Carbon nanotubes possess various unique and interesting properties. They have very high thermal and electrical conductivities, high stiffness, mechanical strength, and optical properties. Due to these properties, CNTs are widely used materials in a variety of fields. It is used for biotechnological and biomedical applications, as chemical and biosensor, in energy storage and field emission transistor. Experimentally synthesized CNTs are generally found in bundle form due to the strong vander Waals (vdW) at-traction between the individual tubes. To use CNTs in real life applications, we often require specific nanotubes with particular characteristics. The nanotube bundle is a mixture of various chirality, diameters and electronic properties (metallic and semiconducting). Only thermal energy is not sufficient to disperse nanotubes from the bundle geometry overcoming the strong vdW attraction between nanotubes. The hydrophobic and insoluble nature of CNTs in the aqueous medium makes the dispersion of CNTs even more difficult. So, it is a big challenge to get single pristine nanotube from the bundle geometry. Many experimental and theoretical studies have addressed the problem of nanotube dispersion from the bundle geometry. Ultrasonic dispersing method is a widely used technique for this purpose where ultrasonic sound is applied to agitate particles in a system. Other methods include using different organic and inorganic solutions, various surfactant molecules, different polymers as dispersing agents. In this study we extend our e orts to develop some better methods and improved dispersing agents. In this thesis, we address the problem of CNT dispersion. To address this issue, we rst give a quantitative estimation of the effective interaction between nanotubes. Next, we introduce different polymers (ssDNA and dendrimers) as external agents and show that they help to overcome the strong adhesive interaction between CNTs and make nanotube dispersion possible from the bundle geometry. For all of the works presented in this thesis, we have used fully atomistic MD simulation and DFT level calculations. We study ssDNA-CNT complex using all-atom MD simulation and calculate various structural quantities to show the stability of ssDNA-CNT complex in aqueous medium. The adsorption of ssDNA bases on CNT surface is driven by - interaction between nucleic bases and CNT. Using the potential of mean forces (PMF) calculation, we study the binding strength of the polynucleotide ssDNA for poly A, T, G, and C with CNT of chirality (6,5). From the PMF calculation, we show the binding sequence to be A > T > C > G. Except for poly G, our result is in good agreement with earlier reported single molecule force spectroscopy results where the sequence of binding interaction was reported to be A > G > T > C. To explore how the interaction between two CNTs mod-i ed in presence of ssDNA between them, we perform PMF calculation between the two ssDNA-wrapped CNTs. The PMF shows the sequence of interaction strength between two ssDNA-wrapped CNTs for different nucleic bases to be T > A > C > G. Thus, from PMF calculations we show the poly T to have the highest dispersion efficiency, which is consistent with earlier reported experimental study. Our PMF calculation shows that poly C and poly G reduce the attraction between two CNTs drastically, whereas poly A and poly T make the interaction fully repulsive in nature. We also present microscopic pictures of the various binding conformations for ssDNA adsorbed on CNT surface. We also study the dendrimer-CNT complex for both the PAMAM and PETIM dendrimers of different generations at various protonation states and present microscopic pictures of the complex. We calculate PMF between two dendrimer wrapped CNTs and show that protonated and higher generations (G3, G4, and so forth) non-protonated PAMAM dendrimers can be used as e ective agents to disperse CNTs from bundle geometry. We also study the chirality dependence of PMF respectively. Finally, we study the interaction of mannose dendrimer with CNTs and show that the wrapping of mannose dendrimer can drive a metal to semiconducting transition in a metallic CNT. We attribute the carbon-carbon bond length assymetry in CNT due to the wrapping of mannose dendrimer as the reason for this band gap opening which leads to metal-semiconductor transition in CNT. Thus, the wrapping of mannose dendrimer on CNT can change its electronic properties and can be used in the band gap engineering of CNT in future nanotechnology. Thus, the works carried out here in this dissertation will help to address the problem of nanotube dispersion from the bundle geometry which will in turn help to use CNT for various applications in diverse fields.

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With the development of modern industrial engineering technology, increasing demands of multifunctional materials drive the exploration of new applications of electrical conductive polymer nanocomposites (CPNCs). Toward applications of smart materials, sensing performance of CPNCs has gained immense attention in the last decade. Among them, strain sensors, based on piezoresistive behavior of CPNCs, are of high potential to carry out structural health monitoring (SHM) tasks. Poly(vinylidene fluoride) (PVDF) is highly thought to be potential for SHM applications in civil infrastructures like bridges and railway systems, mechanical systems, automobiles, windgenetors and airplanes, etc. because of its combination of flexibility, low weight, low thermal conductivity, high chemical corrosion resistance, and heat resistance, etc. This work aimed to achieve high piezoresistive sensitivity and wide measurable strain ranges in carbon nanotube based poly(vinylidene fluoride) (PVDF) nanocomposites. Four strategies were introduced to tune the sensitivity of the relative electrical resistance change (ΔR/R0) versus the applied tensile strain for such nanocomposites. Issues like the influence of dispersion of multi-walled carbon nanotubes (MWCNTs) on initial resistivity of PVDF nanocomposites and conductive network structure of MWCNTs, as well as piezoresistive properties of the nanocomposites, were addressed when using differently functionalized MWCNTs (strategy 1). In addition, the effects of crystalline phases of PVDF, mechanical ductility of its nanocomposites and interfacial interactions between PVDF and fillers on piezoresistive properties of PVDF nanocomposites were studied. Using hybrid fillers, to combine MWCNTs with conductive carbon black (strategy 2) or isolating organoclay (strategy 3), piezoresistive sensitivity and sensing strain ranges of PVDF nanocomposites could be tuned. Besides, both higher sensitivity and larger measurable strain ranges are achieved simultaneously in PVDF/MWCNT nanocomposites when using the ionic liquid (IL) BMIM+PF6- as interface linker/modifier (strategy 4). The detailed results and highlights are summarized as following: 1. The surface functionalization of MWCNTs influences their dispersion in the PVDF matrix, the PVDF-nanotube interactions and crystalline phases of PVDF, which finally results in different ΔR/R0 and the strain at the yield point (possibly the upper limit of sensing strain ranges). As a whole, regarding to the fabrication of strain sensors based on PVDF/MWCNT nanocomposite, in contrast to pristine CNTs, CNTs-COOH and CNTs-OH, CNT-NH2 filled PVDF nanocomposites possess not only high piezoresistive sensitivity but also wide measurable strain ranges. Gauge factor, i.e. GF, is ca.14 at 10% strain (strain at the yield point) for the nanocomposites containing 0.75% CNTs-NH2. 2. Using hybrid fillers of CNTs and CB to construct strain-susceptible network structure (conductive pathway consisting of string-like array of CNTs and CB particles) enhances the piezoresistive sensitivity of PVDF nanocomposites, which is tightly associated with the CNT content in hybrid fillers and mCNTs/mCB. The best piezoresistive effect is achieved in PVDF nanocomposites with fixed CNT content lower than the ΦC (0.53 wt. %) of PVDF/CNT nanocomposites. 3. ΔR/R0 and possible sensing strain ranges of PVDF nanocomposites were tailored by changing crystalline phases of PVDF and PVDF-MWCNT interactions. Besides, the increase of the strain at yield point in PVDF nanocomposites filled by CNTs-OH is more obvious than that in the nanocomposites containing the same amount of clay and CNTs. The nanocomposite consisting of 0.25% clay and 0.75% CNTs-OH have ca. 70% increase of the strain at the yield point (17%) and the GF at this strain is ca. 14, while GF for the nanocomposite filled by only 0.75% CNTs-OH is ca. 5 at 10% strain. 4. IL BMIM+PF6- served as interface linker for PVDF and MWCNTs, which significantly increased the values of ΔR/R0 and strain at the yield point of PVDF nanocomposites simultaneously. Besides, this increases with increasing IL content. With the aid of IL, the dispersion of nanotube and toughness of the nanocomposites are greatly improved, but the electrical conductivity of the nanocomposites is decreased with the incorporation of IL, which is related to the IL modified PVDF-MWCNT interface connection or bonding. GF reaches ca. 60 at 21% strain (the strain at the yield point) for PVDF nanocomposites filled by 10% IL premixed 2%CNTs-COOH.

Thesis (MSc)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: The experimental observation of the quantum Hall effect in a two-dimensional electron gas posed an intriguing question to theorists: Why is the quantization of conductance so precise, given the imperfections of the measured samples? The question was answered a few years later, when a connection was uncovered between the quantum Hall effect and topological quantities associated with the band structure of the material in which it is observed. The Hall conductance was revealed to be an integer topological invariant, implying its robustness to certain perturbations. The topological theory went further than explaining only the usual integer quantum Hall effect in a perpendicular magnetic field. Soon it was realized that it also applies to certain systems in which the total magnetic flux is zero. Thus it is possible to have a quantized Hall effect without Landau levels. We study a carbon nanotube in a magnetic field perpendicular to its axial direction. Recent studies suggest that the application of an electric field parallel to the magnetic field would induce a gap in the electronic spectrum of a previously metallic carbon nanotube. Despite the quasi onedimensional nature of the carbon nanotube, the gapped state supports a quantum Hall effect and is associated with a non zero topological invariant. This result is revealed when an additional magnetic field is applied parallel to the axis of the carbon nanotube. If the flux due to this magnetic field is varied by one flux quantum, exactly one electron is transported between the ends of the carbon nanotube. / AFRIKAANSE OPSOMMING: Die eksperimentele waarneming van die kwantum Hall effek in ’n twee-dimensionele elektron gas laat ’n interessante vraag aan teoretiese fisikuste: Waarom sou die kwantisasie van die geleiding so presies wees al bevat die monsters, waarop die meetings gedoen word, onsuiwerhede? Hierdie vraag word ’n paar jaar later geantwoord toe ’n konneksie tussen die kwantum Hall effek en topologiese waardes, wat verband hou met die bandstruktuur van die monster, gemaak is. Dit is aan die lig gebring dat die Hall geleiding ’n heeltallige topologiese invariante is wat die robuustheid teen sekere steurings impliseer. Die topologiese teorie verduidelik nie net die gewone kwantum Hall effek wat in ’n loodregte magneetveld waargeneem word nie. Dit is ook moontlik om ’n kwantum Hall effek waar te neem in sekere sisteme waar die totale magneetvloed nul is. Dit is dus moontlik om ’n gekwantiseerde Hall effek sonder Landau levels te hˆe. Ons bestudeer ’n koolstofnanobuis in ’n magneetveld loodreg tot die aksiale rigting. Onlangse studies dui daarop dat die toepassing van ’n elektriese veld parallel aan die magneetveld ’n gaping in die elektroniese spektrum van ’n metaliese koolstofnanobuis induseer. Ten spyte van die een-dimensionele aard van die koolstofnanobuis ondersteun die gapings-toestand steeds ’n kwantum Hall effek en hou dit verband met ’n nie-nul topologiese invariante. Hierdie resultaat word openbaar wanneer ’n bykomende magneetveld parallel tot die as van die koolstofnanobuis toegedien word. Indien die vloed as gevolg van hierdie magneetveld met een vloedkwantum verander word, word presies een elektron tussen die twee kante van die koolstofnanobuis vervoer.

Phonons are primary heat carriers in carbon nanotubes (CNTs) and graphene; a fundamental understanding of phonon transport in these nano-structures is required for the energy efficient design of their devices such as integrated circuit, flexible displays, and transparent electrodes. In this work, atomistic simulations have been performed to investigate thermal transport at interfaces of CNT and graphene that are typically encountered in their applications, e.g., CNT-CNT junctions on silicon oxide substrate, interfaces between shells of double-wall CNTs (DWNTs), and graphene-metal interfaces. Firstly, heat dissipation at CNT junctions supported on the silicon dioxide substrate is investigated using molecular dynamics (MD) simulations and methods for phonon spectrum analysis. The results show the inefficient heat removal from CNTs not making direct contact with the oxide substrate is responsible for the breakdown of CNT network. At interfaces between shells of DWNTs, the radial vibration modes are identified as phonons that are strongly coupled and can efficiently exchange energy between shells of DWNTs. Secondly, the thermal conductivity of suspended single layer graphene (SLG) and SLG supported on Cu is determined using equilibrium MD simulations following Green-Kubo method and relaxation time approximation approach at room temperature. It is demonstrated that the interaction with Cu substrate can significantly reduce the thermal conductivity of SLG, and that the reduction of thermal conductivity from three acoustic phonons is the major reason. Lastly, using atomistic Green’s function method and density function theory calculations, the thermal boundary conductance at interfaces across graphene layers sandwiched by different metals including Cu, Au, and Ti is predicted. The work shows how the bonding strength changes the graphene/metal and graphene/graphene phonon coupling, and demonstrated the transition of thermal transport mechanism from metal/graphene dominated resistance to graphene/graphene dominated resistance as the metal/graphene bonding strength increases in metal/MLG/metal structure.

We characterized the thermoacoustic and photoacoustic properties of large-area, few-layer graphene by pulsed microwave and optical excitations. Due to its high electric conductivity and low heat capacity per unit area, graphene lends itself to excellent microwave and optical energy absorption and acoustic signal emanation due to the thermoacoustic effect. When exposed to pulsed microwave or optical radiation, distinct thermoacoustic and photoacoustic signals generated by the few-layer graphene are obtained due to microwave and laser absorption of the graphene, respectively. Clear thermoacoustic and photoacoustic images of large-area graphene sample are achieved. A numerical model is developed and the simulated results are in good accordance with the measured ones. This characterization work may find applications in ultrasound generator and detectors for microwave and optical radiation. It may also become an alternative characterization approach for graphene and other types of two-dimensional materials. (C) 2016 AIP Publishing LLC.

Acrylic bone cement is widely used as a structural material in orthopaedics, dentistry, and orofacial surgery. Although bone cement celebrates four decades of success, it remains susceptible to fatigue fracture. This type of failure can directly lead to implant loosening, revision surgery, and increased healthcare expenditures. The mechanism of fatigue failure is divided into three stages: 1) fatigue crack initiation, 2) fatigue crack propagation, and 3) fast, brittle fracture. Adding reinforcing fibers and particles to bone cement is a proposed solution for improving fatigue performance. The mechanical performance of these reinforced bone cements is limited by fiber ductility, fibermatrix de-bonding, elevated viscosity, and mismatch of fiber size and scale of fatigue induced damage. In this dissertation, I report that adding small amounts (0% - 10% by weight) of multiwall carbon nanotubes (MWNTs) enhances the strength and fatigue performance of single phase bone cement. MWNTs (diameters of 10-9 10-8 m; lengths of 10-6 10-3 m) are a recently discovered nanomaterial with high surface area to volume ratios (conferring MWNT bone cement composites with large interfaces for stress transfer) that are capable of directly addressing sub-microscale, fatigue induced damage. MWNTs (2wt%) significantly increased the flexural strength of single phase bone cement by a modest 12%; whereas, similar additions of MWNTs dramatically enhanced fatigue performance by 340% and 592% in ambient and physiologically relevant conditions, respectively. Comparing the fatigue crack propagation behaviors of reinforced and unreinforced single phase bone cements revealed that the reinforcing mechanisms of MWNTs are strongly dependent on stress intensity factor, K, a numerical parameter that accounts for the combinatorial effect of the applied load and the crack size. As the crack grows the apparent stress at the crack tip intensified and the MWNTs lost their reinforcing capabilities. For that reason, it is likely that the predominant role of the MWNTs is to reinforce the bone cement matrix prior to crack initiation and during the early stages of crack propagation. Therefore, MWNTs are an excellent candidate for improving the clinical performance of bone cement, thereby improving implant longevity and reducing patient risk and healthcare costs.

Molecular transport through hollow cores of crystalline carbon nanotubes (CNTs) are of considerable interest from the fundamental and application point of view. This dissertation focuses on understanding molecular transport through a membrane platform consisting of open ended CNTs with ~ 7 nm core diameter and ~ 1010 CNTs/cm2 encapsulated in an inert polymer matrix. While ionic diffusion through the membrane is close to bulk diffusion expectations, gases and liquids were respectively observed to be transported ~ 10 times faster than Knudsen diffusion and ~ 10000-100000 times faster than hydrodynamic flow predictions. This phenomenon has been attributed to the non-interactive and frictionless graphitic interface. Functionalization of the CNT tips was observed to change selectivity and flux through the CNT membranes with analogy to gate-keeper functionality in biological membranes. An electro-chemical diazonium grafting chemistry was utilized for enhancing the functional density on the CNT membranes. A strategy to confine the reactions at the CNT tips by a fast flowing liquid column was also designed. Characterization using electrochemical impedance spectroscopy and dye assay indicated ~ 5-6 times increase in functional density. Electrochemical impedance spectroscopy experiments on CNT membrane/electrode functionalized with charged macro-molecules showed voltage-controlled conformational change. Similar chemistry has been applied for realizing voltage-gated transport channels with potential application in trans-dermal drug delivery. Electrically-facilitated transport ( a geometry in which an electric field gradient acts across the membrane) through the CNT and functionalized CNT membranes was observed to be electrosmotically controlled. Finally, a simulation framework based on continuum electrostatics and finite elements has been developed to further the understanding of transport through the CNT membranes.

The main objective of this thesis is to efficiently disperse and align SWNTs in two different polymer matrices to obtain an orthotropic composite whose strength, stiffness and electrical properties depend on the orientation of the SWNTs. The SWNTs are successfully dispersed and aligned in a polyimide matrix and a polymer blend of UDMA/HDDMA. In-situ polymerization under sonication is used to disperse the SWNTs in polyimide matrix and sonication is used to disperse SWNTs in the UDMA/HDDMA matrix. In both cases, an electric field is used to align the SWNTs in the polymer matrices. In the polyimide, the SWNTs are aligned by electrospinning technique, and in (UDMA/HDDMA) the SWNTs are aligned by applying an AC electric field, while the composite is cured.The electrical and mechanical properties of randomly dispersed SWNT polyimide composites and SWNT/UDMA/HDDMA composite are measured. The dielectric constant and storage modulus of SWNT polyimide composite increased with SWNT concentration. Low percolation (0.06 wt%) and an increase of 113% in storage modulus with 0.2 wt% SWNTs, both indicate good dispersion of SWNTs in the polyimide matrix. The dielectric constants, conductivity for the unaligned SWNT/UDMA/HDDMA composite are isotropic. The electrical and mechanical properties of the randomly dispersed SWNT polyimide composite and SWNT/UDMA/HDDMA composite are used as references when analyzing the aligned counter parts. Different characterization methods are used to assess the alignment of the SWNTs in the polyimide and (UDMA/HDDMA) matrices. A variety of characterization techniques, i.e. microscopy, Raman spectroscopy, electrical conductivity, dynamic dielectric spectroscopy and dynamic mechanical analysis, indicate preferential alignment of SWNTs in two types of polymers: Polyimide and (UDMA/HDDMA). Optical microscope images showed alignment of the SWNTs in the UDMA/HDDMA composite. Inspection of the Raman spectra on aligned SWNT polyimide composite fibers and aligned SWNT/UDMA/HDDMA composite indicates a decrease in the intensity of the tangential peak of the SWNT with increase in the polarizer angle. The difference in the perpendicular and parallel Raman peaks indicate preferential alignment of SWNTs in both the polymer matrices. In the aligned polyimide composite, percolation transition is at 0.2 wt% SWNT concentrations when dielectric constant is measured parallel to the aligned SWNTs. But percolation transition is at 0.65 wt% SWNT concentrations when dielectric constant is measured perpendicular to the aligned SWNTs. Electrical measurements on aligned SWNT polyimide and UDMA/HDDMA composite are highly anisotropic. In both cases, the dielectric constant values parallel to the direction of SWNT alignment are higher than the values perpendicular to the direction of SWNT alignment. To analyze the resulting anisotropy in the dielectric constant, Bruggeman's effective medium approach is used. The effective medium theory predicts the effective dielectric constant of a composite with aligned anisotropic inclusions. The effective dielectric constant, perpendicular to the aligned inclusions and parallel to the aligned inclusions is estimated. The dielectric constant values of aligned SWNT polyimide and aligned SWNT/UDMA/HDDMA composites are compared to the experimental results. Both the values from the theory and experiment show anisotropy in dielectric constant. The theory indicated that the dielectric constant parallel to the aligned inclusions is highly influenced by the dielectric constant of the inclusion and the dielectric constant perpendicular to the aligned inclusions is highly influenced by the dielectric constant of the polymer matrix. Results from the different characterizing techniques indicate that SWNTs are successfully aligned in the polyimide matrix and (UDMA/HDDMA) matrix by electrospinning technique and by an AC electric field respectively.

L’incorporation de nanotubes de carbone dans une matrice polymère permet d’obtenir des matériaux nanocomposites avec des propriétés exceptionnelles. Toutefois, ces dernières dépendent de l’état de dispersion et distribution des nanotubes dans la matrice. Afin de conférer de meilleures propriétés, il est essentiel que le procédé de synthèse des nanocomposites permette une répartition contrôlée des nanotubes dans la matrice. Un procédé de polymérisation in situ, en présence de nanotubes de carbone, a été choisi. Ce dernier permet de contrôler la répartition des nanotubes dans la matrice grâce à l’utilisation des ultrasons. Afin d’optimiser ce procédé, et notamment lors de la polymérisation anionique activée de l’e-caprolactame, l’influence de la présence des nanotubes sur la vitesse de polymérisation et les propriétés rhéologiques du milieu polymérisant a été déterminée. Grâce à une étude calorimétrique suivie d’une étude rhéocinétique, il a été démontré que la présence de nanotubes ralentit la polymérisation et augmente fortement la viscosité du milieu. Cette inhibition provient probablement d’une réaction entre les nanotubes et le catalyseur utilisé pour la polymérisation et dépend donc de l’état de dispersion des nanotubes dans la matrice, lequel peut ainsi être estimé par les études cinétiques. L’étude des propriétés rhéologiques et électriques des nanocomposites à matrice polystyrène et à renforts de nanotubes de carbone a également été entreprise. Suivant l’état de dispersion ainsi que les différents paramètres opératoires, les seuils de percolation électrique et rhéologique ont ainsi pu être déterminés / The introduction of carbon nanotubes into polymers leads to nanocomposite materials with exceptional properties. These later depend, however, on the dispersion and distribution of carbon nanotubes inside the matrix. A key objective, in nanocomposite preparation, is the set up of incorporation processes allowing a good state of dispersion of the nanotubes into the matrix. An in situ polymerization process, coupled with an ultrasound processor, was chosen to best fulfill this objective. The optimization of this process implies the knowledge of the evolution of reaction kinetics and rheological properties during the polymerization. The influence of carbon nanotubes on the anionic activated polymerization of e-caprolactam was investigated by calorimetric and rheokinetic studies. Carbon nanotubes were found to slow down polymerization kinetics and highly increase the viscosity after a certain conversion degree. This inhibition phenomenon could be produced by a reaction between carbon nanotubes and the catalyst employed for the polymerization reaction. The inhibition effect depended also on the state of dispersion of the nanotubes, consequently, kinetic and rheokinetic measurements are an indirect method to estimate the state of dispersion. The electrical and rheological properties of the nanocomposites were also investigated. The influence of the state of dispersion and other parameters, such as temperature, on the electrical and rheological percolation thresholds was identified