Thesis (M.Tech.: Mechanical Engineering)-Dept. of Mechanical Engineering, Durban University of Technology, 2007 xiii, 101 leaves / Polymer nanocomposites may be defined as structures that are formed by infusing layered-silicate clay into a thermosetting orthermoplastic polymer matrix. The nanocomposites are normally particle-filled polymers for which at least one dimension of the dispersed particles is in nanoscale. These clay-polymer nanocomposites have thus attracted great interest in industry and academia due to their exhibition of remarkable enhancements in material properties when compared to the virgin polymer or conventional micro and macro-composites. The present work describes the synthesis, mechanical properties and morphology of nano-phased polypropylene structures. The structures were manufactured by melt- blending low weight percentages of montmorillonite (MMT) nanoclays (0.5, 1, 2, 3, 5 wt. %) and polypropylene (PP) thermoplastic. Both virgin and infused polypropylene structures were then subjected to quasi-static tensile tests, flexural tests, micro-hardness tests, impact testing, compression testing, fracture toughness analysis, dynamic mechanical analysis, tribological testing. Scanning electron microscopy studies were then conducted to analyse the fracture surfaces of pristine PP and PP nanocomposite. X-ray diffraction studies were performed on closite 15A clay and polypropylene composites containing 0.5, 1, 2, 3 and 5 wt. % closite 15A nanoclay to confirm the formation of nanocomposites on the addition of organo clays. Transmission electron miscopy studies were then performed on the PP nanocomposites to determine the formation of intercalated, exfoliated or agglomerated nanoclay structures. Analysis of test data show that the mechanical properties increase with an increase in nanoclay loading up to a threshold of 2 wt. %, thereafter the material properties degrade. At low weight nanoclay loadings the enhancement of properties is attributed to the lower percolation points created by the high aspect ratio nanoclays. The increase in properties may also be attributed to the formation of intercalated and exfoliated nanocomposite structures formed at these loadings of clay. At higher weight loading, degradation in mechanical properties may be attributed to the formation of agglomerated clay tactoids. Results of XRD, transmission electron microscopy studies and scanning electron microscopy studies of the fractured surface of tensile specimens verify these hypotheses.

Developments in the interdisciplinary field of quantum information open up previously impossible abilities in the realms of information processing and communication. Quantum entanglement has emerged as one property of quantum systems that acts as a resource for quantum information processing and, in particular, enables teleportation and secure cryptography. Therefore, the creation of entangled resources is of key importance for the application of these technologies. Despite a great deal of research the efficient creation of entanglement over long distances is limited by inevitable noise. This problem can be overcome by creating entanglement between nodes in a network and then performing operations to distribute the entanglement over a long distance. This thesis contributes to the field of entanglement distribution within such quantum networks. Entanglement distribution has been extensively studied for one-dimensional networks resulting in "quantum repeater" protocols. However, little work has been done on higher dimensional networks. In these networks a fundamentally different scaling, called "long distance entanglement distribution", can appear between the resources and the distance separating the systems to be entangled. I reveal protocols that enable long distance entanglement distribution for quantum networks composed of mixed state and give a few limitations to the capabilities of entanglement distribution. To aid in the implementation of all entanglement distribution protocols I finish by introducing a new system, composed of an optical nanofibre coupled to a carbon nanotube, that may enable new forms of photo-detectors and quantum memories.

This project addressed two main problems pertaining to Al₂O₃-FeAl2O4 nanocomposites developed via solid state precipitation: the mechanisms for precipitation in ceramic solid solution via reduction reaction, and the mechanisms for the improved mechanical properties and wear resistance of the developed Al2O3-FeAl2O4 nanocomposites. A model was proposed for precipitation in ceramic solid solutions via reduction reactions (the PRCS model). The thermodynamics of reduction reactions during aging treatments under various atmospheres were calculated and discussed relative to the second phase precipitate formation. Attempts were made to measure the corresponding diffusion kinetics using a new theory developed here based on volume fraction profiles of second phase particles in the aged samples. It was found that the measured apparent oxygen vacancy diffusivities conform well to the oxygen vacancy grain boundary diffusion coefficients reported in the literature, and the measured apparent matrix diffusivity conforms well to the Fe3+ ion matrix diffusion coefficients reported in literature. Based on the thermodynamics calculations, diffusion kinetics and some essential mechanisms that were discussed, the PRCS model was proposed. This has two aspects: macroscopic and microscopic. The macroscopic aspect of PRCS model was mainly used to explain the general aspects of microstructure and the distribution of intergranualar second phase particles. The microscopic aspect of the PRCS model was mainly used to explain the precipitation of intragranualar nanoparticles. The mechanical properties, thermal residual stress and wear resistance of selected Al2O3-FeAl2O4 nanocomposites were measured. The results revealed that the Al2O3-FeAl2O4 possessed improved fracture toughness (by around 46%), flexural strength (by around 30%) and abrasive wear resistance (by a factor of around 5) with respect to monolithic alumina. Several mechanisms were proposed to explain the improvements in both mechanical properties and wear resistance. Compressive residual stress was found in the surface layer of Al2O3-FeAl2O4 nanocomposites due to the thermal expansion coefficient mismatch between surface layer and bulk parts. Such residual stress was also interpreted as the main reason for the improvements in both mechanical properties and wear resistance.

This dissertation summarises the study of different aspects of the aerosol-assisted chemical vapour deposition (AACVD) technique for the production of multi-wall carbon nanotubes (MWCNTs). Upscaling the synthesis while retaining the quality of MWCNTs has been a prime objective throughout the work. A key aspect of this work was the study of different growth parameters and their influence on the homogeneity of the products across the reactor. The effect of the precursor composition on the yield and quality of MWCNTs were also investigated. It was shown that the synthesis rate can be significantly (60 – 80 %) increased by tuning the composition of the precursor. Moreover, by optimising the synthesis recipe and using a larger reactor, the synthesis rate and efficiency of the precursor were increased fivefold (up to 14 g/hr) and twice (up to 88 %) respectively. Large area (up to 90 cm²), mm-thick carpets of MWCNTs which were both free-standing and on substrate were produced. The carpets could withstand normal handlings without tearing apart, making them suitable for macroscopic characterisations and applications. By in-situ qualitative and quantitative gas analysis of the atmosphere of the reactor, the thermocatalytic cracking behaviour of 25 precursors was investigated and a mechanism for successive formation of different hydrocarbon fragments inside the reactor was proposed. A number of dedicated gas analysis methods and apparatuses such as a probe for zone-by-zone gas analysis of reactor and a heated chamber for preparation of standard gas analysis samples were developed to explore some of the least investigated aspects of the thermocatalytic cracking of precursors. Mapping the reactor revealed that some single-wall and double-wall carbon nanotubes (SWCNTs and DWCNTs) were also produced near the exhaust of the reactor. The SWCNTs were partly covered by fullerene-like species and resembled different forms of carbon nanobuds. In addition, the effect of the electron beam on the interaction of the SWCNTs and the fullerene-like species was studied in situ using high-resolution transmission electron microscopy (HRTEM).

This work presents the development and application of analytical, numerical, and experimental methods for the study of thermal and electrical transport in nanoscale systems, with special emphasis on those materials and phenomena which can be important in thermoelectric and semiconductor device applications. Analytical solutions to the Boltzmann transport equation (BTE) using the relaxation time approximation (RTA) are presented and used to study the thermal and electrical transport properties of indium antimonide (InSb), indium arsenide (InAs), bismuth telluride (Bi₂Te₃), and chromium disilicide (CrSi₂) nanowires. Experimental results for the thermal conductivity of single layer graphene supported by SiO₂ were analyzed using an RTA-based model and compared to a full quantum mechanical numerical BTE solution which does not rely on the RTA. The ability of these models to explain the measurement results as well as differences between the two approaches are discussed. Alternatively, numerical solutions to the BTE may be obtained statistically through Monte Carlo simulation for complex geometries which may prove intractable for analytical methods. Following this approach, phonon transport in silicon (Si) sawtooth nanowires was studied, revealing that thermal conductivity suppression below the diffuse surface limit is possible. The experimental investigation of energy transport in nanostructures typically involved the use of microfabricated devices or non-contact optical methods. In this work, two such approaches were analyzed to ascertain their thermal behavior and overall accuracy as well as areas for possible improvement. A Raman spectroscopy-based measurement design for investigating the thermal properties of suspended and supported graphene was examined analytically. The resulting analysis provided a means of determining from measurement results the thermal interface conductance, thermal contact resistance, and thermal conductivity of the suspended and supported graphene regions. Previously, microfabricated devices of several different designs have been used to experimentally measure the thermal transport characteristics of nanostructures such as carbon nanotubes, nanowires, and thin films. To ascertain the accuracy and limitations of various microdevice designs and their associated conduction analyses, finite element models were constructed using ANSYS and measurements of samples of known thermal conductance were simulated. It was found that designs with the sample suspended were generally more accurate than those for which the sample is supported on a bridge whose conductance is measured separately. The effects of radiation loss to the environment of certain device designs were also studied, demonstrating the need for radiation shielding to be at temperatures close to that of the device substrate in order to accurately calibrate the resistance thermometers. Using a suspended microdevice like those analyzed using finite element analysis, the thermal conductivities of individual bismuth (Bi) nanowires were measured. The results were correlated with the crystal structure and growth direction obtained by transmission electron microscopy on the same nanowires. Compared to bulk Bi in the same crystal direction, the thermal conductivity of a single-crystal Bi nanowires of 232 nm diameter was found to be 3 - 6 times smaller than bulk between 100 K and 300 K. For polycrystalline Bi nanowires of 74 nm to 255 nm diameter the thermal conductivity was reduced by a factor of 18 - 78 over the same temperature range. Comparable thermal conductivity values were measured for polycrystalline nanowires of varying diameters, suggesting a grain boundary scattering mean free path for all heat carriers in the range of 15 - 40 nm which is smaller than the nanowire diameters. An RTA-based transport model for both charge carriers and phonons was developed which explains the thermal conductivity suppression in the single-crystal nanowire by considering diffuse phonon-surface scattering, partially diffuse surface scattering of electrons and holes, and scattering of phonons and charge carriers by ionized impurities such as oxygen and carbon of a concentration on the order of 10¹⁹ cm⁻³. Using a similar experimental setup, the thermoelectric properties (Seebeck coefficient, electrical conductivity, and thermal conductivity) of higher manganese silicide (HMS) nanostructures were investigated. Bulk HMS is a passable high temperature thermoelectric material which possesses a complex crystal structure that could lead to very interesting and useful nanoscale transport properties. The thermal conductivities of HMS nanowires and nanoribbons were found to be reduced by 50 - 60 % compared to bulk values in the same crystal direction for both nanoribbons and nanowires. The measured Seebeck coefficient data was comparable or below that of bulk, suggesting unintentional doping of the samples either during growth or sample preparation. Difficulty in determining the amorphous oxide layer thickness for nanoribbons samples necessitated using the total, oxide-included cross section in the thermal and electrical conductivity calculation. This in turn led to the determined electrical conductivity values representing the lower bound on the actual electrical conductivity of the HMS core. From this approach, the measured electrical conductivity values were comparable or slightly below the lower end of bulk electrical conductivity values. This oxide thickness issue affects the determination of the HMS nanostructure thermoelectric figure of merit ZT as well, though the lower bound values obtained here were found to still be comparable to or slightly smaller than the expected bulk values in the same crystal direction. Analytical modeling also indicates higher doping than in bulk. Overall, HMS nanostructures appear to have the potential to demonstrate measurable size-induced ZT enhancement, especially if optimal doping and control over the crystallographic growth direction can be achieved. However, experimental methods to achieve reliable electrical contact to quality four-probe samples needs to be improved in order to fully investigate the thermoelectric potential of HMS nanostructures. / text

<p>Thin films of cobalt oxide, iron oxide and niobium oxide, and nanostructured thin films of iron oxide, titanium oxide and multilayered iron oxide/titanium oxide have been deposited by Atomic Layer Deposition (ALD). The metal oxides were grown using the precursor combinations CoI2/O2, Fe(Cp)2/O2, NbI5/O2 and TiI4/H2O. The samples were analysed primarily with respect to phase content, morphology and growth characteristics.</p><p>Thin films deposited on Si (100) were found to be amorphous or polycrystalline, depending on deposition temperature and the oxide deposited; cobalt oxide was also deposited on MgO (100), where it was found to grow epitaxially with orientation (001)[100]Co3O4||(001)[100]MgO. As expected, the polycrystalline films were rougher than the amorphous or the epitaxial films. The deposition processes showed properties characteristic of self-limiting ALD growth; all processes were found to have a deposition temperature independent growth region. The deposited films contained zero or only small amounts of precursor residues.</p><p>The nanostructured films were grown using anodic aluminium oxide (AAO) or carbon nanosheets as templates. Nanotubes could be manufactured by depositing a thin film which covers the pore walls of the AAO template uniformly; free-standing nanotubes retaining the structure of the template could be fabricated by removing the template. Multilayered nanotubes could be obtained by depositing multiple layers of titanium dioxide and iron oxide in the pores of the AAO template. Carbon nanosheets were used to make titanium dioxide nanosheets with a conducting graphite backbone. The nucleation of the deposited titanium dioxide could be controlled by acid treatment of the carbon nanosheets.</p>

The successful utilization of carbon nanomaterials in future electron spin-based technologies is highly dependent upon the ability to control their assembly at the nanoscale to form tailored solid-state architectures. Spin active metallofullerenes (MFs), Sc@C₈₂ and La@C<sub>82,/sub>, can be self assembled in 3D fullerene crystals or inside a carbon nanotube to form peapod structures. Single walled carbon nanotubes (SWCNTs) are an architect material to potentially allow the formation of 1-D spin chains. SWCNTs should be optimised to allow formation of spin chains and free of magnetic catalyst and carbon impurities, which have previously limited investigations of SWCNT spin properties. To address this, SWCNTs produced by laser ablation with a non-magnetic PtRhRe catalyst were purified through a multiple step centrifugation process in order to remove amorphous carbon and catalyst impurities. Centrifugation of SWCNT solutions resulted in sedimentation of carbon nanotube bundles containing clusters of catalyst particles, while isolated nanotubes with reduced catalyst particle content remained in the supernatant. Electron paramagnetic resonance (EPR) signals were detected only for samples which contained catalyst particles, with the ultracentrifuged SWCNTs showing no EPR signal at X-band (9.4 GHz) and fields ≤0.4 T. Integration of MFs into future devices requires a clear understanding of the nature of the spin and spin-spin interactions. Evaluating the spin properties of MFs, in both 3D (crystals) and 1D (peapods), will identify the spin-spin interactions and the affect of the surrounding SWCNT. Diluting spin active Sc@C₈₂ and La@C₈₂ MFs in a diamagnetic C₆₀ matrix, between 0.4% and 100%, permitted the tuning of the mean fullerene separation and thus interfullerene spin interactions. In dilute concentrations of MFs the hyper ne structure was resolved in EPR and with increasing concentration exchange narrowing was observed as a single narrow EPR peak. Encapsulation of Sc@C₈₂ MFs, of varying dilutions, into purified SWCNTs allowed formation of highly ordered 1-D array of metallofullerenes. Changing the spin environment from 3D crystal to 1D peapod resulted in the loss of the observed hyperfine structure in EPR. A single narrow peak was observed for Sc@C₈₂:C₆₀ peapods, indicating significant affect of the surrounding SWCNT structure upon the spin interactions of 1D metallofullerenes. Peapods of Ce@C₈₂ showed a similar EPR signal, suggesting that the observed narrow peak arises from charge transfer between the MF cage and the surrounding SWCNT.

Optoelectronic characterisation techniques are assessed in their application to three solar cell systems. Charge injection barriers are found in PbS/ZnO colloidal quantum dot solar cells through the use of temperature dependent current-voltage and capacitance-voltage measurements. The injection barriers are shown to complicate the Mott-Schottky capacitance analysis which determines built-in bias and doping density. A model that incorporates depletion capacitance and a constant capacitance arising from the injection barriers is given to explain the Mott-Schottky plots. The junction mechanism at the PbS/ZnO interface is found to transition from excitonic to p-n behaviour based on the amount of UV photodoping the cell has received. External quantum efficiency analysis at different photodoping times reveals a growing charge collection region within the material, demonstrating the shift to p-n behaviour. This is further supported by the observance of depletion capacitance behaviour after, but not before, UV photodoping. Defects within GaAs cells containing InAs quantum dots are found to enhance the sub-bandgap performance of the cell using external quantum efficiency analysis. This is verified by illuminated current-voltage analysis using a 1000 nm high pass optical filter to block photons of larger energy than the bandgap. Using capacitance-voltage analysis, high temperature rapid thermal annealing is shown to induce defects in dilute nitride cells, which explains the drop in open circuit voltage compared to lower temperature annealed cells. The doping level of polymer solar cells exposed to air is found to increase with continued exposure using Mott-Schottky capacitance analysis. Current-voltage measurements show the formation of an Al2O3 barrier layer at the polymer/aluminium interface. The usefulness of capacitance-voltage measurements to probe the polymer/fullerene interface is investigated in thermally evaporated thiophene/C60 cells.

Nanostructures are promising building blocks for quantum technologies due to their reproducible nature and ability to self-assemble into complex structures. However, the need to control these nanostructures represents a key challenge. Hence, this thesis investigates the manipulation and creation of quantum states in certain nanostructures. The results of this thesis can be applied to quantum information processing and to extremely sensitive magnetic-field measurements. In the first research chapter, we propose and examine methods for entangling two (remote) nuclear spins through their mutual coupling to a transient optically excited electron spin. From our calculations we identify the specific molecular properties that permit high entangling power gates for different protocols. In the next research chapter, we investigate another method to create entanglement; this time between two remote electronic spins. This method uses a very sensitive magnetic-field sensor based on a crystal defect that allows the detection of single magnetic moments. The act of sensing the local field constitutes a two-qubit projective measurement. This entangling operation is remarkably robust to imperfections occurring in an experiment. The third research chapter presents an augmented sensor consisting of a nitrogen-vacancy centre for readout and an `amplifier' spin system that directly senses tiny local magnetic fields. Our calculations show that this hybrid structure has the potential to detect magnetic moments with a sensitivity and spatial resolution far beyond that of a sensor based on only a nitrogen-vacancy centre, and indeed this may be the physical limit for sensors of this class. Finally, the last research chapter investigates measurements of magnetic-field strength using an ensemble of spin-active molecules. Here, we describe a quantum strategy that can beat the common standard strategy. We identify the conditions for which this is possible and find that this crucially depends on the decoherence present in the system.

A resonant cavity operating in TE011 mode was used to study the adsorption response of single walled carbon nanotubes (SWCNTs) and other nanomaterials for different types of gas molecules. The range of the frequency signal as a probe was chosen as geometry dependent range between 9.1 -9.8 GHz. A highly specific range can be studied for further experiments dependent on the type of molecule being investigated. It was found that for different pressures of gases and for different types of nanomaterials, there was a different response in the shifts of the probe signal for each cycle of gassing and degassing of the cavity. This dissertation suggests that microwave spectroscopy of a complex medium of gases and carbon nanotubes can be used as a highly sensitive technique to determine the complex dielectric response of different polar as well as non-polar gases when subjected to intense electromagnetic fields within the cavity. Also, as part of the experimental work, a range of other micro-porous materials was tested using the residual gas analysis (RGA) technique to determine their intrinsic absorption/adsorption characteristics when under an ultra-high vacuum environment. The scientific results obtained from this investigation, led to the development of a chemical biological sensor prototype. The method proposed is to develop operational sensors to detect toxin gases for homeland security applications and also develop sniffers to detect toxin drugs for law enforcement agency personnel.