The design and performance of an instrument is presented whose purpose is the extraction of samples highly enriched in one species of single-walled carbon nanotubes from density gradient ultracentrifugation. This instrument extracts high purity samples which are characterized by various optical studies. The samples are found to be enriched in just a few species of nanotubes, with the major limitation to enrichment being the separation, rather than extraction. The samples are then used in optical and microscopic studies which attempt to determine the first absorption coefficient (S1) of the (6,5) species of nanotube. Initial experiments give a value of 9.2 ± 2.6 cm2 C atom-1. Future work is proposed to improve upon the experiment in an attempt to reduce possible errors

As pointed out more and more frequently in the literature, there is a pressing need for research into the health and environmental impact of nanoparticles. This work represents a joint effort between scientists in nanotechnology, chemistry and biology to answer this call and to investigate the environmental effects of carbon nantoubes (CNTs) from a brand new aspect. The results showed clearly the dose-dependent effects of single-walled carbon nanotubes (SWNTs) on the ingestion and digestion of bacteria by Tetrahymena thermophila, a ciliated protozoan, propagated to its prey bacteria, Escherichia coli. Investigated by confocal microscopy Tetrahymena were able to internalize large quantities of SWNTs and then excrete SWNTs and undigested bacteria in aggregates. Inhibition of ciliate bacterivory measured by Ciliate Bacterivory assay was evident at far below lethal concentrations. At high tube concentrations (above 6.8 μg∙ml-1), cell viability was affected. In addition, explored by fluorescence microscopy and scanning electron microscopy, SWNTs stimulated Tetrahymena to abnormally egest viable bacteria inside membrane protected structures, which enhanced bacterial survival during antimicrobial treatments, bacteriostatic or bacteriocidal. This phenomenon may have important implications to public health. In general, research on toxicity of nanoparticles is in a very early stage with most studies on direct fatality (kill or not to kill) of a single organism or certain type of cells. This work is believed to be among the first few investigating extrapolated effects. Hopefully, this wok will stimulate a line of research towards better understanding of the effects of nanomaterials on diverse organisms, and stimulate not only toxicology but also ecotoxicology studies.

As pointed out more and more frequently in the literature, there is a pressing need for research into the health and environmental impact of nanoparticles. This work represents a joint effort between scientists in nanotechnology, chemistry and biology to answer this call and to investigate the environmental effects of carbon nantoubes (CNTs) from a brand new aspect. The results showed clearly the dose-dependent effects of single-walled carbon nanotubes (SWNTs) on the ingestion and digestion of bacteria by Tetrahymena thermophila, a ciliated protozoan, propagated to its prey bacteria, Escherichia coli. Investigated by confocal microscopy Tetrahymena were able to internalize large quantities of SWNTs and then excrete SWNTs and undigested bacteria in aggregates. Inhibition of ciliate bacterivory measured by Ciliate Bacterivory assay was evident at far below lethal concentrations. At high tube concentrations (above 6.8 μg∙ml-1), cell viability was affected. In addition, explored by fluorescence microscopy and scanning electron microscopy, SWNTs stimulated Tetrahymena to abnormally egest viable bacteria inside membrane protected structures, which enhanced bacterial survival during antimicrobial treatments, bacteriostatic or bacteriocidal. This phenomenon may have important implications to public health. In general, research on toxicity of nanoparticles is in a very early stage with most studies on direct fatality (kill or not to kill) of a single organism or certain type of cells. This work is believed to be among the first few investigating extrapolated effects. Hopefully, this wok will stimulate a line of research towards better understanding of the effects of nanomaterials on diverse organisms, and stimulate not only toxicology but also ecotoxicology studies.

The interfacial micromechanics of both high modulus and low modulus carbon fibres have been investigated using Raman spectroscopy. The innovative step was to make low modulus carbon fibres more Raman active by coating them with SWNTs to act as as a strain sensor. Two types of SWNTs have been employed; namely HiPCO SWNTs and COOH SWNTs. Single fibre deformation tests were carried out and the Raman band shift rates with respect to fibre strain have been determined. Meanwhile, different SWNTs coating methods have been investigated. The method of adding COOH SWNTs into the silane layer and within a hot cured epoxy layer was found to generate the highest band shift rates. Furthermore, an investigation of the effect of SWNTs on the strength of the interface was also carried out. A coating of COOH SWNTs was found to significantly improve the interfacial shear strength. Micromechanical tests have been carried out and the stress transfer between the carbon fibres and an epoxy resin was monitored using three different model composite geometries; namely microdroplet-fibre, a film-fibre and a standard fragmentation approach. The result of interfacial shear stress determined from microdroplet-fibre method varied and was found to be highly dependent on the droplet size and shape; this gave the lowest values of interfacial shear stress (ISS). The method of film-fibre obtained an intermediate ISS value which is between that from the microdroplet model test and the fragmentation test. The standard fragmentation test using Raman technique gives the highest ISS and HiPCO SWNTs were found to be a better strain sensor without affecting the original interfacial properties.

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Electronic applications have expanded to encompass a variety of materials. In particular, allotropes of carbon interest researchers for their electronic applications. Knowledge of carbon allotropes and their applications has expanded significantly since the discovery of C60 Buckminsterfullerene in 1985, the discovery of multi- and single-walled carbon nanotubes in the early 1990s, and the isolation of graphene in 2004. Single-walled carbon nanotubes (SWNTs) have the potential to bring next-generation electronic devices to fruition. Such devices could be flexible, conformable, and inexpensive. SWNT-based electronics are promising for chemical and biological sensing applications, for example, where high carrier mobilities are unnecessary, and material conformity and inexpensive processing are significant advantages. Considerable progress has been made in separating semiconducting SWNTs from metallic SWNTs, enabling SWNT incorporation into semiconducting electronic technologies. Selective sorting of semiconducting SWNTs using π-conjugated polymers is an effective and efficient technique to enrich large quantities of ultra-pure semiconducting SWNTs. Following semiconducting enrichment, SWNTs can be incorporated into electronic devices. This thesis focuses on the enrichment of semiconducting SWNTs via conjugated polymer extraction and incorporating the resulting polymer-SWNT dispersions into thin-film transistors (TFTs). Novel copolymers were investigated for their capacity to selectively sort and disperse large-diameter sc-SWNTs synthesized using the plasma torch technique. Absorption and Raman spectroscopy were employed to monitor the efficacy of the conjugated polymer extraction procedure. Following enrichment, the polymer-SWNT dispersions were incorporated into TFTs. The interaction between the conjugated polymer and the SWNT and the conjugated polymer and dielectric was an essential component of TFT optimization. Furthermore, the procedure of sorting and dispersing sc-SWNTs is investigated for its effect on TFT performance and was another component of TFT optimization. TFTs were electrically characterized in terms of carrier mobility, threshold voltage, hysteresis, and current on/off ratio. The film morphology of the SWNT TFTs was also investigated. Atomic force microscopy and Raman mapping were used to provide insight into the nanometre and micrometre scale film morphology, respectively.

The outstanding properties of carbon nanotubes (CNTs) have stimulated a large number of researches to explore the potential of using them as reinforcement in polymer composites. Although many studies have reported the enlighten improvement of the materials properties by using CNTs as reinforcement, there are no promising and optimal results have been concluded to date. This thesis aims at studying the mechanical properties on thermoset polymer, Epoxy, by employing a small amount of carbon nanotubes as reinforcement. Two different types of nanotube-based composites are prepared i.e. a raw single-walled carbon nanotube (SWNT) composites and a functionalized single-walled carbon nanotube (FSWNT) composite. Chemical functionalization on SWNTs with carboxyl functional group (COOH) aims at modifying the end caps of nanotubes, so to provide covalent bonding of SWNTs to the polymer matrix during manufacturing of composite systems. Different weight percentages (wt %) of each type of SWNTs are added into the composite system. Standard test methods are performed on these nanotube composite systems and satisfactory results were achieved when the weight percentages of both types of SWNTs increased. Through the comparison between two systems (raw SWNTs and FSWNTs), the FSWNT reinforced composite is found to provide a better improvement on the mechanical properties as compared with the SWNT reinforced system. The integrity of both composite systems is examined by using Scanning Electronic Microscopy (SEM). The SEM images of the composites indicated the derivation in wetting and bonding between the nanotubes (both SWNTs and FSWNTs) and epoxy resin, and the FSWNTs provide an eminent dispersion when compared with the SWNTs in the composite system. Moreover, thermal testings are employed to further investigate the interfacial interaction between the nanotubes and the polymer matrix. xiv Molecular Dynamics (MD) simulations are also carried out to investigate the structural change of a SWNT under different temperature-controlled manufacturing environments. Swivel of the SWNT was noticed as the temperature increased. Such alteration in structure form can provide physical interlocking between SWNT and its surrounding polymer system. Thus, its overall mechanical and thermal properties can be enhanced.

Single-Walled Carbon Nanotube (SWCNT) based Very Large Scale Integrated circuit (VLSI) interconnect is one of the emerging technologies, and has the potential to overcome the thermal issues persisting even with the advanced copper based interconnect. This is because of it’s promising electrical and thermal transport properties. It can be stated that thermal energy transport in SWCNTs is highly anisotropic due to the quasi one dimensionality, and like in other allotropes of carbon, phonons are the dominant energy carriers of heat conduction. In case of conventional interconnect materials, copper and aluminium, although their thermal conductivity varies over orders of magnitude at temperatures below100 K, near room temperature and above they have almost constant value. On the other hand, the reported experimental studies on suspended metallic SWCNTs illustrate a wide variation of the longitudinal lattice thermal conductivity (κl) with respect to the temperature(T)and the tube length(L)at low, room and high temperatures. Physics based analytical formulation of κl of metallic SWCNT as a function of L and T is essential to efficiently quantify this emerging technology’s impact on the rising thermal management issues of Integrated Circuits. In this work, a physics based diameter independent analytical model for κl of metallic SWCNT is addressed as a function of Lover a wide range of T. Heat conduction in metallic SWCNTs is governed by three resistive phonon scattering processes; second order three phonon Umklapp scattering, mass difference scattering and boundary scattering. For this study, all the above processes are considered, and the effective mode dependent relaxation time is determined by the Matthiessen’s rule. Phonon Boltzmann transport equation under the single mode relaxation time approximation is employed to derive the non-equilibrium distribution function. The heat flux as a function of temperature gradient is obtained from this non-equilibrium distribution function. Based on the Fourier’s definition of thermal conductivity, κl of metallic SWCNT is formulated and the Debye approximations are used to arrive at analytical model. The model developed is validated against both the low and high temperature experimental investigations. At low temperatures, thermal resistance of metallic SWCNT is due to phonon-boundary scattering process, while at high temperatures it is governed by three phonon Umklapp scattering process. It is understood that apart from form factor due to mass difference scattering, boundary scattering also plays the key role in determining the peak value. At room temperature, κl of metallic SWCNT is found to be an order of magnitude higher than that of most of metals. The reason can be attributed to the fact that both sound velocity and Debye temperature which have direct effect on the phonon transport in a solid, are reasonably higher in SWCNTs. Though Umk lapp processes reduce the κl steeper than 1/T beyond room-temperature, it’s magnitude is round1000 W/m/K upto 800 K for various tube lengths, which confirms that this novel material is indeed an efficient conductor of heat also, at room-temperature and above.

Two major projects involving the use of solution processed blended semiconductors for organic field effect transistors (OFET) were explored. The first incorporated unsorted single walled carbon nanotubes (SWCNTs) into a diketopyrrolopyrrole-quarterthiophene (DPP-QT) semiconductor to enhance the mobility of the OFET. 2 wt % SWCNT was found to be the optimal blend ratio, nearly doubling the device mobility (0.6 to 0.98 cm^2/V·s). Beyond this ratio, the metallic content of the SWCNT’s dropped the on/off ratio below acceptable levels. When source drain metals who’s work function poorly matched that of the DPP-QT semiconductors highest occupied molecular orbital (HOMO) were used, the SWCNT could dramatically reduce the charge injection ratio with best results achieved for Al, dropping the contact resistance from 10^5 to 45 MΩ. The second project explored the addition of small molecule additives into a UV-sensitive semiconductor 2,7-dipentyl[1]benzothieno[3,2-b][1] benzothiophene (C5-BTBT) mixed with a polymethyl methacrylate (PMMA) polymer binder. We generated a C5-BTBT based phototransistor sensitive to UV-A light. The HOMO and lowest unoccupied molecular orbital (LUMO) of C5-BTBT and the various additives were measured and discovered to play a critical role in how the device operates. We discovered if an additive has a LUMO lower in energy than C5-BTBT, it can act as a charge trap for a photogenerated electron. Electron deficient additives were found to retain a trapped electron for an extended period of time, allowing the device to remain in a high current state for an extended period of time (>1 hour). This provides an opportunity for the device to be used as an optical memory system or photoswitch. The best system could detect UV-A with a Pill > 10^5 and a photoresponsivity of 40 A/W at a Pinc of 0.0427 mW/cm^2. / Thesis / Doctor of Philosophy (PhD) / An emerging field of electronics is the use of organic materials that can be solution processed, to reduce manufacturing costs and make new and interesting products. Here we used unsorted carbon nanotubes blended into the semiconductor layer of a transistor, providing a bridge for the energy mismatch between the electrodes and the semiconductor. This allowed us the freedom to choose different metals to act as our electrodes when making electronic devices. Additionally through the correct choice of semiconductor, we added device functionality, making it responsive to UV-A light. This produced a device that could act as a UV-A sensor, logic switch or memory device. These devices are air stable and solution processable, a necessity if they are to be used in real world applications.

Photophysical, electronic, and compositional properties of single-walled carbon nanotubes (SWCNTs) and bulk nanotube samples were investigated together with graphene oxide photoluminescence. First, we studied the effect of external electric fields on SWCNT photoluminescence. Fields of up to 10 7 V/m caused dramatic, reversible decreases in emission intensity. Quenching efficiency was proportional to the projection of the field on the SWCNT axis, and showed inverse correlation with optical band gap. The magnitude of the effect was experimentally related to exciton binding energy, as consistent with a proposed field-induced exciton dissociation model. Further, the electronic composition of various SWCNT samples was studied. A new method was developed to measure the fraction of semiconducting nanotubes in as- grown or processed samples. SWCNT number densities were compared in images from near-IR photoluminescence (semiconducting species) and AFM (all species) to compute the semiconducting fraction. The results provide important information about SWCNT sample compositions that can guide controlled growth methods and help calibrate bulk characterization techniques. The nature of absorption backgrounds in SWCNT samples was also studied. A number of extrinsic perturbations such as extensive ultrasonication, sidewall functionalization, amorphous carbon impurities, and SWCNT aggregation were applied and their background contributions quantified. Spectral congestion backgrounds from overlapping absorption bands were assessed with spectral modeling. Unlike semiconducting nanotubes, metallic SWCNTs gave broad intrinsic absorption backgrounds. The shape of the metallic background component and its absorptivity coefficient were determined. These results can be used to minimize and evaluate SWCNT absorption backgrounds. Length dependence of SWCNT optical properties was investigated. Samples were dispersed by ultrasonication or shear processing, and then length-fractionated by gel electrophoresis or controlled ultrasonication shortening. Fractions from both methods showed no significant absorbance variations with SWCNT length. The photoluminescence intensity increased linearly with length, and the relative quantum yield gradually increased, approaching a limiting value. Finally, a strong pH dependence of graphene oxide photoluminescence was observed. Sharp and structured excitation/emission features resembling the spectra of molecular fluorophores were obtained in basic conditions. Based on the observed pH-dependence and quantum calculations, these spectral features were assigned to quasi-molecular fluorophores formed by the electronic coupling of oxygen-containing addends with nearby graphene carbon atoms.