This report describes a 3 year study carried out to determine the effects of modern coal power generation technologies on the properties of fly ash and how these may affect the use of the material in concrete. A total of 18 fly ashes, from 11 different sources, produced under a range of conditions and technologies were investigated. These primarily included co-combustion, low NOx, supercritical and oxy-fuel technologies, although other available materials (run-of-station, air-classified, processed and stockpiled fly ashes) were included for comparison. The initial experimental work involved physical and chemical characterization of the fly ash samples. Thereafter, tests covering fresh properties, strength development and durability were carried out on selected concretes. A fly ash level of 30% was used with w/c ratios covering the practical range considered (0.35 to 0.65). Equal strength comparisons were also made where appropriate. Finally, granular (unbound fly ash) and monolithic (fly ash concrete) leaching tests were carried out to assess the environmental implications of using the fly ashes. The results from the physical and chemical characterization tests suggest that modern technologies used for coal fired power generation can have an influence on the properties of fly ash produced. The co-combustion, oxy-fuel and in-combustion low NOx fly ashes had reduced fineness and greater LOI, which had a negative effect on foam index and water requirement of the materials. However reactivity was largely unaffected. The post-combustion low NOx and supercritical fly ashes appeared to be unaffected by their production methods compared to that produced by conventional/establish means. Tests on fresh concrete properties showed that fly ashes with high LOI and low fineness required higher SP doses than the reference PC concrete. However, fly ashes with high fineness and low surface area were found to require a lower SP dose than the PC concrete. The concrete compressive strength tests indicate that, in general, finer fly ash concretes tended to have higher strengths than those containing coarser material. However, there did not appear to be any significant difference in performance between fly ash concretes, which suggests that, although modern technologies can have an impact on fly ash properties, if account is taken of these they should not have any significant influence on strength development. Comparison with an earlier study from the 1990s considering BS EN 450-1 fly ashes showed general agreement between the data. The durability study showed that finer, low LOI fly ashes had higher chloride resistance and at equal strength fly ash concretes performed better than those with PC. Equal strength fly ash concretes covering the modern technologies were found to have similar levels of durability for sulfate attack, abrasion and carbonation. High alkali concrete (following the BS 812-123 method) gave similar expansion levels and good resistance with respect to AAR. With air-entrainment, it was found that the fly ash concretes required high doses of AEA (relative to the PC concrete), with high LOI/BET fly ashes requiring greatest quantities. At equal strength, the fly ash concretes had poorer freeze-thaw scaling resistance than PC concrete. However, the majority of the fly ashes did manage to achieve acceptable scaling resistance according to the Swedish criteria. In general, the findings of the durability study are in agreement with the earlier study from the 1990s. Overall, no effect of production technology on the durability of concrete was observed. The leaching studies showed that, in general, in both granular and concrete form, modern fly ashes met the non-hazardous waste requirements in the WAC for all components tested except chromium. For the granular test, there were instances where elevated chromium levels were observed. Similarly, the fly ash concretes failed to meet the non-hazardous limit for chromium. However, chromium from the cement may have contributed to this, since the PC reference also failed to meet this requirement. Based on the results, there is no effect of production technology on the leaching characteristics of fly ash or concrete and the materials do not appear to pose a significant environmental risk. The practical implications of the study have been considered and overall, it has been shown that modern fly ashes behave in much the same way as traditional materials, and therefore, if these materials meet the requirements of BS EN 450-1, and their properties are taken into account in the proportioning of concrete, they should give satisfactory performance.

The thesis is focused on the possibility of using secondary energy resources as an additive to concrete to improve some of its resulting properties. The theoretical part is devoted to the problems of shrinkage and prominence hydration process during hydration of the concrete. This section also contains the results of research work from domestic and foreign sources of high temperature fly ash and fluidized bed combustion fly ash use and their using in concrete. The practical part verifies the possibility of using these materials and their combination as an additive to concrete with impact on the physical and mechanical properties.

Secondary energy products are used in the construction industry for a long time. More strict environmental limits for emissions to air have created new technologies combustion of materials in thermal power plants. In this way combustion are produced a new secondary energy products. It is an attempt to find of suitable use for these products. Their use will have ecological impact on the environment and it will allow prepare of new compositions of higher utility properties. The aim of this study was to develop a new mixture, using the new secondary energy products, for production concrete with high utility properties.

>Magister Scientiae - MSc / The aim of this study was to produce useful composite materials from fly ash, a major waste product of coal combustion from power plants. Polyaniline-fly ash (PANI-FA) composites were prepared by in situ polymerisation of aniline in the presence of Fly Ash (FA) by two slightly different methods. In one case polystyrene sulphonic acid (PSSA) was used as a stabilizer and in another case the starting materials (aniline and FA) were aged before oxidation. The aging procedure formed nanotubes that have cross-sectional diameters of 50-110 nm. The other procedure produced nanotubes with a diameter of 100-500 nm and the length of up to 10μm. The presence of metal oxides and silica in FA were responsible for the formation of nanorods in PANI-PSSA-FA.. The formation of the composites was confirmed by UV-Vis and FTIR. The UV-Vis showed maximum absorbance at 330-360 nm ( due to π-π* transition of benzoid rings) and 600-650 nm(due to charge transfer excitons of quinoid rings), which are characteristics of emaraldine base. The electrochemical analysis of the composites showed that the composites were conductive and electroactive. The Cyclic Voltammetry of PANI-PSSA-FA showed three redox couples which are characteristics of sulphonated PANI. The morphology of the composites was studied by Scanning Electron Microscopy (SEM) and showed that our methods gave composites with improved homogeneity as compared to other reported methods. Thermo Gravimetric analysis (TGA) showed that the presence of FA in the composites improves the thermal stability of the composites by up to 100 0C.

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The deliberate use of fly ash in the production of concrete has been used for decades, but recent trends tend to maximise its utility properties. These are different types of activations from chemical through thermal to mechanical. An alkaline agent is added to chemical activation which, by etching the glass structure of the ash grain, promotes its reactivity. Mechanical activation is mainly focused on granulometry and particle size distribution curve. In this thesis three mechanical activation methods are compared: separation the ash into fractions by grain size, mixing these fractions to achieve the ideal particle size distribution curve and grinding. Four types of ash were collected from the Tušimice power plant – ash from individual electrostatic separators (I, II and III) and SESYP ash which represents the total volume of production. Ash from individual separators differ not only in the particle size but also in the chemical composition and reactivity. Better properties generally have smaller ash particles. This is used by mechanical activation by sorting. When mixing the individual ash fractions, the aim is to achieve an optimal grading curve of either the ash itself or the fine particle set in the concrete. In this work, ash is only used to calculate the mixing ratio and the grading curve according to Funk was selected as optimal. The last compared option of activation was grinding ash. Grinding was carried out in an industrial mill for 15, 30, 45, 60 and 75 minutes. The efficiency of the modified ash was monitored for cement paste in terms of rheology and for concrete in terms of consistency, strength and durability. Based on the results we can say that mechanical activation by sorting is suitable for special purposes, but it’s necessary to realise that coarser ash fractions remain unused. When mixing the fractions to ensure matrix density, the efficiency was shown mainly on the durability characteristics. Grinding cause positive effect.

About 27 million metric tons of municipal solid waste are used annually as fuel in U.S. Waste-to-Energy (WTE) power plants, which annually generate seven million tons of bottom ash (BA) and fly ash (FA). In the U.S., bottom ash and fly ash residues are mixed to “combined ash” (CA) in the approximate ratio of 6 to 1, and are disposed in landfills after metal separation. The disposal of WTE ash is a significant cost and land use item of waste management. This dissertation aims to (i) comprehensively understand the characterization and properties of WTE ash; (ii) provide practical and economic stabilization technologies to reduce the leachability of heavy metals in WTE ash and assessing whether it can be further beneficially used as secondary materials; (iii) utilize the stabilized/processed WTE ash as secondary construction materials in civil engineering applications, thus diverting materials from landfills and contributing to the circular economy. The Characterization section provides a comprehensive assessment of WTE bottom ash, fly ash, and combined ash, including chemical composition (XRF, ICP-OES, IC), mineral composition (X-ray diffraction-XRD quantification), thermogravimetric analysis (TGA), particle size distribution, and scanning electron microscopy (SEM). The physical properties of WTE residues were also investigated, including moisture, bulk density, specific gravity, void content, and water absorption. Leaching Environmental Assessment Framework (LEAF) Method 1313 of the U.S. Environmental Protection Agency (EPA) was used to understand the effect of eluate pH on the leachability of heavy metals. Combination of the above methods was applied to quantify the crystalline and amorphous phases present in WTE residues and produced specimens. In the U.S., WTE BA is discharged from the combustion chamber into a water tank. The BA includes 50-70% mineral fraction, 15-30% glass and ceramics, 5-13% ferrous metals, 2-5% non-ferrous metals, and 1-5% unburned organics. This thesis received the BA samples after ferrous and non-ferrous metal recycling. The major chemical composition includes SiO2 (34%), CaO (21%), Al2O3 (9%), and Fe2O3 (11%). According to XRD quantification results, BA consists of 76% amorphous phases (glass and metastable minerals), and the dominant crystalline mineral is quartz (SiO2, 12%). The calcium silicate (aluminate) hydrates (C-S-(A)-H) gel formed during the water quenching process embeds fine particles in the amorphous phases. The U.S. WTE air pollution control systems commonly include semi-dry scrubbers, with a few plants using dry scrubbers. FA consists of two kinds of particles: the furnace particles carried in the process gas and the newly-formed particles in the scrubber. The major chemical composition in FA includes CaO (40%), Cl (15%), SO3 (8%), CO2 (8%), and activated carbon/organic matter (3%) due to the injection of absorbents (hydrated lime and activated carbon) and the effects of flue gas scrubbing. The empirical formulae of the constituent crystalline (40-50%) and amorphous (50-60%) phases were derived. The excess water in semi-dry scrubbers improved the hydration reaction between newly-formed particles and furnace particles and resulted in the transformation of amorphous phase to calcium silicate hydrates (C-S-H) phase. The hydration products of semi-dry FA immobilized some heavy metals and reduced their leachability to below the levels of the Resource Conservation and Recovery Act (RCRA) by Toxic Characteristic Leaching Procedure (TCLP) test, as compared to dry scrubber FA, which exceeded the limits of RCRA. The U.S. combined ash can pass the TCLP test and comply with the RCRA standards for non-hazardous landfill disposal. The Stabilization section examines the effects of processing combined ash. CA undergoes water washing, crushing, and size separation processes to three fractions: coarse (27%, CCA, 9.5-25 mm), medium (37%, MCA, 2-9.5 mm), and fine (25%, FCA, < 2 mm), identified by particle size distribution results. The by-products of the washing process are extra fine filter cake ash (EFFCA, 8% of CA) collected from the water treatment system and ash dissolved in the wastewater (3% of CA). The characterization (chemical composition, mineral composition, and leachability) of ash the fractions (CCA, MCA, and FCA) showed that their mineral changed during the processing and exhibited significantly lower leachability (LEAF Method 1313-pH dependence), in comparison to as-received CA. The processed ash fractions with reduced leachability of heavy metals, can be further beneficially used as secondary materials. The effect of pH of the washing agents (water, acid and alkaline solutions) on the chemical/mineral transformation and the heavy metals leachability of the FA, BA, and CA was assessed. A novel technique of determining the distribution of various elements in washed ash (product), filter cake (by-product), and wastewater (dissolution) during ash processing was developed to compare the effectiveness of the washing process, which is dominated by dissolution and precipitation reactions. As-received FA, BA, and CA contained 50-75% of amorphous phases in metastable status, which are transformed to crystalline phases during the washing process. It was concluded that water washing is the most practical method for transforming WTE CA to construction material. The Utilization section examined the use of WTE ash in civil engineering applications, i.e. (i) Using the CCA and MCA fractions as stone aggregate substitute in structural concrete; (ii) Using FCA as sand substitute or using the milled FCA (MFCA) powder as mineral addition in cement mortar; (iii) Using FCA and EFFCA powder as metakaolin substitute in artificial aggregate; (iv) Using FA and phosphate FA (PFA) as cement substitute in cement mortar. In conclusion, the CA size fractions, i.e., MCA and CCA, are suitable for use as aggregate substitutes in the production of structural concrete. Up to 100 wt.% of stone aggregate in concrete can be substituted by MCA and CCA. The compressive strength of the optimal products exceeds 28 MPa after 28 days of curing, which is comparable to commercial concrete products using natural stone aggregate. The optimum concrete mixture composition was 40 wt.% of MCA or CCA, 30 wt.% sand, 20 wt.% cement, 10 wt.% water, and superplasticizer, with compressive strength of 28-30 MPa and elastic modulus of 6,300-6,600 MPa. The optimal products complied with stringent leaching standards, and the properties of the final products were comparable to the conventional civil engineering materials. All FCA or MFCA products were effectively stabilized/solidified and transformed to non-hazardous material that can be used in construction. The main challenge in the utilization of FCA or MFCA in cement mortar is the cementitious phase expansion due to the metallic aluminum present in FCA or MFCA. It was concluded that up to 50 vol.% of sand in cement mortar can be directly substituted by FCA, and up to 25 vol.% of MFCA can be utilized as mineral addition to replace cement in the production of cement mortar. In the production of artificial aggregates, up to 15% of FCA or up to 10% of EFFCA can replace metakaolin by volume. The produced samples indicated crushing strength of 4 and 1.5 MPa, respectively. The specific gravity and water absorption of optimal ash aggregate is 1.3 and 30%. The FCA and EFFCA aggregates exhibited good chemical stability and reduced the cracks observed in the fire resistance test. The ash aggregates can be used as a lightweight aggregate for non-structural applications. FCA can improve the workability of the metakaolin mixture and extend the setting time, which is beneficial for geopolymer aggregate manufacturing. The heavy metals from FCA and EFFCA can be effectively stabilized/solidified in artificial aggregate. Phosphoric acid can effectively stabilize the as-received FA, so that the dry scrubber FA passes the TCLP test and complies with the RCRA standards. The mineral transformations of individual ash and ash-cement paste were investigated by the XRD quantification analysis. FA and PFA enhanced the hydration degree of cement, and received higher mechanical performance than reference in 0-25 vol.% cement replacement. The leachability of heavy metals was effectively reduced in a wide leaching range (eluate pH 0-12.5), realized the stabilization/solidification purposes under restricted non-hazardous landfill standards.

D. Tech. (Department of Mechanical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Cracked concrete slabs are a problem due to several factors such as poor maintenance, insufficient reinforcement or steel corrosion leading to crack propagation. There is a need to increase the load-bearing capacity of concrete slabs and increase their life span. The use of waste Polyethylene Terephthalate (PET) fibres and fly ash in a hybrid composite slab dramatically alleviates the problem of crack propagation and failure sustainably. This study aimed to optimize a waste PET fibre/fly ash hybrid cement composite for use in slabs. This study characterized the raw materials used, including fly ash and aggregates. After that, concrete test specimens were fabricated using the PET fibres and fly ash following the full factorial experimental design. The developed specimens were then tested to ascertain their material strength properties. Model development was carried out using Minitab Software Version 14, and subsequent experimental validation was carried out. After that, the PET and fly ash optimisation for maximum favourable response outcome was carried out. The fly ash was found to belong to the Class F category with particle size ranging from 0.31 μm to 800 μm. The fly ash was mainly spherical and consisted of Ca, Al, P, Si, and trace amounts of Ti and Mg. The spherical shape of the fly ash helped improve the concrete's workability. The river sand had a fineness modulus of 3.69, considered coarse sand. The fine aggregate showed uniform particle size distribution with a uniformity coefficient of 4.007. The coarse aggregate characterisation was carried out and revealed that the aggregate particle size was 13 mm in size. The coarse aggregate had a uniformity coefficient of 4.007, which implied the aggregate was well graded. The coarse aggregate had a high flakiness index of 74.82 % and an acceptable elongation index of 46.72 %. Full factorial methodology experimental design was employed to fabricate the test specimens by simultaneously varying the independent factors to develop a model for overall response variation. The slump value was observed to increase with the addition of fly ash. However, the addition of PET fibre decreased the slump value with incremental amounts of fibre. The combined effect of fibre addition and fly ash showed a general decreasing slump value for all quantities of fly ash content. The compressive strength of PET fibre only composite had maximum strength at 0.5% fibre addition, and the composite with fly ash alone had the maximum compressive strength at 15%. The combined optimum compressive strength for fibre and fly ash was at 0.5 % and 15 %, respectively, with a 15.54 N/mm2. The split tensile strength decreased with an increase in fibre content. However, the fibre provided crack retardation. Fly ash increased the split tensile strength significantly to a peak of 2.35 N/mm2 for 20 % fly ash addition. The combined addition of fibre and fly ash had an optimum split tensile strength of 2.79 N/mm2 at 0.5 % fibre and 20 % fly ash. The addition of fibre had an optimum split tensile strength at 0.5% of 1.82 N/mm2. The fly ash increased the flexural strength, with optimum strength at 15 %. The combined addition of fibre and fly ash created optimum flexural strength at 0.5% and 30 %, respectively. The trend observed by the rebound number followed that of the compressive strength. However, the non-destructive rebound hammer method gave significantly lower strength values than the destructive test method. The addition of fly ash had the effect of lowering the cost of producing the slab. However, the addition of fibres marginally increased the cost. The combined effect of fibre and fly ash resulted in a significant cost saving. Numerical optimisation was carried out concerning the fibre reinforced concrete's fresh and hardened mechanical properties. Predictive modified quadratic equations were developed for slump value, compressive, flexural, split tensile strength and total cost. Analysis of variance test carried out for all the responses indicated that the model could predict the slump value and mechanical properties of the fibre reinforced concrete correctly and effectively with a coefficient of determination in the range of 0.4151 to 0.9467. The developed model can predict the required fibre reinforced fresh and hardened properties in order to assist in decision making in construction in slabs. The optimum constituent combination for maximum mechanical strength at the lowest possible cost was found to be 15.7576 % Fly ash and 0.3232 % PET fibre with optimum responses as shown in Table 4-26. These predictions were validated experimentally, and a good correlation was observed between the actual and predicted values based on the observed standard deviations of 0.1335, 0.031, 0.005, 0.676, 0.02 for compressive strength, flexural strength, tensile strength, slump value and cost, respectively. Concrete slabs were optimised for various possible end uses, and the optimum PET fibre % and fly ash % were ascertained as shown in Table 4-27.

Published Article / Fly Ash is a by-product at thermal power stations, also otherwise known as residues of fine particles that rise with flue gases. An industrial by-product may be inferior to the traditional materials used construction applications, but, the lower the cost of these inferior materials make it an attractive alternative if adequate performance can be achieved. The objective of this study is to evaluate the chemical and physical effectiveness of self-cementing fly ashes derived from thermal power stations for construction applications with combined standards. Using laboratory testing specimens, suitable types of Fly Ashes namely: Kendal Dump Ash, Durapozz and Pozzfill, were tested to the required standards to evaluate the potential properties. All three Fly Ashes have been classified as a Class F Fly Ash, which requires a cementing agent for reactions to take place and for early strength gains in the early stages of the reaction processes. The Fly Ashes conformed to the combination of standards and have shown that the proper reactions will take place and will continue over period of time. The use of fly ash is accepted worldwide due to saving in cement, consuming industrial waste and making durable materials, especially due to improvement in the quality fly ash products.