Fly ash and blast furnace slag are the two major industrial solid by-products generated in most countries including India. Although their utilization rate has increased in the recent years, still huge quantities of these material remain unused and are stored or disposed of consuming large land area involving huge costs apart from causing environmental problems. Environmentally safe disposal of Fly ash is much more troublesome because of its ever increasing quantity and its nature compared to blast furnace slag. Bulk utilization of these materials which is essentially possible in civil engineering in general and more particular in geotechnical engineering can provide a relief to environmental problems apart from having economic benefit. One of the important aspects of these waste materials is that they improve physical and mechanical properties with time and can be enhanced to a significant level by activating with chemical additives like lime and cement. Class-C Fly ashes which have sufficient lime are well utilized but class-F Fly ashes account for a considerable portion that is disposed of due to their low chemical reactivity. Blast furnace slag in granulated form is used as a replacement for sand to conserve the fast declining natural source. The granulated blast furnace slag (GBS) is further ground to enhance its pozzolanic nature. If GBS is activated by chemical means rather than grinding, it can provide a good economical option and enhance its utilization potential as well. GGBS is latent hydraulic cement and is mostly utilized in cement and concrete industries. Most uses of these materials are due to their pozzolanic reactivity. Though Fly ash and GGBS are pozzolanic materials, there is a considerable difference in their chemical composition. For optimal pozzolanic reactivity, sufficient lime and silica should be available in desired proportions. Generally, Fly ash has higher silica (SiO2) content whereas GGBS is rich in lime (CaO) content. Combining these two industrial wastes in the right proportion may be more beneficial compared to using them individually. The main objective of the thesis has been to evaluate the suitability of the class-F Fly ash/GGBS mixtures with as high Fly ash contents for Geotechnical and Geo-environmental applications. For this purpose, sufficient amount of class-F Fly ash and GGBS were collected and their mixtures were tested in the laboratory for analyzing their mechanical behavior. The experimental program included the evaluation of mechanical properties such as compaction, strength, compressibility of the Fly ash/GGBS mixtures at different proportions with GGBS content varying from 10 to 40 percent. An external agent such as chemical additives like lime or cement is required to accelerate the hydration and pozzolanic reactions in both these materials. Hence, addition of varying percentages of lime is also considered. However, these studies are not extended to chemically activate GBS and only GGBS is used in the present study. Unconfined compressive strength tests have been carried out on various Fly ash/ GGBS mixtures at different proportions at different curing periods. The test results demonstrated rise in strength with increase in GGBS content and with 30 and 40 percent of GGBS addition, the mixture showed higher strength than either of the components i.e. Fly ash or GGBS after sufficient curing periods. Addition of small amount of lime increased the strength tremendously which indicated the occurrence of stronger cementitious reactions in the Fly ash/GGBS mixtures than in samples containing only Fly ash. Improvement of the strength of the Fly ash/GGBS mixtures was explained through micro-structural and mineralogical studies. The microstructure and mineralogical studies of the original and the stabilized samples were investigated by scanning electron microscopy (SEM) and X-Ray diffraction techniques respectively. These studies together showed the formation of cementitious compounds such as C-S-H, responsible for imparting strength to the pozzolanic materials, is better in the mixture containing 30 and 40 percent of GGBS content than in individual components. Resilient and permanent deformation behavior on an optimized mix sample of Fly ash and GGBS cured for 7 day curing period has been studied. The Resilient Modulus (Mr) is a measure of subgrade material stiffness and is actually an estimate of its modulus of elasticity (E). The permanent deformation behavior is also important in predicting the performance of the pavements particularly in thin pavements encountered mainly in rural and low volume roads. The higher resilient modulus values indicated its suitability for use as subgrade or sub-base materials in pavement construction. Permanent axial strain was found to increase with the number of load cycles and accumulation of plastic strain in the sample reduced with the increase in confining pressure. Consolidation tests were carried on Fly ash/GGBS mixtures using conventional oedometer to assess their volume stability. However, such materials develop increased strength with time and conventional rate of 24 hour as duration of load increment which requires considerable time to complete the test is not suitable to assess their volume change behavior in initial stages. An attempt was thus made to reduce the duration of load increment so as to reflect the true compressibility characteristics of the material as close as possible. By comparing the compressibility behavior of Fly ash and GGBS between conventional 24 hour and 30 minutes duration of load increment, it was found that 30 minutes was sufficient to assess the compressibility characteristics due to the higher rate of consolidation. The results indicated the compressibility of the Fly ash/GGBS mixtures slightly decreases initially but increase with increase in GGBS content. Addition of lime did not have any significant effect on the compressibility characteristics since the pozzolanic reaction, which is a time dependent process and as such could not influence due to very low duration of loading. Results were also represented in terms of constrained modulus which is a most commonly used parameter for the determination of settlement under one dimensional compression tests. It was found that tangent constrained modulus showed higher values only at higher amounts of GGBS. It was also concluded that settlement analysis can also be done by taking into account the constrained modulus. The low values of compression and recompression indices suggested that settlements on the embankments and fills (and the structures built upon these) will be immediate and minimal when these mixtures are used. In addition to geotechnical applications of Fly ash/GGBS mixture, their use for the removal of heavy metals for contaminated soils was also explored. Batch equilibrium tests at different pH and time intervals were conducted with Fly ash and Fly ash/GGBS mixture at a proportion of 70:30 by weight as adsorbents to adsorb lead ions. It was found that though uptake of lead by Fly ash itself was high, it increased further in the presence of GGBS. Also, the removal of lead ions increased with increase in pH of the solution but decreases at very high pH. The retention of lead ions by sorbents at higher pH was due to its precipitation as hydroxide. Results of the adsorption kinetics showed that the reaction involving removal of lead by both the adsorbents follow second-order kinetics. One of the major problems which geotechnical engineers often face is construction of foundations on expansive soils. Though stabilization of expansive soils with lime or cement is well established, the use of by-product materials such as Fly ash and blast furnace slag to achieve economy and reduce the disposal problem needs to be explored. To stabilize the soil, binder comprising of Fly ash and GGBS in the ratio of 70:30 was used. Different percentages of binder with respect to the soil were incorporated to the expansive soil and changes in the physical and engineering properties of the soil were examined. Small addition of lime was also considered to enhance the pozzolanic reactions by increasing the pH. It was found that liquid limit, plasticity index, swell potential and swell pressure of the expansive soil decreased considerably while the strength increased with the addition of binder. The effect was more pronounced with the addition of lime. Swell potential and swell pressure reduced significantly in the presence of lime. Based on the results, it can be concluded that the expansive soils can be successfully stabilized with the Fly ash-GGBS based binder with small addition of lime. This is also more advantageous in terms of lime requirement which is typically high when Fly ash, class-F in particular, is used alone to stabilize expansive soils. Based on the studies carried out in the present work, it is established that combination of Fly ash and GGBS can be advantageous as compared to using them separately for various geotechnical applications such as for construction of embankments/fills, stabilization of expansive soils etc. with very small amount of lime. Further, these mixtures have better potential for geo-environmental applications such as decontamination of soil. However, it is still a challenge to activate GBS without grinding.

Thirty million tons of coal fly ash are produced each year in South Africa of which approximately 5% is utilised beneficially. With the growing concern about pollution and increasing landfill costs, the study of the utilisation and application of coal fly ash has increased worldwide. The morphology and particle size of fly ash make it suitable for application as filler in polymers, but its application is hindered by the lack of compatibility between the inorganic surface of the ash and the organic matrix of the polymer. Another concern is the agglomeration between fly ash particles. For this reasons, surface treatment is usually performed on mineral fillers to enhance workability and compatibility between the polymer and filler. This study involved the surface modification of South African coal fly ash with an anionic surfactant, sodium lauryl sulphate (SLS), under different treatment conditions. Surface and physical properties of the untreated and treated fly ash were studied systematically by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in order to determine the extent of interaction between the SLS and the fly ash surface. Other analytical techniques applied include Thermogravimetric analysis (TGA-FTIR), Particle size distribution, X-ray diffraction (XRD) and X-ray fluorescence spectroscopy (XRF), Raman spectroscopy and Fourier Transform Infrared spectroscopy FTIR). Although the overall chemical composition of the SLS modified coal fly ash investigated in this study was not altered extensively, significant changes could be observed in its physical properties. The hydrophilic surface of untreated fly ash was rendered hydrophobic after SLS treatment. SEM results indicated a decrease in agglomeration between fly ash spheres upon surfactant treatment, while results obtained from TEM have shown agglomerates on the surface of most of the fly ash spheres. There is a distinct difference between the morphology of agglomerates on the untreated and SLS modified fly ash, and also between samples treated under different conditions. Not all SLS modified fly ash particles were covered with agglomerates to the same degree. Results obtained from FTIR and TGA-FTIR studies were promising in the sense that hydrocarbon fractions could be observed in the TGA-FTIR decomposition products. The possibility of interactions between fly ash and SLS could be deduced from the FTIR results of the solid samples, due to a small shift in peak positions of the S-O stretch vibration, which may be indicative of electrostatic interactions rather than bonding interactions between SLS and fly ash. The presence of SLS could not be confirmed by Raman spectroscopy, but rendered information about the spatial distribution of the various phases in the fly ash. Feasibility tests were performed on the application of fly ash samples as filler in PVC. These results indicate that SLS treated fly ash can successfully replace CaCO3 as filler in PVC under conditions of low filler loadings / Dissertation (MSc)--University of Pretoria, 2013. / Chemistry / unrestricted

Call number: LD2668 .T4 1986 E42 / Master of Science / Entomology

Philosophiae Doctor - PhD / Mine water poses a serious environmental challenge and contains elements such as Fe, Al, and Mn in potentially toxic concentrations. The major anion in mine water is sulphate. The complexity and diversity of mine water composition makes its treatment very expensive, and there is no “one-fits-all” treatment option available for mine water. Active treatment of mine water produces water with good quality but the processes are not sustainable because of the costs. Previous studies have shown that acid mine drainage can be treated with coal FA to produce better quality water. The use of coal FA, a waste material from coal fired power station and mine water would go a long way in achievement of sustainable treatment of mine water as per previous studies. In this study mine water and coal FA were characterized to determine their physiochemical properties. This study linked the modelling results obtained by using the Geochemist’s workbench (GWB) software to the results obtained during the actual treatment of Matla mine water and Rand Uranium mine water using coal FA and lime. The chemistry involved when Matla mine water and Rand Uranium mine water were treated with flocculants was also investigated. Lastly the chemistry and kinetics involved was investigated when mine water was treated with various ameliorants such as Matla coal FA, lime and/or Al(OH)3 using jet loop mixing or overhead stirring. Mine water from Matla coal mine had a pH of 8 and therefore was classified as neutral mine drainage (NMD). Rand Uranium mine water had a pH of less than 3 and therefore was classified as acid mine drainage (AMD). The concentration of sulphate, Na, Ca, Mg, B, Hg, Se and Cd ions in Matla mine water was 1475, 956, 70, 40, 15, 2.43, 1.12 and 0.005 mg/L respectively. The concentration of sulphate, Fe, Ca, Mn, Mg, Al, B, Cr, Pb, U, Cd, Se and As ions in Rand Uranium mine water was 4126, 896, 376, 282, 155, 27, 5.43, 3.15, 0.51, 0.29, 0.007, 0.06 and 0.006 mg/L respectively . These concentrations were above the target water quality range (TWQR) for potable water set by the Department of Water Affairs (DWA) and World Health Organization (WHO). The gross alpha radioactivity was 6.01 Bq/L and gross beta radioactivity was 6.05 Bq/L in Rand Uranium mine water.

Philosophiae Doctor - PhD / Zeolites are widely used as environmentally friendly solid catalysts or catalyst supports in the refining and petrochemical industries. ZSM-5 zeolite is composed of a three-dimensional medium pore structure (openings of 5-5.5 Å) with high silica content, high temperature stability and strong acidity making it a well-known and an established catalyst for several petroleum derived chemical processes such as cracking, aromatic alkylation, disproportionation, Methanol-to-Gasoline, isomerisation, etc. Nowadays, the synthesis of ZSM-5 zeolite from silica, alumina sources and structure directing agents (templates) is well known. Its synthesis is possible from fly ash, which is a low cost source of both silica and alumina. Fly ash is an inorganic residue resulting from the combustion of coal in electricity generating plants, consisting mostly of SiO₂ and Al₂O₃. ZSM-5 zeolite has not been synthesised from South African coal fly ash and the literature reports that fly ash-based ZSM-5 zeolite was synthesised only with tetrapropylammonium (TPA+) as structure directing agent and required an excessive amount of additional silica. The final ZSM-5 product was reported to still contain fly ash mineral phases after synthesis. This prevents the use of fly ash as a ZSM-5 zeolite precursor. Moreover, the synthesis of a high purity ZSM-5 zeolite from fly ash without additional silica has not been yet reported. This study aimed to synthesise high purity ZSM-5 zeolite from South African coal fly ash without additional silica, and with tetrapropylammonium bromide (TPABr), 1,6- hexanediamine (HDA) or 1-propylamine (PA) as structure directing agent. This aim was achieved by first optimising the synthesis of ZSM-5 zeolite from South African coal fly ash based on a formulation reported in the literature with fumed silica and TPABr as additional source of silica and structure directing agent respectively. Thereafter, the obtained optimum conditions were used to synthesise other fly ash-based ZSM-5 zeolite products by substituting TPABr with HDA or PA. Two routes of treating the as-received fly ash prior to the hydrothermal synthesis were applied in order to improve the quality of the final products or reduce the amount of the fumed silica that was used. The first route consisted of treating the as-received fly ash with concentrated H₂SO₄ in order to remove a certain amount of aluminium and increase the Si/Al in the acid treated fly ash solid residue but also remove some other elements such as Fe, Ca, Mg, and Ti which might have an undesirable effect on the product quality. The acid treated fly ash solid residue was used as ZSM-5 precursor with fumed silica as additional silica source and TPABr, HDA or PA as structure directing agent. The ZSM-5 zeolite products that were synthesised from the as-received fly ash as well as from the H₂SO₄ treated fly ash were treated with oxalic acid solution in order to reduce the aluminium content in the final products. The second route consisted of fusing the as-received fly ash with NaOH and treating the powder fused fly ash extract with oxalic acid solution. The obtained fused and oxalic acid treated fly ash extracts were used as ZSM-5 precursors without additional fumed silica and with TPABr, HDA or PA as structure directing agent. ZSM-5 zeolite was synthesised from the as-received South African coal fly ash not only with the commonly used structure directing agent TPABr but also with two other, lower cost structure directing agents, HDA and PA. The synthesis process did not generate any solid waste as fly ash was used as bulk, which could be a way of valorising South African coal fly ash. However, the final products contained some fly ash mineral phases such as mullite and quartz, and had poor physical and chemical properties compared to a commercial H-ZSM-5 zeolite. The treatment of the as-received fly ash with H₂SO4 resulted in fly ash-based ZSM-5 zeolite products with better physical and chemical properties than those of ZSM-5 zeolite products that were synthesised from the as-received fly ash. Moreover, the post-synthesis treatment of the fly ash-based ZSM-5 zeolite products with oxalic acid resulted in an increase in the Si/Al ratio, offering a post-synthesis route to adjust the acidity of the catalysts. However, mullite and quartz phases were still present in the synthesised products. Alternatively, high purity ZSM-5 zeolite was synthesised from the fused and oxalic treated fly ash extracts without additional silica and with TPABr, HDA or PA as structure directing agent. Moreover, these synthesised fly ash-based ZSM-5 zeolite products had similar physical and chemical properties to the commercial H-ZSM-5 zeolite. The synthesised fly ash-based ZSM-5 zeolite products were used as solid catalysts in the Methanol-to-Olefins (MTO) and Nazarov reactions. The ZSM-5 zeolite products that were synthesised from the H₂SO4 treated fly ash as well as fused and oxalic treated fly ash were successfully used as solid catalysts in the MTO and Nazarov reactions. The ZSM-5 zeolite products that were synthesised from the H₂SO₄ treated fly ash presented a similar trend in MTO and Nazarov reactions depending on the structure directing agent that was used, and the ZSM-5 zeolite that was synthesised with HDA as structure directing agent had the highest MTO and Nazarov conversion. However these catalysts deactivated more quickly compared to the commercial H-ZSM-5 zeolite. On the other hand, the zeolites that were synthesised from the fused and oxalic acid treated fly ash had a high initial MTO conversion equivalent to the commercial H-ZSM-5 zeolite. However, they deactivated after 5 h of time on stream due to diffusional constraints, because of their large crystal sizes. This study developed novel routes in the synthesis of high value zeolites from fly ash. ZSM-5 zeolite was synthesised from fly ash with structure directing agents other that TPA+ cation and had acceptable Brønsted acidity and high initial conversion in MTO and Nazarov reactions. This has not been yet reported in the literature. Moreover, for the first time a high purity ZSM-5 zeolite was synthesised from fly ash without additional silica and had similar properties to a commercial H-ZSM-5 zeolite. This constituted a breakthrough in the fly ash-based ZSM-5 zeolite synthesis procedure, which will promote the valorisation of fly ash through ZSM-5 synthesis due to avoiding the addition of silica source in the hydrothermal gel and preventing the presence of fly ash mineral phases in the final products. This study can have a significant economic and environmental impact in South Africa if the synthesis process is scaled up as it provides a potentially cheap and innovative way of using waste for making a high value green and acid catalyst, namely ZSM-5 zeolite that has several catalytic applications; and it promotes the valorisation of South African coal fly ash that is considered by many as waste material. / National Research Foundation (NRF)

This master’s thesis responds to the worldwide problem concerning in the search of new material base for the future usage. Solid residues from high temperature or fluid coal combustion could be one of many alternatives to the raw materials. The study deals with the analysis of side energy products produced by power plant industry in the Czech Republic. Based on the fly ash chemical composition, possibilities of aluminium and even iron and titanium separation were proposed and then proved in the laboratory scale. Extracted components were separated selectively using apropriate methods. Then a couple of sintering reactions leading to improvement the leachability of selected elements from the fly ash matrix were carried out. Appropriate input material modification by high-temperature sintering reaction combined with extraction process in the sulfuric acid solution leads in dissolution up to 99 % of aluminium from the fluid and high-temperature fly ash.

Emission of carbon dioxide gas has been a source of major concern for the construction industry. To curb this emission, geopolymer concrete has been deemed as a potential alternative in the recent studies. Previous research also indicates that silica and fibers provide strength benefits to ordinary Portland cement concrete OPC. This study was undertaken to recognize the benefits of adding silica and basalt fibers in Class F fly ash based geopolymer concrete and comparing it with OPC concrete. One OPC and four Geopolymer mixtures were prepared. The results show a tremendous potential of using geopolymer concrete in place of OPC concrete with Nano silica proving to be the most advantageous. Nano silica provided 28% increase in compressive strength, 8% increase in resistivity when compared with normal Fly ash based geopolymer concrete. The SEM analysis of geopolymer concrete indicates that nano silica improved the compactness of concrete providing a dense microstructure.

In this study, the freeze-thaw performance and other engineering properties of different cementitious mixtures containing Type I/II portland cement, Type IL (10) portland Limestone cement (PLC) and Coarse Ground cement (CG-P) with or without partial replacement of fly ash (Class F) were examined. The goal was to develop a concrete mixture with better or similar freeze-thaw durability without adversely affecting other engineering properties of concrete. Crucial engineering properties reviewed include compressive strength, splitting tensile strength, workability, the degree of hydration, setting time, shrinkage and resistivity. The study was divided into two parts, one consisting of mechanical testing of engineering properties including the freeze-thaw test. The second part consisted of microstructure study which involved detection and quantification of micro-cracks/defects using μ-CT and fluorescence microscopy. The results showed that the portland limestone cement in combination with fly ash demonstrated better or similar durability in comparison to the conventional portland cement concrete mixtures.

This thesis is dealing with selection of proper airplane data bus for distributed Fly-by-Wire system. The parameters of such data bus are defined here and description of such data buses are given as well. The proper data bus which fulfils the given parameters is selected. Next the safety and time-delay analysis are provided.

Digitální Fly-by-Wire systém je novým přístupem k řídícímu systému letadla, na jehož základě firma Honeywell - HTS CZ začala výzkumný projekt s názvem “Next Generation Distributed Fly-by-Wire System” a tato práce je jeho součástí. Řídící plochy letadla jsou řízeny dvěma nebo třemi elektrohydraulickými (či elektrickými) servy a každé servo je ovládáno nezávislou řídící jednotkou. Díky provozním tolerancím systému a drobným odchylkám vstupních dat v řídících jednotkách, dostává každé servo mírně odlišné povely a rozdíl v poloze serv vede k namáhání řídící plochy i k namáhání serv. Hlavním cílem této práce je navrhnout algoritmus, který bude eliminovat rozdíly mezi polohami jednotlivých serv, a tudíž sníží sílu, která namáhá řídící plochu, na přípustnou mez. Implementace řídícího systému letadla byla do detailu analyzována a algoritmus redukce síly na kontrolní ploše letadla byl navržen a implementován v prostředí Simulink. Iterační kriteriální ladící metoda byla vyvinuta a za účelem co nejlepšího nastavení algoritmu redukce síly. Práce také analyzuje vliv časových zpoždení na sběrnici na kvalitu algoritmu redukce síly.