3D Nanotomography of calcium silicate hydrates by transmission electron microscopy

Calcium silicate hydrate (C-S-H), is the principal hydration product of Portland cement that mainly contributes to the physical and mechanical properties of concrete. This paper aims to investigate the three-dimensional structure of C-S-H with Ca/Si ratios of 1.0 and 1.6 at the nanoscale using electron tomography. The 3D reconstructions and selected region of interest analysis confirm that the morphology of both C-S-H materials are foil-like structures. The difference between the two materials is the density of elongated structures. C-S-H with Ca/Si ratio 1.6 is clearly composed of denser particles compared to the other C-S-H material due to overlapping of the foil-like structure. Pore analysis shows that C-S-H 1.0 and C-S-H 1.6 have porosities 69.2% and 49.8% respectively. Pore size distribution also reveals that C-S-H 1.0 has pore size range between 0-250 nm and C-S-H 1.6 between 0-100 nm. The pore network's size of C-S-H 1.0 is significantly larger than 1.6. This study illustrates the capability of using electron tomography to determine the 3D nanoscale structure of cementitious products and to distinguish between C-S-H 1.0 and 1.6.     

纳米C-S-H对矿粉-水泥体系水化的影响

C-S-H是通用硅酸盐水泥主要的水化产物,对水泥基材料的性能起着十分重要的作用,但水泥水化产物复杂,难以从水化产物中分离出纯净的C-S-H并研究其对水泥基材料的影响。故本文通过双分解法制备了纳米C-S-H(NC)颗粒,并将其掺入矿粉-水泥体系中,通过无接触式电阻率测定仪、X射线衍射仪、差热分析仪(DSC-TG)、扫描电镜、压汞测试仪(MIP)等探究了NC对矿粉-水泥体系水化的影响。研究发现,在1%~4%(质量分数)掺量范围内,掺入NC可缩短基体的凝结时间,并为水泥早期水化提供更多的活性位点,加速水化产物的形成和沉淀,促进水化产物之间的搭接,从而降低了基体孔隙率并使基体早期强度和水化浆体电阻率均有所提升。     

激发条件对脱硫石膏-矿渣体系水硬强度的影响

利用正交实验研究了硅酸盐水泥和其他两种矿物组分复合激发对脱硫石膏-矿渣体系强度的影响,用SEM、XRD分析了水化样品的微观结构.研究结果表明:硅酸盐水泥等多组分复合激发下,脱硫石膏-矿渣体系在水中标准条件养护,3 d抗压强度达17 MPa以上,28 d抗压强度达58 MPa以上.复合激发剂3种组分的优化组合为6:6:5,复合激发剂的用量为脱硫石膏-矿渣体系质量的17%左右.脱硫石膏-矿渣体系在复合激发条件下的水化产物主要是钙矾石和C-S-H.大量钙矾石、石膏晶体相互交叉连生,未水化石膏、矿渣颗粒所填充其间,在C-S-H凝胶的胶结下,形成了较为致密的晶胶搭配构成的微观结构.     

Effect on fresh C-S-H gels of the simultaneous addition of alkali and aluminium

Reducing Portland cement content in cementitious binders offers a means to address the adverse environmental impacts of Portland cement manufacture. This paper investigates the impacts on hydration product chemistry of partially replacing Portland cement with alkali-activated aluminosilicates. Here, short-term effects of soluble alkali and aluminium, likely to be available in an alkali-activated system, on the structure of synthetic C-S-H gels are assessed. .C-S-H gels (synthesized at pH values of over 13) were mixed with different concentrations of aluminium nitrate and sodium hydroxide. The gels were characterized by FTIR, TEM/EDX and XRD 72 h later. The results showed that both alkali and aluminium increased the degree of silicate polymerisation in the C-S-H gels and precipitated a crystalline calcium aluminosilicate phase.     

Phase equilibria of hydrated Portland cement

A model is described for predicting the equilibrium phase assemblage in hydrated Portland cement and for calculating the relative contents and composition of phases present in the assemblage, from the chemical composition of the cement and the water/cement ratio. The method is also used to calculate the content of capillary pores using the best available data for the densities for each of the phases. These calculations were carried out on three different Portland cements (two white Portland cements and one grey) at water/cement ratios of 0.70. Energy dispersive spectroscopy (EDS) analysis on the SEM was used to verify the presence of all phases predicted by the model. A density for the C-S-H phase of approximately 2.10 g/cm³ and an evaporable water content in the C-S-H of approximately 19% provided the best agreement between the predicted values of chemical shrinkage, loss of ignition and content of evaporable water, and experimental data. Other results included compositional data on the C-S-H phase corresponding to molar ratios of Al/Ca=0.04 and S/Ca=0.03 in all cements investigated, and Fe/Ca=0.02 in the grey Portland cement.     

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.     

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.     

Variation with solid-phase concentration of composition,structure and strength of cement pastes at high age

Portland and white cement pastes of widely-variable water/cement ratios were studied after six years' hydration by means of quantitative X-ray diffractometric analysis of the CH and C-S-H gel contents. The results obtained have led to certain conclusions on the crystallinity and possible crystal structure of the gel. It was also observed that the flexural strength was considerably reduced for the cement pastes of lowest water/cement ratios.     

Retention of alkali ions by hydrated low-pH cements: Mechanism and Na+/K+ selectivity

Low-pH cements, also referred to as low-alkalinity cements, can be designed by replacing significant amounts of Portland cement by pozzolanic materials. Their pore solution is characterized by a pH near 11, and an alkali concentration much lower than that of Portland cement. This work investigates the retention of sodium and potassium by a hydrated low-pH cement comprising 60% Portland cement and 40% silica fume. It is shown that sorption of potassium is higher than that of sodium and mainly results from counterion charge balancing of the C-S-H negative surface charge. To explain the greater retention of potassium compared to sodium, it is postulated that potassium, unlike sodium, may enter the interlayer of C-S-H to compensate the negative charges in the interlayer, in addition to the external surfaces. This assumption is supported by structural characterization of C-S-H using X-ray diffraction.     

Slag–Portland Cement Based DSP Paste

The partial replacement of Portland cement and silica fume by ground granulated blast furnace slag in DSP cement pastes has been investigated under different curing regimens. The influence of long-term hydration at 25°C, as well as hydrothermal curing (at 80°C) and strong drying (at 200° and 400°C), on the composition and microstructures of slag–Portland cement DSP materials was investigated by nsing QXRD, TGA, MIP, and TMS-GPC methods in this study. Slag is found to be an additive improving intrinsic properties of the DSP paste. CaO/SiO₂ molar ratios of C-S-H phase in the DSP cement past have been calculated.     

硅酸盐水泥耐高温性能研究

研究硅酸盐水泥在20 ℃、200 ℃、400 ℃、600 ℃、800 ℃以及1000 ℃六个温度条件下的耐高温性能,通过外观变化,质量损失以及抗压强度等宏观数据表征硅酸盐水泥的耐高温性能,并通过扫描电镜(SEM)、X衍射分析(XRD)和差热分析(DTA)研究了硅酸盐水泥在不同温度下稳定性变化的机理.试验结果表明:硅酸盐水泥在400 ℃以下的温度,仍能保持一定程度的外观完整和抗压强度;当温度超过600 ℃时,其稳定性开始急剧下降,试件内部出现大量的蜂窝状孔洞,使得C-S-H凝胶被完全分解,导致强度完全丧失而被破坏.     

The effect of two types of C-S-H on the elasticity of cement-based materials: Results from nanoindentation and micromechanical modeling

It has long been recognized, in cement chemistry, that two types of calcium-silicate-hydrate (C-S-H) exist in cement-based materials, but less is known about how the two types of C-S-H affect the mechanical properties. By means of nanoindentation tests on nondegraded and calcium leached cement paste, the paper confirms the existence of two types of C-S-H, and investigates the distinct role played by the two phases on the elastic properties of cement-based materials. It is found that (1) high-density C-S-H are mechanically less affected by calcium leaching than low density C-S-H, and (2) the volume fractions occupied by the two phases in the C-S-H matrix are not affected by calcium leaching. The nanoindentation results also provide quantitative evidence, suggesting that the elastic properties of the C-S-H phase are intrinsic material properties that do not depend on mix proportions of cement-based materials. The material properties and volume fractions are used in a novel two-step homogenization model, that predicts the macroscopic elastic properties of cement pastes with high accuracy. Combined with advanced physical chemistry models that allow, for a given w/c ratio, determination of the volume fractions of the two types of C-S-H, the model can be applied to any cement paste, with or without Portlandite, Clinker, and so on. In particular, from an application of the model to decalcified cement pastes, it is shown that that the decalcification of the C-S-H phase is the primary source of the macroscopic elastic modulus degradation, that dominates over the effect of the dissolution of Portlandite in cement-based material systems.     

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.     

Modelling elasticity of a hydrating cement paste

Concrete is a complex multi-scale composite involving multi-physics processes. As it is the only evolving component of concrete, the cement paste has a major influence on the mechanical properties of concrete at early age. This paper focuses on the increase of the elastic properties of a cement paste during its hydration. The homogenization theory for disordered media is used in order to estimate the evolution of the effective elastic moduli of the hydrating paste. The morphological model refers to two types of C-S-H (calcium silicate hydrates, main hydration products of Portland cements) distinguished by many authors: inner products or high density C-S-H build up layers surrounding the anhydrous particles, while the outer products or low density C-S-H play the role of a porous matrix.The simulations of the effective Young's modulus at late age during hydration and at the end of hydration prove to be in excellent agreement with the experimental results available in the literature.     

A model for the C-A-S-H gel formed in alkali-activated slag cements

For first time, an experimental and computational study has been conducted to define a structural model for the C-A-S-H gel forming in alkali-activated slag (AAS) pastes that would account for the mechanical properties of these materials. The study involved a comparison with the C-S-H gel forming in a Portland cement paste.The structure of the C-A-S-H gels in AAS pastes depends on the nature of the alkali activator. When the activator is a NaOH, the structure of the C-S-H gel falls in between tobermorite 1.4 nm with a mean chain length of five, and tobermorite 1.1 nm with a mean length of 14. When waterglass is the activator the structure of the C-A-S-H gel is indicative of the co-existence of tobermorite 1.4 nm with a chain length of 11 and tobermorite 1.1 nm with a chain length of 14. This very densely packed structure gives rise to excellent mechanical properties.     

Analysis of C-S-H gel and cement paste by small-angle neutron scattering

The role of small-angle X-ray and neutron scattering (SAXS and SANS) in the characterization of cement is briefly reviewed. The unique information obtainable from SANS analysis of C-S-H gel in hydrating cement is compared with that obtainable by other neutron methods. Implications for the nature of C-S-H gel, as detected by SANS, are considered in relation to current models. Finally, the application of the SANS method to cement paste is demonstrated by analyzing the effects of calcium chloride acceleration and sucrose retardation on the resulting hydrated microstructure.     

Solubility and structure of calcium silicate hydrate

The poorly crystalline calcium silicate hydrate (C-S-H) phases that form near room temperature, which include the technically important C-S-H gel phase formed during the hydration of Portland cement, have a broad similarity to the crystalline minerals tobermorite and jennite, but are characterized by extensive atomic imperfections and structural variations at the nanometer scale. Relationships between the aqueous solubility and chemical structure are reported for specimens formed by different preparation methods and with a broad range of compositions. Both new and previously published data show that these phases generate a family of solubility curves in the CaO-SiO₂-H₂O system at room temperature. As demonstrated by ²⁹Si magic-angle spinning (MAS) NMR data and by charge balance calculations, the observed solubility differences arise from systematic variations in Ca/Si ratio, silicate structure, and Ca-OH content. Based on this evidence, the solubility curves are interpreted as representing a spectrum of metastable phases whose structures range from purely tobermorite-like to largely jennite-like. These findings give an improved understanding of the structure of these phases and reconcile some of the discrepancies in the literature regarding the structure of C-S-H at high Ca/Si ratios.     

酸雨侵蚀下水泥石物相组成变化的微观分析

用X射线衍射、Fourier变换红外光谱、扫描电子显微镜和X射线能量色散谱等方法研究了浸泡在pH值为2的模拟酸阿中硅酸盐水泥石物相组成的变化.结果表明:硬化水泥浆体的破坏土要是酸雨中H+与SO42-共同作用的结果..方面.H'使硬化水泥Fee的Ca(OH)2,水化硅酸钙(C-S-H)凝胶.xCaO·Al2O3·yH2O(CxAHy)等物质发生分解、转化.而引起结构溃散性腐蚀:另-方面,SO42-与水泥fi作用,生成膨胀性的物质CaSO4·2H2O, 向引起膨胀性腐蚀.在酸雨持续作用下,水泥石由表及里逐渐遭到侵蚀破坏,直至完全溃散,最终转变成由石膏、硅胶和铝胶等组成的一种白色稀泥状混合物.     

Binding of chloride and alkalis in Portland cement systems

A thermodynamic model for describing the binding of chloride and alkalis in hydrated Portland cement pastes has been developed. The model is based on the phase rule, which for cement pastes in aggressive marine environment predicts multivariant conditions, even at constant temperature and pressure. The effect of the chloride and alkalis has been quantified by experiments on cement pastes prepared from white Portland cements containing 4% and 12% C₃A, and a grey Portland cement containing 7% C₃A. One weight percent calcite was added to all cements. The pastes prepared at w/s ratio of 0.70 were stored in solutions of different Cl (CaCl₂) and Na (NaOH) concentrations. When equilibrium was reached, the mineralogy of the pastes was investigated by EDS analysis on the SEM. A well-defined distribution of chloride was found between the pore solution, the C-S-H phase, and an AFm solid solution phase consisting of Friedel's salt and monocarbonate. Partition coefficients varied as a function of iron and alkali contents. The lower content of alkalis in WPC results in higher chloride contents in the C-S-H phase. High alkali contents result in higher chloride concentrations in the pore solution.     

普通硅酸盐水泥改性脱硫建筑石膏耐水性能

石膏的耐水性能差限制了其在建筑领域的应用,本文以郑州地区脱硫建筑石膏为主要原料,普通硅酸盐水泥为辅料制备了耐水性能好且成本较低的改性脱硫建筑石膏,系统研究了水泥用量对样品水化后的物理性能、物相组成和显微结构的影响。结果表明,随着水泥掺量的增加,其水化后生成的钙钒石(AFt)、氢氧化钙(CH)和水化硅酸钙(C-S-H)凝胶逐渐增多并填充气孔,使样品水化后的吸水率呈先降低后升高的趋势,而软化系数、接触角和硬度则呈相反的趋势,当水泥的用量为18%(质量分数)时,样品耐水性能较佳。本研究为制备耐水性能好且经济环保的脱硫建筑石膏及其制品提供了技术依据,并对脱硫石膏的推广应用及建材行业的绿色发展具有重要意义。