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.     

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.     

Behavior of blended cement mortars exposed to sulfate solutions cycling in relative humidity

In recent years, several cases of damage to concrete structures due to sulfate exposure have occurred essentially in the above ground parts of structures. Such distress, often characterized by white efflorescence and surface scaling, is driven by salt crystallization in pores and/or repeated reconversions of certain sulfates between their anhydrous and hydrated forms under cycling temperature and relative humidity (RH). However, the effect of the water/cementitious materials ratio (w/cm), pozzolanic additions, and other parameters on the durability of cement-based materials under such exposure conditions is still misunderstood. In this study, 12 cement mortars having different w/cm (0.30, 0.45, and 0.60) and made with ordinary portland cement (OPC) or OPC incorporating 8% silica fume, 25% class F fly ash, or 25% blast furnace slag were made. Standard bars from each of these mortars were submerged in both 10% magnesium sulfate (MgSO₄) and 10% sodium sulfate (Na₂SO₄) solutions; their expansion and surface degradation was monitored for up to 9 months. In addition, cylinders made from these 12 mortars were partially submerged in 50-mm-deep 10% MgSO₄ and 10% Na₂SO₄ solutions. Half of the cylinders were maintained under constant temperature and RH, whereas the others were subjected to cycling RH. The effect of the w/cm and mineral additions on the classic chemical sulfate attack and development of efflorescence was investigated, and the results are discussed in this article.     

Magnesium sulfate attack on hardened blended cement pastes under different circumstances

This paper describes the sulfate resistance of some hardened blended Portland cement pastes. The blending materials used were silica fume (SF), slag, and calcium carbonate (CaCO₃, CC?). The blended cement pastes were prepared by using W/S ratio of 0.3. The effects of immersion in 10% MgSO₄ solution under different conditions (room temperature, 60 °C, and drying-immersion cycles at 60 °C) on the compressive strength of the various hardened blended cement pastes were studied. Slag and CC? improve the sulfate resistance of ordinary Portland cement (OPC) paste. Mass change of the different mixes immersed in sulfate solution at 60 °C with drying-immersion cycles was determined. The drying-immersion cyclic process at 60 °C accelerates sulfate attacks. This process can be considered an accelerated method to evaluate sulfate resistance of hardened cement pastes, mortars, and concretes.     

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.     

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).     

Effects of aluminate and sulfate contents on the hydration and strength of Portland cement pastes and mortars

Evaluation of effects of C₃A and SO₃ contents in Portland cement on its compressive strength, hydration rate and products. Three cement samples varying in C₃A content and one varying in SO₃ content were used, hydrated initially at three temperatures. Compressive strength, bound water content, free lime content and Differential Scanning Calorimeter curves were determined during the progression of hydration. In interpretation bound water was used as a measure of quantity of binding material and Free Lime to Bound Water Ratio (FLWR) - of chemical constitution and quality.     

Multi-criteria analysis of the mechanism of degradation of Portland cement based mortars exposed to external sulphate attack

This work aims to contribute to the design of durable concrete structures exposed to external sulphate attacks (ESA). Following a preliminary study aimed at designing a representative test, the present paper suggests a study on the effect of the water-to-cement (w/c) ratio and the cement composition in order to understand the degradation mechanisms. Length and mass measurements were registered continuously, leached calcium and hydroxide ions were also quantified. In parallel, scanning electron microscopy observations as well as X-ray microtomography were realised at different times to identify the formed products and the crack morphology. Test results provide information on the basic aspects of the degradation mechanism, such as the main role of leaching and diffusion in the sulphate attack process. The mortar composition with a low w/c ratio leads to a better resistance to sulphate attack because the microstructure is less permeable. Reducing the C₃A content results in a macro-cracking decrease but it does not prevent expansion, which suggests the contribution of other expansive products, such as gypsum, in damage due to ESA. The observation of the cracks network in the microstructure helps to understand the micro-mechanisms of the degradation process.     

[SO4]^2-阴离子团对改性硅酸盐水泥力学性能的影响

磷铝酸盐水泥[1](简称PALC)是以P-O和Al-O为主阴离子团的新型胶凝材料,文献[2-4]将其掺入与以Si-O为主阴离子团普通硅酸盐水泥(OPC)制备的改型硅酸盐水泥具有良好的力学性能和耐水性.本文借助于X射线衍射(XRD)、扫描电子显微镜(SEM)等手段研究了[SO4]2-阴离子团对改性水泥力学性能的影响.     

抗硫酸盐硅酸盐水泥的研制

为适应GB748—2005《抗硫酸盐硅酸盐水泥》新标准,满足用户需求,我们进行了抗硫酸盐水泥的研制。1新老标准质量控制指标的对比情况新标准增加了对材料的要求;水泥标号改为强度等级;取消了水泥抗硫酸盐侵蚀试验方法;增加抗硫酸盐性指标;改用新的ISO水泥强度检验方法。其中新增的     

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.     

氧化镁对硅酸盐熟料的影响

韶峰水泥集团公司拥有Φ３０ｍ×１４５ｍ华新窑一台,Φ４０／３５／４０ｍ×１４５ｍ湘乡窑三台及Φ４０ｍ×４３ｍ窑外分解窑一台,规模为年产水泥２０２万ｔ,生产工艺条件完善,原燃材料质量比较稳定。通过多年对公司湿法回转窑熟料质量的探讨、总结发现:硅酸盐熟料中ＭｇＯ含量在２０%以下较合理;在２０%～２６%时,熟料强度呈无规律波动;而在３０%左右时,熟料强度大多呈下降趋势。本文就ＭｇＯ对熟料的烧成、晶体结构及强度的影响作探讨分析。１熟料ＭｇＯ含量与强度的关系本公司１９８８～１９９４年的熟料ＭｇＯ含量在１７%～３０%的…     

The effect of fillers on strength of cement mortars

The effect of three fillers (ground limestone, dolomite and basalt) on the strength of cement mortars was studied on 1:2.75 mixes having a w/c ratio of 0.70. The filler content ranged from 10 to 40% of the cement weight and their fineness (specific surface) from 1,150 to 11,200 sq. cm per g. Results confirmed earlier conclusions that fillers effect on strength is primarily an accelerating effect on the cement hydration. The improvement in strength is essentially the same for all non-pozzolonic fillers increasing with both filler content and fineness. In part, this improvement in strength is attributable to the increase in the density of the mix (i.e. a lower air content) associated with the use of fillers. There is some indirect evidence that monocalcium carboaluminate is formed when the finest limestone filler (10,300 sq. cm per g) is used. This formation, however, apparently does not affect strength.     

The absorption rate of CO2/SO2/NO2 into a blended aqueous AMP/ammonia solution

The Inter-governmental Panel on Climate Change (IPCC) reported that human activities result in the production of greenhouse gases (CO₂, CH₄, N₂O and CFCs), which significantly contribute to global warming, one of the most serious environmental problems. Under these circumstances, most nations have shown a willingness to suffer economic burdens by signing the Kyoto Protocol, which took effect from February 2005. Therefore, an innovative technology for the simultaneously removal carbon dioxide (CO₂) and nitrogen dioxide (NO₂), which are discharged in great quantities from fossil fuel-fired power plants and incineration facilities, must be developed to reduce these economical burdens. In this study, a blend of AMP and NH₃ was used to achieve high absorption rates for CO₂, as suggested in several publications. The absorption rates of CO₂, SO₂ and NO₂ into aqueous AMP and blended AMP+NH₃ solutions were measured using a stirred-cell reactor at 293, 303 and 313 K. The reaction rate constants were determined from the measured absorption rates. The effect of adding NH₃ to enhance the absorption characteristics of AMP was also studied. The performance of the reactions was evaluated under various operating conditions. From the results, the reactions with SO₂ and NO₂ into aqueous AMP and AMP+NH₃ solutions were classified as instantaneous reactions. The absorption rates increased with increasing reaction temperature and NH₃ concentration. The reaction rates of 1, 3 and 5 wt% NH₃ blended with 30 wt% AMP solution with respect to CO₂/SO₂/NO₂ at 313 K were 6.05～8.49×10^?6, 7.16–10.41×10^?6 and 8.02～12.0×10^?6 kmol m^?2s^?1, respectively. These values were approximately 32.3–38.7% higher than with aqueous AMP solution alone. The rate of the simultaneous absorption of CO₂/SO₂/NO₂ into aqueous AMP+NH₃ solution was 3.83–4.87×10^?6 kmol m^?2s^?1 at 15 kPa, which was an increase of 15.0–16.9% compared to 30 wt% AMP solution alone. This may have been caused by the NH₃ solution acting as an alternative for CO₂/SO₂/NO₂ controls from flue gas due to its high absorption capacity and fast absorption rate.     

A method for measuring transient thermal diffusivity in hydrating Portland cement mortars using an oscillating boundary temperature

The transient thermal diffusivity in early‐age, type I Portland cement mortars is difficult to quantify because the exothermic reactions cause significant heat generation which complicates the analysis of heat transfer. This paper outlines the theory and setup for a method of determining the transient thermal diffusivity of Portland cement mortars by forcing an oscillating temperature on one side of the material and measuring the attenuation of the temperature oscillation with distance. This experimental method also controls temperature to acquire data over a specific and narrow temperature range. The method is illustrated using computer models and laboratory experiments on wet and dry sand and Portland cement mortar. The values of thermal diffusivity of sand and mortar determined by this method correspond well to values found in literature. This general method could be applied to other materials, including cement paste, concrete, reactive solids, or biological tissue with appropriate modification to the apparatus.     

The action of some aggressve solutions on Portland, pozzolanic and blastfurnace slag cement mortars

An account of the results of a systematic investigation on the effects of percolation by solutions of magnesium sulphate and magnesium chloride of the same normality, respectively, through mortar samples manufactured with different types of cement is given by the Authors. The aim of the investigation is the comparative evaluation of the behaviour of the single cements under the attack from the two aggressive solutions, as well as the search for possible relationships between the manifold factors responsible, to a different extent, for the lowering of the mechanical strength of the resultant mortars.     

Diffusion of chloride ions in limestone filler blended cement pastes and mortars

The diffusion of chloride ions in neat cement pastes and mortars made with and without a limestone filler was investigated. In order to study the effect of the limestone filler, all mixtures were prepared at a fixed water/cement ratio (0,55). Test results indicate that the addition of a limestone filler reduces the diffusion coefficient of chloride ions. This reduction is attributed to the effect of the limestone filler particles on the tortuosity of the system. Results also indicate that the presence of interfaces has only a limited effect on the diffusion coefficient of chloride ions.     

Effect of temperature on the pore solution, microstructure and hydration products of Portland cement pastes

The effect of temperature on the hydration products and the composition of the pore solution are investigated for two Portland cements from 5 to 50 °C. Increased temperature leads to an initially fast hydration and a high early compressive strength. At 40 and 50 °C, the formation of denser C-S-H, a more heterogeneous distribution of the hydration products, a coarser porosity, a decrease of the amount of ettringite as well as the formation of very short ettringite needles has been observed. At 50 °C, calcium monosulphoaluminate has formed at the expenses of ettringite. In addition, the amount of calcium monocarboaluminate present seems to decrease. The composition of the pore solution mirrors the faster progress of hydration at higher temperatures. After 150 days, however, the composition of the pore solution is similar for most elements at 5, 20 and 50 °C. Exceptions are the increased sulphate concentrations and the slightly lower Al and Fe concentrations at 50 °C.     

Thermodynamic modelling of the effect of temperature on the hydration and porosity of Portland cement

The composition of the phase assemblage and the pore solution of Portland cements hydrated between 0 and 60 °C were modelled as a function of time and temperature. The results of thermodynamic modelling showed a good agreement with the experimental data gained at 5, 20, and 50 °C. At 5 and at 20 °C, a similar phase assemblage was calculated to be present, while at approximately 50 °C, thermodynamic calculations predicted the conversion of ettringite and monocarbonate to monosulphate.Modelling showed that in Portland cements which have an Al₂O₃/SO₃ ratio of > 1.3 (bulk weight), above 50 °C monosulphate and monocarbonate are present. In Portland cements which contain less Al (Al₂O₃/SO₃ < 1.3), above 50 °C monosulphate and small amounts of ettringite are expected to persist. A good correlation between calculated porosity and measured compressive strength was observed.     

The effect of gyrolite additive on the hydration properties of Portland cement

The influence of gyrolite additive on the hydration properties of ordinary Portland cement was examined. It was found that the additive of synthetic gyrolite accelerates the early stage of hydration of OPC. This compound binds alkaline ions and serves as a nucleation site for the formation of hydration products (stage I). Later on, the crystal lattice of gyrolite becomes unstable and turns into C–S–H, with higher basicity (C/S ~ 0.8). This recrystallization process is associated with the consumption of energy (the heat of reaction) and with a decrease in the rate of heat evolution of the second exothermic reaction (stage II). The experimental data and theoretical hypothesis were also confirmed by thermodynamic and the apparent kinetic parameters of the reaction rate of C₃S hydration calculations. The changes occur in the early stage of hydration of OPC samples and do not have a significant effect on the properties of cement stone.