D.Phil. / The existence of radioactive waste (or ‘radwaste’) has become a problem that afflicts the nuclear industry worldwide. The search for a social consensus on radwaste management strategies is proving to be one of the most complex challenges facing nuclear technological development. The categories of radwastes that are currently of greatest concern are spent nuclear fuel (SF) that is discharged from nuclear power reactors and high level waste (HLW) arising from reprocessing of SF, as they continue to accumulate in storage facilities around the world and perceived to be without an end solution to their existence. Like many other nuclear countries, South Africa too is facing major decisions about future management of SF that is generated from its nuclear power and research reactors. It remains undecided on which of the available spent fuel management (SFM) options it must adopt. This research study seeks to produce a framework for evaluating SFM options that will identify and characterise the elements or aspects to be analysed, and use it to evaluate the SFM options in order to identify a preferred or optimum option for South Africa. The methodological approach to this study involves the use of literature research, a case study on Eskom’s SFM approach and a questionnairebased survey complemented by in-depth interviews with key stakeholders of nuclear power in South Africa. These qualitative methods are used to verify and validate the SFM evaluation framework. To complement the qualitative approach, a cost analysis of the options based on input from Eskom and literature data as well as on assumed scenarios, is carried out. Both the qualitative and the cost analysis lead to identification of a preferred SFM option for South Africa. Three principal SFM options were identified and evaluated: the reprocessing and recycling (or closed fuel cycle) option, the direct disposal (or once-through fuel cycle) option, and the indefinite storage (or deferral-of-a-decision) option. There are at least nine categories of issues that have been identified as factors affecting these SFM options: technology, safety, environmental impact, proliferation resistance, physical security, economics, sociopolitical influence, ethical principles and institutional capability. These formed the evaluation framework and were used as the criteria for the assessment of the SFM options. Based on the analysis conducted in the study concerning the feasibility of the SFM options for the South African context in terms of these criteria, it is concluded that the direct disposal option is the most favourable option for implementation in the South African nuclear power programme. However, all three options have their technical merits but are also contentious in various degrees both within the nuclear industry and the public domain.

This research has been directed at furthering the utilization of crude glycerol oversupply formed as a by-product from the biodiesel manufacturing process. Phosphorylation of hydroxyl groups is a synthetic route that was investigated for the conversion of glycerol into a glycerol-phosphate (GPE) ester mixture. The process investigated for the synthesis of a GPE product was based on phosphorylation reaction procedures that were previously reported in the literature. The reaction to convert glycerol into a GPE mixture has been thoroughly investigated and the hydrogen chloride gas formed as a reaction by-product has been optimized. The chemical properties of GPE have been studied and discussed together with a mass balance of the overall glycerol phosphorylation process. The phosphate groups contained in polyhydric phosphate molecules have a potential chelating effect on cations. There are several cations that may be chelated by the phosphate ester group of polyhydric phosphate molecules. These cations include ammonium (NH4+), Potassium (K+), Calcium (Ca2+) etc, which are essential as nutrients in plant fertilizer formulations. This research has investigated the use of a GPE synthesized from glycerol in the laboratory and the use thereof as a phosphorus containing base in the formulation and evaluation of Nitrogen, Phosphorus and Potassium (NPK) containing fertilizer solution, Ammonium-Potassium-Glycerol-Phosphate (APGP) fertilizer solution. The APGP fertilizer solution has further been evaluated by growing two week old tomato seedlings under controlled conditions. The performance of the APGP fertiliser solution has been evaluated using design of experiments by comparison with traditionally used liquidAmmonium-Potassium-Phosphate inorganic fertilizer. This fertilizer solution has been prepared in similar manner as APGP formulation with the difference between them being the source of phosphorus. The results have been evaluated using statistic analysis where a significant difference between the evaluated fertilizer formulations was found. The comparative study of these formulations was monitored by the observed plant weights. A blank treatment was used as a control to determine if a significant difference among these formulations was observed. Anova single factor and t-Test methods (Two-Samples assumed of equal variances) are statistical models that were applied to interpret the observed experimental data with respect to wet and dry weighed masses of tomato seedlings. These methods indicated a confirmed conclusion that there was a significant difference between APPO4 solution and APGP solution. The observed data have shown that the APPO4 solution provided significantly better fertigation performance than APGP solution. Consequently, further investigation has been conducted to determine the cause of the poorer performance of the APGP solution. The further study of the APGP fertilizer solution included nutrient stability testing, biological analysis and other observed physical changes of the APGP solution over time. Biological results have revealed the presence of a Fusarium fungus species that has grown and is suspended in APGP fertilizer solution. This microbe species has been observed to play a vital role in consuming fertilizer nutrients. In addition, the observed abnormal plant growth and nutrient decomposition of the APGP formulation has been proposed to be mostly a result of the pathogenicity of the fusarium fungi species that was suspended in the APGP solution. Further work has been proposed in which the effect of such biological contamination is eliminated through adequate sterilization procedures and the APGP formulation re-evaluated.

Magister Economicae - MEcon / Against the backdrop of rising fuel prices and increasing transport fuel demand, biofuel production, driven by the potential to contribute to energy security, climate change mitigation and rural development has experience rapid growth in recent years. Apart from a few private initiatives, South Africa has no commercialized biofuel industry to date. The concerns are that economic, environmental and socio economic issues can be a hindrance to the success of the industry. In response to these concerns this research intends to ascertain whether biofuel production could offer a viable economic alternative to fossil fuels in South Africa. For decision makers it is hard to find reliable reference material and solid guidance. Uncertainty over the potential risks and benefits has left potential investors unsure whether biofuel production could be a viable investment opportunity. The aim of this study was to determine if the benefits derived from biofuel production are significant enough to justify the substantial investment required. The findings reveal that in the absence of clear government strategies and the availability of low cost feedstocks the production of biofuel cannot be viewed as viable. The results show that bioethanol from grain sorghum and sugarcane are not economically viable since the results turn out to be negative in terms of both net present values (NPV) and internal rate of return (IRR) calculations, thus rendering a viable payback (PBP) period as unattainable. Similarly, the NPV and IRR for biodiesel from soya beans and sunflower is negative and the PBP also unattainable. Sensitivity analyses indicate that these crops (except for sunflowers) could only become viable if there were to be a substantial reduction in feedstock prices. All other changes in parameters would not render any of the production plant viable.

Orientador: Eduardo René Pérez González / Banca: Luiz Carlos da Silva Filho / Banca: Gil Valdo José da Silva / O Programa de Pós Graduação em Ciência e Tecnologia de Materiais, PosMat tem carater institucional e integra as atividades de pesquisa em materiais de diversos campi / Resumo: A modificação química do biodiesel tem sido uma proposta interessante para obtenção de diversos compostos oleoquímicos com propriedades e aplicações semelhantes aos derivados do petróleo, com o diferencial de serem obtidos através de rotas limpas e ambientalmente benigmas, utilizando insumos naturais como óleo vegetal e dióxido de carbono, atendendo diversos princípios da Química Verde. Este trabalho têm como proposta realizar uma série de modificações químicas do biodiesel de linhaça, partindo de sua síntese, epoxidação e cicloadição de CO2 para obtenção de epóxidos e carbonatos cíclicos biodegradáveis. O biodiesel de linhaça foi produzido através de catálise com ácido de Lewis (NbCl5) e teve seu teor de insaturação concentrado via purificação com uréia. A epoxidação do biodiesel concentrado teve sua cinética acompanhada pelo progresso do valor de oxigênio oxirano além de ser estudada via GC-FID e GC-MS. Os carbonatos cíclicos foram obtidos pela cicloadiação de CO2 supercrítico nos epóxidos catalisada por TEAB sem solvente e mostraram-se bons reagentes frente a diversas aminas para formação de carbamatos (uretanos). Espectros de FT-IR e RMN (1H e 13C) identificaram as transformações de todos os principais grupos funcionais comprovando êxito nas modificacões químicas propostas / Abstract: The chemical modification of biodiesel has been an interesting proposal for obtaining various oleochemical compounds with similar porperties and aplications to petroleum derivates, with the difference of being obtained through clean and environmentally benign routes, using natural feedstock as vegetables oil and carbon dioxide, according to several principles of Green Chemistry. This work proposes to conduct a series of chemical modifications of flaxseed biodiesel, from its synthesis, epoxidation and cycloaddtion of CO2 to obtain biodegradable epoxides and cyclic carbonates. The flaxseed biodiesel was produced through Lewis acid catalysis (NbCl5) and had its unsaturation content concentrated by urea purification. The epoxidation of the concentrated biodiesel had its kinetics monitored by the evolution of oxygen oxirane value and studied by GC-FID and GC-MS. The cyclic carbonates were obtained from the solventless cycloaddition of supercritical CO2 in the opoxides catalyzed by TEAB, and have shown good reactants for a wide range of amines to from its respective carbamates (urethanes). FT-IR and NMR (1H and 13C) spectra identified the transformatios of all maior functional groups proving successful in the proposed chemical modifications / Mestre

Pillared clays present interesting possibilities for use as acid catalysts. The present research investigated the effect that pillaring has on the physical and catalytic properties of some smectite clays. The effect of using a hydroxy-Al solution to pillar a predominantly octahedrally ,substituted clay (montmorillonite) and a tetrahedrally substituted clay (beidellite) were compared. The effects of pillaring tetrahedrally substituted clays with different swellable properties (beidellite, SMM, and Ni-SMM) were investigated. In an attempt to enhance the acidic properties of the pillars, montmorillonite was pillared with a hydroxy-Al solution containing tetraethyl orthosilicate. Montmorillonite was also pillared with a hydroxy-Ni/Al solution in an effort to produce a clay with an increased pillar density. The pillared and unpillared clays were characterised using x-ray diffraction, surface area measurements, thermogravimetric analysis and ammonia TPD. The possible shape selective properties of the different clays for the conversion of trimethylbenzene were investigated, and the catalytic activities and product selectivities of these clays for high pressure propene oligomerisation were studied.

Among various sources for biofuels, microalgae provide at least three-orders-of-magnitude higher production rate of biodiesel at a given land area than conventional crop-based methods. However, microalgal biodiesel still suffers from significantly lower harvesting efficiency, making such a fuel less competitive. To increase the separation efficiency of microalgae from cultivation solution, an orbital microchannel was utilized that enabled the isolation of biofuel-algae particles from the effluent. The results obtained showed that the separation efficiency in the microfluidic centrifugal separator can be as high as 76% within a quick separation time of 30 seconds. Multiple parameters of algae behaviors and separation techniques such as initial concentration, pH and temperature were studied and manipulated to achieve better efficiencies. It was found that changing these factors altered the separation efficiency by increasing or decreasing flocculation, or “clumping” of the microalgae within the microchannels. The results suggested that an acidic condition would enhance the separation efficiency since in a basic environment, large flocs of microalgae would block and hinder the separation process. Furthermore, a hot temperature solution (around 33 °C) yielded to a higher separation efficiency. The important characteristics of the separator geometry and the infusion rate on algae separation were also very effective in the separation process. This study revealed that there is an opportunity to improve the currently low efficiency of algae separation in centrifugal systems using much smaller designs in size, ensuring a much more efficient algae harvesting. / Includes bibliography. / Thesis (MS)--Florida Atlantic University, 2021. / FAU Electronic Theses and Dissertations Collection

In this study, the response of a liquid-fueled resonant pulse combustor to changes in liquid fuel composition was investigated. Experiments were performed with gasoline- ethanol, gasoline-diesel, and gasoline-heptane mixtures selected to produce meaningful variations in the ignition delay time. A review of ignition quality tester (IQT) data provided an expected increase in the overall delay for gasoline-ethanol mixtures with increasing ethanol concentrations, and a decrease for gasoline-diesel mixtures with increasing diesel concentrations in the mixture. By taking the phase of the ion signal as an indicator of heat release timing, the experimental results showed an agreement of gasoline-ethanol cases with the IQT data with a near linear increase with increasing ethanol concentrations. However, for gasoline-diesel, there exit no linear relation with the IQT data. For the case of gasoline-heptane mixtures, the results showed a linear decrease in delay with increasing heptane concentrations. Furthermore, it was shown that small changes in the physical properties of the fuel can significantly in sequence the cold-start operation of the combustor and alter the coupling between the unsteady heat release and resonant acoustic pressure wave during resonant operation. Dynamic combustion chamber pressure, stagnation temperature and pressure are recorded after a fixed warm-up time to characterize the performance and operation of the device. Results are interpreted in the context of fuel sensitivity and performance optimization of a resonant pulse combustor for pressure gain turbine applications.

Thesis (B.S.)--Massachusetts Institute of Technology, Dept. of Nuclear Engineering, 1980. / Bibliography: leaf 49. / by Gerald Ellsworth Hammond Jr. / Thesis (B.S.)--Massachusetts Institute of Technology, Dept. of Nuclear Engineering, 1980.

Thesis: M.S., Massachusetts Institute of Technology, Department of Nuclear Engineering, 1979 / Bibliography: leaves 195-198. / M.S. / M.S. Massachusetts Institute of Technology, Department of Nuclear Engineering

Pre-ignition is a type of irregular combustion that occurs in boosted direct injection gasoline engines when one or more auto-ignition events occur before to spark ignition. Due to the direct injection of fuel into the cylinder, some liquid fuel may splash off the walls, dragging along lubricating oil. The self-ignition of liquid fuel/lubricant droplets is one of the pre-ignition sources studied. To test this stochastic behavior in a controlled manner, we examined the auto-ignition of a single droplet of a hexadecane-fuel mixture, with hexadecane serving as a surrogate for the lub oil. This experiment involved suspending a single hexadecane-fuel mixture droplet on a thermocouple bead in preheated air at temperatures ranging from 150 to 300 ° C over a wide range of pressures (4-30 bar). Various fuels with RON values ranging from 0 to 120 were blended with hexadecane at varying volume percentages of fuel in hexadecane from 0% to 100% to determine the droplet's time to ignition, denoted by TI. TI was determined by concurrently recording the history of the droplet temperature and imaging it at high speed. The ignition of the droplet is triggered by the self-ignition of the combustible mixture created by the vapor of the hexadecane-fuel mixture reacting with the heated ambient air surrounding the droplet. The increase in RON increased the TI as high RON fuels are difficult to ignite. However, the TI of the mixture depended on the fuel mixture properties even when the RON of the mixture was relatively high. Furthermore, the metal additives were added to the oil surrogate to investigate their effect on getting a pre-ignition event. The lubricant oil additives were phosphate, magnesium, and calcium. These additives were mixed with hexadecane at different concentrations. The experiments were conducted in a constant volume combustion chamber at 300 ⁰C temperature and the pressure was varied from 5 to 15 bar. The resulting TI were then compared with the TI of pure hexadecane. The results showed that addition of phosphate reduces the chances of getting a pre-ignition event, magnesium showed neutral effect while calcium enhanced the chances of getting a pre-ignition event.