<p>Currently, fossil fuels and nuclear power are our primary energy sources. However, both have critical disadvantages due to the limited supply and the hazard issues. Renewable energy research becomes one of most important research topics in the 21st century. Nanostructured materials show unique electrochemical properties in various energy conversion or storage devices. This dissertation starts with fundamental optical studies of nanomaterials (carbon nanotubes), followed by synthesizing novel nanomaterials for energy conversion (solar cells) and storage (lithium ion batteries) devices. </p><p> (1) There is an on-going debate concerning the ability of double walled carbon nanotubes (DWNTs) to exhibit photoluminescence (PL). We aim to clearly resolve this debate through the study of carefully separated DWNTs using density gradient ultra-centrifugation (DGU). Here, we clearly show that light is emitted from the inner wall of DWNTs. Interestingly, it was found that a very narrow range of diameters of the inner walls of DWNTs is required for photoluminescence (PL) to be observable. All other diameters led to complete PL quenching in DWNTs. (2) Inexpensive dye sensitized solar cells (DSSCs) on flexible plastic substrates have a bright future, but they require low temperature annealing (< 200°C). The method to fabricate low temperature DSSCs should resolve poor electron transfer between titanium dioxide (TiO2) nanoparticles (NPs) due to their incomplete contiguity and insulating layer of organic residues from binders in the photoactive film. Here, we have developed uniform CNTs/TiO2 composites for low temperature DSSCs by using modified sol gel method. DSSCs were fabricated to study incorporating functionalized few walled carbon nanotubes (f-FWNTs) effect on TiO2 NPs. Incorporating f-FWNTs can be beneficial for the low temperature annealing process of DSSCs to overcome extremely poor electron transport through TiO2 photoactive film. Incorporating f-FWNTs with TiO2 active layer improves electrons transport in some degree, but this advantage is limited. (3) Conductive fillers, such as amorphous carbon, carbon nanotube and graphene, have been mixed with nanostructured metal oxide materials to improve the performance of electrode materials in energy storage devices. However, ineffective junctions between conductive fillers are limiting the overall conductivity of the electrode. Therefore, we developed a convenient, inexpensive and scalable method for synthesizing hybrid carbon and titanium dioxide (C/TiO2) co-gels and co-aerogels to improve their electrochemical capacity in lithium ions batteries (LIBs). The monolith of the hybrid C/TiO2 co-aerogel can be directly used as active electrodes without the addition of binders. As a result, the capacitance of LIB anodes using the hybrid co-aerogel is significantly improved over current LIBs based on carbon/titanium oxide composite. Other metal oxides could also form co-gels with carbon to improve their potentials in numerous electrochemical, photocatalytic, and photoelectronic devices.</p> / Dissertation

The telescoping cantilever beam structure is applied in many different engineering sectors to achieve weight/space optimisation for structural integrity. There has been limited theory and analysis in the public domain of the stresses and deflections involved when applying a load to such a structure. This thesis proposes (a) The Tip Reaction Model, which adapts classical mechanics to predict deflection of a two and a three section steel telescoping cantilever beam; (b) An equation to determine the Critical buckling loads for a given configuration of the two section steel telescoping cantilever beam assembly derived from first principles, in particular the energy methods; and finally (c) the derivation of a design optimization methodology, to tackle localised buckling induced by shear, torsion and a combination of both, in the individual, constituent, hollow rectangular beam sections of the telescopic assembly. Bending stress and shear stress is numerically calculated for the same structure whilst subjected to inline and offset loading. An FEA model of the structure is solved to verify the previous deflection, stress and buckling predictions made numerically. Finally an experimental setup is conducted where deflections and stresses are measured whilst a two section assembly is subjected to various loading and boundary conditions. The results between the predicted theory, FEA and experimental setup are compared and discussed. The overall conclusion is that there is good correlation between the three sets of data.

Ce travail de thèse consiste en une étude des mécanismes de croissance des nanotubes de carbone monofeuillets par spectroscopie Raman in situ. La première partie de ce travail est consacrée à la mise en évidence des limites en température et en pression partielle de précurseur carboné du domaine de croissance des nanotubes de carbone monofeuillets. L’atout principal de la spectroscopie Raman in situ étant de pouvoir corréler informations structurales et cinétiques, cette approche a aussi permis d'étudier l'influence des principaux paramètres de synthèse (T, P, nature du précurseur carboné et du catalyseur) sur les cinétiques de croissance et de désactivation, ainsi que sur la nature et la quantité des espèces carbonées désordonnées produites. Enfin, l’influence de la température et de la pression partielle de précurseur sur le diamètre des nanotubes formés a également été étudiée. Ce travail a finalement conduit à la mise en évidence de plusieurs processus élémentaires impliqués dans : l’activation, la croissance, la désactivation, la qualité structurale, la pureté et la sélectivité en diamètre des nanotubes. / This work presents a study of the Single-Walled Carbon Nanotubes growth mechanisms by in situ Raman measurements. The first part of the manuscript is devoted to the determination of the temperature and precursor partial pressure limits of the Single-Walled Carbon Nanotubes growth domain. Furthermore, in situ Raman spectroscopy allows to correlate structural information and kinetics: this approach permits to study the influence of the main synthesis parameters (T, P, nature of the carbon precursor and of the catalyst) on the growth and deactivation kinetics, and on the nature and the quantity of disordered carbon species synthesized. Lastly, a study on the temperature and precursor partial pressure effects on the nanotubes diameters is reported. All the data collected have finally led to a discussion about the elementary processes involved in: activation, growth, deactivation, structural quality, purity and diameter selectivity of Single-Walled Carbon Nanotubes.

Large wind turbine blades, manufactured from fibre reinforced laminated composite materials, are key structural components of wind turbine systems. The demands for efficient and accurate modelling techniques of these composite blades have significantly increased. Over past decades, although complex computational models have been widely developed, more analytically based models are still very much desired to drive the design and optimization of these composite blades forward to be lighter, stronger, efficient and durable. The research work in this thesis aims to develop such more analytically based aerodynamic, structural and aero-elasticity models for large wind turbine blades manufactured from fibre reinforced laminated composite materials. Firstly, an improved blade element momentum (BEM) model has been developed by collectively integrating the individual corrections with the classic BEM model. Compared to other existing models, present BEM model accounts for blade tip and root losses more accurately. For laminar flow, the 3-D cross-flow is negligibly small. In this case, present BEM model with statically measured 2-D aerodynamic coefficients agrees closely to experimental measurements. However, stall delay correction is required for a 3-D rotating blade in stall. A new stall delay model is developed based on Snel s stall delay model. Verifications are performed and discussed for the extensively studied NREL UAE phase-VI test. The predictions of distributive and collective factors, e.g. normalised force coefficients, shaft torque and etc. have been compared to experimental measurements. The present BEM model and stall delay model are original and more accurate than existing models. Secondly, significant deficiency is discovered in the analytical thin-walled closed-section composite beam (TWCSCB) model proposed by Librescu and Vo, which is widely used by others for structural modelling of wind turbine blades. To correct such deficiency, an improved TWCSCB model is developed in a novel manner that is applicable to both single-cell and multi-cell closed sections made of arbitrary composite laminates. The present TWCSCB model has been validated for a variety of geometries and arbitrary laminate layups. The numerical verifications are also performed on a realistic wind turbine blade (NPS-100) for structural analysis. Consistently accurate correlations are found between present TWCSCB model and the ABAQUS finite element (FE) shell model. Finally, the static aero-elasticity model is developed by combining the developed BEM model and TWCSCB model. The interactions are accounted through an iterative process. The numerical applications are carried out on NPS-100 wind turbine. The numerical results show some significant corrections by modelling wind turbine blades with elastic coupling.

Ce travail de thèse est d’utilisation de nanotubes de carbon (NTCs) comme support pour confiner de nanoparticules métalliques ou comme gabarit pour le confinement de la phase active. Le chapitre I présente l’état actuel des connaissances sur les effets de confinement dans les NTCs. Le chapitre II décrit la préparation et la caractérisation de catalyseurs métalliques à base de ruthénium, de cobalt et de palladium, confinées à l’intérieur de NTCs. Dans ce cadre, l’étude de l’influence de différents paramètres tels que les conditions opératoires, la nature du métal ou du précurseur, ou un prétraitement du support NTC, sur la sélectivité du confinement est présentée. Le chapitre III comporte deux parties : l’une est consacrée à l’utilisation de NTCs comme gabarit pour la synthèse de nanotubes de silice (NTSs, en présence ou non de particules de ruthénium confinées dans leur canal). L’autre partie concerne l’immobilisation du catalyseur (complexe métallique de rhodium) dans une phase liquide ionique comme phase catalytique active avant le remplissage dans les NTCs. Le chapitre IV concerne l’application tous les systèmes catalytiques à base de catalyseurs confinés à l’intérieur de nanotubes dans les réactions d’hydrogénation du cinnamaldéhyde et du 1-hexène. L’effet de confinement sur les performances catalytiques est présenté. / This thesis is refer of carbon nanotubes (CNTs) as a support to confine metal nanoparticles or as a template for the confinement of the active phase. Chapter I give a comprehensive review of the state of knowledge on the effects of confinement in CNTs. Chapter II describes the preparation and characterization of the metals (ruthenium, palladium and cobalt) confined inside CNTs catalysts. In this context, the study of the influence of various parameters such as operating conditions, nature of the metal or precursor or nanosupport pretreatment, on the selectivity of confinement is presented. Chapter III consists of two parts: one is devoted to the using of CNTs as a template for the synthesis of silica nanotubes (SNTs in the presence or absence of ruthenium particles confined in their channel). The other part is the immobilization of the catalyst (rhodium metallic complex) in an ionic liquid phase as active catalytic phase before filling in CNTs. Chapter IV concernes the application all catalyst-filled CNTs systems in the hydrogenation of cinnamaldehyde and 1-hexene reaction. The confinement effect on the catalytic performance is presented.

Os perfis de aço formados a frio possuem até 3 modos de flambagem: local, distorcional e global. Essa diversificação torna muito complexa a verificação de esforços resistentes nesses perfis. Recorre-se, então a métodos simplificados e interativos, com o intuito de fornecer ao engenheiro civil ferramentas que sejam práticas e apresentem um bom resultado. Métodos numéricos, como o MFF (métodos das faixas finitas), apesar de serem mais precisos, não são ainda, de uso corrente em projetos. O enfoque principal deste trabalho são as normas brasileiras de perfis formados a frio NBR 14762:2001 “Dimensionamento de estruturas de aço constituídas por perfis formados a frio" e NBR 6355:2003 “Perfis estruturais de aço formados a frio - Padronização". Comparam-se as tabelas D1 e D2 na NBR14762:2001, referentes à flambagem distorcional, a resultados calculados por meio do processo recomendado pela norma. Verificaram-se quais perfis padronizados pela NBR 6355:2003 dispensam a verificação da resistência por distorção da seção transversal. Uma análise geral de perfis de aço formados a frio, a fim de identificar aqueles que possuem melhor eficiência (perfis que resistem esforços mais elevados com menor área da seção transversal) também é feita. Para a realização desta pesquisa foi desenvolvido um programa de computador. / The cold formed steel members have up to 3 buckling modes: local, distortional and global. This diversification makes very complex the verification of these members’ resistance. For this reason it is used simple and interactive methods to provide the Civil Engineers tools that are practical and present a good result. Although numerical methods such as FDM (Finite Strip Methods) are more precise, they are still not currently used in projects. The main focus of this dissertation is the Brazilian rules regarding the cold formed steel members NBR 14762:2001 “Dimensioning steel structures made of cold formed profiles" and NBR 6355:2003 “Cold formed steel members – Standardizing". It compares the D1 and D2 tables of NBR14762:2001, regarding the distortional buckling, with the calculated results recommended by these rules. In this way it is verified which NBR 6355:2003 standardized profiles do not require the verification of resistance by distortional buckling. It is also made a general analysis of these cold formed steel members. And to make this research it was developed a computer program.

Cette thèse est consacrée à l'étude d'encres, de composites et de dépôts de nanotubes de carbone monofeuillets (SWNT). Le contrôle de la dispersion et de l'orientation des nanotubes dans ces matériaux composites nanostructurés vise à optimiser leurs propriétés, en particulier électriques et optiques.La première partie du travail est consacrée à l'optimisation de la dispersion des SWNT dans des suspensions aqueuses stabilisées par des tensio-actifs, des sels biliaires, et à l'étude de leurs propriétés optiques, et en particulier de leur photoluminescence (PL) dans le proche infrarouge. La spectroscopie d'absorption nous permet de sonder la dispersion des SWNT et de mesurer leur coefficient d'absorption. Nous montrons que ce dernier est très sensible au degré d'individualisation des nanotubes. Par ailleurs, nous revisitons l'interprétation des spectres de PL excités dans le proche infrarouge (en particulier à 1,17 et 1,58 eV) et attribuons les différents pics mesurés à différents mécanismes : transitions excitoniques directes, à des couplages exciton-phonon ou à des transferts d'énergie entre nanotubes. Nous montrons que l'évolution de l'intensité de PL avec l'individualisation permet de distinguer ces différents mécanismes.La seconde partie du travail est dédiée à la préparation de suspensions aqueuses stabilisées par des polymères hydrosolubles (PVA et PVP), et de composites SWNT/polymère, sans tensio-actifs. Les suspensions de nanotubes sont mélangées à des solutions de polymère, puis dialysées pour éliminer le tensio-actif. Le rendement, i.e. la concentration de la suspension finale, est de l'ordre de 75 fois plus élevée que pour une suspension préparée directement avec des polymères. Par ailleurs, les spectres de PL sont sensibles à l'environnement diélectrique des nanotubes et leur étude permet de mettre en évidence un échange entre les agents dispersants tensio-actifs/PVA à la surface des nanotubes, échange qui n'est pas observé dans le cas du PVP. Dans la troisième partie de la thèse, nous utilisons la technique d'impression jet d'encre pour imprimer des lignes continues micrométriques de SWNT, et proposons des méthodes originales pour étudier leur morphologie et leur anisotropie. La morphologie des dépôts peut varier entre deux cas limites, le dépôt homogène et la ‘‘paire de rails'', en faisant varier la concentration de nanotubes dans les encres, la distance entre gouttes et la température du substrat. L'orientation des nanotubes au bord des dépôts est très élevée (paramètre d'ordre orientationnel S entre 0,6 et 0,9), les nanotubes sont également bien orientés dans les rails (S~0.5) et dans une moindre mesure dans les lignes homogènes S~0.3. / This thesis focus on the study of inks, composites and deposits of single-wall carbon nanotubes (SWNT). The control of dispersion and orientation of nanotubes in such nanostructured composites materials allows to optimize their properties, and especially their electrical and optical properties.The first part of the work is devoted to the optimization of dispersion of SWNT in aqueous suspensions stabilized by bile salts surfactants, and to the study of their optical properties, and especially their near infrared photoluminescence (PL). Dispersion of the nanotubes is probed by absorption spectroscopy. We show that their absorption coefficient is very sensitive to the individualization of the nanotubes. On the other hand, we revisit the interpretation of the PL spectra excited in the near infrared (especially at 1.17 and 1.58 eV), and we assign the different peaks to different mechanisms, namely direct excitonic transitions, exciton-phonon coupling, and energy transfer between nanotubes. We show that the evolution of PL intensity as a function of individualization allows to distinguish the different mechanisms.The second part of the work is dedicated to the preparation of aqueous suspensionsstabilized by hydrosoluble polymers (PVA and PVP), and SWNT/polymer composites, without surfactants. SWNT suspensions are mixed with polymer solutions, and then the surfactant is removed by dialysis. The yield, i.e. the relative concentration of SWNT in the dialyzed suspension, is ~75 times higher than for a suspension prepared directly with polymers. On the other hand, PL signatures are sensitive to the dielectric environment of the nanotubes which allows to evidence an exchange between the dispersing agents bile salts/PVA on the nanotube surface, such an exchange is not observed in the case of PVP.In the third part of the thesis, we use the inkjet printing technique to print continuous micrometric lines of SWNT, and we propose original methods to study their morphology and their anisotropy. The morphology of the deposits varies between two limit cases, an homogeneous deposit and a ‘‘pair of tracks'', by varying nanotube concentration in the inks, inter-drop distance and substrate temperature. The orientation of the nanotubes is very high at the edge of the deposits (orientational order parameter S between 0.6 y 0.9), the nanotubes are well-oriented as well in the tracks (S~0.5) and to a lesser extent in the homogeneous lines (S~0.3).

Este trabalho traz a aplicação de alta pressão e alta pressão/temperatura (4.0 GPa e 400º C), em amostras de nanotubos de carbono de paredes múltiplas (NTCPM) comerciais para a obtenção de amostras compactas. Os NTCPM foram funcionalizados com ácido nítrico e ácido nítrico/ácido sulfúrico e, também foram usados nanotubos de carbono dopados com nitrogênio. Foram também processadas amostras contendo nanotubos de carbono de paredes múltiplas incorporados em matriz de zircônia obtida pelo método sol-gel. Para aplicação da alta pressão foi usado um sistema com câmaras do tipo toroidal, utilizando grafite como meio transmissor de pressão. Foram obtidas amostras macroscópicas autossuportadas e com resistência ao manuseio principalmente nas amostras de nanotubos de carbono funcionalizados com ácido nítrico/ácido sulfúrico incorporados em zircônia. Para a caracterização das amostras foram utilizadas as técnicas de Microscopia Eletrônica de Transmissão, Espectroscopia Raman, Difração de Raios X e isotermas de adsorção/dessorção de nitrogênio com as quais foi possível determinar que mesmo após a aplicação de alta pressão/temperatura os nanotubos de carbono não sofrem significativas modificações na sua estrutura e nas suas propriedades morfológicas e texturais, confirmando então que os NTCPM mantém suas características originais, apresentando condições para aplicações em dispositivos. As amostras macroscópicas contendo nanotubos de carbono de paredes múltiplas incorporados em zircônia apresentaram ainda resistência à carga de milhares de vezes o seu peso e comportamento de materiais semi-condutores. / This work presents the application of high pressure and/or high pressure/temperature (4.0 GPa and 400 ° C), on different samples of commercial multi-walled carbon nanotube (MWCNT) to obtain compacted samples. MWCNT were functionalized with nitric acid and nitric acid/sulfuric acid, and also carbon nanotubes doped with nitrogen. MWCNT incorporated in a zirconia matrix obtained by sol-gel method were also processed. For high pressure application it was used a system with the toroidal-type chamber, using graphite as a pressure transmitting medium. Self-supported macroscopic samples were obtained, easy to handle, especially in samples of functionalized carbon nanotubes with nitric and sulfuric acid and also incorporated in zirconia. To characterize the samples it was used Transmission Electron Microscopy, Raman Spectroscopy, X-ray diffraction and nitrogen adsoption/desorption isotherms and it was determined that even after application of high pressure/temperature carbon nanotubes do not suffer significant changes in their structure and in their morphological and textural properties, confirming that the CNT keeps its original characteristics and providing conditions for device applications. The macroscopic samples containing MWCNT incorporated in zirconia also exhibited resistance to load of thousands times its own weight and behavior like semiconductor materials.

Les nanotubes de carbone (NTC) n'ont eu de cesse, depuis leur (re)-découverte par Sumio Iijima en 1991, de passionner la communauté scientifique. Leurs propriétés électroniques, optiques et mécaniques exceptionnelles en font l'un des matériaux les plus prometteurs dans le domaine des nanotechnologies. Néanmoins, l'utilisation des NTC en microélectronique se heurte à de nombreux problèmes. En particulier, les propriétés électroniques de ces nanotubes sont dépendantes de plusieurs paramètres : leur diamètre, leur organisation et le nombre de feuillets qui le composent. Ainsi, l’obtention de nanotubes exclusivement semiconducteurs (recherchées pour réaliser un dispositif microélectronique tel qu’un transistor) ne peut être garantie par les techniques de synthèse actuelles. Ces techniques (CVD, ablation laser, etc…) ne conduisent en général qu’à un mélange de nanotubes semiconducteurs et métalliques, difficiles à trier.Dans le cas spécifique des nanotubes de carbone « zig-zag », leur comportement électronique n’est défini que par le diamètre. Une synthèse de nanotubes exclusivement « zig-zag » et de diamètres contrôlés apporterait donc une solution définitive à ce problème.La chimie des calixarènes peut apporter des réponses à cette problématique. On utiliserait alors la chimie moléculaire pour former le NTC de façon séquentielle. L’objectif du travail réalisé est d'obtenir une structure de type « zig-zag » avec un diamètre strictement contrôlé par la taille du calixarène de départ.Nous avons abordé plusieurs méthodes de synthèse en fonction du motif de répétition envisagé pour la croissance séquentielle du nanotube de carbone. Dans un premier temps, une stratégie basée sur le motif cyclacène a été utilisée. Les résultats de ces travaux seront présentés dans le chapitre II. Au cours de ce chapitre nous présenterons la synthèse et la fonctionnalisation des calixarènes de départ, en vue de leur utilisation pour des réactions de types Wittig Horner ou Oléfination de Julia.Enfin, au cours du chapitre III, nous présenterons les résultats obtenus par utilisation d’une autre stratégie, basée sur la répétition d’un motif métacyclopolyphénylène. Cette stratégie est basée sur une succession de réactions de couplage de Suzuki, catalysés par des complexes de palladium. / Since their re-discovery in 1991 by Sumio Ijima, carbon nanotubes (CNT’s) have not stopped fascinating the scientific community. Their electronic, optical, and mechanical properties render them one of the most promising materials in the field of nanotechnology. Nevertheless, the use of CNT’s is has been hampered by a number of problems due to the fact that the electronic properties of CNT’s are dependent on several parameters such as diameter, organization and number of sheets that make them up. Because of these factors, obtaining nanotubes that function exclusively as semiconductors (such as those used for fabricating microelectronic devices such as transistors) cannot be guaranteed with the synthetic methods used today. These techniques (CVD, laser ablation, etc) are only capable of yielding a mixture of semiconducting and metallic nanotubes difficult to separate.In the particular case of « zig-zag » nanotubes, their electronic behavior is defined by their diameter. Thus, a synthetic method capable of rendering exclusively « zig-zag » nanotubes with discrete diameters would yield a solution to the problem.Calixarene chemistry can give answers to this problem. Using molecular chemistry in order to form CNT’s in a sequential fashion, the objective of this work will be to obtain exclusively « zig-zag » nanotubes with discrete diameters that are imposed by the size of the calixarene used as a starting block. We have tried several methods for the synthesis of CNT’s depending on the repetition motif used for the sequential growth of the desired carbon nanotube. Firstly, a strategy based on the acene functionality was used. The results of this work are presented in chapter II, where we will describe the synthesis and functionalization of the starting calixarenes used in reaction types such as Wittig Horner and Julia Olefination.Chapter III shows the results obtained using a different strategy based on the repetition of the metacyclopolyphenylene unit. This strategy is based on the reiteration of successive Suzuki coupling reactions catalyzed by palladium complexes.

This thesis is focused on the analysis and on the design of the milling technology of the components for the aerospace industry which are characterised by a high aspect ratio, reduced stiffness and all covered by a high demand on the fatigue performance. This work includes the experimental verification of the proposed technology using CNC machining center, evaluation of surface structure using optical high-resolution 3D surface measurement system ALICONA, analysis of the force loading using KISTLER device, fatigue testing and fatigue fracture analysis.