Studies on lithium salts to mitigate ASR-induced expansion in new concrete: a critical review

This paper provides a critical review of the research work conducted so far on the suppressive effects of lithium compounds on expansion due to alkali-silica reaction (ASR) in concrete and on the mechanism or mechanisms by which lithium inhibits the expansion. After a thorough examination of the existing literature regarding lithium salts in controlling ASR expansion, a summary of research findings is provided. It shows that all the lithium salts studied, including LiF, LiCl, LiBr, LiOH, LiOH·H₂O, LiNO₃, LiNO₂, Li₂CO₃, Li₂SO₄, Li₂HPO₄, and Li₂SiO₃, are effective in suppressing ASR expansion in new concrete, provided they are used at the appropriate dosages. Among these compounds, LiNO₃ appears to be the most promising one. Although the mechanism(s) for the suppressive effects of lithium are not well understood, several mechanisms have been proposed. A detailed discussion about these existing mechanisms is provided in the paper. Finally, some recommendations for future studies are identified.     

Influence of lithium-based products proposed for counteracting ASR on the chemistry of pore solution and cement hydrates

Low- and high-alkali cement pastes were made with or without LiNO₃ or a Li-bearing glass. The [Li]/[Na+K] molar ratio was kept constant to 0.74. The specimens were stored at 23, 38, and 60 °C in sealed containers. After 3, 7, 28, and 91 days, their pore solutions were extracted and analysed, and their residual water contents were obtained by drying. The Li glass was found to react quite slowly, and the corresponding [Li⁺] in solution progressively increased with time, temperature, fineness (as-received glass vs. ground glass), and the [Na⁺+K⁺] concentration in solution. This glass increased the pH by about 0.1, and by about 0.2 after it was finely ground. In contrast, LiNO₃ decreased the pH by about 0.1, despite significantly increasing the [Na⁺+K⁺] in the pore solution. The higher the total %Na₂O_e content (including Li) in the original mixtures, the higher the total alkali content incorporated in the cement hydrates. The [Li⁺]-[Na⁺+K⁺] ratio in solution was about half of the initial ratio (0.74), while this ratio in the cement hydrates was always over 1.1. Li is the alkali most preferentially incorporated into the cement hydrates, while K is the least.     

The influence of potassium-sodium ratio in cement on concrete expansion due to alkali-aggregate reaction

In concrete containing potentially reactive aggregates, deleterious alkali-aggregate-reaction (AAR) can be prevented by the use of suitable mineral admixtures or by limiting cement content and alkalis (Na₂O-equivalent) of the cement. However, the Na₂O-equivalent of cement may not always accurately define the potential of cement to cause AAR. In this study, the potential reactivity of concrete produced with cements having similar Na₂O-equivalents but different K/Na-ratios has been measured and the composition of gel has been analyzed. Additionally, pastes and mortars have been produced to study the development of pore solution composition.The expansion of the concrete mixtures shows significant differences depending on the cement used. The different K/Na-ratio present in the cements is reflected in the pore solution of pastes and mortars and in the gel present in aggregates of the concrete mixtures. As the hydroxide concentration in the pore solutions of pastes and mortars produced with the different cements is nearly identical, the difference in K/Na-ratio has to be the reason for the observed differences in concrete expansion.     

Change of pore size in concrete due to electrochemical chloride extraction and possible implications for the migration of ions

Electrochemical chloride extraction (ECE) is used for the rehabilitation of chloride-contaminated concrete. Anions such as chloride and hydroxide are pushed away from the cathode (reinforcement), and cations such as sodium, potassium and calcium are attracted to the cathode. During ECE an increase of the concrete resistance can be observed. The results of a petrography study on ECE-treated concrete are presented in this paper. It also investigates the influence of pore size on ion migration using a concrete substitute model with known pore size. Findings showed that the pore size and pore size distribution of concrete are altered due to ECE. It is therefore suggested that concrete acts as active migration medium in the migration process by releasing ions into the pore solution. Moreover, small pores hinder the migration of ions, which may partially be responsible for changes in concrete resistance.     

Role of fibers in controlling unrestrained expansion and arresting cracking in Portland cement concrete undergoing alkali-silica reaction

An experimental study was undertaken to investigate the role of polypropylene or brass-coated steel fibers in controlling unrestrained expansions and delaying and arresting cracking in Portland cement concrete due to alkali-silica reaction. Portland cement concrete and fiber-reinforced concrete (FRC) mixtures were prepared at a w/c ratio of 0.40 using modified Type I cement, reactive fine particles, and coarse limestone aggregates. Prism (5×5×30 cm) and plate (13.5×13.5×3 cm) specimens were prepared and cured for 7 or 28 days before exposure to a special treatment to accelerate ASR. Expansion, time of cracking, and ultrasonic pulse velocity were determined over a treatment period of 65 days using prism specimens. Ultimate cracking pattern and extent were determined after a treatment period of 85 days using plate specimens. The results showed that while fibers did not contribute significantly to controlling pre-cracking and post-cracking expansions, they played a significant role in delaying cracks formation and limiting their extent. Considering its lower cost and content, the performance of polypropylene fibers was superior to that of brass-coated steel ones. The potential of brass-coated fibers in arresting ASR cracking was significantly affected by age of concrete when subjected to treatment.     

The pH measurement of concrete and smoothing mortar using a concrete powder suspension

A simple method is presented to determine the pH value of concrete and fine smoothing mortar. The method is based on mixing powdered samples with a solvent and measuring the pH of the suspension. The parameters affecting the result are investigated. The validity of the pH results is tested by comparing the values measured from a suspension of pulverized specimen with the extracted pore solution. Measurements were done by using a pH electrode and by titration. The technique investigated furnishes results with good reproducibility and has been proven feasible. The pH value results of the proposed suspension method could be compared with the results of the extracted pore solution in two normal-strength concretes and the fine smoothing. Sufficient pore solution of the extra-air-entrained concrete and high-strength concrete could not be obtained in the reference method of extraction of the pore solution. The difference between the results of the suspension method and the extraction method was 0.07 pH units on the average with a standard deviation of 0.27 pH units when the powder-to-suspension ratio in the suspension method was 0.5.     

Influence of acetate and formate-based deicers on ASR in airfield concrete pavements

In the past few years, the issue of external alkalis and their influence on ASR in concrete has become more important since several concrete airfield pavements have shown ASR-distress related to the use of alkali-containing airfield deicers based on acetates and formates.Experiments with model pore solutions and cement pastes as well as speciation calculations and ASR performance tests were conducted to investigate possible mechanisms. The obtained results indicate that the solubility of portlandite is increased in the presence of acetate-based and formate-based deicers due to the formation of Ca-acetate and Ca-formate complexes. The additional release of OH⁻ ions from portlandite and the supply of alkalis can initiate and highly accelerate ASR in concretes with reactive aggregates. There is also evidence for a reaction of ettringite with such airfield deicers.     

Methods of obtaining pore solution from cement pastes and mortars for chloride analysis

Two techniques for the recovery of pore solution from cement mortars are examined: pore solution expression and miscible displacement using a high pressure permeameter. In the former, the pore solution is expressed from the mortar by crushing; in the latter, it is eluted from the mortar over 30 min by miscible displacement with water. Experimental results are presented for a range of cement pastes and mortars into which known amounts of chloride ion have been incorporated by using sodium chloride solution as the mix water. The results show that both eluted and expressed solutions exhibit a decrease in chloride ion concentration as the cement matrix ages, with the elution method showing a greater sensitivity to mix composition. Both methods show a decrease in chloride concentration as the water: cement ratio of the mix is increased. Overall, the high pressure elution method is capable of recovering a significantly higher proportion of the incorporated chloride. The application of these techniques to pore solution analysis is discussed.     

Laboratory and field investigations of the influence of sodium chloride on alkali-silica reactivity

Concrete cylinders, 255 mm in diameter, were made with high- and low-alkali cements, a highly alkali-silica-reactive coarse aggregate, and subjected to various conditions at 38 °C: (1) immersion in 3% NaCl solution; (2) immersion in 6% NaCl solution; (3) humid air at 100% RH, and (4) 14-day cycles including 12 days in humid air, 2 days of drying, and 3 h in 6% NaCl solution. After 1 year, a number of cylinders were drilled to obtain dry powder samples from different depths, which were analyzed for total and soluble chloride and for soluble sodium and potassium. Concrete cores were also taken in a number of parapets and abutments, either exposed to deicing salts or not, on which chemical analyses were also performed on slices taken at different depths from the exposed surface. The results obtained suggest that making concrete with a low-alkali content is an effective way to prevent expansion due to alkali-silica reaction even for concretes exposed to seawater or deicing salts; this is attributed to the fact that the OH⁻ ion concentration in the pore solution, and then the pH, is decreased in the near-surface layers of concrete exposed to sodium chloride, which does not penetrate at depth in concrete.     

Effects of lithium salts on ASR gel composition and expansion of mortars

Suppression of alkali-silica reaction (ASR) expansion in mortar and concrete by the addition of lithium salts has been confirmed by some workers. It has been revealed that lithium hydroxide tended to reduce the reaction between sodium or potassium hydroxide and reactive silica, and that the ASR gel incorporating lithium was less expansive. However, it has not been reported how the addition of a lithium salt influenced the composition of the ASR gel. The calcium in ASR gel is considered to play an important role in the expansion of the gel. Thus, it is significant to characterize ASR gel composition in mortars containing lithium salts by BSE-EDS analysis. This study aims to discuss the mechanisms of suppression of ASR expansion in mortar by lithium salts from the viewpoint of ASR gel composition. The average CaO/SiO₂ ratio in ASR gels decreased with increasing amount of added lithium salts. It should be noted that the extent of variations in the CaO/SiO₂ ratio in ASR gels significantly decreased with increasing amount of lithium salts. The addition of relatively small amounts of LiOH and Li₂CO₃ resulted in increased expansion. We also obtained an unexpected result that ASR gels became homogeneous with respect to their CaO contents at high dosage levels. However, the reduction in average CaO/SiO₂ ratios and the homogenization in the CaO content of ASR gels due to the addition of lithium salts may not be related to the expansion of mortars.     

A study on chloride-induced depassivation of mild steel in simulated concrete pore solution

The effect of chloride ions on passivity breakdown of steel in simulated concrete pore (SCP) solution was studied using electrochemical techniques. In this regards, the sensitivity of cyclic potentiodynamic parameters such as ΔE (difference between E_pit and E_rep), i_peak and AC-impedance parameters like R_ct, R_f, C_i, R_ad and C_ad to chloride ion concentration was investigated. Adsorption of OH⁻ ions on the metal surface in free chloride SCP solution and also displacement of those ions by Cl⁻ ions were demonstrated in high frequency part of Nyquist plots. In addition, a severe decrease in resistance of interfacial reaction (R_f+R_ct) was observed through breakdown of passive film in the [Cl⁻]/[OH⁻] ratio of 0.6. The interfacial capacitance, C_i, was abruptly raised when localized corrosion changed to general one.     

Dual effectiveness of lithium salt in controlling both delayed ettringite formation and ASR in concretes

The influence of lithium nitrate on expansions due to delayed ettringite formation (DEF) and alkali-silica reaction (ASR) has been investigated. Effects of the lithium salt were examined in heat-cured mortars and concretes containing one or both damage mechanisms. The mortars and concretes made using reactive and/or non-reactive aggregates were subjected to heat treatment consisting of a hydration delay period of 4 h at 23 °C followed by steam-curing at 95 °C and then stored in limewater. Results showed that the lithium salt admixture was able to reduce the occurrence of deleterious expansion due to delayed ettringite formation in addition to controlling alkali-silica reaction in cementitious systems containing one or both mechanisms. In concretes made using non-reactive limestone aggregates, incorporation of lithium nitrate in a proportion of 0.74 M ratio of Li to (Na + K) was found to control delayed ettringite formation during the one-year period of this study.By analyzing the leaching properties of lithium and other alkalis from mortars during storage, it was found that a substantial amount of lithium was retained in the cementitious system in a slightly soluble form, and is expected to be responsible for reducing DEF.     

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.     

Porosity, pore size distribution and in situ strength of concrete

In this study, in situ strength of concrete was determined through compression test of cores drilled out from laboratory cast beams. The apparent porosity and pore size distribution of the same concrete were determined through mercury intrusion porosimetry, performed on small-drilled cores. The normal-strength concrete mixes used in the experimental investigation were designed to exhibit a wide variation in their strengths. To ensure further variation in porosity, pore size distribution and strength, two modes of compaction, two varieties of coarse aggregates, different levels of age, curing period and exposure condition of concrete were also introduced in experimental scheme. With the data so generated, an appraisal of the most frequently referred relationships involving strength, porosity and pore size of cement-based materials was carried out. Finally, a new empirical model relating the in situ strength of concrete with porosity, pore size characteristics, cement content, aggregate type, exposure conditions, etc., is presented.     

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.     

Effects of aggregate size and alkali content on ASR expansion

Attempts to model ASR expansion are usually limited by the difficulty of taking into account the heterogeneous nature and size range of reactive aggregates. This work is a part of an overall project aimed at developing models to predict the potential expansion of concrete containing alkali-reactive aggregates. The paper gives measurements in order to provide experimental data concerning the effect of particle size of an alkali-reactive siliceous limestone on mortar expansion. Results show that no expansion was measured on the mortars using small particles (under 80 µm) while the coarse particles (0.63-1.25 mm) gave the largest expansions (0.33%). When two sizes of aggregate were used, ASR-expansions decreased with the proportion of small particles. Models are proposed to study correlations between the measured expansions and parameters such as the size of aggregates and the alkali and reactive silica contents. The pessimum effect of reactive aggregate size is assessed and the consequences on accelerated laboratory tests are discussed.     

Development of a galvanic sensor system for detecting the corrosion damage of the steel embedded in concrete structures: Part 1. Laboratory tests to correlate galvanic current with actual damage

The correlation between sensor output and corrosion rate of reinforcing steel was evaluated by laboratory electrochemical tests in saturated Ca(OH)₂ with 3.5 wt.% NaCl. In this paper, two types of electrochemical probes were developed: galvanic cells containing of steel/copper and steel/stainless steel couples. The corrosion behavior in saturated Ca(OH)₂ solution with and without 3.5 wt.% NaCl addition for the different electrodes was investigated by potentiodynamic test. Weight loss measurement and galvanic corrosion test were conducted to obtain the corrosion rate of reinforcing steel and the charge of sensor in saturated Ca(OH)₂ solution with 3.5 wt.% NaCl addition, respectively.

The results of the potentiodynamic test indicated the possibility of detecting an ingress point of chlorides by measuring the galvanic current. In galvanic corrosion tests, the galvanic current of steel/copper couple was higher than that of steel/stainless steel couple, i.e., the steel/copper sensor is more suitable for high resistance environment. The steel/stainless sensor showed a better linear correlation than the steel/copper sensor. Through the relationship between the sensor system output and the weight loss (mg/cm²) of steel, real corrosion damage of the steel embedded in concrete can be detected.     

Transport of a surface-applied corrosion inhibitor in cement paste and concrete

Surface-applied corrosion inhibitors are a kind of repair material and usually contain an aminoalcohol and a component forming a salt with the aminoalcohol. According to the manufacturers, this type of inhibitor penetrates very rapidly into concrete; however, the transport mechanisms have not been sufficiently investigated so far. The major part of the study therefore focused on the transport of the ingredients of an inhibitor in cement paste and concrete, which contained an aminoalcohol and a phosphorous compound. It has been shown that the latter forms an insoluble calcium salt in the environment of cement and precipitates quantitatively. It is thus unable to penetrate from the outside into the alkaline concrete zone and cannot develop its inhibiting effect there. The aminoalcohol, on the other hand, is not bound by cement, but remains largely dissolved in the pore liquid, thus providing optimal conditions for high mobility. The analysis of the transport mechanisms involved has revealed that diffusion in the dissolved state is by far the most efficient transport mechanism. While basically the transport of the aminoalcohol via the gaseous phase is possible, it does play an inferior role only. Surprisingly, the substance had hardly been absorbed by concrete by capillary suction, but at first remained close to the concrete surface.     

Alteration of alkali reactive aggregates autoclaved in different alkali solutions and application to alkali-aggregate reaction in concrete (II) expansion and microstructure of concrete microbar

The effect of the type of alkalis on the expansion behavior of concrete microbars containing typical aggregate with alkali-silica reactivity and alkali-carbonate reactivity was studied. The results verified that: (1) at the same molar concentration, sodium has the strongest contribution to expansion due to both ASR and ACR, followed by potassium and lithium; (2) sufficient LiOH can completely suppress expansion due to ASR whereas it can induce expansion due to ACR. It is possible to use the duplex effect of LiOH on ASR and ACR to clarify the ACR contribution when ASR and ACR may coexist. It has been shown that a small amount of dolomite in the fine-grained siliceous Spratt limestone, which has always been used as a reference aggregate for high alkali-silica reactivity, might dedolomitize in alkaline environment and contribute to the expansion. That is to say, Spratt limestone may exhibit both alkali-silica and alkali-carbonate reactivity, although alkali-silica reactivity is predominant. Microstructural study suggested that the mechanism in which lithium controls ASR expansion is mainly due to the favorable formation of lithium-containing less-expansive product around aggregate particles and the protection of the reactive aggregate from further attack by alkalis by the lithium-containing product layer.     

Effect of drying-rewetting on the alkali concentration of the concrete pore solution

Experience has shown that the pore solution alkalinity of resaturated concrete was lower than expected. Laboratory-concrete specimens were made with reactive aggregates, stored over water at 38 °C, and then broken into two pieces. The pore solution of half-specimens was extracted by high-pressure squeezing. The other half-specimens were dried at ambient air and rewetted in humid air to their initial weight. The pore solution was then extracted and compared with the composition results of the first extraction. The results obtained from this investigation confirmed that a certain part of the alkali ions in pore solution that had become fixed by drying are not subsequently extracted after rewetting. The alkali concentration [Na+K] was reduced from 34% to 61% by the drying and rewetting treatments.