The production of cellulose derived hybrid carbon nanofibre (CNF)/carbon nanotubes (CNTs) electrodes for the fabrication of supercapacitors and carbon fibre composites was investigated. The CNTs were grown via a floating catalyst chemical vapor deposition (CVD) method on the top surface of electrospun cellulose derived CNFs. These CNF and CNF/CNTs samples were then used as electrodes to produce liquid electrolyte-based supercapacitors. The growth of CNTs leads to an improvement of electrochemical performance compared to the plain CNFs. This improvement is due to the grown CNTs enlarging the reactive sites through enhanced surface area and porosity, and thereby increasing the conductivity of the system. CNTs have been also grown onto CNFs containing ferrocene and SiC particles. Composites were fabricated by combining the fibres and CNTs grown fibres with model polymers. The stress transfer properties of these materials have been estimated using an in situ Raman spectroscopic method by observing the shift of the Raman band during the tensile deformation of model polymer composites. Using this method, the elastic modulus of CNF/SiC/CNTs fibres has been estimated to be 208 ± 26 GPa. No shifts in the peak positions of bands relating to the carbon structure were obtained for in situ Raman spectroscopic studies of the CNF/CNTs fibres made from the ferrocene embedded fibres. This was thought to be due to the low yield of CNTs on the surface of the fibres. Furthermore, CNF/CNTs electrode-based structural supercapacitors, combining a solid electrolyte with the carbonized fibres, have been produced. These CNF/CNTs electrodes have a better capacitive performance than the plain CNF electrodes. There was a decrease in this performance with increased curing time of the resin, from 2 to 24 h, due to a lack of charge carrier mobility in the latter samples. A Raman spectroscopic study of the deformation of the carbon structures showed that the G-band shift towards a lower wavenumber position for the CNF and CNF/CNTs samples processed at a carbonization temperature of 2000 °C. Moduli of these fibres were estimated to be ~145 GPa and ~271 GPa, respectively, suggesting the growth of CNTs not only enhances the capacitive performance but also the mechanical properties of the structural supercapacitors. No Raman bend shift was found for the CNFs and CNF/CNTs samples processed below a carbonization temperature of 2000 °C, e.g. 900 °C and 1500 °C. This is because the graphitic structures are not well developed at carbonization temperatures below 1500 °C.

Thesis (MScEng)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: In this research the possible utilization of carbon nanomaterials in gas sensing applications are investigated. These materials include the 2-dimensional honeycomb-lattice carbon structure called graphene, and the 1-dimensional structures referred to as carbon nanotubes (CNTs). The extraordinary properties and unique morphology of these nanomaterials, make them excellent candidates for sensory applications. This research thus entails the investigation and development of gas sensors with these carbon nanomaterials. This includes the synthesis of CNTs via a chemical vapour deposition (CVD) technique and the fabrication of resistive thin film sensors with the various materials. The functionalization of carbon nanomaterials is also explored, which delivers promising results for sensing gases at room temperature, especially acetylene (C2H2). Furthermore, a unique method is developed to fabricate ultra thin aluminium microstructures. These metallic electrodes are found to be ideal for nanomaterial integration. An experiment is performed to manufacture an integrated sensor with MWCNTs and following the results, a refinement of the procedure and the investigation of FET-based devices are recommended. The results obtained during this work, indicate that engineered carbon nanostructures, such as CNTs and graphene, can potentially be applied in future sensing technologies. / AFRIKAANSE OPSOMMING: Hierdie navorsing ondersoek die moontlike toepassing van koolstof nano-materiale as gas-sensor tegnologie. Hierdie materiale sluit die 2-dimensionele koolstof struktuur, grafeen, asook die sogenaamde 1-dimensionele koolstof nano-buise in. Die buitengewone eienskappe en unieke morfologie van hierdie nano-materiale, maak hul uitstekende kandidate vir sensor toepassings. Hierdie navorsing ondersoek dus die ontwikkeling van gas-sensors met koolstof nano-materiale, insluitend die sintese van koolstof nano-buise deur middel van ’n chemiese damp-neerslag proses, asook die fabrikasie van resistiewe dun film sensors. Die funksionalisering van koolstof nano-materiale is ook ondersoek en belowende resultate is opgelewer met betrekking tot die deteksie van gasse by kamertemperatuur, veral vir asetileen (C2H2) gas. Verder is ’n unieke metode ontwikkel om ultra dun aluminium mikrostrukture te vervaardig en hierdie metaal elektrodes word as ideaal beskou vir die integrasie van nano-materiale. ’n Eksperiment is uitgevoer om ’n geïntegreerde sensor te vervaardig met multi-wand koolstof nano-buise, waarvan die resultate aandui dat die proses verfyn moet word en dat die moontlike toepassing van veld-effek-transistor toestelle ondersoek moet word. Die resultate wat opgelewer is gedurende hierdie navorsing dui daarop dat ontwikkelde nanostrukture, soos koolstof nano-buise en grafeen, as toekomstige sensor tegnologie geïmplementeer kan word.

A small-scale model of a CVD reactor was built. Axial and radial of major species concentrations and temperature profiles were obtained with a micro gas chromatograph and a fine thermocouple. Those temperature and species concentrations revealed detailed thermal and chemical structures of the CVD reactor. The concentrations of argon plus hydrogen, methane, and C2Hx (C2H2 + C2H4 + C2H6) resulting from xylene decomposition were measured along the CVD at different temperatures. Ferrocene was added to xylene to investigate the effect of a catalyst on composition profiles. The results with ferrocene indicated an increase in CH4 and C2Hx concentrations. At 1000 C and above, the increase of C2Hx concentration is higher than that for CH4. The effect of ferrocene was very minor on the concentration of the gases. Finally composition and temperature profiles were measured and plotted for the radial direction at X=75 cm and T=1200 C. The overall rate constant for the gas-phase reaction was calculated based on the measured species concentration data using the Benson and Shaw reaction mechanism. Our study showed that the Benson and Shaw mechanism could be used in the temperature range lower than 800 C. Also the effect of hydrogen in the syntheses of CNTs, in the CVD reactor using xylene and ferrocene, was studied. Both single-step and two-step methods were applied. In the single-step method, the ferrocene was dissolved in the xylene. In the two step-method the catalyst preparation step was performed first; ferrocene powder was placed in the preheater for a certain period of time and carried by a mixture of argon and hydrogen at fixed concentration to get catalyst nanoparticles deposited on the reactor wall. Xylene then was injected to the reactor. To study the effect of hydrogen, the synthesized materials were observed by SEM and TEM. The results showed that the presence of hydrogen is essential for CNTs to be synthesized by the CVD method, and also the concentration of hydrogen in the reactor has a great effect on the quality of CNTs. The yield of CNTs in the two-step method was slightly higher than that in the one-step method.

Recently there have been considerable interests in nanometerial study. In this work, we have used carbon nanotubes (CNTs) and polypyrrole (PPy) conducting polymers (CPs) as models to make a nanotube and conducting polymer composite material. Under electro-oxidation condition, the PPy/CNT films can be grown on conventional substrates such as a glassy carbon electrode in aqueous and non-aqueous media. These nano-conjugated materials are based on the doping of CNTs particles into conducting polymer network while oxidatively polymerizing. CNTs serve as dopants and solely supporting electrolytes in the preparation. The CP/CNT new composite materials have showed promise not only in a potential environmental remedy such as conversion of highly toxic Cr(VI) into less harmful Cr(III), but also in electrocatalysis of the quinone/hydroquinone redox reaction. Voltammetry, bulk electrolysis with coulometry, AC impedance, and EQCM techniques have been used to elucidate the preparation, ion transport, and intermolecular interaction processes within these composites.

Lors de la mise au point de biocapteurs, le contrôle de l'état de surface sur laquelle sontimmobilisées les biomolécules est un paramètre crucial pour la fiabilité et la reproductibilité desmesures. Pour ce travail de Thèse, deux objectifs principaux ont été fixés :- obtenir de façon reproductible des films organiques fonctionnels capables de rendre lessurfaces inorganiques biocompatibles afin d'immobiliser des biomolécules sans les dénaturer.- se doter d'outils innovants afin d'analyser la distribution de biomolécules sur la surface etd'évaluer leur activité biologique à l'échelle de la molécule unique.L'immobilisation a été réalisée sur des SAMs terminées par une fonction acide carboxylique.Pour imager les surfaces nous avons choisi la Microscopie Atomique de Force (AFM) qui permetd'obtenir des informations à l'échelle nanométrique et de mesurer des interactions moléculaires del'ordre du piconewton (10-12 N).Des CNTs, générés par dépôt chimique en phase vapeur, sont fixés sur une pointe AFM. Puis Ilssont biofonctionnalisés selon un protocole de trempage original afin d'obtenir une modificationchimique sélective de leur apex. Les interactions entre un récepteur, immobilisé sur la surface, et sonligand, lié de façon covalente au CNT, sont mesurées à l'échelle de la molécule unique. / During the development of biosensors, control of the surface on which the biomolecules areimmobilized is a crucial parameter for the reliability and reproducibility of the measurements. For thisPhD work, two main objectives were set:- obtain in a reproducible way functional organic films able to make inorganic surfacebiocompatible for the immobilization of biomolecules without any denaturation.- develop innovative tools in order to analyze the distribution of biomolecules on the surface etevaluate their biological activity at single molecule scaleThe immobilization step was done on SAMs terminated by a carboxylic acid function.In order to image surfaces, Atomic Force Microscopy (AFM) was chosen. This technique permits toobtain information at nanometric scale and to measure molecular interactions in the range ofpiconewton forces (10-12 N).MWCNTs were linked to a commercial AFM tip by micro-welding under optical microscopy. CNTswere biofunctionalized at the nanotube apex by an original dipping procedure.The interactions between a ligand, immobilized on the surface, and a receptor covalently linked to aCNT have been characterized.

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.

This diploma thesis focuses on the influence of carbon nanotubes (CNTs) on the mechanical properties of a composite material with polyurethane (PU) matrix. The material was supplied in the form of thin films with thickness from 0.2 mm to 1.2 mm. The theoretical part of this thesis describes the production technology, properties and applications of composite materials PU/CNTs, and also deals with preparation technology and properties of both components of this composite material separately. The theoretical part also describes the principle of tensile testing of polymer materials. The experimental part of the thesis was primarily focused on comparing the tensile properties of a composite material PU/CNTs with tensile properties of pure PU. At first, tensile properties of pure PU were investigated, while the influence of various factors like strain rate, specimen thickness, heat treatment and aging was examined. In adition, stress relaxation tests and tests with strain rate jumps were performed on pure PU specimens. Then composite PU/CNTs was tested in tension and the results were compared with the results of tensile tests of pure PU. Composite material PU/CNTs was prepared with various concentrations, so it was possible to determine the effect of CNTs content on the tensile properties of the composite. The last part of this thesis deals with tensile tests of PU composite material with functionalized carbon nanotubes (PU/FCNTs), where the influence of surface modification (functionalization) of CNTs on the tensile properties composites was investigated. It was shown that the effect of both CNT and FCNT on mechanical properties of the composite is not significant. This conclusion was discussed on basis of the works of other authors, which do not unambiguously proved the positive effect of CNT or FCNT on mechanical properties of composites with polymer matrix.

Carbon nanotubes (CNTs) have gathered a lot of interest because of their extraordinary mechanical, electrical and thermal properties and have potential applications in a wide variety of areas such as material-reinforcement and nano-electronics. The properties of nanotubes are dependent on their diameter and methods for determining this using atomic force microscopy (AFM) in tapping mode assume that the measured height of the tubes represent the real diameter. Based on early, faulty calculations, the forces in tapping mode were assumed to be much lower than in contact mode, however it was later shown that forces in tapping mode can at point of impact rival the forces present in contact mode. This means that there is a potential risk of tube deformation during tapping mode measurements, resulting in incorrectly determined diameters. This work studies CNTs deposited on a silicon-substrate to analyze the effect of three common AFM settings (tapping frequency, free oscillation amplitude and setpoint) to determine their effect on measured CNT diameters and recommendations for choosing settings are given. / Kolnanorör har skapat mycket intresse på grund av sina extraordinära mekaniska, elektriska och termiska egenskaper och har lovande tillämpningar inom en mängd olika områden så som materialförstärkning och nanoelektronik. Kolnanorörens egenskaper påverkas kraftigt av deras diameter och de metoder som använder sig av atomkraftsmikroskopi(AFM) för att mäta diametern hos rören antar att den höjd-data man får fram är ett bra mått på den verkliga diametern hos rören. Baserat på tidiga, felaktiga beräkningar, antog man att kraften i ’tapping mode’ skulle vara mycket lägre än i ’contact mode’ vilket skulle leda till att man inte deformerar ytan man undersöker. Senare forskning visade att kraften mellan spets och prov kan vara lika stor eller rentutav större i tapping mode än i contact mode under det ögonblick då spetsen slår ner i provytan. Det medför att det finns en potentiell risk för att man deformerar kolnanorören när man mäter på dom vilket skulle resultera i att man får felaktiga värden på deras diametrar. Under det här projektet har kolnanorör som placerats på ett kisel-substrat undersökts för att analysera hur tre vanliga inställningar hos AFMet påverkar de erhållna värdena för diametern hos kolnanorören. De tre inställningarna som testats är svängnings-frekvensen, svängnings-amplituden i luft och börvärdet hos svängnings-amplituden.

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.

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.