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.     

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).     

Modeling the effects of solution temperature and concentration during sulfate attack on cement mortars

Simple chemistry-based empirical models have been developed to assess the role of temperature and concentration of the sulfate solution in the process of expansion of cement mortars that are subjected to external sulfate attack. ASTM Type I PC mortars, prepared according to ASTM C-109, were immersed in sodium and magnesium sulfate solutions at five different concentrations and four different temperatures. For both solutions, the trends in the measured expansion suggested the use of a simple rate law to analyze the effect of concentration. For the effect of temperature, an Arrhenius relationship was developed to determine the activation energy required to initiate expansion in sodium sulfate solution. Regression-based statistical models were found to be sufficient to explain the effect of temperature of magnesium sulfate solution on the expansion. Implications of using these models for developing potential test methods, as well as to enable interpretation of data from nonstandard test methods, are discussed.     

Effect of sulfate solution on the frost resistance of concrete with and without steel fiber reinforcement

Properties of plain concrete (PC) and steel fiber reinforced concrete(SFRC) (with water/cement ratio of 0.44, 0.32 and 0.26) subjected to freeze-thaw cycles in 5.0% sodium sulfate solution were investigated in this paper. It was found that during the initial 300 freeze-thaw cycles, sulfate solution had little effect on the relative dynamic modulus of elasticity (E_d) of concrete. In further freeze-thaw cycling, the effect of sulfate solution on E_d was much more obvious. Both PC and SFRC specimens with w/c of 0.44 failed before 300 cycles and exhibited similar developing trends of the E_d whether freezing and thawing in sulfate solution or in fresh water. As for the concrete specimens with w/c of 0.26, the decline of E_d was more serious when freezing and thawing in sulfate solution than that in fresh water after 300 cycles. The adoption of steel fiber greatly restrained the decline of E_d and changed the failure mode of the specimen from brittle crack in midspan of PC to gradually decline of E_d up to failure under the combined action of freeze-thaw cycles and sulfate attack. Test results also demonstrated that there was an interaction effect between the action of freeze-thaw cycles and sulfate attack.     

Differentiating seawater and groundwater sulfate attack in Portland cement mortars

The study reported in this article deals with understanding the physical, chemical and microstructural differences in sulfate attack from seawater and groundwater. Portland cement mortars were completely immersed in solutions of seawater and groundwater. Physical properties such as length, mass, and compressive strength were monitored periodically. Thermal analysis was used to study the relative amounts of phases such as ettringite, gypsum, and calcium hydroxide, and microstructural studies were conducted by scanning electron microscopy. Portland cement mortars performed better in seawater solution compared to groundwater solution. The difference in performance could be attributed to the reduction in the quantity of the expansive attack products (gypsum and ettringite). The high Cl concentration of seawater could have played an important role by binding the C₃A to form chloroaluminate compounds, such as Friedel's salt (detected in the microstructural studies), and also by lowering the expansive potential of ettringite. Furthermore, the thicker layer of brucite forming on the specimens in seawater could have afforded better protection against ingress of the solution than in groundwater.     

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.     

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.     

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.     

Influence of fly ash fineness on strength, drying shrinkage and sulfate resistance of blended cement mortar

In this paper, the influence of fineness of fly ash on water demand and some of the properties of hardened mortar are examined. In addition to the original fly ash (OFA), five different fineness values of fly ash were obtained by sieving and by using an air separator. Two sieves, Nos. 200 and 325, were used to obtain two lots of graded fine fly ash. For the classification using air separator, the OFA was separated into fine, medium and coarse portions. The fly ash dosage of 40% by weight of binder was used throughout the experiment. From the tests, it was found that the compressive strength of mortar depended on the fineness of fly ash. The strength of mortar containing fine fly ash was better than that of OFA mortar at all ages with the very fine fly ash giving the highest strength. The use of all fly ashes resulted in significant improvement in drying shrinkage with the coarse fly ash showing the least improvement owing primarily to the high water to binder ratio (W/B) of the mix. Significant improvement of resistance to sulfate expansion was obtained for all fineness values except for the coarse fly ash where greater expansion was observed. The resistance to sulfuric acid attack was also improved with the incorporation of all fly ashes. In this case the coarse fly ash gave the best performance with the lowest rate of the weight loss owing probably to the better bonding of the coarse fly ash particles to the cement matrix and less hydration products. It is suggested that the fine fly ash is more reactive and its use resulted in a denser cement matrix and better mechanical properties of mortar.     

Influence of lightweight aggregate on the microstructure and durability of mortar

The results of an investigation on the effect of dry and prewetted lightweight aggregates on the microstructure and durability of mortar are presented in this paper. The results are compared with those obtained for normal aggregate mortar. There appears to be only a small difference in the microstructure of the interfacial transition zone (ITZ) between dry and prewetted lightweight aggregate mortars. The porous ITZ surrounding lightweight aggregate appears to extend for about 10 and 15 μm from the aggregate surface for dry and prewetted lightweight aggregates, respectively. The ITZ for dry and prewetted lightweight aggregates seems to be surrounded by dense paste that extends from 10 to about 50 μm from the aggregate surface. This dense paste has lower porosity than that observed in the bulk paste located 50 μm and farther from aggregate surface. The normal aggregate mortar prepared with the same water/cement ratio appears to have porous ITZ that extends beyond 35 μm from the aggregate surface. The dry and prewetted lightweight aggregate mortars seem to have a lower sorptivity and electrical conductivity than does the normal aggregate mortar. Lightweight aggregate mortars also appear to have excellent resistance to sulfate attack as compared with normal aggregate mortar.     

Mechanism of sulfate attack: A fresh look: Part 1: Summary of experimental results

This paper reports the results of an investigation on the effects of sodium and magnesium sulfate solutions on expansion and microstructure of different types of Portland cement mortars. The effects of using various sulfate concentrations and of using different temperatures are also reported. The results suggest that the expansion of mortars in sodium sulfate solution follows a two-stage process. In the initial stage, Stage 1, there is little expansion. This is followed by a sudden and rapid increase in the expansion in Stage 2. Microstructural studies suggest that the onset of expansion in Stage 2 corresponds to the appearance of cracks in the chemically unaltered interior of the mortar. Beyond this point, the expansion proceeds at an almost constant rate until the complete deterioration of the mortar specimen. In the case of magnesium sulfate attack, expansion occurs at a continually increasing rate. Microstructural studies suggest that a layer of brucite (magnesium hydroxide) on the surface forms almost immediately after the introduction of the specimens into the solution. The attack is then governed by the steady diffusion of sulfate ions across the brucite surface barrier. The ultimate failure of the specimen occurs as a result of the decalcification of the calcium silicate hydrate (C-S-H), and its conversion to magnesium silicate hydrate (M-S-H), after prolonged exposure to the solution. The effects of using various admixtures, and of changing the experimental variables such as the temperature and concentration of the solution, are also summarized in this paper. Models for the mechanism of the attack resulting from sodium and magnesium sulfate solutions will be presented in Part 2.     

The use of tension testing to investigate the effect of W/C ratio and cement type on the resistance of concrete to sulfate attack

Concrete specimens were cast and partially immersed in a sulfate solution for varying periods of time up to 1 year. The effects of water/cement ratio (0.45 and 0.65) and cement type (ordinary and sulfate resistant) were investigated. Concrete performance was evaluated based on compressive strength and tensile strength, which was measured with the pressure tension test. Results indicated that water/cement ratio had a greater influence on the resistance of the concretes to sulfate attack than did cement type. The pressure tension test appeared to be more sensitive than the compressive strength test in detecting internal damage, particularly at early ages.     

The thaumasite form of sulfate attack in concrete of Yongan Dam

According to microanalytical investigations, it is shown that the concrete of Yongan Dam is deteriorated due to the thaumasite form of sulfate attack (TSA). Analysis results of scanning electron microscopy (SEM), Energy Disperse X-ray (EDX) and X-ray Diffraction (XRD) are supported by the analysis of the concrete composition and the geographical conditions of the dam.     

The kinetics of ettringite formation and dilatation in a blended cement with β-hemihydrate and anhydrite as calcium sulfate

The phase formation, heat of hydration and dilatation in a blended cement consisting of 50 wt.% calcium aluminate cement, 25 wt.% Portland cement and 25 wt.% calcium sulfate were studied (w/c=1). The calcium sulfate was β-hemihydrate, anhydrite and mixes of the two. Kinetic expressions describing the ettringite formation in the pastes with the pure calcium sulfates were found. Hydration reactions were suggested and the phase development was compared to the hydration heat by mass and heat balances. When the calcium sulfate was 75 and 50 wt.% β-hemihydrate, the systems behaved as a linear combination of the 100 and 0 wt.% blends. At 25 wt.%, the hydration kinetics differed from the other blends. With only β-hemihydrate, the last 50% of ettringite formation was accompanied by expansion, mainly caused by interaction of crystals growing radially on cement grains. In the paste with only anhydrite, ettringite crystals grew in solution and produced no expansion.     

功能添加剂对石膏凝胶晶体生长习性影响的研究进展

二水石膏的结晶形态和晶粒大小从宏观上对石膏硬化体的凝结时间、稠度、吸水率、强度、耐水性等影响很大。缓凝剂能抑制石膏晶体晶核的形成和生长,导致晶粒变粗,延长石膏凝结硬化时间;煅烧会导致石膏晶体晶格发生畸变,化学激发剂可促进石膏晶体生长,提高硬石膏水化活性,形成的石膏晶体多呈柱状且晶体间搭接更紧密,使石膏强度增加;除有机硅防水剂外,其它防水剂均会在石膏晶体表面形成一层薄膜,使形成后的晶体细小、搭接紧密,从而提高防水性能;不同减水剂对石膏晶体生长的影响各不相同,但成形石膏晶体之间的搭接均变致密,降低了水膏比。     

顶板岩性对近距离石膏矿层上行开采采场稳定性的影响

文章就顶板岩性对石膏矿层上行开来采场稳定性的影响进行探讨，认为直接顶的岩性是影响采场稳定性的主要因素；而老顶的岩性对采场稳定性的影响较小。     

Solution properties of solids in the ettringite—thaumasite solid solution series

The thaumasite form of sulfate attack (TSA) has received considerable research attention since its discovery in several motorway bridge foundations in the UK in 1998. Its significance as a deterioration mechanism in concrete, leading to the fluidisation of the matrix in extreme cases, is now acknowledged. Despite the continuing uncertainties that exist with regard to mechanisms for thaumasite formation, there is now reasonable agreement on conditions that favour TSA, and, as with all deleterious reactions affecting concrete structures, there is a desire to be able to anticipate the likelihood of occurrence so that such problems can be ‘designed out’ in the formulation stage. Inevitably, this points to the development of suitable models and the generation of reliable data. It is towards this latter goal that this paper is focused. Building on our previous studies, which reported on the means of fixing intermediate compositions in the ettringite-thaumasite solid solution series, this paper describes the treatment of solubility data, which can be utilised in phase development and solubility models involving this system.     

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.     

Influence of the heat exchangers’ construction material on catalytic incineration

In industrial scale catalytic volatile organic compounds (VOCs) incineration it is sometimes observed that the VOC conversions are higher than expected, based on the laboratory scale experiments at the same temperatures. One reason for this is that the construction material of the industrial scale catalytic incinerator may have an effect on the total VOC conversion. In this study, the effect of construction material on VOC removal activity is studied through laboratory experiments, by thermodynamic calculations and by flow modelling. The results showed that copper and Aluzinc decreased the light-off temperature (T₅₀) of n-butyl acetate compared to thermal experiments. Copper and Aluzinc did not, however, further decrease the T₅₀ when they were introduced into the reactor packed with the catalyst. The higher total VOC conversion observed in the industrial scale incinerator is presumably due to the higher temperatures at the outlet of the catalyst, which is maintained by the heat exchangers.     

Durability of geopolymer materials in sodium and magnesium sulfate solutions

This paper presents an investigation into the durability of geopolymer materials manufactured using class F fly ash and alkaline activators when exposed to a sulfate environment. Three tests were used to determine resistance of geopolymer materials. The tests involved immersions for a period of 5 months into 5% solutions of sodium sulfate and magnesium sulfate, and a solution of 5% sodium sulfate+5% magnesium sulfate. The evolution of weight, compressive strength, products of degradation and microstructural changes were studied.In the sodium sulfate solution, significant fluctuations of strength occurred with strength reduction 18% in the 8FASS material prepared with sodium silicate and 65% in the 8FAK material prepared with a mixture of sodium hydroxide and potassium hydroxide as activators, while 4% strength increase was measured in the 8FA specimens activated by sodium hydroxide. In the magnesium sulfate solution, 12% and 35% strength increase was measured in the 8FA and 8FAK specimens, respectively; and 24% strength decline was measured in the 8FASS samples. The most significant deterioration was observed in the sodium sulfate solution and it appeared to be connected to migration of alkalies into solution. In the magnesium sulfate solution, migration of alkalies into the solution and diffusion of magnesium and calcium to the subsurface areas was observed in the specimens prepared using sodium silicate and a mixture of sodium and potassium hydroxides as activators. The least strength changes were found in the solution of 5% sodium sulfate+5% magnesium sulfate. The material prepared using sodium hydroxide had the best performance, which was attributed to its stable cross-linked aluminosilicate polymer structure.