The main objective of the study was to characterise, by electron spin resonance (ESR) spectroscopy, novel halogen containing a* radicals. These species are formed by ?-irradiation in a variety of halogen containing systems at liquid nitrogen temperatures. In Chapter One, a brief description of the first halogen a* radical to be identified, the Vx centre in potassium chloride (C12.-), is given in order to illustrate the general magnetic properties of the species. The dependence of these properties on the host matrix is also described. Accepted radiation damage mechanisms are presented with particular reference to dihalogen a* radicals. Some theoretical aspects of the ESR experiment is discussed in Chapter Two which explains briefly some of the phenomena encountered in the study. Sample preparation and analysis are also mentioned. Chapter Three describes the characteristics of the simplest halogen containing a* radical: the hydrogen halide radical anion. Hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide radical anions isolated in a variety of host matrices are reported. The large matrix dependence of their magnetic parameters is explained in terms of intermolecular hydrogen bonding to the halogen. Attention is focused on nitrogen-halogen a* radicals in Chapter Four, where they are shown to be radiolytically formed in ammonium halides, mono, di and trialkylammonium iodides and monoalkylammonium bromides. Alkylamanium chloride radicals could not be identified. Chapter Five primarily explores the effect of the halide counter ion on the solid-state radiolysis of some tetraalkylammonium, trialkylsulphonium and trialkylsulphoxonium cations. During the course of the investigation, sulphur-halogen a* radicals are identified in the trialkylsulphonium salts after annealing. The last chapter investigates the factors which determine the type of species formed following electron capture by carbon halogen bonds. Both adducts and a* radicals are characterised and with particular reference to the specific example of iodoacetamide, consideration is given to the factors influencing their stability.

An investigation of panel crack formation in steel ingots was undertaken to improve understanding of the mechanisms by which they develop and to evaluate possible solutions to the problem. The investigation revealed that two distinct types of panel cracks, both of which are partly caused by intermediate-temperature embrittlement of steel involving aluminum nitride precipitation, operate under different mechanisms. Isothermal, physical modelling experiments were conducted to determine the flow patterns, velocity profiles and flame geometry in a bottom-fired soaking pit and the resultant effects on heat transfer. An investigation involving comparison with analytical solutions determined the optimum numerical method to employ for the mathematical modelling of complex, two-dimensional, transient, heat-conduction problems. This method was formulated to calculate the temperature distribution in a steel ingot during the various processing stages from initial casting up to rolling and was verified with industrial measurements. A transient, elasto-visco-plastic, thermal-stress model employing the finite-element method was formulated, developed and verified using analytical solutions. Based on the temperatures calculated by the finite-element, heat-transfer model as input data, the transient, internal stress state of the ingot was calculated, taking into account the effects of phase-transformation volume changes and kinetics, creep, and temperature-dependent mechanical property behavior. The simulated stress histories were found to be directly linked to the progress of the phase-transformation front and were used to clarify the role of stress generation in panel crack formation. Finally, the results of a metallurgical investigation of steel ingot samples containing off-corner panel cracks were synthesized with the results of the physical and mathematical models to determine mechanisms and to suggest solutions for the formation of both mid-face and off-corner panel cracks. Mid-face panel cracks are apparently formed during air cooling when the mid-face surface is between the Ar₁ and 500 °C. Off-corner panel cracks appear to initiate internally during the early stages of reheating, but do not propagate to the surface until air cooling after removal from the soaking pit. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

No description available.

Silicon carbide is known for its potential in high power, high radiation and high temperature applications. It is also one of the first materials observed with phenomenon of electroluminescence. Depending on the mechanism of recombination, carriers inside silicon carbide recombine and release photons at different wavelengths. As one of the third-generation semiconductors, many studies focus on the effects of defects on silicon carbide device stability and performance. Especially for defects like stacking faults, which can be generated either during fabrication or induced by current under forward bias, can cause severe device degradation and limits the use of silicon carbide. By testing electroluminescence of silicon carbide, one can analyses the recombination event and identify the defects that trapped carriers, as each recombination mechanism would be shown as a unique emission peak on the sample EL spectra. In addition to the as-grown and recombination-induced defects, the changes of spectrum due to stress and chemical etching indicate the influence of external factors to the defects that are either existed prior to the external forces or that were induced during the testing. Such analysis could be helpful to understand the defect generation mechanism, reduce the density of the defects and to create innovative ideas for future applications. A general introduction to silicon carbide will be given in Chapter 1 with some detailed description of silicon carbide defect generation and characterization mechanisms in Chapter 2. In Chapters 3 and 4, the focus is to analyse the external effects to the spectrum of 4H silicon carbide, like chemical etching and mechanical stress. Before giving the conclusion in Chapter 6, Chapter 5 will be focusing on analysing the effect of external forces on the silicon carbide with stacking faults existed prior to the testing. / Thesis / Master of Applied Science (MASc)

No description available.

The oscillatory de Haas-van Alphen (DHVA) magnetization has been studied in Pt crystals containing more than 100 ppm vacancies. Magnetic fields as high as 75 kG were used. The oscillations were observed at temperatures as low as 0.45 k, and found to be strongly attenuated by the vacancies in this concentration range. The emphasis of this work is on the measurement of this attenuation for the purpose of studying conduction electron scattering due to single vacancies. Dingle (scattering) temperatures due to vacancies are reported for four cyclotron orbits with the field in a (110) plane, along with a new measurement of the cyclotron effective mass (m* = 2.31 ± 0.03) for the electron orbit 33° away from <100>. Vacancies were generated by quenching Pt single crystals from temperatures as high as 1730 °C in air, using a technique which minimizes the induced strain. The vacancy contribution to the electron scattering rate was separated by measuring the Dingle temperature in both quenched and annealed specimens which had been subjected to the same quenching process. The results suggest that there is only a moderate variation in this scattering rate over the s-p-like electron sheet of the Fermi surface. However, the scattering rate for the d-like open hole sheet, which contacts the Brillouin zone, is about 49% larger than that for the electron sheet. This anisotropy is attributed mainly to the lattice distortion around a vacancy and to the difference between the hole and electron wave-function symmetries.

Extrusion is a continuous solid state deformation process which is widely used in the aluminium industry. The demand for aluminium extrudates are growing and extruders are pressurized to extrude products as fast as possible without lowering the quality of the product. Important extrusion parameters and conditions are exit temperature, extrusion speed and alloy composition. It is widely accepted in extrusion industry that extrusion surface defects increase when the extrusion speed and exit temperature are increased for a constant alloy. One of the major surface defects is the so-called die pick-up and it is presently uncertain if increase with extrusion speed (from a low 25m/min) would result in an increase of the number of die pick-up defect.Die pick-up appears like a scratch mark or comet on the surface of the extrudate which damages the appearance. Previous research suggests that second phase particles, eutectic reactions (555°C - 600°C), extrusion process conditions and die conditions may influence the cause of die pick-up. However the influencing factors for die pick-up are not well established.The research started by determining the lowest melting temperature for AA6060 alloy as this temperature limit the highest temperature above which incipient melting starts. This temperature corresponds to the eutectic melting temperature for AA6060 alloy. Eutectic melting was only detected above 610°C and therefore the exit temperature could be increased to a maximum of 610°C. For an AA6xxx alloy system the lowest melting temperature is 555°C if Mg2Si and excess silicon were present. However as Mg2Si may have fully dissolved into the solid solution, no reaction can take place.A preliminary investigation was conducted to study the characteristics of the newly installed extrusion control and monitoring system. Through this study the relationship between the set extrusion speed and the actual extrusion speed was established. It was found that the actual extrusion speed was lower than the set extrusion speed and was further complicated by the capacity limit of the extrusion pressure. Exit temperature measurements were accurate, however it was measured about 1m away from the die exit. Experiments were carried out to estimate the exit temperature drop and hence the exit temperature measurements were corrected accordingly.Thus, the aim of the present research was to establish the relationship between die pick-up and extrusion conditions (extrusion speed, exit temperature and die condition) and to propose the likely formation mechanism for die pick-up.In this research AA6060 alloy was used and was extruded at 25m/min, 30m/min, 35m/min, 40m/min and 45m/min. The exit temperature was found to increases from 542°C to 567°C. Three types of die pick-up was identified which were named as normal pick-up, die line pick-up and lump pick-up. Normal pick-up occurred regardless of the extrusion speed and exit temperature; however the amount of normal pick-up did not increase when the extrusion speed was increased. Die line pick-up occurred when the extrusion speed was 45m/min and appeared only on the die lines. Lump pick-up is not significant since it was very rare.AA6060 (0.4%Mg and 0.5%Si) alloy has about 0.27% excess silicon and therefore at 555°C, Mg2Si particles react with aluminium and excess silicon to form liquid. However normal pick-up and die line pick-up still occurred at temperatures lower and higher than 555°C and therefore it confirms that eutectic reactions do not influence formation of pick-up. Therefore die pick-up is most likely to be caused due to a mechanical process rather than a metallurgical process.

Nuclear techniques such as perturbed angular correlation (PAC) sample the hyperfine interactions of a large number of probe atoms in specific crystallographic sites. Real crystals contain static defects producing a distribution of electric field gradients (EFGs) that add to the ideal EFG of the crystal at any given probe site. Also, dynamic defects like moving vacancies and interstitial atoms can be present in the crystal and contribute to the distribution of EFGs. The distribution of EFGs leads to line broadening and a change in the observed asymmetry parameter η since the total EFG no longer has the symmetry of the perfect crystal. When both defects are present in a material, obtaining quantitative information from the analysis of PAC spectra is usually very difficult since great care has to be taken to ensure that the source of line broadening is identified correctly. In order to relate the relationship between the static line broadening and changes in the asymmetry parameter η, a uniform random distribution of point charges was used to simulate the static defect EFG. PAC spectra collected on cubic niobium metal, cubic stabilized zirconia and Nb-doped tetragonal zirconia were fitted with this model. Although the quality of the fits is good, more work is needed to clarify the relationship between the new model parameters and the line broadening and asymmetry parameter derived from conventional model fits. The PAC spectra of Nb-doped tetragonal zirconia were fitted with a conventional static model to establish a reliable relationship between line broadening and the asymmetry parameter when only static defects are present in a sample. To account for effects of dynamic defects, a four state stochastic model for vacancy motion was adapted in order to include the line broadening and changes in the asymmetry produced by static defects. As a result, the activation energies corresponding to the rates at which a oxygen vacancy is trapped by, detraps from, and hops among equivalent sites about a PAC probe atom were calculated. The values that were found are physically reasonable, indicating that the dynamics of an oxygen vacancy around a PAC probe atom are satisfactorily described. / Graduation date: 2003

This thesis uses multiscale computational modelling to find the fundamental principles that govern defects forming during the operation of new electro-optical devices and the processing of spider silk fibers. The generalized approach developed in this thesis bridges engineering devices and biological processes based on liquid crystalline materials. / Three types of defects are encountered: inversion walls, lines and points. Inversion wall defects are found in the electro-optical device when a nematic thin film undergoes a temperature-induced surface anchoring transition. Point defects naturally occur in the tubular extrusion duct of spiders, while line defects present close topological connections with point defects and are widespread in many high-performance industrial fibers. Three models are used in this thesis and their usage is dependent on the characteristics of the defects studied. / In the case of inversion wall defects, computational modelling is used to verify, complement and analyze experimental measurements made with fluorescence confocal polarizing microscopy by our collaborator at the Georgia Institute of Technology. The various simulation results agree and explain very well experimental observations and provide a thorough understanding of the wall defects behavior. A computational technique is developed to enable the precise determination of the interaction between the liquid crystal and the device substrate. Understanding the behavior of wall defects and estimating interfacial properties are indispensable to the development and optimization of the electro-optical device as they affect properties like temperature of operation, switching voltages and response time. / Computational modelling is also used to investigate the behavior of nematic point defects confined in cylindrical cavities as observed along spiders' spinning apparatus, and to examined textural connections with other well know structures seen in industrial fibers. The various scenarios investigated include: interactions between point defects, topological transformations between point, line and ring defects as well as interactions between ring defects. The simulation results agree and complement previous investigations but also offer a new fundamental understanding on the nature and stability of defects in cylindrical cavities. Understanding the behavior of nematic point and line defects in cylindrical geometries is important as they play a fundamental role in the processing of natural and industrial high-performance fibers.

The defects and fault tolerance study is essential in the QCA devices in order to know its characteristics. Knowing the characteristics, one can understand the flow of information in a QCA system with and without manufacturing and operational defects. The manufacturing defects could be at device level or cell level. At the device level, the cell could be rotated, displaced vertically or horizontally, the cell could be missing or the size of the cell could be different. At the cell level, there could be a missing dot, dot could be displaced from its position or the size of the dots could be different. The operational defects are due to its surrounding, such as temperature or stray charge. Each of these defects and fault tolerances can be studies in detail in order to find the optimum working conditions where the information can be safely transmitted to the appropriate locations in the device.The theoretical studies have shown that at absolute temperature and without any defect, the QCA devices are operational. But it is almost impossible to manufacture a perfect or defect free device, and also it is impractical to think about operating a system at absolute zero temperature environment.Therefore, it is important to investigate the fault tolerant properties with defects and higher temperatures to see how far the QCA device can operate safely. Many studies have been done to investigate the fault tolerant properties in QCA devices. However, these studies have not completely exhausted the study of defects and temperature effects. In this study, the dot displacement and missing dots with temperature effects are investigated for the basic QCA devices and a Full Adder. In order to study fault tolerant properties, the existing theoretical model and computer simulation programs have been expanded and used. The defect characteristics have been simulated using normal distribution. / Department of Physics and Astronomy