical model. A uniaxial life time model was proposed to explain the different necessary couplings between the mechanical and physico-chemical parts but also to optimize the resolution algorithms. This model enabled to identify the coefficients for two grades of materials. In order to carry out tests of structures, a multiaxial life time model was proposed and implemented in the ZéBuLoN Finite Element code. A protocol of identification was also proposed in this work even if the characterization tests so far realized are not sufficient to identify the 3D-Model for these materials.

Les composites à matrice céramique (CMC) sont destinés à remplacer les superalliages comme constituants de l'architecture des chambres de combustion des moteurs aéronautiques. Dans ces conditions, la durée de vie de ces matériaux diminue fortement du fait de leurs dégradations par oxydation. Pour pallier à ce problème, des CMC à matrice autocicatrisante sont élaborés. Ils possèdent la particularité de s'auto-protéger vis-à-vis de l'oxydation par la formation d'oxyde passivant limitant la diffusion des espèces oxydantes au sein des fissures matricielles. Dans le cadre de ces travaux de thèse, la durabilité d'un composite SiC/[Si-B-C] est évaluée. Son comportement en oxydation/corrosion est alors étudié entre 450 et 1000°C sous air à des pressions partielles d'humidité variables. Une approche multi-échelle (échelle constituants et composite) est envisagée pour comprendre les différents mécanismes mis en jeu lors de la non-cicatrisation/cicatrisation du matériau. / Ceramic matrix composites are potential candidate to replace the nickel-based alloys in advanced aeronautic engines as in civilian ones. These composites display cracks due to their elaboration process but also due to mechanical loading in use. These matrix cracks become an extended network for oxygen diffusion, and cause the premature damage of the material. To avoid this process, composites with a sequenced self-healing matrix have been developed and investigated. To resume, the self-healing process consists to consume part of incoming oxygen by sealing the matrix cracks with an oxide phase. In this work, a SiC/[Si-B-C] composite is investigated and a multi-scale approach is used. In a first time, the oxidation rate of each constituent is evaluated and in a second, composite specimens are aged between 450 and 1000°C in different gas mixtures and total pressures. This approach is a good way to better understand the contribution of each element under oxidizing environment and thus the self-healing process.

A corrosão é um processo eletroquímico espontâneo e, sabendo que diversos metais estão sujeitos a este fenômeno, a sua deterioração é inevitável, o que impõe à comunidade científica desafios para retardar tal efeito. A literatura sobre o tema aponta como uma das ações mais recorrentes para alcançar esse retardo a aplicação superficial de películas poliméricas, dentre as quais destaca-se o desenvolvimento de revestimentos inteligentes. A incorporação na tinta de formadores de filmes encapsulados confere ao revestimento a característica de autorreparação, e a escolha de silanos como agentes reticulantes se destaca positivamente, uma vez que o filme gerado pela molécula apresenta caráter hidrofóbico. Nesse contexto, o objetivo deste estudo é verificar, primeiro, a melhor condição de reticulação do silano na presença de radiação ultravioleta e, segundo, se a adição de microcápsulas de poli(ureia-formaldeído-melamina) contendo metacriloxissilano em uma tinta epóxi base solvente confere a este revestimento proteção contra a corrosão, pelo efeito de autorreparação. Para isso, estudou-se a cinética de polimerização do formador de filme e o seu encapsulamento em microcápsulas de poli(ureia-formaldeído-melamina). Determinada a melhor condição de encapsulamento, corpos de prova de aço carbono foram pintados com a tinta contendo as microcápsulas produzidas. O efeito de autorreparação - desencadeado pela ruptura das microcápsulas ao se provocar um defeito mecânico no revestimento - foi comprovado pelas técnicas de espectroscopia de impedância eletroquímica (EIE), técnica de varredura por eletrodo vibratório (SVET) e por ensaio acelerado de corrosão em câmara de névoa salina. / Corrosion is a spontaneous electrochemical process and, knowing that several metals are subjected to this phenomenon, its deterioration is inevitable, which imposes challenges for scientific community to delay this effect. The literature on this subject points out, as one of the most recurrent actions to achieve this delay, the superficial application of polymer films, which stands out the development of smart coatings with self-healing properties. The incorporation of encapsulated film formers gives to coatings the self-healing ability, and the choice of silanes as film-forming agent stands out positively since the film has a hydrophobic character. In this context, the aims of this study are, firstly, verify the best crosslinking condition of silane induced by UV light and, secondly, investigate whether the addition of poly(urea-formaldehyde-melamine) microcapsules containing methacryloxysilane into the solvent-based epoxy coating brings protection to this coating against corrosion by self-healing effect. For this purpose, the polymerization kinetics of the film former by ultraviolet radiation and their encapsulation in poly(urea-formaldehyde-melamine) microcapsules were studied. Given the best encapsulation condition, carbon steel panels were coated with the self-healing paint. The self-healing effect - triggered by the rupture of the microcapsules caused by an induced mechanical defect in the coating - was demonstrated by techniques as electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) and by accelerated corrosion tests in salt spray chamber.

The present work is devoted to establishing of a new generation of self-healing anti-corrosion coatings for protection of metals. The concept of self-healing anticorrosion coatings is based on the combination of the passive part, represented by the matrix of conventional coating, and the active part, represented by micron-sized capsules loaded with corrosion inhibitor. Polymers were chosen as the class of compounds most suitable for the capsule preparation. The morphology of capsules made of crosslinked polymers, however, was found to be dependent on the nature of the encapsulated liquid. Therefore, a systematic analysis of the morphology of capsules consisting of a crosslinked polymer and a solvent was performed. Three classes of polymers such as polyurethane, polyurea and polyamide were chosen. Capsules made of these polymers and eight solvents of different polarity were synthesized via interfacial polymerization. It was shown that the morphology of the resulting capsules is specific for every polymer-solvent pair. Formation of capsules with three general types of morphology, such as core-shell, compact and multicompartment, was demonstrated by means of Scanning Electron Microscopy. Compact morphology was assumed to be a result of the specific polymer-solvent interactions and be analogues to the process of swelling. In order to verify the hypothesis, pure polyurethane, polyurea and polyamide were synthesized; their swelling behavior in the solvents used as the encapsulated material was investigated. It was shown that the swelling behavior of the polymers in most cases correlates with the capsules morphology. Different morphologies (compact, core-shell and multicompartment) were therefore attributed to the specific polymer-solvent interactions and discussed in terms of “good” and “poor” solvent. Capsules with core-shell morphology are formed when the encapsulated liquid is a “poor” solvent for the chosen polymer while compact morphologies are formed when the solvent is “good”. Multicompartment morphology is explained by the formation of infinite networks or gelation of crosslinked polymers. If gelation occurs after the phase separation in the system is achieved, core-shell morphology is present. If gelation of the polymer occurs far before crosslinking is accomplished, further condensation of the polymer due to the crosslinking may lead to the formation of porous or multicompartment morphologies. It was concluded that in general, the morphology of capsules consisting of certain polymer-solvent pairs can be predicted on the basis of polymer-solvent behavior. In some cases, the swelling behavior and morphology may not match. The reasons for that are discussed in detail in the thesis. The discussed approach is only capable of predicting capsule morphology for certain polymer-solvent pairs. In practice, the design of the capsules assumes the trial of a great number of polymer-solvent combinations; more complex systems consisting of three, four or even more components are often used. Evaluation of the swelling behavior of each component pair of such systems becomes unreasonable. Therefore, exploitation of the solubility parameter approach was found to be more useful. The latter allows consideration of the properties of each single component instead of the pair of components. In such a manner, the Hansen Solubility Parameter (HSP) approach was used for further analysis. Solubility spheres were constructed for polyurethane, polyurea and polyamide. For this a three-dimensional graph is plotted with dispersion, polar and hydrogen bonding components of solubility parameter, obtained from literature, as the orthogonal axes. The HSP of the solvents are used as the coordinates for the points on the HSP graph. Then a sphere with a certain radius is located on a graph, and the “good” solvents would be located inside the sphere, while the “poor” ones are located outside. Both the location of the sphere center and the sphere radius should be fitted according to the information on polymer swelling behavior in a number of solvents. According to the existing correlation between the capsule morphology and swelling behavior of polymers, the solvents located inside the solubility sphere of a polymer give capsules with compact morphologies. The solvents located outside the solubility sphere of the solvent give either core-shell or multicompartment capsules in combination with the chosen polymer. Once the solubility sphere of a polymer is found, the solubility/swelling behavior is approximated to all possible substances. HSP theory allows therefore prediction of polymer solubility/swelling behavior and consequently the capsule morphology for any given substance with known HSP parameters on the basis of limited data. The latter makes the theory so attractive for application in chemistry and technology, since the choice of the system components is usually performed on the basis of a large number of different parameters that should mutually match. Even slight change of the technology sometimes leads to the necessity to find the analogue of this or that solvent in a sense of solvency but carrying different chemistry. Usage of the HSP approach in this case is indispensable. In the second part of the work examples of the HSP application for the fabrication of capsules with on-demand-morphology are presented. Capsules with compact or core-shell morphology containing corrosion inhibitors were synthesized. Thus, alkoxysilanes possessing long hydrophobic tail, combining passivating and water-repelling properties, were encapsulated in polyurethane shell. The mechanism of action of the active material required core-shell morphology of the capsules. The new hybrid corrosion inhibitor, cerium diethylhexyl phosphate, was encapsulated in polyamide shells in order to facilitate the dispersion of the substance and improve its adhesion to the coating matrix. The encapsulation of commercially available antifouling agents in polyurethane shells was carried out in order to control its release behavior and colloidal stability. Capsules with compact morphology made of polyurea containing the liquid corrosion inhibitor 2-methyl benzothiazole were synthesized in order to improve the colloidal stability of the substance. Capsules with compact morphology allow slower release of the liquid encapsulated material compared to the core-shell ones. If the “in-situ” encapsulation is not possible due to the reaction of the oil-soluble monomer with the encapsulated material, a solution was proposed: loading of the capsules should be performed after monomer deactivation due to the accomplishment of the polymerization reaction. Capsules of desired morphologies should be preformed followed by the loading step. In this way, compact polyurea capsules containing the highly effective but chemically active corrosion inhibitors 8-hydroxyquinoline and benzotriazole were fabricated. All the resulting capsules were successfully introduced into model coatings. The efficiency of the resulting “smart” self-healing anticorrosion coatings on steel and aluminium alloy of the AA-2024 series was evaluated using characterization techniques such as Scanning Vibrating Electron Spectroscopy, Electrochemical Impedance Spectroscopy and salt-spray chamber tests. / In Anlehnung an den Selbstheilungsmechanismus der menschlichen Haut entwickeln wir ein innovatives Verfahren zur Funktionalisierung von Korrosionsschutzbeschichtungen, um auch diese in die Lage zu versetzen Beschädigungen selbstständig „auszuheilen“. Dazu werden winzige Mikro- und Nanobehälter mit aktiven Substanzen (z. B. Korrosionshemmstoffen, Versiegelungsmitteln, Bioziden etc.) befüllt und anschließend in eine Korrosionsschutzbeschichtung eingebettet. Kommt es nun im Zeitablauf zu korrosionsauslösenden Beschädigungen der Schutzbeschichtung (z. B. durch Kratzer oder Risse) werden an der Defektstelle die eingebetteten Behälter zerstört und aktiv wirkende Gegensubstanzen freigesetzt. Dadurch wird die verletzte Stelle sofort wieder verschlossen und die Korrosionsgefahr eliminiert. Der entscheidende Vorteil derart funktionalisierter Schutzbeschichtungen ist ihre aktive Rückkopplung mit dem Korrosionsauslöser: Die aktive Schutzsubstanz wird nur an der Defektstelle und nur in der zur Korrosionsvermeidung erforderlichen Menge freigegeben. Somit werden eine länger anhaltende Wirkdauer sowie eine deutlich höhere Nachhaltigkeit der Beschichtungen ermöglicht. Dieses „intelligente Verhalten“ der neuen aktiven Korrosionsschutzbeschichtungen ist nur dank ihrer innovativen Mikrostruktur möglich. Die winzigen Mikro- und Nanobehälter beinhalten nicht nur aktive Substanzen in ihrem Inneren sondern besitzen auch eine intelligent konstruierte Hüllenstruktur, deren Durchlässigkeit sich je nach Art des Korrosionsauslösers ändert. Wird die eingekapselte aktive Substanz freigesetzt, fängt diese sofort an gegen die korrosionsverursachenden Einflüsse zu wirken. Ist die Gefahr beseitigt verringert sich die Durchlässigkeit der Behälterhülle wieder. Diese bedingte Reversibilität zwischen geschlossenem und geöffnetem Zustand des Behälters sorgt für einen sehr sparsamen Verbrauch der aktiven Substanz und für die stark verbesserte Schutzwirkung darauf basierender Antikorrosionsbeschichtungen. Diese Arbeit befasst sich mit dem Aufbau polymerer Kern-Schale-Mikrokapseln, die entsprechende Korrosionsinhibitoren und Biocide enthalten. Der Morphologie wird für zahlreiche Lösungsmittel und Polymere mit Hilfe der Hansen-Löslichkeitsparameter in guter Übereinstimmung mit elektronenmikroskopischen Experimenten beschrieben. Die Wirkungsweise in technischen Beschichtungen wird quantifiziert anhand von elektrochemischer Impedanzspektroskopie, Rastervibrationssondenmessungen und industrienahen Testverfahren.

Observou-se nos últimos anos um grande aumetno na complexidade das redes. Surgiram também novos desa os para gerenciamento dessas redes. A dimensão atual e as tendências de crescimento das infraestruturas tem inviabilizado as técnicas de gerencimento de redes atuais, baseadas na intervenção humana. Por exemplo, a heterogeneidade dos elementos gerenciados obrigam que administradores e gerentes lidem com especi cidades de implanta ção que vão além dos objetivos gerenciais. Considerando as áreas funcionais da gerência de redes, a gerência de falhas apresenta impactos operacionais interessantes. Estima-se que 33% dos custos operacionais estão relacionados com a prevenção e recuperação de falhas e que aproximadamente 44% desse custo visa à resolução de problemas causados por erros humanos. Dentre as abordagens de gerência de falhas, o Self-Healing objetiva minimizar as interações humanas nas rotinas de gerenciamento de falhas, diminuindo dessa forma erros e demandas operacionais. Algumas propostas sugerem que o Self-Healing seja planejado no momento do projeto das aplicações. Tais propostas são inviáveis de aplicação em sistemas legados. Otras pesquisas sugerem à análise e instrumentação das aplicações em tempo de execução. Embora aplicáveis a sistemas legados, análise e instrumentação em tempo de execução estão fortemente acopladas as tecnologias e detalhes de implementação das aplicações. Por esse motivo, é difícil aplicar tais propostas, por exemplo, em um ambiente de rede que abrange muitas entidades gerenciadas implantadas através de diferentes tecnologias. Porém, parece plausível oferecer aos adminitradores e gerentes facilidades através das quais eles possam expressar seus conhecimentos sobre anoamlias e falhas de aplicações, bem como mecanismos através dos quais esses conhecimentos possam ser utilizado no gerenciamento de sistemas. Essa dissertação de mestrado tem como objetivo apresentar e avaliar uma solução comum que introduza nas redes capacidades de self-healing. A solu- ção apresentada utiliza-se de workplans para capturar o conhecimento dos administradores em como diagnosticar e recuperar anomalias e falhas em redes. Além disso, o projeto e implementação de um framework padrão para detecção e noti cação de falhas é discutido no âmbito de um sistema de gerenciamento baseado em P2P. Por último, uma avaliação experimental clari ca a viabilidade do ponto de vista operacional. / In recent years, a huge raise in networks' complexity was witnessed. Along the raise in complexity, many management challenges also arose. For instance, managed entities' heterogeneity demands administrators and managers to deal with cumbersome implementation and deployment speci cities. Moreover, infrastructures' current size and growth-trends show that it is becoming infeasible to rely on human-in-the-loop management techniques. Inside the problem domain of network management, Fault Management is appealing because of its impact in operational costs. Researches estimate that more than 33% of operational costs are related to preventing and recovering faults, where about 40% of this investment is directed to solve human-caused operational errors. Hence, addressing human interaction is mostly unarguably a need. Among di erent approaches, Self-Healing, a property of Autonomic Network Management's proposal, targets to avoid humans' interactions and decisions on Fault Management loops, thereupon unburden administrators and managers from performing Fault Management-related tasks. Some researches on Self-Healing enabling approaches suppose that Fault Management capabilities should be planned in design-time. These approaches are impossible to apply on legacy systems. Other researches suggest runtime analysis and instrumentation of applications' bytecode. Albeit applicable to some legacy systems, these last proposals are tightly-coupled to implementation's issues of underlaying technologies. For this reason, it is hard to apply such proposals end-toend, for example, in a scenario encompassing many managed entities implemented through di erent technologies. However, it is possible to o er to administrators and managers facilities to express they knowledge about networks' anomalies and faults, and facilities to leverage this knowledge. This master dissertation has as objective to present and evaluate a solution to imbue network management systems with self-healing capabilities. The solution relies on workplans as a mean to gather administrators and managers' knowledge on how to diagnose and heal networks' anomalies and faults. Besides that, the design and implementation of a standard framework for fault detection and noti cation customization is discussed while considering a P2P-Based Network Management System as its foundations. At last, an experimental evaluation renders clear the proposal's feasibility from the operational point of view.

Orientador: Prof. Dr. Jeverson Teodoro Arantes Junior / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2017. / Uma estrutura que pode autorregenerar em condições ambiente é um desafio enfrentado atualmente e é uma das áreas mais promissoras na ciência de materiais inteligentes. O presente projeto visa a utilização de métodos teóricos para o estudo das propriedades estruturais e funcionais de nanocompósitos intrinsecamente autorregenerativos, permitindo estratégias mais eficientes para o desenvolvimento de novos materiais. As simulações são baseadas na Teoria do Funcional da Densidade (DFT). Estudamos os componentes isolados que constituem o nanocompósito funcional: diarilbibenzofuranona (DABBF), SHP e nanopartículas de (óxido de) níquel. Estudando a formação da DABBF contra a reação da arilbenzofuranona (ABF) e O2 (auto-oxidação), vemos que a reação de formação sem barreira da DABBF é preferida à auto-oxidação porque existe um processo de transferência de carga que resulta no superóxido fracamente ligado. Realizamos um estudo sistemático por meio de cálculos ab initio para investigar a reação de clusters de Ni13 com moléculas de O2. Avaliamos dinamicamente o efeito sobre as propriedades estruturais, eletrônicas e magnéticas e compreendemos o mecanismo de quimissorção do oxigênio (primeiro estágio da oxidação). Finalmente, estudamos as interações entre os oligômeros do SHP e as nanopartículas, levando ao nanocompósito autorregenerativo. Sugerimos como trabalhos futuros simular as interações entre todos esses materiais levando ao nanocompósito autorregenerativo por meio de uma abordagem multiescala via métodos DFT e de dinâmica molecular (MD). / A structure that can sustain self-healing repair under standard conditions is a challenge faced nowadays and is one of the most promising areas in smart materials science. The present project aims at the use of theoretical methods for the study of structural and functional properties of intrinsically self-healing nanocomposites, allowing improved design strategies for novel materials. The simulations are based on Density Functional Theory (DFT). We studied the isolated components that constitute the functional nanocomposite network: diarylbibenzofuranone (DABBF), SHP, and oxidated nickel nanoparticles. Studying DABBF bond formation against arylbenzofuranone (ABF) and O2 reaction (autoxidation), we see that the barrierless DABBF bond formation is preferred over autoxidation because there is a charge transfer process that results in the weakly bonded superoxide. We performed a systematic study by means of ab initio calculations to investigate Ni13 clusters reaction with O2 molecules. We evaluate dynamically the effect on structural, electronic, and magnetic properties and understand the oxygen chemisorption (first oxidation stage) mechanism. Finally, we study the interactions between SHP oligomers and the nanoparticles, leading to the selfhealing nanocomposite. We suggest as future work simulating the interactions between all these materials leading to the self-healing nanocomposite through a multiscale approach via DFT and molecular dynamics (MD) methods.

[pt] O presente trabalho tem como objetivo o estudo do comportamento mecânico, os mecanismos de fissuração e a autocicatrização de compósitos cimentícios reforçados com fibras de curauá. Desenvolveram-se três tipos de compósitos distintos, cada um reforçado com uma, três ou cinco camadas de tecido unidirecional de curauá. O comportamento mecânico foi avaliado por meio de ensaios de tração direta e flexão a quatro pontos. Estudaram-se os mecanismos de fissuração por meio de fotografias obtidas ao longo dos ensaios, além de análises por correlação digital de imagens (Digital Image Correlation - DIC). Estágios de carregamento foram identificados e associados com o espaçamento entre as fissuras formadas. Os corpos de prova de flexão foram instrumentados com strain gauges nas faces inferior e superior, a fim de medir as deformações de tração e compressão. Dessa forma, foi possível realizar um estudo sobre o desenvolvimento da linha neutra e correlacionar as deformações com espaçamento entre fissuras. A capacidade de autocicatrização dos compósitos foi avaliada por meio de ensaios mecânicos cíclicos e de carregamento contínuo, e também por acompanhamento da evolução das fissuras. Estas foram monitoradas com o auxílio de microscópio estereoscópico. As amostras foram expostas a diferentes ambientes (seco, ciclos de água borrifada, imersão em água) e a influência deles foi avaliada. Todos os compósitos apresentaram strain/deflection hardening com formação de múltiplas microfissuras. Fissuras na presença de água apresentaram cicatrização total e parcial, demostrando que o material desenvolvido é promissor para a ocorrência de autocicatrização. / [en] The present work aims to study the mechanical behavior, cracking mechanisms and the autogenous healing capability of cementitious composites reinforced with curauá fabric. Composites with one, three and five fabric layers were produced. Their mechanical behavior was evaluated through direct tensile and four point bending tests. The cracking mechanisms were studied using image analysis of both photographs took during the tests and Digital Image Correlation (DIC). Various stages of loading were identified and associate with the crack formation. The effect of flexural cracking on the composite neutral axis position was analyzed using strain-gages and correlated with the crack spacing. The autogenous healing capability of the three layered composite system was analyzed by means of the mechanical behavior, in cyclic bending and constant load tests. The crack evolution was follow with microscope stereoscope. The samples were subject to several conditions (RH of 55 percent, cycles of spayed water, water immersion) and their influence was evaluated. All the composites presented strain/deflection hardening behavior with multiple microcrack formation. Cracks exposed to water were partially or totally healed, demonstrating that three layered composite is a promising material for autogenous healing.

Observou-se nos últimos anos um grande aumetno na complexidade das redes. Surgiram também novos desa os para gerenciamento dessas redes. A dimensão atual e as tendências de crescimento das infraestruturas tem inviabilizado as técnicas de gerencimento de redes atuais, baseadas na intervenção humana. Por exemplo, a heterogeneidade dos elementos gerenciados obrigam que administradores e gerentes lidem com especi cidades de implanta ção que vão além dos objetivos gerenciais. Considerando as áreas funcionais da gerência de redes, a gerência de falhas apresenta impactos operacionais interessantes. Estima-se que 33% dos custos operacionais estão relacionados com a prevenção e recuperação de falhas e que aproximadamente 44% desse custo visa à resolução de problemas causados por erros humanos. Dentre as abordagens de gerência de falhas, o Self-Healing objetiva minimizar as interações humanas nas rotinas de gerenciamento de falhas, diminuindo dessa forma erros e demandas operacionais. Algumas propostas sugerem que o Self-Healing seja planejado no momento do projeto das aplicações. Tais propostas são inviáveis de aplicação em sistemas legados. Otras pesquisas sugerem à análise e instrumentação das aplicações em tempo de execução. Embora aplicáveis a sistemas legados, análise e instrumentação em tempo de execução estão fortemente acopladas as tecnologias e detalhes de implementação das aplicações. Por esse motivo, é difícil aplicar tais propostas, por exemplo, em um ambiente de rede que abrange muitas entidades gerenciadas implantadas através de diferentes tecnologias. Porém, parece plausível oferecer aos adminitradores e gerentes facilidades através das quais eles possam expressar seus conhecimentos sobre anoamlias e falhas de aplicações, bem como mecanismos através dos quais esses conhecimentos possam ser utilizado no gerenciamento de sistemas. Essa dissertação de mestrado tem como objetivo apresentar e avaliar uma solução comum que introduza nas redes capacidades de self-healing. A solu- ção apresentada utiliza-se de workplans para capturar o conhecimento dos administradores em como diagnosticar e recuperar anomalias e falhas em redes. Além disso, o projeto e implementação de um framework padrão para detecção e noti cação de falhas é discutido no âmbito de um sistema de gerenciamento baseado em P2P. Por último, uma avaliação experimental clari ca a viabilidade do ponto de vista operacional. / In recent years, a huge raise in networks' complexity was witnessed. Along the raise in complexity, many management challenges also arose. For instance, managed entities' heterogeneity demands administrators and managers to deal with cumbersome implementation and deployment speci cities. Moreover, infrastructures' current size and growth-trends show that it is becoming infeasible to rely on human-in-the-loop management techniques. Inside the problem domain of network management, Fault Management is appealing because of its impact in operational costs. Researches estimate that more than 33% of operational costs are related to preventing and recovering faults, where about 40% of this investment is directed to solve human-caused operational errors. Hence, addressing human interaction is mostly unarguably a need. Among di erent approaches, Self-Healing, a property of Autonomic Network Management's proposal, targets to avoid humans' interactions and decisions on Fault Management loops, thereupon unburden administrators and managers from performing Fault Management-related tasks. Some researches on Self-Healing enabling approaches suppose that Fault Management capabilities should be planned in design-time. These approaches are impossible to apply on legacy systems. Other researches suggest runtime analysis and instrumentation of applications' bytecode. Albeit applicable to some legacy systems, these last proposals are tightly-coupled to implementation's issues of underlaying technologies. For this reason, it is hard to apply such proposals end-toend, for example, in a scenario encompassing many managed entities implemented through di erent technologies. However, it is possible to o er to administrators and managers facilities to express they knowledge about networks' anomalies and faults, and facilities to leverage this knowledge. This master dissertation has as objective to present and evaluate a solution to imbue network management systems with self-healing capabilities. The solution relies on workplans as a mean to gather administrators and managers' knowledge on how to diagnose and heal networks' anomalies and faults. Besides that, the design and implementation of a standard framework for fault detection and noti cation customization is discussed while considering a P2P-Based Network Management System as its foundations. At last, an experimental evaluation renders clear the proposal's feasibility from the operational point of view.

Observou-se nos últimos anos um grande aumetno na complexidade das redes. Surgiram também novos desa os para gerenciamento dessas redes. A dimensão atual e as tendências de crescimento das infraestruturas tem inviabilizado as técnicas de gerencimento de redes atuais, baseadas na intervenção humana. Por exemplo, a heterogeneidade dos elementos gerenciados obrigam que administradores e gerentes lidem com especi cidades de implanta ção que vão além dos objetivos gerenciais. Considerando as áreas funcionais da gerência de redes, a gerência de falhas apresenta impactos operacionais interessantes. Estima-se que 33% dos custos operacionais estão relacionados com a prevenção e recuperação de falhas e que aproximadamente 44% desse custo visa à resolução de problemas causados por erros humanos. Dentre as abordagens de gerência de falhas, o Self-Healing objetiva minimizar as interações humanas nas rotinas de gerenciamento de falhas, diminuindo dessa forma erros e demandas operacionais. Algumas propostas sugerem que o Self-Healing seja planejado no momento do projeto das aplicações. Tais propostas são inviáveis de aplicação em sistemas legados. Otras pesquisas sugerem à análise e instrumentação das aplicações em tempo de execução. Embora aplicáveis a sistemas legados, análise e instrumentação em tempo de execução estão fortemente acopladas as tecnologias e detalhes de implementação das aplicações. Por esse motivo, é difícil aplicar tais propostas, por exemplo, em um ambiente de rede que abrange muitas entidades gerenciadas implantadas através de diferentes tecnologias. Porém, parece plausível oferecer aos adminitradores e gerentes facilidades através das quais eles possam expressar seus conhecimentos sobre anoamlias e falhas de aplicações, bem como mecanismos através dos quais esses conhecimentos possam ser utilizado no gerenciamento de sistemas. Essa dissertação de mestrado tem como objetivo apresentar e avaliar uma solução comum que introduza nas redes capacidades de self-healing. A solu- ção apresentada utiliza-se de workplans para capturar o conhecimento dos administradores em como diagnosticar e recuperar anomalias e falhas em redes. Além disso, o projeto e implementação de um framework padrão para detecção e noti cação de falhas é discutido no âmbito de um sistema de gerenciamento baseado em P2P. Por último, uma avaliação experimental clari ca a viabilidade do ponto de vista operacional. / In recent years, a huge raise in networks' complexity was witnessed. Along the raise in complexity, many management challenges also arose. For instance, managed entities' heterogeneity demands administrators and managers to deal with cumbersome implementation and deployment speci cities. Moreover, infrastructures' current size and growth-trends show that it is becoming infeasible to rely on human-in-the-loop management techniques. Inside the problem domain of network management, Fault Management is appealing because of its impact in operational costs. Researches estimate that more than 33% of operational costs are related to preventing and recovering faults, where about 40% of this investment is directed to solve human-caused operational errors. Hence, addressing human interaction is mostly unarguably a need. Among di erent approaches, Self-Healing, a property of Autonomic Network Management's proposal, targets to avoid humans' interactions and decisions on Fault Management loops, thereupon unburden administrators and managers from performing Fault Management-related tasks. Some researches on Self-Healing enabling approaches suppose that Fault Management capabilities should be planned in design-time. These approaches are impossible to apply on legacy systems. Other researches suggest runtime analysis and instrumentation of applications' bytecode. Albeit applicable to some legacy systems, these last proposals are tightly-coupled to implementation's issues of underlaying technologies. For this reason, it is hard to apply such proposals end-toend, for example, in a scenario encompassing many managed entities implemented through di erent technologies. However, it is possible to o er to administrators and managers facilities to express they knowledge about networks' anomalies and faults, and facilities to leverage this knowledge. This master dissertation has as objective to present and evaluate a solution to imbue network management systems with self-healing capabilities. The solution relies on workplans as a mean to gather administrators and managers' knowledge on how to diagnose and heal networks' anomalies and faults. Besides that, the design and implementation of a standard framework for fault detection and noti cation customization is discussed while considering a P2P-Based Network Management System as its foundations. At last, an experimental evaluation renders clear the proposal's feasibility from the operational point of view.