Geopolymer cements present a unique opportunity to make concrete binders almost entirely out of waste stream materials. Geopolymers made from fly ash, a waste product of coal power generation, as the aluminosilicate source and caustic activating solution were the focus of this study. However, the use of waste stream materials presents many challenges. One major stumbling block is that fly ash is inherently variable in composition and difficult to comprehensively characterize. The purpose of this work was to clarify the relationship between fly ash composition and reactivity in geopolymer cements. Ten fly ashes comprising a wide compositional spectrum were selected for the study and were characterized using quantitative x-ray diffraction and multispectral image analysis (MSIA) of x-ray maps coupled with point compositional analysis. The fly ashes were mixed into geopolymer mortars to determine their reactivity when activated as geopolymers. I hypothesized that the fly ashes that performed well under geopolymer formation conditions would have similarities in the glassy phases identified in them. The fly ashes that resulted in geopolymers with high compressive strengths did have several glassy phases in common. The phases were typically high in calcium, high in silicon, and somewhat low in aluminum. To determine whether the common phases were soluble and therefore likely to be dissolved, a dissolution method was used in which fly ash was mixed with concentrated caustic solution and continuously agitated; after 7 d and 28 d, the solid residues from the dissolution were studied using MSIA. The results showed that most of the glassy phases hypothesized to react were reactive, although the results were somewhat complex due to the heterogeneity of fly ash. The MSIA method proposed in previous work was further developed through this study, and a new way of selecting the training classes for phase composition assignment in the images was proposed. / text

It is common practice to purposely trap small air-voids in concrete in order to give it frost resistance. A large number of factors have been recognized to impact the ability to entrain and stabilize these microscopic air-voids in concrete. This dissertation investigates a number of these variables. However, the primary focus of this work is on investigating problems entraining and stabilizing air in concrete utilizing fly ash. These investigations include: evaluation of existing and newly created test methods to measure the impact of fly ash on the ability to air-entrain concrete, and the fresh and hardened properties of air-entrained fly ash concrete is investigated. Additional work is presented concerning some of the fundamental physical and chemical properties of air-void shells separated from cement paste and how they change with time.

published_or_final_version / Botany / Master / Master of Philosophy

published_or_final_version / Civil and Structural Engineering / Doctoral / Doctor of Philosophy

Fly Ash was tested in relation to its ability to mitigate alkali-silica reaction, its contribution to strength, electrical resistance and heat release with the aim of recommending improvements to fly ash specifications. ASTM C 1567 accelerated mortar bar test results were in agreement with an expansion limit of 0.10 % at 14 days. A non-standard alkali leaching test showed that with high alkali fly ashes as replacement level increases the amount of alkalis leached increases while prism expansions decrease. Measures of pozzolanic activity can be improved by measuring against non-pozzolanic fillers, This requires high replacement levels to reduce statistical variability. Isothermal calorimetry tests showed that high calcium fly ashes can lead to delays in hydration, these delays can be reduced by calcium hydroxide additions. Calcium sulphate additions can also improve hydration.

Fly Ash was tested in relation to its ability to mitigate alkali-silica reaction, its contribution to strength, electrical resistance and heat release with the aim of recommending improvements to fly ash specifications. ASTM C 1567 accelerated mortar bar test results were in agreement with an expansion limit of 0.10 % at 14 days. A non-standard alkali leaching test showed that with high alkali fly ashes as replacement level increases the amount of alkalis leached increases while prism expansions decrease. Measures of pozzolanic activity can be improved by measuring against non-pozzolanic fillers, This requires high replacement levels to reduce statistical variability. Isothermal calorimetry tests showed that high calcium fly ashes can lead to delays in hydration, these delays can be reduced by calcium hydroxide additions. Calcium sulphate additions can also improve hydration.

&Ccedil / ayirhan soil is a collapsible soil. Collapsible soils are generally unsaturated, low-density soils with high voids between grains where the binding agents are sensitive to saturation. When exposed to water, binding agents break, soften or dissolve such that the soil grains shear against each other and reorient in denser configurations. This reconfiguration causes a net decrease in the soil mass, resulting in large and often unexpected settlements, which can totally destroy roads, underground utilities, and structures and alter surface drainage. Uses of collapsible soils as a natural construction material in fills or embankments also may cause serious stability problems. In this study, an extensive research program was carried out to investigate some geotechnical properties such as compaction, triaxial strength, bearing ratio and permeability of collapsible soil, found in &Ccedil / ayirhan Thermal Power Plant area, by treating with Class C fly ash and desulphogypsum (thermal power plant by-products that are to be handled for environmental reasons) in various proportions. The study has revealed that 20% and 25% fly ash or 5% desulphogypsum treatments (by dry weight of the mixture) improve the strength and bearing characteristics of &Ccedil / ayirhan soil.

Particulate filled polymer composites are gaining growing acceptance in the commodity industry because the properties can be adjusted according to the industry's requirements. As particulate filler, fly ash is ready to compete with other particular fillers in polymer composites industries. Although fly ash is a cheap material but the fact that fly ash is grey-black in colour, limits the application of fly ash only to product where colour is not important. As such, a method was needed to be developed to increase the whiteness of fly ash without reducing the advantages of it as a cheap material. In this research, twelve commercially provided fly ash samples from Australian thermal power stations were investigated with respect to composition. Seven of them were thermally modified and further investigated and characterized with respect to colour, size, size distribution, and density. Of these seven fly ashes a particular grade was modified to a whiteness of 93.3 in L*a*b* scale (using barium sulfate as standard), without changing other inherent properties such as particle size and density. By comparison L*a*b* value for Omy carb 20, based on calcium carbonate is 96.9. The whiteness of fly ash was increased using a one stage thermal method ensuring the related cost of production would be not a major hurdle. The next aspect of the thesis involved incorporating as-received and heat treated fly ash samples in isotactic polypropylene up to 80 parts of fly ash per hundred resins (phr), demonstrating that fly ash content in polypropylene composites can be quite high with properly maintained combination of mechanical properties -- in particular up to 200 % improvement in Young's modulus and 63 % gain in notched impact properties, as explained in the thesis. Whilst the Young's modulus properties of the fly ash PP composites match very well with Kerner model, they lie in between the Rule of Mixture series and parallel. The tensile strength properties obtained in this research are at least 25 % higher than those predicted by Nielsen, Landon and Nicolais; whereas the strain to failure values are between 25 - 50 % higher than those predicted by Nielsen, and Smith. Whilst tensile strength of the fly ash filled polypropylene composites were less than the original polypropylene samples, as normally reported in the literature, in this thesis surface modification of fly ash particles by using 10% vinyl triethoxy silane (VTES) coupling agent gave a nominal increase in tensile strength especially at higher fly ash content. The final aspect involved study of oxidation behavior of fly ash filled polypropylene composites. Fillers, including fly ash can shorten the life time of polymers from both chemical as well as physical factors. As-received fly ash contains iron based impurities which may catalyze the anti oxidant in polypropylene, therefore reducing the service life time of the polymer. In this work, thermal treatment studies showed that the iron in fly ash can be changed to a chemically inert material so the effective service life of the polymer will only be influenced by physical factors. Therefore thermal treatment of fly ash not only increases the whiteness but also it reduces the risk of the filler on the life time of the polymer, and hence the composites.

This is partly because the requirements for such an ultimate material change with people’s perception about its properties as well as its environmental impact. Thus, the once-believed ultimate Portland cement binder is now becoming unacceptable for a number of reasons including poor durability as well as severe environmental impact during production. Thus, an improved mineral binder is required by modern society to serve the same purposes as the existing Portland cement binder, as well as to reduce the current environmental impact caused by Portland cement production. / Geopolymerisation is such a ‘green’ technology capable of turning both natural ‘virginal’ aluminosilicates and industrial aluminosilicate wastes, such as fly ash and blast furnace slag, into mechanically strong and chemically durable construction materials. However, the source materials for geopolymer synthesis are less reactive than Portland cement clinkers and the chemical compositions of these source materials can vary significantly. Consequently, product quality control is a major engineering challenge for the commercialisation of geopolymers. / This thesis is therefore devoted to the mechanistic understanding of the interfacial chemical interactions between a number of natural and industrial aluminosilicates and the various activating solutions, which govern the reactivity of the aluminosilicate source materials. The effects of activating solution alkalinity, soluble silicate dosage and anionic contamination on the reactivity of the aluminosilicate source materials to produce geopolymeric binders, as well as their bonding properties to natural siliceous aggregates for concrete making, are examined. In particular, a new set of novel ‘realistic’ reaction models has been developed for such purposes. These reaction models have been further utilised to develop a novel analytical procedure, which is capable of studying geopolymerisation on ‘real’ geopolymers in situ and in real time. This novel procedure is invaluable for the total understanding of geopolymerisation, which is in turn vital for effective geopolymer mix designs.

Thesis (Ph.D.)--University of Melbourne, Dept. of Chemical Engineering, 2003. / Typescript (photocopy). Includes bibliographical references.