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.     

Improving the performance of ternary blended cements by mixing different types of fly ashes

For overcoming certain drawbacks characterizing both basic types of fly ashes (of high and low calcium content), different ash intermixtures consisting of two types of fly ashes were prepared. The principal idea lying beneath the effort presented herein is that beneficial assets of the one type of ash could compensate for the shortcomings of the other. Compressive strength development, pozzolanic activity potential and nature of hydration products of all ternary cements were closely monitored and presented in comparison to the respective properties of the initial binary blends. Moreover, efficiency factors were calculated for all new systems and were further used to validate previously reported expressions describing Binary Fly ash-Cement (BFC) systems. In accordance with previous works, ternary fly ash systems examined here outperformed the respective binary systems almost throughout the curing period. Synergy between the different types of fly ashes was considered the main reason for the excellent performance of the ternary mixtures. Results obtained indicate that previously developed analytical expressions, correlating active silica of SCMs and k-values, can be applied in the case of multicomponent ash systems as well.     

Effect of lime putty addition on structural and durability properties of concrete

The effect of lime putty addition on main structural and durability properties of concrete was studied. Different types of cement were used for concrete preparation: a Portland cement, a pozzolanic cement and a Portland cement with the addition of 20% fly ash. The measured concrete properties were compressive strength, setting times, length change, porosity, carbonation depth and degree of steel bar corrosion. It was found that the lime putty addition has a positive effect on the properties of concrete that contain pozzolans and a slightly negative effect on the properties of pure Portland cement. This behavior was correlated with the availability of active silica of cementitious materials. The active silica of pozzolans reacts with the added calcium hydroxide giving constituents, which improve the concrete stability and durability.     

Hydration of fly ash-portland cements

Hydration products of fly ash-portland cements were studied with x-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) as part of a continuing research effort to understand the pozzolanic activity of fly ashes. It was found that the amount of calcium hydroxide crystals in the cement pastes is diminished due to the addition of fly ash to the cement. Ettringite was produced in the early age, and the consumption of sulfate by the formation of ettringite was accelerated by the addition of fly ash. A partial conversion of ettringite to monosulfate within the first 7 days of hydration in the fly ash-portland cement pastes, but the formation of ettringite continued to form up to at least 28 days of hydration in the pastes without fly ash. Examination of the fly ash bearing pastes showed, in all cases, varying amounts of calcium hydroxide and unreacted portland cement, with minor quartz and gehlenite hydrate. It appears that hydration reactions actually occur in the fly ash cement pastes more or less on a particle-by-particle basis.     

Activation of fly ash cementitious systems in the presence of quicklime. Part II: Nature of hydration products, porosity and microstructure development

Following the first paper of a two-part series study on the activating effect of industrial quicklime upon different fly ashes, the current paper concludes on its beneficial role by focusing on the nature of hydration products, pore size and microstructure evolution of each system that was investigated. By looking into the development of these properties, the exact effect of the chemical activator could be elucidated, but furthermore a first approximation of the durability efficiency of the examined systems could be obtained. In the frame of this second part, it was demonstrated that, apart from portlandite, calcium sulphoaluminates (ettringite and monosulfoaluminate) along with some gismondine and gehlenite hydrate (C₂ASH₈) crystals are formed in activated fly ash-cement pastes from the first week of hydration. Mercury intrusion porosimetry data confirmed the beneficial action of quicklime, towards decreasing the total pore volume (and concurrent increase in the volume occupied by fine pores) in high-lime ash blends. Gel/space ratios were estimated for each blended paste, and fine, almost linear, correlation was established with total porosity values. Microscopical observations revealed that the critical contribution of quicklime in the production of secondary C–S–H nearby the ash particles. The flocculent-like gel collaborates smoothly with needle-like products and finely-dispersed crystals towards the gradual impletion of the pores and strengthening of the paste.     

Use of recycled copper slag for blended cements

Copper slag is a by‐product generated during smelting to extract copper metal from the ore. The copper slag obtained may exhibit pozzolanic activity and may therefore be used in the manufacture of addition‐containing cements. In this paper the effect of the incorporation of the copper slag in cement is measured. Blends of copper slag with Portland cement generally possess properties equivalent to Portland cement containing fly ash, but very different to the silica fume incorporation. Copper slag and fly ash reduce the heat of hydration more effectively than silica fume in mortars. The replacement of 30% cement by copper slag reduces the flexural and compressive strength in a similar way to fly ash; however, after 28 days, the reduction is less than the percentage of substitution. Hydrated calcium aluminate phases were analysed using scanning electron microscopy (SEM) and X‐ray diffraction (XRD) techniques. The pozzolanic activity of copper slag is similar to that of fly ash and higher than silica fume. In the presence of low water/cement ratios, certain pozzolanic materials produce a very compact cement paste that limits the space available for hydration products, a determining factor in the formation of hydrated calcium aluminates. SEM was found to be a useful analytical technique when aluminates are formed and can be clearly detected by XRD. Copyright © 2008 Society of Chemical Industry     

Steam reactivation of 16 bed and fly ashes from industrial-scale coal-fired fluidized bed combustors

The hydration behaviour of sixteen ashes, obtained from different commercial-scale fluidized bed combustors, has been investigated. Hydration is important for both ash disposal and reactivation of excess lime present in the ashes for further use in flue gas desulphurization. The techniques used were instrumental and conventional chemical analysis, thermogravimetry and X-ray diffraction. The ashes comprised both fly ash and bottom ash, with particle size less than 2 mm. The ashes were heat treated in air to oxidize free carbon and then hydrated with pressurized steam at about 170 °C, alone and with addition of pure CaO.It has been shown that steam hydration is effective in quantitatively converting CaO to Ca(OH)₂, but in most cases the free lime content (i.e. CaO+Ca(OH)₂), expressed as CaO, decreases and added CaO enters into pozzolanic reactions with coal ash components, in part or even completely. Both the chemical evidence and X-ray phase analyses indicate that hydrated silicates and silicoaluminates are formed. The hydrated ashes are all able to take up additional SO₂ and it appears that the presence of amounts of Ca(OH)₂ detectable by phase analysis is not necessary for such capture.     

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.     

外掺料对磷石膏基胶凝材料力学及导热性能的影响

将磷石膏应用于建筑业,可以解决磷化工副产物堆积的问题。采用单因素实验,通过改变水灰质量比、粉煤灰掺量、生石灰掺量等条件来研究各因素对磷石膏基胶凝材料力学性能及保温性能的影响,借助X射线衍射（XRD）、X射线荧光光谱（XRF）、扫描电镜（SEM）等手段来分析磷石膏基胶凝材料的物化性质和形貌结构。结果表明,磷石膏基胶凝材料的导热系数和抗压强度都与水灰质量比呈负相关,在水灰质量比为0.250时胶凝材料的抗压强度最大、水灰质量比为0.550时胶凝材料的导热系数最小;粉煤灰在磷石膏基胶凝体系中除了提供胶凝性能外,还会被生石灰激发出活性,增强胶凝体系的综合性能,粉煤灰掺量为50%（质量分数）时胶凝体系的综合性能最佳;生石灰在磷石膏基胶凝体系中对杂质的吸附效果明显,生石灰掺量超过7%（质量分数）以后对胶凝体系的保温性能和力学性能的增强效果明显。     

矿渣-粉煤灰混合材料水化产物、微观结构和性能

用X射线衍射仪和扫描电子显微镜等对矿渣、粉煤灰混合材料的水化产物、硬化体微观结构及强度进行了检测和分析,确定了水化产物的组成及微观结构特点,揭示了矿渣粉煤灰材料的水化作用特点及强度特征.结果表明:矿渣在激发剂作用下使玻璃体首先发生表面水解,产生水化反应,进而引发粉煤灰的火山灰作用;混合材料的水化产物组分以水化硅酸钙凝胶为主,硬化体具有与油井水泥相类似的网络状微观结构;随养护时间增长,混合材料后期强度持续增加.     

粉煤灰基地聚水泥的研究

地聚水泥是一种新型的化学激发胶凝材料，其制备工艺和原材料以及水化硬化机理等都完全不同于普通硅酸盐水泥．性能及应用领域也远比普通硅酸盐水泥优越，是一种在某些工程领域有望取代硅酸盐水泥的极有发展潜力的化学激发胶凝材料。通过正交试验，在不掺水泥或水泥熟料及石灰的情况下，以原状低钙粉煤灰为原料，在碱性激发剂的作用下，制备了地聚水泥。重点探讨了碱激发剂种类，粉煤灰种类以及养护制度等因素对制备地聚水泥的影响。     

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.     

Alkali release characteristics of blended cements

This paper presents results of an experimental program conducted to investigate the capacity of hydration products of different cementing materials to retain “bound” alkalis when the alkalinity of the surrounding solution drops. The study covered paste samples containing high-alkali Portland cement and various levels of silica fume and/or fly ash. The results showed that the ability of the hydration products of cement-fly ash systems to bind alkalis is a function of the CaO content of the fly ash, the binding increasing as the calcium content decreases. High-alkali fly ashes (Na₂O_e > 5.0% and CaO in the range of 15% to 20%) showed considerable amounts of alkali contributed to the test solutions. Silica fume does not have a high capacity to retain alkalis in its hydration products; however, ternary blends containing silica fume and fly ash have excellent capacity to bind and retain alkalis.     

Hydration of Portland cement with high replacement by siliceous fly ash

The effects of two different low calcium fly ashes on the hydration of ordinary Portland cement (OPC) pastes containing 50 wt.% of fly ash were investigated over a hydration time of 550 days. The results were compared with a reference blend of OPC containing 50 wt.% of inert quartz powder allowing the distinction between "filler effect" and pozzolanic reaction.Until 2 days, no evidence of fly ash reaction was measured and its influence on the hydration is mainly related to the “filler effect”. From 7 days on, the effects of the pozzolanic reaction were observed by the consumption of portlandite, the change of the pore solution chemistry, the formation of a presumably water-rich inner hydration product and the change of the C–S–H composition towards higher Al/Si ratio compared to the C–S–H of neat OPC. Additional strength due to the pozzolanic reaction developed after 28 days of hydration.     

Effect of silica fume and fly ash on heat of hydration of Portland cement

Results of calorimeter tests on Portland cement-silica fume-fly ash mixtures are presented. Data indicate that silica fume accelerates cement hydration at high water/cementitious ratios and retards hydration at low water/cementitious ratios. On the other hand, fly ash retards cement hydration more significantly at high water/cementitious ratios. When silica fume and fly ash are added together with cement, the reactivity of the silica fume is hampered and the hydration of the cementitious system is significantly retarded.     

Packing effect and pozzolanic reaction of fly ash in mortar

This research is to study the effect of particle size of fly ash on packing effect and pozzolanic reaction of mortar when 20% of fly ash is used to replace Portland cement type I. Both effects can be determined by using fly ash and insoluble material which have almost the same particle size to replace Portland cement type I. Normally, the compressive strength of fly ash mortar is contributed from hydration reaction, packing effect, and pozzolanic reaction. For mortar mixed with insoluble material, the compressive strength is due to hydration reaction and packing effect. Thus, compressive strength due to pozzolanic reaction can be determined from the difference in compressive strength between fly ash mortar and insoluble material mortar. The results show that the strength activity index of fly ash mortar depends on the median particle size of fly ash and curing ages of mortar samples. At early ages, the strength activity index of fly ash mortar due to packing effect is higher than that due to pozzolanic reaction. At the ages of 3 to 90 days, the difference in strength activity index due to packing effect of fly ashes with median particle size of 2.7 and 160 μm is almost constant about 22% of the strength of standard mortar (STD). The differences in strength activity index due to pozzolanic reaction of fly ashes with median particle size of 2.7 and 160 μm are 3%, 20%, and 27%, respectively, at the ages of 3, 28, and 90 days.     

The effects of fly ash composition on the chemistry of pore solution in hydrated cement pastes

This paper reports the findings of an investigation to determine the influence of fly ash composition on the evolution of the pore solution chemistry in Portland cement/fly ash systems. Twelve fly ashes, selected to represent the wide range of composition of North American ashes, were used in the study. In addition to pore solution expression and analysis, inner hydration products were analyzed using energy-dispersive X-ray analysis. The study shows that the alkalinity of pore solution increases as the calcium and alkali content of the fly ash increase, and decreases as the silica content of the ash increases. However, there is no consistent trend between the composition of the inner calcium-silicate hydrate and fly ash composition.     

An examination of the ASTM Lime Pozzolanic Activity Test for class C fly ashes

The role of the type of calcium hydroxide (“lime”) used in the ASTM C 311-81 Lime Pozzolanic Activity Test (LPAT) has been studied. Three types of lime (reagent grade Ca(OH)₂, a commercial lime and a mixture of the reagent grade lime and MgO) were used with four fly ashes (three Class C and one Class F) in the LPAT. The same four fly ashes were used in the ASTM Cement Pozzolanic Activity Test. The formation of crystalline reaction products in the lime test was monitored by x-ray powder diffraction. All three Class C fly ashes failed to meet the LPAT seven-day 800 psi compressive strength criterion when the reagent grade lime was used but all three passed the test when the other two types of lime were used. X-ray diffractograms of pastes cured for three days at 55°C showed different reaction products formed from the pastes containing reagent grade lime compared to the other two lime sources. It is proposed that impurities in the commercial lime play a key role in determining the pozzolanic activity of Class C fly ashes.     

钾基碱性电解水对粉煤灰混凝土性能的影响

碱性电解水具有高活性、强碱性、强离子性和吸附性等优点。利用碱性电解水作为拌合水制备不同取代率的粉煤灰混凝土,系统研究碱性电解水对粉煤灰混凝土的工作性能、力学性能和抗氯离子渗透性能的影响,并结合X射线衍射仪(XRD)、扫描电镜(SEM)和差热分析试验(TG/DTA)分析碱性电解水混凝土的水化产物及微观结构形貌。结果表明:碱性电解水能够促进混凝土中水泥早期水化反应,改善混凝土的工作性能,除了生成更多的C-S-H凝胶体和Ca(OH)₂等水化产物外,还生成了钾长石,降低了孔隙率,提高结构密实度,改善了混凝土的力学性能和抗渗性能;同时,碱性电解水在一定程度上可以激发粉煤灰的早期活性效应,使得粉煤灰玻璃体网络结构加速断裂,粉煤灰中的SiO₂和Al₂O₃大量溶出与混凝土中的水化产物Ca(OH)₂发生二次反应,生成更多的硅酸钙和铝酸钙等胶凝性产物。相较于普通自来水混凝土,当粉煤灰取代率为20%和30%(质量分数)时,碱性电解水混凝土的56 d抗压强度分别增长了8.7%和3.5%。     

粉煤灰基地聚水泥的研究

地聚水泥是一种新型的化学激发胶凝材料,在某些工程领域有望取代硅酸盐水泥,极有发展潜力.通过正交试验,在不掺水泥或水泥熟料及石灰的情况下,以原状低钙粉煤灰为原料,在碱性激发剂的作用下,制备了地聚水泥.探讨了碱激发剂种类、粉煤灰种类以及养护制度等因素对制备地聚水泥的影响.