含粉煤灰或石英粉复合胶凝材料的抗压强度发展规律

用细度基本相同的粉煤灰和石英粉作为活性和惰性矿物掺和料,研究了不同水胶比、不同养护温度条件下,矿物掺和料的种类和掺量对复合胶凝材料抗压强度发展特性的影响.在水化初期,颗粒形貌等物理因素比反应程度等化学因素更能影响含有矿物掺和料的复合胶凝材料的抗压强度发展特性,活性与惰性矿物掺和料的作用基本相同.热激发能明显促进粉煤灰的火山灰反应,有利于含粉煤灰的复合胶凝材料的抗压强度发展.含大掺量粉煤灰的复合胶凝材料特别适合用于内部能较长时间维持较高温度的大体积混凝土结构.     

Efficiency of mineral admixtures in mortars: Quantification of the physical and chemical effects of fine admixtures in relation with compressive strength

This work is the fourth part of an overall project the aim of which was the development of general mix design rules for concrete containing different kinds of mineral admixtures. The two first parts presented the separation and quantification, by means of an empirical model based on semi-adiabatic calorimetry measurements, of the different physical effects responsible for changes in cement hydration (short terms) when chemically inert quartz powders were used in mortars. Part three dealt with an intensive experimental program, presenting and commenting more than 2000 compressive strength measurements. This program concerned 1 day to 6 months old mortars containing up to 75% of inert and pozzolanic admixtures. All these compressive strength results are analyzed in this fourth part and the influence of three effects, namely dilution, heterogeneous nucleation and the pozzolanic effect, are discriminated and quantitatively evaluated. An efficiency concept is proposed in order to take into account the effect of mineral admixture in mortars from both the physical and chemical points of view. It uses an efficiency function ξ(p) that has notable properties: it is independent of time, independent of fineness and independent of the type of mineral admixture.     

含有活性或惰性掺合料的复合胶凝材料硬化浆体的微观结构特征

用压汞法测定了不同温度条件下养护的含有粉煤灰或石英粉的复合胶凝材料硬化浆体的孔隙率.用扫描电镜观察了硬化浆体的微观形貌,同时测定了各种组成的复合胶凝材料的净浆强度.常温水化初期,活性与惰性矿物掺合料都只具有物理填充的作用,硬化浆体的孔隙率和强度由矿物掺合料的掺量所决定.高温水化条件下粉煤灰的火山灰反应提前发生.随水化龄期延长,粉煤灰逐渐发生火山灰反应,使硬化浆体结构密实,其强度逐步提高.活性与惰性矿物掺合料对复合胶凝材料浆体结构与性能的影响的差异在水化后期逐渐显现.     

Mineral admixtures in mortars: Effect of inert materials on short-term hydration

This work is the first part of an overall project the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The separation of the different physical effects responsible for the modification of cement hydration, when chemically inert quartz powders are used in mortars, is presented. The phenomenological approach, based on semi-adiabatic calorimetry, is only associated with first-order phenomena, and the study excludes the complex physicochemical details involved in the chemistry of cement. The results, obtained for a wide range of fineness (between 180 and 2000 m²/kg) and replacement rates (up to 75%), show that short-term degrees of hydration in mortars containing a chemically inert mineral admixture (quartz) are always higher than for a reference mortar. This study confirms that cement hydration is enhanced by inert mineral admixtures. The two main physical effects responsible for the modification of the hydration of cement are identified as the dilution effect and heterogeneous nucleation. The dilution effect of the cement is highlighted with a coarse mineral admixture. The heterogeneous nucleation effect, although it increases with fineness of mineral admixtures, presents an optimum depending on the replacement rate. In the following part of this work, these results will be used for the development of an empirical model allowing us to quantify both physical effects.     

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.     

Mineral admixtures in mortars: Quantification of the physical effects of inert materials on short-term hydration

This work is the second part of an overall project, the aim of which is the development of general mix design rules for concrete containing different kinds of mineral admixtures. The first part presented the separation of the different physical effects responsible for changes in cement hydration when chemically inert quartz powders are used in mortars. This second part describes the development of an empirical model, based on semiadiabatic calorimetry measurements, which leads to the quantification of the enhancement of cement hydration due to the heterogeneous nucleation effect at short hydration times. Experimental results show that not all the admixture particles participate in the heterogeneous nucleation process. Consequently, the concept of efficient surface S_eff is introduced in the model. S_eff is the total admixture surface S (m² of mineral admixture/kg of cement) weighted by a function ξ(p). The efficiency function ξ(p) depends only on the replacement rate p and is independent of time, fineness and type of mineral admixture used. It decreases from 1 to 0: Low replacement rates give an efficiency value near 1, which means that all admixture particles enhance the hydration process. An efficiency value near 0 is obtained for high replacement rates, which indicates that, from the hydration point of view, an excess of inert powder does not lead to an increase in the amount of hydrates compared with the reference mortar without mineral admixture. The empirical model, which is mainly related to the specific surface area of the admixtures, quantifies the variation of the degree of hydration induced by the use of inert mineral admixtures. One application of the model, coupled with Powers' law, is the prediction of the short-term compressive strength of mortars.     

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.     

矿物掺合料细度对水泥胶砂力学性能的火山灰效应

通过分析单掺矿粉、单掺不同磨细程度的粉煤灰及复掺粉煤灰和矿粉的胶砂早期强度的变化规律,得出粉煤灰的磨细程度及粉煤灰与矿粉的复掺比例会影响胶砂的早期强度。粉煤灰越细,越有利于提高胶砂早期强度,复合掺合料之间各成分的最佳配合比可以充分发挥各自的活性,从而提高胶砂早期力学性能。     

The effect of mechanically and chemically activated fly ashes on mortar properties

Fly ash is a waste material from coal-burning power plants that consume pulverized solid fuels. Two fly ashes from Asturias (Spain) were activated mechanically by wet milling and chemically by leaching with sulfuric acid. The activated fly ashes were characterized in terms of physico-chemical characterization, granulometry, density, blaine, BET, XRD and SEM.A comparative study was carried out of several mortars, in some cases using different additions of silica fume or activated fly ash. The influence that these additives have on the mechanical resistance of the mortars was studied. As well as the possible use of these activated fly ashes as a replacement for silica fume in producing high-strength mortar or concrete. It was found that mortars containing activated fly ash presented higher compressive strengths.A mercury intrusion porosimetry study was carried out on cement mortars made with mineral additives such as silica fume and activated fly ashes. In general, the porosities values of these mortars showed that mineral admixtures improved mechanical resistance due to the decrease in pore size.     

Compressive strength studies on portland cement mortars containing fly ash and superplasticizer

The effects of two super water-reducing admixtures on the compressive strengths and elastic moduli of portland cement mortars containing fly ash were determined. The results show that the effectiveness of the chemicals for improving the strengths of mixtures in which portland cement is partially replaced by fly ash decreases with an increase in the percentage of ash. Increased strength can be nil or too low to justify the additional expense associated with the chemicals. The mixtures did exhibit normal stress-strain relationships: the elastic moduli were related to the ultimate compressive strengths in the usual manner. The results are based on mixes with equal workabilities.     

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     

Influence of steam curing on the compressive strength of concrete containing supplementary cementing materials

Heat treatment is widely used to accelerate the strength-gaining rate of concrete. In general, the ultimate strengths of the heated-treated concrete are lower than those of the standard cured specimens. When ultrafine fly ash (UFA) is included in concrete, the pozzolanic reaction is accelerated through the heat treatment. Sometimes, various chemical activators were used to activate the reactivity of fly ash. In the current study, UFA and slag were used as a replacement for cement, steam curing and chemical activators were used to accelerate hydration of cement and fly ash, and then compared with moist curing. This paper presents the influence of steam curing on the compressive strength of concrete containing UFA with or without slag. The experimental results indicated that the concrete containing UFA has low early strength after 13-h steam curing and that the difference between the 28-day compressive strength of concrete through 13-h steam curing and that of moist-cured concrete is large, but the concrete with UFA and CaSO₄ or Ca(OH)₂ has a high early strength, thus, the reactivity of fly ash must be accelerated. Concrete containing UFA and ground slag was prepared, whose compressive strengths were improved.     

石灰石粉-粉煤灰细度变化对水泥基胶凝材料体系水化动力学的影响

为研究混磨不同细度石灰石粉-粉煤灰对水泥基胶凝材料水化进程和早期力学性能的影响规律,本文采用等温量热法测定了不同细度复合胶凝体系在水化温度为20 ℃时的水化放热速率和放热量,根据Krstulovic-Dabic提出的水化动力学模型计算了复合胶凝体系水化反应各阶段的动力学参数。结果表明:增加石灰石粉和粉煤灰的细度可促进复合胶凝体系水化产物的结晶成核与晶体生长,缩短水化诱导期结束时间和达到最大放热速率时间,加速水泥的水化反应速率。石灰石粉和粉煤灰细化会缩短相边界反应过程时间,使复合胶凝体系在水化程度更高时发生反应控制机制转变。抗压强度试验表明增加细度可明显提高胶砂试件的早期强度,其后期强度保持稳定。     

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.     

Use of ground coarse fly ash as a replacement of condensed silica fume in producing high-strength concrete

This paper presents a method of improving coarse fly ash in order to replace condensed silica fume in making high-strength concrete. The coarse fly ash, having the average median diameter about 90-100 μm, yields a very low pozzolanic reaction and should not be used in concrete. In order to improve its quality, the coarse fly ash was ground until the average particle size was reduced to 3.8 μm. Then, it was used to replace Portland cement type I by weights of 0%, 15%, 25%, 35%, and 50% to produce high-strength concrete. It was found that concrete containing the ground coarse fly ash (FAG) replacement between 15% and 50% can produce high-strength concrete and 25% cement replacement gave the highest compressive strength. In addition, the concrete containing FAG of 15-35% as cement replacement exhibited equal or higher compressive strengths after 60 days than those of condensed silica fume concretes. The results, therefore, suggest that the FAG with high fineness is suitable to use to replace condensed silica fume in producing high-strength concrete.     

矿物掺合料对蒸养水泥净浆性能的影响

研究了蒸养条件下粉煤灰、矿渣的掺量对水泥净浆化学结合水量和抗压强度的影响,揭示了矿物掺合料对蒸养水泥净浆水化性能和力学性能的影响。试验结果表明,与标准养护相比,蒸汽养护更有利于激发粉煤灰和矿渣的火山灰活性,促进水泥的早期水化,提高水泥浆体的早期强度;但无论是蒸汽养护还是标准养护,随着矿物掺合料掺量的增加,复合胶凝材料的水化性能和力学性能明显减弱,因此矿物掺合料掺量不宜太大。     

粉煤灰和矿渣粒度分布对混凝土微观结构和抗氯离子渗透性的影响

针对胶凝材料比表面积和粒度分布等物理性质存在的差异,将P·Ⅱ水泥,Ⅰ级、Ⅱ级粉煤灰和S95级、S105级矿渣进行互掺,固定水泥用量,设计了4种粉煤灰和矿渣的组合方式,通过流动度试验分析了组合方式对净浆流动性的影响,并将粒度分布曲线与Fuller分布曲线进行了比较。在净浆配合比的基础上,对不同组合方式的混凝土进行了工作性、力学性能及自由氯离子浓度测试,探讨了粉煤灰和矿渣的粒度分布对混凝土强度和抗氯离子渗透性的影响,并对硬化浆体水化产物的微观形貌和化学组成进行了分析,揭示了影响机理。研究结果表明,矿物掺合料的粒度分布是决定颗粒级配优劣的重要因素。Ⅰ级粉煤灰具有更强的滚珠效应,在提高流动性方面起了关键性作用。粉煤灰和矿渣的水化及火山灰反应程度影响着混凝土的力学性能和耐久性能,由于Ⅰ级粉煤灰有更大的比表面积,火山灰活性也较高,因此Ⅰ级粉煤灰和S95/S105级矿渣组合的净浆流动度,混凝土的工作性、抗压强度和抗氯离子渗透性均明显高于Ⅱ级粉煤灰和S95/S105级矿渣组合。其中Ⅰ级粉煤灰和S95级矿渣组合的胶凝材料粒度分布曲线与Fuller曲线最为接近,粒度分布最优,水化浆体中Ca(OH)₂含量最低,火山灰反应最为充分,对应的混凝土微观结构致密,抗氯离子渗透性最好。     

Effects of the incorporation of Municipal Solid Waste Incineration fly ash in cement pastes and mortars: I. Experimental study

This work falls within the scope of a general problem regarding the assessment of concrete manufactured from waste materials. The main objective is to study the long-term evolution of these materials during the leaching process, using the cellular automaton-based hydration model developed at the National Institute of Standards and Technology. The work is based on the analysis of mortars and cement pastes containing experimental waste: Municipal Solid Waste Incineration fly ash (MSWI fly ash). The study therefore aims to develop a methodology for assessing concrete manufactured from waste, and not to study a process or a formulation enabling the incorporation of the waste in concrete. The physical, chemical and mineralogical characteristics of MSWI fly ash were first analysed to introduce them into the model. A simplified quantitative mineralogical composition of the ash was proposed. The performance characteristics (setting times, compressive strengths, shrinkage, etc.) for mortars containing ash were then studied.     

碱激发钢渣矿渣复合基层材料的强度特性及微观机制

围绕钢渣再利用、钢渣矿渣复合材料强度提升及微观作用机理这3个问题,从无侧限抗压强度和劈裂强度两个指标分析混合料不同养护龄期下的宏观强度,同时进行XRD、SEM和热重分析等微观试验,探讨了在石灰激发作用下,钢渣矿渣基层材料的水化产物生成和强度变化内在机制。强度试验结果表明:当矿渣掺量在10%(质量分数)以内,石灰与矿渣的质量比在1∶1~1∶2时,混合材料各龄期的无侧限抗压强度和劈裂强度较高。微观试验结果表明:适量Ca(OH)₂能够提高矿渣中SiO₂的水化反应速率,从而提升复合材料早期强度。此外,水化反应生成钙矾石、粉煤灰及钢渣中惰性组分的细料填充作用也是材料早强增长的有利因素。而粉煤灰的火山灰效应和钢渣中C₂S的持续水化反应则有助于复合材料后期强度的提升。     

Pozzolanic activity of Jordanian oil shale ash

The ash of the retort residue of the oil shale from central Jordan has been further tested to evaluate its pozzolanic activity. According to the preliminary experiments the ash had cementive properties. Thermogravimetric analyses were performed on ash, cement, ash blended cement and ash-lime pastes. In the blended pastes, addition of ash seemed to decrease the amount of lime generated. In the ash-lime paste the lime consumption by ash with time followed a similar trend to the reactions of trass and silica fume with lime. The ash-lime reaction was mainly a diffusion controlled process obeying the Ginstling-Brounshtein equation. The pozzolanic activity of the ash, as indicated by its lime activity and rate constant, was not as high as the other pozzolans compared, mainly due to its lower fineness. Tests on compressive strengths of cement and lime mortars blended with ash confirmed the findings, indicating that up to 20% of cement could be replaced by ash used as an admixture. Ash-lime mortars could gain moderate strengths under accelerated curing, suitable for some building units.