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.     

Microstructural study of sulfate attack on ordinary and limestone Portland cements at ambient temperature

This paper presents an investigation on the mechanism of sulfate attack on Portland cements (PCs) containing limestone filler. It is based on the analysis of microstructure and composition of mortar specimens (ASTM C 1012) stored for 2 years in sodium sulfate solution (0.352 M). Microstructure was studied using quantitative X-ray diffraction (XRD) on samples taken from the surface to the core of the specimens. The profile of compounds formed by sulfate attack was determined millimeter by millimeter at 1 and 2 years. Results show that sulfate attack in mortars containing limestone filler is characterized by an inward movement of the reaction front leading first to the formation of ettringite, later to gypsum deposition, and finally to thaumasite formation when the decalcification of mortar leads to the breakdown of C-S-H.     

特性环境对水泥砂浆硫酸盐侵蚀类型的影响

研究了硫酸盐种类(Na2SO4,MgSO4)及温度(5 ℃,20 ℃)等影响因素对水泥砂浆硫酸盐侵蚀类型的影响,以明确碳硫硅酸钙型硫酸盐侵蚀的特性环境条件.试验结果表明:掺加石灰石粉的水泥砂浆试件置于5% MgSO4溶液、5 ℃及20 ℃温度环境下浸泡450 d后,均能生成碳硫硅酸钙.而一般水泥砂浆试件置于5% Na2SO4溶液、5 ℃及20 ℃温度环境浸泡侵蚀后,未生成碳硫硅酸钙.证明水泥混凝土在＞15 ℃的硫酸盐侵蚀环境下亦可生成碳硫硅酸钙,而Mg2 的存在对碳硫硅酸钙的形成过程具有加速催化作用.     

Microstructure of 5-year-old mortars containing limestone filler damaged by thaumasite

This paper presents the findings of a long-term study on the microstructure of Portland cement mortar specimens containing 5%, 15% and 35% limestone filler, as cement replacement, after exposure to a solution of magnesium sulfate at a concentration of 1.44% SO₄, for 5 years at 5 °C. The findings are compared to results reported earlier, obtained from the same systems but after 1-year exposure. It was found that the deterioration due to thaumasite advanced with the increased exposure period and limestone content. Thaumasite solid solutions (Tss) formed as the dominant phases within the deteriorated cement matrix and at the paste-aggregate interface resulting in cracks and delamination. Thaumasite was also found as an inner product in various clinker grains. Interestingly, the control specimens, with no limestone filler, were found to exhibit cracks due to the formation of Tss, with atmospheric carbon dioxide being the most likely source for the carbonates.     

低温硫酸盐侵蚀环境中水泥石腐蚀产物

研究了水胶比为0.45,掺35%石灰石粉水泥基材料标准养护28d后在(5±2)℃浸泡于SO2-4质量分数为3.38%的钠盐、镁盐、铝盐3种硫酸盐侵蚀溶液中15周时的破坏状况和强度损失率.采用Fourier红外光谱、X射线衍射、扫描电子显微镜、能谱以及Raman光谱确定水泥石腐蚀物相和组成.结果表明:镁盐溶液中试件抗压强度损失率最大,其次是钠盐溶液中试件,铝盐溶液中试件抗压强度损失率最小;钠盐溶液和铝盐溶液中水泥石主要腐蚀产物是钙矾石和石膏;镁盐溶液中水泥石主要腐蚀产物是钙矾石、石膏、碳硫硅酸钙和少量水镁石.     

Effect of limestone filler on the deterioration of mortars and pastes exposed to sulfate solutions at ambient temperature

This paper presents data on engineering properties such as compressive strength, visual change and expansion of mortar specimens incorporating limestone filler subjected to severe sulfate attack at ambient temperature. Specimens with four replacement levels of limestone filler (0, 10, 20 and 30% of cement by mass) were immersed in sodium and magnesium sulfate solutions with 33,800 ppm of SO₄²⁻ concentration. In order to identify the products formed by sulfate attack, microstructural analyses such as XRD and SEM were also performed on the paste samples with similar replacement levels of limestone filler.The test results demonstrated that mortar and paste samples incorporating higher replacement levels of limestone filler were more susceptible to sulfate attack irrespective of types of attacking sources. However, the deterioration modes were significantly dependent on the types of sulfate solutions. Additionally, although the samples were exposed to sulfate solutions at 20 ± 1 °C, the deterioration was strongly associated with thaumasite formation in both sulfate solutions.The deterioration mechanism and resistance to sulfate attack of cement matrix incorporating limestone filler at ambient temperature is discussed in the light of the test results obtained.     

Effect of the cement chemistry and the sample size on ASR expansion of concrete exposed to salt

Mortar bars and concrete prisms made with a very alkali-silica reactive limestone were stored at 38 °C in 1 M NaOH and NaCl solutions. A high-alkali (HA) cement and a low-alkali (LA) cement were used in order to evaluate the cement chemical composition on the expansion and on the chemistry of the pore water. The mortar bars immersed in 1 M NaOH presented much more expansion than mortar bars stored at 100% RH or in 1 M NaCl. The behaviour of the concrete prisms was completely different. Low expansion was obtained for concrete prisms made with the LA cement immersed for more than 5 years in 1 M NaCl solution, while the expansion was over 0.45% for concrete prisms made with the HA cement. Chemical equilibrium between the pore waters and the immersion solution was much longer to obtain for the concrete prisms (near 3 years) than for the mortar bars (less than 3 months). The results obtained in this study show that the type of sample used (mortar bars or concrete prisms) and the cement composition strongly influence the harmful effects of ASR in concrete exposed to salt.     

Mechanical behaviour of various mortars made by combined fly ash and limestone in Moroccan Portland cement

Physico-chemical properties and mechanical behaviour of ternary cements made by Portland cement, fly ash and limestone are studied. The mixtures at various compositions of clinker, gypsum fly ash and limestone are intimately ground and compared to other compositions without fly ash. Blended fly ash cements are also studied. The results show that fly ash acts as grinding agent by reducing the required time to obtain the same percentage of particles retained on a 80-μm sieve as the standard cement. Fly ash cements lead to an important extension of setting time than limestone cements. The replacement of clinker by limestone gives better mechanical strengths than the mixtures containing fly ash at early days; after 28 days, the cements prepared by incorporation of fly ash gain an important strength. From mechanical point of view, an optima dosage was obtained at 77% clinker, 2% gypsum, 7.5% fly ash and 13% limestone composition.     

The role of carbon dioxide in the formation of thaumasite

The development of the thaumasite form of sulfate attack (TSA) has received considerable attention since its discovery in the foundations of motorway bridges in England in 1998. When TSA occurs in siliceous aggregate concrete and mortars, particularly in samples from the field, it is normally assumed that the carbonate source necessary for the formation of thaumasite was either present as a minor component in the aggregate, as a limestone filler in the binder, or from the groundwater. Recent laboratory studies carried out by the authors have identified a further source of carbonate ions, and that is from atmospheric carbonation. However, in other studies, it appears that an initial air cure can improve the resistance of concretes to TSA. This apparent dichotomy suggests that there is insufficient understanding of the relationship between atmospheric carbonation and TSA.The performances of small mortar cubes made using fine aggregates of either high quality silica sand or limestone under different curing regimes have been compared. Detailed analyses of the nature of the thaumasite-ettringite solid solutions that formed have been carried out, and the mechanism of thaumasite formation, in particular, the role of calcium bicarbonate, is discussed in the light of the results obtained.     

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).     

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.     

Sulfate attack on cementitious materials containing limestone filler — A review

This review summarizes the results of sulfate performance in laboratory and field tests where limestone is used as a constituent of cement (PLC) or as a sand replacement where it is particularly beneficial to the properties of self compacting concretes (SCC).Laboratory studies on paste, mortar or concrete specimens exposed to Na₂SO₄ and MgSO₄ solutions in a wide range of concentrations at different temperatures as well as mixtures with different compositions, cement compositions and limestone proportions are considered in a conceptual analysis as for the resistance to external sulfate attack and, especially, thaumasite sulfate attack.A detailed analysis of environmental aggressiveness (concentration, temperature and pH), mixture composition and cement composition used in each study are presented for PLC and SCC. Reported field studies are also shown, only a few cases have used limestone filler in their composition. A conceptual graphical analysis is then proposed to relate the degree of surface deterioration and mineralogical composition of attacked surface to the main variables of external sulfate attack: water/cementitious material ratio, limestone content and C₃A content of the cement. Observation of graphical analysis clearly shows that deterioration by ESA is mainly governed by effective w/c ratio and C₃A content of the cement. Surface damage is controlled when low effective w/c ratio and low C₃A are used. In MgSO₄ solution, low temperatures increase the degree of deterioration. Thaumasite is the last attack stage in the different sulfate environments.     

The influence of mineral admixtures on sulfate resistance of limestone cement pastes aged in cold MgSO4 solution

The influence of slag (S), fly ash (FA) and silica fume (SF) on the sulfate resistance of limestone cements was evaluated. Hardened pastes were exposed to MgSO₄ solution at 5 °C. Visible changes of the samples during the exposure were followed. Absorption of sulfate was measured and changes in mineralogical composition were evaluated by thermogravimetric analysis and X-ray diffraction (XRD). It was found that among admixtures used, only the addition of silica fume to limestone cement significantly improved its sulfate resistance. Cement with lower contents of C₃A and C₃S also showed favorable performance compared to cement having higher contents of these minerals.     

高温环境下碳硫硅钙石-钙矾石固溶体的研究

由碳硫硅钙石引起的硫酸盐侵蚀破坏在许多国家都有相关工程案例.铝相可以加速碳硫硅钙石的生成,并能够与钙矾石形成固溶体,但铝相的作用机理目前尚无定论.在不同温度下合成了一系列固溶体,并利用XRD,SEM-EDS及红外对固溶体进行了测试分析,结果表明:40℃温度下亦可以生成碳硫硅钙石/固溶体;20℃与40℃均能够形成碳硫硅钙石型与钙矾石型两种形态固溶体;a轴固溶体间隙随温度升高而增大,20℃环境下固溶体间隙为1.1076～1.1182nm,40℃时固溶体间隙为1.1069～1.1189nm;随温度升高碳硫硅钙石-钙矾石固溶体晶体形貌更加细长.     

Hydration of a low-alkali CEM III/B–SiO2 cement (LAC)

The hydration of a low-alkali cement based on CEM III/B blended with 10 wt.% of nanosilica has been studied. The nanosilica reacted within the first days and 90% of the slag reacted within 3.5 years. C-S-H (Ca/Si ~ 1.2, Al/Si ~ 0.12), calcite, hydrotalcite, ettringite and possibly strätlingite were the main hydrates. The pore water composition revealed ten times lower alkali concentrations than in Portland cements. Reducing conditions (HS^?) and a pH value of 12.2 were observed. Between 1 month and 3.5 years of hydration more hydrates were formed due to the ongoing slag reaction but no significant differences in the composition of the pore solution or solid phase assemblage were observed.On the basis of thermodynamic calculations it is predicted that siliceous hydrogarnet could form in the long-term and, in the presence of siliceous hydrogarnet, also thaumasite. Nevertheless, even after 3.5 year hydration, neither siliceous hydrogarnet nor thaumasite have been observed.     

Effect of solution concentrations and replacement levels of metakaolin on the resistance of mortars exposed to magnesium sulfate solutions

This paper reports an experimental study on the magnesium sulfate resistance of mortar and paste specimens incorporating 0%, 5%, 10% and 15% metakaolin (MK). The resistance of mortar specimens was evaluated using visual examination, reduction in compressive strength and expansion measurements.Results confirmed that mortar specimens with a high replacement level of metakaolin showed lower resistance to a higher sulfate concentration of magnesium solution. However, in a lower concentration, there were no visibly remarkable differences in the deterioration of mortar specimens, even up to 360 days of exposure, regardless of replacement levels of metakaolin.The negative effect of metakaolin on the magnesium sulfate resistance is partially attributed to the formation of gypsum but not ettringite and thaumasite. In addition, the reduction of calcium hydroxide and the increase of secondary C-S-H in the cement matrix due to pozzolanic reaction of metakaolin provided an opportunity to lead to the conversion of primary and secondary C-S-H gel into the M-S-H gel.It is concluded that it is necessary to pay special attention when using metakaolin in concrete exposed to highly concentrated magnesium sulfate solution.     

Cement Formulations in the Calcium Phosphate H2O–H3PO4–H4P2O7 System

Despite numerous reports of calcium phosphate cement materials, a calcium cement that sets to form a matrix consisting of a pyrophosphate phase has not been reported. The formulation of such a material from the mixture of α-tricalcium phosphate (TCP), β-TCP, or tetracalcium phosphate with a solution containing pyro- and orthophosphoric acid is reported in this study. The effects of liquid and solid compositions on the setting times, compressive strengths and phase compositions of the resultant cements were investigated. It was found that cements could be produced that set to form up to 28 wt% dicalcium pyrophosphate, which appeared by comparison with Rietveld refinement and chemical methods to be entirely amorphous in nature. The solubilities of the different solid components were shown to have a marked effect on the composition of the cements. The strongest cement formulations exhibited compressive strengths comparable with those previously reported in the literature for brushite cements and set within clinically relevant time scales. This class of cement would appear to demonstrate potential as a bone replacement material.     

氯离子对碳硫硅钙石形成的影响

研究了氯离子对碳硫硅钙石形成的影响,将水泥-石灰石粉净浆样品浸泡在(5±2)℃不同质量分数的NaCl/Na2SO4复合溶液中,观察侵蚀后样品的外观,并对腐蚀产物进行x射线衍射、红外光谱分析.结果表明:纯Na2SO4溶液中的样品发生碳硫硅钙石型硫酸盐侵蚀,腐蚀产物以碳硫硅钙石及石膏为主,随着时间的延长而日益严重,由表及里...     

Durability of self-consolidating concrete incorporating high-volume replacement composite cements

Self-consolidating concrete (SCC) decreases construction time, labor and equipment on construction sites, makes the construction of heavily congested structural elements and hard to reach areas easier, reduces noise- and vibration-related injuries, and helps in achieving higher quality finish surfaces. However, because it usually requires a larger content of binder and chemical admixtures compared to ordinary concrete, its material cost is generally 20-50% higher, which has been a major hindrance to a wider implementation of its use. There is growing evidence that incorporating high volumes of mineral admixtures and microfillers as partial replacement for portland cement in SCC can make it cost effective. However, the durability of such SCC needs to be proven. This research investigates the rapid chloride ion penetrability, sulfate expansion and deicing salt surface scaling resistance of SCC mixtures made with high-volume replacement binary, ternary, and quaternary cements. The fresh concrete properties and compressive strength at 1, 7, 28 and 91 days of such SCC mixtures were measured. Moreover, rapid chloride ion penetrability was investigated for the various SCC mixtures at 28 and 91 days, while the deicing salt surface scaling under 50 freezing-thawing cycles and sulfate expansion after up to 9 months of immersion in a 5% Na₂SO₄ solution were investigated as per the ASTM C-672 and ASTM C1012 guidelines, respectively. Results indicate that SCC can be made with high-volume replacement composite cements and achieve good workability, high long-term strength, good deicing salt surface scaling resistance, low sulfate expansion and very low chloride ion penetrability.     

Effects of atmospheric acids on Portland cements

Mortar prisms made from three Portland cement types, were exposed at a city centre site (London) and at a suburban site (Horsted). At each site, a set of prisms was exposed either open to the rain or sheltered from it. The chemical analysis of the cements and of the collected rainwater during the experimental period are reported, together with estimates of dry deposited pollutants. The effects of the exposure were assessed by various physical and physicochemical tests of the surface and of the bulk properties of the exposed prisms. The weight increase, the most sensitive indicator of weathering effects, was greater for the sheltered prisms than for prisms open to the rain; the latter, however, showed more visual weathering. Increase in the porosity of the mortars resulted in increased mass gain. The higher acidity of the rain at the Horsted site had an insignificant effect on the percentage mass increase. The effect of this higher acidity was reflected, though inconclusively, by the lower bulk porosity of prisms made from Sulphate Resisting Portland Cement (SRPC) exposed at the Horsted site compared with the set similarly exposed at the London site. The effect of the cement type on the properties of the tested prisms was clearest in the decrease in the ultrasonic pulse velocity (UPV) of the exposed prisms made from Portland Blast Furnace Cement (PBFC) compared with the increase in UPV in prisms made from the other two cements. It seems that the changes in the properties of the prisms exposed to the atmosphere were associated both with the products of the reaction of atmospheric acids with the cement components and the products of continued hydration beyond the 28‐day curing period. © 2001 Society of Chemical Industry