Les récents progrès dans le domaine des MEMS organiques suscitent un intérêt croissant dans la substitution de micropoutres inorganiques par des micropoutres organiques pour diverses applications. N’ayant été étudiée qu’en mode statique, la réponse électrostrictive des MEMS organiques est présentée pour la première fois en mode dynamique. L’une des originalités de ce travail est de fabriquer un micro-récupérateur d’énergie mécanique avec une approche « tout-organique ». Dans cette thèse, des matériaux nanocomposites à base d’oxyde de graphène réduit (rGO) dispersé dans du poly-dimethyl siloxane (PDMS), sont utilisés pour la récupération de l'énergie mécanique vibratoire avec une transduction électrostrictive. Le dispositif génère une densité de puissance électrique de 8,15 W/cm3 pour une accélération de 1 g au premier mode de résonance (≈ 17 Hz). / Recent advances in the field of organic MEMS have generated interest in the substitution of inorganic microbeams by organic ones for various applications. Until now, the use of electrostrictive materials is limited to the MEMS operating mostly in static mode. The electrostrictive response of organic MEMS is presented here for the first time in dynamic mode. One of the originality of this work is to produce a micro-mechanical energy harvester fabricated in an all-organic approach. In this thesis, strain sensitive nanocomposite materials based on reduced graphene oxide (rGO) dispersed in polydimethylsiloxane (PDMS) are used for mechanical vibratory energy harvesting with an electrostrictive transducer. With an acceleration of 1 g of the microcantilever base, actuation at the first resonant mode (≈ 17 Hz) generates an electrical power density of 8.15 μW/cm3.

The unique electronic, mechanical and physical properties led Carbon nanotubes (CNTs) to be potential candidate for field emitter, hydrogen storage, sensors, nano electronic devices, nano electromechanical systems, polymer composites. In order to make them in the industrial scale we need large quantity production of CNTs with low cost. The present thesis work deals with the preparation of CNTs by pyrolysis method from xylene and further studies on the grown CNTs. Magnetic characterization of CNTs has been done using SQUID. The interaction of CNTs with the microwave irradiation is studied and it was found for the first time that there is light emission from the CNTs apart from direct electric field. In this process we also observed that the static charge develops on the CNTs. A composite of CNTs/DNA has been prepared with varying CNT content and the electrical conductivity measurements have been done. The first chapter of the thesis provides an introduction to carbon family. Carbon nanotubes, which are potential candidates from carbon family, is a growing field for research in science and technology. A glimpse of various methods of preparation of CNTs like arc-discharge, laser ablation, chemical vapour deposition (CVD), hot-filament CVD, plasma enhanced chemical vapor deposition (PECVD), electron cyclotron resonance (ECR PECVD), high-pressure catalytic decomposition of carbon monoxide (HiPCO), pyrolysis are discussed. Some applications of CNTs are also included in this chapter. The second chapter deals with the experimental techniques employed for the preparation of CNTs and their characteristics studied by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD) and Raman Spectroscopy (RS). The preparation of CNTs from xylene as carbon source and ferrocene as catalyst in pyrolysis method is described in detail. Well aligned CNTs with a length of several tens of micrometers and diameter of 40 to 80 nanometers were obtained as confirmed by SEM. TEM and XRD confirms the graphitic crystal structure of the CNTs. RS also confirms the information about the crystal structure. The third chapter discusses the magnetic studies on CNTs using Superconducting Quantum Interference Device (SQUID) as a function of magnetic field and temperature. In the random mixture of parallel, perpendicular and oblique nanotubes, the applied field produces diamagnetic behavior, although the sample possess different kinds of tubes with various chirality and radii. Paramagnetic deviation was observed on the diamagnetic susceptibility at weak fields and low temperature, confirming qualitatively with the Aharonov-Bhom effect on the energy gap for the magnetic field parallel to the tube axis Chapter four presents the light emission from the CNTs. It describes the light emission from different processes reported in the literature. Here we have observed a new process to generate light from CNTs through microwave irradiation. Along with the light emission some of the tubes get charged and some tubes are physically broken. We provide a simple approach as to why the tubes break and the nature of the breakage is also discussed. The fifth chapter discusses the preparation of CNTs/DNA composites. The conductivity increases with increasing carbon nanotube weight percentage. The increase in conductivity as a function of the CNTs weight percent is attributed to the introduction of conducting CNTs path in the DNA matrix. A summary of the results obtained and the scope for future work are included in the chapter six of the thesis.

The main focus of this project was to prepare transparent and conductive electrodes (TCEs). TCEs were made out of multi-walled carbon nanotubes (MWCNTs), reduced graphene oxide (rGO), and polyvinylpyrrolidone (PVP). Based on the theoretical aspect, MWCNTs has emerged as a promising nanofiller in the polymer matrix due to its high electrical conductivity. As a nanofiller, MWCNTs were used with a small ratio of rGO with PVP as a polymer matrix in this project to prepare TCEs having low sheet resistance with high transparency. An appropriate amount of PVP has been shown to be a good combination with MWCNTs and rGO in the solvent to keep MWCNTs dispersed for a long time. Carboxyl group (-COOH) functionalized MWCNTs (FMWCNTs) was produced in a controlled oxidative procedure due to enabling good dispersion of FMWCNTs in water and ethanol solvents. In contrast, water dispersible rGO was chemically prepared by using GO and sodium borohydride where GO was produced from graphite by using improved Hummer's method. Drop casting and spray coating methods were applied to fabricate TCEswhere only water was used as the solvent for drop casted TCEs and a mixing ratio of water and ethanol was 70:30 as solvent for spray coated TCEs. It was also determined in this project that the spray coating method was more suitable for preparing TCEs rather than thedrop casting method due to easy fabrication, large area coating possibility, and the smoothness of the coated film surface. The sheet resistance was obtained as 5026 Ω/ ⃣  where the transparency was 65% in the case of the drop casted electrode for the ratio of rGO:FMWCNTs:PVP was 1.2:60:1 with 0.02 mg FMWCNTs. In the case of spray coated electrode at the same ratio of rGO:FMWCNTs:PVP, the sheet resistance was measured as 5961 Ω/ ⃣  where the transparency was 73%. But in the case of 60:1 mass ratio of FMWCNTs:PVP with 0.02 mg FMWCNTs, the sheet resistance was 7729 Ω/ ⃣  and transparency was 77% for spray coated electrode. So, it is clear that the sheet resistance was improved by adding a small mass ratio of rGO with FMWCNTs:PVP.

In this study, we developed and standardized a sanding method to evaluate the emission of airborne particles from products that contain carbon nanotubes (CNTs) under different conditions, including three types of sandpaper and three sanding disc speed. We also characterized the emission of the airborne particles from one neat epoxy test sample, four CNTs-incorporating test samples with different CNTs loading, and two commercial products. The total number concentration, respirable mass concentration, and particle size number/mass distribution of the emitted particles were calculated and compared, followed by an electron microscopy (EM) analysis. These data suggest that the sanding process can produce substantial quantities of airborne particles. Also, the emission of airborne particles was associated with different test conditions. EM analysis of the airborne particle samples showed embedded CNTs protruding from the outer surface, which was different from CNTs-incorporating bulk material. Our study suggests a potential generation of particles during the life cycle event of sanding. Further studies should be carried out to investigate the potential human health hazard in other life cycle events.

Diese Arbeit beschäftigt sich mit den niedrigdimensionalen Kohlenstoffmaterialien Fullerene, Kohlenstoffnanoröhren (CNTs) und der Diamantoberfläche. Es werden jeweils zwei der genannten Materialien kombiniert und im Hinblick auf die dadurch entstehenden magnetischen und elektronischen Eigenschaften untersucht. Durch die Füllung von Fullerenen in CNTs mit entsprechenden Durchmessern ergibt sich eine eindimensionale Anordnung der Fullerene. Diese Strukturen werden als peapods bezeichnet. Bei der Verwendung von endohedralen, magnetischen Fullerenen ergibt sich durch die Einschränkung der Dimension die Möglichkeit einer wohl-definierten Kopplung und dadurch eine mögliche Änderung der magnetischen Eigenschaften. Die hier betrachteten Moleküle sind die paramagnetischen Fullerene N@C60 und Er3N@C80 sowie das ferromagnetische Dy2ScN@C80-Fulleren, welches auch als ein Einzelmolekülmagnet (SMM) bezeichnet wird. Für die Herstellung von peapods wurde im Rahmen dieser Arbeit eine Füllanlage aufgebaut, welche die speziellen Anforderungen der Fullerene berücksichtigt und mit der auch CNTs auf Substraten gefüllt werden können. Der Erfolg der Füllung wird mit hochauflösender Transmisssions-Elektronenmikroskopie (HRTEM), energiedispersiver Röntgen-Spektroskopie (EDX) und optischer Emissions- Spektrometrie (OES) überprüft. Durch weitergehende Untersuchungen im HRTEM konnte eine Reaktion von metallischen Atomen aus den Fullerenen innerhalb der CNTs zu neuen, metallischen Clustern beobachtet werden. Für die Untersuchungen möglicher Änderungen der magnetischen Eigenschaften sind magnetische Messungen notwendig. Diese können mit der Methode des magnetischen zirkularen Röntgendichroismus (XMCD) durchgeführt werden. Für das Ziel von nanoskopischen XMCD-Messungen einzelner peapods wurden Rastertransmissions- Röntgenmikroskopie-Messungen (STXM) am Synchrotron durchgeführt. Diese wurden mit HRTEM-Messungen derselben Probenpositionen korreliert, um die spektroskopische mit der räumlichen Auflösung zu verknüpfen. Dabei konnte ein Röntgenabsorptions- Spektrum von einem dünnen peapod-Bündel gemessen werden. Zusätzlich wurde mit makroskopischen XMCD-Messungen von Er3N@C80-Fullerenen, gefüllt in CNTs, gezeigt, dass diese Methode auch für peapods anwendbar ist. Erste XMCDMessungen von ferromagnetischen Dy2ScN@C80-Fullerenen zeigen eine deutliche Änderung der magnetischen Eigenschaften durch die eindimensionale Anordnung in CNTs. Im Zusammenhang mit der eindimensionalen Anordnung von paramagnetischen Fullerenen wurde außerdem ein Konzept eines Quantenregisters betrachtet, welches auf N@C60- peapods basiert. Diese sollen dabei auf eine Diamantoberfläche deponiert werden, um oberflächennahe Stickstoff-Fehlstellen-Zentren zum Auslesen der Spinzustände der N@C60- Fullerene verwenden zu können. Die in diesem Fall auftretende elektronische Wechselwirkung zwischen unterschiedlich terminierten Diamantoberflächen und CNTs sowie Fullerenen wurde mit Kelvinsonden-Mikroskopie- Messungen (KPFM) untersucht. Dabei wurde erstmalig ein Elektronentransfer von der wasserstoffterminierten Diamantoberfläche in CNTs experimentell nachgewiesen, während dieser bei Sauerstoffterminierung nicht beobachtet wurde. Die präsentierten Messungen geben Auskunft über den auftretenden Ladungstransfer, indem Ladungen in C60- Fullerenen und CNTs lokal aufgelöst abgebildet werden. Zusammenfassend können die in dieser Arbeit gewonnenen Erkenntnisse helfen, zukünftige Bauelemente von klassischen Computern oder Quantencomputern, basierend auf niedrigdimensionalen Kohlenstoffmaterialien, zu entwickeln.

Nanotechnology has reached the status of the 21st century's leading science and technology based on fundamental and applied research during the last two decades. An important feature of nanotechnology is to bridge the crucial dimensional gap between the atomic and molecular fundamental sciences and microstructural scale of engineering. Accordingly, it is very important to have an in-depth understanding of the synthesis of nanomaterials for the use of state-of-the-art high technological devices with enhanced properties. Recently, the 'bottom-up' approach for the fabrication of nanomaterials has received a great deal of attention for its simplicity and cost effectiveness. Tailoring the various parameters during synthesis of selected nanoparticles can be used to fabricate technologically important components. During the last decade, carbon nanotubes (CNTs) have been envisioned for a host of different new applications. Although carbon nanotubes can be synthesized using a variety of techniques, large-scale synthesis is still a great challenge to the researchers. Three methods are commonly used for commercial and bulk productions of carbon nanotubes: arc-discharge, chemical vapor deposition and laser ablation. However, low-cost, large-scale production of high-quality carbon nanotubes is yet to be reported. One of the objectives of the present research is to develop a simplified synthesis method for the production of large-scale, low-cost carbon nanotubes with functionality. Herein, a unique, simple, inexpensive and one-step synthesis route of CNTs and CNTs decorated with nanoparticles is reported. The method is simple arc-discharge in solution (ADS). For this new method, a full-fledged optoelectronically controlled instrumen is reported here to achieve high efficiency and continuous bulk production of CNTs. In this system, a constant gap between the two electrodes is maintained using a photosensor which allows a continuous synthesis of the carbon nanostructures. The system operates in a feedback loop consisting of an electrode-gap detector and an analogue electronic unit, as controller. This computerized feed system was also used in single process step to produce in situ-decorated CNTs with a variety of industrially important nanoparticles. To name a few, we have successfully synthesized CNTs decorated with 3-4 nm ceria, silica and palladium nanoparticles for many industrially relevant applications. This process can be extended to synthesize decorated CNTs with other oxide and metallic nanoparticles. Sixty experimental runs were carried out for parametric analysis varying process parameters including voltage, current and precursors. The amount of yield with time, rate of erosion of the anode, and rate of deposition of carbonaceous materials on the cathode electrode were investigated. Normalized kinetic parameters were evaluated for different amperes from the sets of runs. The production rate of pristine CNT at 75 A is as high as 5.89 ± 0.28 g.min-1. In this study, major emphasis was given on the characterizations of CNTs with and without nanoparticles using various techniques for surface and bulk analysis of the nanostructures. The nanostructures were characterized using transmission electron microscopy, high resolution transmission electron microscopy, scanning transmission electron microscopy, energy dispersive spectroscopy and scanning electron microscopy, x-ray photo electron spectroscopy, x-ray diffraction studies, and surface area analysis. Electron microscopy investigations show that the CNTs, collected from the water and solutions, are highly pure except the presence of some amorphous carbon. Thermogravimetric analysis and chemical oxidation data of CNTs show the good agreement with electron microscopy analysis. The surface area analysis depicts very high surface area. For pristine multi-walled carbon nanotubes, the BET surface area is approximately 80 m2.g-1. X-ray diffraction studies on carbon nanotubes shows that the products are clean. Nano-sized palladium decorated carbon nanotubes are supposed to be very efficient for hydrogen storage. The synthesis for in-situ decoration of palladium nanoparticles on carbon nanotubes using the arc discharge in solution process has been extensively carried out for possible hydrogen storage applications and electronic device fabrication. Palladium nanoparticles were found to form during the reduction of palladium tetra-chloro-square planar complex. The formation of such a complex was investigated using ultraviolet-visible spectroscopic method. Pd-nanoparticles were simultaneously decorated on carbon nanotubes during the rolling of graphene sheets in the arc-discharge process. Zero-loss energy filtered transmission electron microscopy and scanning transmission electron microscopy confirm the presence of 3 nm palladium nanoparticles. The deconvoluted X-ray photoelectron spectroscopy envelope shows the presence of palladium. Surface area measurements using BET method show a surface area of 28 m2.g-1. The discrepancy with pristine CNTs can be explained considering the density of palladium (12023 kg.m-3). Energy dispersive spectroscopy suggests no functionalization of chlorine to the sidewall of carbon nanotubes. The presence of dislodged graphene sheets with wavy morphology as observed with high-resolution transmission electron microscopy supports the formation of CNTs through the 'scroll mechanism'.

Strengthening potential of single-walled carbon nanotubes (SWCNTs) in a phenolic resin composite was evaluated by characterization of purified and phenyl sulfonated SWCNTs, investigation of the load transfer capability of the purified SWCNTs, and characterization of the composites. Purified and phenyl sulfonated SWCNTs, as well as their composites, were examined by Raman spectroscopy, thermogravimetric analysis, scanning electron microscopy equipped with energy dispersive spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and ultra violet-visible spectrometry. Fabrication of the SWCNT/phenolic resin composite was performed by first dispersing the SWCNTs in ethylene glycol and then homogenizing the mixture with phenolic resin. The ethylene glycol was then evaporated from the mixture and the SWCNT/phenolic resin composite was cured at 200°C for 1 hour. The dispersion of SWCNTs in the phenolic resin was reduced with higher SWCNT concentrations. Load was transferred from the phenolic resin to the purified SWCNTs. This demonstrated the potential to strengthen phenolic resin composite with SWCNT reinforcement. The load transfer efficiency in total tension (0.8%) decreased with an increase in SWCNT concentration, while in total compression (-0.8%), the load transfer efficiency remained constant. At very low strain (± 0.2%), the load transfer efficiency remained constant regardless of SWCNT concentration in both tension and compression. Characterization of the phenyl sulfonated SWCNTs indicated that calcium was introduced as a contaminant that interfered with functionalization of the SWCNTs. The use of contaminated phenyl sulfonated SWCNTs resulted in macroscopic inhomogeneity within the composite.

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Dans ce travail, nous décrivons les différentes formes, la structure, les propriétés et la croissance catalytique de nanotubes et nanofibres de carbone (Chapitre I). L'hydroxyapatite a été utilisée comme support de la phase active pour la synthèse de nanotubes de carbone multi-feuillet (MWCNTs) et de nanofibres de carbone (CNFs-H) par la technique de dépôt chimique en phase de vapeur catalytique (C-CVD) en lit fluidisé (Chapitre II). Après l'élimination du support par un simple lavage à l'acide chloridrique dilué, une étude théorique et expérimentale de l'oxydation de la surface de nanotubes de carbone par un traitement à l'acide nitrique a permis d'une part d'identifier et de quantifier les groupes formés à la surface de nanostructures carbonées et d'autre part de proposer un mécanisme pour la formation de ces groupes (Chapitre III). Les matériaux résultants après génération des fonctions carboxyliques de surface ont été utilisés comme support de catalyseur. L'hydrogénation du p-halogénonitrobenzène a été choisit comme réaction modèle pour comparer les performances catalytiques de catalyseurs à base de ruthénium en fonction de la nature du support utilisé, MWCNTs ou CNFs-H. L'influence de certains paramètres tels que la température, la nature du substrat et un traitement thermique du catalyseur (activation) est présentée. Une explication des performances catalytiques est proposée après caractérisation du catalyseur par MET, TPD, TPR et PZC (Chapitre IV). Les nanostructures carbonnées produites et caractérisées ont été utilisées comme charge de renforcement d'hydroxyapatites connue comme biomatériaux. Nous avons étudié en particulier la capacité de germination du phosphate octocalcique par la méthode de croissance cristalline à composition constante (C4) (Chapitre V). / In this work, we describe the different forms, the catalytic growth, the structure and properties of carbon nanotubes and nanofibres (Chapter I). Hydroxyapatite was used as catalyst support for the synthesis of multi-walled carbon nanotubes (MWCNTs) and nanofibres (CNFs) by catalytic chemical vapour deposition (C-CVD) in a fluidized bed reactor (Chapter II). After support removal by washing with diluted hydrochloric acid, a theoretical and experimental study of surface oxidation of carbon nanotubes by nitric acid treatment has been performed. It allows to identify and quantify the groups formed on the surface of carbon nanostructures and also to propose a mechanism for the formation of these groups (Chapter III). The functionalized nanotubes and nanofibers have been used as supports for heterogeneous catalysis. The hydrogenation of p-halonitrobenzene was used as model reaction to compare the catalytic performances of ruthenium supported on MWCNTs or CNFs-H catalysts. The influence of experimental parameters such as temperature, nature of the substrate and prior heat treatment (activation) of the catalyst on the catalytic activity and selectivity is presented. The catalytic performances have been correlated to the structure of the catalyst as determined from TEM, TPD, TPR and PZC analysis (Chapter IV). The carbon nanostructures produced have also been used as reinforcement fillers for hydroxyapatite-nanotube composites. We have studied in particular, the germination of octacalcium phosphate crystals under conditions of constant solution composition on the surface of the composite (Chapter V).