Investigations on the cementitious grouts containing supplementary cementitious materials

Concrete structures often exhibit distress during their service life due to one or more of the following causes: faulty design, use of substandard materials, poor construction, misuse or overloading. Of these, poor construction practices result in porous concrete which necessitates remedial and strengthening measures, if a structure is to meet the strength, serviceability and durability requirements, for which it has been originally designed. However, before strengthening the structure, the integrity of the concrete should be restored, which is often carried out through grouting using cement slurry, followed by grouting with epoxy or low viscous monomer. Grouting using cement slurry to fill up the voids in porous matrix of the concrete is the most simple and economical method, requiring less capital investment and skills. However, there are problems associated with cement grouting, such as shrinkage, stability of the grouts, etc. These problems associated with cement grouting can be solved by using cementitious grouts, i.e., grouts containing supplementary cementitious materials (SCMs) such as fly ash, ground granulated blast furnace slag (GGBS) and silica fume (SF) as admixtures in cement grout. This paper gives the results of the investigation undertaken to evaluate the flow, strength and durability characteristics of the cementitious grouts.     

The effect of supplementary cementitious materials on chloride binding in hardened cement paste

This paper reports the results of a study to determine the effects of supplementary cementitious materials (SCMs) on the chloride binding of portland cement pastes. The results show that SCMs with significant quantities of alumina increase the binding capacity of cement paste. Pastes with metakaolin (45% Al₂O₃) showed the greatest chloride binding capacity and pastes with silica fume (< 0.5% Al₂O₃) showed the least binding. The chemical binding in solutions of high chloride concentration is mainly attributed to the formation of Friedel's salt, C₃A·CaCl₂·10H₂O. When pastes originally exposed to high chloride concentrations are subsequently exposed to chloride-free solution, a portion of the bound chloride is released, but a significant portion remains irreversibly bound. There is some evidence that Friedel's salt may partially convert to Kuzel's salt, C₃A·(0.5CaCl₂)(0.5CaSO₄)·12H₂O, under these conditions. The binding relationships were best described by the Freundlich isotherm and binding coefficients are given for all the binders tested.     

The retarding action of sugars on cement hydration

Sugars retard the hydration of Portland cement. The effectiveness of different sugars is compared from studies of solution analysis, calorimetry, calcium binding ability and alkaline stability. The best retarders, sucrose and raffinose, have a remarkable ability to solubilize cement constituents and in particular give rise to dramatic increases in the amount of silica in solution. However, ¹³C and ²⁹Si N.M.R. do not reveal the existence of sucrose-silicate complexes. The retarding action of sugars is explained in terms of adsorption onto and poisoning of hydrate surfaces.     

The influence of superabsorbent polymers on the autogenous shrinkage properties of cement pastes with supplementary cementitious materials

Fly ash and blast-furnace slag containing binders are frequently used in the construction industry and it is important to know the extent of autogenous shrinkage and its (ideal) mitigation by superabsorbent polymers in these systems as a function of their age. In this paper, the autogenous shrinkage was determined by manual and automated shrinkage measurements. Autogenous shrinkage was reduced in cement pastes with the supplementary cementitious materials versus Portland cement pastes. At later ages, the rate of autogenous shrinkage is higher due to the pozzolanic activity. Internal curing by means of superabsorbent polymers is successful, independent of this long term higher rate of shrinkage in mixtures with supplementary cementitious materials.     

蔗糖和过磷酸钙作外加剂延缓水泥凝结时间的试验研究

用蔗糖和过磷酸钙分别作外加剂延缓水泥凝结时间的试验研究得出结论：蔗糖和过磷酸钙作为外加剂均可起到较好的缓凝效果，同时对水泥的后期强度也有一定的促进作用。     

氧化钙高温改性磷石膏对水泥基胶凝材料性能的影响研究*

磷石膏是磷化工产业过程中产生的固体废弃物，其主要成分为CaSO4 ·2H2O，具有产量大、组分复杂等特征，阻碍了其在胶凝材料中的应用。本研究利用氧化钙的碱性来去除磷石膏中的酸性杂质，探究氧化钙改性磷石膏的机理，对磷石膏水泥基胶凝材料的物理性能进行考察，结合SEM分析胶凝材料水化产物情况。结果表明：氧化钙能够消除磷石膏中的酸性杂质，减弱其对二水石膏晶体定向生长的抑制作用；掺入氧化钙后胶凝材料的安定性合格，初凝时间和终凝时间均下降；氧化钙的掺入有利于水泥基胶凝材料强度的发展，最佳的氧化钙掺量为2%；SEM结果显示，氧化钙消除了杂质的抑制作用，水化作用增强，层状的二水石膏晶体出现，有利于胶凝材料强度的发展。     

The activation and hydration of glassy cementitious materials

This paper summarizes the relationship among structure, composition, and activity of glassy cementitious materials with low-calcium additions including slag and fly ash (FA). On the basis of silicate physical chemistry, silicate structure chemistry, silicate crystal chemistry, and coordination chemistry theory, five levels of glass structure have been described. Their influence on the reactivity and hydration properties of slag and FA are discussed using SEM, X-ray diffraction (XRD), thermal gravimetry analysis (TGA), DSC-TG, and pore structure analysis. On the other hand, differences in activity between slag and FA are studied.     

胶凝材料水化热计算问题探讨

0引言 胶凝材料的水化热是进行大体积混凝土温度裂缝控制设计的主要参考因素,在没有条件对胶凝材料的水化热进行测量时,其主要靠选用拟合公式获得。为了弄清选用哪个拟合公式以及拟合公式中的参数是否需要调整等问题,需要对影响胶凝材料水化放热的因素以及各拟合公式中参数取值的情况进行分析。     

Effects of supplementary cementing materials on the properties of cement and concrete

The effect of bentonite, colemanite ore waste (CW), coal fly ash (FA) and coal bottom ash (BA) on the properties of cement and concrete has been investigated through a number of tests. The properties examined include setting time, bending strength, volume expansion, compressive strength and water consistency of the mortar. The result showed that setting time of the cements was generally accelerated when bentonite replaced a part of the cement. Bentonite exhibited a significant retarding effect when used in combination with CW in Portland cement at lower replacement level and showed an accelerating effect at higher replacement level. Although the inclusion of bentonite at replacement levels of 5-10% resulted in an increase in compressive strength at early ages, it decreased the compressive strength when used in combination with other materials. The results obtained were compared with Turkish standards and, in general, were found to be acceptable.     

Effect of supplementary cementitious materials on the compressive strength and durability of short-term cured concrete

This research focuses on studying the effect different supplementary cementitious materials (silica fume, fly ash, slag, and their combinations) on strength and durability of concrete cured for a short period of time—14 days. This work primarily deals with the characteristics of these materials, including strength, durability, and resistance to wet and dry and freeze and thaw environments. Over 16 mixes were made and compared to the control mix. Each of these mixes was either differing in the percentages of the additives or was combinations of two or more additives. All specimens were moist cured for 14 days before testing or subjected to environmental exposure. The freeze-thaw and wet-dry specimens were also compared to the control mix.Results show that at 14 days of curing, the use of supplementary cementitious materials reduced both strength and freeze-thaw durability of concrete. The combination of 10% silica fume, 25% slag, and 15% fly ash produced high strength and high resistance to freeze-thaw and wet-dry exposures as compared to other mixes. This study showed that it is imperative to cure the concrete for an extended period of time, especially those with fly ash and slag, to obtain good strength and durability. Literature review on the use of different supplementary cementitious materials in concrete to enhance strength and durability was also reported.     

The chemistry of hydration of high alumina cement in the presence of accelerating and retarding admixtures

The effect of accelerators, and in particular lithium salts and citric acid solutions, on the setting time of high alumina cement has been studied using calorimetry, solution analysis and X-ray diffraction techniques. Results are discussed with respect to the ternary CaOAl₂O₃H₂O solubility diagram. It appears that there is a nucleation barrier to the precipitation of the main products of hydration, CAH₁₀ and C₂AH₈ and that lithium salts function as accelerators by precipitation of a lithium aluminate hydrate which acts as a heterogenous nucleation substrate. It is suggested that retardation by citric acid is due to the precipitation of protective gel coatings around the cement grains which impede hydrolysis or inhibit growth of the hydration products.     

A new hydration kinetics model of composite cementitious materials,part 1: Hydration kinetic model of Portland cement

This work is the first part of an overall research project that aims to model the hydration kinetics of modern composite cementitious materials. The aim of this part is to build a hydration kinetic model to characterize the hydration behavior of cement at all ages. In this paper, the nucleation and growth of CSH and the diffusion of water are described by a modified BNG model and a modified Jander's model. The kinetic parameters are obtained by simulative fitting of the model to the experimental data. The linear functions between the nucleation and growth rates and the W/C ratios are given in this paper. The apparent activation energy of the nucleation rate constant, growth rate constant, and generalized diffusion constant are approximately 36.0, 37.5, and 42.0 kJ/mol, respectively. Finally, the phase compositions of hardened cement paste are calculated according to the kinetic model and the reaction formula of cement.     

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。     

Enhanced mechanical properties of wood ash and fly ash as supplementary cementitious materials

The incorporation of fly ash (FA) and wood ash (WA) in concrete as supplementary cementitious materials (SCM) was studied. The chemical composition of ordinary Portland cement, FA and WA was determined according to ASTM C-114. SEM and optical microscopy were used for the analysis of concrete. Setting time, compressive strength, water absorption and acid resistance of the concrete with different percentages of SCM ranging from 0 to 60% were evaluated. The results obtained showed that setting time and rate of water absorption increased with the increase in percentage of SCM. After 7 and 28 days, the compressive strength of concrete with 20% FA as SCM was higher than that with substitution with 20% WA. Resistance of concrete against sulphate attack increased with an increase in the percentage of FA. It was found that incorporating more than 20% WA resulted in a decrease in sulphate attack resistance.     

BSE-IA reveals retardation mechanisms of polymer powders on cement hydration

The retardation effects of two polymer powders, styrene butadiene rubber and ethylene-vinyl acetate, on cement hydration and the mechanisms in terms of hydration degree and microstructure characteristics were investigated by the combination of backscattered electron image analysis, scanning electron microscopy, energy dispersive spectrometer, and X-ray diffraction. Results show that the cement hydration can be significantly retarded by both polymers with the reductions in cement hydration degrees and hydration products thickness. Polymers retard cement hydration by agglomerating the polymer particles on the surfaces of cement grains, forming films in different thickness and bonding the calcium ions in the pore solutions. Consequentially, the formation of C-S-H and CH is depressed and the Ca/Si ratios in the hydration product layer are raised. The retardation is enhanced with the increase in polymer content. This work helps understand the retardation effect of polymers on cement hydration in depth, which enables rational development of polymer-modified cement-based materials for further applications.     

氧化石墨烯对水泥水化产物及聚集状态的调控作用

通过对石墨的氧化及超声波分散制备了氧化石墨烯(GO)纳米片层,采用FTIR、XPS、SEM、AFM对其结构进行了表征。测试结果表明:GO纳米片层尺寸为100~800 nm,GO上羟基和羧基的质量分数分别为22.1%和29.4%。将GO掺入水泥基复合材料,在GO的加入质量为水泥质量的0.03%时,水泥基体主要由多面体状晶体通过交织、嵌入等方式聚集而成,形成了具有花型形貌的微观结构,与空白样比较,其28 d时平均抗折强度和抗压强度分别增加了93.9%和80.0%。     

煤矸石制备水泥辅助胶凝材料的应用研究

煤矸石制备水泥辅助胶凝材料的应用研究对水泥行业的节能减排与大宗固废的高值利用均具有重要意义。本文以河北某地不同矿区的6种煤矸石为原料,采用XRD,热重等方法分析判断其化学成分和矿物组成,通过静态煅烧实验研究了其煅烧活化条件,并通过胶砂实验测定其胶凝活性。结果表明,煅烧温度和时间会影响产品的胶凝活性,不同矿物组成的样品需要的煅烧条件不同,所测样品其3 d早期强度相较于基准水泥有所下降,但28 d活性指数增长明显,除#4矿区外均达到了制备辅助胶凝材料的要求。     

The effect of acid treatment on the reactivity of natural zeolites used as supplementary cementitious materials

This work investigated the use of acid treatment as a method for increasing the reactivity of natural zeolite used as a supplementary cementitious material. The effects of treating a natural clinoptilolite zeolite with nine acid solutions, 0.1 M, 0.5 M, or 1 M hydrochloric or nitric acid or 0.1 M, 0.5 M, or 0.87 M acetic acid, were measured using x-ray diffraction, particle size analysis, pore size distribution and surface area analysis. The zeolite pozzolanic reactivity was determined by measuring the quantity of portlandite in hydrated zeolite-cement paste after 28 and 90 days. Results showed that acid treatment increased zeolite surface area, resulting in increased zeolite pozzolanic reactivity, independent of the solution concentration used. Cement hydration was also increased, evidenced by greater rates of heat evolution from cement-zeolite pastes. Additionally, although reductions of portlandite occurred most quickly in pastes with zeolites treated with strong acids, by 90 days the zeolites treated with acetic acid solutions showed comparable portlandite reductions.     

多组分水泥基材料的水化放热行为

研究了复掺粉煤灰、矿渣、硅灰的多组分水泥基材料的水化放热行为。研究结果表明,与纯P·O42.5水泥水化放热行为不同的是,多组分水泥基水化体系的诱导期延长,加速期和减速期的出现推迟,并且明显降低各水化阶段的水化放热速率,第2放热峰的出现发生了明显的推迟;温度为303K时,多组分体系的第2放热峰可细化成2个小峰,分别对应于熟料和掺合料的水化;323K下由于温度作用,矿物掺合料和水泥熟料的水化速率差距减小,第2放热峰基本没有明显分化现象;矿物掺合料的种类和掺量对多组分体系水化放热行为有较大影响,尤其是掺加硅灰时,早期水化速率明显增加。     

Impact of sand and filler materials on the hydration behavior of calcium aluminate cement

In earlier work, we have observed discrepancies relating to the early hydration of calcium aluminate cement (CAC) when comparing data from heat flow calorimetry of CAC paste with results from mortar strength tests using the crushing method. Here, we investigated on this phenomenon and found that the sand which is used as a filler exerts a major influence on CAC hydration resulting in acceleration. Furthermore, in particular fine filler materials such as, for example, microsilica, fine limestone powder, and especially α- and γ-Al₂O₃ also produced a strong hydration accelerating effect which is dependent on their specific surface area. The mechanism underlying the acceleration is that under alkaline conditions their negative surface charge attracts calcium ions as was confirmed via inductively coupled plasma atomic emission measurements. Such a layer generates favourable conditions for the nucleation of CAC hydration products (C-A-H phases). The resulting crystalline hydrates which form on the surface of the filler particles submerged in CAC cement pore solution were visualized via SEM imaging. This way, specifically selected fillers can significantly accelerate CAC hydration and save precious lithium salts which are commonly used to boost the early strength of CAC.