As an electromagnetic response detection technique, non-resonant microwave absorption (NRMA) has been without doubt, one of the fundamental tools in characterizing high temperature superconductors (HTSC). The technique can explicitly give factual information on flux pinning, granularity, magnetization, and detection of iota superconducting phases among many more. The emergence of iron pnictides superconductors has brought an enormous impact on HTSC field due to their relatively high 𝑇c, high critical fields 𝐵c2, huge critical current density and low anisotropy. Accordingly, they look appealing candidates in industrial applications more especially in high magnetic field applications. As of yet, its electromagnetic response particularly the low field microwave absorption (LFMA) or the non-resonant microwave absorption (NRMA) is relatively unknown. Consequently, in this work, systematic studies have been done on SmFeAs(O,F), superconductors to determine the low field sweep microwave absorption. Furthermore, effect of varying temperature, microwave power and field modulation amplitude on NRMA line shape have been addressed and the results obtained are compared with NRMA results of cuprates superconductors. Interestingly, the NRMA line shape has been found to evolve as a function of temperature, microwave power and field modulation amplitude. A structure i.e a broad peak 1 and a narrow peak 2 have been identified. Furthermore, the line shape shows a phase reversal at moderately high microwave power. This dissertation presents the theoretical background of superconductors, experimental techniques, working principles of the equipments, results, discussions and conclusions. As pertains to the future work, recommendations have been suggested in trying other forms of sample and also different sample materials of iron based superconductors to fully understand the NRMA and ensure a progressive and continuous work in this field. Also, we will carry out extensive studies on critical current density, fluxon dynamics and irreversibility fields on iron-based superconductors by means of NRMA technique. / Physics / M. Sc. (Physics)

The interfacial properties of a surfactant in a CO₂-aqueous system at a temperature above 100 °C, and how they influence foams are essentially unknown. A cationic surfactant, C₁₂₋₁₄N(EO)₂ in the protonated state below pH 5.5, was demonstrated to be soluble in an aqueous phase with up to 22% total dissolved salt (TDS) at 120 °C. Moreover, the strong solvation in brine (high cloud point) and simultaneous affinity for CO₂ led to significant adsorption of the surfactant at the CO₂-water interface. Given that the surfactant favored the brine phase over the CO₂ phase, the preferred curvature was a CO₂-in-water (C/W) macroemulsion (foam). The surfactant stabilized foam in the presence of crushed calcium carbonate at ~ pH 4 upon suppressing the dissolution of calcium carbonate upon addition of Ca²⁺ and Mg²⁺ according to the common ion effect. Cationic alkyltrimethylammonium surfactants with an alkyl tail of average carbon number less than 15 were soluble in 22% TDS brine up to 120 oC. The head group was properly balanced with a C₁₂₋₁₄ hydrocarbon tail for a sufficiently dense surfactant layer at the CO₂-water interface to reduce the interfacial tension. For C₁₂₋₁₄N(CH₃)₃Cl the solubility in brine and the surfactant adsorption were sufficient to stabilize C/W foam at 120 °C in both a crushed calcium carbonate packed bed (76 Darcy) and a capillary tube at the downstream of the bed. The stability of the foam at high temperature may be attributed to the high surfactant adsorption at the interface. The use of nonionic surfactants as a foam stabilizer is usually limited by their poor aqueous solubility at elevated temperatures, particularly at high salinity. A nonionic surfactant C₁₂₋₁₄(EO)₂₂ with high degree of ethoxylation gave higher salt tolerance at elevated temperature. The surfactant stabilize C/W foam at 80 °C in the presence of 90 g/L NaCl brine in a 30 Darcy sand pack, which has not yet been reported by a nonionic surfactant. Both the formation of strong foam in the porous media and the low of oil-brine partition coefficient suggest C₁₂₋₁₄(EO)₂₂ is a potential candidate for a CO₂ EOR field trial. / text

High alloy Fe-Cr-Ni-C austenitic stainless steels have become the principal alloys for use in steam-methane reforming furnaces within the petrochemical industry. Each furnace contains a large array of vertically oriented centrifugally cast tubes through which a mixture of methane and steam is flowed across a nickel-oxide catalyst in order to obtain a mixture of hydrogen, carbon monoxide and carbon dioxide and water commonly known as synthesis gas (or syngas). Generally, the tubes operate at temperatures between 850-1050°C, internal pressures between 1-3.5MPa and are expected to withstand service lives in excess of 100,000 hours. The combination of high temperatures and moderate stresses causes creep to be the dominant failure mechanism experienced by these tubes in service. The HP austenitic alloys are the latest in a series of heat resisting (H-series) stainless steels developed to provide high temperature strength, ductility, and corrosion resistance in the oxygen, carbon, and sulphur rich environments typical of these furnaces. Extensive work has been carried out to optimise HP alloys’ microstructure in order to maximise the alloy’s creep resistance. Strength increases have largely been realized through the use of niobium and/or titanium additions, which modify the primary precipitates (formed during solidification) and secondary precipitates (formed during exposure to the service temperatures). These strength increases have typically been observed during laboratory accelerated creep testing of the ‘modified’ HP alloys where the temperature and/or stress is increased to achieve failure of the material within reasonable time period (typically between 1000-2000 hours). However, since the duration of typical accelerated creep tests often represent less than 2% of the tubes’ actual service life, uncertainty surrounds the validity of using this testing method as the basis to predict the tubes actual service life. This uncertainty has largely arisen due to the significant microstructural evolution that occurs within these alloys during prolonged service exposure and is not captured within the typical accelerated testing time-frame. In the present work, the microstructures of HP alloys modified with a single addition of niobium (HP-Nb) and dual additions of niobium and titanium (HP-NbTi) have been characterized in the as-cast condition and after long-term (10,000 hours) isothermal laboratory ageing at 1000, 1050 and 1100°C. The main focus of this study is to provide further insight into the microstructural features that increase the HP-NbTi alloy’s creep resistance in comparison to the HP-Nb alloy when performing accelerated creep testing and determine if these microstructural features remain stable during long-term ageing. The microstructure and crystallography of the primary and secondary precipitates in each alloy have been studied in detail using light optical microscopy, high resolution scanning electron microscopy, transmission electron microscopy, various electron diffraction methods (EBSD, SAD and CBED), Powder X-ray Diffraction and energy dispersive X-ray spectroscopy. Specific attention has been paid to the niobium-rich and niobium-titanium-rich phases that form as a direct result of HP alloy’s modification with niobium and titanium. The current research is part of a wider project conducted in collaboration with Quest Integrity Group Ltd. (Wellington, New Zealand) that aims to characterize the microstructural and mechanical properties of the HP-Nb and HP-NbTi alloys during long-term service exposure. The microstructural characterization presented in this thesis will subsequently be used by Quest Integrity Group to build a comprehensive understanding of the relationship between HP-Nb and HP-NbTi alloy’s microstructure and creep properties. This understanding will allow Quest Integrity Group to more accurately predict the service life of HP-Nb and HP-NbTi alloy tubes within steam-methane reforming furnaces.

Student Number : 0413336G - MSc(Eng)dissertation - School of Chemical and Metallurgical Engineering - Faculty of Engineering and the Built Environment / This dissertation reports systematic work aimed at determining the plastic deformation mechanisms that led to strains at fracture as high as 4.7% in WC-Co alloys at 1000°C when subjected to 3-point bending tests. The three grades investigated have a Co content of 15wt% and WC grain sizes of 1.3, 0.35 and 0.3 μ m respectively and were received after they were tested in bending. Fractography, macrostructural and microstructural investigations were carried out in attempts to identify the mechanisms leading to the large strains. Techniques used included light microscopy, scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) and quantitative image analysis. Through comparisons of the results from the three grades at various temperatures, it was possible to establish that the large strain at 1000°C are mainly due to cracking and cobalt drift. During the fractographic investigations it was found that the grades which contained VC as a grain refiner exhibited steps on the WC grains and that fracture propagated preferentially along the stepped WC grain boundaries.

High-temperature processing of rice needs close attention due to the susceptibility of rice grains to fissures. The present study was carried out to redress the lack of information on the quality of rice dried at high-temperatures using a range of drying air temperatures from 160 - 200??C and grain moisture contents varying from 27 to 33%wb. A laboratory type high temperature dryer-oven was developed and constructed, and the performance was compared with commercial fluidized-bed and spouted-bed dryers. The new column type treatment plant, targeted at small-scale rice farmers was designed to reduce milling breakages was tested for high-temperature treatments. Short term drying (160 ??? 180 seconds) of high moisture rough rice at high-temperatures such as 160 - 200??C increased head rice yield by 5 - 8% in long grain rice and 7 - 11% in medium grain rice. The head rice yield increase achieved was very close to the highest potential head rice recovery possible for a given sample. The head rice yield increase was mainly due to a hardened surface layer of the rice kernel, formed by two effects, a surface fusion and surface gelatinization during high-temperature treatment. This stress protection layer is only effective for a short period (1 - 2 minutes) at high temperatures. Tempering of treated grains, either by storing in gunny bags or rapid cooling, can secure the grains to some extent from grain breakage. The highest head rice yield increase was obtained by ceasing the high-temperature effect at the grain moisture level of 24 - 25%wb. The colour and appearance of high-temperature treated grains were closer to those of untreated grains with the toughness closer to that of parboiled rice. The setback values of high-temperature treated rice measured by RVA, which is a preferred character by consumers, were closer to aged rice. High-temperature treatments did not affect the cooking qualities except a slight increase in water absorption. The alterations in the grain due to high-temperature treatment are limited to only for 8 - 9% of the total volume (mainly outer region) of the rice grain, preserving more than 90% of the grain with raw-rice quality. Structural changes such as complexing of amylose ??? lipid, amylose -protein and denaturation of protein play a dominant role on quality changes than gelatinization. A new method introduced to measure the degree of gelatinization of pre-gelatinized rice, using hot paste viscosity by rapid visco analyser (RVA), was successful. The peak viscosity parameter in the RVA was more suitable for measuring the chemical changes in high-temperature treated rice. Spouted-bed drying technology is not suitable for high-temperature treatment due to the unfavourable conditions for the formation of a hardened layer under intermittent heating and cooling. Fluidized-bed dryers could be used for high-temperature drying, but is not cost effective for the small-scale farmer level. The novel type treatment plant was successful in reducing the amount of broken grains to almost zero, increasing the head rice yield by 50 - 120kg per 1000kg of rough rice. It was also effective as a germination arrester, inhibiting the germination ability within a very short period such as 30 - 60 seconds. This equipment is more effective as a treatment Plant as it reduces moisture by only 1.5 - 2.0% at highest head rice yield recovery. An empirical model was successfully established (R2 = 0.99) for grain moisture content (db) and drying temperature during high-temperature processing. In model validation process, a good agreement was found between predicted and experimental data. The modelling between head rice yield and high-temperature drying was unsuccessful (R2 = 0.89) mainly due the interference from other factors such as initial moisture stress due to re-wetting and uncontrolled post treatment drying environment conditions. The study revealed some breakthrough for the rice industry in addition to its quantitative evaluation of increase in head rice yield. 1. Ability to produce grains with twice the toughness of milled untreated rice, without losing colour and appearance. 2. Fissured grains, previously weakened due to moisture-stress (considered as a loss), can be successfully recovered by treating this high-temperature technique. Currently there is no method available to increase the head rice yield of this type of fissured grains except parboiling, which is not widely accepted among consumers. 3. Drying at 200??C drying temperature completely destroyed the viability of seeds within 40 -60 seconds, hence providing a remedy for germination problems in wet harvests. 4. Since high-temperature drying needs wet rough rice, early harvesting can be done which will reduce shattering losses. This enable the farmers to use the field for an inter-seasonal crop which can utilise higher residual soil moisture in the paddy fields compared to other crops.

SUMMARY GTD-111 DS is a directionally solidified superalloy currently used in turbine engines. To accurately predict the life of engine components it is essential to examine and characterize the microstructural evolution of the material and its effects on material properties. The as-cast microstructure of GTD-111 is highly inhomogeneous as a result of coring. The current post-casting heat treatments do not effectively eliminate the inhomogeneity. This inhomogeneity affects properties including tensile strength, fracture toughness, fracture path, and corrosion behavior, primarily in terms of the number of grains per specimen. The goal of this work was to link microstructural features to these properties. Quantitative fractography was used to determine that the path of cracks during failure of tensile specimens is influenced by the presence of carbides, which are located in the interdendritic regions of the material as dictated by segregation. The solvus temperature of the precipitate phase, Ni3(Al, Ti), was determined to be 1200C using traditional metallography, differential thermal analysis, and dilatometry. A heat-treatment was designed to homogenize the microstructure for tensile testing that isolates the carbide by dissolving all of the eutectic Ni3(Al, Ti) precipitate phase, which is also found in the interdendritic areas. High temperature oxidation/sulfidation tests were conducted to investigate the corrosion processes involved when GTD-111 DS is utilized in steam and gas combustion turbine engines. The kinetics of corrosion in both oxidizing and sulfidizing atmospheres were determined using thermogravimetric analysis. Additionally, metallography of these samples after TGA revealed a correlation between the presence of grain boundaries and sulfur attack, which led to catastrophic failure of the material under stress-free conditions in a sulfur bearing environment. In summary, this work correlates the inhomogeneous microstructure of GTD-111 DS to tensile fracture, and the corrosion process in turbine engines.

published_or_final_version / abstract / toc / Physics / Doctoral / Doctor of Philosophy

Methods of processing large grained textured superconductor have been successfully developed, based on a melt texturing process. Large grained textured superconductor with grain size over 10mm along the growth direction and Jc over 3600A/cm² (77K, 0.5 Tesla) has been produced in both one - zone and two - zone furnaces with good reproducibility. Two kinds of design of reactive metal contacts have been proposed and investigated, aiming to make low resistivity contacts with strong mechanical strength. Three possible reactive contact metals have been tested for contact making, and the microstructures at the interfaces have been studied to find the relations between contact resistivity and contact processing conditions. Titanium/noble metal multilayer contacts is a promising type of contact technique for low resistivity and strong mechanical bonds. Gold and silver contacts give resistivities among the best reported results in the literature, and they turned out to be extremely stable in time, could withstand repeated thermal cycling from room temperature to 10K and yield very reproducible R-T curves. The electrochemical titration method has been used to increase the oxygen stoichiometry of bulk textured YBa₂Cu₃O_7-x samples. The electrochemical titration method can further oxidize melt textured thick film YBa₂Cu₃O_7-x samples in which it may be difficult to further improve oxygen content by conventional annealing. The solid state electrochemical cell has been used to study the thermodynamic properties of the Y-Ba-Cu-O system at high oxygen pressure by measuring the oxygen activity versus time continuously immediately after the electrochemical titration. A series of computer models have been set up according to the microstructure of the contact interface to simulate the complicated contact resistivity behaviours. The nature of, and geometry of, the reaction products at the contact interfaces may be revealed by the temperature dependence of the contact resistance. This information combined with direct observations on the structure and chemistry of the contacts provided a fuller understanding of conduction mechanism at the contact interface.

High-temperature processing of rice needs close attention due to the susceptibility of rice grains to fissures. The present study was carried out to redress the lack of information on the quality of rice dried at high-temperatures using a range of drying air temperatures from 160 - 200??C and grain moisture contents varying from 27 to 33%wb. A laboratory type high temperature dryer-oven was developed and constructed, and the performance was compared with commercial fluidized-bed and spouted-bed dryers. The new column type treatment plant, targeted at small-scale rice farmers was designed to reduce milling breakages was tested for high-temperature treatments. Short term drying (160 ??? 180 seconds) of high moisture rough rice at high-temperatures such as 160 - 200??C increased head rice yield by 5 - 8% in long grain rice and 7 - 11% in medium grain rice. The head rice yield increase achieved was very close to the highest potential head rice recovery possible for a given sample. The head rice yield increase was mainly due to a hardened surface layer of the rice kernel, formed by two effects, a surface fusion and surface gelatinization during high-temperature treatment. This stress protection layer is only effective for a short period (1 - 2 minutes) at high temperatures. Tempering of treated grains, either by storing in gunny bags or rapid cooling, can secure the grains to some extent from grain breakage. The highest head rice yield increase was obtained by ceasing the high-temperature effect at the grain moisture level of 24 - 25%wb. The colour and appearance of high-temperature treated grains were closer to those of untreated grains with the toughness closer to that of parboiled rice. The setback values of high-temperature treated rice measured by RVA, which is a preferred character by consumers, were closer to aged rice. High-temperature treatments did not affect the cooking qualities except a slight increase in water absorption. The alterations in the grain due to high-temperature treatment are limited to only for 8 - 9% of the total volume (mainly outer region) of the rice grain, preserving more than 90% of the grain with raw-rice quality. Structural changes such as complexing of amylose ??? lipid, amylose -protein and denaturation of protein play a dominant role on quality changes than gelatinization. A new method introduced to measure the degree of gelatinization of pre-gelatinized rice, using hot paste viscosity by rapid visco analyser (RVA), was successful. The peak viscosity parameter in the RVA was more suitable for measuring the chemical changes in high-temperature treated rice. Spouted-bed drying technology is not suitable for high-temperature treatment due to the unfavourable conditions for the formation of a hardened layer under intermittent heating and cooling. Fluidized-bed dryers could be used for high-temperature drying, but is not cost effective for the small-scale farmer level. The novel type treatment plant was successful in reducing the amount of broken grains to almost zero, increasing the head rice yield by 50 - 120kg per 1000kg of rough rice. It was also effective as a germination arrester, inhibiting the germination ability within a very short period such as 30 - 60 seconds. This equipment is more effective as a treatment Plant as it reduces moisture by only 1.5 - 2.0% at highest head rice yield recovery. An empirical model was successfully established (R2 = 0.99) for grain moisture content (db) and drying temperature during high-temperature processing. In model validation process, a good agreement was found between predicted and experimental data. The modelling between head rice yield and high-temperature drying was unsuccessful (R2 = 0.89) mainly due the interference from other factors such as initial moisture stress due to re-wetting and uncontrolled post treatment drying environment conditions. The study revealed some breakthrough for the rice industry in addition to its quantitative evaluation of increase in head rice yield. 1. Ability to produce grains with twice the toughness of milled untreated rice, without losing colour and appearance. 2. Fissured grains, previously weakened due to moisture-stress (considered as a loss), can be successfully recovered by treating this high-temperature technique. Currently there is no method available to increase the head rice yield of this type of fissured grains except parboiling, which is not widely accepted among consumers. 3. Drying at 200??C drying temperature completely destroyed the viability of seeds within 40 -60 seconds, hence providing a remedy for germination problems in wet harvests. 4. Since high-temperature drying needs wet rough rice, early harvesting can be done which will reduce shattering losses. This enable the farmers to use the field for an inter-seasonal crop which can utilise higher residual soil moisture in the paddy fields compared to other crops.

Thesis (MScIng)--University of Stellenbosch, 2007. / Bibliography. Also available via the Internet.