自燃煤矸石胶凝材料中钙矾石形成研究

采用XRD分析了自燃煤矸石胶凝材料中活性Al2O3在不同因素影响下水化形成钙矾石的情况.研究结果表明,在相同条件下芒硝存在,时自燃煤矸石中活性Al2O3水化生成钙矾石,而含等量硫的石膏存在时水化浆体中不但有水化产物钙矾石还有未反应的石膏;胶凝体系中不含熟石灰时,活性Al2O3水化首先生成石膏,随着水化的进行再转化成钙矾石,而在有熟石灰时水化则直接生成钙矾石;矿渣促进了自燃煤矸石中Al2O3水化形成钙矾石.     

Influence of curing temperatures on the hydration of calcium aluminate cement/Portland cement/calcium sulfate blends

In this paper, the effects of curing temperature on the hydration of calcium aluminate cement (CAC) dominated ternary binders (studied CAC: Portland cement: calcium sulfate mass ratio were 22.5: 51.7: 25.8) were estimated at 0, 10, 20 and 40 °C, respectively. Both α-hemihydrate and natural anhydrite were employed as the main source of sulfate. The impacts of temperature on the phase assemblages, morphology and pore structure of pastes hydrated up to 3 days were determined by using X-ray diffraction (XRD), backscattered electron imaging (BEI) and mercury intrusion porosimetry (MIP). Results reveal that the main hydration products are firmly related to calcium sulphoaluminate based phases. Increasing temperature would result in a faster conversion from ettringite to plate-like monosulfate for both calcium sulfate doped systems. When the temperature increases to 40 °C, an extraordinary formation of strätlingite (C₂ASH₈) and aluminium hydroxide is observed in anhydrite doped pastes. Additionally, increased temperature exerts different effects on the pore structure, i.e. the critical pore diameter shifts to finer one for pastes prepared with α-hemihydrate, but changes to coarser one for those made with anhydrite. From the mechanical point of view, increased temperature accelerates the 1-day strength development prominently, while exerts marginal influence on the development of 3-day strength.     

Ettringite and calcium sulfoaluminate cement: investigation of water content by near-infrared spectroscopy

Calcium sulfoaluminate (CSA) cement is a sulfate-based binder whose high-performance hydraulic behavior depends on the rapid formation of ettringite, when grinded clinker is hydrated in presence of gypsum. Ettringite is a calcium aluminum sulfate mineral characterized by high water content, estimated as 32 water molecules per formula unit. Three examples of utilization of near-infrared (NIR) spectroscopy are here shown. First of all, information on water distribution in pure ettringite was deduced and compared with infrared analyses. Then its thermal behavior has been followed up to 400 °C, allowing to improve the knowledge about water loss and thermal decomposition of this hydrated phase. Finally, the obtained results have been employed in order to follow hydration of CSA cement sample, demonstrating thus that NIR spectroscopy, being highly sensitive to water amount and distribution, can be an extremely useful tool for hydration studies.     

石膏对石灰石粉水泥基材料水化及硬化性能的影响

针对我国目前非荷载作用下混凝土严重开裂的问题,以"比表面积较低的水泥熟料-比表面积较高的掺合料-足够掺量的石膏"构成的胶凝材料体系为研究对象,通过水化热速率、X射线衍射(XRD)、扫描电子显微镜(SEM)、压汞法(MIP)及热重-差示扫描量热法(TG-DSC)等手段,研究石膏对石灰石粉水泥基材料水化及硬化体微结构的影响。结果表明,石灰石粉能够加速C3A与石膏作用生成钙矾石相,在足量石膏存在的条件下,能够阻碍钙矾石向低硫型硫铝酸钙转变;石灰石粉的掺入与石膏一起延缓了C3A的水化;在石灰石粉和足够石膏同时存在的情况下,C3A水化生成具有膨胀性的水化碳铝酸钙和高硫型硫铝酸钙,补偿了收缩,提高了水泥基材料的抗裂性能;熟料粗磨、掺合料细磨及较高石膏掺量的胶凝材料体系配制的C30和C50等级混凝土,强度能持续增大,从28d到180d,强度分别提高了36.7%和33.3%,混凝土结构紧密、孔隙率低、有害孔含量少。     

Rheological and hydration characterization of calcium sulfoaluminate cement pastes

Calcium sulfoaluminate (CSA) cements are currently receiving a lot of attention because their manufacture produces less CO₂ than ordinary Portland cement (OPC). However, it is essential to understand all parameters which may affect the hydration processes. This work deals with the study of the effect of several parameters, such as superplasticizer (SP), gypsum contents (10, 20 and 30 wt.%) and w/c ratio (0.4 and 0.5), on the properties of CSA pastes during early hydration. This characterization has been performed through rheological studies, Rietveld quantitative phase analysis of measured X-ray diffraction patterns, thermal analysis and mercury porosimetry for pastes, and by compressive strength measurements for mortars. The effect of the used SP on the rheological properties has been established. Its addition makes little difference to the amount of ettringite formed but strongly decreases the large pore fraction in the pastes. Furthermore, the SP role on compressive strength is variable, as it increases the values for mortars containing 30 wt.% gypsum but decreases the strengths for mortars containing 10 wt.% gypsum.     

Effect of calcium sulfate source on the hydration of calcium sulfoaluminate eco-cement

The availability of cements, including eco-cements, with tailored mechanical properties is very important for special applications in the building industry. Here we report a full study of the hydration of calcium sulfoaluminate eco-cements with different sulfate sources (gypsum, bassanite and anhydrite) and two water/cement ratios (0.50 and 0.65). These parameters have been chosen because they are known to strongly modify the mechanical properties of the resulting mortars and concretes. The applied multi-technique characterization includes: phase assemblage by Rietveld method, evolved heat, conductivity, rheology, compressive strength and expansion/retraction measurements. The dissolution rate of the sulfate sources is key to control the hydration reactions. Bassanite dissolves very fast and hence the initial setting time of the pastes and mortars is too short (20 min) to produce homogeneous samples. Anhydrite dissolves slowly so, at 1 hydration-day, the amount of ettringite formed (20 wt%) is lower than that in gypsum pastes (26 wt%) (w/c = 0.50), producing mortars with lower compressive strengths. After 3 hydration-days, anhydrite pastes showed slightly larger ettringite contents and hence, mortars with slightly higher compressive strengths. Ettringite content is the chief parameter to explain the strength development in these eco-cements.     

On the interaction of Class C fly ash with Portland cement–calcium sulfoaluminate cement binder

Shrinkage cracking in concrete is a widespread problem, especially in concrete structures with high surface-to-volume ratio such as bridge decks. Expansive cements based on calcium sulfoaluminate phase were developed to mitigate the shrinkage cracking of concrete. The compressive stress induced due to restrained expansion of concrete has been shown to counteract the tensile stress generated during drying shrinkage. This research attempts to address the differential behavior of fly ash type (i.e., Class C vs. Class F) on early-age expansion and hydration characteristics of ordinary Portland cement (OPC)–calcium sulfoaluminate (CSA) cement blend. It was observed earlier that the presence of Class C fly ash (CFA), unlike Class F fly ash, shortened the expansion duration of OPC–CSA cement blend, which was hypothesized to be correlated to early depletion of gypsum. This paper presents a detailed verification of the hypothesis. Addition of external gypsum to OPC–CSA–CFA blend led to simultaneous increase in expansion and disappearance of a shoulder peak in the calorimetric curve. Thermodynamic calculations using a geochemical modeling program (GEMS-PSI) revealed higher saturation levels of ettringite in presence of external gypsum, which led to higher crystallization stress, and thereby increased expansion.     

Mechanical properties,drying and autogenous shrinkage of blast furnace slag activated with hydrated lime and gypsum

This article reports the characteristics of blast furnace slag (BFS) pastes activated with hydrated lime (5%) and hydrated lime (2%) plus gypsum (6%) in relation to compressive strength, shrinkage (autogenous and drying) and microstructure (porosity, hydrated products). The paste mixtures were characterized using powder X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) and thermogravimetric analysis (TG/DTG). BSF activated with lime and gypsum (LG) results in larger amounts of ettringite when compared with BFS activated with lime (L). Although the porosities of the L and LG mixtures were about the same, there was a greater pore refinement for the BFS activated with lime, with an increase in mesopores volume with age. The presence of ettringite and the higher volumes of macropores cause the compressive strength of BSF activated with hydrated lime plus gypsum to be smaller than that of BFS activated with lime. For both chemical activators, compressive strength developed slowly at early ages. Autogenous and drying shrinkage were greater for the BFS activated with lime, believed to result from the more refined porous structure in comparison with the mixture activated with gypsum plus lime.     

The formation,stability and microstructure of calcium sulpoaluminate hydrates present in hydrated cement pastes,usingin situ synchrotron energy-dispersive diffraction

Synchrotron radiation-energy dispersive diffraction has been used for the first time to study the formation and stability of the calcium sulphoaluminate hydrates in hydrated Portland cement pastes. By using this technique it has also been possible to investigate microstructural and compositional characteristics of the ettringite (AFt) phase. The longer term slow development of the monosulphate (AFm) phase has also been monitored, although the characterized content is quite low. Differences were detected between the microstructural characteristics of the AFt phase formed in the high ferrite sulphate-resisting-type cement pastes, as compared with the equivalent phase formed from the ordinary Portland cements. These differences were especially significant at later hydration times and have been ascribed to compositional differences between the ettringite (AFt) formed from the two different types of cement.     

Contribution of limestone to the hydration of calcium sulfoaluminate cement

Calcium sulfoaluminate (CSA) cements can be blended with mineral additions such as limestone for properties and cost optimization. This study investigates the contribution of limestone to the hydration of a commercial CSA clinker regarding the hydration kinetics, hydrate assemblage and compressive strength. Nine formulations were defined at M-values of 0, 1.1 and 2.1 (M = molar ratio of anhydrite to ye’elimite) without and with medium and high limestone contents.Calorimetric results indicate that limestone accelerates the hydration reaction especially at M = 1.1, probably due to the filler effect. The phase assemblages were calculated by thermodynamic modeling using Gibbs Energy Minimization Software (GEMS). With increasing limestone content the formation of ettringite and calcium monocarboaluminate is predicted at the expense of calcium monosulfoaluminate. With increasing M-value more ettringite is predicted at the expense of the monocarbonate and less calcite takes part in the hydration reactions.The modeled results compare well with the experimental data after 90 d of hydration, except that calcium hemicarboaluminate was found instead of monocarbonate, which is assumed to be due to kinetics considerations.The lowest compressive strength occurs in ternary formulations, whereas in the absence of calcium sulfate, strength is significantly higher.The results presented here indicate that in CSA cements, limestone accelerates early hydration kinetics, takes part in the hydration reactions at M < 2, and has a positive effect on strength development in systems without anhydrite.     

赤泥-煤矸石基中钙体系胶凝材料的水化特性*

采用XRD、IR、TG-DTA、MIP等手段表征赤泥-煤矸石基中钙体系胶凝材料的水化产物及其硬化浆体的孔结构, 研究了解赤泥-煤矸石基中钙体系胶凝材料的水化特性。结果表明, 赤泥-煤矸石基中钙体系胶凝材料的水化产物主要有C-S-H凝胶、钙矾石和Ca(OH)₂, 前两者对其强度的发展有促进作用; 水化1 d至90 d其中Ca(OH)₂的含量呈先升高后降低的趋势; 随着水化反应的进行在CaO/SiO₂比值较低的赤泥-煤矸石基中钙体系胶凝材料中Si-OH基团之间发生聚合反应, 水化产物的聚合度升高; CaO/SiO₂比值为0.95和1.04的赤泥-煤矸石基中钙体系胶凝材料的硬化浆体具有较好的孔结构, 而CaO/SiO₂比值为1.13的胶凝材料硬化浆体的孔结构相对较差。     

Identification of hydration stage of calcium sulfoaluminate cement at an early age with helium pycnometry

This work is to study the mechanism of the hydration of calcium sulfoaluminate (CSA) cement at an early age by identifying the hydration stage with helium pycnometry, heat evolution test, X-ray diffraction, thermo-gravimetric/differential scanning calorimetry and scanning electron microscope. The results show that the hydration process of CSA cement has four stages: rapid dissolution stage, dissolution-crystallization stage, crystal growth stage and stable stage. In the rapid dissolution stage, exothermic wetting and fast hydration result in the shrinkage occurring from 0 to 15 min. A significant volume decrease happens in the dissolution-crystallization stage. In the crystal growth stage, ettringite prefers to crystalize at the neighboring places of pores at the nano scale due to the combined action of crystallization pressure and size effect. The volume increase considerably slows down throughout the stable stage indicating the deceleration of CSA cement hydration. In addition, the influence of the proportions of clinker and gypsum in the CSA cement on its hydration is studied as well.     

Investigations on the influence of cement type on thaumasite formation

A high sulfate resistance is required if cements are to be used in sulfate bearing waters and soils especially under conditions favouring thaumasite formation. A long period program of laboratory investigations was carried out on CEN cements to assess thaumasite and ettringite formation. The experimental concept involved mixing ground cement pastes with stoichiometrical components of gypsum, calcite and water. The specimens were stored at 6 °C whereby chemical worst case conditions for thaumasite formation were simulated. At time intervals XRD analysis was conducted. Apart from pure cements mixtures containing additives, pure C₃S pastes with and without Al₂O₃ addition were investigated. The results confirm that thaumasite formation can be accelerated by Al₂O₃ bearing components in cements. However, thaumasite formation is also possible without active participation of Al³⁺. The assessment of sulfate resistance of cements only from the chemical point of view apparently gives results which are contrary to the field experience.     

活化煤矸石对水泥水化的影响

研究了活化煤矸石-氢氧化钙体系的水化热、水化产物成分以及活化煤矸石水泥体系的水化过程、水化产物的微结构,结果表明,在石膏的激发下,活化煤矸石能够发生二次水化,与Ca（OH）2反应形成钙矾石、水化硅酸钙、水化铝酸钙等有利于提高水泥石强度的水化产物;活化煤矸石水泥硬化浆体中Ca（OH）2的含量在水化3d时最多,而后随龄期逐渐减少;阐明了活化煤矸石能够降低水化产物中氢氧化钙的含量、抑制氢氧化钙晶体的生长和聚集,并改善水泥石结构．     

Pozzolanic cements

Natural and artificial pozzolanas have been used to obtain hydraulic binders for over a thousand years. Hardening of pozzolanic cement pastes can result from the reaction between pozzolana and the lime that is added to the mix as hydrated lime or is produced following hydration of portland cement silicates. The pozzolanic reaction does not alter cement clinker hydration; it complements and integrates the hydration process because it results in a lower portlandite content and an increase in calcium silicate hydrates.

Besides reviewing the most recent investigations on pozzolana-containing cements, this paper shows that the behaviour of different types of pozzolana can be quite similar when they are blended and become hydrated along with portland cement clinker. Portland cement properties may undergo several qualitative modifications the extent of which substantially depends on the pozzolana/clinker ratio. So, a maximum is reached in pozzolanic cements.

As in the case of pozzolanic cements, for which the current pozzolana content is about one third by weight of cement, the most outstanding variations induced in the behaviour of portland cement can be summarised as follows. Heat of hydration decreases whilst the rate of clinker hydration increases, paste porosity increases and permeability decreases, both portlandite content and Ca/Si ratio in C-S-H decrease and the C-S-H content increases.

Chemical and physical properties of pozzolanic cements eventually affect engineering ones. Early strength of both pastes and concretes decreases while ultimate strength is often found to exceed that of the reference portland cement.

If cements contain small amounts of very active pozzolana (silica fume, for example), both early and ultimate strengths may be higher than those of the substituted cement.

Creep is found to increase definitely with increasing pozzolana content whereas shrinkage remains practically unaffected.

Chemical and microstructural variations in the paste also influence resistance of concretes to environmental attacks.

The low basicity and permeability resulting from the presence of pozzolana increase the concrete's resistance to lime leaching, sulphate and sea water attacks, and chloride penetration. Carbonation depth is practically unaffected. Pozzolana containing cements can help avoid expansion induced by alkali-silica reaction. Concrete resistance to freezing is not affected by the use of pozzolanic cement since it basically depends on the entrained air content.

The results of a variety of studies introducing a comparison between pozzolana-containing cements and corresponding portland cements can be summarised as follows: cements with appreciable pozzolana contents perform better in the long term rather than at an early age.

In most cases, however, the differences between the two types of cements are not so marked and as a consequence both cements are interchangeable especially for the most common building types.     

硫铝酸钙-贝利特水泥熟料的低温制备及其水化性能研究

以煤矸石、脱硫石膏、石灰为主要原料,采用水热合成-低温煅烧方法制备了硫铝酸钙-贝利特水泥熟料,通过X射线衍射(XRD)、扫描电镜(SEM)等分析了水热合成物、煅烧试样及水化产物的矿物相,利用等温量热仪测定了水泥早期水化放热随时间的变化,并测定了水泥的力学性能。结果表明:在120℃下水热合成前驱体后再经煅烧,可在1 050℃低温下制成硫铝酸钙-贝利特水泥熟料。与一步法相比,该低温水泥的早期水化放热速率较高。当水泥中的二水石膏掺量为13%(质量分数)时,水泥1d、28d的抗压强度分别为30.2 MPa和57.3 MPa,28d的水化产物主要为长纤维状的AFt。     

Calcium sulphate anhydrite based composite binders; effect of Portland cement and four pozzolans on the hydration and strength

The strength, hydration products, microstructure and heat of early hydration were investigated on alternative hydraulic green cements based on calcium sulphate anhydrite partially blended with Portland cement and pozzolans. Four pozzolans of different physical and chemical nature, namely a geothermal waste, silica fume, metakaolin and pulverized fuel ash were characterized. The composite binders showed hydraulic behavior. The use of Portland cement favoured the strength, which was also higher with the incorporation of siliceous nanometric pozzolans compared to the micrometric silicoaluminate pozzolans. The nanoparticles enhanced the early hydration and changed the gypsum morphology promoting denser matrices of hydration products. The geothermal waste pozzolan was the most effective, while one of the composites with metakaolin showed formation of ettringite and strength losses. The heat of hydration of the composites was considerably lower than that of the neat Portland cement.     

A conduction calorimetric study of early hydration of ordinary Portland cement/high alumina cement pastes

Conduction calorimetry was applied to an investigation of the early hydration of ordinary Portland cement (OPC)/high alumina cement (HAC) pastes. Three different rate of heat-evolution profiles were observed, depending on the HAC/OPC ratio. Relevant processes affecting heat development include ettringite formation, HAC and OPC hydration. Results from SEM examination and X-ray diffraction studies are also presented. An acceleration of OPC hydration was observed in pastes containing less than 12.5% HAC. A similar acceleration effect on HAC hydration was also obtained with the addition of OPC. A large amount of ettringite was formed and OPC hydration delayed in the pastes containing 15%–30% HAC. The latter could be one of the factors attributed to poor strength development in these HAC/OPC systems. Early hydration mechanisms of OPC/HAC systems are also discussed. This revised version was published online in November 2006 with corrections to the Cover Date.     

Synthesis of low-temperature calcium sulfoaluminate-belite cements from industrial wastes and their hydration: Comparative studies between lignite fly ash and bottom ash

The aim of this research was to study the production of calcium sulfoaluminate-belite (CŜAB) cement from industrial waste materials via hydrothermal-calcination process. Lignite fly ash and bottom ash were used as starting materials for comparison. Other waste materials viz., Al-rich sludge and flue gas desulfurization gypsum were also key players in raw mixes for the synthesis of CŜAB cement. For lignite fly ash as a starting material, mixed phases between ye'elimite and larnite were obtained, whereas for lignite bottom ash as starting material, only ye'elimite was obtained The hydration reaction was studied in terms of heat evolution, setting time, compressive strength and hydration product formation with various gypsum contents. The results showed a rapid formation of ettringite as a main hydration product mixed with calcium silicate hydrate, monosulfate and strätlingite phases as minority, with a fast final setting time of 24–26 min and high early compressive strength of 16.0 and 18.0 MPa in 1 day for CŜAB cements made of fly ash and bottom ash, respectively.     

Modeling diffusion of sulfate through concrete using mixture theory

Concrete exposed to sulfates deteriorates. Here, an attempt is made to see whether the framework of mixture theory can be used to model the changes that occur in concrete exposed to sodium sulfate. Toward this, diffusion and reaction of sulfates with concrete is modeled within the framework of mixture theory. Appropriate choices are made for the Helmholtz free energy and interaction momentum so that the process of diffusion of sulfates in concrete can be captured. As expected in mixture theory, diffusion causes deformation of the solid. The parameters in the mixture theory model are determined by comparing the steady-state concentration profile of the diffusing sodium sulfate solution and inlet velocity of the fluid with that of Fick’s solution for the same boundary conditions. An assumption is made for the mass production term to capture the reaction of sulfates with concrete. The rate constant and order of the reaction are estimated using the concentration of gypsum, calcium hydroxide and ettringite reported in the literature, for various duration of exposure of cement pastes to known concentration of sodium sulfate solution. Finally, the governing equations for the combined problem of steady-state diffusion and reaction of sulfates with concrete are presented. A numerical scheme to solve the governing equations is outlined. Long-term concentration profiles of sodium sulfate predicted by the framework agree qualitatively with the experimentally observed profile reported in the literature.