How does fly ash mitigate alkali–silica reaction (ASR) in accelerated mortar bar test (ASTM C1567)?

ASTM C1567 [1] is a commonly used accelerated test method to determine the required dosage of supplementary cementitious materials (SCMs) to mitigate alkali–silica reaction (ASR) in mixtures containing reactive siliceous aggregates. Past research suggested that fly ash and other SCMs inhibit ASR, primarily through alkali dilution and binding. In ASTM C1567, however, the alkalinity of the pore solution is largely influenced by the penetration of NaOH from the external soak solution; and this could erase the beneficial effects of alkali dilution and binding. To better understand why fly ash inhibits ASR in this test, the present study performs a quantitative evaluation of six potential ASR mitigation mechanisms: (1) alkali dilution, (2) alkali binding, (3) mass transport reduction, (4) increasing tensile strength, (5) altering ASR gel, and (6) reducing aggregate dissolution rate. The results suggest that (2), (3), (4), and (6) are the primary mitigation mechanisms, while (1) and (5) show a negligible impact.     

Decoupling the effects of chemical composition and fineness of fly ash in mitigating alkali-silica reaction

A comprehensive investigation was conducted to determine the individual effects of the chemical composition and particle size of fly ash on alkali-silica reaction (ASR). Test results indicated that the combined oxides content of fly ash showed a better correlation with the ASR expansions than its individual oxides. Mixtures containing finer fly ash fractions registered lower expansions than those containing the corresponding virgin fly ashes or its coarser fractions.Within the usual range of average particle size of 10 to 30 microns, of fly ash, the chemical composition had a more dominant influence on ASR mitigation than the particle size. However, when the average particle size of fly ash decreases below 10 microns, the fineness of fly ash becomes significant in mitigating ASR. In addition, the fineness of fly ash had a more significant influence in mitigating ASR in mixtures containing high-lime fly ashes than those containing low-lime fly ashes. Hence, reducing the particle size of fly ash to finer fractions is an effective strategy to mitigate ASR. The decoupling of the chemical composition of fly ash from its particle size indicated that ASR mitigation can be achieved with any fly ash having a D₅₀ below 5 μm. However, low-lime fly ashes were effective in mitigating ASR even without reducing their particle size.     

Properties of alkali activated slag–fly ash blends with limestone addition

In this article, the effects of raw materials’ composition on fresh behavior, reaction kinetics, mechanical properties and microstructure of alkali activated slag–fly ash–limestone blends are investigated. The results indicate that, with the increasing content of fly ash and limestone, the slump flow increases. The setting times are shortened when increasing the slag content, while both fly ash and limestone show a negligible influence. The reaction process is slightly accelerated by the presence of limestone due to the extra provided nucleation sites, but the reaction process is mainly governed by the slag. The slag content exhibits a dominant role on strength in this ternary system, while for a constant slag content, the compressive strength increases with the increasing limestone content up to 30%. The microstructure analysis shows that the gel characteristics are independent of the limestone powder content. The presence of limestone in initially high Ca and Al conditions does not lead to the formation of additional crystalline phases, which is different from Portland cement systems. Both physically and chemically bound water contents are slightly increased when limestone powder is incorporated.     

Sustainability-based decision support framework for choosing concrete mixture proportions

A framework is proposed, along with two objective indices, for the selection of concrete mixture proportions based on sustainability criteria. The indices combine energy demand and long-term strength as energy intensity, and carbon emissions and durability parameters as A-indices, which represent the apathy toward these essential features of sustainability. The decision support framework is demonstrated by considering a set of 30 concretes with different binders, including ordinary portland cement (OPC), fly ash, slag and limestone calcined clay cement (LC3). In addition to the experimental data on compressive strength, chloride diffusion and carbonation, life cycle assessment has been performed for the concretes considering typical situations in South India. The most sustainable of the concretes studied here, for service life limited by chloride ingress, are those with LC3, OPC replaced by 50% slag, and ternary blends with 20% each of slag and fly ash. In the case of applications where carbonation is critical, the appropriate concretes are those with OPC replaced by 15–30% slag or 15% fly ash, or with ternary blends having 20% slag and 20% Class F fly ash.     

A method for predicting the alkali concentrations in pore solution of hydrated slag cement paste

The alkalinity of the pore liquid in hardened cement paste or concrete is important for the long-term evaluation of alkali-silica reaction (ASR) expansion and corrosion prevention of steel bar in steel reinforced structures among others. It influences the reactivity of supplementary cementitious materials as well. This paper focuses on the alkali binding in hydrated slag cement paste and a method for predicting the alkali concentrations in the pore solution is developed. The hydration of slag cement is simulated with a computer-based model CEMHYD3D. The amount of alkalis released by the cement hydration, quantities of hydration products, and volume of the pore solution are calculated from the model outputs. A large set of experimental results reported in different literatures are used to derive the alkali-binding capacities of the hydration products and practical models are proposed based on the computation results. It was found that the hydrotalcite-like phase is a major binder of alkalis in hydrated slag cement paste, and the C?CS?CH has weaker alkali-binding capacity than the C?CS?CH in hydrated Portland cement paste. The method for predicting the alkali concentrations in the pore solution of hydrated slag cement paste is used to investigate the effects of different factors on the alkalinity of pore solution in hydrated slag cement paste.     

Simulation of a temperature rise in concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are among the industrial by-products and have been widely used as mineral admixtures in normal and high strength concrete. Due to the reaction between calcium hydroxide and fly ash or slag, compared with Portland cement, the hydration of concrete containing fly ash or slag is much more complex. In this paper, by considering the producing of calcium hydroxide in cement hydration and the consumption of it in the reaction of mineral admixtures, a numerical model is proposed to simulate the hydration of concrete containing fly ash or slag. The heat evolution rate of fly ash or slag blended concrete is determined from the contribution of both cement hydration and the reaction of mineral admixtures. Furthermore, a temperature rise in blended concrete is evaluated based on the degree of hydration of cement and mineral admixtures. The proposed model is verified with experimental data on the concrete with different water-to-cement ratios and mineral admixtures substitution ratios.     

A new approach to assessing the performance of ASR inhibitors in concrete

A methodological approach, based on some innovative reactivity parameters such as the threshold alkali level (TAL) of aggregates and the tolerable driving force (Δ_tol) of the deleterious expansive process associated with alkali–silica reaction (ASR), is proposed in order to assess the alkali-reactivity of aggregates and compare the effectiveness of different types of ASR inhibitors (low-alkali Portland cements, lithium compounds, and blended cements manufactured with active mineral additions). The effectiveness of the ASR inhibitors, expressed in terms of Δ_tol, is related to the naturally available alkali content of concrete and the TAL of the aggregate used in the concrete mix. The potential minimum contribution of alkalis (L _im) by a given ASR inhibitor to the concrete mix is proposed as a specific efficacy parameter. The relationships between the effective dose levels of mineral additions or lithium compounds and the efficacy parameters Δ_tol and L _im have also been identified. The test procedures for the experimental determination of such parameters are described and some methodology applications to published ASR expansion data are reported.     

Microstructural Studies of Alkali-Silica Reaction in Fly Ash Concrete Immersed in Alkaline Solutions

This article presents expansion and microstructural data for a series of concrete mixes containing reactive flint aggregate, with a range of fly ash levels, exposed to various alkaline salt solutions. This study was undertaken to determine whether fly ash has any influence on alkali-aggregate reaction beyond changes in pore solution chemistry; in these tests the external source of alkalis should neutralize pore solution effects. Fly ash was found to be effective in reducing expansion even after extended periods (44 months) of exposure in 1N NaOH at 80°C, notwithstanding the presence of abundant reactive silica and an inexhaustible supply of alkali hydroxides. Higher levels of ash (40%) prevent damaging expansion and cracking in this environment despite considerable evidence of reaction. In some cases, flint grains had been completely removed by dissolution. The addition of Ca(OH)₂ at the mixing stage was found to increase the expansion of all the concretes; the effect on concrete with 40% ash was most marked, the expansion increasing by nearly 20 times. The most noticeable difference between deteriorated control specimens (no ash) and concrete with 40% ash was the formation of a calcium-alkali-silica rim on certain flint grains in concrete without ash. Such particles were invariably sites of expansive reaction with cracks emanating from them. The absence of such a feature in concrete with 40% ash is probably linked to the reduction in Ca(OH)₂ at the cement-aggregate interface. It is possible that the formation of this reaction rim produces expansive forces itself or acts as a semi-permeable membrane preventing diffusion of alkali silicate solution from the reaction site, thereby leading to osmotic pressure generation. Regardless of the actual mechanism, the presence of Ca(OH)₂ appears to be critical for the development of expansion due to alkali-silica reaction. It was observed that the alkalis of the reaction product were distributed in bands. In the Portland cement concrete specimens, the distribution of the gel consisted of a high calcium reaction rim at the aggregate-cement interface with a sodium-rich silica gel adjacent to it, followed by a potassium-rich silica gel. The potassium-rich silica gel appears to have a crystalline, needle-like structure, whereas the sodium-rich silica gel is amorphous. In fly ash concrete specimens in which the formation of calcium-rich reaction rim was prevented, it was observed that the sodium-rich gel had diffused into the surrounding cement matrix, and the potassium-rich gel had remained within the original aggregate boundary.     

The utilization of recycled concrete aggregate to produce controlled low-strength materials without using Portland cement

This paper reports the results of an experimental study that investigated the feasibility of using fine and coarse recycled concrete aggregate (RCA) with slag or fly ash to produce Controlled Low-Strength Materials (CLSM). The main objective was to produce CLSM using only recycled and by-product materials without the need to add Portland cement. In addition to the hydraulic activity of slag and high-calcium fly ash (HCFA), their pozzolanic reaction was activated by the alkalis and calcium hydroxide present in the residual paste of the RCA. Preliminary tests showed mixtures with slag to have 7-day compressive strengths 70% higher than mixtures with fly ash.Two types of CLSM with slag were investigated in further detail: one with fine and the other with fine/coarse RCA. The results showed that the developed CLSMs are suitable for a wide range of applications particularly those requiring structural support and fast hardening.     

Degree of hydration based prediction of early age basic creep and creep recovery of blended concrete

An accurate estimation of the early-age creep behavior is not only required to successfully control the early age cracking of concrete, but also to analyse the vertical and differential deformations of super high-rise buildings during construction. The fictitious degree of hydration model was developed to study basic creep behavior of hardening concrete, however, nowadays more complex binder systems are applied, consisting of several different types of powders, requiring further validation of the applicability of this creep model. The compressive basic creep and creep recovery of concrete based on ternary blends including Portland cement, blast furnace slag, and fly ash is experimentally studied. The tests are conducted at different ages of loading at early age under varying stress level. It is shown that the fictitious degree of hydration method can be successfully applied to ternary blends, even simplifying the hydration process to one overall reaction, considering only one degree of hydration.     

The effect of meta-halloysite on alkali–aggregate reaction in concrete

Damage to concrete structures may occur as a result of internal effects. Alkali silica reaction (ASR) is a long term reaction between alkalis and reactive aggregate present in the concrete. The reaction product is sodium–potasium–calcium silica gel, able to absorb water, resulting in the expansion and cracking of concrete. The key problem is to find the right method for mitigating the internal damage. This paper presents the results of an investigation into the effectiveness of calcined halloysite (meta-halloysite) in improving the resistance to alkali-silica reaction (ASR). The pozzolanic reactivity of meta-halloysite was also evaluated using Thermo-Gravimetric Analysis. Microstructures of mortar bars were observed by Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (EDS) to investigate the location and chemical composition of ASR gel. The results from this study showed satisfactory level of pozzolanic reactivity when cement was partially replaced by meta-halloysite. It was demonstrated that a 20% addition of meta-halloysite are able to mitigate ASR and lower expansion of mortar bars with reactive aggregate to a safe level of not more than 0.1% at 14 days. Microstructural observations of the specimens containing meta-halloysite indicated the presence of a calcium–alkali–silicate–hydrate gel. But fewer reaction products and with different composition than those forming in the pastes without mineral additives are present.     

Continuous expansion measurement in accelerated concrete prism testing for verifying ASR-expansion models

The susceptibility of concrete structures due to alkali–silica reaction (ASR) can be assessed by means of ASR concrete prism testing at 60 °C, according to RILEM AAR 4.1. There, expansion of concrete prisms indicates alkali-reactivity of the examined concrete mix. This work applies in situ expansion measurement to accelerated concrete prism testing. Automated measuring facilitates both storage without the usually necessary interruptions for manual measurement and acquisition of quasi-continuous expansion data. A comparative experimental programme showed that conventional testing resulted in stronger expansion and leaching of alkalis than automated testing. Experimental simulation of interruptions, typically associated with manual measurements in conventional testing, could prove the influence of these cooling–heating cycles. Two phenomenological approaches, frequently used for describing reaction kinetics of ASR by linking it to expansion results from ASR-testing, were validated with continuous expansion data of three types of aggregate. Experimental expansion depicted s-shaped curves similar to them of the modelling approaches. However, strong swelling recorded in the beginning of the test was not covered by the model curves. Auxiliary measurement of acoustic emissions and ultrasonic velocity helped characterising mechanisms such as hydration and cracking, which also influence prism expansion. The proposed modification of the measurement procedure provides an extended basis to analyse expansion mechanisms. Regarding data for validation of ASR-expansion models, continuous expansion results are preferable to conventional test results.     

Microscopy and microanalysis of inorganic polymer cements. 1: remnant fly ash particles

Accurate and precise electron microscopic analysis of the remnant solid precursor (fly ash and blast furnace slag) particles embedded in an inorganic polymer cement (or “fly ash geopolymer”) provides critical information regarding the process of gel binder formation. Differential solubility of phases in the fly ash is seen to be important, with insoluble mullite crystals becoming exposed by the retreat of the surrounding glassy phases. High-iron particles appear to remain largely unreacted, and the use of sectioned and polished specimens provides a view of the inside of these particles, which can show a wide variety of phase separation morphologies and degrees of intermixing of high iron and other phases. Calcium appears to be active in the process of alkali activation of ash/slag blends, although the competitive and/or synergistic effects of ash and slag particles during the reaction process remain to be understood in detail.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Drying-induced changes in the structure of alkali-activated pastes

Drying of cement paste, mortar, or concrete specimens is usually required as a pre-conditioning step prior to the determination of permeability-related properties according to standard testing methods. The reaction process, and consequently the structure, of an alkali-activated slag or slag/fly ash blend geopolymer binder differs from that of Portland cement, and therefore there is little understanding of the effects of conventional drying methods (as applied to Portland cements) on the structure of the geopolymer binders. Here, oven drying (60 °C), acetone treatment, and desiccator/vacuum drying are applied to sodium silicate-activated slag and slag/fly ash geopolymer pastes after 40 days of curing. Structural characterization via X-ray diffraction, infrared spectroscopy, thermogravimetry, and nitrogen sorption shows that the acetone treatment best preserves the microstructure of the samples, while oven drying modifies the structure of the binding gels, especially in alkali-activated slag paste where it notably changes the pore structure of the binder. This suggests that the pre-conditioned drying of alkali activation-based materials strongly affects their microstructural properties, providing potentially misleading permeability and durability parameters for these materials when pre-conditioned specimens are used during standardized testing.     

垃圾焚烧炉渣-粉煤灰复合水泥的性能研究

研究了垃圾焚烧炉渣及粉煤灰单掺和复掺时硬化水泥浆体的力学性能和水化机理,比较了两者的活性,探讨了两者作为辅助性胶凝材料利用的可行性.研究表明:掺有垃圾焚烧炉渣及粉煤友的复合水泥,其强度均有不同程度的下降,它们的掺入在一定程度上延缓了水泥的水化过程,且垃圾焚烧炉渣的水化反应活性稍高于粉煤灰;掺垃圾焚烧炉渣及粉煤灰的复合水泥中重金属离子浸出量小,在等掺20%的条件下,浸出量远低于国家标准,说明在一定的情况下,焚烧炉渣及粉煤灰作为辅助性胶凝材料使用是安全的.     

Cementitious composites with glass waste from recycling of cathode ray tubes

Cathode ray tubes (CRTs) glass waste with a high lead concentration can be used as supplementary cementitious material in mortars based on portland cement and slag cement, as well as for the partial replacement of the solid component in alkali activated slag/fly ash binders. The values of cumulative lead released at 64 days, assessed by monolith leaching test NEN 7345, were below the emission limit stipulated in current legislation and consequently the mortars can be used without environmental restriction. The substitution of the active binding component (cement, slag or fly ash) with CRT glass waste decreases the rate of hardening processes, but due to its high fineness, the CRT glass waste powder exerts also a filler effect which can compensate the compressive strength reduction. Compressive strengths of mortar specimens cured in different conditions (air or water with different pH values) were assessed in order to evaluate their possible use as building materials.     

Thixotropy and structural breakdown properties of self consolidating concrete containing various supplementary cementitious materials

In this study, thixotropy and structural breakdown of 57 self-consolidating concrete (SCC) mixtures containing various supplementary cementitious materials (SCM) were investigated by different approaches. The effects of SCM type and content on high range water reducer demand and plastic viscosity were also studied. For these purposes, various amounts of silica fume (SF), metakaolin (MK), Class F fly ash (FAF), Class C fly ash (FAC) and granulated blast-furnace slag (BFS) were utilized in binary, ternary, and quaternary cementitious blends in three water/binder (w/b) ratios. Results showed that except BFS, use of SCM in SCC mixtures increased thixotropy values in comparison with the mixtures containing only portland cement (PC). Good correlations were established between structural breakdown area and drop in apparent viscosity values for all w/b ratios. The different methods used to evaluate the thixotropy and structural breakdown got more consistent with each other as w/b decreased.     

Leaching behaviour of major and trace elements from concrete: Effect of fly ash and GGBS

The leaching of major and trace elements from concrete made with Portland cement, fly ash and GGBS (ground granulated blast-furnace slag) was studied using pH static availability and tank leach tests. The release of substances during the tank leach test occurs by surface dissolution of phases at the concrete surface and diffusion inside the concrete, the amounts depending on the phases controlling solubility and concrete porosity. Alkali release is controlled by diffusion and is thus reduced by lower water/binder ratios and the replacement of Portland cement by fly ash. Ca, Al and S release occurs mainly by surface dissolution of portlandite and AFt/AFm, respectively. The release of V is determined by surface dissolution of V substituted ettringite and/or calcium vanadate. Although fly ash can increase the total V content of concrete, enhancing release, only 2% of the total V content in concrete was available for release.     

Influence of starting material on the early age hydration kinetics,microstructure and composition of binding gel in alkali activated binder systems

The influence of starting material on the hydration kinetics and composition of binding gel in alkali activated binder systems was evaluated. The starting materials used were ground granulated blast furnace slag, class C fly ash and class F fly ash. All starting materials were activated using alkaline solution with a SiO₂/Na₂O ratio of 1.5. The hydration kinetics were monitored using in situ isothermal conduction calorimetry and the chemical compositions of the binder gels were determined by energy dispersive X-ray spectroscopy. In the fly ash systems, the calorimetric curves had only one peak, which occurred in the first 30 min of reaction, and lacked an induction period. Two peaks were distinguishable in slag systems, though the induction period was much shorter than that of a typical OPC system. The gel composition ratios, including Ca/Si, Na/Si, Na/Al and Al/Si, were different in each of the systems and are discussed in detail.