Hydration study of limestone blended cement in the presence of hazardous wastes containing Cr(VI)

Considering the increasing use of limestone cement manufacture, the present paper tends to characterize limestone behavior in the presence of Cr(VI). The research reported herein provides information regarding the effect of Cr(VI) from industrial wastes in the limestone cement hydration.The cementitious materials were ordinary Portland cement, as reference, and limestone blended cement.The hydration and physicomechanical properties of cementitious materials and the influence of chromium at an early age were studied with X-ray diffraction (XRD), infrared spectroscopy (FTIR), conductimetric and mechanical tests. Portland cement pastes with the addition of Cr(VI) were examined and leaching behavior with respect to water and acid solution were investigated.This study indicates that Cr(VI) modifies the rate and the components obtained during the cement hydration.     

纳米氧化铝对硅酸盐水泥浆体流变、水化和硬化强度的影响

本文研究了纳米氧化铝(NA)对硅酸盐水泥浆体的早期流变性、中期水化特性和后期力学性能的影响,并且分析了三个阶段之间参数的相关性。结果表明,NA的掺入增大了新拌水泥浆体的屈服应力和塑性黏度,且当NA掺量范围为3%~5%时,屈服应力和塑性黏度最大增幅均超过110%。在水泥浆体中掺入NA明显改变了硅酸盐水泥早期的水化放热速率和放热量,并且使得浆体在各龄期的抗压强度和抗折强度有所增长。对于该复合胶凝体系,早期的水化放热量与流变参数呈指数增长的变化趋势,而放热峰值速率与抗压强度则存在近似线性的函数关系。     

The influence of municipal solid waste incinerator fly ash slag blended in cement pastes

This study investigates the effect of mixing Type I, Type II, and Belite cements with municipal solid waste incinerator (MSWI) fly ash slag-blended cement (FASBC). The experimental results showed that a 10-40% slag replacement of by caused an increase in the initial and the final setting time. The toxicity characteristic leaching procedure (TCLP) results show that the heavy metal content met the Environmental Protection Administration (EPA) regulatory limits. From the results, it can be seen that the effect of the replacement of 10-40% of the cement by slag caused an increase in the initial and final setting time. Compressive strength results indicate that the slag-blended cement (SBC) pastes had slower compressive strength development in the early stages, but this strength obviously increased at later ages. Variations in the Portland cements can affect early strength development but have no significant effect on the degree of hydration at later ages. MSWI slag gives a relatively slower increase in early strength but may show a greater degree of reaction at later ages.     

Alkali binding in hydrated Portland cement paste

The alkali-binding capacity of C-S-H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C-S-H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data reported in literatures concerning thirteen different recipes are analyzed and used as references. A three-dimensional computer-based cement hydration model (CEMHYD3D) is used to simulate the hydration of Portland cement pastes. These model predictions are used as inputs for deriving the alkali-binding capacity of the hydration product C-S-H in hydrated Portland cement pastes. It is found that the relation of Na⁺ between the moles bound in C-S-H and its concentration in the pore solution is linear, while the binding of K⁺ in C-S-H complies with the Freundlich isotherm. New models are proposed for determining the alkali-binding capacities of C-S-H in hydrated Portland cement paste. An updated method for predicting the alkali concentrations in the pore solution of hydrated Portland cement pastes is developed. It is also used to investigate the effects of various factors (such as the water to cement ratio, clinker composition and alkali types) on the alkali concentrations.     

Properties of Portland Cement Pastes Incorporating Nanometer-Sized Franklinite Particles Obtained from Electric-Arc-Furnace Dust

The present work presents preliminary results concerning ordinary portland cement (OPC) blended with electric-arc-furnace dust (EAFD) obtained from steel-smelting plants. The powder obtained after acid treatment of the EAFD consisted basically of nanometer-sized particles of ZnFe₂O₄. Incorporation of the EAFD in the OPC produced retardation of the setting process. Nevertheless, after 7 d, the compressive strength of the OPC/EAFD pastes was superior to undoped OPC, and, after 28 d, the extent of hydration of the OPC/EAFD pastes was equivalent to undoped OPC. A compressive strength of 72 MPa was attained after 42 d for OPC doped with 10 wt% EAFD.     

Influence of time addition of superplasticizers on the rheological properties of fresh cement pastes

It is well known that the fluidity and the fluidity loss of fresh cement pastes are affected by the kind and the time of addition of organic admixtures. The influence of the time addition of two chemical admixtures, namely, melamine formaldehyde sulfonate (MFS) and naphthalene formaldehyde sulfonate (NFS), on the rheological properties of ordinary Portland and sulfate-resisting cement pastes through the first 120 min of hydration was investigated. The admixture addition was delayed by 0, 5, 10, 15, 20, and 25 min. Shear stress and apparent viscosity of the cement pastes were determined at different shear rates (3-146 s⁻¹) and hydration times of 30, 60, 90, and 120 min. The concentration of Ca²⁺ and the combined water content of the cement pastes were determined after 120 min. Yield stress and plastic viscosity values were also determined by using the Bingham model. The results show that an increase in the addition time of the admixture reduces the shear stress, the yield stress, and the plastic viscosity of the cement pastes at the early ages (15 min) as well as at later early ages (120 min). The optimum delaying time of admixture addition is found to be 10-15 min. This time does not depend on the cement and superplasticizer type.     

粉煤灰水泥硬化浆体微结构的交流阻抗研究

采用交流阻抗方法对掺有粉煤灰的水泥硬化浆体的微结构及对不同龄期粉煤灰水泥硬化浆体的交流阻抗参数和硬化水泥浆体微结构的关系、抗压强度进行了研究,并与纯硅酸盐水泥体系进行了比较。结果表明,与纯硅酸盐水泥相比,粉煤灰水泥水化后期的水化程度较高,浆体总孔隙率较低。     

重金属污泥磨细粉对硅酸盐水泥基材料性能的影响

为了更好地实现对重金属污泥的资源化利用,研究了高温无害化处理重金属污泥与建筑渣土混合渣料磨细粉对硅酸盐水泥基材料工作性、力学性能、早期收缩变形、抗氯离子渗透性能及重金属浸出的影响及机理。研究结果表明,随着磨细粉掺量的增加,硅酸盐水泥基材料的工作性没有降低,但其力学性能均有一定程度下降,这说明磨细粉与硅酸盐水泥的需水比相差不大,但其掺量越大水泥基材料中水泥的量越低,其强度均会有一定程度下降。磨细粉不会引起硅酸盐水泥基材料的体积安定性问题,可以提高早期抗裂性,但会降低其抗氯离子渗透性能。含磨细粉试件中重金属的浸出浓度、水胶比的下降与龄期的上升呈负相关,且在28 d龄期下含40%(质量分数)磨细粉的硅酸盐水泥基材料中重金属Cu、Ni、Zn和Cr的浸出量均低于GB 30760—2014《水泥窑协同处置固体废弃物技术规范》规定的浸出浓度限值。     

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。     

Monitoring Portland cement hydration: Comparison of methods

Various experimental methods of monitoring Portland cement hydration are compared. The methods are quantitative X-ray diffraction analysis (QXRD), measurement of non-evaporable water as loss on ignition and by thermogravimetry, conduction calorimetry and measurement of chemical shrinkage. Correlations between these different measures of hydration are obtained using samples of paste for three different Portland cements. The correlation between non-evaporable water and QXRD data was dependent on the chemical composition of the cement and shows that less water was chemically bound at early ages, for a given amount of cement reacted. A near-linear relationship was found between chemical shrinkage and QXRD data. The correlation between heat of hydration and QXRD data was approximately linear and not greatly affected by cement type.     

碳化过程中大水灰比水泥浆体孔结构的变化(英文)

使用特殊的增黏剂与聚羧酸减水剂,制备了掺加石灰石粉、高炉矿渣、硅灰等混合材的普通波特兰水泥浆体和和低热硅酸盐水泥浆体(水粉比为1.0)。这些水泥浆体在20℃的水中养护4年后基本完全水化。这些硬化水泥浆体在5%(质量分数)CO2、相对湿度66%和温度20℃条件下进行碳化,对比研究碳化前后水泥浆体孔结构的变化。结果显示:碳化浆体内孔直径大于10nm的孔体积明显减少;碳化浆体的孔径分布向大孔径范围偏移;掺加混合材的硬化水泥浆体结构明显趋于松散;与不掺加任何混合材的水泥浆体相比,掺加混合材的水泥浆体的孔径更大。     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

A porosimetric study of calcium sulfoaluminate cement pastes cured at early ages

Calcium sulfoaluminate and Portland cement pastes, both prepared with a water/solid mass ratio equal to 0.5 and cured for time periods comprised between 2 h and 28 days, show completely different pore size distributions by mercury intrusion. Portland cement pastes aged at 12 h and 1 day exhibit a unimodal distribution of pore sizes related to a continuous network of capillary pores with a threshold pore radius decreasing from nearly 650 to 350 nm. After 7 and 28 days of curing, this parameter shifts to about 150 nm and a region having smaller pores appears (with a second threshold pore radius roughly comprised between 10 and 30 nm), made discontinuous by blockages of hydration products which occlude the interconnected pore system and isolate the interior space. For calcium sulfoaluminate cement pastes, a bimodal distribution is rapidly established, in which the regions with a lower porosity (threshold pore radii up to about 25 nm) are dominant, while the decrease of total porosity almost ceases at later ages. The porosimetric behaviour of calcium sulfoaluminate-based cement is related to its very fast hydration rate and to the lack of water needed to continue the hydration reactions.     

Hydration kinetics modeling of Portland cement considering the effects of curing temperature and applied pressure

A hydration kinetics model for Portland cement is formulated based on thermodynamics of multiphase porous media. The mechanism of cement hydration is discussed based on literature review. The model is then developed considering the effects of chemical composition and fineness of cement, water-cement ratio, curing temperature and applied pressure. The ultimate degree of hydration of Portland cement is also analyzed and a corresponding formula is established. The model is calibrated against the experimental data for eight different Portland cements. Simple relations between the model parameters and cement composition are obtained and used to predict hydration kinetics. The model is used to reproduce experimental results on hydration kinetics, adiabatic temperature rise, and chemical shrinkage of different cement pastes. The comparisons between the model reproductions and the different experimental results demonstrate the applicability of the proposed model, especially for cement hydration at elevated temperature and high pressure.     

Water dynamics in cement paste at early age prepared with pozzolanic volcanic ash and Ordinary Portland Cement using quasielastic neutron scattering

Early age hydration kinetics of Portland cement with pozzolanic volcanic ash was examined using quasielastic neutron scattering. Volcanic ash consisting of two different particle sizes was used to prepare cement pastes with different ratios of Portland cement to volcanic ash. The concentration of the volcanic ash played a major role in the bound water index and self-diffusion coefficients of hydration water confined in the cement paste. An increase in the particle size of the volcanic ash affected the degree of hydration by allowing more free and mobile water in the gel pores, suggesting that volcanic ash may not have completely reacted during the experimental time frame. This study shows that the particle size along with variation in volcanic ash composition governs the early age hydration process in volcanic ash cements.     

利用城市垃圾焚烧飞灰开发新型生态水泥混合材料

研究了城市垃圾焚烧飞灰的化学成分及矿物组成，以及掺入水泥后对水泥浆体的凝结时间和力学性能的影响；并借助SEM、XRD和ICP等测试手段对硬化水泥浆体的微观结构、水化产物和重金属的浸出与固化机理进行了研究，探索了将城市垃圾焚烧飞灰开发成新型混合材料的可行性。     

-3 ℃养护下考虑矿物掺合料影响的水泥水化程度计算模型

针对多年冻土地区工程施工时混凝土养护的问题,采用10%、20%、30%的矿粉和粉煤灰替代量等量替代水泥,测试了-3 ℃恒温养护条件下0.38水胶比水泥浆体在各个龄期的水泥水化热,计算了水泥水化程度;分析了龄期及矿物掺合料对水泥水化程度的影响规律,建立了综合考虑龄期和矿物掺合料替代量的水泥水化程度计算模型.结果表明:-3 ℃恒温养护下,矿物掺合料等量替代水泥,水泥浆体的水化程度会降低,粉煤灰降低水化程度的值要比矿粉高;在相同矿物掺合料替代量下,随着龄期的增长,矿物掺合料对水泥水化程度的影响逐渐减弱;同一龄期时,随着矿物掺合料的增加,矿物掺合料对水泥水化程度的影响逐渐增强;利用建立的模型计算了分别掺入15%矿粉和粉煤灰的水泥水化程度,与实测值相比,计算值偏离值较少,预测精度较高.     

石膏掺量对高阿利特水泥防腐抗渗性能的影响研究

研究了石膏掺量对高阿利特水泥抗海水侵蚀和抗渗性能的影响,并与普通水泥进行了比较。利用XRD、SEM—EDS等测试方法对水泥水化产物的物相组成和形貌进行分析、观察;用压汞法对水泥硬化浆体的孔结构进行了分析。结果表明,石膏掺量对高阿利特水泥硬化浆体的致密性有较大影响,进而影响水泥砂浆的抗海水侵蚀性能,石膏的适宜掺量为5％,在此掺量下高阿利特水泥的抗蚀系数达1．01,而普通水泥的抗蚀系数仅为0．87,高阿利特水泥的有害孔较少,总孔隙率较低,抗渗性能得到较大改善。     

High intakes of Cr, Ni, and Zn in clinker: Part II. Influence on the hydration properties

This work presents the results of the hydration of cements with high intakes of Cr, Ni, and Zn. The cements were produced from clinkers that were doped with 200 to 25,000 ppm of heavy metal. Investigations on the clinkers were presented in Part I. In this paper the rate of heat generation of the cements in the first 2 days was analysed by differential scanning calorimetry. The hydration products were investigated by scanning electron microscopy combined with energy-dispersive X-ray spectrometer and also by X-ray powder diffraction. The initial setting of some samples was tested, as well as the strength. The results show that heavy metals only have an influence on the hydration properties of the cements if the dosage is much higher than in ordinary Portland cement.