Thermoelectric generators are solid state machines used to convert temperature gradients into electrical energy. They are formed by several thermoelectric units connected electrically in series and thermally in parallel. These units are made by creating a junction between a p-type and an n-type conductor. This investigation documents the characterisation of the thermoelectric properties of carbon nanotube (CNT) films and the fabrication process of carbon nanotube-based thermoelectric devices. The Seebeck coefficient is a intrinsic property of a thermoelectric material that correlates the voltage produced by a conductor and the temperature gradient applied to it. To measure the Seebeck coefficient of films, an experimental set-up was fabricated and calibrated using constantan as standard material. CNT films of aligned nanotubes fabricated using a chemical vapour deposition method were analysed. The Seebeck coefficient along and across the samples did not show significant variations, with values between 40$\mu$V/K and 80$\mu$V/K. Using these CNT films, thermoelectric cells were fabricated with the CNT as the p-type conductor and constantan as the n-type. As a proof of concept, two hand-made thermoelectric generators were assembled by connecting hundreds of these thermoelectric cells. These devices were subjected to a temperature gradient of $\approx$200K, which was enough to produce enough power to light an LED. Other analytical techniques were used to characterise the materials used in this work. Electrical conductivity measurements, thermogravimetric analysis, Raman spectroscopy and scanning electron microscopy were performed. Using a deposition technique, films of nanotubes were produced from a liquid phase. The impact of the production method on their properties was evaluated. Characterisation equipment was developed to measure the Seebeck coefficient and thermal conductivity. Thermoelectric devices made with the carbon nanotube films were fabricated and characterised. The values of thermal conductivity of the CNT films analysed in this work are between 0.86Wm$^{-1}$K$^{-1}$. The electrical conductivity of these materials is between 3500Sm$^{-1}$ and 14100Sm$^{-1}$. The maximum figure of merit of the carbon nanotube thermoelectric devices fabricated in this work is $ZT$=0.35.

The ability to construct materials that are specialized for specific tasks is an important challenge for the scientific community. A mature field in this right is that of metal organic materials. These materials are infinitely customizable crystalline materials constructed from metals/metal containing nodes and organic multitopic linkers. Numerous subfields of materials research seek to exploit some of the characteristics and seen-nowhere-else properties of metal organic materials. A nascent, yet promising subfield is the use of metal organic materials in water treatment. The diminishing access to safe clean water continues to grow as a worldwide problem. Freshwater reserves are decreasing and the human populations who rely on them are increasing. It is a clear need to revolutionize the way the scientific community treats and delivers safe water. Our research group discovered a metal organic material made from hexavalent uranium and the organic ligand iminodiacetate. This material was coined the UMON for its nanotubular shape (uranium metal organic nanotube) and early on it was proven to be unique in the way it allowed water to enter the tube channel and bar any other species from doing the same. I sought to use this material as a vehicle to learn and discover new ways that metal organic materials could be used in the water treatment revolution. This dissertation will narrate my investigations into specific hypotheses regarding the UMON’s special water properties. Specifically I sought to construct other materials with hexavalent uranium to test whether the presence of uranium was an important factor in a materials discretion for water. I also helped establish new knowledge regarding the UMON itself by discovering its negative thermal expansion and its ability to select for light water (H2O) over heavy water species (D2O, HDO, HTO).

Du fait de leurs propriétés intrinsèques exceptionnelles, les nanotubes de carbone (CNTs) sont des matériaux bien adaptés pour renforcer les polymères thermodurcissables. Le nanocomposite multifonctionnel ainsi obtenu possède des propriétés électriques, thermiques et mécaniques sensiblement meilleures que le polymère seul, ce qui lui procure de nombreuses applications potentielles, et tout particulièrement dans le domaine de l'électronique ou de l'aéronautique. Le but de cette thèse de doctorat est orienté suivant deux axes. Il s'agit dans un premier temps de mettre au point un matériau nanocomposite avec des propriétés multifonctionnelles à partir de techniques d'élaborations efficaces. Puis dans un second temps, l'objectif consiste à proposer des alternatives permettant d'améliorer ces propriétés. Le premier chapitre de cette thèse établit une revue de l'état de l'art au sujet des matériaux qui ont été étudiés au cours de ce travail de recherche. Parmi ces matériaux, nous pouvons citer tout particulièrement les CNTs, les renforts hybrides nano/micrométriques constitués de CNTs et d'alumine, les polymères conducteurs électroniques et les polymères thermodurcissables. Il s'agit plus précisément de présenter pour chaque matériau les techniques d'élaboration, leurs structures et finalement leurs propriétés. Dans la seconde partie du manuscrit, nous décrivons en premier lieu les procédés d'élaboration permettant d'obtenir des nanocomposites conformes aux normes internationales. Ensuite, nous présentons les différentes techniques de caractérisation de ces nanomatériaux. Il s'agit notamment de déterminer les phénomènes de transports électriques et thermiques. Des techniques d'analyses supplémentaires permettent de mieux comprendre la structure des matériaux obtenus dans une gamme d'échelle allant de l'état macroscopique à l'atomique. Ainsi, nous avons eu recours à l'utilisation de la microscopie électronique à balayage et en transmission, et aussi la microscopie à force atomique (AFM). Différentes études spectroscopiques de types : Raman, perte d'énergie des électrons (EELS), photoélectrons X (XPS) fournissent des informations additionnelles sur ces matériaux. Les résultats obtenus sur ces nanocomposites en matière de transports électronique et thermique montrent que certaines améliorations sont nécessaires pour optimiser les propriétés multifonctionnelles de ces nanomatériaux. Nous avons concentré nos efforts sur les phénomènes physicochimiques à l'interface matrice/renfort. Par conséquent, nous avons décidé de modifier la surface des CNTs afin de favoriser la cohésion matrice/renfort, mais aussi et surtout, pour diminuer les résistances de contacts entre les CNTs lorsqu'ils sont distribués aléatoirement dans une matrice polymère. Le dernier chapitre de la thèse s'articule autour de la fonctionnalisation des CNTs par un polymère conducteur électronique (ECP). Dans un premier temps, nous avons mis au point des techniques électrochimiques permettant de déposer une couche homogène d'épaisseur nanométrique d'ECP à la surface des CNTs. Ce polymère conducteur et en même temps biocompatible est le polypyrrole (Ppy). La précision et l'efficacité de notre démarche sont démontrées par les différents outils de caractérisation, et tout particulièrement grâce à la microscopie électronique en transmission à haute résolution. Des études supplémentaires par AFM couplé à un résiscope ont montré l'évolution de la résistance électrique d'hybrides CNT-Ppy plus ou moins isolés. Dans une seconde partie, nous avons mis au point une méthode permettant de contrôler finement l'épaisseur de Ppy déposé à la surface des CNTs.

The main objectives of the present Ph.D. thesis are comprehensive studies on activity, selectivity and stability of iron catalysts supported on carbon nanotubes (CNTs) for Fischer-Tropsch (FT) reactions. In order to prepare iron catalyst supported on CNTs, it was necessary to study CNT synthesis in bulk scale. Therefore, a part of this research was devoted to the production and characterization of CNTs. High purity, aligned films of multi-walled carbon nanotubes were grown on quartz substrates by feeding a solution of ferrocene in toluene, in a carrier gas of Ar/H2, into a horizontal chemical vapour deposition (CVD) reactor. Results for CNTs synthesized using a wide range of toluene concentrations indicated that, for carbon concentrations higher than ~9.6 mol/m3, catalyst deactivation occurs due to encapsulation of iron metal particles.<p> As the first step of catalyst development for FT reactions a fixed bed micro-reactor system was built and the effects of acid treatment on the activity, product selectivity and stability of iron Fischer-Tropsch catalysts supported on carbon nanotubes were studied. The results of Raman analysis showed that the acid treatment increased the number of functional groups as anchoring sites for metal particles. Fe catalysts supported on CNTs which were pre-treated with nitric acid at 110°C were more stable and active compared to the un-treated catalysts. In order to study the effects of catalytic metal site position on FT reactions, a method was developed to control the position of the deposited metal clusters on either the inner or outer surfaces of the CNTs. According to the results of the FT experiments, the catalyst with catalytic metal sites inside the pores exhibited higher selectivity (C₅⁺ = 36 wt%) to heavier hydrocarbons compared to one with sites on the outer surfaces (C₅⁺ = 24 wt%) . In addition, deposition of catalytic sites on the interior surfaces of the nanotubes resulted in a more stable catalyst.<p> The effects of pore diameter and structure of iron catalysts supported on CNTs on Fischer-Tropsch reaction rates and selectivities were also studied. In order to examine the effects of pore diameter, two types of CNTs with similar surface areas and different average pore sizes (12 and 63 nm) were prepared. It was found that the deposition of metal particles on the CNT with narrow pore size (in the range of larger than 10-15 nm) resulted in more active and selective catalyst due to higher degree of reduction and higher metal dispersion.<p> Promotion of the iron catalyst supported on CNTs with Molybdinium in the range of 0.5-1 wt % resulted in a more stable catalyst. Mo improves the stability of the iron catalyst by preventing the metal site agglomeration. Promotion of the iron catalysts with potassium increased the activity of FT and water-gas-shift reactions and the average molecular weight of the hydrocarbon products. Promotion of the iron catalyst supported on CNTs with 0.5% Cu and 1wt% K resulted in an active (5.6 mg HC/g-Fe.h), stable and selective catalyst (C₅⁺ selectivity of 76%) which exhibited higher activity and better selectivity compared to the similar catalysts reported in the literature. Kinetic studies were conducted to evaluate reaction rate parameters using the developed potassium and copper promoted catalyst. It was found that the CO₂ inhibition is not significant for FT reactions. On the other hand, water effects and presence of vacant sites should be considered in the kinetic models. A first-order reaction model verified that the iron catalyst supported on CNTs is more active than precipitated and commercial catalysts. The results of the present Ph.D. thesis research provide a map for designing catalysts using carbon nanotubes as a support. The key messages of the present thesis are as follows:<p> 1- If the interaction of the metal site and support is strong, which poses negative effects on the catalytic performance, carbon nanotubes can be one solution.<p> 2- Acid pre-treatments are required prior to impregnating nanotubes with metal salt solution. Also, the strong acid treatment should be used for deposition of catalytic sites inside the pores of nanotubes.<p> 3- The structure and pore size of nanotubes have significant influence on the stability, activity and selectivity of the target catalyst.<p> 4- The position of the catalytic sites has to be selected based on the type of reaction. In the case of Fischer-Tropsch reactions, the deposition of catalytic sites inside the pores of nanotubes results in higher activity, longer life span.<p> The outcome of this Ph.D. thesis has been published/submitted in the form of 13 journal papers, one patent, one technical report and presented at 11 conferences.

The objective of this research is to build a prototype of a carbon nanotube (CNT)-based micro X-ray tube array, which can be used in a real-time cone-beam computed tomography (CT) scanner for cancer research. The X-ray tube array consists of an electron source, control grids, focusing electrodes, and an anode plate. All the experiments have been executed in an ultra high vacuum environment at a pressure of 10⁻⁷ Torr. A thin film consisting of multi-wall carbon nanotubes (MWNTs) was used as the electron source. A diode configuration was employed to test the field emission performance of the CNT thin film. The current density achieved was 1mA/cm² at 10V/µm. After the initial burn-in process, a relatively steady emission current was obtained for duration of 170 hours. The control grid was made of 25% opening space stainless steels mesh. Meshes with different wire diameters were tested in a triode structure, and some differences were observed. Multi-anode field emission tests and multi-tube electric field simulations were executed. Experiments and simulations have revealed crosstalk between pixels during field emission. Based on the above experiments and simulations, a signal pixel prototype has been fabricated and is being tested. Moreover, some potential optimizations that will be used in the second prototype are also discussed

The main objectives of the present Ph.D. thesis are comprehensive studies on activity, selectivity and stability of iron catalysts supported on carbon nanotubes (CNTs) for Fischer-Tropsch (FT) reactions. In order to prepare iron catalyst supported on CNTs, it was necessary to study CNT synthesis in bulk scale. Therefore, a part of this research was devoted to the production and characterization of CNTs. High purity, aligned films of multi-walled carbon nanotubes were grown on quartz substrates by feeding a solution of ferrocene in toluene, in a carrier gas of Ar/H2, into a horizontal chemical vapour deposition (CVD) reactor. Results for CNTs synthesized using a wide range of toluene concentrations indicated that, for carbon concentrations higher than ~9.6 mol/m3, catalyst deactivation occurs due to encapsulation of iron metal particles.<p> As the first step of catalyst development for FT reactions a fixed bed micro-reactor system was built and the effects of acid treatment on the activity, product selectivity and stability of iron Fischer-Tropsch catalysts supported on carbon nanotubes were studied. The results of Raman analysis showed that the acid treatment increased the number of functional groups as anchoring sites for metal particles. Fe catalysts supported on CNTs which were pre-treated with nitric acid at 110°C were more stable and active compared to the un-treated catalysts. In order to study the effects of catalytic metal site position on FT reactions, a method was developed to control the position of the deposited metal clusters on either the inner or outer surfaces of the CNTs. According to the results of the FT experiments, the catalyst with catalytic metal sites inside the pores exhibited higher selectivity (C₅⁺ = 36 wt%) to heavier hydrocarbons compared to one with sites on the outer surfaces (C₅⁺ = 24 wt%) . In addition, deposition of catalytic sites on the interior surfaces of the nanotubes resulted in a more stable catalyst.<p> The effects of pore diameter and structure of iron catalysts supported on CNTs on Fischer-Tropsch reaction rates and selectivities were also studied. In order to examine the effects of pore diameter, two types of CNTs with similar surface areas and different average pore sizes (12 and 63 nm) were prepared. It was found that the deposition of metal particles on the CNT with narrow pore size (in the range of larger than 10-15 nm) resulted in more active and selective catalyst due to higher degree of reduction and higher metal dispersion.<p> Promotion of the iron catalyst supported on CNTs with Molybdinium in the range of 0.5-1 wt % resulted in a more stable catalyst. Mo improves the stability of the iron catalyst by preventing the metal site agglomeration. Promotion of the iron catalysts with potassium increased the activity of FT and water-gas-shift reactions and the average molecular weight of the hydrocarbon products. Promotion of the iron catalyst supported on CNTs with 0.5% Cu and 1wt% K resulted in an active (5.6 mg HC/g-Fe.h), stable and selective catalyst (C₅⁺ selectivity of 76%) which exhibited higher activity and better selectivity compared to the similar catalysts reported in the literature. Kinetic studies were conducted to evaluate reaction rate parameters using the developed potassium and copper promoted catalyst. It was found that the CO₂ inhibition is not significant for FT reactions. On the other hand, water effects and presence of vacant sites should be considered in the kinetic models. A first-order reaction model verified that the iron catalyst supported on CNTs is more active than precipitated and commercial catalysts. The results of the present Ph.D. thesis research provide a map for designing catalysts using carbon nanotubes as a support. The key messages of the present thesis are as follows:<p> 1- If the interaction of the metal site and support is strong, which poses negative effects on the catalytic performance, carbon nanotubes can be one solution.<p> 2- Acid pre-treatments are required prior to impregnating nanotubes with metal salt solution. Also, the strong acid treatment should be used for deposition of catalytic sites inside the pores of nanotubes.<p> 3- The structure and pore size of nanotubes have significant influence on the stability, activity and selectivity of the target catalyst.<p> 4- The position of the catalytic sites has to be selected based on the type of reaction. In the case of Fischer-Tropsch reactions, the deposition of catalytic sites inside the pores of nanotubes results in higher activity, longer life span.<p> The outcome of this Ph.D. thesis has been published/submitted in the form of 13 journal papers, one patent, one technical report and presented at 11 conferences.

The objective of this research is to build a prototype of a carbon nanotube (CNT)-based micro X-ray tube array, which can be used in a real-time cone-beam computed tomography (CT) scanner for cancer research. The X-ray tube array consists of an electron source, control grids, focusing electrodes, and an anode plate. All the experiments have been executed in an ultra high vacuum environment at a pressure of 10⁻⁷ Torr. A thin film consisting of multi-wall carbon nanotubes (MWNTs) was used as the electron source. A diode configuration was employed to test the field emission performance of the CNT thin film. The current density achieved was 1mA/cm² at 10V/µm. After the initial burn-in process, a relatively steady emission current was obtained for duration of 170 hours. The control grid was made of 25% opening space stainless steels mesh. Meshes with different wire diameters were tested in a triode structure, and some differences were observed. Multi-anode field emission tests and multi-tube electric field simulations were executed. Experiments and simulations have revealed crosstalk between pixels during field emission. Based on the above experiments and simulations, a signal pixel prototype has been fabricated and is being tested. Moreover, some potential optimizations that will be used in the second prototype are also discussed

<p>Nanostructures are being intensely studied due to unusual material properties and simple scaling concerns in the microelectronics industry. Fabricating useful nano-scale structures and devices, either by arranging existing nanoparticles such as carbon nanotubes or by manipulating bulk materials into nanometer-scale geometries, is a challenging prospect. One promising approach is to generate a nanometer-scale pattern and transfer that geometry into another material. The research described in this dissertation concerns the fabrication of nanometer-scale patterns, by Atomic Force Microscope-based methods and Electron Beam Lithography, on planar surfaces and the transfer of those patterns into functional materials. Differences in surface energy were used to guide the growth of bulk conducting polymer along predefined nano-scale patterns. Carbon nanotubes were assembled into an ordered and continuous material with no guidance and used to lithographically write silicon oxide nanopatterns on a silicon surface. Finally, the two previous projects were combined, and surface energy patterns were used to guide the deposition of dense carbon nanotube bundles along a planar substrate.</p> / Dissertation

This work is mainly focused upon the preparation, processing and evaluation of mechanical and material properties of epoxy/single walled carbon nanotube (SWCNT) nanocomposite thin films. B-staged epoxy/SWCNT nanocomposite thin films at 50% of cure have been prepared for improving conductivity and mechanical performance of laminated composites. The SWCNTs were functionalized by oxidation and subsequent grafting using polyamidoamine generation 0 dendrimers (PAMAM-G0). The epoxy nanocomposites containing SWCNTs were successfully cast into thin films by manipulating degree of cure and viscosity of epoxy. The first section of this study focuses on the covalent oxidation and functionalization of single-walled carbon nanotubes (SWCNTs), which is necessary in order to obtain the full benefit of the SWCNTs inherent properties for reinforcement. In the second section of this work the preparation of B-staged epoxy/SWCNT nanocomposite thin films is discussed and what the purposes of thin films are. Additionally, the morphology as well as mechanical properties is evaluated by numerous means to obtain a clear picture as to the mechanisms of the epoxy/SWCNT nanocomposites. Furthermore, the effects of using sulfanilamide as a more attractive surface modifier for improved dispersion and adhesion and the effects of nylon particles for improved toughening on epoxy/SWCNT nanocomposites are discussed which displays improvements in numerous areas. Finally, based on these findings and previous studies, the B-staged epoxy/SWCNT nanocomposite thin films can be seamlessly integrated into laminated composite systems upon heating, and can serve as interleaves for improving conductivity and mechanical strengths of laminated fiber composite systems.

Transport Properties of Nanocomposites were studied in this work. A Monte Carlo technique was used to model the percolation behavior of fibers in a nanocomposite. Once the percolation threshold was found, the effect of fiber dimensions on the percolation threshold in the presence and absence of polymer particles was found. The number of fibers at the percolation threshold in the presence of identically shaped polymer particles was found to be considerably lower than the case without particles. Next, the polymer particles were made to be of different shapes. The shapes and sizes of the fibers, as well as the polymers, were made the same as those used to obtain experimental data in literature. The simulation results were compared to experimental results, and vital information regarding the electrical properties of the fibers and fiberfiber junctions was obtained for the case of two stabilizers used during composite preparation ? Gum Arabic (GA) and Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). In particular, the fiber-fiber connection resistances, in the case of these 2 stabilizers, were obtained. A ratio between the fiber path resistance and the total connection resistance, giving the relative magnitude of these resistances in a composite, was defined. This ratio was found through simulations for different fiber dimensions, fiber types and stabilizers. Trends of the ratio with respect to composite parameters were observed and analyzed, and parameters to be varied to get desired composite properties were discussed. This study can serve as a useful guide to choose design parameters for composite preparation in the future. It can also be used to predict the properties of composites having known fiber dimensions, fiber quality and stabilizing agents.