Pozzolanic properties of reject fly ash in blended cement pastes

Low-grade fly ash (reject fly ash, r-FA), a significant portion of the pulverized fuel ash (PFA) produced from coal-fired power plants and rejected from the ash classifying process, has remained unused due to its high carbon content and large particle size. But it may be used in certain areas, such as in solidification and stabilization processes of hazardous waste and materials for road base or subbase construction, which require relatively lower strength and reactivity. It is therefore necessary to extend research on the properties of r-FA and explore its possible applications. This paper presents experimental results of a study on the mechanical and hydration properties of cementitious materials prepared by blending r-FA with ordinary Portland cement (OPC). Parallel mixes were also prepared with the good ash [i.e., classified fine fly ash (f-FA)] for comparison. Selective chemical activators were added to the mix to study the effects of the activators on the properties of the blend system. The results show that r-FA generally has a lower rate of hydration than f-FA particularly at the early stage of hydration. Adding Ca(OH)₂ alone almost had no effect on accelerating the hydration of r-FA. But adding a small quantity of Na₂SO₄ or K₂SO₄ together with Ca(OH)₂ significantly accelerated the hydration reaction. The results of the compressive strength measurement correlated nicely with the degree of hydration results. It was also found that water-to-binder ratio (w/b) was an important factor in affecting the strength development and the hydration degree of r-FA pastes.     

Studies on blended cement with a large amount of fly ash

The influence of the contents of the clinker, activators and fly ash on the properties of blended cement with high fly ash content was studied. Experimental data from X-ray diffraction and pore size distribution indicated that the main hydration product of the fly ash blended cement was C-S-H gel, ettringite and a small amount of Ca(OH)₂. The volume porosity of the pores with diameter bigger than 0.1 μm was lower than that of the micro pores and gel pores with diameter lower than 0.05 μm. The amount of chemical combined water has increased with the curing age duration, while the content of Ca(OH)₂ has reduced after 7 days.     

Steam reactivation of 16 bed and fly ashes from industrial-scale coal-fired fluidized bed combustors

The hydration behaviour of sixteen ashes, obtained from different commercial-scale fluidized bed combustors, has been investigated. Hydration is important for both ash disposal and reactivation of excess lime present in the ashes for further use in flue gas desulphurization. The techniques used were instrumental and conventional chemical analysis, thermogravimetry and X-ray diffraction. The ashes comprised both fly ash and bottom ash, with particle size less than 2 mm. The ashes were heat treated in air to oxidize free carbon and then hydrated with pressurized steam at about 170 °C, alone and with addition of pure CaO.It has been shown that steam hydration is effective in quantitatively converting CaO to Ca(OH)₂, but in most cases the free lime content (i.e. CaO+Ca(OH)₂), expressed as CaO, decreases and added CaO enters into pozzolanic reactions with coal ash components, in part or even completely. Both the chemical evidence and X-ray phase analyses indicate that hydrated silicates and silicoaluminates are formed. The hydrated ashes are all able to take up additional SO₂ and it appears that the presence of amounts of Ca(OH)₂ detectable by phase analysis is not necessary for such capture.     

The effect of inorganic salts on tricalcium silicate hydration

Hydration of C₃S in salt solutions having ions in common with its hydration products was investigated by calorimetry and aqueous phase analyses. Soluble calcium salts, which depress hydroxyl ion concentrations in solution by promoting Ca(OH)₂ precipitation, were observed to accelerate hydration. Acceleration did not occur prior to Ca(OH)₂ precipitation. A saturated CaSO₄ solution, which delayed Ca(OH)₂ precipitation, was initially retarding but subsequently accelerated hydration as the hydroxyl ion concentration in solution decreased. Of the solutions investigated, a 0.2M CaCl₂ solution was the most effective in depressing the hydroxyl ion concentration and caused the greatest acceleration.     

Effect of lignosulfonate, calcium chloride and their mixture on the hydration of RHA-blended portland cement

Hydration of 10 wt.% rice husk ash (RHA)-blended Portland cement has been studied in the presence of 2 wt.% CaCl₂, 1 wt.% lignosulfonate (LS) and a mixture of the two admixtures by using different methods. Free lime determinations and differential thermal analysis have shown that CaCl₂ accelerates the pozzolanic reaction of Ca(OH)₂ and RHA. In the presence of mixture of two admixtures, lower amount of water is required for consistency of the paste. IR spectral studies have supported that the mixture of the two admixtures act as a strong accelerator for cement hydration. The compressive strength is highest in the presence of a mixture of the two admixtures at 28 days of hydration. The admixtures did not prevent the deterioration of the blended cement in corrosive atmosphere.     

Mineralogical and engineering characteristics of dry flue gas desulfurization products

Fifty-nine coal combustion products were collected from coal-fired power plants using various dry flue gas desulfurization (FGD) processes to remove SO₂. X-ray diffraction analyses revealed duct injection and spray dryer processes created products that primarily contained Ca(OH)₂ (portlandite) and CaSO₃·0.5H₂O (hannebachite). Most samples from the lime injection multistage burners process contained significant amounts of CaO (lime), CaSO₄ (anhydrite), and CaCO₃ (calcite). Bed ashes from the fluidized bed process were often dominated by CaSO₄ but also contained CaCO₃, CaO (lime), and MgO (periclase). Cyclone ashes were similar in composition to the bed ashes but contained more unspent sorbent and CaSO₄ and less MgO. Fly ash in all samples ranged from 10 to 79 wt%. Samples usually exhibited two distinct swelling episodes. One occurred immediately after water was applied due to hydration reactions, especially the conversion of CaO to Ca(OH)₂ and CaSO₄ to CaSO₄·2H₂O (gypsum). The second began between 10 and 50 d later and involved formation of the mineral ettringite (Ca₆[Al (OH)₆](SO₄)₃·26H₂O). The final pH after 112 d ranged from 10.0 to 12.1. If samples are incubated under ‘closed’ (i.e. incomplete recarbonation with atmospheric CO₂) and alkaline weathering conditions, gypsum and portlandite are initially formed followed by the conversion of the gypsum to ettringite. Closed, alkaline conditions typically can occur when FGD products are placed in confined settings such as a road embankment or buried as a discrete layer as occurs in some surface mine reclamation projects.     

Influence of steam curing on the compressive strength of concrete containing supplementary cementing materials

Heat treatment is widely used to accelerate the strength-gaining rate of concrete. In general, the ultimate strengths of the heated-treated concrete are lower than those of the standard cured specimens. When ultrafine fly ash (UFA) is included in concrete, the pozzolanic reaction is accelerated through the heat treatment. Sometimes, various chemical activators were used to activate the reactivity of fly ash. In the current study, UFA and slag were used as a replacement for cement, steam curing and chemical activators were used to accelerate hydration of cement and fly ash, and then compared with moist curing. This paper presents the influence of steam curing on the compressive strength of concrete containing UFA with or without slag. The experimental results indicated that the concrete containing UFA has low early strength after 13-h steam curing and that the difference between the 28-day compressive strength of concrete through 13-h steam curing and that of moist-cured concrete is large, but the concrete with UFA and CaSO₄ or Ca(OH)₂ has a high early strength, thus, the reactivity of fly ash must be accelerated. Concrete containing UFA and ground slag was prepared, whose compressive strengths were improved.     

Differential thermal method of estimating calcium hydroxide in calcium silicate and cement pastes

DTA is applied to estimate Ca(OH)₂ in cementitious phases by determining the peak areas caused by the decomposition of Ca(OH)₂ to CaO+H₂O. In the hydration of C₃S generally, the chemical method yields slightly higher values. DTA is also used as a monitoring technique in preparing a practically Ca(OH)₂-free product from hydrated portland cement or hydrated C₃S. Hydrated portland cement or C₃S has now been exposed to an unsaturated Ca(OH)₂ solution and extraction continued until the sample indicate no endothermal peak for Ca(OH)₂. The thermal method permits determination of the rate of formation of Ca(OH)₂ in portland cement hydrated in the presence of 0, 1, 2 and $\text{3}\text{1}\text{2}$ per cent CaCl₂.     

Predicting Ca(OH)2 content and chemical shrinkage of hydrating cement pastes using analytical approach

A semiempirical model is proposed to predict the evolution of chemical shrinkage and Ca(OH)₂ content of cement paste at early age of hydration. The model is based on chemical equations and cement compound hydration rates. Chemical shrinkage and Ca(OH)₂ amount are computed using the stoichiometric results of the hydration reactions considered in the model and the density of hydration products and reactants. The model validation is conducted by comparison between computed and experimental results achieved on ordinary cement pastes with different water-to-cement (w/c) ratios (0.25, 0.30, 0.35 and 0.40) cured at 10, 20, 30, 40 and 50 °C, respectively. Hydration degree and Ca(OH)₂ content are determined using the thermogravimetric analysis (TGA) and chemical shrinkage evolution using a gravimetric method.The comparison reveals a good consistency between modelled and experimental data at early age of hydration.     

Characteristics and so2 capture capacities of sorbents prepared from products of spray-drying flue gas desulfurization

The characteristics and the SO₂ capture capacities of sorbents prepared from products of spray-drying flue gas desulfurization (FGD) have been studied. Sorbents were prepared by first slurrying Ca(OH)₂ and CaSO₃ and/or CaSO₄ with and without the addition of fly ash and then drying. Compared to the use of pure Ca(OH)₂, the SO₂ capture and Ca(OH)₂ utilization decreased for sorbents prepared without fly ash and increased for sorbents with fly ash. Flakelike ill-crystallized tobermorites were observed for all the sorbents containing fly ash. In addition, significant amounts of needle-shape Ca₄Al₂(OH)₁₂SO₄ . 6H₂O and Ca₆Al₂ (OH)₁₂(SO₄)₃ . 26H₂O (ettringite) were also observed for the sorbents containing CaSO₃ and/or CaSO₄. These newly formed compounds dissociated into CaSO₃ . 0.5 H₂O and inert precursors upon sulfation, and were responsible for the high SO₂ capture capacities and Ca(OH)₂ utilizations of the sorbents prepared with fly ash.     

The hydration characteristics of MSWI fly ash slag present in C3S

This paper reports on an investigation of the hydration characteristics of C₃S and the mixing of C₃S with municipal solid waste incinerator (MSWI) fly ash slag. The results can be summarized as follows: TGA observations show lower amounts of CSH and Ca(OH)₂ in samples that incorporated MSWI slag into C₃S, possibly due to the partial replacement of the C₃S by slag with less activity. In general, the incorporation of slag into C₃S decreases the initial hydration reactions, but it increases the pozzolanic reactions at a later stage by consuming Ca(OH)₂. As the hydration precedes, the C₃S peaks decrease, up to 90 days, due to the activation of the slag by liberated Ca(OH)₂. As well, the amount of hydration products (Ca(OH)₂) from the pure C₃S pastes are more than for the C₃S-slag pastes. Moreover, the degree of hydration of the C₃S pastes increases with the curing time, the C₃S-slag paste also shows that lower hydration degree values at all ages.     

Fly ash effects: II. The active effect of fly ash

This paper examines the method for determining the hydration degree of cement clinker and the pozzolanic reaction degree of fly ash in the system of cement and fly ash. In the base, the active effect of fly ash is studied. The studied results show that the active effect includes two aspects: (1) Fly ash has stronger pozzolanic activity and can react with Ca(OH)₂, and (2) it can promote the hydration of cement. When the content of fly ash is less, its pozzolanic activity can exert well, but its promoting role to the hydration of cement is weaker. When the content of fly ash is more, it is less than its pozzolanic activity can be used, but its promoting role to the hydration of cement is stronger.     

Study on the pozzolanic properties of rice husk ash by hydrochloric acid pretreatment

The pozzolanic properties of rice husk ash by hydrochloric acid pretreatment are reported in the paper. Three methods have been used to estimate the pozzolanic activity of rice husk ash. The heat evolution and the hydration heat of cement, the Ca(OH)₂ content in the mortar and the pore size distribution of mortar are determined. It is shown that compare with the rice husk ash heated untreated rice husk, the sensitivity of pozzolanic activity of the rice husk ash heated hydrochloric acid pretreatment rice husk to burning conditions is reduced. The pozzolanic activity of rice husk ash by pretreatment is not only stabilized but also enhanced obviously. The kinetics of reaction of rice husk ash with lime is consistent with diffusion control and can be represented by the Jander diffusion equation. A significant increase in the strength of the rice husk ash (pretreated) specimen is observed. The results of heat evolution indicate that the rice husk ash by pretreatment shows the behavior in the increase of hydration of cement. The cement mortar added with the rice husk ash by pretreatment has lower Ca(OH)₂ content after 7 days and the pore size distribution of the mortar with the rice husk ash with pretreatment shows a tendency to shift towards the smaller pore size.     

Sulphur dioxide removal using South African limestone/siliceous materials

This study presents an investigation into the desulfurization effect of sorbent derived from South African calcined limestone conditioned with fly ash. The main aim was to examine the effect of chemical composition and structural properties of the sorbent with regard to SO₂ removal in dry-type flue gas desulfurization (FGD) process. South African fly ash and CaO obtained from calcination of limestone in a laboratory kiln at a temperature of 900 °C were used to synthesize CaO/ash sorbent by atmospheric hydration process. The sorbent was prepared under different hydration conditions: CaO/fly ash weight ratio, hydration temperature (55-75 °C) and hydration period (4-10 h). Desulfurization experiments were done in the fixed bed reactor at 87 °C and relative humidity of 50%. The chemical composition of both the fly ash and calcined limestone had relatively high Fe₂O₃ and oxides of other transitional elements which provided catalytic ability during the sorbent sorption process. Generally the sorbents had higher SO₂ absorption capacity in terms of mol of SO₂ per mol of sorbent (0.1403-0.3336) compared to hydrated lime alone (maximum 0.1823). The sorbents were also found to consist of mesoporous structure with larger pore volume and BET specific surface area than both CaO and fly ash. X-ray diffraction (XRD) analysis showed the presence of complex compounds containing calcium silicate hydrate in the sorbents.     

The system CaO-Al2O3-CaCl2-H2O at 23±2 °C and the mechanisms of chloride binding in concrete

The stable quaternary diagram for the system CaO-Al₂O₃-CaCl₂-H₂O at 23±4 °C has been constructed. Among the phases in this system are the calcium oxychlorides Ca(OH)₂.CaCl₂.H₂O and 3Ca(OH)₂.CaCl₂.12H₂O. The formation of Friedel's salt (FS) and calcium oxychlorides provides a mechanism for chloride binding in Portland cement concrete. The compatibility relationships involving these compounds, FS and Ca(OH)₂, were established empirically, and 3Ca(OH)₂.CaCl₂.12H₂O was found not to coexist in equilibrium with FS. The solubility behaviors of these compounds may play a role in affecting temperature-dependent corrosion rates. Additionally, the formation of oxychlorides from solutions containing elevated concentrations of NaCl may provide a mechanism by which ASR is facilitated.     

Hydration characteristics of waste sludge ash utilized as raw cement material

In this study, the hydration characteristics and the engineering properties of three types of eco-cement pastes, including their compressive strength, speciation, degree of hydration, and microstructure, were studied and compared with those of ASTM type I ordinary Portland cement. The results indicate that it is feasible to use sludge ash and steel-making waste to replace up to 20% of the mineral components of the raw material of cement. Furthermore, all the tested clinkers met the toxicity characteristic leaching procedure requirements. The major components of Portland cement, C₃S (i.e., 3CaO·SiO₂), C₂S (i.e., 2CaO·SiO₂), C₃A (i.e., 3CaOAl₂O₃) and C₄AF (i.e., 4CaO·Al₂O₃·Fe₂O₃), were all found in the waste-derived clinkers. All three types of eco-cements were confirmed to produce calcium hydroxide (Ca(OH)₂) and calcium silicate hydrates (CSH) during the hydration process, increasing densification with the curing age. The thermal analysis results indicate that the hydration proceeded up to 90 days, with the amount of Ca(OH)₂ and CSH increasing. The chemical shift of the silicates, and the resultant degree of hydration, and the increase in the length of the CSH gels with the curing age, were confirmed by ²⁹Si NMR techniques. Compressive strength and microstructural evaluations confirm the usefulness of eco-cement.     

Mechanism of the CaCl2 attack on portland cement concrete

It is known that concentrated solutions of CaCl₂ can cause the breakdown of Portland cement concrete. Recently it has been shown that the severity of CaCl₂ attack decreases with increasing temperature and above 40°C concrete is not affected. From the above observation it was inferred that the breakdown is due to some compound formation at temperatures below about 20°C. In order to gain a better understanding of the mechanisms of CaCl₂ attack, powders of Portland cement (both anhydrous and partly hydrated) were shaken in CaCl₂ solutions of various strengths up to 180 days. The temperatures of these suspensions were maintained at 40, 20 and 5°C. The X-ray diffraction and microscopic study of the reacted solids showed that (i) C₃A.CaCl₂.XH₂O forms at all temperatures. (ii) concentrated solution of CaCl₂ leaches out Ca(OH)₂ irrespective of the temperature of storage: (iii) at temperatures below about 20°C complex salts containing CaCl₂, Ca(OH)₂ and/or CaCO₃ crystallalise out if the CaCl₂ concentration of the mother liquor is 15% or higher. The results indicate that the breakdown of Portland cement concrete, when placed in a concentrated CaCl₂ solution, is not due to the formation of C₃A.CaCl₂.XH₂O or the leaching of Ca(OH)₂ but associated with the formation of complex salts. Subsidiary experiments support the above hypotheses.     

Studies on improving moisture resistance of sulfur-infiltrated mortars

High-strength products can be made by sulfur infiltration of dried portland cement mortars or concretes. However, on exposure to moisture, strength deterioration takes place due to complex chemical reactions involving Ca(OH)₂ and sulfur.This paper presents the results of two series of tests. In the first series an attempt was made to inhibit the reaction between sulfur and Ca(OH)₂ by coating the Ca(OH)₂ with a film of insoluble calcium salts. In the second series, cements which did not contain Ca(OH)₂ in hydration products were investigated for sulfur infiltration. Both the approaches gave encourging results in improving moisture resistance of sulfur-infiltrated mortars.     

Strength and microstructural characteristics of chemically activated fly ash-cement systems

The use of fly ash as a cement replacement material increases the long-term strength and durability of concrete. Despite these great benefits, the use of fly ash is limited due to the low early strength of fly ash concrete. To eliminate this problem, many studies have been conducted on accelerating the pozzolanic properties of fly ash. The study reported below investigated the strength and microstructural characteristics of fly ash-cement systems containing three kinds of activators—Na₂SO₄, K₂SO₄, and triethanolamine—to accelerate the early strength of fly ash mortars. Through the use of thermal gravity analysis, it was demonstrated that the activators not only decreased or maintained the amount of Ca(OH)₂ products, but also increased the production of ettringite at early ages. X-ray diffraction, scanning electron microcopy, and mercury intrusion porosimetry also confirmed that in the early curing stages of fly ash-cement pastes containing activators, large amounts of ettringite were formed, resulting in a reduction in the pore size ranging from 0.01 to 5 μm. The research results support the supposition that the addition of small amounts of activators is a viable solution for increasing the early-age compressive strength of fly ash concrete.