氢氧化钙对硫铝酸盐水泥-粉煤灰复合胶凝材料的水化影响

通过凝结时间、抗压强度和电阻率等分析手段,研究了Ca(OH)2对硫铝酸盐水泥-粉煤灰复合胶凝材料水化过程的影响.结果表明,掺入Ca(OH)2明显缩短了硫铝酸盐水泥-粉煤灰复合胶凝材料的凝结时间;当Ca(OH)2掺量为0.5%时,初凝时间最短,1 d、28 d强度均明显提高;当Ca(OH)2的掺量为2%时,28 d强度相比空白样提高了61.9%;掺入Ca(OH)2后,硫铝酸盐水泥-粉煤灰复合胶凝材料的1 d电阻率减小,随着Ca(OH)2掺量增大,电阻率逐渐减小,电阻率变化率极大值提前,说明Ca(OH)2加快了该复合胶凝材料的早期水化进程.XRD分析表明,掺入Ca(OH)2后,水化1 d时钙矾石的生成量增多,消耗无水硫铝酸钙的量增多;水化28 d时钙矾石的生成量相对变化较小,但强度明显增大,粉煤灰对硫铝酸盐水泥强度的贡献较为明显.     

Reactions of fly ash with calcium aluminate cement and calcium sulphate

The hydration processes in the ternary system fly ash/calcium aluminate cement/calcium sulphate (FA/CAC/C$) at 20 °C were investigated; six compositions from the ternary system FA/CAC/C$ were selected for this study. The nature of the reaction products in these pastes were analysed by X-ray diffraction (XRD) and infrared spectroscopy (FTIR). At four days reaction time, the main hydration reaction product in these pastes was ettringite and the samples with major initial CAC presented minor ettringite but calcium aluminates hydrates. The amount of ettringite developed in the systems has no direct relation with the initial components.     

高掺量混合材复合水泥的水化性能

通过水化微量热、化学结合水测定和X射线衍射、热重-差热分析、扫描电镜等测试方法研究了3种高掺量矿渣、粉煤灰、石灰石复合水泥的水化性能,并与硅酸盐水泥的水化进行了对比。结果表明：高掺混合材复合水泥的水化放热特征与硅酸盐水泥有明显不同,早期水化反应速度低于硅酸盐水泥,但后期由于矿渣、粉煤灰的二次水化反应使其水化速度增长较快。主要的水化产物亦为水化硅酸钙凝胶、钙钒石和Ca(OH)2晶体,但Ca(OH)2含量明显低于硅酸盐水泥浆体中的Ca(OH)2含量。     

Very High Volume Fly Ash Cements. Early Age Hydration Study Using Na2SO4 as an Activator

The early age ambient temperature hydration of a hybrid cement formulation containing very high volumes of coal fly ash (~80% by dry mass) and activated by Na₂SO₄ is presented. The Na₂SO₄ salt acts as a safe and convenient in situ source of alkali to activate fly ash glassy phases without undesirable effects on cement clinker hydration. Comparison to a reference paste with gypsum instead of sodium sulfate revealed that Na₂SO₄ reduced setting times, shortened the induction period, and increased early alite hydration and compressive strength development, but also restricted ettringite formation. When replacing the active fly ash component for milled sand of a similar particle size, the Na₂SO₄‐activated pastes set even quicker, no ettringite was observed, and early strengths were considerably reduced. Possible reaction mechanisms in the hybrid pastes are discussed.     

水泥窑灰-粉煤灰体系的水化与强度发展(英文)

研究了配合比与养护温度对水泥窑灰(cement kiln dust,CKD)—粉煤灰(fly ash,FA)净浆的水化与强度发展的影响。净浆采用5种不同的水泥窑灰与粉煤灰比例配制,部分试件添加硅酸盐水泥作添加剂。试件在24、38℃及50℃的条件下进行养护。采用热重分析与X射线衍射测试试件的水化产物。结果表明在50℃的养护条件下,75%CKD+25%FA与45%CKD+45%FA+10%OPC试件的28 d与56 d强度分别达到了100%OPC水泥净浆强度的70%与80%以上。CKD-FA体系中的主要结晶水化产物是钙矾石。无论CKD与FA比例多大,CKD-FA浆体中钙矾石的含量显著高于水泥净浆。CKD-FA体系中钙矾石在90d的龄期仍可保持稳定。     

垃圾焚烧飞灰胶凝活性和水泥对其固化效果的研究

垃圾焚烧飞灰是生活垃圾焚烧后烟气除尘器收下的物质,其主要成分属CaO-SiO_2-Al_2O_3-Fe_2O体系,与目前常用的高炉矿渣、粉煤灰等辅助性胶凝材料非常接近,因其中含有能被水浸出的重金属物质而被认为是危险废物,必须对之进行稳定及固化处理。通过试验研究了掺入垃圾焚烧飞灰的硬化水泥浆体的力学性能和水化机理,考察了水泥固化垃圾焚烧飞灰的效果,探讨了垃圾焚烧飞灰作为辅助性胶凝材料利用的可行性。研究表明:垃圾焚烧飞灰的水化反应活性较低,它的掺入在一定程度上延缓了水泥的水化过程,虽然其水化过程可以形成适量的钙矾石,对强度发展有利,但掺量较大时会显著降低水泥强度;采用水泥稳定及固化垃圾焚烧飞灰的效果良好,垃圾焚烧飞灰中重金属可以通过包容、替代或吸收等形式固化进水化产物结构中。     

Suppression of Sulfate Attack on a Stabilized Soil

A soil containing calcium sulfates was stabilized at 40°C, with ample moisture, by cementitious mixtures producing a range of calcium hydroxide upon hydration. Maximum expansion occurred when the stabilizing agent was lime, whereas a mixture containing portland cement, Class C fly ash, and an amorphous silica stopped the expansion. X-ray diffraction peak width and scanning electron microscopy (SEM) based image analysis showed that maximum expansion correlated with crystallization of colloidal ettringite. Ettringite was seen by SEM within an hour of mixing the soil with lime. Colloidal ettringite was not observed when portland cement, with supplementary cementing materials, was used for stabilization.     

Fire resistance of fired clay bricks-fly ash composite cement pastes

This work aims to study the effect of substitution of fly ash for homra on the hydration properties of composite cement pastes. The composite cements are composed of constant proportion of OPC (80%) with variable amounts of fly ash and homra. The addition of fly ash accelerates the initial and final sitting time, whereas the free lime and combined water contents decrease with fly ash content. The fly ash acts as nucleation sites which may accelerate the rate of formation of hydration products which fill some of the pores of the cement pastes. The fire resistance of composite cement pastes was evaluated after firing at 250, 450, 600, 800 °C with rate of firing 5 °C/min with soaking time for 2 h. The physico-mechanical properties such as bulk density and compressive strength were determined at each firing temperature. Moreover, the phase composition, free lime and microstructure for some selected samples were investigated. It can be concluded that the pozzolanic cement with 20 wt% fly ash can be used as fire resisting cement.     

粉煤灰对水泥浆体的电阻率与化学收缩的影响

研究了粉煤灰掺量分别为0、20%和40%,水胶比为0.4的水泥浆体的抗压强度、电阻率、化学收缩以及水化产物的变化规律.电阻率采用无电极电阻率法进行测试,化学收缩采用ASTM C1608-12规定的膨胀测定法进行测试.结果表明,在250 d龄期时,粉煤灰掺量为20%的硬化水泥浆体抗压强度仅比空白组低5%;当粉煤灰掺量增大时,水泥浆体在3 d龄期时的强度、电阻率和化学收缩均减小,抗压强度与电阻率之间具有很好的线性关系.XRD及热重分析表明,随着粉煤灰掺量增加,水化硅酸钙含量减少,在3 d龄期时水化产物中出现了钙矾石.     

The influence of calcium lignosulphonate-sodium bicarbonate on the status of ettringite crystallization in fly ash cement paste

Calcium lignosulphonate (CL)-sodium bicarbonate (SB) (a total of 0.7% by weight of cement and CL to SB ratio of 1:1.8) will cause the fluidity of fly ash cement paste to decrease rapidly. It is the variation of the status of ettringite crystallization that causes this phenomenon. Experimental results show that CL-SB affects the liquid-phase composition of fly ash cement paste remarkably. As a result, ettringite crystallizes out in the shape of needles from the solution. These needle-like crystal particles are distributed in the solution at a certain distance from the surface of clinker particles. At the initial hydration stage, the crystallization of ettringite is stronger in fly ash cement with calcined gypsum than in fly ash cement with gypsum.     

复杂环境下粉煤灰水泥石的离子浓度分布与维氏硬度劣化规律

地铁工程混凝土结构处于硫酸盐、氯盐及杂散电流共存的复杂环境。本文针对地铁工程环境下混凝土的耐久性问题,研究了硫酸盐、氯盐及电场共同作用下,粉煤灰掺量对水泥石内硫酸根离子浓度分布、氯离子浓度分布和维氏硬度分布的影响,并基于Logistic函数建立维氏硬度预测模型,最后采用XRD分析了水泥石劣化的机理。结果表明:随侵蚀深度的增加,水泥石内硫酸根离子浓度不断降低,氯离子浓度呈现先增后降的趋势;侵入水泥石的氯离子和硫酸根离子的含量都随粉煤灰掺量的增加而先减后增,当粉煤灰掺量为10%(质量分数)时,侵入水泥石的氯离子与硫酸根离子的含量最低;被侵蚀后的水泥石内维氏硬度分布分为劣化区、增强区和完好区三个区域;预测模型可以准确表征水泥石内维氏硬度分布规律;适量粉煤灰的掺入可以减少受侵蚀后试件内的钙矾石(AFt)和石膏含量。     

The effectuation of seawater on the microstructural features and the compressive strength of fly ash blended cement at early and later ages

The current work scrutinizes the effectuation of seawater on morphological properties, pore structure, and compressive strength during the hydration process of fly ash blended cement at 3, 7, 28, 56, and 90 days to better understand the influence of salinity conditions of seawater on the microstructural modification and strength development of the hydration products as well as the total porosity. The chemical reaction's mechanism of mightily soluble salts, for example, Mg₂SO₄ and NaCl, with hydrated fly ash and blended cement (calcium-bearing phases) was also confirmed. Fourier-transform infrared spectroscopy has been appointed to observe and characterize the energetics of variation in the formulation of portlandite (CH), calcium silicate hydrate, gypsum (Gy), ettringite (AFt), and calcium chloroaluminate (Friedel's salt [FS]) throughout the hydration process of fly ash blended cement with seawater in comparison with deionized water. X-ray diffraction analysis exposed that the peak intensities of FS, portlandite, and some particular phases of the hydrated fly ash blended cement in seawater are higher and sharper than the comparable peaks in deionized water. Mercury intrusion porosimetry-measurements have been appointed that the total porosity of artificial seawater (ASW) was decreased from 28.9% at 3 days to 19.4% at 56 days. In addition, the average, median, and critical pore diameter were decreased in ASW while compared to deionized water (DIW). The reaction products of this work were also characterized using scanning electron microscopy, EDS, compressive strength, and isothermal calorimeter.     

Utilization of fly ash coming from a CFBC boiler co-firing coal and petroleum coke in Portland cement

Fly ash coming from a circulating fluidized bed combustion (CFBC) boiler co-firing coal and petroleum coke (CFBC fly ash) is very different from coal ash from traditional pulverized fuel firing due to many differences in their combustion processes, and thus they have different effects on the properties of Portland cement. The influences of CFBC fly ash on the strength, setting time, volume stability, water requirement for normal consistency, and hydration products of Portland cement were investigated. The results showed that CFBC fly ash had a little effect on the strength of the Portland cement when its content was below 20%, but the strength decreased significantly if the ash content was over 20%. The water requirement for normal consistency of cement increased from 1.8% to 3.2% (absolute increment value) with an addition of 10% CFBC fly ash; and the free lime (f-CaO) content of CFBC fly ash affected the value of increasing. The setting time decreased with an increase of CFBC fly ash content. The volume stability of the cement was qualified even when the content of SO₃ and f-CaO reached 4.48% and 3.0% in cement, respectively. The main hydration productions of cement with CFBC fly ash were C-S-H (hydrated calcium silicate), AFt (ettringite), and portlandite.     

粉煤灰对水泥浆体早期水化和孔结构的影响

通过硬化水泥浆体力学性能、交流阻抗和孔结构等性能的测试,以及扫描电镜分析,研究了不同掺量的粉煤灰对硬化水泥浆体早期水化和孔结构的影响。结果表明：随着粉煤灰掺量的增加,水泥的凝结时间增加,抗压强度降低,熟料矿物的水化速率提高,但水泥-粉煤灰体系的水化速率降低,水泥浆体中孔溶液电阻和阻抗相应降低,硬化水泥浆体中大孔数量减少,微孔数量增加。     

Effects of the incorporation of Municipal Solid Waste Incineration fly ash in cement pastes and mortars: II: Modeling

This work falls within the scope of the general problem of the assessment of concretes manufactured from waste materials. The main objective is to study the long-term evolution of these materials during leaching using the cellular automata-based hydration model developed at the National Institute of Standards and Technology (NIST). The work is based on the analysis of mortars and cement pastes containing experimental waste: Municipal Solid Waste Incineration fly ash (MSWI fly ash). After having determined the mineralogical composition of the MSWI fly ash and its interactions with cement during hydration, presented previously as Part I, the phases comprising the fly ash have been incorporated into the hydration model. The increase in porosity of cement pastes containing MSWI fly ash during leaching has then been simulated. Finally, a simplified leaching model has been developed to study the influence of the changes in microstructure on the release of calcium and sodium.     

Modeling the hydration of concrete incorporating fly ash or slag

Granulated slag from metal industries and fly ash from the combustion of coal are industrial by-products that have been widely used as mineral admixtures in normal and high strength concrete. Due to the reaction between calcium hydroxide and fly ash or slag, the hydration of concrete containing fly ash or slag is much more complex compared with that of Portland cement. In this paper, the production of calcium hydroxide in cement hydration and its consumption in the reaction of mineral admixtures is considered in order to develop a numerical model that simulates the hydration of concrete containing fly ash or slag. The heat evolution rates of fly ash- or slag-blended concrete is determined by the contribution of both cement hydration and the reaction of the mineral admixtures. The proposed model is verified through experimental data on concrete with different water-to-cement ratios and mineral admixture substitution ratios.     

低品位粉煤灰的改性及其对水泥浆体强度和自收缩的影响

采用石灰石粉对低品位粉煤灰进行煅烧改性,利用X射线衍射、扫描电镜和能谱分析等方法对改性粉煤灰的矿物组成和化学组成进行表征.同时测定了掺改性粉煤灰的水泥浆体的抗压强度和自收缩,并采用背散射扫描电镜和压汞测孔仪研究了掺改性粉煤灰水泥浆体的微观结构.结果表明,粉煤灰经煅烧改性生成了水硬性矿物β-C2S,水化可生成CSH凝胶,改善了等外粉煤灰颗粒与水泥基体的界面粘接,降低了复合水泥浆体的孔隙率和自收缩,提高了复合水泥浆体的强度.     

Mineralogical Characterizations and Reaction Path Modeling of the Pozzolanic Reaction of Fly Ash–Lime Systems

Mineralogical studies show that fly ash–lime systems without NaOH produced Al-rich calcium silicate hydrates and a small amount of ettringite. The presence of NaOH accelerates the pozzolanic reaction of fly ash. Fly ash–lime systems with NaOH produced Al-rich calcium silicate hydrates, calcite, meixnerite, and NaX-type zeolite (or zeolite precursor) after 28 days of reaction time. Carbonation of alkali-activated fly ash–lime systems call for specific studies. The experimental work was supplemented with reaction path modeling, which provided a quantitative procedure to decipher the chemical nature of fly ash hydration and cementitious system formation.     

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.     

Characteristics of the ultrafine component of fly ash

Post-production processing of fly ash (FA) is an important issue for its use in concrete. Given (i) the need for environmental protection, (ii) the measures being applied on coal-fired power stations to reduce acidic gas emissions and (iii) the effect these have had on fly ash quality, there is a need to consider efficient post-production processing to enhance fly ash characteristics. This is particularly important for fly ash used as a cement in concrete production, since the additional residual carbon content and decreased fineness significantly affect its quality. This paper details the material characteristics of an ultrafine, low-lime fly ash (UF-FA), produced, in this case, by processing a coarse FA (referred to as parent FA) from a bituminous coal-fired power station via air-cyclonic separation. The UF-FA is shown to have much improved material characteristics compared to the parent FA in terms of morphology, mineralogy and chemical composition. Further results are presented on the effect of UF-FA on the properties of cementitious systems. Improved consistence and compressive strengths of combined Portland cement (PC) and UF-FA mortars were observed, whilst enhanced PC hydration and a high degree of FA reactivity were concluded from heat of hydration measurements and calcium hydroxide contents of pastes.