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.     

海水环境下矿物掺合料对硫铝酸盐水泥的水化影响

研究了海水环境下掺入硅灰、粉煤灰、矿渣对硫铝酸盐水泥抗压强度、化学收缩和水化产物的影响规律.结果表明:当硅灰的掺量为2.5%时,水泥浆体的抗压强度比空白组高.矿渣掺量为10%的水泥浆体28 d抗压强度明显超过掺入硅灰和粉煤灰时的强度,60 d强度高于空白组.掺入2.5%硅灰后,水泥浆体的化学收缩增大;在水化早期,粉煤灰和矿渣的火山灰活性很低,导致水泥浆体的化学收缩降低.掺入10%硅灰加快了硫铝酸盐水泥3 d水化反应,钙矾石生成量增多,水泥浆体早期强度比掺其它掺合料有所提高,但体积过快膨胀会破坏其内部结构,对水泥浆体的强度发展不利.     

海工水泥原料组成的优化试验研究*

根据国家标准对海工水泥原材料组成的要求,本文以粉煤灰、矿粉、硅灰为混合材与硅酸盐水泥熟料、石膏复合,通过水泥砂浆物理性能试验、抗渗性能试验、抗硫酸盐侵蚀试验和混凝土氯离子扩散系数试验,优化、确定了海工水泥合理的原材料组成范围。试验结果表明,当熟料掺量≥33%,硅灰掺量≤3%时,所制备的海工水泥的力学性能满足国家标准42.5级海工水泥的要求;以33%的熟料、7%的石膏、17%的粉煤灰、40%的矿粉和3%的硅灰制备的海工水泥具有较好的早期、后期强度和良好的耐久性能。XRD和SEM分析结果表明,与普通硅酸盐水泥相比,海工水泥水化体系中AFt含量多,可提高水泥石的致密度,减小孔隙率,使水泥硬化体具有优异的力学性能和耐久性能。     

聚合硫酸铝改性低碱度水泥性能研究

以水泥、硅灰和粉煤灰为主要胶凝材料制备的低碱度水泥可应用于放射性焚烧灰的固化,但其存在早期强度发展慢、后期强度不高的问题。本文以聚合硫酸铝作为添加剂激发火山灰材料反应活性,通过测定不同掺量聚合硫酸铝加入后固化体的抗压强度、孔隙率及pH值变化,并结合水化产物组成与含量、水化放热特性等表征手段,分析了聚合硫酸铝对低碱度水泥早期水化过程的影响规律和作用机理。结果表明:掺入聚合硫酸铝可以显著提高低碱度水泥固化体的早期抗压强度,使水化放热峰提前,促进了火山灰反应的发生,提高了水化产物的生成量,使微观结构更加密实,同时有效降低试样的早期碱度,有利于抑制焚烧灰中活性铝的腐蚀反应。     

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.     

蒸汽养护条件下复合水泥胶凝材料的优化匹配

利用XRD、SEM、TG/DSC、MIP等测试方法,对常压高温蒸汽养护下矿渣和粉煤灰等不同组成的复合胶凝材料物理性能及水化特性差异进行研究.结果表明,85℃常压蒸养条件下水泥水化产物与标准养护下基本相同,但水化产物数量有大幅提高,且有少量C9S6H18和钙矾石(AFt)稳定存在.辅助胶凝材料的适宜匹配,使水泥石结构较致密,蒸养强度较高.少量硅灰的掺加,有利于优化水泥石结构,促进蒸养条件下水泥石强度发展.     

含C_4A_3矿物硅酸盐水泥中混合材反应程度的研究

采用非蒸发水量法测定含硫铝酸钙矿物水泥的水化程度 ,萃取法测定该水泥中混合材的反应程度 ,通过SEM/EDS观察分析水化产物形貌和种类。结果表明 :粉煤灰水泥的水化程度高于同龄期的矿渣水泥的水化程度 ,粉煤灰的反应程度高于矿渣的反应程度。同龄期粉煤灰水泥中的水化产物多于矿渣水泥的水化产物 ,且水化产物发育更良好     

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.     

海工高性能混凝土用复合胶凝材料的试验研究

在调查分析海工混凝土工程实例的基础上，试验研究了硅酸盐水泥中掺入矿粉、粉煤灰、硅灰等混合材料对海工混凝土性能的影响。研究结果表明，在硅酸盐水泥中掺加矿粉、粉煤灰、硅灰等混合材料可以改善海工混凝土的综合性能。矿物混合材料的复合掺入比单独掺入能更好地改善混凝土抗Cl^-侵蚀性能。海工专用复合胶凝材料生产时宜尽可能地采用多种混合材料。     

Investigation of blended cement hydration by isothermal calorimetry and thermal analysis

Hydration of portland cement pastes containing three types of mineral additive; fly ash, ground-granulated slag, and silica fume was investigated using differential thermal analysis, thermogravimetric analysis (DTA/TGA) and isothermal calorimetry. It was shown that the chemically bound water obtained using DTA/TGA was proportional to heat of hydration and could be used as a measure of hydration. The weight loss due to Ca(OH)₂ decomposition of hydration products by DTA/TGA could be used to quantify the pozzolan reaction. A new method based on the composition of a hydrating cement was proposed and used to determine the degree of hydration of blended cements and the degree of pozzolan reaction. The results obtained suggested that the reactions of blended cements were slower than portland cement, and that silica fume reacted earlier than fly ash and slag.     

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.     

Assessment of a synchrotron X-ray method for quantitative analysis of calcium hydroxide

Thermogravimetric analysis (TGA) and quantitative X-ray diffraction (QXRD) are widely used to determine the calcium hydroxide (CH) content in cementitious systems containing blends of Portland cement, fly ash, blast furnace slag, silica fume and other pozzolanic and hydraulic materials. These techniques, however, are destructive to cement samples and subject to various forms of error. While precise weight losses can be measured by TGA, extracting information from samples with multiple overlapping thermal events is difficult. And, however, while QXRD can offer easier deconvolution, the accuracy for components below about 5 wt.% is typically poor when a laboratory X-ray source is used. Furthermore, the destructive nature of both techniques prevents using them to study the in situ hydration of a single contiguous sample for kinetic analysis. In an attempt to overcome these problems, the present research evaluated the use of synchrotron X-rays for quantitative analysis of CH.A synchrotron X-ray source was used to develop calibration data for quantification of the amount of CH in mixtures with fly ash. These data were compared to conventional laboratory XRD data for like samples. While both methods were found to offer good quantification, synchrotron XRD (SXRD) provided a broader range of detectability and higher accuracy than laboratory diffraction and removed the subjectivity as compared to TGA analysis. Further, the sealed glass capillaries used with the synchrotron source provided a nondestructive closed, in situ environment for tracking hydrating specimens from zero to any desired age.     

Incorporation of Waste Materials into Portland Cement Clinker Synthesized from Reagent-Grade Chemicals

In this study, the feasibility of using waste materials to manufacture Portland cement was investigated. Reagent-grade chemicals were used to synthesize a Portland cement clinker with a tightly controlled composition. Then, calcium oxide-bearing waste materials, specifically fly ash and blast furnace slag, were combined with the reagent-grade chemicals. The synthetic cements were characterized using X-ray diffraction, scanning electron microscopy, and isothermal calorimetry. Results show that Portland cement can be successfully synthesized by replacing reagent-grade chemicals with up to 40% fly ash and 60% slag incorporation. These synthetic cements possess early-age hydration behavior similar to a commercial Type I/II Portland cement.     

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.     

偏高岭土对水泥基胶凝材料耐久性能的影响

以粉煤灰、矿粉和硅灰为混合材,与硅酸盐水泥熟料和石膏复合制备一种水泥基胶凝材料,通过内掺法研究偏高岭土对水泥基胶凝材料力学性能和耐久性能的影响,并利用激光粒度分布曲线、XRD和SEM验结果表明,随偏高岭土掺量的增加,水泥砂浆3d强度逐渐下降,28d强度逐渐增加,然后趋于稳定。当掺量超过9%时,强度的改善效果不显著;同时,偏高岭土的掺入,提高了砂浆的抗渗性能、降低了混凝土的氯离子扩散系数,并在偏高岭土掺量为0%-9%范围内作用效果明显。     

Supplementary cementing materials in concrete: Part II: A fundamental estimation of the efficiency factor

For comparing the relative performance of various supplementary cementing materials (SCMs: silica fume, fly ash, slag, natural pozzolans, etc.) as regards Portland cement, the practical concept of an efficiency factor may be applied. The efficiency factor (or k value) is defined as the part of the SCM in an SCM-concrete that can be considered as equivalent to Portland cement. In the present work, an alternative procedure for experimental determination of the k value is proposed, using the concept of the pozzolanic activity index. For the first time, also, the k value for equivalent strength was correlated with the active silica content of the SCM through analytical expressions. Artificial pozzolanic materials of various compositions and some natural pozzolans were studied. It was found and verified by experimental comparison that these expressions are valid only for artificial SCMs (fly ash, slag), whereas in the case of natural SCMs the k value is overestimated. Thus, knowing primarily the active silica content of the SCM, a first approximation of the k value can be obtained and, further, the strength of a concrete incorporating artificial SCM can be predicted.     

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.     

An investigation on microstructure of cement paste containing fly ash and silica fume

In this study, high-calcium fly ash (HCFA) and silica fume (SF) were used as mineral admixtures. The effect of these admixtures on the microstructure of cement paste was investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The reaction of HCFA and SF with portlandite, which occurs in Portland cement (PC), forms a new calcium-silicate-hydrate (C-S-H) gel.     

矿物掺合料对水泥耐酸性的影响及配比设计

以硅粉、粉煤灰和矿渣为矿物掺和料,采用XRD和SEM研究了矿物掺和料对水泥水化产物、水泥石结构和形貌的影响,探讨了酸溶液对水泥的腐蚀机理,并对矿物掺和料配比进行优化设计,以提高水泥的耐酸性.研究结果表明:掺加矿物掺和料有利于改善水泥石孔结构,降低水泥碱度,当硅粉、粉煤灰和矿渣以占水泥质量5%,10%和15%的配比掺入时,水泥的耐酸性最好.     

含硫铝酸钙硅酸盐水泥中粉煤灰活化机理

用差示扫描-热重分析扫描电镜和化学分析法研究了含硫铝酸钙粉煤灰硅酸盐水泥和含硫铝酸钙矿渣硅酸盐水泥水化过程中水化产物的种类、形状、数量和孔溶液离子浓度等方面的变化规律.借助固体高分辨核磁共振波谱技术对水泥中硅氧四面体不同聚合状态的分布,Al的不同配位状态进行分析.结果表明:含硫铝酸钙硅酸盐水泥对粉煤灰激发作用大于对矿渣的激发作用,含硫铝酸钙粉煤灰水泥水化放热量多,促进粉煤灰玻璃体中AlO2-的溶出,在较高温度粉煤灰玻璃体网络结构激活,解聚速率加快.