Philosophiae Doctor - PhD / Power generation in South Africa depends majorly on the combustion of coal and the increasing demand for energy due to industrialisation and population growth signifies the continuous consumption of coal. During this process, a by-product known as coal fly ash (CFA) is generated which poses several environmental issues. The common management of the waste involves the disposal of CFA in landfills or the direct disposal to open uncultured lands, thus contaminating water bodies by the leaching of constituent CFA metals and salts that render arable land uncultivable.

This thesis examines the possibility of creating composite mainly from waste materials. The matrix of this composite was prepared from fly ash type F, which was activated by sodium water glass. Wood chips were used as a filler. This thesis includes theoretical and experimental parts. The theoretical part deals with the most important issues of wood composites with an inorganic matrix as well as basic components of investigated composite, ie alkaline activated fly ash and wood. In the experimental part, the fly ash pastes were prepared, from which the most suitable mixture was chosen for the composite preparation. Properties of wood composite with alkali activated fly ash matrix were investigated depending on the dose of wood chips.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg In fulfillment of the requirements for the degree of Master of Science in Geography and Environmental Studies 31 May 2018 / South Africa will be dependent on coal for power generation for many decades to come, before a complete transition is achieved where more energy will be generated from non-fossil fuel sources. Through case studies of Hendrina and Kendal Power Stations, this study explored how the management of fly ash (FA) waste in South Africa can be improved to minimise its impact on the environment and human health and examined the potential recycling applications that can benefit local communities. The study drew insights from an environmental justice framework to examine the pollution impacts that FA is exposing to the local community. The environmental justice theory is based on the principle that all people have a right to live in an environment that enhances their wellbeing. Empirical evidence obtained from local community’s in-depth interviews revealed that FA is impacting on the health of communities by exposing them to respiratory and other illnesses and it is also affecting their livelihoods which primarily involves farming. A just transition theory was employed to examine potential socio economic opportunities that can be derived from FA recycling to fulfil redistributive measures that can reduce inequality and eradicate poverty in local communities. Some of Eskom’s power stations like Hendrina are nearing the end of their lifespan since their commissioning in the 1960’s and 1970’s. To aid a just transition, ash recycling was found to have the potential to address the socio economic situation of the power station’s employees and the local communities. The study found that local communities generally lack knowledge about coal ash recycling and need to be empowered and supported to partake in ash recycling ventures. The study argues that a shift in the ash recycling regime is needed in order to benefit local communities and facilitate a just transition to a clean energy production. / MT 2018

Degree: PhD Department: Engineering / 1997, South African’s major power utility, recognised the need to improve the understanding of fly ash formation and slag deposition of South African coals. This requirement is due to the predicted quality changes of power station feedstocks and the limited research into the slagging propensity of South African coals. This research seeks to develop an analytical technique and a fly ash formation model for predicting the slagging propensity of coals. The research will establish if the models based on Carboniferous coals can be applied to South African Permian coals. A water-cooled suction pyrometer with a custom designed slag probe was used to obtain samples of fly ash and slag from within a 200 MWe pulverised fuel boiler. Simultaneously, samples of pulverised fuel feedstock were collected. The mineral attributes in the pulverised fuel and the phases in fly ash and slag deposit were quantified by CCSEM. The analytical procedure, CCSEM, has been developed with a novel procedure for identifying minerals and C-bearing phases. The new fly ash formation model assumes that the mineral attributes of the combusting pulverised fuel particle controls the size and elemental signature of the resultant fly ash particle(s). The new model has shown that the inherent mineral attributes controls the physical and chemical characteristics of the initial fly ash phases. Thereafter, conditions (stoichiometric, temperature and turbulence) within the combustion chamber promote the physical and/or chemical interaction of the initial fly ash particles. Slag deposits are enriched in Ca- and Fe-bearing alumino-silicates. The new slagging propensity index is based on either predicting or measuring the proportion of Ca- and Fe-bearing alumino-silicates. iv The numerous fly ash formation models, based on Carboniferous coals are not necessarily valid for South African coals. It is not the integrity of the actual fly ash formation mechanisms that is questioned, but rather the experimental scale on which the models are based. This research has produced an analytical technique and a fly ash formation model to predict the slagging propensity of coals. This forms a platform for further research into the role that organically bound cations, combustion conditions and boiler configuration has on the formation of Ca- and Fe-bearing alumino-silicates.

Finding innovative technologies for building our roads has always been of paramount importance. From moving to warm mix asphalt to decrease our indulgence in high energy consumption to substituting fly ash for asphalt binders to reduce dependence on pure asphalt binders from petroleum, engineers have painstakingly tried to develop new ways to improve the ways that flexible pavements are made. The major problem facing the next generation of civil engineers is sustainable practices on the field. Over the years, significant progress has been made in this regard on the impacts of building pavements on the environment. Characterizing these improvements tends to be difficult, and that is where Life Cycle Assessment (LCA) comes in. LCA is a technique used to analyze and quantify the environmental impacts of a product, system, or process. LCA shows where the significant impacts occur and how improvements can be made while recommending better practices. Even with its many advantages, its use is very constrained, especially in the United States, as it is still a very novel approach in design coupled with limited datasets and protocol for its operation. With modern technologies of substitute materials for binders like bio-oil from food waste, reclaimed asphalt pavement (RAP), and fly ash, there is a need to understand their environmental impacts. Furthermore, in this regard is where LCA can help using three significant areas: selection of materials, normalization, and characterization. Characterization refers to the identification and quantification of the relationships between the life cycle results and the environmental impacts. This research explores the environmental impacts of substituting other materials for asphalt binders using LCA. With variations in modifying levels of substitutes, results show promising levels in emissions of harmful gasses to both the air and water. This study explores ways used in normalizing this process as well as setting up a pathway for other asphalt binder substitutes. / Civil Engineering

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worse than degradation at the crown of the sewer pipe. Furthermore, results from this study show that high resistance under the static acid corrosion exposure condition cannot be extended to mean high resistance under the erosion-corrosion exposure condition for some concrete mixes. In this study, the static HCl test and the dynamic HCl test were used to measure the resistance of concrete mixes under the static corrosion exposure condition and erosion-corrosion exposure condition respectively. However, concretes that exhibited high resistance to the erosion-corrosion exposure condition were consistent in exhibiting high resistance to the static corrosion exposure condition. This finding is consistent with the sequence of corrosion processes in MIC, wherein dissolution of the concrete components occurs before the precipitation of corrosion products. Therefore, it expected that high resistance in the dynamic acid test (i.e. resistance to dissolution) implies high resistance in the static test, which measures the combined resistance of dissolution and resistance emanating from corrosion products. Both static and dynamic acid corrosion tests revealed that the geopolymer concretes tested in this study outperformed PC and CAC concretes. Results from the static HCl test showed that GP-ferro-quartz concrete, the most durable concrete specimen, provided a 69-fold improvement in resistance when compared to PC-dolomite mixes (control #1) and a 4.72-fold improvement in resistance when compared to CAC-dolomite mixes (control #2). Results from the dynamic HCl test show that the GP-ferro-quartz mix provided a 180-fold increase in resistance when compared to the PC-dolomite mix and a 275-fold increase when compared to CAC-dolomite mix. The CACdolomite mix was found to have the lowest resistance to the erosive-corrosive exposure conditions of the dynamic HCl test. Thus, in terms of the concrete MIC resistance properties identified in this study, it is suggested that the CAC-dolomite mix had poor kinetic resistance to dissolution. However, under the static acid test (static corrosion exposure condition), the CAC-dolomite mix performed better than the PC-dolomite mix and GP-dolomite mix. CAC-dolomite concrete performed inferiorly only to the set of GP-siliceous-aggregate mixes in the static HCl test. The difference in the performance of CAC-dolomite concrete performance between the static and dynamic test is largely attributed to the formation of alumina gel, an acid corrosion product of CAC hardened paste, which envelopes the concrete specimen and reduces the rate of surface corrosion in the static HCl test. However, under v the dynamic HCl test, the gel layer is brushed off the surface of the concrete specimen rendering it ineffective in protecting the concrete specimen from corrosion. Previous research on the acid attack of concrete posits that the chemical make-up of concrete materials has a strong bearing on corrosion behaviour. To this end, various measures have been suggested such as the ratio of calcium to silicon (Ca/Si) in concrete. The approach utilised in this study was to calculate the “basicity value” which provides the ratio of major basic to acidic oxides found in the concrete. XRF analysis of the hardened cement pastes and the 5 aggregate types used in the experiments enabled the calculation of basicity values. The combined basicity value for concrete specimens was determined by proportionally summing (according to mass) the basicity values of the aggregate and hardened cement paste parts. A strongly correlated linear relationship between the basicity value of concrete and the corrosion rate from the dynamic HCl test was established. This empirical relationship warrants further investigation and verification, as it would, in principle provide a means to estimate the dissolution rate of concrete by calculating its basicity instead of undertaking laboratory acid tests. Basicity was also found to be useful in determining the corrosion compatibility of binder type and aggregate types. It was found that the difference between the basicity value of hardened cement paste and the basicity value of the aggregate was useful in determining the type and extent of preferential corrosion of a concrete specimen tested under the dynamic HCl test. For ease of reading, this difference was called the “basicity differential”. By visually assessing corroded concrete specimens from the dynamic HCl test, it is was possible to determine whether the hardened cement paste or aggregate component was preferentially corroded, and to gauge the extent of preferential corrosion visually. GP-ferro-quartz and GP-granite concretes had the lowest levels of preferential corrosion which corresponded to their low basicity differential values. In contrast, CAC-dolomite concrete had the highest basicity discrepancy which corresponded visually to a high preferential corrosion of the hardened cement paste. Mineralogical analysis via XRD, found that the hardened cement pastes of the three binder types consisted mainly of amorphous phases (>70%). The crystalline phase of the geopolymer hardened cement paste was mostly constituted by insoluble minerals such as mullite. This partially explains the higher corrosion resistance of geopolymer concretes. However, a more comprehensive explanation needs to include analysis of the amorphous phases, which fell outside the scope of this study. SEM analysis of HCl corroded geopolymer hardened cement paste found that fly ash spheres embedded within the geopolymer matrix were preferentially corroded. This indicates that fly ash content negatively affected the rate of corrosion of the geopolymer hardened cement paste. Furthermore, SEM analysis showed that the geopolymer matrix surrounding the fly ash spheres was relatively intact.

The biogenic amines serotonin (5HT), dopamine (DA), and octopamine (OA) have been indicated in the regulation of behaviors, including aggression. The flesh fly, Sarcophaga crassipalpis, was used to investigate ontogenetic and circadian changes in amines and aggression. Heads of male flies were analyzed for amine content using high performance liquid chromatography with electrochemical detection (HPLC-ECD) at 3 time points on each of 4 consecutive days in 2 light cycles, 12:12 LD and 15:9 LD. Both DA and OA levels decreased with age. Light-cycle dependent differences were observed for all amines in overall levels and patterns of change throughout the day. A behavioral assay quantified interactive and aggressive behaviors at three time points in the light period for 2 age groups. The daily changes in behavioral profiles differed dependent on age. Correlations from these data can be made between changes in amine levels and time of day, photoperiod, age, and aggressive state.

This thesis has determined that using fly ash as a mineral filler in asphalt pavements can help strengthen and reduce asphalt moisture damage. Also, dynamic shear rheometer tests show that these additives have a stiffening effect on asphalt binder. Moisture related damage is considered one of the main causes of asphalt pavement failure. As water infiltrates a layer of asphalt, it slowly strips away asphalt binder, weakening the aggregate/binder bond. This process, combined with the cyclic loading of traffic, can lead to several different types of asphalt failure including rutting, raveling, bleeding, and cracking. For several decades, research has been conducted to find a solution to this problem. Currently in practice, hydrated lime and a variety of amine-based chemicals are being used as anti-stripping agents. However, as an emphasis towards sustainability has increased, waste products are now being investigated for this purpose. This thesis investigated the anti-stripping effectiveness of two waste products: fly ash and cement kiln dust (CKD), and compared them with hydrated lime and an amine-based chemical additive. The results indicate that class C fly ash can be used as an asphalt anti-stripping additive; however it is more costly than lime or amine chemicals.

Biomass represents an important sustainable energy resource, with biomass-coal cofiring representing among the most effective and cost efficient CO2 reduction strategies. Fly ash generated during coal combustion represents a technically advantageous, inexpensive, and environmentally beneficial admixture in concrete production, partially replacing cement. However, strict interpretation of American Society of Testing and Materials (ASTM) and American Concrete Institute (ACI) standards prohibits use of fly ashes from any source other than coal in concrete production; therefore, fly ash from biomass coal cofiring is excluded from use in concrete. This dissertation discusses biomass impacts on concrete properties through experiments conducted on several combinations of blended and pure biomass fly ash in concrete mixtures to determine the effects on freshly mixed concrete, strength and durability of hardened concrete, and implication for long-term material properties. The results show that the performance of biomass and blended biomass-coal fly ash is comparable to that of traditional (neat) coal fly ash. Pozzolanic reactions occur simultaneously but not necessarily proportionally to strength development. Mixtures of biomass and coal fly ash in all proportions mitigate alkali-silica-reaction-based (ASR-based) expansion in concrete. Biomass-specific results indicate that biomass-containing fly ash samples can generate 3-6 times the strength of some neat coal fly ash samples in terms of pozzolanic reactions and that biomass-containing fly ash samples have better or comparable ASR mitigation performance relative to neat coal fly ash. Biomass fly ash applications in concrete production involve pozzolanic, cementitious, and ASR reactions in combination with mixture compositions and preparation techniques to dictate ultimate properties. In these practical applications, biomass fly ash demonstrates no consistent improvement or deprecation of concrete properties relative to coal fly ash. Quantitative pozzolanic reaction mechanism and kinetic analyses indicate biomass and coal fly ashes exhibit comparable reaction rates and react by similar mechanisms. The general conclusion from the experiments is that biomass-containing fly ash, when used in concrete, performs comparable to or better than similar neat coal fly ash preparations in most respects; Substantial efforts were made to ensure samples represent typical commercial samples. Therefore, there exists no reason to exclude biomass from cofiring applications on the basis of fly ash performance in concrete and the related standards should be revised.