Modeling the linear elastic properties of Portland cement paste

The linear elastic moduli of cement paste are key parameters, along with the cement paste compressive and tensile strengths, for characterizing the mechanical response of mortar and concrete. Predicting these moduli is difficult, as these materials are random, complex, multi-scale composites. This paper describes how finite element procedures combined with knowledge of individual phase moduli are used, in combination with a cement paste microstructure development model, to quantitatively predict elastic moduli as a function of degree of hydration, as measured by loss on ignition. Comparison between model predictions and experimental results are good for degrees of hydration of 50% or greater, for a range of water : cement ratios. At early ages, the resolution of the typical 100³ digital microstructure is inadequate to give accurate results for the tenuous cement paste microstructure that exists at low degrees of hydration. Elastic computations were made on higher resolution microstructures, up to 400³, and compared to early age elastic moduli data. Increasing agreement with experiment was seen as the resolution increased, even when ignoring possible viscoelastic effects.     

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 Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC.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.     

Comparison of methods for arresting hydration of cement

Arresting of cement hydration, followed by drying, is necessary to prepare samples for many techniques of microstructural analysis. This paper reviews the effects on microstructure and composition of cement paste caused by the most common drying techniques, including direct drying (oven, microwave, D-drying, P-drying, and freeze drying) and solvent exchange methods. Supercritical drying is proposed as a method that could effectively preserve the cement microstructure, but which has not been applied to cementitious materials. Experiments are reported that systematically quantify the effects of drying from several solvents, freeze drying, and direct drying of young paste. Freeze drying is an effective drying method to prepare samples for chemical analysis, but it might change the microstructure. Isopropanol exchange followed by ambient drying is the best known method for preserving the microstructure with minimal effect on the composition of cement.     

三异丙醇胺对石灰石硅酸盐水泥的水化机理及微观结构的影响

通过水泥净浆和砂浆强度试验、测量水化热、硬化水泥浆体的热分析、微观结构的扫描电镜观察和孔结构的测量,研究了三异丙醇胺（triisopropanolamine,TIPA）对石灰石硅酸盐水泥强度、水化过程和硬化水泥浆体的微观结构的影响。结果表明：掺加TIPA能够显著提高石灰石硅酸盐水泥净浆和砂浆的后期强度;TIPA对C4A...     

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。     

Experimental study and numerical simulation on the formation of microstructure in cementitious materials at early age

The formation of microstructure in early age cement paste and concrete was examined with an ultrasonic experimental set-up. Research parameters included the influence of curing temperature (isothermal curing at 20, 30 and 40 °C), water/cement ratio (0.40, 0.45 and 0.55) and amount of aggregate. In parallel with the experiments, the cement hydration model HYMOSTRUC was utilized to simulate the formation of the microstructure. In this study, the cement paste was considered as a four-phase system consisting of water, unhydrated cement, hydration products and that part of the hydration product that causes the contact between the hydrating cement grains (so called “bridge volume”). A correlation has been found between the growth of bridge volume calculated with the model and the changes in the pulse velocity. It is believed that ultrasonic pulse velocity (UPV) measurements can represent a valuable tool to investigate the development of the microstructure at early age.     

掺石灰石粉水泥的水化过程及微观结构

用微量热仪测定了含石灰石粉水泥浆体的水化放热。用扫描电镜观察了掺石灰石粉水泥硬化浆体的微观结构。试验结果表明:一定细度的石灰石粉可加速水泥的水化,掺石灰石粉水泥的水化放热量低于不掺石灰石粉水泥的水化放热量。水泥硬化浆体中沿着石灰石粉片状方解石晶体的边缘容易形成平整断面。     

Quantitative analysis of the microstructure of interfaces in steel reinforced concrete

This article reports the results of a backscattered electron imaging study of the microstructure of the steel– and aggregate–cement paste interfaces in concrete containing 9 mm ribbed reinforcing bars. The water to cement (w/c) ratio, hydration age, steel orientation, and surface finish were varied. For vertically cast bars, there was more calcium hydroxide (CH) and porosity and less unreacted cement at both the steel– and aggregate–cement paste interfaces when compared to the bulk cement paste. As the hydration age increased, the porosity near the interfaces decreased, and the CH increased with more CH close to the steel than to the aggregate. Horizontal bars had more porosity and less CH under them than above. An increase in the w/c ratio produced interfaces of higher porosity and lower levels of CH. Wire-brush cleaned bars had higher levels of CH at the steel–cement paste interface at 365 days when compared to uncleaned bars.     

Mechanism for performance of energetically modified cement versus corresponding blended cement

The microstructure of cement paste of 50/50 mixes of cement/quartz and cement/fly ash, both ground in a special mill [energetically modified cement (EMC) process] and simply blended, have been studied under sealed curing conditions. The grinding process reduced the size of both cement grains and quartz/fly ash markedly and created flaky agglomerates of high inner surface for the finer particles. EMCs had much higher degree of hydration at 1 day, but similar as blends at 28 days. The pores were much finer for EMC paste due to smaller particles as also reflected in the strength. The morphology of calcium hydroxide in EMC paste appeared more mass like. Pozzolanic reaction was insignificant for quartz in EMC, but increased for fly ash. Thus, improved performance of EMC versus OPC can be explained by increased early hydration and extensive pore size refinement of the hardened binder resulting in reduced permeability and diffusivity for concrete.     

Study on the high‐temperature behavior and rehydration characteristics of hardened cement paste

The high‐temperature behavior and rehydration characteristics of the hardened cement paste and their mechanisms have been studied in this paper. X‐ray diffraction and thermogravimetry are used to establish the effect of elevated temperatures on the mineralogical changes that occurred in the hardened cement paste. The change of microstructure was characterized by scanning electron microscopy. The results showed that with the temperature increased, the compressive strength of hardened cement paste first increased and then decreased. According to micromeasurements, at 400°C, the porosity and average pore diameter of hardened cement paste increased slightly, while at 800°C, the porosity and average pore diameter of hardened cement paste increased sharply. When hardened cement paste was cured after exposing to 400°C, its pore structure and phase composition had no change, while when hardened cement paste was cured after exposing to 800°C, there are new hydration products, and its pore structure may be finer, but it cannot fully recover to the original state. Copyright © 2014 John Wiley & Sons, Ltd.     

CoFeMgAl-LDHs/CNTs复合材料对水泥水化及微观结构的影响

通过进行水化热测试、非蒸发水含量测试、X射线衍射分析、扫描电镜分析、压汞测试及强度试验,研究了钴铁镁铝水滑石-碳纳米管复合材料(CoFeMgAl-LDHs/CNTs)对水泥水化过程、硬化水泥净浆孔结构及强度的影响。结果表明,CoFeMgAl- LDHs/CNTs复合材料通过成核作用显著提升了水泥3 d内的水化程度,从而显著提高了水泥净浆3 d内的抗压强度,3 d后强度提高效果逐渐减小,7 d后复合材料对硬化水泥浆体强度没有明显的提高作用。掺入CoFeMgAl-LDHs/CNTs复合材料的水泥净浆与空白净浆相比,胶凝孔和毛细孔含量明显增多,大孔含量有所降低,同时复合材料的桥联作用进一步优化了水泥净浆的微观结构,从而提高了水泥基体薄弱部位的应力承载能力。因此在同一龄期,复合材料掺入后硬化水泥净浆的强度有所增大。由于复合材料掺量的变化对孔径分布没有明显的影响,改变复合材料的掺量对同龄期硬化水泥净浆强度提升影响较小。     

Influence of hydration on the fluidity of normal Portland cement pastes

The rheological properties of cement paste strongly influence the workability of concrete. It is known that early hydration processes alter phase composition and microstructure of cement pastes. These processes affect fluidity and setting behaviour of cement paste. While many studies tried to measure and model rheological properties of cement pastes, only a few studies assessed the influence of the hydrate morphology on the fluidity of cement pastes.Results of the present study compare the influence of long prismatic hydrates (i.e. syngenite, secondary gypsum) on the fluidity of cement pastes with the effect of other hydrates (AFm).To induce the formation of certain hydration products the cement composition was modified by addition of set regulators and alkali sulphates. Furthermore a combination of various analytical methods such as fluidity (viscometric) testing and microstructural analysis (phase quantification by XRD-Rietveld analysis, investigation by Environmental SEM, BET analysis etc.) was performed. Results are implemented into a fundamental discussion on the influence of various hydration products on the fluidity of the paste.     

玻璃粉水泥浆的初期水化产物和浆体结构

采用SEM、XRD研究了玻璃粉水泥浆的初期水化产物、浆体结构.并用化学结合水量和有效结合水法来定性和定量分析玻璃粉对水化初期复合体系及水泥的促进或抑制作用以及作用程度.研究表明:在水化反应初期(1d内),因为玻璃粉的掺入既由此而产生的稀释作用使有效水灰比增加而产生的对水泥熟料水化的促进作用,因此,硅酸盐水泥熟料的水化程度较高,但从整体来看,大掺量(50%)的玻璃粉延缓了复合胶凝材料总水化程度;水化开始(6 h~1 d)时,水化反应开始加速进行,水化产物的数量迅速增加,主要为纤维状CSH凝胶、针棒状钙矾石晶体和Ca(OH)2,这些水化产物彼此间相互搭接、交错生长,部分未水化的水泥颗粒镶嵌其中,并将玻璃粉粘结成整体,构成体系骨架.     

Microstructurally-designed cement pastes: A mimic strategy to determine the relationships between microstructure and properties at any hydration degree

This paper proposes a new strategy to study the relationships between cement paste microstructure and its properties. In this perspective, microstructurally-designed cement pastes are produced by replacing a specific part of the actual binder by inert particles of similar fineness. This strategy is referred to as ‘mimic’ in this paper. It is shown that, after complete hydration of the reactive part, the microstructure obtained, in which the inert particles play the role of unhydrated binder particles, exhibits similar properties as a cement paste at a lower hydration degree. The concept is tested and validated on pore profile measured by mercury intrusion porosimetry and compressive strength. The same concept could be applied to other properties. In particular, the obtained materials are fully hydrated, which allows performing time-consuming testing (such as e.g. creep and drying-shrinkage tests) on microstructures equivalent to low degrees of hydration, which would not be possible on the hydrating material counterparts.     

Modeling of hydration reactions using neural networks to predict the average properties of cement paste

This paper presents a hydration model that describes the evolution of cement paste microstructure as a function of the changing composition of the hydration products. The hydration model extends an earlier version by considering the reduction in the hydration rate that occurs due to the reduction of free water and the reduction of the interfacial area of contact between the free water and the hydration products. The BP Neural Network method is used to determine the coefficients of the model. Using the proposed model, this paper predicts the following properties of hardening cement paste: the degree of hydration, the rate of heat evolution, the relative humidity and the total porosity. The agreement between simulation and experimental results proves that the new model is quite effective and potentially useful as a component within larger-scale models designed to predict the performance of concrete structures.     

The influence of admixed micelles on the microstructural properties and global performance of cement-based materials

In this study, the influence of the admixed micelles (poly(ethylene oxide)-block-polystyrene micelles) on the microstructure and hydration rate of cement paste and more global performance of mortar were investigated. In cement paste, the cement hydration rate was only slightly influenced by the admixed micelles; on the other hand, the micelles lead to a reduced porosity and a denser matrix. The nano indentation combined with MIP and microstrutural analyses proves that the admixed micelles lead to a more uniform distribution of hydration products. In mortar, the compressive strength of the micelle-containing mortar was almost unaffected; the coefficient of water permeability was 3 orders of magnitude lower for the micelle-containing specimens, compared to the control (micelle-free) specimens. All experimental results indicate that the micelles act as nucleation sites for the formation of new hydration products and possibly induce defloculation of un-hydrated cement particles, resulting in a more uniform and homogeneous cement matrix.     

硫酸腐蚀后油井水泥石的性能及微观结构

研究了硫酸对油井水泥石强度及微观结构的影响。结果表明：水泥石被硫酸腐蚀后,强度明显下降,硬化浆体中100 nm以上有害孔的数量显著增多,水化产物变得疏松多孔,硬化水泥浆体的物相组成发生变化,有新的腐蚀产物CaSO4·2H2O生成;水泥石抵抗酸性介质腐蚀的能力不仅与其致密程度有关,还与其硬化浆体的矿物组成密切相关;不同水化产物抵抗腐蚀的能力不同,Ca（OH）2比C-S-H凝胶更容易受到酸性介质的腐蚀;C-S-H凝胶被腐蚀后产生的孔隙主要是细小孔隙,而Ca（OH）2被腐蚀后产生的孔隙主要是100 nm以上有害孔,降低硬化浆体中Ca（OH）2的含量是提高水泥石抗腐蚀性能的关键。     

钢渣作为混合材在复合水泥中的应用

对钢渣作为一种混合材在复合水泥中的综合利用进行了研究,并通过X线衍射(XRD)、扫描电镜(SEM)、水化热测试、孔结构测试等现代物相检测手段,揭示钢渣复合水泥微观结构与宏观性能之间的内在联系。结果表明:钢渣能显著降低水泥的水化热,降低水泥的标准稠度用水量;钢渣水泥浆体线膨胀率很小,均没有超过0.1%,体积稳定性良好;一定掺量混合材能有效降低浆体孔隙率,改善孔径分布,提高浆体致密度;复合掺加20%钢渣、10%粉煤灰时,水泥的28 d抗折、抗压强度分别达到了8.3、48.9 MPa;钢渣和粉煤灰复合掺加有利于水泥强度发展。     

水泥浆体的微结构及其与强度的关系

在亚微观尺度上描述了水泥石的微结构，简要回顾了其研究进程，详细介绍了主要水化产物以及掺加不同混合材可改变水化产物组分含量。归纳了水泥石的微观结构与强度的关系，并展望了其研究前景。     

Microstructure of tricalcium silicate and Portland cement systems at middle periods of hydration-development of Hadley grains

The development of the microstructure of C₃S paste and a Portland cement paste was studied between 7 and 24 h by means of backscattered electrons in a field-emission SEM. The course of hydration was measured by isothermal calorimetry. While the abundant occurrence of Hadley grains (hollow-shells) in Portland cement systems is well documented from a number of SEM and other microscopy studies, some earlier reports have noted that Hadley grains do not form in C₃S or alite paste alone. This report shows evidence of Hadley grains in C₃S paste, and follows their development from middle to late hydration stages. At around 10 h the microstructure with respect to Hadley grains were seen to develop in a very similar manner in C₃S and cement. In both systems, a narrow gap often developed between the receding anhydrous cores and layer of reaction product enveloping the cores. By 1 day, Hadley grains had continued to develop only in the cement paste, where they became a prominent feature. Only small ‘hollowed-out’ hydration shells were observed in the C₃S paste by 1 day. These were presumably reminiscences of the small gapped Hadley grains seen at the earlier hydration stages.