Implications of pre-formed microcracking in relation to the theories of DEF mechanism

Microcracks were induced in cementitious systems by freeze-thaw action and by alkali-silica reaction. These mechanisms often co-exist with delayed ettringite formation in concretes. Mortars and concretes were subjected to a heat treatment cycle consisting of a pre-set period of 4 h at 23 °C followed by accelerated curing at 95 °C. To isolate the mechanical effects of induced microcracking, heat-cured specimens were subjected to varied prescribed damage induced by freeze-thaw or alkali-silica reaction prior to the onset of delayed ettringite formation. It was found that inducement of pre-formed microcracks led to an earlier onset of expansion due to delayed ettringite formation. Initially, microcracks enhanced ultimate expansion until a certain relatively high extent of microcracking was reached. Thereafter, ultimate expansion decreased with any further increase in microcracking. This report gives support to the paste expansion theory.     

Some factors affecting delayed ettringite formation in heat-cured mortars

Although more than 10 years of studies on delayed ettringite formation (DEF) have led to consensus in numerous areas of past disagreements, some questions remain experimental work is needed to complete the knowledge of this pathology. Following this objective, this paper studies the influence of pre-existing microcracking, wetting/drying cycles and the type of sulfated addition on DEF in steam cured mortars. The mortar specimens were prepared using an Ordinary Portland Cement and two types of sulfate were added to the mixtures: calcium sulfate (CaSO₄) or sodium sulfate (Na₂SO₄). The results confirm the well-known effect of temperature: no expansion was observed in any of the mixtures cured at room temperature. Moreover, no expansion was observed after 800 days for the reference mortar or for the mortar containing calcium sulfate but all the specimens of heat-cured mortars containing sodium sulfate expanded markedly after about 50 days whatever the supplementary treatments applied (thermal shrinkage or wetting/drying cycles). These results show the significant role played by alkalis in the occurrence of delayed ettringite. The supplementary treatments intended to cause prelimiray microcracking of the specimens did not promote expansion but contributed to a slight acceleration of the reaction. The ultimate values of expansion were similar to those obtained with sound mortars.     

Delayed ettringite formation symptoms on mortars induced by high temperature due to cement heat of hydration or late thermal cycle

Cases of delayed ettringite formation (DEF) have mainly been detected on mortars or precast concretes steam-cured according to a predefined temperature cycle during hydration. The present study shows that other situations in which the material is submitted to a temperature cycle can induce DEF expansions. Mortar bars were made with three different cements (types 10, 20M, and 30). As a first heat treatment, the mortar bars were steam-cured to reproduce the temperature cycle they would undergo if they were at the center of a large mortar member. The dimensional variations of these specimens were studied for 1 year. After 1 year, half of the specimens were steam-cured for 1 month at 85 °C. The expansions were followed for two more years. The early-age steam-cure-induced expansions for mortar types 10 and 30. Late steam-curing induced expansions for the three cements tested. In one case (cement type 20M), the early-age steam cure has suppressed or delayed the expansion induced by the late steam cure. A scanning electron microscopy (SEM) study showed that typical DEF symptoms are associated with the expansions.     

Delayed ettringite formation in Swedish concrete railroad ties

A petrographic examination of cracked Swedish concrete railroad ties identified delayed ettringite formation (DEF) as the damaging mechanism. This was unexpected because the concrete railroad ties were steam-cured with a maximum concrete temperature below 60 °C.The consensus in the published literature is that DEF only occurs in concrete subjected to heat curing above 70 °C. However, DEF is not only influenced by the curing temperature, but also by various other factors, such as cement composition (alkalis, C₃S, C₃A, SO₃, and MgO), fineness, etc. If an unfavorable combination of these parameters exists, delayed ettringite may occur at lower temperatures than 70 °C.In this paper, the influence of various parameters on DEF is discussed with reference to the investigated concrete.     

The current state of the accelerated concrete prism test

Expansions due to alkali-silica reaction (ASR) in the accelerated concrete prism test (ACPT-60 °C) show a significant reduction at 13 weeks compared to 52 week testing in the standard concrete prism test (CPT-38 °C). Previous work indicated that increased leaching, higher mass loss and a reduction in the pH were observed when temperature was increased from 38 to 60 °C. After further investigation the authors have revealed that non-reactive fine aggregate from certain sources combined with the same reactive coarse aggregate exhibited further reduction in expansion in the ACPT. Expansion data for a wide range of reactive coarse aggregates in 38 and 60 °C testing regimes is shown. Data investigating the Spratt reactive coarse aggregate combined with seven different non-reactive sands will be shown to demonstrate the dramatic effect of the non-reactive sand. Selected pore solution analyses will be given to further elucidate this issue.     

The behavior of silicocarbonatite aggregates from the Montreal area

In a previous paper, it was concluded that silicocarbonatite aggregates from the Francon quarry, Montreal contributed to durability problems in Portland cement concrete. Results show that, at 2 days after casting, concrete made with silicocarbonatite aggregates contained over 1.5% more Na₂O than similar bars made with Exshaw limestone aggregates. A reaction involving the rare mineral dawsonite in the silicocarbonatite is thought responsible for the higher Na₂O content. In turn, this caused increased expansion of concrete bars made with alkali expansive aggregates. Also, concrete made with alkali-carbonate reactive Pittsburg aggregate showed more expansion when cured at 80 °C than bars cured at 23 °C. Concrete bars made with Exshaw limestone aggregates cured for 4 h at 85 °C showed late-stage expansion, which is attributed to delayed ettringite formation (DEF). However, no expansion was shown by heat-cured concrete prisms or mortar bars made with silicocarbonatite aggregates. Release of alkalis, aluminates and carbonates by the dawsonite reaction may have inhibited DEF. Concrete bars made with nonreactive Nelson dolostone and 10% silicocarbonatite cured at 80 °C for 4 h showed up to 0.15% expansion after several years at 23 °C and 100% relative humidity (R.H.), indicating that a deleterious reaction did occur.     

Hydration Characteristics of Portland Cement after Heat Curing: II, Evolution of Crystalline Aluminate-Bearing Hydrates

The development of crystalline aluminate-bearing hydrates in portland cement mortars during water storage at room temperature for periods of up to 1 year after an initial heat cure for 12 h has been observed by quantitative X-ray diffraction analysis and backscattered electron imaging. Ettringite was present in the mortars immediately after a short-term cure at 20° and 60°C, calcium carboaluminate (C₄ĀH₁₁) at 60°C, monosulfate at 85°C, and hydrogarnet at 85°C and above. Ettringite started to form after an induction period ranging from several days to several months after the initial heat cure at 85/100°C, and developed substantially during the period of expansion of the mortar associated with delayed ettringite formation (DEF). Ettringite growth was also observed in the nonexpansive cement mortars. Development of the ettringite bands occurred exclusively in the expansive mortars. Although monosulfate observed in the mortars that had been heat cured at 85°C sometimes increased in amount on initial storage at room temperature, it appeared to vary little in amount for up to 1 year. The amount of hydrogarnet in the heat-cured cement product did not change significantly during storage at room temperature for more than 1 year. DEF expansion of the heat-cured mortars was attributed to ettringite band formation, which started to form at the surface of the cement product and gradually developed inwards.     

Alkali-aggregate reaction in activated fly ash systems

Certain aspects of the durability of a new cementitious material, alkali activated fly ash, are addressed in this article; specifically, a series of findings relating to the alkali-silica reaction are reported. The approach adopted in the study was to compare the new cementitious systems to analogous Portland cement mortars using aggregates of differing reactivity and a procedure based on the test described in ASTM standard C 1260. The results of SEM/EDX and XRD analysis of the materials showed that activated fly ash mortars performed better than the Portland cement equivalents.     

Pessimum effect of externally applied chlorides on expansion due to delayed ettringite formation: Proposed mechanism

Mortars and concretes were subjected to a heat treatment cycle consisting of a pre-set period of 4 h at 23 °C followed by accelerated curing at 95 °C prior to storage at room temperature in water or limewater, 0.5 M, 2.8 M sodium chloride solutions. It was found that the specimens stored in 0.5 M sodium chloride solution gave a much greater expansion than those stored in limewater or 2.8 M sodium chloride solution. This pessimum influence of chlorides on expansion due to delayed ettringite formation deviates from the commonly held view that chlorides mitigate sulphate attack in concretes. The mechanism of the pessimum effect of chlorides on expansion due to delayed ettringite formation, and the final products of the associated phase transformations have been proposed. X-ray diffraction and differential thermal analysis techniques were used to follow phase transformations.     

Studies on delayed ettringite formation in early-age, heat-cured mortars: I. Expansion measurements, changes in dynamic modulus of elasticity, and weight gains

Mortars were prepared from laboratory cements blended from a set of six representative ground clinkers and Terra Alba gypsum. The addition of gypsum was such that cements containing 1% SO₃ less than the optimum SO₃ content, the optimum SO₃ content, and 1% greater than the optimum SO₃ content were produced. Mortar bars and mortar cubes containing each of these cements were exposed to continuous room temperature (23 °C) curing, or to early-age curing cycles involving maximum temperatures of 55 and 85 °C, followed by long-term exposure at 100% RH over water, but not immersed in water. Measurements of expansion, dynamic elastic modulus, and weight gain were recorded at intervals of up to 900 days. Severe cracking and prominent delayed ettringite formation (DEF)-induced expansions were observed in 85 °C cured mortar bars derived from four of the six “oversulfated” cements. Much smaller expansions were observed in mortar bars from two cements with optimum SO₃ content cements also cured at 85 °C. No expansion or other visible indication of distress was observed for any of the 55 °C or continuously room-temperature-cured mortars. The dynamic elastic modulus increased progressively on prolonged exposure for the unaffected mortar bars, but it decreased precipitously after the onset of expansion in affected mortar bars. Significant weight increases also accompanied the processes of expansion. Mortars that showed severe cracking and deterioration when exposed as mortar bars suffered almost no visible damage when exposed as cubes.     

Alkali–silica reaction: Kinetics of chemistry of pore solution and calcium hydroxide content in cementitious system

This paper presents the results of the investigations on the chemistry of pore solutions, the contents of calcium hydroxide, and the expansions in mortars containing both reactive and non-reactive aggregates. In order to examine the effect of the temperature, experiments were performed at three different temperatures (23 °C, 38 °C and 55 °C).The compositions of the pore solution were measured at short time intervals for a period of up to 130 days in order to capture the kinetics of the chemistry of pore solution. The results showed that the changes in the concentrations of alkali ions can be best explained by the first order reaction. In addition, the proposed rate equation could reasonably simulate the changes in the actual concentrations of alkalis. Finally, the results in this paper suggest that the rate of the alkali–silica reaction in cementitious system containing highly reactive aggregate can be also expressed as the first order reaction.     

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.     

The so-called alkali-carbonate reaction (ACR) — Its mineralogical and geochemical details, with special reference to ASR

Typical examples of so-called alkali-carbonate reaction (ACR) in the Canadian field concretes in Ontario, CSA concrete prism, RILEM concrete microbars and RILEM mortar bar containing Pittsburg aggregate, were examined petrographically based on polarizing microscopy, SEM observation and quantitative SEM-EDS analysis of the reaction products. It was revealed that ASR gel was the main product responsible for the crack formation in concretes, and that this gel had a common nature to that in the typical ASR. That is, ASR gel presented distinctive compositional trend lines, passing from low-Ca ASR gel at [Ca/Si] = 1/2-1/6, [Ca]/[Na + K] = 1.0 to the “convergent point” with [Ca/Si] = 1.3-1.8, [Ca]/[Na + K] = 100 at which chemical equilibrium is attained with CSH gel. The so-called ACR is a combination of deleteriously expansive alkali-silica reaction (ASR) of cryptocrystalline quartz, and harmless dedolomitization which produces brucite and carbonate halo. In laboratory specimens, fine dolomitic aggregate undergoes dedolomitization, and brucite and ASR gel react to form non-expansive Mg-silicate gel on the dolomite crystals. This explains why the mortar bar produces smaller expansion than the concrete microbar, and why the reaction products are so minute that they escape attention by optical microscopy. As a crystalline counterpart, mountainite is a candidate for low-Ca ASR gel, while sepiolite is one for Mg-silicate gel. Concealed ASR was detected in ACR-affected field concretes undergoing ingress of deicing salt which formed Friedel's salt and Cl-doped CSH gel. Compositions of ASR products, methods of sample preparation and analysis for correct identification of ACR, and artifacts were critically reviewed.     

ASR pessimum behaviour of siliceous limestone aggregates

Siliceous limestone aggregates have “pessimum” behaviours similar to those observed for pure siliceous aggregates such as flint or opal. For high alkali contents concretes based on fine and coarse reactive siliceous limestone aggregates swell less than concretes based on fine reactive siliceous limestone aggregates and non-reactive coarse aggregates. The reduction of the swelling is more significant for a “micritic” limestone containing highly reactive free silica than for a “sparitic” limestone containing less reactive free silica. The consumption of a part of the alkalis by non-expansive processes such as chemical sorption on silanol sites of reactive silica and pozzolanic C-S-H is expected to explain the reduction of the swelling.     

Reactive powder based concretes: Mechanical properties, durability and hybrid use with OPC

The basic mechanical properties, frost durability and the bond strength with normal strength concretes of the ultra high strength (UHS) mortars and concretes were studied. The produced mixes had plastic or fluid-like consistency. The 28-day compressive strength varied between 170 and 202 MPa for the heat-treated specimens and between 130 and 150 MPa for the non-heat-treated specimens. The shrinkage values were two times higher for the UHS mortars in comparison with the UHS concretes. After the initial shrinkage, swelling was noticed in the UHS mortars. The lowest creep values were measured for the non-heat-treated UHS concretes. The frost-deicing salts durability of the UHS mortars and concretes appeared to be very good even despite the increased water uptake of the UHS concretes. The study of the hybrid concrete beams indicated the formation of low strength transition zone between the UHS mortar and normal strength concrete.     

Electrochemical chloride extraction: efficiency and side effects

Some specimens of reinforced concrete cast with an alkali-resistant aggregate, previously maintained in a solution of NaCl, were subjected to an electrochemical chloride extraction (ECE). The chloride profiles before and after treatment were determined. Likewise, alkali ions profiles before and after treatment were determined. After treatment, some specimens were stored in a controlled atmosphere (60 °C and 100% RH) in order to accelerate the alkali-silica reaction, if any.Results of chloride content after treatment show that about 40% of the initial chloride is removed within 7 weeks. About one-half of the chloride close to steel was removed, but at the same time, significant amounts of alkali ions were observed around the steel.Microstructural observations by scanning electron microscopy (SEM) showed that after treatment, new cementitious phases containing higher concentrations of sodium, aluminum and potassium were formed. Moreover, alkali-silica gel was observed in the specimens stored at 60 °C and 100% RH. It may be possible that the ECE accumulates locally high amounts of alkali ions that stimulate the alkali-silica reaction even though the concrete contained nominally inert siliceous aggregates. The specimen expansions were not recorded, but no cracks were observed.     

Metakaolin and fly ash alkali-activated mortars compared with cementitious mortars at the same strength class

Alkali-activated and cementitious mortars belonging to R1 ≥ 10 MPa, R2 ≥ 15 MPa and R3 ≥ 25 MPa strength classes were tested and compared in terms of workability, dynamic modulus of elasticity, porosimetry, and water vapor permeability. Capillary water absorption, drying shrinkage, resistance to sulfate attack, and corrosion behavior of embedded bare and galvanized reinforcements were also investigated.In alkali-activated mortars, drying shrinkage is higher than that of cementitious mortars but restrained shrinkage is lower due to lower modulus of elasticity. Pore dimensions affect water vapor permeability, more pronounced in alkali-activated mortars, and capillary water absorption, much lower in fly ash ones. The high alkalinity of fly ash and metakaolin mortars delayed the achievement of the passive state in particular for the galvanized reinforcements but after 1 month of curing they reached the same corrosion rates of those embedded in cementitious mortars.     

The influence of polymers on the hydration of portland cement phases analyzed by soft X-ray transmission microscopy

The soft X-ray transmission microscope, which allows the in situ observation of wet samples of cement at normal pressures with high spatial resolutions (25 nm), was used to observe and compare the effects of two polymers — a water soluble polymer (HPMC — hydroxypropyl methylcellulose) and a latex [EVA-poly(ethylene-co-vinyl acetate)] on the early hydration of C₃S and C₃A. These polymers are used to modify the properties of fresh and hardened mortars and concretes, especially when adhesive characteristics are required. The images show that the cellulose ether delays the hydration of the cementitious particles and promotes the formation of inner products rather than outer products. On the other hand, EVA particles agglomerate around the hydrating C₃S grains, and act as nucleation agents in the development of the composite microstructure. While HPMC slightly changed the aspect of C₃A hydration, EVA inhibited or even prevented the formation of ettringite crystals during the early stage of hydration, and resulted in a cloud of small, bright particles concentrated around the hydrating C₃A grains.     

Composite systems fluorgypsum-blastfurnance slag-metakaolin, strength and microstructures

The hydration and properties of composite cementitious pastes with 75% fluorgypsum were investigated; blastfurnace slag and metakaolin were the complementary cementitious materials. The pastes were cured under water at 20 °C for 360 days. All pastes developed and maintained strength under water, except those of commercial gypsum. The addition of metakaolin had a positive effect, after 360 days compressive strengths of 13.4, 13.8 and 14.6 MPa were registered for systems with 0%, 5% and 10% of metakaolin, respectively. The microstructure of the composite pastes was formed of a framework of gypsum crystals, which formed in the initial stages; the matrix was later densified by the formation of C-S-H and ettringite, as a result of the slag and metakaolin reactions. The fluorgypsum reacted rapidly in the first days, however it was still present after one year; the slag reacted in a slower fashion, and the metakaolin was very reactive and contributed with the ettringite since the early ages, which enhanced the strength.     

Studies on delayed ettringite formation in heat-cured mortars: II. Characteristics of cement that may be susceptible to DEF

Expansions of mortar bars, stored over (but not in) water after simulated steam curing to 85 °C, were related to certain cement compositional parameters. The relationship is expressed in the form of a “delayed ettringite formation (DEF) index.” The DEF index is computed as the joint product of the SO₃/Al₂O₃ molar ratio of the cement, the sum of its SO₃ and Bogue C₃A percentages divided by 10 and the square root of the alkali content expressed as equivalent % Na₂O. The mortars studied were made with 18 different cements, prepared from a set of six representative clinkers by incorporating Terra Alba gypsum to total SO₃ contents that were 1% below optimum, at optimum and 1% above optimum (as defined in ASTM C 563). Measurements of expansion were recorded at intervals for up to 1400 days. Severe cracking and prominent DEF-induced expansions were observed in mortar bars derived from four of the six ‘oversulfated’ cements and lesser expansions from three of the six cements prepared at optimum SO₃ contents. No expansion was found for cements of DEF index below a threshold value; above this value expansions were approximately proportional to the difference between DEF index and its threshold value. The relationship confirms the significance of all three compositional parameters making up the index, e.g., the SO₃/Al₂O₃ molar ratio, the joint contents of SO₃ and C₃A, and the alkali content, in influencing the extent of DEF-induced expansion. In these measurements, the apparent pessimum effect for SO₃ content previously reported by others was not found, although SO₃ contents examined spanned the supposed pessimum value of 4%. Rather, expansion increased with increasing SO₃ content for mortars made with all clinkers exhibiting expansion.