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.     

On the relevance of volume increase for the length changes of mortar bars in sulfate solutions

The ingress of sulfate ions into cementitious materials leads to the formation of ettringite, gypsum and other phases. The increase in solid volume through the formation of these phases is often assumed to be the only reason for expansion. In this paper we systematically compare the volume increase predicted by thermodynamic modeling to macroscopic expansion for mortars made with CEM I in different sulfate solutions and for mortars made with a range of blended cements in sodium sulfate solution. It is shown that the length changes cannot be explained by simple volume increase alone.A more plausible explanation of expansion lies in the theory of crystallization pressure, in which crystals forming from a supersaturated solution may exert pressure on their surroundings. It is observed that expansion occurs in systems where thermodynamic modeling predicts the co-existence of ettringite with gypsum. In such a case, if monosulfate and gypsum are both present locally, the solution can be highly supersaturated with respect to ettringite, whose formation in confined conditions (such as within C–S–H) can then exert expansive forces.     

Sulfate attack on alkali-activated slag concrete

This paper presents an investigation into durability of alkali-activated slag (AAS) concrete in sulfate environment. Two tests were used to determine resistance of AAS concrete to sulfate attack. These tests involved immersion in 5% magnesium sulfate and 5% sodium sulfate solutions. The main parameters studied were evolution of compressive strength, products of degradation, and microstructural changes. After 12 months of exposure to the sodium sulfate solution, the strength decrease was up to 17% for AAS concrete and up to 25% for ordinary Portland cement (OPC) concrete. After the same period of exposure to the magnesium sulfate solution, the compressive strength decrease was more substantial, up to 37% for OPC and 23% for AAS. The main products of degradation were ettringite and gypsum in the case of Portland cement and gypsum in AAS. OPC samples had significant expansion, cracking, and loss of concrete, while AAS samples were not expanded but cracked in the test. During experiments with the sodium sulfate solution, some increase in strength of AAS concrete was recorded, likely due to continuing hydration.     

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.     

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.     

石灰石粉对水泥基材料抗硫酸盐侵蚀性的影响及其机理

用天然石灰石粉等质量取代水泥20%和30%,将制备的水泥净浆和砂浆试件常温浸泡在0.35 mol/L Na2SO4溶液中,测量试件的线长度和抗折强度随浸泡时间的变化.结果表明:石灰石粉对水泥基材料的抗硫酸盐性有严重的影响,它们使水泥基材料在硫酸盐环境中的强度急剧下降并导致水泥基材料产生较大体积膨胀,引起开裂.掺石灰石粉的水泥基材料主要因形成大量较大尺寸的石膏晶体而膨胀开裂.石膏的形成导致硫酸盐侵蚀水泥基材料产生膨胀开裂.因此,在硫酸盐侵蚀环境下,不宜采用含石灰石粉的复合水泥或将石灰石粉作为矿物掺合料制备的混凝土.     

石膏掺量对高阿利特水泥防腐抗渗性能的影响研究

研究了石膏掺量对高阿利特水泥抗海水侵蚀和抗渗性能的影响,并与普通水泥进行了比较。利用XRD、SEM—EDS等测试方法对水泥水化产物的物相组成和形貌进行分析、观察;用压汞法对水泥硬化浆体的孔结构进行了分析。结果表明,石膏掺量对高阿利特水泥硬化浆体的致密性有较大影响,进而影响水泥砂浆的抗海水侵蚀性能,石膏的适宜掺量为5％,在此掺量下高阿利特水泥的抗蚀系数达1．01,而普通水泥的抗蚀系数仅为0．87,高阿利特水泥的有害孔较少,总孔隙率较低,抗渗性能得到较大改善。     

超硫酸盐水泥净浆的酸性侵蚀劣化机制

本文对比研究了超硫酸盐水泥(SSC)与硅酸盐水泥在盐酸侵蚀条件下的力学性能变化规律,探讨了SSC的酸性侵蚀劣化机制。测试了SSC净浆试件正常养护后在盐酸溶液以及清水中抗压强度的变化,并计算了抗压强度保持率;采用X射线衍射(XRD)、扫描电子显微镜(SEM)和热重分析(TG-DTG)等微观测试方法分析了SSC在盐酸侵蚀下水化产物种类和数量的变化,并探究了其微观结构的演化过程,分析了劣化机理。结果表明:不同于硅酸盐体系,SSC体系主要水化产物为钙矾石和水化硅酸钙;与硅酸盐水泥相比,SSC在酸中具有较高的抗压强度保持率和更好的抗酸性侵蚀性能;盐酸侵蚀SSC后,SSC主要水化产物均被分解,体系中存在二水石膏和大量的二氧化硅胶体,而硅酸盐水泥体系中则存在大量的二氧化硅胶体。     

Cement substitution by a combination of metakaolin and limestone

This study investigates the coupled substitution of metakaolin and limestone in Portland cement (PC). The mechanical properties were studied in mortars and the microstructural development in pastes by X-ray diffraction, thermogravimetry analysis, mercury intrusion porosimetry and isothermal calorimetry. We show that 45% of substitution by 30% of metakaolin and 15% of limestone gives better mechanical properties at 7 and 28 days than the 100% PC reference. Our results show that calcium carbonate reacts with alumina from the metakaolin, forming supplementary AFm phases and stabilizing ettringite. Using simple mass balance calculations derived from thermogravimetry results, we also present the thermodynamic simulation for the system, which agrees fairly well with the experimental observations.It is shown that gypsum addition should be carefully balanced when using calcined clays because it considerably influences the early age strength by controlling the very rapid reaction of aluminates.     

Influence of bicarbonate ions on the deterioration of mortar bars in sulfate solutions

This work investigates the influence of bicarbonate ions on the deterioration of cementitious material exposed to sulfate ions. Mortars based on a CEM I and on a CEM III/B cement were investigated. Experimental investigations were compared to thermodynamic modeling and phase characterization to understand the differences in deterioration.The presence of bicarbonate ions significantly reduced the expansion of the CEM I mortars. Thermodynamic modeling showed that at high concentrations of bicarbonate ettringite and gypsum become unstable. Microstructural characterization combined with information from thermodynamic modeling suggests that conditions of high supersaturation with respect to ettringite are unlikely in the samples exposed in solutions containing bicarbonate. Consequently, expansive forces are not generated by the crystallization pressure of ettringite.There was little expansion of the CEM III/B sample even in the sodium sulfate solution. In the bicarbonate solution this mortar showed a highly leached zone at the surface in which calcite was observed.     

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.     

The effect of pozzolans and slag on the expansion of mortars cured at elevated temperature: Part II: Microstructural and microchemical investigations

The microstructural and microchemical development of heat-cured Portland cement mortars containing silica fume, metakaolin, blast-furnace slag, and fly ash were analysed using pore solution analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy-dispersive X-ray analysis (EDX). Incorporation of these materials into the mixture modifies the composition of the C-S-H gel, the quantities of the hydration products, and the microstructure. Ettringite was formed during moist storage in all specimens, but was not accompanied by expansion where a sufficient amount of metakaolin, blast-furnace slag, or a suitable fly ash replaced a proportion of the Portland cement; replacement with silica fume was not as effective at eliminating expansion. The different behaviour of silica fume from the other supplementary cementing materials is believed to reflect a difference in the way ettringite is formed in the presence of Al₂O₃-bearing mineral admixtures.     

On the role of free calcium oxide in expansive cements

Results of research, tending to elucidate the effect of free CaO content in portland cement clinker upon the expansion of specimens of expansive cements, prepared in semi-commercial scale by intergrinding of portland cement clinker, C₄A₃$\text{S}$-phase containing special clinker and gypsum, by means of examination of liquid phase composition and porosity of mortars, have been presented. Special clinker was obtained by burning a mix of limestone, fly ash with high Al₂O₃ content and gypsum. Obtained results confirm the advantageous effect of free lime upon the hydration process and properties of expansive cements. The concentration of CaO in the liquid phase seems to influence rather the rate of ettringite formation than the size of its crystals.     

Early hydration behaviour of portland cement containing tartaro- and titanogypsum

Portland cements containing tartaro- and titanogypsum were respectively hydrated for up to two hours at a water: cement ratio of 0.5. They were compared with a Portland cement containing high grade natural gypsum hydrated similarly. The cement containing tartarogypsum produced much more ettringite than those with titanogypsum and natural gypsum. Comparisons were made with previous examinations of the hydration of Portland cements containing other by-product gypsums. Reasons for the observed hydration behaviour of the Portland cements with tartaro- and titanogypsum are discussed.     

Superplasticized portland cement: production and compressive strength of mortars and concrete

This paper deals with the effect of intergrinding different percentages of a naphthalene-based superplasticizer with Portland cement clinker and gypsum on the fineness of the product, and on the water requirement and the compressive strength of the mortars made with the superplasticized cement. The properties of the fresh and hardened concrete made with the superplasticized cements were also investigated. The results showed that the intergrinding of a given amount of a naphthalene-based superplasticizer with Portland clinker and gypsum reduced the grinding time required for obtaining the same Blaine fineness as that of the control Portland cement without the superplasticizer. The water requirement of the mortars made with the superplasticized cements was similar to that of the mortars made with the control Portland cements when the same amount of the superplasticizer was added at the mortar mixer; for a given grinding time and a Blaine fineness of 4500 cm²/g, the mortars made with the superplasticized cement had higher compressive strength than those made with the control Portland cement. For a given grinding time or Blaine fineness of cement ≥5000 cm²/g, the slump loss, air content stability, bleeding, autogenous temperature rise, setting times, and compressive strength of the concrete made with the superplasticized cements were generally comparable to those of the concrete made with the control Portland cements when the superplasticizer was added at the concrete mixer.     

铝土矿选尾矿制备硅铝聚合材料的反应产物及抗化学侵蚀性能(英文)

以煅烧铝土矿选尾矿为硅铝质原料,以矿渣微粉为促硬剂,以水玻璃为激发剂,制备得到了硅铝聚合材料。运用X射线衍射、扫描电镜、热分析研究了硬化浆体的反应产物及其微观形貌、热性质。通过观察3%硫酸钠溶液、3%硫酸镁溶液、5%硫酸溶液、5%盐酸溶液对砂浆试样外观、质量、强度的影响,研究了其抗化学侵蚀性能,并比较了其与铝酸盐水泥、快硬早强硫铝酸盐水泥、中抗硫酸盐硅酸盐水泥及矿渣硅酸盐水泥的区别。结果表明:反应并不生成晶体物质,而是无定形态的铝硅酸盐;硬化体中呈现片层状显微形貌的物质能够吸附水分,从而在灼烧过程中表现为脱水吸热及质量损失;该片层状物质随着龄期的延长而变得愈发细小和复杂,进而在宏观上表现为强度增长及脱水温度升高;硅铝聚合砂浆分别经3%硫酸钠溶液、3%硫酸镁溶液浸泡28d后,与各水泥砂浆试样比较,其不仅外观完整,而且强度并没有下降,反而具有几乎相同的强度增长,即说明其具有更优异的抗硫酸侵蚀性能;硅铝聚合砂浆与各水泥砂浆经稀酸溶液浸泡28d后,前者不仅能保持原始外观,而且表现为更低的质量及强度损失。     

激发条件对脱硫石膏-矿渣体系水硬强度的影响

利用正交实验研究了硅酸盐水泥和其他两种矿物组分复合激发对脱硫石膏-矿渣体系强度的影响,用SEM、XRD分析了水化样品的微观结构.研究结果表明:硅酸盐水泥等多组分复合激发下,脱硫石膏-矿渣体系在水中标准条件养护,3 d抗压强度达17 MPa以上,28 d抗压强度达58 MPa以上.复合激发剂3种组分的优化组合为6:6:5,复合激发剂的用量为脱硫石膏-矿渣体系质量的17%左右.脱硫石膏-矿渣体系在复合激发条件下的水化产物主要是钙矾石和C-S-H.大量钙矾石、石膏晶体相互交叉连生,未水化石膏、矿渣颗粒所填充其间,在C-S-H凝胶的胶结下,形成了较为致密的晶胶搭配构成的微观结构.     

High-slag cement mortars for brickwork and renderings

The suitability of clinker-activated high-slag cement mortars for use in brickwork construction and in rendered finishes, has been investigated. The study was carried out on a slag cement composed of 80% granulated slag, 15% clinker and 5% raw gypsum; its specific surface area was 4000 cm²/g. It was found that the slag cement mortars and cement-lime mortars of the proportions commonly used in practice, have higher water-retentivity than the corresponding mortars of ordinary Portland cement, and that their strengths are comparable to those of the latter mortars.     

Early hydration behaviour of portland cement containing boro-, citro- and desulphogypsum

Portland cements containing boro-, citro- and desulphogypsum, respectively, were hydrated at water:cement ratio 0.5 for up to two hours and compared with a Portland cement containing high grade natural gypsum hydrated similarly. It was found that the cements containing boro- and citrogypsum produced considerably more ettringite than those with desulpho- and natural gypsum. Comparisons were made with previous investigations of Portland cements containing fluoro-, formo- and phosphogypsum, respectively, hydrated under analogous conditions. Reasons for the observed hydration behaviour of the Portland cements containing the aforementioned chemical gypsums are discussed.     

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).