SARAIVA, Gilberto Dantas. Espectroscopia Raman ressonante em nanotubos de carbono funcionalizados. 2008. 145 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2008. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-05-04T19:13:31Z No. of bitstreams: 1 2008_tese_gdsaraiva.pdf: 6765379 bytes, checksum: ded06cc237d77dabfc5886e3ed738be4 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-05-07T14:32:02Z (GMT) No. of bitstreams: 1 2008_tese_gdsaraiva.pdf: 6765379 bytes, checksum: ded06cc237d77dabfc5886e3ed738be4 (MD5) / Made available in DSpace on 2015-05-07T14:32:02Z (GMT). No. of bitstreams: 1 2008_tese_gdsaraiva.pdf: 6765379 bytes, checksum: ded06cc237d77dabfc5886e3ed738be4 (MD5) Previous issue date: 2008 / In this Thesis we report a study of the synthesis and functionalization of carbon nanotubes. Regarding the synthesis, we produced carbon nanotubes samples using the chemical vapor deposition method. Both single-wall and multi-wall carbon nanotubes were produced. The basic difference between these two growth results was the catalyst employed. We also have changed the exposure time of catalyst particle to the hydrogen gas to find out the optimal parameters for growing the nanotubes. The obtained samples were characterized by resonance Raman spectroscopy and thermal analysis. The obtained samples show higher thermal stability compared with some commercially available samples. Regarding functionalization of the tubes we studied three different systems. Firstly, we investigated the effect of Si+ and C+ ions bombardment on the structural and electronic properties of highly pure double wall carbon nanotubes (DWNTs). The implantation was performed at room temperature with high fluencies of ions varying from 1 to 100 x( 10 13 ions/cm2) and the Raman spectroscopy was the main technique employed for studying the ion implantation-induced changes in the nanotubes. The effects of the Si+ implantation is stronger than that of C+ and this is attributed to the larger ionic radius of Si. The D to G band intensity ratio was used for probing the ion concentration for which the system looses its sp2 character leading to a highly disordered system with a high concentration of sp3 bonds. We observed that as the ion implantation dosage increases, the D-band intensity increases and the radial breathing modes (RBM) of the semiconducting (outer) and metallic (outer) tube disappear first, before from the inner tubes. At higher ion-implantation dosage, the carbon nanotubes are completely deformed and the Raman spectrum is typical of highly disordered graphite. Secondly, we investigated the effects of H2SO4 doping on DWNTs and SWNTs where the diameter of SWNTs are in the same range as the inner tube of the DWNTs. The comparison of these two systems allow to further improve the knowledge of doping effects on the constituents of DWNTs as well as to establish differences between the exohedral doping of SWNTs and DWNTs bundles. Upon doping with H2SO4 the Breit-Wigner-Fano lineshape of metallic tubes in the SWNTs samples decreases and the G band frequencies increase thus indicating that an electronic charge transfer is occurring from the nanotubes to the dopant molecule. The effect on the DWNTs is opposite to that of SWNTs thus evidencing that the inner and outer shell interaction seems to affect the inner tube electronic transitions more than those of the outer tubes. Thirdly, we report a detailed characterization of a novel carbon nanotube-based system that is a coaxial nanocable made of carbon as core and selenium as shell. Carbon nanotube bundles are wrapped up within a trigonal selenium shell. We have demonstrated that the Butyl-lithium compound plays an important role in promoting the interaction between the carbon nanotubes and the selenium shells and thus enables the preparation of these nanocable structures. The Raman spectra of the SWNTs in the residue and the Se-CNT nanocables suggests that this selenium-carbon interaction is stronger for semiconducting nanotubes than for metallic nanotubes. The chemistry of Selenium would allow the synthesis of carbon nanotubes decorated with other functional Se-based structures, such as CdSe, ZnSe, among others. / Esta tese consiste no estudo do processo de síntese e funcionalização de nanotubos de carbono. A síntese dos nanotubos de carbono foi realizada usando a técnica de deposição química a partir da fase vapor (CVD). Foram sintetizados Nanotubos de parede simples (SWNTs) e múltipas (MWNTs) . A diferença básica das metodologias usadas para preparar as amostras foi o uso de diferentes catalisadores expostos ao gás hidrogênio por diferentes intervalos de tempo. As amostras obtidas foram caracterizadas por espectroscopia Raman ressonante e análise térmica. Os resultados de análise térmica mostraram que as amostras sintetizadas apresentam uma excelente estabilidade térmica, quando comparada com algumas amostras disponíveis no mercado. Foram estudados três diferentes sistemas em relação ao processo de funcionalização de nanotubos de carbono. No primeiro sistema, investigamos o efeito da irradiação de íons de silício (Si+) e carbono (C+) nas propriedades eletrônicas e estruturais dos nanotubos de parede dupla (DWNTs). A implantação foi realizada à temperatura ambiente com concentrações de íons que variam de 1 a 100 x (1013 íons/cm2); e a espectroscopia Raman ressonante foi a principal técnica utilizada para estudar os efeitos da implantação. Os efeitos da implantação dos íons de Si+ na estrutura dos nanotubos são mais fortes do que os íons de C+ o que é atríbuido ao maior raio iônico do Si+. A razão das intensidades das bandas D e G foi usada para investigar a concentração de íons para a qual o sistema perde a característica sp2, deixando o sistema muito desordenado e com grande concentrações de ligações sp3. Observamos que o aumento da dosagem de íons aumenta a intensidade da banda D e os modos radiais de respiração dos nanotubos semicondutores (tubo externo) e metálicos (tubo externos) desaparecem primeiramente do que os tubos internos. Para altas dosagens de implantação de íons de silício ou carbono observamos que os nanotubos são completamente deformados e os espectros Raman apresentam aspectos de grafite altamente desordenados. No segundo sistema estudado, investigamos os efeitos da dopagem da molécula de H2SO4 nos SWNTs e DWNTs com distribuição de diâmetros dos SWNTs similar aos tubos internos dos DWNTs. A comparação destes dois sistemas permitiu ter um maior conhecimento dos efeitos da molécula H2SO4 nos sistemas DWNTs como também estabelecer diferenças entre a dopagem por intercalação nos feixes de SWNTs e DWNTs. A dopagem com H2SO4 torna o perfil Breit-Wigner-Fano (BWF) dos nanotubos metálicos nos sistemas SWNTs menos acentuado e a freqüência da banda G aumenta indicando que uma transferência de carga ocorre dos nanotubos para as moléculas de H2SO4. O efeito nos DWNTs é o oposto ao que foi evidenciado para os SWNTs, mostrando que a interação entre os tubos internos e externos no sistema DWNTs parece afetar mais fortemente as transições eletrônicas dos tubos internos do que as transições dos tubos externos. No terceiro sistema estudado, caracterizamos de maneira detalhada um novo sistema híbrido baseado em nanotubos de carbono que consiste de um cabo coaxial com carbono no interior e uma casca de selênio como tubo exterior. Demonstramos que o composto Butil-Lítio promove a interação entre os nanotubos de carbono e a casca de selênio levando a formação destes nanocabos. O espectro Raman dos SWNTs da amostra resíduo e selênio-nanotubos sugere que os nanocabos de selênio carbono interagem mais fortemente com os nanotubos semicondutores do que com os nanotubos metálicos. Estimamos que a química do selênio permitirá sintetizar nanocabos de selênio-carbono decorados com outros compostos funcionais tais como CdSe, ZnSe entre outros.

Le Génie Electrique, en général, et l'électronique de puissance, en particulier, prend une part de plus en plus importante dans les systèmes embarqués. La fiabilité des systèmes électroniques dépend fortement de la gestion de leur température. Les systèmes de refroidissement actuels sont lourds, volumineux, et consommateurs d'énergie, ce qui est en désaccord avec les systèmes embarqués. Il est donc nécessaire de chercher de nouveaux systèmes, plus fiables, plus légers, et moins énergivores. Le sujet de cette thèse porte sur l'utilisation des ferrofluides, suspensions colloïdales magnétiques, à basse température de Curie, dont les propriétés magnétiques varient fortement avec la température entre l'ambiante et une centaine de degrés Celsius afin de les utiliser comme liquide caloporteur dans les systèmes de refroidissement. Les propriétés magnétiques fortement dépendantes de la température d'un tel fluide permettent la mise en mouvement de ce dernier par l'action couplée d'un champ magnétique et d'un gradient de température alors que toutes les pièces solides restent fixes. Le système de refroidissement n'est alors plus assujetti à l'usure de la pompe permettant la circulation du fluide caloporteur. Le système est ainsi globalement plus fiable et moins consommateur d'énergie. L'énergie de mise en mouvement du ferrofluide étant extraite directement des pertes des composants. Le comportement des ferrofluides est trop méconnu à l'heure actuelle pour concevoir et optimiser une pompe statique magnétothermique. Un effort important de modélisation et de caractérisation doit être mené. Ce manuscrit présente une étude pratique vérifiant le principe de création de pression hydrostatique par couplage magnétothermique. Une modélisation de la distribution des forces locales mettant en mouvement le ferrofluide ainsi que la mise en place d'outil permettant la caractérisation des ferrofluides sont également présentées. Les efforts de caractérisation se sont concentrés sur la rhéologie, au regard du champ magnétique, du cisaillement et de la température, ainsi que sur le comportement magnétique du ferrofluide à différentes températures. / The Electrical Engineering in general and power electronics, in particular, plays an increasingly important role in embedded systems. The reliability of electronic systems strongly depends on the management of their temperature. Cooling systems today are heavy, bulky, and consumers of energy, which is in disagreement with embedded systems. It is therefore necessary to look for new systems, more reliable, lighter and use less energy. The subject of this thesis focuses on the use of ferrofluids, magnetic colloidal suspensions at low Curie temperature, the magnetic properties vary strongly with temperature between ambient and one hundred degrees Celsius, for use as coolant in cooling systems. The magnetic properties strongly dependent on the temperature of such fluid allow the actuation of the latter by the action of a magnetic field coupled at a temperature gradient so that all solid parts are stationary. The cooling system is no longer subject to the wear of the pump for the circulation of the coolant. The system is thus globaly more reliable and less energy consuming. The energy for moving the ferrofluid being extracted directly losses components. The behavior of ferrofluids is too little known today to design and optimize a pump magneto static. A major effort of modeling and characterization should be conducted. This manuscript presents a practical study verifying the principle of hydrostatic pressure created by magnetothermal coupling. A modeling of the distribution of local forces by moving the ferrofluid and the development tool for the characterization of the ferrofluids are also presented. Characterization efforts focused on rheology, under the magnetic field, shear and temperature, as well as on the magnetic behavior of the ferrofluid at different temperatures.

Les systèmes solaires thermiques combinés à un système d’appoint tel que une chaudière, une pompe à chaleur ou intégrant une machine à absorption, peuvent jouer un rôle important dans la réduction des consommations des bâtiments pour les besoins de chauffage, de climatisation et de production d’eau chaude sanitaire. Dans ce sens, la caractérisation des performances énergétiques des systèmes thermiques est un enjeu crucial.Les méthodes de caractérisation actuellement disponibles sont soit basées sur plusieurs essais physiques séparés des composants du système à évaluer, chose qui ne prend pas en compte les vraies interactions entre ces derniers, soit sur des modèles physiques qui peuvent être complexes et difficilement identifiables notamment du fait que les systèmes actuels sont compacts et préfabriqués en usine. En l’absence de méthode fiable pour estimer les performances des systèmes solaires thermiques avant leur intégration au bâtiment, le marché de ses derniers subit de fortes contraintes pour son développement.Dans ce contexte il devient indispensable de développer une méthodologie générique qui peut être appliquée à différentes typologies de systèmes et qui pallie les difficultés rencontrées par les méthodes actuelles.L’approche d’évaluation proposée dans ce mémoire est constituée de quatre étapes principales : la détermination d’une séquence de test, l’essai du système dans un banc d’essai semi-virtuel selon la séquence déterminée, l’acquisition des données et l’identification d’un réseau de neurones artificiels (RNA) du système et enfin la simulation du modèle en vue de l’estimation de la consommation du système dans l’environnement désiré. L’avantage d’utiliser un modèle complètement « boîte noire » du système complet à l’aide des RNA la rend totalement « non intrusive ». La connaissance des paramètres internes aux systèmes (rendements, conductivités thermiques, régulation etc.) n’est en conséquence pas nécessaire pour l’application de la méthodologie.La validation de la méthodologie a été réalisée à travers plusieurs expérimentations numériques, pour 7 systèmes issus de 3 typologies différentes, durant lesquelles les estimations des RNA ont été comparées aux calculs des modèles physiques dans plusieurs conditions différentes (qualité du bâtiment, climat et surface du capteur). Une application de l’approche développée dans le cas de 5 systèmes réels a permis la confirmation de la pertinence de la méthodologie. / Solar thermal systems combined with a backup system such as a boiler, a heat pump or incorporating an absorption chiller, can play an important role in reducing buildings energy consumption for heating, cooling and hot water production needs. In this sense, characterizing the energy performance of thermal systems is crucial.Currently available methods of system characterization are either based on several separate physical tests of system components to be evaluated, which do not take into account the real interactions between them, or on physical models that can be complex and difficult to identify especially because systems nowadays are compact and prefabricated in the factory. Due to the lack of a reliable method to estimate the performance of solar thermal systems before their integration into buildings, their market faces a lot of impediment to be developed.In this context, it becomes essential to develop a generic methodology that can be applied to different types of systems which overcomes the difficulties encountered by the current ones.The proposed evaluation approach in this manuscript is composed of four main steps: determining a test sequence, testing the system in a semi-virtual test bench according to predetermined sequence, data acquisition and identifying an artificial neural network (ANN) of the system and finally the model simulation in order to estimate the system consumption in the desired boundary condition. Using a completely "black box" model of the whole system using the ANN makes the methodology totally "non-intrusive". No prior knowledge about the systems internal parameters (yields, thermal conductivities, regulation etc.) is necessary to apply the proposed approach.The methodology validation was performed through several numerical experiments for seven systems coming from three different typologies. During the validation process, ANN estimates were compared with calculations of physical models in several different conditions (quality of building, climate and collector area). The developed approach was applied to five real systems as well. The application results allowed the confirmation of the methodology relevance.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The phenotypic characteristics [morphology, biochemical fermentation, antimicrobial susceptibility, index of multiple resistances to antimicrobials (MAR), minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of benzilpenicilin] of 38 Streptococcus equi isolates were evaluated in this study. The phenotypic analyses demonstrated three colony patterns, three carbohydrate fermentation patterns and variation from 0 to 0.4 in the index of multiple resistances to antimicrobials. All the isolates of S. equi demonstrated sensitivity to penicillin, both by the disc diffusion method and microdilution method. The average MIC and MBC for benzilpenincillin were of 0,0095 μg/mL and 0.0267 μg/mL for S. equi subsp. equi and of 0.0128 μg/mL and 0.0380 μg/mL for S. equi subsp. zooepidemicus. The samples of S. equi differed in the values of MIC and MBC (p<0,05). The size of the penicillin inhibition halo demonstrated a relation with the MIC and MBC for S. equi subsp. equi, however for the samples of S. equi subsp. zooepidemicus this relation was only verified with the MBC. The MIC of benzilpenincillin of the samples isolated from the Central, Planalto and South regions of Rio Grande do Sul were statistically similar, although different from the Paraná state sample, suggesting the atypical character of this strain. All S. equi isolates are sensitive to penicillin and sulfazotrim, confirming these as antibiotics of choice for the treatment of infections caused by this agent in the clinical veterinary practice. Genotypic characteristics were also analyzed (hsp60 gene partial sequencing and analysis) in 20 isolates of Streptococcus equi from clinical samples of horses with strangles. The phylogenetic analysis showed a politomy among the isolates, suggesting that the hsp60 gene does not allow the differentiation between S. equi subspecies. New studies are suggested with expansion of territory sampled or even with the application of other markers, in order to clarify the evolutionary patterns not resolved and to confirm or not the real genetic differences between subspecies. / As características fenotípicas [morfológicas, bioquímicas, susceptibilidade aos antimicrobianos, índice de resistência múltipla aos antimicrobianos - IRMA, concentração inibitória mínima (CIM), concentração bactericida mínina (CBM) da benzilpenicilina] de 38 isolados de Streptococcus equi foram avaliadas neste estudo. A fenotipia demonstrou três padrões de colônias, três perfis de fermentação de carboidratos e variação de 0 a 0,4 no índice de resistência múltipla aos antimicrobianos. Todos os isolados de S. equi demonstraram sensibilidade à penicilina, tanto pelo método de disco difusão quanto pelo método de microdiluição. A CIM e CBM média de benzilpenicilina foi de 0,0095 μg/mL e 0,0267 μg/mL para S. equi subesp. equi e de 0,0128 μg/mL e 0,0380 μg/mL para S. equi subesp. zooepidemicus. As amostras de S. equi diferiram para valores de CIM e CBM (p<0,05). O diâmetro do halo de inibição de penicilina demonstrou relação com a CIM e a CBM para S. equi subesp. equi, entretanto para as amostras de S. equi subesp. zooepidemicus esta relação somente foi verificada para a CBM. A CIM de benzilpenicilina frente às amostras isoladas da região Central, Planalto e Sul do estado do Rio Grande do Sul foram estatisticamente semelhantes, mas diferiram do isolado do estado do Paraná, sugerindo o caráter atípico desta cepa. Todos os isolados de S. equi são sensíveis à penicilina e sulfazotrim, antimicrobianos de eleição para as afecções por este agente na clínica veterinária. Também foram analisadas as características genotípicas (sequenciamento parcial e análise do gene hsp60) de 20 isolados de Streptococcus equi oriundos de amostras clínicas de animais com adenite equina. A filogenia mostrou uma politomia entre os isolados, e indicou que este marcador (gene hsp60) não permite a diferenciação das subespécies de S. equi. Sugere-se a realização de novos estudos com a ampliação da região amostrada ou mesmo com a aplicação de outros marcadores, a fim de esclarecer os padrões evolutivos não-resolvidos e confirmar ou não a diferenciação genética real entre as subespécies.

La corrosion des armatures est reconnue comme la première cause de dégradation des structures en béton armé dans les domaines du génie civil et des monuments historiques. La corrosion peut survenir lorsque le béton d'enrobage est carbonaté ou lorsque les ions chlorure sont présents en quantité suffisante au niveau de l'armature.Les objectifs de cette thèse visent à appréhender les processus de corrosion des armatures lorsque le béton est doublement contaminé (carbonatation et ions chlorure) et d'évaluer une solution de réparation de type traitement électrochimique d’extraction des ions chlorure (ECE).Pour répondre à ces objectifs, trois phases ont été programmées : (1) des vieillissements artificiels, (2) un traitement ECE et (3) un suivi de la durabilité du traitement. Pour chacune de ces phases, les évolutions (1) de la corrosion des armatures dans le béton, (2) des produits de corrosion à l'interface armature/béton et (3) de la matrice cimentaire ont été investiguées. L'approche scientifique de l'étude, avec des analyses multiples d'observations à différentes échelles et l'utilisation de techniques non destructives, destructives ou in situ, a permis de rendre compte des processus de corrosion avant et après traitement et de discuter les résultats en fonction de critères d'efficacité proposés.L'étude a été réalisée en prenant en compte deux ciments (CEM I et CEM III/A) et en considérant deux modes de vieillissements artificiels. Trois cent vingt éprouvettes en micro-béton armé répondant à quatre formulations ont ainsi été étudiées. Les techniques principales utilisées sont des caractérisations électrochimiques non destructives, des caractérisations au MEB et EDS, des analyses destructives de déterminations quantitative pour la teneur en ions chlorure et qualitative pour l'évaluation du pH et enfin la microspectrométrie Raman qui permet de déterminer la nature des produits de corrosion in situ.L’exploitation de l’ensemble des résultats a mis en évidence l’évolution des caractéristiques étudiées au cours des phases de l’étude. Avant traitement, l'enrobage béton était entièrement carbonaté et la teneur en ions chlorure libres au voisinage de l'armature était comprise entre 0,9 et 2,1% par rapport à la masse de ciment en fonction des formulations. Les courants de corrosion étaient de l’ordre de 10 µA/cm² et une épaisseur de corrosion homogène de l’ordre de 5-10 µm était observée. Lors des analyses Raman in situ, de la rouille verte chlorurée a été identifiée, synonyme de corrosion active. Après traitement, plus de 90% des ions chlorure ont été extraits et le pH du béton au voisinage de l'armature a augmenté (pH>9) sur une épaisseur d’environ 1 cm. Les courants de corrosion sont devenus inférieurs à 0,1 µA/cm² (niveau de corrosion négligeable). La formation de magnétite a majoritairement été observée avec néanmoins la présence résiduelle très locale de rouille verte. Aucune évolution délétère significative de la matrice cimentaire n’a été identifiée. L’efficacité du traitement a donc été démontrée. L'évaluation de la durabilité du traitement sur une période de 4 à 12 mois a montré que les caractéristiques électrochimiques restaient stables. En revanche, la diminution de l'épaisseur de béton dont le pH avait augmenté pour les éprouvettes fabriquées avec le ciment CEM III/A peut laisser craindre une reprise de corrosion sur du plus long terme. Enfin, le suivi Raman in situ, montre des différences de la durabilité en fonction de la durée du traitement / Reinforcement corrosion is known as the first cause of reinforced concrete degradation in the fields of civil engineering structures and historical monuments. Corrosion occurs when concrete cover is carbonated or when chloride ions are present in sufficient quantity at the reinforcement vicinity.The main objectives of this thesis are to investigate the corrosion processes of the reinforcement when the concrete is contaminated by carbonation as well as chloride ions and to evaluate a cathodic electrochemical treatment as a repair solution.To meet these objectives, three phases were investigated: (1) artificial agings, (2) an electrochemical chloride extraction (ECE) treatment and (3) durability. For each of these phases, the evolutions (1) of the rebar corrosion in concrete, (2) of the corrosion products at the reinforcement/concrete interface and (3) of the cementitious matrix were studied.The scientific approach gathered multiple analyzes at different scales and the use of non-destructive, destructive or in situ technique. It allowed to study the corrosion processes before and after treatment and to discuss results according to efficiency criteria suggested.The study was carried out taking into account two cements (CEM I and CEM III/A) and considering two modes of artificial aging. More than three hundred specimens of reinforced micro-concrete, corresponding to four concrete designs, were therefore studied. The main techniques used were non-destructive electrochemical characterizations, SEM and EDS characterizations, destructive quantitative determinations (chloride ion content) and qualitative determinations (pH evaluation), and finally Raman microspectrometry to determine the nature of the corrosion products.The results highlighted some evolutions of different characteristics studied during the phases of the study. Before treatment, the concrete cover was entirely carbonated and the free chloride content at the reinforcement level was in the range of 0.9-2.1% by weight of cement depending on the concrete design. A 10 μA/cm² average corrosion currents was reported and a homogeneous corrosion layer thickness of about 5-10 μm was observed. During in situ Raman analysis, chloride green rust was identified indicating an active corrosion.After treatment, more than 90% of the chloride ions were extracted and the thickness of the concrete which had a pH value higher than 9 around the reinforcement, was about 1 cm. The corrosion currents became less than 0.1 μA/cm² (negligible corrosion level). The formation of magnetite was mostly observed with nevertheless a local presence of residual green rust. No significant deleterious evolution of the cementitious matrix was identified. The treatment efficiency was therefore demonstrated. The evaluation of the treatment durability over a period of 4 to 12 months showed that the electrochemical characteristics remained stable. On the other hand, a decrease in the concrete area which pH increased during the electrochemical treatment was observed for CEM III/A cement which could lead to a corrosion recovery over the longer term. Finally, the in situ Raman study revealed differences in durability as a function of the treatment duration

Cette thèse est essentiellement consacrée à la caractérisation et à l’analyse des propriétés mécaniques de matériaux composites constitués d’un renfort taffetas verre et d’une résine acrylate (Elium®). Avant l’apparition de la résine Elium® sur le marché en 2013, les polymères acrylates n’étaient pas utilisés dans l’industrie des composites fibres longues. Dans le volet expérimental de la thèse, nous nous intéressons principalement à l’influence de l’ensimage (traitement de surface appliqué aux fibres pour favoriser l’adhésion de la matrice) sur le comportement mécanique de nos composites. En complément de différents essais mécaniques macroscopiques « classiques » (traction, flexion etc.), nous avons utilisé des techniques d’analyse locales fines (mesures de champ cinématique, microtomographie X, Microscopie Électronique à Balayage, nanoindentation…) qui nous ont permis de caractériser et d’étudier certains mécanismes locaux de déformation et d’endommagement. L’influence de l’ensimage sur les propriétés en fatigue a été mise en évidence grâce à des mesures d’autoéchauffement pour lesquelles nous avons développé un traitement original des données. A l’issue de nos investigations, nous avons pu quantifier le bénéfice qui résulte de l’utilisation d’un ensimage spécifiquement conçu pour favoriser l’adhésion d’un polymère acrylate sur des fibres de verre. Dans le volet « simulation numérique » de la thèse, nous avons modélisé le comportement mécanique de nos composites taffetas verre/matrice acrylate grâce au solveur spectral CraFT (Composite response and Fourier Transforms). Le détail des champs de contrainte et de déformation a été obtenu à l’échelle de la mésostructure et révèle une structuration périodique induite par la présence du renfort tissé. Une analyse quantitative a permis de vérifier que les champs de déformation qui ont été obtenus grâce au solveur CraFT sont en très bon accord avec des mesures réalisées par corrélation d’images. A partir du champ de contrainte, nous avons mis en évidence les régions de la mésostructure qui subissent les plus fortes sollicitations mécaniques. En visualisant par microtomographie X la structure interne d’éprouvettes précédemment déformées, nous avons pu établir le lien entre la localisation de l’endommagement au sein de la mésostructure et les régions de concentration de contrainte que la simulation numérique avait mises en évidence / This thesis is devoted to the characterization and the analysis of the mechanical properties of composite materials made of a plain weave glass fiber reinforcement and an acrylic resin (Elium®). Before the commercialization of the Elium resin in 2013, acrylics polymers were not used in the composite industry. In the experimental part of this thesis, we mainly focused on the sizing effect (surface treatment of the fibers to enhance the bonding between the matrix and the fibers) on the mechanical behavior of our composites. The characterizations were carried out through classical macroscopic mechanical tests (tensile, bending, shearing…) but using metrological tools for local analysis (full-field strain measurements, X ray micro-tomography, Scanning Electron Microscopy, Nano-indentation etc.). We were able to study strain and damage phenomena at local scales. Fatigue properties of the sizing were highlighted by heat build-up experiments. To analyze these measurements, an original data treatment has been developed which makes clear the benefit of an acrylic sizing in order to enhance the bonding between glass fibers and our acrylic matrix. In the theoretical part of this thesis, we studied the mechanical behaviour of our glass fiber plain weave/acrylic resin composite through a numerical simulation based on the CraFT spectral solver (Composite response and Fourier Transforms). Local stress and strain fields were obtained at the mesoscopic scale. The strain field analysis shows a periodic structure induced by the presence of the plain weave reinforcement. By a quantitative study, a good agreement between the numerical strain field obtained by CraFT and the 3D-DIC experimental strain measurements was found. The numerical stress field analysis reveals regions were a high local stress occurs. Comparing with X ray micro-tomography observationsof the internal structure of previously loaded composite sampleswe noticed that the damages occurring inside the mesostructure are totally correlated with the local stress concentration revealed by CraFT numerical simulations

Este trabalho procurou analisar os fatores influentes nos processos erosivos na bacia do córrego Tuncum, município de São Pedro-SP, através de características observadas, tanto no campo como em laboratório (ensaios geotécnicos de caracterização de solos e ensaio de erodibilidade), onde se constatou que as áreas que apresentam alta susceptibilidade aos processos erosivos estão associados principalmente ao material geológico constituinte da bacia. Para o estudo da evolução das feições erosivas foram utilizadas fotografias aéreas de três diferentes datas (1972, 1995 e 2000), e com auxílio de técnicas de geoprocessamento realizou-se um tratamento qualificado das informações adquiridas. A análise das informações obtidas permitiu o estabelecimento da susceptibilidade à erosão que associada às informações de uso e ocupação conduziu a definição de prognósticos acerca da evolução dos processos erosivos na área. Os documentos cartográficos elaborados foram o mapa de documentação, mapa de Landforms, carta de declividade, mapa de materiais inconsolidados, carta de susceptibilidade à erosão e carta de prognósticos ao desenvolvimento de erosões lineares. / This work aims to analyze the main factors related to the erosion processes in the Tuncum creek watershed, city of São Pedro-SP, based on the observed geological-geotechnical characteristics in the field and laboratory (soil geotechnical characterization and erodibility tests). It was verified that high susceptibility area to the erosion processes are mainly associated to geological materials of the watershed. For the study of the evolution erosion features were used aerial photographs of three different dates (1972, 1995 and 2000), and with aid of geoprocessing techniques realized a qualified treatment to the acquired informations. The analysis of the obtained informations allowed the establishment of the erosion susceptibility that associated to the information of use and occupation lead the definition of prognostics concerning the evolution of the erosive processes in the area. The cartographic documents elaborated were documentation, landforms and unconsolidated materials maps, declivity, susceptibility to erosion and prognostic to the development of linear erosions charts.

Esta tese consiste no estudo do processo de sÃntese e funcionalizaÃÃo de nanotubos de carbono. A sÃntese dos nanotubos de carbono foi realizada usando a tÃcnica de deposiÃÃo quÃmica a partir da fase vapor (CVD). Foram sintetizados Nanotubos de parede simples (SWNTs) e mÃltipas (MWNTs) . A diferenÃa bÃsica das metodologias usadas para preparar as amostras foi o uso de diferentes catalisadores expostos ao gÃs hidrogÃnio por diferentes intervalos de tempo. As amostras obtidas foram caracterizadas por espectroscopia Raman ressonante e anÃlise tÃrmica. Os resultados de anÃlise tÃrmica mostraram que as amostras sintetizadas apresentam uma excelente estabilidade tÃrmica, quando comparada com algumas amostras disponÃveis no mercado. Foram estudados trÃs diferentes sistemas em relaÃÃo ao processo de funcionalizaÃÃo de nanotubos de carbono. No primeiro sistema, investigamos o efeito da irradiaÃÃo de Ãons de silÃcio (Si+) e carbono (C+) nas propriedades eletrÃnicas e estruturais dos nanotubos de parede dupla (DWNTs). A implantaÃÃo foi realizada à temperatura ambiente com concentraÃÃes de Ãons que variam de 1 a 100 x (1013 Ãons/cm2); e a espectroscopia Raman ressonante foi a principal tÃcnica utilizada para estudar os efeitos da implantaÃÃo. Os efeitos da implantaÃÃo dos Ãons de Si+ na estrutura dos nanotubos sÃo mais fortes do que os Ãons de C+ o que à atrÃbuido ao maior raio iÃnico do Si+. A razÃo das intensidades das bandas D e G foi usada para investigar a concentraÃÃo de Ãons para a qual o sistema perde a caracterÃstica sp2, deixando o sistema muito desordenado e com grande concentraÃÃes de ligaÃÃes sp3. Observamos que o aumento da dosagem de Ãons aumenta a intensidade da banda D e os modos radiais de respiraÃÃo dos nanotubos semicondutores (tubo externo) e metÃlicos (tubo externos) desaparecem primeiramente do que os tubos internos. Para altas dosagens de implantaÃÃo de Ãons de silÃcio ou carbono observamos que os nanotubos sÃo completamente deformados e os espectros Raman apresentam aspectos de grafite altamente desordenados. No segundo sistema estudado, investigamos os efeitos da dopagem da molÃcula de H2SO4 nos SWNTs e DWNTs com distribuiÃÃo de diÃmetros dos SWNTs similar aos tubos internos dos DWNTs. A comparaÃÃo destes dois sistemas permitiu ter um maior conhecimento dos efeitos da molÃcula H2SO4 nos sistemas DWNTs como tambÃm estabelecer diferenÃas entre a dopagem por intercalaÃÃo nos feixes de SWNTs e DWNTs. A dopagem com H2SO4 torna o perfil Breit-Wigner-Fano (BWF) dos nanotubos metÃlicos nos sistemas SWNTs menos acentuado e a freqÃÃncia da banda G aumenta indicando que uma transferÃncia de carga ocorre dos nanotubos para as molÃculas de H2SO4. O efeito nos DWNTs à o oposto ao que foi evidenciado para os SWNTs, mostrando que a interaÃÃo entre os tubos internos e externos no sistema DWNTs parece afetar mais fortemente as transiÃÃes eletrÃnicas dos tubos internos do que as transiÃÃes dos tubos externos. No terceiro sistema estudado, caracterizamos de maneira detalhada um novo sistema hÃbrido baseado em nanotubos de carbono que consiste de um cabo coaxial com carbono no interior e uma casca de selÃnio como tubo exterior. Demonstramos que o composto Butil-LÃtio promove a interaÃÃo entre os nanotubos de carbono e a casca de selÃnio levando a formaÃÃo destes nanocabos. O espectro Raman dos SWNTs da amostra resÃduo e selÃnio-nanotubos sugere que os nanocabos de selÃnio carbono interagem mais fortemente com os nanotubos semicondutores do que com os nanotubos metÃlicos. Estimamos que a quÃmica do selÃnio permitirà sintetizar nanocabos de selÃnio-carbono decorados com outros compostos funcionais tais como CdSe, ZnSe entre outros. / In this Thesis we report a study of the synthesis and functionalization of carbon nanotubes. Regarding the synthesis, we produced carbon nanotubes samples using the chemical vapor deposition method. Both single-wall and multi-wall carbon nanotubes were produced. The basic difference between these two growth results was the catalyst employed. We also have changed the exposure time of catalyst particle to the hydrogen gas to find out the optimal parameters for growing the nanotubes. The obtained samples were characterized by resonance Raman spectroscopy and thermal analysis. The obtained samples show higher thermal stability compared with some commercially available samples. Regarding functionalization of the tubes we studied three different systems. Firstly, we investigated the effect of Si+ and C+ ions bombardment on the structural and electronic properties of highly pure double wall carbon nanotubes (DWNTs). The implantation was performed at room temperature with high fluencies of ions varying from 1 to 100 x( 10 13 ions/cm2) and the Raman spectroscopy was the main technique employed for studying the ion implantation-induced changes in the nanotubes. The effects of the Si+ implantation is stronger than that of C+ and this is attributed to the larger ionic radius of Si. The D to G band intensity ratio was used for probing the ion concentration for which the system looses its sp2 character leading to a highly disordered system with a high concentration of sp3 bonds. We observed that as the ion implantation dosage increases, the D-band intensity increases and the radial breathing modes (RBM) of the semiconducting (outer) and metallic (outer) tube disappear first, before from the inner tubes. At higher ion-implantation dosage, the carbon nanotubes are completely deformed and the Raman spectrum is typical of highly disordered graphite. Secondly, we investigated the effects of H2SO4 doping on DWNTs and SWNTs where the diameter of SWNTs are in the same range as the inner tube of the DWNTs. The comparison of these two systems allow to further improve the knowledge of doping effects on the constituents of DWNTs as well as to establish differences between the exohedral doping of SWNTs and DWNTs bundles. Upon doping with H2SO4 the Breit-Wigner-Fano lineshape of metallic tubes in the SWNTs samples decreases and the G band frequencies increase thus indicating that an electronic charge transfer is occurring from the nanotubes to the dopant molecule. The effect on the DWNTs is opposite to that of SWNTs thus evidencing that the inner and outer shell interaction seems to affect the inner tube electronic transitions more than those of the outer tubes. Thirdly, we report a detailed characterization of a novel carbon nanotube-based system that is a coaxial nanocable made of carbon as core and selenium as shell. Carbon nanotube bundles are wrapped up within a trigonal selenium shell. We have demonstrated that the Butyl-lithium compound plays an important role in promoting the interaction between the carbon nanotubes and the selenium shells and thus enables the preparation of these nanocable structures. The Raman spectra of the SWNTs in the residue and the Se-CNT nanocables suggests that this selenium-carbon interaction is stronger for semiconducting nanotubes than for metallic nanotubes. The chemistry of Selenium would allow the synthesis of carbon nanotubes decorated with other functional Se-based structures, such as CdSe, ZnSe, among others.

L'introduction du SiGe dans les pMOS (Bulk et FDSOI) exige un bon contrôle de la tension de seuil (VT). Ceci nécessite une extraction précise des paramètres électriques ainsi qu'une compréhension des effets électriques du Ge dans de tels dispositifs. Dans cette thèse, nous avons d'abord proposé des méthodes pour une identification précise des paramètres électriques du « gate stack »: VT, la tension de bande plate (VFB) et l'épaisseur équivalente d'oxyde (EOT). Ces méthodes ont été validées avec des simulations Poisson-Schrödinger (PS) et appliquées avec succès aux mesures. Dans un second temps, nous avons étudié les effets électriques du Ge sur les paramètres du « gate stack » des pMOS. La comparaison des caractérisations électriques (C-V) avec les simulations PS a montré un décalage supplémentaire du travail de sortie effectif qui croit avec le Ge. Des caractérisations STEM, EELS et SIMS ont prouvé que ce décalage est due à la présence de dipôles à l'interface SiGe/oxyde. / Maintaining good threshold voltage (VT) centering is a paramount challenge for CMOS technology. The SiGe introduction in bulk and FDSOI pFETs requires VT control for such devices. To this end, we have to extract accurately electrical parameters and to understand Ge integration effects in SiGe based pFETs. In this thesis, first, we have proposed extraction methods to determine VT, flat band voltage (VFB) and equivalent oxide thickness (EOT) parameters in bulk and FDSOI transistors. The extraction methods have been validated via Poisson-Schrodinger (PS) simulations and successfully applied to measurements. Second, we have highlighted and explained electric effects of Ge on pMOS gate stack parameters. Electrical characterizations compared with PS simulations have evidenced an additional effective work function increase, induced by Ge, related to interfacial dipoles. STEM, EELS and SIMS characterizations have demonstrated that dipoles are located at SiGe/IL interface.

Submitted by Maike Costa (maiksebas@gmail.com) on 2016-05-04T14:36:33Z No. of bitstreams: 1 arquivo total.pdf: 1858990 bytes, checksum: 3b9c1c92812cc3daa634b61430ba84d6 (MD5) / Made available in DSpace on 2016-05-04T14:36:33Z (GMT). No. of bitstreams: 1 arquivo total.pdf: 1858990 bytes, checksum: 3b9c1c92812cc3daa634b61430ba84d6 (MD5) Previous issue date: 2014-03-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Recently there have arisen new compounds of Schiff base type synthesized from the condensation of Meldrum's acid (or its derivatives) with a diamine (ethylenediamine or o-phenylenediamine) providing compounds classified as melens or melophens, which are structural analogues to the classical salens and salophens. The melophens have been used as ligands to form metal complexes analogous to salophens aiming its application in biomimetic catalysis. Herein, we describe the voltammetric electrochemical characterization to four ligands (H2melen, H2Cy2melen, H2melophen and H2Cy2melophen) and two complexes (MnII(Cy2melofen) and NiII(melophen)) on aprotic medium (DMF) using glassy carbon electrode work, and Ag|Ag+ (0,1 mol·L-1 TBAP, 10 mmol AgNO3) as reference electrode. The H2melen and H2Cy2melen behaved similarly showing an irreversible one electron reduction process (1e-). The proposed mechanism for those compounds involves a step dimerization. The H2melophen and H2Cy2melophen demonstrated similar behavior showing two reductions and two irreversible oxidations, where one of the processes is adsorption of reactant and product. The MnII(Cy2melophen) complex showed a single quasi-reversible redox process centered on the metal MnIII/MnII, which involves the transfer of one electron. The NiII(melophen) presented four cases, being a quasi-reversible (1e-) and the others irreversible processes involving a total of 5 electrons. All potentials were corrected across the redox couple of ferrocene (Fc/Fc+), and the effect of addition of acids and bases in the medium is discussed. / Recentemente, novos compostos do tipo base de Schiff, análogos estruturais aos clássicos salens e salofens, foram obtidos a partir da condensação do ácido de Meldrum (ou seus derivados) com uma diamina (etilenodiamina ou orto-fenilenodiamina), fornecendo compostos denominados melens ou melofens. Os melofens têm sido utilizados como ligantes a fim de formar complexos metálicos análogos aos salofens, visando sua aplicação em catálise biomimética. Neste trabalho é apresentada a caracterização eletroquímica de quatro ligantes (H2melen, H2Cy2melen, H2melofen e H2Cy2melofen) e dois complexos (MnII(Cy2melofen) e NiII(melofen)) em meio aprótico (DMF), empregando carbono vítreo como eletrodo de trabalho, mediante a aplicação de técnicas voltamétricas. O H2melen e o H2Cy2melen apresentaram comportamentos semelhantes exibindo uma redução irreversível envolvendo um elétron (1e-). O mecanismo proposto para esses compostos envolve uma etapa de dimerização. O H2melofen e o H2Cy2melofen apresentaram comportamentos semelhantes exibindo duas reduções e duas oxidações irreversíveis, onde em um dos processos ocorre adsorção do reagente e do produto. O complexo MnII(Cy2melofen) apresentou um único processo redox quase-reversível centrado no metal MnIII/MnII, o qual envolve 1e-. O NiII(melofen) apresentou quatro processos, sendo um quase-reversível (1e-) e os demais irreversíveis envolvendo um total de 5e-. Todos os potenciais foram corrigidos frente o par redox do ferroceno (Fc/Fc+), e o efeito da adição de ácidos e bases ao meio é discutido.