Effect of cement C3A content, temperature and storage medium on thaumasite formation in carbonated mortars

The purpose of this study is to determine the effect of cement C₃A content, temperature and composition of the immersion medium (water, gypsum and magnesium sulphate solution) on the rate of thaumasite formation in cement mortars. It also aims to ascertain how the C₃A content influences the composition of the salt formed.The mortar prisms for this study were made with two different cements, one with low and the other with high Al₂O₃ content, with or without gypsum and/or calcium carbonate. After hydration, curing and carbonation, the prisms were partially immersed in distilled water and stored at temperatures ranging from 0 to 5 °C for up to 5 years. Some of the prisms were immersed in a 2% (w/w) gypsum solution or in 1.4% (w/w) magnesium sulphate solution at ambient temperature. Samples were taken at different ages and mineralogical and micro-structurally characterised.Some of the specimens tested were observed to expand, in a process concurring with the formation of thaumasite or a solid solution of thaumasite and ettringite, at both ambient and cooler temperatures. A correlation was found between cement C₃A content and the composition of the deterioration product involved in the expansive process: thaumasite forms in mortars made with low C₃A cement, whereas mixed crystals or solid solutions of thaumasite and ettringite form in mortars made with high C₃A content cement.     

A thermodynamic and experimental study of the conditions of thaumasite formation

The formation of thaumasite was investigated with the progressive equilibrium approach (PEA). This approach experimentally simulates the conditions of various levels of sulfate addition in hardened cement pastes. The influence of limestone, time, C₃A content, temperature and leaching on thaumasite formation was investigated. The results show that thaumasite formation is favoured at lower temperatures (8 °C) independently of the type of cement clinker (high or low C₃A content) used. Thaumasite was found to form only in systems where limestone was present and where sufficient sulfate had been added. Thaumasite precipitated only in systems where the Al present has already been consumed to form ettringite and the molar SO₃/Al₂O₃ ratio exceeded 3. In leached samples (reduction of portlandite and alkalis) slightly less thaumasite was formed whereas gypsum and ettringite are favoured under these conditions. The PEA, used to investigate the chemical aspects of sulfate attack was found to be a good tool for simulating external sulfate attack. Generally, thaumasite was detected were it was modelled to be stable in significant amounts. However, in this study equilibrium conditions were not reached after 9 months.     

Quantitative X-ray diffraction analysis of ettringite,thaumasite and gypsum in concretes and mortars

A method for quantitative Xray diffraction analysis (QXDA) of three sulphate minerals frequently associated with building materials has been devised. Sulphate minerals which form within concretes, mortars and other cementitious-based materials include ettringite, (3CaO.Al₂O₃.3CaSO₄.31H₂O), thaumasite (CaSiO₃.CaCO₃.CaSO₄.15H₂O) and gypsum (CaSO₄.2H₂O). Calibration standards were prepared using pure samples of these minerals and incorporating boehmite as an internal standard. The equations obtained from the standard calibration curves were used to calculate the percentage of ettringite, thaumasite and gypsum in a) samples which contained known percentages of these minerals mixed together and b) laboratory prepared concrete cubes undergoing sulphate attack. The cubes contained 0%, 20% or 40% pulverized fuel ash (pfa) by weigth of cementitious material and had been stored in various sulphate solutions including sea water for one year.Quantitative Xray diffraction analysis of the standard mixtures successfully detected the expected ettringite, thaumasite and gypsum concentrations. The concrete cube results showed that the sulphate mineral concentration within the surface of the cubes decreased when larger amounts of pfa were used in the concrete mixes. This effect was less noticeable in the sea water cubes.     

Effects of gypsum formation on the performance of cement mortars during external sulfate attack

Sodium sulfate attack was studied on C₃S mortars, along with ASTM Type I Portland cement (PC) mortars, in an attempt to independently evaluate the effect of gypsum formation on the performance. The quantity of gypsum and ettringite, as measured by differential scanning calorimetry (DSC), increased with the time of immersion in the sulfate solution. An increase in length of the mortar specimens was also registered along with the increase in the quantity of gypsum. This result suggests that the formation of gypsum could be expansive. Indeed, considerable expansion, although delayed compared to PC mortars, was observed in the C₃S mortars. Thus, it can be concluded that the expansion of the PC mortars occurred due to the combined effect of gypsum and ettringite formation, while the expansion of C₃S mortars occurred as a result of gypsum formation.Thaumasite formation as small inclusions was also detected in both the C₃S and the PC mortars, especially in regions of high gypsum deposition. The formation of thaumasite, despite the absence of carbonate bearing minerals and low temperatures, could be because of the carbonation of the surface zones of the mortars. However, it would be speculative to attribute any expansion to the formation of thaumasite, since it was detected only in minute amounts in the microstructural investigation.     

Phase changes during the early hydration of Portland cement with Ca-lignosulfonates

The influence of two Ca-lignosulfonates (LS), one softwood (LSs) and one hardwood (LSh) based, on the phase changes during the early hydration of ordinary Portland cements was investigated using isothermal calorimetry, in-situ XRD, and thermal analysis. In the presence of LS the hydration of C₃S and C₃A was retarded. LS was found to influence the solubility of the sulphate phase; in case of bassanite/gypsum the initial dissolution was accelerated. An acceleration of the initial ettringite formation was observed in the presence of LS. However, the second ettringite formation was retarded. The amounts of bound water (H) and calcium hydroxide (CH) formed were measured using TG/DTG on cement pastes hydrated for 90 min, 5, 12 and 24 h. At 90 min the amount of H was increased the higher the concentration of LS. The amount of CH formed between 5–24 h was decreased the higher the concentration of LS.     

Mechanisms and parameters controlling the tricalcium aluminate reactivity in the presence of gypsum

To understand the mechanisms and the parameters controlling the reactivity of tricalcium aluminate in the presence of gypsum at an early age, a study of the hydration of the “C₃A-sulphate” system by isothermal microcalorimetry, conductimetry and a monitoring of the ionic concentrations of diluted system suspensions have been carried out with various gypsum quantities. The role of C₃A source and its fineness were also studied. This work shows the fast initial formation of AFm phase followed by ettringite formation during the period when the sulphate is consumed. It has been highlighted that the time necessary to consume all the gypsum varies with the type of C₃A and it has been attributed to the intrinsic reactivity of each one and mainly to the change of fineness from one C₃A to another. Results are discussed alongside hypothesis from the literature to explain the slowing down of C₃A hydration process in the presence of calcium sulphate.     

XRD, EDX and IR analysis of solid solutions between thaumasite and ettringite

Solid solutions between thaumasite and ettringite were prepared by methods analogous to those well established for the preparation of thaumasite and ettringite. The extent of immiscibility in this system is investigated by varying the Al:Si and SO₄²⁻:CO₃²⁻ ratios in reactant mixtures. The solids produced were analysed by quantitative X-ray diffraction, with Rietveld refinement also providing accurate unit cell dimensions, energy-dispersive X-ray analysis and infrared spectroscopy. The compositional and unit cell variations in the solid solution are discussed. A wide variety of solid solution compositions were produced with both the thaumasite and ettringite structures, but all preparations were considerably diluted by secondary amorphous products.     

Early hydration of C3A–gypsum pastes with Ca- and Na-lignosulfonate

The early age phase development during the hydration of C₃A–gypsum pastes with 1 and 4% Ca- or Na-lignosulfonate (CLS and NLS) was investigated using isothermal calorimetry, in-situ XRD, thermogravimetry, mass spectroscopy, and SEM analysis. With 1% CLS or NLS neither retardation of C₃A dissolution nor retardation of ettringite formation was observed. When LS was added in a concentration of 4%, C₃A and gypsum dissolution were slightly retarded. Gypsum depletion was delayed in all pastes containing CLS or NLS. 1% CLS or NLS increased the amount of AFm-phases formed within 24 h, while the amount of AFm was reduced with 4% CLS or NLS. The initial heat flow increased and the heat flow in the gypsum depletion peak was reduced with 1 and 4% CLS. With 4% NLS no initial heat flow was measured and the heat developed slowly within the first 15 min of hydration in the C₃A–gypsum paste.     

Physical and microstructural aspects of sulfate attack on ordinary and limestone blended Portland cements

The consequences of external sulfate attack were investigated by traditional test methods, i.e. length and mass change, as well as by a newly developed, surface sensitive ultrasonic method, using Leaky Rayleigh waves (1 MHz). The macroscopic changes are discussed and compared with thermodynamic calculations and microstructural findings (SEM/EDS). The results show that the main impact of limestone additions on resistance to sulfate degradation are physical — i.e. addition of a few percent in Portland cement reduces the porosity and increases the resistance of Portland cement systems to sulfate; but higher addition of 25% increase porosity and lower resistance to sulfate. The kinetics of degradation were dramatically affected by the solution concentration (4 or 44 g Na₂SO₄/l) and the higher concentration also resulted in the formation of gypsum, which did not occur at the low concentration. However the pattern of cracking was similar in both cases and it appears that gypsum precipitates opportunistically in pre-formed cracks so it is not considered as making a significant contribution to the degradation. At 8 °C limited formation of thaumasite occurred in the surface region of the samples made from cement with limestone additions. This thaumasite formation led to loss of cohesion of the paste and loss of material from the surface of the samples. However thaumasite formation was always preceded by expansion and cracking of the samples due to ettringite formation and given the very slow kinetics of thaumasite formation it was probably facilitated by the opening up of the structure due to ettringite induced cracking.The expansion of the samples showed a steady stage, followed by a rapidly accelerating stage, with destruction of the samples. The onset of the rapidly accelerating stage occurred when the thickness of the cracked surface layer reached about 1–1.5 mm–10–15% of the total specimen thickness (10 mm).     

Ettringite decomposition in the presence of barium carbonate

The interaction between cement paste and sulfate-rich solutions or soils induces gypsum, ettringite or thaumasite precipitation. These expansive processes may be mitigated by using BaCO₃ (witherite) as a setting regulator. The present study explored ettringite decomposition in the presence of witherite at different temperatures (25, 40 and 65 °C) and reaction times (up to 90 days) to further the understanding of this process as grounds for developing new sulfate-resistant cements (SR-PC).According to the XRD, FTIR and DSC-TG findings, sulfoaluminate decomposition and barite formation begin in the first 24 h of the reaction, even at ambient temperature (25 °C), and progress rapidly for the first 30 days. The reaction follows a different pathway at 65 °C than at 25 and 40 °C due to ettringite instability at high temperatures.     

Thausamine in failed cement mortars and renders from exposed brickwork

The mineral thaumasite occurs within certain cement-based building materials as a direct result of sulphate attack. It readily forms within certain types of brickwork and not only contributes to expansive cracking of the brickwork but is also accompanied by severe softening of the cement matrix. Samples were taken of both brickwork mortars and renders, some of which were still relatively sound whereas others had deteriorated into a paste. The mortar samples were investigated using a quantitative Xray diffraction technique in order to determine the amounts of thaumasite, ettringite and gypsum present. Results show that if conditions are favourable then thaumasite formation can proceed rapidly and can even result in the complete breakdown of very strong renders.     

Influence of the availability of calcium on the hydration of tricalcium aluminate (C3A) in seawater-mixed C3A–gypsum system

This work examined the effects of seawater (SW) on the hydration of tricalcium aluminate (C₃A) in C₃A–gypsum and C₃A–gypsum–Ca(OH)₂ systems through the characterization of hydration heat release, the evolution of aqueous phase composition and hydration products with the hydration time. It was found that SW increased the dissolution driving force of C₃A and solubility of gypsum, which accelerated the early hydration of C₃A and the formation of ettringite (AFt), leading to a higher hydration degree of C₃A at an early age compared with the deionized (DI) water–mixed pastes. After gypsum depletion to form AFt, and in the absence of Ca(OH)₂, the formation of chloroaluminate hydrates was slower due to the insufficient Ca resulted in an accumulation of Al in solution. This would delay the subsequent transformation of AFt to monosulfate (SO₄–AFm) and the formation of hydrogarnet (C₃AH₆), which would further reduce the hydration degree of the C₃A at the later ages. However, in the presence of Ca(OH)₂, the hydration degree of C₃A–gypsum–Ca(OH)₂ at later ages was increased, which was similar to that of the corresponding DI pastes. This can be inferred that the amount of Ca available in SW-mixed cement concrete can affect the hydration degree of C₃A in cement.     

Stability and reactivity of thaumasite at different pH levels

Thaumasite (CaCO₃·CaSO₄·CaSiO₃·15H₂O) has been reported to form at low temperatures (below 15 °C) during sulfate attack. Reactions between calcium silicate hydrate (C-S-H) and Ca⁺², CO₃⁻², SO₄⁻², CO₂ and water, or between ettringite and C-S-H, CO₃⁻² and/or CO₂ and water, result generally in the formation of thaumasite. In some instances, thaumasite may be affected by the presence of other chemicals in the surrounding environment (i.e., phosphates and ammonia in agricultural soil). There are insufficient data regarding the stability of thaumasite at different pH levels in the presence of other chemical ions. Understanding this issue might help in the detection of the thaumasite form of sulfate attack, and, therefore, in one's choice of the appropriate protection technique. This work reports the reactivity of thaumasite with phosphate, carbonate and bicarbonate ions at different pH levels ranging from 6.00 to 12.00, as well as the stability of thaumasite at high pH levels (greater than 12.00). Thaumasite was found to react with these ions at pH levels at and below 12.00; however, thaumasite was stable with minimal reactivity at pH levels greater than 12.00.     

Scanning electron micrographic studies of ettringite formation

The morphology of ettringite, formed by various reactions (C₃A + gypsum, C₃A + anhydrite, CA + magnesium sulfate, in the presence and absence of calcium hydroxide) was studied by scanning electron microscopy. Methods included immersion of solid samples into saturated solutions of the other reactant, and paste hydration. It is concluded that slender needles and spherulites are formed only if sufficient space is available; alternately (e.g. in pastes of lower water-to-solid ratios) ettringite occurs as short, prismatic crystals. Ettringite is formed in C₃A-gypsum pastes near the surface of C₃A grains by a through-solution mechanism; a topochemical mechanism can be definitely excluded. Results are significant for a better understanding of mechanism of expansion and set retardation by gypsum.     

Thaumasite formation in a tunnel of Bapanxia Dam in Western China

A site investigation and sampling was carried out on a sulfate-attacked concrete structure in Bapanxia Hydraulic Power Plant in Western China. The concrete had been exposed to ground water containing substantial concentrations of salts (SO₄²⁻, CO₃²⁻ and Cl⁻) for about 6 years and was analyzed with X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), laser-Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. It is shown that a white mushy mixture consisting of thaumasite, ettringite, gypsum and calcite is present in the residual concrete. This paper reports the first instance of the thaumasite form of sulfate attack of concrete in China.     

Effect of temperature on sulphate adsorption/desorption by tricalcium silicate hydrates

Sulphate adsorption from internal sources was studied in hydrating systems containing C-S-H gel and gypsum with respect to delayed ettringite formation. The influence of C₃A addition on sulphate desorption was also investigated. Research indicates that C-S-H gel will adsorb sulphate faster at high temperature resulting in quick depletion of the gypsum phase in C-S-H - gypsum mixtures. Sulphate adsorbed at high temperature is desorbed more slowly than that adsorbed at normal temperature. Slower release of sulphate from an internal sulphate source may be a critical condition for delayed ettringite formation in high temperature cured Portland cement paste.     

Influence of polymer on cement hydration in SBR-modified cement pastes

The influence of styrene-butadiene rubber (SBR) latex on cement hydrates Ca(OH)₂, ettringite, C₄AH₁₃ and C-S-H gel and the degree of cement hydration is studied by means of several measure methods. The results of DSC and XRD show that the Ca(OH)₂ content in wet-cured SBR-modified cement pastes increases with polymer-cement ratio (P/C) and reaches a maximum when P/C is 5%, 10% and 10% for the pastes hydrated for 3 d, 7 d and 28 d, respectively. With wet cure, appropriate addition of SBR promotes the hydration of cement, while the effect of SBR on the content of Ca(OH)₂ and the degree of cement hydration is not remarkable in mixed-cured SBR-modified cement pastes. XRD results illustrate that SBR accelerates the reaction of calcium aluminate with gypsum, and thus enhances the formation and stability of the ettringite and inhibits the formation of C₄AH₁₃. The structure of aluminum-oxide and silicon-oxide polyhedron is characterized by ²⁷Al and ²⁹Si solid state NMR spectrum method, which shows that tetrahedron and octahedron are the main forms of aluminum-oxide polyhedrons in SBR-modified cement pastes. There are only [SiO₄]⁴⁻ tetrahedron monomer and dimer in the modified pastes hydrated for 3 d, but there appears three-tetrahedron polymer in the modified pastes hydrated for 28 d. The effect of low SBR dosage on the structure of aluminum-oxide and silicon-oxide polyhedron is slight. However, the combination of Al³⁺ with [SiO₄]⁴⁻ is restrained when P/C is above 15%, and the structure of Al³⁺ is changed obviously. Meantime, the polymerization of the [SiO₄]⁴⁻ tetrahedron in C-S-H gel is controlled.     

Early C3A hydration in the presence of different kinds of calcium sulfate

Hydration reactions of C₃A with various amounts of calcium sulfate hemihydrate, gypsum or a mixture of the two, were investigated by isothermal microcalorimetry, and a monitoring of the ionic concentrations of diluted suspensions. This study shows that sulfate type used modifies the early C₃A–CaSO₄ hydration products and the rate of this hydration. The fast initial AFm formation observed before ettringite precipitation in the C₃A–gypsum system is avoided as soon as hemihydrate is present in the suspension. This was attributed to higher super saturation degrees and then higher nucleation frequency with regard to the ettringite obtained in the presence of hemihydrate. Moreover, replacement of gypsum by hemihydrate also leads to an increase of the ettringite formation rate during at least the five first hours under experimental conditions.     

Very High Volume Fly Ash Cements. Early Age Hydration Study Using Na2SO4 as an Activator

The early age ambient temperature hydration of a hybrid cement formulation containing very high volumes of coal fly ash (~80% by dry mass) and activated by Na₂SO₄ is presented. The Na₂SO₄ salt acts as a safe and convenient in situ source of alkali to activate fly ash glassy phases without undesirable effects on cement clinker hydration. Comparison to a reference paste with gypsum instead of sodium sulfate revealed that Na₂SO₄ reduced setting times, shortened the induction period, and increased early alite hydration and compressive strength development, but also restricted ettringite formation. When replacing the active fly ash component for milled sand of a similar particle size, the Na₂SO₄‐activated pastes set even quicker, no ettringite was observed, and early strengths were considerably reduced. Possible reaction mechanisms in the hybrid pastes are discussed.