The behaviour of iodine, before and after annealing, in pyrolytic carbon (PyC) has been studied using the Rutherford backscattering spectrometry (RBS), X-ray diffraction (XRD) and scanning electron microscopy (SEM). PyC is used as a coating material in the design of the nuclear fuels such as the TRISO particles. TRISO particles are used to produce nuclear energy in nuclear reactors such as the PBMR. Iodine is one of the radioactive fission products produced during the production of nuclear energy by the nuclear fuels. The PyC layers in TRISO particles acts as a barrier for fission products. The main aim of this study was to investigate the effectiveness of PyC as a barrier of iodine diffusion. 360 keV iodine ions were implanted into the PyC to a fluence of 1×1015 iodine ions per cm2, at room temperature. After implantation the PyC samples were annealed (in vacuum) isochronally at 900 °C, 1000 °C, 1100 °C and 1200 °C; all for 9 hours. XRD measurements were performed using a cobalt (Co) XRD spectrometer on θ-2θ configuration; before and after the annealing temperatures. In-lens SEM images were also obtained for the PyC samples before and after heat treatment. RBS measurements were performed using a Van de Graaff accelerator and a 1.6 MeV He+ beam. XRD and SEM were used to study the structure of PyC before and after the annealing. Ion implantation and high temperature treatment affected the structure of PyC. Literature has shown that ion implantation caused structural damages in the implanted region of the PyC, reducing the degree of preferred orientation of the graphitic layers of the PyC in that region. The XRD results showed that high temperature annealing caused an increase in the degree of preferred orientation of the graphitic layers in the PyC used which is in agreement with other studies. Comparison of our SEM results to other reports has shown that the PyC used has a structure similar or close to the laminar structures of PyCs, with medium to high degree of preferred orientation. RBS was used to produce the iodine depth profiles, which provided insight on implantation depth of iodine in PyC as well as iodine behaviour after annealing. The results showed that iodine concentration in the implanted profile decreased with increasing annealing temperature. The full width at half maximum (FWHM) of the iodine profiles, obtained using the computer program Genplot, showed that after heat treatments of 900 °C, 1000 °C and 1100 °C more iodine initially diffused deeper into the PyC bulk than towards the PyC surface. At 1200 °C, the diffusion of iodine towards the PyC surface increased. It was proposed that this iodine behaviour was associated with the changes in the PyC structure due to ion implantation and high temperature treatment of the PyC. The obtained iodine profiles and the corresponding FWHM did not show evidence that the diffusion of iodine in both directions could be attributed to Fickian diffusion mechanism; hence no activation energy for the iodine diffusion in laminar PyC was determined. Copyright / Dissertation (MSc)--University of Pretoria, 2012. / Physics / unrestricted

High-temperature reactors make use of tri-structural coated fuel particles as basic fuel components. These TRISO particles consist of fissionable uranium dioxide fuel kernels, about 0.5 mm in diameter, with each kernel individually encased in four distinct coating layers, starting with a porous carbon buffer, then an inner pyrolytic carbon (IPyC) layer, followed by a layer of ceramic silicon carbide (SiC) and finally an outer pyrolytic carbon layer (OPyC). Collectively, the coating layers provide the primary barrier that prevents release of fission products generated during burn up in the UO2 fuel kernel. It is crucial to understand how the fission products contained within the fuel interact with the coating layers and how they are distributed within the fuel. The first step commonly performed to obtain the information on distribution is removal of the coating layers. The purpose of this study was to investigate the possible use of wet chemical etching techniques with the aim of removing the coating layers of ZrO2 coated fuel particles in a controlled way and to establish experimental parameters for controlled dissolution of irradiated fuel particles. Stepwise dissolution of coated fuel particle coating layers, containing zirconia kernels has been investigated by chemical etching experiments with acidic solutions of different mixtures. The heating methods used include heating by conventional methods, hot plates and a muffle furnace, a reflux-heating system and microwave-assisted digestion. The etching mixtures were prepared from a number of oxidizing acids and other dehydrating agents. The capability of each reagent to etch the layer completely and in a controlled manner was examined. On etching the first layer, the OPyC, the reflux heating method gave the best results in removing the layer, its advantage being that the reaction can be carried out at temperatures of about 130 ºC for a long time without the loss of the acid. The experimental results demonstrated that a mixture composed of equal amounts of concentrated nitric and sulfuric acid mixed with chromium trioxide dissolves the OPyC layer completely. The most favourable experimental conditions for removal of OPyC from a single coated fuel particle were identified and found to depend on the etching solution composition and etching temperature. Light microscopy yielded first-hand information on the surface features of the samples. It allowed fast comparison of etched and untreated sample features. The outer surface of particles prior to chemical etching of the outer pyrolytic carbon layer appeared black in colour with an even surface compared to the etched surfaces which appeared to have an uneven metallic grey, shiny texture. The scanning electron microscope (SEM) examination of the chemically treated outer carbon layer samples gave information on the microstructure and it demonstrated that the outer pyrolytic carbon layer could be readily removed using a solution of HNO3/H2SO4/CrO3, leaving the exposed SiC layer. Complete removal of the layer was confirmed by energy dispersive X-ray spectroscopic (EDS) analysis of the particle surface. For etching the second layer, the silicon carbide layer, microwave-assisted chemical etching was the only heating technique found to be useful. However, experimental results demonstrated that this method has limited ability to digest the sample completely. Also common chemical etchants were found to be ineffective for dissolving this layer. Only fluoride containing substances showed the potential to etch the layer. The results show that a mixture consisting of equal amounts of concentrated hydrofluoric and nitric acid under microwave heating at 200 ºC yielded partial removal of the coating and localized attack of the underlying coating layers. The SEM analyses at different intervals of etching showed: partial removal of the layer, attack of the underlying layers and, in some instances, that attack started at grain boundaries and progressed to the intra-granular features. The SEM results provide evidence that etching of the silicon carbide layer is strongly influenced by its microstructure. From these findings, it is concluded that etching of the silicon carbide under the investigated experimental conditions yields undesirable results and that it does not provide complete removal of the layer. This method has the potential to etch the layer to some extent but has limitations. Copyright / Dissertation (MSc)--University of Pretoria, 2013. / Chemical Engineering / unrestricted

The purpose of this research is to explore the potential of using carbon-infiltrated carbon nanotubes (CI-CNT) as a material for coronary artery stents. Stents are commonly fabricated from metal, which may not perform as well as many polymers and ceramics in biomedical applications. Pyrolytic carbon, a ceramic, is currently used in medical implant devices due to its preferrable biocompatibility properties. Micro-patterned pyrolytic carbon devices can be created by growing carbon nanotubes, and then filling the space between with amorphous carbon via chemical vapor deposition. We prepared multiple samples of two different planar stent-like flexible geometries and smaller cubic structures out of carbon infiltrated carbon nanotubes. These samples were tested in tension to failure. The cubic structures were used for separate compression tests. We also examined existing auxetic patterns for possible application in the stent designs and a second iteration of design and fabrication was performed using data and understanding obtained from the work in the first iteration. Slight changes were made to the mask design and fabrication processes based on the new geometries and testing considerations. The auxetic planar designs were tested in compression to demonstrate flexibility and collect material data. The testing results show that CI-CNTs can be designed and fabricated into flexible geometries capable of stent-like compression. The samples in this work were found to have moduli ranging from 5 to 27 GPa, with the majority being between 10 and 20 GPa. We also found fracture strength greater than 100 MPa, with it sometimes getting as high as 200 MPa. Lastly, fracture strain values were measured, with the maximum reaching 1.4% and the average between 0.75-1%. We also found that the CI-CNTs material lends itself to fracture at weak locations (if present) before the anticipated fracture strength has been reached and concluded that a tightly controlled process (including fabrication machines) environment is necessary to ensure consistent results and a CI-CNT material whose imperfections have been minimized.

The purpose of this research was to design, develop, and test coronary stent designs composed of carbon-infiltrated carbon nanotubes (CI-CNTs). Coronary stents currently have two major complications: restenosis and thrombosis. CI-CNT stents have potential to address both of these issues, and therefore may provide improved clinical outcomes. CI-CNT stent geometry is patterned using high-resolution photolithography that provide advantages in design possibilities.To develop a coronary stent, a standard design process was followed including: background, design specifications, concept generation, development, analysis, and testing. Background research was first completed and general design specifications for coronary stent performance were compiled. Multiple design concepts were generated, evaluated, and finally a design was selected. This stent design was further developed and optimized using analytical tools along with finite element analysis. This stent design used tapered struts in repeating segments to reduce stress and improve radial force. The design was modeled and analyzed as both a flat geometry as well as in a cylindrical configuration. Mechanics of materials equations and geometry specific finite element analysis were used to guide the final coronary stent design. The stent design was tested mechanically, and additional tests were performed to verify the blood compatibility of the CI-CNT material. The flat version of the stent design was manufactured and mechanically tested to verify performance. The performance of the cylindrical stent configuration was analyzed using an FE model of an atherosclerotic artery. This arterial FE model was created and validated by analyzing balloon angioplasty of a common stainless steel stent. The biocompatibility of CI-CNTs was explored and studied. Blood compatibility testing of CI-CNT samples was performed with results comparable in performance to stainless steel. A method of stent deployment was planned, and several other stent design concepts were analyzed. This research demonstrates that a functioning coronary stent can be manufactured from CI-CNTs. The optimized design has potential to address problems currently associated with stents. However, a major challenge for CI-CNT stent designs is meeting the design requirement of sufficient radial force. CI-CNT stents also need to have excellent blood compatibility to justify being used in stent applications.

This thesis is focused on two topics: (i) synthesis and characterization of bilayer graphene and pyrolytic carbon by atmospheric pressure chemical vapor deposition, and (ii) application of graphene in the fabrication of a buckyball memory device. Monolayer and bilayer graphene are semi-metal with zero bandgap. One can induce a bandgap in bilayer graphene by applying a gate voltage in the stacking direction. Thus, bandgap and Fermi level in bilayer graphene can be controlled simultaneously with a double-gate device, making it a useful material for future semiconducting applications. Controlled synthesis of bilayer graphene would be the first step to fabricate bilayer graphene based devices. In this context, we report a uniform and low-defect synthesis of bilayer graphene on evaporated nickel films. Ultra-fast cooling is employed to control the number of layers and sample uniformity. The process is self-limiting, which leads to bilayer graphene synthesis over a wide range of growth-time and precursor flow-rate. Pryolytic carbon is another important carbon nanomaterial, due to its diverse applications in electronic and biomedicalengineering. We employ chemical vapor deposition with ultra-fast cooling technique to synthesize pyrolytic carbon. Furthermore, we elucidate a method to calculate the in-plane crystal size by using Raman spectroscopy. Finally, the use of bilayer graphene in a write-once read-many memory device has been demonstrated. The device showed irreversible switching from low-resistance to high-resistance state, with hysteresis in the transport characteristics. The control sample showed random switching and hysteresis due to electromigration of metal atoms into the active material of the device. We attribute the reliability and performance of the reported device to the ultra-smooth graphene contacts, which additionally inhibits electromigration from the underlying metallic film. Moreover, the memory device showed excellent endurance and retention characteristics.

Biotribology, the study of lubrication, wear and friction within the body, has become a topic of high importance in recent times as we continue to encounter debilitating diseases and trauma that destroy function of the joints. A highly successful surgical procedure to replace the joint with an artificial equivalent alleviates dysfunction and pain. However, the wear of the bearing surfaces in prosthetic joints is a significant clinical problem and more patients are surviving longer than the life expectancy of the joint replacement. Revision surgery is associated with increased morbidity and mortality and has a far less successful outcome than primary joint replacement. As such, it is essential to ensure that everything possible is done to limit the rate of revision surgery. Past experience indicates that the survival rate of the implant will be influenced by many parameters, of primary importance, the material properties of the implant, the composition of the synovial fluid and the method of lubrication. In prosthetic joints, effective boundary lubrication is known to take place. The interaction of the boundary lubricant and the bearing material is of utmost importance. The identity of the vital active ingredient within synovial fluid (SF) to which we owe the near frictionless performance of our articulating joints has been the quest of researchers for many years. Once identified, tribo tests can determine what materials and more importantly what surfaces this fraction of SF can function most optimally with. Surface-Active Phospholipids (SAPL) have been implicated as the body’s natural load bearing lubricant. Studies in this thesis are the first to fully characterise the adsorbed SAPL detected on the surface of retrieved prostheses and the first to verify the presence of SAPL on knee prostheses. Rinsings from the bearing surfaces of both hip and knee prostheses removed from revision operations were analysed using High Performance Liquid Chromatography (HPLC) to determine the presence and profile of SAPL. Several common prosthetic materials along with a novel biomaterial were investigated to determine their tribological interaction with various SAPLs. A pin-on-flat tribometer was used to make comparative friction measurements between the various tribo-pairs. A novel material, Pyrolytic Carbon (PyC) was screened as a potential candidate as a load bearing prosthetic material. Friction measurements were also performed on explanted prostheses. SAPL was detected on all retrieved implant bearing surfaces. As a result of the study eight different species of phosphatidylcholines were identified. The relative concentrations of each species were also determined indicating that the unsaturated species are dominant. Initial tribo tests employed a saturated phosphatidylcholine (SPC) and the subsequent tests adopted the addition of the newly identified major constituents of SAPL, unsaturated phosphatidylcholine (USPC), as the test lubricant. All tribo tests showed a dramatic reduction in friction when synthetic SAPL was used as the lubricant under boundary lubrication conditions. Some tribopairs showed more of an affinity to SAPL than others. PyC performed superior to the other prosthetic materials. Friction measurements with explanted prostheses verified the presence and performance of SAPL. SAPL, in particular phosphatidylcholine, plays an essential role in the lubrication of prosthetic joints. Of particular interest was the ability of SAPLs to reduce friction and ultimately wear of the bearing materials. The identification and knowledge of the lubricating constituents of SF is invaluable for not only the future development of artificial joints but also in developing effective cures for several disease processes where lubrication may play a role. The tribological interaction of the various tribo-pairs and SAPL is extremely favourable in the context of reducing friction at the bearing interface. PyC is highly recommended as a future candidate material for use in load bearing prosthetic joints considering its impressive tribological performance.