Formation of ASR gel and the roles of C-S-H and portlandite

Experimental investigations of the reactions between silica, alkali hydroxide solution, and calcium hydroxide show that alkali-silicate-hydrate gel (A-S-H) comparable to that formed by the alkali-silica reaction (ASR) in concrete does not form when portlandite or the Ca-rich, Si-poor C-S-H of ordinary portland cement (OPC) paste is available to react with the silica. Under these conditions, we observe either the formation of additional C-S-H by reaction of Ca(OH)₂ with the dissolving silica or the progressive polymerization of C-S-H. The A-S-H dominated by Q³ polymerization forms only after portlandite has been consumed and the C-S-H polymerized. These conclusions are consistent with previously published results and indicate that the ASR gel of concrete forms only in chemical environments in which the pore solution is much lower in Ca and higher in Si than bulk pore solution of OPC paste. These results highlight the similarity between ASR and the pozzolanic reaction and are supported by data for mortar bar specimens.     

天然沸石对碱-硅酸反应的抑制及其机理

用高碱水泥和天然沸石制备了含沸石水泥，测定了其砂浆棒的膨胀率，可溶性碱量和有效碱量。用能谱分析（EDXA）了C－S－H凝胶的化学组成。讨论了总碱量，可溶性碱量和有效碱量与膨胀率的关系。结果显示，由碱－硅酸反应（ASR）引起的膨胀与可溶性碱量和有效碱量之间有很好的关系。沸石主要通过离子交换和提高C－S－H凝胶对Na^ 和K^ 的吸收，使可溶性碱量和有效碱量降低，从而起到抑制ASR的作用。     

New observations on the mechanism of lithium nitrate against alkali silica reaction (ASR)

In the current study, in order to elucidate the mechanisms for the favorable effects of lithium nitrate in controlling alkali silica reaction (ASR), vycor glass disk immersion specimens and glass disk-cement paste sandwich specimens were prepared and examined by XRD, SEM and Laser Ablation Induction Coupled Plasma Mass Spectrometry (LA-ICP-MS). Results showed that when glass disk was immersed in only NaOH solution, the glass was attacked by hydroxyl ions but no solid reaction product was found, thus the presence of calcium was essential for the formation of ASR gel. In the presence of lithium, the glass surface was covered by a thick layer of Li-Si crystal. With the addition of Ca(OH)₂, the glass surface was completely covered by Li-Si crystal and a lithium-bearing low Ca-Na-(K)-Si gel. These two phases either form a dense matrix with Li-Si crystal serving as the framework, and the gel filling in the void space, or the Li-Si crystal serving as the foundation to completely cover the entire reactive SiO₂ surface, and the gel sitting on top of these crystal particles. Hence, the suppressive effects of LiNO₃ were attributed to the formation of a layer of Li-Si crystals intimately at the reactive SiO₂ particle surface and the formation of Li-bearing low-Ca ASR gel products. The Li-bearing low-Ca ASR gels may have a dense and rigid structure, thus having low capacity to absorb moisture from the surrounding paste, and exhibiting a non-swelling property.     

Quantifying the swelling properties of alkali‐silica reaction (ASR) gels as a function of their composition

Synthetic alkali‐silica reaction (ASR) gels were produced and tested to investigate the effects of chemical composition (Ca/Si, Na/Si, and K/Si atomic ratios) on the gels’ free swelling strain (ε_g,fr) and restrained swelling pressure (P_rs). The gels were cast into disk‐shape molds and exposed to distilled water after curing. Each gel's ε_g,fr was recorded over a period of 28 days, followed by measuring P_rs, defined as the pressure required to fully reverse and eliminate the gel's free swelling under a drained configuration. Regression models were developed linking gels compositions to their swelling properties. The outcomes show that Na/Si and K/Si monotonically increase ε_g,fr. Increasing Ca/Si up to 0.23 drastically reduces ε_g,fr; higher Ca/Si has modest effect on free swelling. P_rs increases by increasing calcium up to a pessimum Ca/Si level; P_rs decreases for higher Ca/Si. The value of (Ca/Si)_pess is related to the alkali content of the gel. P_rs also increases by increasing the gel's alkali content, while a (Na/Si)_pess exists in the range 0.85‐0.95. These observations are linked with the roles of alkalis and calcium in modifying the silica gel network.     

The effects of lithium ions on chemical sequence of alkali-silica reaction

This paper presents the results of the investigation on the effects of Li⁺ ions on the chemical and physical changes in the cementitious system undergoing alkali-silica reaction (ASR). Specifically, this paper focuses on determining which chemical steps of ASR processes are affected by the presence of Li⁺ ions in the pore solution in order to provide better understanding of the role of Li⁺ ions in the mitigation process of ASR.The results presented in this paper strongly support the hypothesis that the Li⁺ ions facilitate the formation of a physical barrier on the surface of reactive silica, and thus prevent further attack on the reactive sites by hydroxyl ions.     

Influence of portlandite on Pyrex glass dissolution and the formation of alkali‐silica chemical reaction products

The dissolution behavior of Pyrex glass in a model system consisting of 1‐M NaOH with varying amounts of portlandite, representing the glass dissolution in alkaline environment and alkali‐silica reaction (ASR) in cementitious materials, is studied. The Pyrex glass dissolution and the reaction products were characterized using X‐ray diffraction (XRD), ²⁹Si nuclear magnetic resonance (²⁹Si‐NMR), and scanning electron microscopy with energy dispersive X‐ray (SEM/EDX), and the silica and calcium concentrations in the liquid phase were determined using inductively coupled plasma atomic emission spectroscopy (ICP‐AES). The experimental results show that the dissolution of the Pyrex glass continued until it consumed the portlandite and then reached a constant rate, with a linear relationship with the amount of portlandite. The absence of calcium and reduction of silica concentration in the liquid phase with the increase in portlandite indicate the formation of high‐reaction products with portlandite, confirmed by XRD and ²⁹Si‐NMR. The calcium sodium silicate hydrate (C–N–S–H) and sodium silicate hydrate (N–S–H) are the main ASR products; their composition and proportions strongly depend on the reaction time and the amount of portlandite added. A thermodynamic model, which couples geochemical code (PHREEQC) and the experimental silica dissolution rate, was used to predict ASR products and the remaining portlandite. The simulation results predicted the experimental data fairly well for different portlandite additions. The mechanism for Pyrex glass dissolution in the presence of varying portlandite additions is discussed with regard to experimental data and simulation results.     

Influence of calcium additions on the compressive strength and microstructure of alkali‐activated ceramic sanitary‐ware

The ceramic sanitary‐ware market generates large amounts of waste, both during the production process and due to construction and demolition practices. In this paper, the effect of different amounts and calcium sources (calcium hydroxide Ca(OH)₂, calcium aluminate cement CAC, Portland cement PC) on the alkaline activation of ceramic sanitary‐ware waste (CSW) was assessed. Blended samples were activated with NaOH and sodium silicate solutions and cured for 3 and 7 days at 65°C. The maximum amount of calcium source‐type added to the system varied according to its influence on the compactability of the mortars.CSW was physico‐chemically characterized and the compressive strength development of activated samples was assessed on the mortars. The nature of the reaction products was analyzed in pastes, by X‐ray diffraction, thermogravimetric analysis, infrared spectroscopy and microscopic studies. The results show a great positive influence with the addition of moderate amounts of Ca(OH)₂, PC and CAC on the mechanical properties. Among the typical hydrates usually observed in plain water‐hydrated PC or CAC, only AH₃ and a small amount of C₃AH₆ were identified in the alkali‐activated CSW/CAC blended pastes, which indicates that Al and Ca from PC, CAC and Ca(OH)₂ are taken up in the newly formed (N,C)‐A‐S‐H or C‐A‐S‐H gels.     

Experimental investigation of the mechanisms by which LiNO3 is effective against ASR

Various series of experiments were carried out on cements pastes, concretes made with a variety of reactive aggregates, composite specimens made of cement paste and reactive aggregate particles, and a variety of reactive natural aggregates and mineral phases immersed in various Li-bearing solutions. The main objective was to determine which mechanisms(s) better explain(s) the effectiveness of LiNO₃ against ASR and variations in this effectiveness as well with the type of reactive aggregate to counteract. The principal conclusions are the following: (1), the pH in the concrete pore solution does not significantly decrease in the presence of LiNO₃; (2), the concentration of silica in the pore solution is always low and not affected by the presence of LiNO₃, which does not support the mechanism relating to higher solubility of silica in the presence of lithium; (3), the only reaction product observed in the LiNO₃-bearing concretes looks like classical ASR gel and its abundance is proportional to concrete expansion, thus is likely expansive while likely containing lithium; this does not support the mechanisms relating to formation of a non or less expansive Si-Li crystalline product or amorphous gel; (4), early-formed reaction products coating the reactive silica grains or aggregate particles, which could act as a physical barrier against further chemical attack of silica, were not observed in the LiNO₃-bearing concretes, but only for a number of reactive materials after immersion in 1 N LiOH at 350 °C in the autoclave (also at 80 °C for obsidian); (5), higher chemical stability of silica due to another reason than pH reduction or early formation of a protective coating over the reactive phases, is the mechanism among those considered in this study that better explains the effectiveness of LiNO₃ against ASR.     

Synthesis of Calcium Silicate Hydrate in Highly Alkaline System

Synthesis of calcium silicate hydrate (C‐S‐H) was conducted over the range of 50°C–90°C and C/S ratio of 0.86–2.14 in the highly alkaline Na₂O–CaO–SiO₂–H₂O system for silicon utilization in high alumina fly ash. Structural change in C‐S‐H formed in the highly alkaline system was investigated using XRD and ²⁹Si MAS NMR spectra. X‐ray photoelectron spectroscopy was used to confirm the amount of sodium ions in C‐S‐H. Conversion of Si may reach 99% under optimum conditions. A higher degree of polymerization of silicate was obtained at lower temperature and C/S ratio. Na⁺ was confirmed to exist as Na–OSi and Na–OH. The amount of Na⁺ is the least at C/S ratio of 1.43, which conform to the prediction of topological constraint theory. High Ca/Si ratio leads to the increasing in Na⁺ combined in the interlayer. Increasing in the Na⁺ concentration in the system also increases the amount of Na⁺ combined in the interlayer and reduces the polymerization. Ion exchange was proven to be an effective way to remove Na⁺ combined in the interlayer of C‐S‐H.     

The influence of aluminium on the dissolution of amorphous silica and its relation to alkali silica reaction

It is known that the addition of supplementary cementitious materials (SCMs) in concretes reduces or even stops expansion due to alkali silica reaction (ASR). It has been widely shown that the main mechanism controlling ASR in blends is the alkali fixation capacity of silica rich C–S–H, which lowers the pH of the pore solution. The role of alumina additions is less clear. It was shown in a previous paper [1] that the alumina present in certain SCMs does not further reduce the alkalinity of the paste pore solution. It is proposed here that aluminium acts directly on the reactive phases of the aggregates. Aluminium species, present in the pore solution, are absorbed on the silica surface and limit the dissolution of amorphous silica of the aggregates, restricting ASR. The effect of aluminium was demonstrated through a study of mortar expansion and SEM image analysis of reactive aggregates in simulated pore solutions.     

Chemical Processes During Energy‐Saving Preparation of Lightweight Ceramics

Lightweight glass‐ceramic material similar to foam glass was obtained at 700°C–800°C directly from alkali‐activated silica clay and zeolitized tuff without preliminary glass preparation. It was characterized by low bulk density of 100–250 kg/m³ and high pore size homogeneity. Chemical processes occurring in alkali‐activated silica clay and zeolitized tuff were studied using X‐ray diffraction, thermal gravimetry, IR‐spectroscopy, and scanning electron microscopy. Pore formation in both compositions is caused by dehydration of hydrated sodium polysilicates (Na₂O·mSiO₂·nH₂O), formed during alkali activation. Additional pore‐forming gas source in alkali‐activated zeolitized tuff is trona, Na₃(CO₃)(HCO₃)·2H₂O, formed during interaction between unbound NaOH and CO₂ and H₂O from air. Influence of mechanical activation of raw materials on chemical processes occurring in alkaline compositions was also studied.     

Alkali fixation of C–S–H in blended cement pastes and its relation to alkali silica reaction

Supplementary cementitious materials (SCM) are known to reduce or even stop expansion due to alkali silica reaction (ASR) in concretes with reactive aggregates. Studies indicate that the main reason for this is the decrease in alkalinity of the pore solution of the cement paste, which in turn is attributed to the change in composition of the C–S–H. In this paper we study the effect of aluminium and silicon incorporation in C–S–H on the composition of the pore solution in cement pastes containing SCMs. Different blended pastes of silica fume and metakaolin were cast, in order to obtain the same Si/Ca ratio of the C–S–H but with different aluminium contents. EDS micro analysis was made to determine the C–S–H compositions. In parallel pore solutions were extracted and analysed. It is found that the incorporation of aluminium does not increase the alkali fixation of the C–S–H found in real cementitious materials, suggesting that the greater effectiveness of SCMs containing alumina is due to other reasons.     

Coupled effects of aggregate size and alkali content on ASR expansion

This work is a part of an overall project aimed at developing models to predict the potential expansion of concrete containing alkali-reactive aggregates. First, this paper reports experimental results concerning the effect of particle size of an alkali-reactive siliceous limestone on mortar expansion. Special attention is paid to the proportions of alkali (Na₂O_eq) in the mixtures and reactive silica in the aggregate. Results show that ASR expansion is seven times larger for coarse particles (1.25-3.15 mm) than for smaller ones (80-160 μm). In mortars for which the two size fractions were used, ASR expansion increased in almost linear proportion to the amount of coarse reactive particles, for two different alkali contents. Then, an empirical model is proposed to study correlations between the measured expansions and parameters such as the size of aggregates and the alkali and reactive silica contents. Starting with the procedure for calibrating the empirical model using the experimental program combined with results from the literature, it is shown that the expansion of a mortar containing different sizes of reactive aggregate can be assessed with acceptable accuracy.     

Factors Influencing the Stability of AFm and AFt in the Ca–Al–S–O–H System at 25°C

The stabilities of Al₂O₃–Fe₂O₃‐mono (AFm) and ‐tri (AFt) phases in the Ca–Al–S–O–H system at 25°C are examined using Gibbs energy minimization as implemented by GEM‐Selektor software coupled with the Nagra/PSI thermodynamic database. Equilibrium phase diagrams are constructed and compared to those reported in previous studies. The sensitivity of the calculations to the assumed solid solubility products, highlighted by the example of hydrogarnet, is likely the reason that some studies, including this one, predict a stable SO₄‐rich AFm phase while others do not. The majority of the effort is given for calculating the influences on AFm and AFt stability of alkali and carbonate components, both of which are typically present in cementitious binders. Higher alkali content shifts the equilibria of both AFt and AFm to lower Ca but higher Al and S concentrations in solution. More importantly, higher alkali content significantly expands the range of solution compositions in equilibrium with AFm. The introduction of carbonates alters not only the stable AFm solid solution compositions, as expected, but also influences the range of solution pH over which SO₄‐rich and OH‐rich AFm phases are dominant. Some experimental tests are suggested that could provide validation of these calculations, which are all the more important because of the implications for resistance of portland cement binders to external sulfate attack.     

Determination of the elastic properties of amorphous materials: Case study of alkali–silica reaction gel

The gel formed during alkali–silica reaction (ASR) can lead to cracking and deterioration of a concrete structure. The elastic properties of the ASR gel using X-ray absorption and Brillouin spectroscopy measurements are reported. X-ray absorption was used to determine the density of the gel as a function of pressure, and the result yields an isothermal bulk modulus of 33 ± 2 GPa. Brillouin spectroscopy was applied to measure isentropic bulk (24.9–34.0 GPa) and shear moduli (8.7–10.1 GPa) of the gel. The range of values obtained is attributed to the variable composition of samples that were collected under field conditions. Results suggested that amorphous silica becomes expanded and compressible as it absorbs water molecules and alkali ions. This could explain high gel migration rates through the complex pore structures in concrete.     

A thermodynamic and kinetic model for paste–aggregate interactions and the alkali–silica reaction

A new conceptual model is developed for ASR formation based on geochemical principles tied to aqueous speciation, silica solubility, kinetically controlled mineral dissolution, and diffusion. ASR development is driven largely by pH and silica gradients that establish geochemical microenvironments between paste and aggregate, with gradients the strongest within the aggregate adjacent to the paste boundary (i.e., where ASR initially forms). Super-saturation of magadiite and okenite (crystalline ASR surrogates) occurs in the zone defined by gradients in pH, dissolved silica, Na⁺, and Ca^2 +. This model provides a thermodynamic rather than kinetic explanation of why quartz generally behaves differently from amorphous silica: quartz solubility does not produce sufficiently high concentrations of H₄SiO₄ to super-saturate magadiite, whereas amorphous silica does. The model also explains why pozzolans do not generate ASR: their fine-grained character precludes formation of chemical gradients. Finally, these gradients have interesting implications beyond the development of ASR, creating unique biogeochemical environments.     

Mineralogy and Microstructure of Hydrated Phases During the Pozzolanic Reaction in the Sanitary Ware Waste/Ca(OH)2 System

Despite technological improvements in its production process, the sanitary ware industry inevitably generates a certain volume of discards, products whose quality is not up to standard. The present paper is the first to scientifically explore clay‐based sanitary ware waste (SW) with a view to its valorization as an addition in the design of new, more environmentally friendly cements. The focus is on characterization of the waste and its pozzolanicity, as well as the structural and microstructural changes taking place in the pozzolan/Ca(OH)₂ system in the first 90 d of reaction. The findings show that pozzolanicity in clay‐based waste is comparable to the activity observed in silica fume (SF) and higher than that found in other clay‐based materials and fly ash (FA). The microstructural study of the clay‐based waste/Ca(OH)₂ system, in turn, reveals that the proportion of C–S–H gels rises with hydration time. These gels are characterized by long mean chain lengths (MCL) and low Ca/Si ratios. The intrinsic characteristics of this thermally activated clay‐based waste qualify it as a type Q pozzolans as defined in the European cement standards, making it apt for use in the manufacture of CEM II, IV, and V cements.     

Evaluation of laboratory test method for determining the potential alkali contribution from aggregate and the ASR safety of the Three-Gorges dam concrete

The releasable alkali from granite, which was used in the Three-Gorges concrete dam project in China, and from gneiss and feldspar was estimated by extraction in distilled water and super-saturated Ca(OH)₂ solution. Results show that: i) the finer the particles and the higher the temperature, the greater and faster the release of alkali; ii) compared with extraction by distilled water, super-saturated Ca(OH)₂ solution had a stronger activation on feldspar than on granite and gneiss; iii) for the three rocks tested, thermal activation had the largest effect on gneiss and a lower and similar effect on granite and feldspar. For very fine particles, temperature had a similar effect on the release of alkali by all three rocks.Because the aggregate used in the Three-Gorges dam concrete is non-reactive and a low calcium fly ash was used in the concrete, ASR would not be an issue for the dam, despite the release of alkali from the aggregate into the concrete.     

Comparison of the morphology of alkali–silica gel formed in limestones in concrete affected by the so-called alkali–carbonate reaction (ACR) and alkali–silica reaction (ASR)

The morphology of alkali–silica gel formed in dolomitic limestone affected by the so-called alkali–carbonate reaction (ACR) is compared to that formed in a siliceous limestone affected by alkali–silica reaction (ASR). The particle of dolomitic limestone was extracted from the experimental sidewalk in Kingston, Ontario, Canada that was badly cracked due to ACR. The siliceous limestone particle was extracted from a core taken from a highway structure in Quebec, affected by ASR. Both cores exhibited marked reaction rims around limestone particles. The aggregate particles were polished and given a light gold coating in preparation for examination in a scanning electron microscope. The gel in the ACR aggregate formed stringers between the calcite crystals in the matrix of the rock, whereas gel in ASR concrete formed a thick layer on top of the calcite crystals, that are of the same size as in the ACR aggregate.