The influence of calcium content on the structure and thermal performance of fly ash based geopolymers

The influence of calcium and its content on the structure formation, hardening, and performance of fly ash based geopolymeric binder was the objective of our investigation. Calcium hydroxide was added to fly ash in different amounts. Since it is known that the formed structure determines certain properties of the material, the coherence between different types and various ratios of the reaction products on thermal properties such as strength after thermal treatment up to 1,100 °C, thermal resistance under load, creep in compression, and axial dilation were investigated. The results were compared to the type and composition of the reaction product, which was detected, for example, by ²⁹Si NMR spectroscopy and X-ray diffraction. Along with calcium containing zeolitic phases, the calcium built C–S–H-phases using the silicon from the fly ash, both of which crystallize or convert into new phases at elevated temperatures.     

Reduction of metal leaching in brown coal fly ash using geopolymers

Current regulations classify fly ash as a prescribed waste and prohibit its disposal in regular landfill. Treatment of the fly ash can reduce the leach rate of metals, and allow it to be disposed in less prescribed landfill. A geopolymer matrix was investigated as a potential stabilisation method for brown coal fly ash. Precipitator fly ash was obtained from electrostatic precipitators and leached fly ash was collected from ash disposal ponds, and leaching tests were conducted on both types of geopolymer stabilised fly ashes. The ratio of fly ash to geopolymer was varied to determine the effects of different compositions on leaching rates. Fourteen metals and heavy metals were targeted during the leaching tests and the results indicate that a geopolymer is effective at reducing the leach rates of many metals from the fly ash, such as calcium, arsenic, selenium, strontium and barium. The major element leachate concentrations obtained from leached fly ash were in general lower than that of precipitator fly ash. Conversely, heavy metal leachate concentrations were lower in precipitator fly ash than leached pond fly ash. The maximum addition of fly ash to this geopolymer was found to be 60wt% for fly ash obtained from the electrostatic precipitators and 70wt% for fly ash obtained from ash disposal ponds. The formation of geopolymer in the presence of fly ash was studied using 29Si MAS-NMR and showed that a geopolymer matrix was formed. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) imaging showed the interaction of the fly ash with the geopolymer, which was related to the leachate data and also the maximum percentage fly ash addition.     

Creep and drying shrinkage of a blended slag and low calcium fly ash geopolymer Concrete

The main purpose of this research is to study the time dependent behaviour of a geopolymer concrete. The geopolymer binder is composed of 85.2 % of low calcium fly ash and only 14.8 % of ground granulated blast furnace slag. Both drying shrinkage and creep are studied. In addition, different curing conditions at elevated temperature were used. All experimental results were compared to predictions made using the Eurocode 2. The curing regime plays an important role in the magnitude and development of both creep and drying shrinkage of class F fly ash based geopolymer concrete. A minimum of 3 days at 40 °C or 1 day at 80 °C is required to obtain final drying shrinkage strains similar to or less than those adopted by Eurocode 2 for ordinary Portland cement (OPC) concrete. Creep strains were similar or less than those predicted by Eurocode 2 for OPC concrete when the geopolymer concrete was cured for 3 days at 40 °C. After 7 days at 80 °C, creep strains became negligible.     

Microstructural changes in alkali activated fly ash/slag geopolymers with sulfate exposure

Sulfate attack is recognized as a significant threat to many concrete structures, and often takes place in soil or marine environments. However, the understanding of the behavior of alkali-activated and geopolymer materials in sulfate-rich environments is limited. Therefore, the aim of this study is to investigate the performance of alkali silicate-activated fly ash/slag geopolymer binders subjected to different forms of sulfate exposure, specifically, immersion in 5 wt% magnesium sulfate or 5 wt% sodium sulfate solutions, for 3 months. Extensive physical deterioration of the pastes is observed during immersion in MgSO₄ solution, but not in Na₂SO₄ solution. Calcium sulfate dihydrate (gypsum) forms in pastes immersed in MgSO₄, and its expansive effects are identified as being particularly damaging to the material, but it is not observed in Na₂SO₄ environments. A lower water/binder (w/b) ratio leads to a greatly enhanced resistance to degradation by sulfate attack. Infrared spectroscopy shows some significant changes in the silicate gel bonding environment of geopolymers immersed in MgSO₄, attributed mostly to decalcification processes, but less changes upon exposure to sodium sulfate. It appears that the process of ‘sulfate attack’ on geopolymer binders is strongly dependent on the cation accompanying the sulfate, and it is suggested that a distinction should be drawn between ‘magnesium sulfate attack’ (where both Mg²⁺ and SO₄ ^2? are capable of inducing damage in the structure), and general processes related to the presence of sulfate accompanied by other, non-damaging cations. The alkali-activated fly ash/slag binders tested here are susceptible to the first of these modes of attack, but not the second.     

Use of a high-calcium fly ash in blended type cement production

Eighty percent of fly ash produced by Greek Public Power Corporation (PPC) is of a high-calcium variety. It has a low insoluble residue and a high content in CaO as well as in SO₃. It also shows self-cementing properties. About 20% of it is used by cement companies in blended type cement production.

In this paper mechanical strengths and some other characteristics concerning blended cement and concrete made with it are presented. Special difficulties anticipated in using such a marginal fly ash in cement are also mentioned.     

Study of electric-arc furnace dust (EAFD) in fly ash and rice husk ash-based geopolymers

Electric-arc furnace dust (EAFD) is an industrial waste produced by the volatilization of metals during scrap melting in electric arc furnaces. This waste is classified as Class I – hazardous, because lead and cadmium concentrations are above the limits set in the leaching test. Processes are carried out in many countries to recover the metals contained in EAFD. In Brazil, these processes are usually not conducted in the industry because the low percentage of commercially valuable metals makes it economically unfeasible to recover them. One of the study alternatives is the use of EAFD in civil construction. Studies have shown that EAFD increases the mechanical strength of mortars and Portland cement-based concretes. However, EAFD delayed cement setting time, which can jeopardize its use in construction. Thus, this study aims to evaluate the effect of EAFD when added to fly ash (FA) and rice husk ash (RHA) based geopolymers. Geopolymer mortars were prepared at a ratio of 1:3 (FA + RHA: sand, four different granulations) and added with 0, 10, 15, and 20% EAFD in relation to the mass of FA + RHA. Compressive mechanical strength and leaching tests were carried out at the ages of 7, 28, and 91 days. Microstructural analyses were performed using XRD, FTIR, and SEM/EDS. EAFD did not negatively influence the geopolymerization process. The highest compressive strength results for the mortars containing the waste were found for 20% of EAFD. All mortars, regardless of EAFD content, were classified as non- hazardous Class II at the age of 91 days.     

An application of blended fly ash and residual rice husk ash for producing green building bricks

The present study investigates the possibility of using a blended class-F fly ash (FA) and residual rice husk ash (RHA) in the production of green building bricks through the application of densified mixture design algorithm (DMDA) in order to provide a new use for solid waste materials. This study uses unground rice husk ash (URHA) as a partial fine aggregate substitution (10–40%) in the studied cementitious mixtures. Solid bricks of 220 × 105 × 60 mm in size were prepared under forming pressure of 25–35 MPa, a curing temperature of 90 °C, and a relative humidity of 50%, for tests that assessed: compressive strength, flexural strength, bulk density, void volume, and water absorption. The test results showed that all brick samples demonstrated excellent properties. Compressive strength and flexural strength ranged, respectively, between 20.2–33 MPa and 5.4–6.9 MPa. Additionally, up to 30% of URHA content, the values of water absorption and void volume ranged, respectively, between 8.8–15.7% and 1.5–2.1%. All of these values not only conformed well to the requirements of the Vietnamese codes but also demonstrated great potential for using a blended FA–RHA in producing green building bricks.     

Utilization of municipal solid waste incineration (MSWI) fly ash in blended cement Part 1: Processing and characterization of MSWI fly ash

This paper is the first of a series of two articles dealing with the processes applied to MSWI fly ash with a view to reusing it safely in cement-based materials. Part 1 presents two stabilization processes and Part 2 deals with the use of the two treated fly ashes (TFA) in mortars. Two types of binder were used: an Ordinary Portland Cement (OPC) containing more than 95% clinker (CEM I 52.5R) and a binary blend cement composed of 70% ground granulated blast furnace slag and 30% clinker (CEM III-B 42.5N). In this first part, two stabilization processes are presented: the conventional process, called "A", based on the washing, phosphation and calcination of the ash, and a modified process, called "B", intended to eliminate metallic aluminum and sulfate contained in the ash. The physical, chemical and mineralogical characteristics of the two TFA were comparable. The main differences observed were those expected, i.e. TFA-B was free of metallic aluminum and sulfate. The mineralogical characterization of the two TFAs highlighted the presence of large amounts of a calcium aluminosilicate phase taking two forms, a crystalline form (gehlenite) and an amorphous form. Hydration studies on pastes containing mixed TFA and calcium hydroxide showed that this phase reacted with calcium hydroxide to form calcium aluminate hydrates. This formation of hydrates was accompanied by a hardening of the pastes. These results are very encouraging for the reuse of such TFA in cement-based materials because they can be considered as pozzolanic additions and could advantageously replace a part of the cement in cement-based materials. Finally, leaching tests were carried out to evaluate the environmental impact of the two TFAs. The elements which were less efficiently stabilized by process A were zinc, cadmium and antimony but, when the results of the leaching tests were compared with the thresholds of the European landfill directive, TFA-A could nevertheless be accepted at landfills for non-hazardous waste. The modifications of the process led to a significant reduction in the stabilization of chromium, selenium and antimony.     

Mechanical and durability characteristics of gypsum-free blended cements incorporating sulphate-rich reject fly ash

To accommodate the wide variations among the different types of fly ash and the growing need for its greater utilization in the construction sector, relevant standards have been established that differentiate the appropriate qualities from the unacceptable ones. Unfortunately, potentially reject fly ashes (rFA), which do not comply with standard requirements, comprise a significant part of the total amount produced in coal or lignite burning stations. High-sulphate fly ash (HSFA) is a typical example of reject material, since all relevant standards (both European and ASTM) clearly define that sulphur trioxide should be kept under a certain low limit (approximately 3–5% depending on the standard) or else concrete’s durability may be threatened. The aim of this work was to design, produce and monitor the properties of a series of blended cements prepared by mixing clinker with a fly ash of high-sulphate content. No gypsum was added in the mixtures, since it is believed that sulphate ions necessary for the prolongation of the setting process (commonly provided by gypsum) could be provided by fly ash enriched in sulphates. All samples tested exhibited satisfactory initial and final setting times as well as decent compressive strength values when compared to the reference specimen containing only gypsum and no fly ash. Additionally, this paper reports on the performance aspects of blended pastes exposed to chloride binding tests and aggressive (a) 2% H₂SO₄ and (b) simulated marine environment solutions. Results revealed that waste materials not up to relevant standards could still contribute to the production of quality products of energy and economical efficiency.     

Damping and microstructure of fly ash-based geopolymers

As environmentally-friendly materials, geopolymers have the potential to replace ordinary Portland cement (OPC) for the construction of railway sleepers and multi-flue chimneys, where the vibration control capabilities of the material must be considered. The critical damping value (ξ) is the main parameter in relation to vibration reduction. In this study, the traditional logarithmic decrement technique was used to measure the ξ of geopolymers. Geopolymers were prepared by activating fly ash using alkali solutions with different SiO₂/Na₂O ratios. The results show that the ξ of the geopolymers is similar to that of the OPC counterpart. Finite element analysis (FEM) based on the Rayleigh damping model was conducted to replicate the test results, and scanning electron microscopy and mercury-intrusion porosimetry were used to study the microstructure of the geopolymers. A discussion of the possible damping mechanisms based on the microstructural investigation and the FEM analysis is presented.     

Workability and strength of coarse high calcium fly ash geopolymer

In this paper, the basic properties viz., workability and strength of geopolymer mortar made from coarse lignite high calcium fly ash were investigated. The geopolymer was activated with sodium hydroxide (NaOH), sodium silicate and heat. The results revealed that the workable flow of geopolymer mortar was in the range of 110 ± 5%–135 ± 5% and was dependent on the ratio by mass of sodium silicate to NaOH and the concentration of NaOH. The obtained compressive strength was in the range of 10–65 MPa. The optimum sodium silicate to NaOH ratio to produce high strength geopolymer was 0.67–1.0. The concentration variation of NaOH between 10 M and 20 M was found to have a small effect on the strength. The geopolymer samples with high strength were obtained with the following practices: the delay time after moulding and before subjecting the sample to heat was 1 h and the optimum curing temperature in the oven was 75 °C with the curing duration of not less than two days.     

The role of weathering on fly ash charge distribution during triboelectrostatic beneficiation

Triboelectrostatic beneficiation of coal combustion fly ashes with high-unburned carbon contents can produce low-carbon ash products having value as mineral admixtures and meeting technical requirements for replacing cement in concrete. This capability is a result of establishing bipolar charge on mineral ash versus carbon particles where, typically, unburned carbon attains positive surface charge and ash attains negative surface charge under the tribocharging conditions employed in triboelectrostatic technologies. However, long-term exposure of fly ash to weathering conditions, such as moisture or high humidity, before beneficiation is known to dramatically diminish carbon-ash separation efficiencies. Although experimentation has shown that water soluble surface species can be redistributed on fly ash particles after exposure to moisture, which could affect the extent of charging and polarities, measurement of the actual amount of charge and polarity on particles after weathering exposure versus after removal of surface moisture has not been accomplished. Hence, a new experimental methodology was developed and applied to measure charge distributions on tribocharged ash and carbon particles in a fly ash that had been exposed to weathering conditions for 6 months before and after removal of the surface moisture. Weathered ash particles were found to have an average zero charge, whereas carbon particles attained an average negative charge, opposite of the normal polarity for carbon. Although the extent of uncharged particles decreased and ash particles attained an average negative charge after drying, carbon particles attained only an average zero charge. These changes were reflected in very small increases in carbon-ash separation efficiency, in contrast to previous beneficiation tests in which fly ash drying led to significant increases in carbon-ash separation efficiency. It is suggested that removal of surface moisture in the absence of other processes like surface ion redistribution would beneficially impact carbon-ash triboelectrostatic beneficiation.     

Ternary binder made of CFBC fly ash,conventional fly ash,and calcium hydroxide: Phase and strength evolution

Coal combustion products present a source of aluminosilicate materials for further utilization. The ternary binder studied here is such an example, consisting of circulating fluidized bed combustion (CFBC) fly ash, conventional fly ash and Ca(OH)² activator. The paste yields a compressive strength of 32 MPa after 28 days of standard sealed curing. Volumetric evolution of crystalline and amorphous phases during hydration is quantified using XRD analysis, differential thermal gravimetry, porosimetry and electron microscopy. A micromechanical model is applied to interpret the evolution of compressive strength due to the growing proportions of C-S-H and ettringite in the system. This opens the way for further optimization and utilization of this ternary binder.     

Effect of fly ash fineness on compressive strength and pore size of blended cement paste

This paper presents an experimental investigation on the effect of fly ash fineness on compressive strength, porosity, and pore size distribution of hardened cement pastes. Class F fly ash with two fineness, an original fly ash and a classified fly ash, with median particle size of 19.1 and 6.4 μm respectively were used to partially replace portland cement at 0%, 20%, and 40% by weight. The water to binder ratio (w/b) of 0.35 was used for all the blended cement paste mixes.Test results indicated that the blended cement paste with classified fly ash produced paste with higher compressive strength than that with original fly ash. The porosity and pore size of blended cement paste was significantly affected by the replacement of fly ash and its fineness. The replacement of portland cement by original fly ash increased the porosity but decreased the average pore size of the paste. The measured gel porosity (5.7–10 nm) increased with an increase in the fly ash content. The incorporation of classified fly ash decreased the porosity and average pore size of the paste as compared to that with ordinary fly ash. The total porosity and capillary pores decreased while the gel pore increased as a result of the addition of finer fly ash at all replacement levels.     

The permeability of fly ash concrete

Oxygen permeability tests were carried out on plain ordinary Portland cement (OPC) and fly ash concretes at three nominal strength grades. Prior to testing the concretes were subjected to a wide range of curing and exposure conditions. The results emphasize the importance of adequate curing to achieve concrete of low permeability, especially when the ambient relative humidity is low. In addition, the results demonstrate the considerable benefit that can be achieved by the use of fly ash in concrete. Even under conditions of poor curing, fly ash concrete is significantly less permeable than equal-grade OPC concrete, the differences being more marked for higher-grade concretes. Attempts were made to correlate strength parameters with permeability but it is concluded that neither the strength at the end of curing nor the 28-day strength provides a reliable indicator of concrete permeability. A reliable correlation was established between the water to total cementitious material ratio [w/(c+f)] and the permeability of concretes subjected to a given curing and exposure regime.     

Stabilisation of clayey soils with high calcium fly ash and cement

The effectiveness of using high calcium fly ash and cement in stabilising fine-grained clayey soils (CL,CH) was investigated in the laboratory. Strength tests in uniaxial compression, in indirect (splitting) tension and flexure were carried out on samples to which various percentages of fly ash and cement had been added. Modulus of elasticity was determined at 90 days with different types of load application and 90-day soaked CBR values are also reported. Pavement structures incorporating subgrades improved by in situ stabilisation with fly ash and cement were analyzed for construction traffic and for operating traffic. These pavements are compared with conventional flexible pavements without improved subgrades and the results clearly show the technical benefits of stabilising clayey soils with fly ash and cement. In addition TG–SDTA and XRD tests were carried out on certain samples in order to study the hydraulic compounds, which were formed.     

Laboratory compaction of fly ash and fly ash with cement additions

The use of power-industry wastes as a material for earthen structures depends on its compactibility. It has been confirmed that a fly ash/bottom ash mix compacted several times in Proctor's moulds are not representative. The relationship between dry density of solid particles and water content for re-used waste samples was determined. The re-compaction effect on grain-size distribution, density of solid particles, specific surface and sand equivalent of wastes was investigated. Tests were conducted on fly ash samples compacted by the Standard and Modified Proctor methods. Another aim of the paper was to investigate the influence of cement additions on the compactibility of a fly ash/bottom ash mix. Waste samples in the natural state and with different percentages of cement additions (2, 5 and 10%) were compacted by both impact compaction methods to obtain compactibility curves rhod(w). It was found that cement addition resulted in an increased rhod max value, while wopt decreased. Linear regression relationships for changes in compaction parameters after cement stabilisation are also given.     

Characterization of carbonation behavior of fly ash blended cement materials by the electrochemical impedance spectroscopy method

The carbonation behavior of fly ash blended cement materials is studied by the electrochemical impedance spectroscopy (EIS) method, and a novel equivalent circuit model R_s(Q₁(R_ct1W₁)) (Q₂(R_ct2W₂)) is proposed to investigate the influence of fly ash on the carbonation process in the cementitious materials. The experimental results demonstrate that the diameter of the impedance arc in high frequency region increases as carbonation progresses. Increasing the amount of fly ash incorporated in the cement paste is also found to enlarge the high frequency arc. The carbonation process can be quantified by the parameter R_ct2 extracted from the equivalent circuit model R_s(Q₁(R_ct1W₁)) (Q₂(R_ct2W₂)). It is found that the R_ct2 value increases with increase in fly ash content. A linear relationship between the R_ct2 value and the carbonation time is also observed. As a consequence, prediction of the carbonation depth of fly ash bended cement materials can be achieved through knowledge of the R_ct2 value.     

Compressive strength and microstructure of fly ash based geopolymer blended with silica fume under thermal cycle

This work aims to reveal the effects of silica fume on properties of fly ash based geopolymer under thermal cycles. Geopolymer specimens were prepared by alkali activation of fly ash, which was partially replaced by silica fume at levels ranging from 0% to 30% with an interval of 10%, by mass. Microstructure, residual strength and mass loss of fly ash based geopolymer blended with silica fume before and after exposed to 7, 28 and 56 heat-cooling thermal cycles at different target temperatures of 200 °C, 400 °C and 800 °C were assessed and compared. The experimental results reveal that silica fume addition enhances strength development in geopolymer. Under thermal cycles, the compressive strength of geopolymer decreases, and the compressive strength loss, as well as the mass loss, increases with increasing target temperature. The strength loss is the same regardless of silica fume content after thermal cycles. Microstructure analysis uncovers that pore structure of geopolymer degrades after thermal cycles. The pores of geopolymer are refined by the addition of silica fume. The incorporation of silica fume optimizes the microstructure and improves the thermal resistance of geopolymer. Silica fume increases the strength of the geopolymer and even though the strength loss is the same, the strength after heat cycle exposure is still good.