Effect of temperature on the microstructure of calcium silicate hydrate (C-S-H)

Temperature affects the properties of concrete through its effect on the hydration of cement and its associated microstructural development. This paper focuses on the modifications to C-S-H induced by isothermal curing between 5 and 60 °C. The results show that as the temperature increases (within the range studied) the C/S ratio of C-S-H changes only slightly, with a higher degree of polymerisation of silicate chains, but there is a significant decrease in its bound water content and an increase of apparent density of 25%. This increase seems to come from a different packing of C-S-H at the nanoscale. As a consequence of these changes, the microstructure of the cement paste is much coarser and porous, which explains the lower final strengths obtained by curing at elevated temperatures.     

A multiscale micromechanics-hydration model for the early-age elastic properties of cement-based materials

The E-modulus of early age cement-based materials, and more importantly, its evolution in time, is one of the most critical material-to-structural design parameters affecting the likelihood of early-age concrete cracking. This paper addresses the problem by means of a multistep micromechanics approach that starts at the nanolevel of the C-S-H matrix, where two types of C-S-H develop in the course of hydration. For the purpose of homogenization, the volume fractions of the different phases are required, which are determined by means of an advanced kinetics model of the four main hydration reactions of ordinary portland cement (OPC). The proposed model predicts with high accuracy the aging elasticity of cement-based materials, with a minimum intrinsic material properties (same for all cement-based materials), and 11 mix-design specific model parameters that can be easily obtained from the cement and concrete suppliers. By way of application, it is shown that the model provides a quantitative means to determine (1) the solid percolation threshold from micromechanics theory, (2) the effect of inclusions on the elastic stiffening curve, and (3) the development of the Poisson's ratio at early ages. The model also suggests the existence of a critical water-to-cement ratio below which the solid phase percolates at the onset of hydration. The development of Poisson's ratio at early ages is found to be characterized by a water-dominated material response as long as the water phase is continuous, and then by a solid-dominated material response beyond the solid percolation threshold. These model-based results are consistent with experimental values for cement paste, mortar, and concrete found in the open literature.     

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.     

纳米水化硅酸钙的制备及对水泥水化影响的研究进展

随着纳米技术的不断发展,纳米材料逐步开始应用于传统混凝土材料中,以提高混凝土的各项服役性能。纳米水化硅酸钙(纳米C-S-H)是一种新型的早强纳米复合材料,可通过晶核效应加快水泥早期水化速率,显著提高水泥基材料的早期力学性能,从而提高施工效率,满足特殊施工要求。本文系统总结了纳米C-S-H的制备方法,及纳米C-S-H对水泥基材料早期和长期性能的影响规律,探讨了其对于水泥水化过程和水化产物的影响机制,其中重点介绍了采用聚合物分散纳米颗粒制备的C-S-H/PCE(聚羧酸型减水剂,简称PCE)纳米复合材料。     

C-S-H及C-S-H脱水相对水泥石结构改性的研究

以C-S-H及C-S-H脱水相作水泥水化物沉淀中心的品种。从理论上阐明了它们是具有较大介电常数、较小物理化学不均匀系数、高分散度的晶种物质,故具有优先吸附的界面效应及优先沉淀的结晶中心作用,可缓和原始矿物表面的高浓度的屏蔽效应及界面的近程析晶,使水化物分布均匀、结构致密,从而提高水泥石强度。C-S-H及C-S-H脱水相两者中,尤以后者作用更显著。     

Micromechanical multiscale fracture model for compressive strength of blended cement pastes

The evolution of compressive strength belongs to the most fundamental properties of cement paste. Driven by an increasing demand for clinker substitution, the paper presents a new four-level micromechanical model for the prediction of compressive strength of blended cement pastes. The model assumes that the paste compressive strength is governed by apparent tensile strength of the C-S-H globule. The multiscale model takes into account the volume fractions of relevant chemical phases and encompasses a spatial gradient of C-S-H between individual grains. The presence of capillary pores, the C-S-H spatial gradient, clinker minerals, SCMs, other hydration products, and air further decrease compressive strength. Calibration on 95 experimental compressive strength values shows that the apparent tensile strength of the C-S-H globule yields approx. 320 MPa. Sensitivity analysis reveals that the “C-S-H/space” ratio, followed by entrapped or entrained air and the spatial gradient of C-S-H, have the largest influence on compressive strength.     

Microstructural development of early age hydration shells around cement grains

An important microstructural aspect of the early hydration of Portland cement (PC) is the formation of a shell of hydration products around cement grains. There is, at present, limited information on the mechanism of formation of the shell and of the chemistry of the phases that constitute the shells. Through the use of STEM imaging of early age hydrated cement pastes as early as 2 h, the present work shows that the shells correspond to the first C-S-H type product formed which has a distinct morphology compared to C-S-H formed later when the main reaction occurs (nucleation and growth stage at setting time). The shells form only around the silicate part of the grain and are not empty but filled with a fragile fibrous C-S-H which appears to have a lower (packing) density than the rest of the hydration products. The cement grains underneath the shells are seen to react unevenly and the hydration seems to follow a reaction front, leaving striations up to 1 µm deep on the grains. Over the long term, the original fragile product seems to densify and gives rise to the usual inner C-S-H. High resolution EDS chemical analysis and mappings were used to get insight into the chemistry associated with the formation of these early age products. The C/S ratio of all C-S-H (inner and outer shell) is the same (within the limits of the analysis accuracy) and evolves insignificantly over the first 24 h of hydration. High concentrations of sulfate are associated with the C-S-H formed during the early development of the microstructure, but these decrease later, the sulfate being mainly incorporated into ettringite.     

不同掺量非晶态C12 A7/CaSO4·2 H2 O体系对OPC早期性能的影响及作用机理

研究了不同掺量非晶态C12 A7/CaSO4·2H2 O体系对OPC净浆凝结时间、流动性和早期抗压强度的影响,通过XRD和SEM对水化产物的物相和形貌进行了表征,并采用量热试验对其水化历程进行了分析。结果表明：非晶态C12 A7/CaSO4·2H2 O体系掺量为5%,非晶态C12 A7与CaSO4·2H2 O的质量比为1.0∶1.0时,非晶态C12 A7/CaSO4·2H2 O体系能够促进C3 S和C2 S的水化,生成C-S-H凝胶相互交织搭接形成网络结构而促进凝结;同时也促使OPC水化早期产生大量针状晶体钙矾石,钙矾石与前期生成的C-S-H凝胶相互填充,使水化产物结构密实,提高早期强度。     

A multi-technique investigation of the nanoporosity of cement paste

The nanometer-scale structure of cement paste, which is dominated by the colloidal-scale porosity within the C-S-H gel phase, has a controlling effect on concrete properties but is difficult to study due to its delicate structure and lack of long-range order. Here we present results from three experimental techniques that are particularly suited to analyzing disordered nanoporous materials: small-angle neutron scattering (SANS), weight and length changes during equilibrium drying, and nanoindentation. Particular attention is paid to differences between pastes of different ages and cured at different temperatures. The SANS and equilibrium drying results indicate that hydration of cement paste at 20 °C forms a low-density (LD) C-S-H gel structure with a range of gel pore sizes and a relatively low packing fraction of solid particles. This fine structure may persist indefinitely under saturated conditions. However, if the paste is dried or is cured at elevated temperatures (60 °C or greater) the structure collapses toward a denser (less porous) and more stable configuration with fewer large gel pores, resulting in a greater amount of capillary porosity. Nanoindentation measurements of pastes cured at different temperatures demonstrate in all cases the existence of two C-S-H structures with different characteristic values of the indentation modulus. The average value of the modulus of the LD C-S-H is the same for all pastes tested to date, and a micromechanical analysis indicates that this value corresponds to the denser and more stable configuration of LD C-S-H. The experimental results presented here are interpreted in terms of a previously proposed quantitative “colloid” model of C-S-H gel, resulting in an improved understanding of the microstructural changes associated with drying and heat curing.     

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.     

Microstructure and Flow Behavior of Fresh Cement Paste

A rheological technique (creep/recovery) was used, in combination with scanning electron microscopy, to study the effects of hydration on both the microstructure and flow properties of fresh cement paste during the induction period, which is the first few hours after cement and water are mixed. The principal hydration product was calcium silicate hydrate (C-S-H), which was first observed in the neck areas between cement particles. At the same time, yield stress increased progressively, which reflected a strengthening of bonds between particles attributed to the C-S-H. Failure strain also increased, which reflected a fundamental change in the nature of that bond. Based on rheological measurements, the activation energy of the hydration process during this time period was estimated to be 5.2 kcal/mol (˜22 kJ/mol).     

Identification of viscoelastic C-S-H behavior in mature cement paste by FFT-based homogenization method

A powerful and robust numerical homogenization method based on fast Fourier transform (FFT) is formulated to identify the viscoelastic behavior of calcium silicate hydrates (C-S-H) in hardened cement paste from its heterogeneous composition. The identification is contingent upon the linearity of the creep law. To characterize cement paste microstructure, the model developed by Bentz at the National Institute of Standards and Technology, which has the resolution of 1 μm, is adopted. Model B3 for concrete creep is adapted to characterize the creep of C-S-H in cement paste. It is found that the adaptation requires increasing the exponent of power law asymptote of creep compliance. This modification means that the rate of attenuation of creep with time is lower in C-S-H than in cement paste, and is explained by differences in stress redistribution. In cement paste, the stress is gradually transferred from the creeping C-S-H to the non-creeping components. The viscoelastic properties of C-S-H at the resolution of 1 μm were identified from creep experiments on cement pastes 2 and 30 years old, having the water-cement ratio of 0.5. The irreversible part of C-S-H creep, obtained from these old specimens at almost saturated state, is found to be negligible unless the specimens undergo drying and resaturation prior to the creep test.     

The physical and chemical characteristics of the shell of air-entrained bubbles in cement paste

Recent research has suggested that the shell of an air-entrained void is important for resisting coalescence between air-voids and diffusion of gas from the surrounding fluid. The current paper describes the physical and chemical properties of an air-void shell during the first 2 h of hydration and chemical characteristics at 60 days. Results from this research suggest that the air-void shells found in air-entrained paste have varied physical properties and the crystalline material of these shells is largely made up of fine cement particles during the first 2 h of hydration. Observations of paste at 60 days of hydration suggest that the shell is made up of calcium silicate hydrate (C-S-H) with a morphology different from that in the bulk paste.     

冻融作用下活化煤矸石粉混凝土损伤劣化规律

为促进寒冷地区煤矸石在混凝土中的应用,通过机械-微波方式对煤矸石进行复合活化,从表观形貌、质量损失率、相对动弹性模量、抗压强度和劈裂抗拉强度等方面对煤矸石粉混凝土的损伤劣化规律进行了研究,并使用扫描电子显微镜、核磁共振波谱仪和X射线衍射仪等研究了活化煤矸石粉对混凝土抗冻性能的改性机理。结果表明:20%(质量分数)掺量下活化煤矸石粉对混凝土抗冻性能改善效果最好,且经300次冻融循环后,质量损失率和相对动弹性模量分别为2.32%和91.32%,抗压强度和劈裂抗拉强度分别下降了16.40%和26.12%;活化煤矸石粉能填充、细化孔隙,且其二次水化能消耗水泥水化产物Ca(OH)₂,产生C-S-H和C-A-S-H,提升水泥石密实程度,改善孔结构,使大孔占比减少。     

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。     

Chloride binding related to hydration products: Part I: Ordinary Portland Cement

This study attempts to correlate the total amount of chloride bound in concrete with the amounts bound by different hydration products. New insights in the quantities of the hydration products formed will be used in order to predict the phase assemblage of hardened cement pastes. The two main chloride binding mechanisms are considered — through physical adsorption and through chemical reactions. Chloride binding isotherms are used, taking into account the external chloride concentration and the quantity of each hydration product formed.A distinction is made between the chloride binding capacities of monosulfate and hydroxy-AFm. Two new models for the maximum chloride binding ability of a hardened cement paste are proposed — a basic one, using only AFm and C-S-H isotherms, and an extended one which also considers the ability of portlandite and Friedel's salt to physically adsorb chlorides. Results obtained using these models are within 10% of collected experimental data.     

钢渣水化产物的特性(英文)

用X射线衍射分析、水化热的测量、化学结合水量的测定、孔结构的测定、扫描电镜观察及强度测试研究了钢渣的水化产物的特性。结果表明:钢渣硬化浆体中主要含有水化硅酸钙(C–S–H)凝胶、Ca(OH)2、惰性组分[RO相、铁酸二钙(C2F)和Fe3O4]和未水化的胶凝相[硅酸三钙(C3S)和硅酸二钙(C2S)];总体而言,钢渣的水化过程与水泥的水化过程相似;钢渣早期的水化速率远低于水泥,但钢渣后期,尤其是90d之后的水化速率高于水泥的。钢渣水化产生的C–S–H凝胶不具有良好的胶凝性能,凝胶之间的相互黏结也不牢固,因此钢渣砂浆的强度很低。     

马来酸三乙醇胺酯对水泥水化的影响

为克服三乙醇胺早强剂对水泥抗折强度和后期强度的影响,合成了马来酸三乙醇胺酯,并通过背散射电子成像(BSE)和BET分析,研究了马来酸三乙醇胺酯对水泥水化程度、C-S-H含量和水泥水化28 d分形维数的影响。结果表明:马来酸三乙醇胺酯可促进水泥水化尤其是水泥中硅酸盐相的水化;复掺马来酸三乙醇胺酯和聚羧酸减水剂,可显著提高水泥水化产物中C-S-H的含量;三乙醇胺降低了水泥石28 d的分形维数,马来酸三乙醇胺酯单掺及与聚羧酸减水剂复掺则使水泥石28 d的分形维数提高。由此可见,马来酸三乙醇胺酯作为增强型水泥早强剂具有广阔的应用前景。     

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.     

Microwave Dielectric Study of Water Structure in the Hydration Process of Cement Paste

Microwave dielectric relaxation measurements, via the time-domain reflectometry method, were performed on portland cement paste for the first time, and the water structure during the hydration process was observed. The relaxation process due to the orientation of free water, which is independent of calcium silicate hydrate (C-S-H), was observed at ∼10 GHz. The relaxation strength, in proportion to the amount of free water, decreased rapidly as the curing time increased for the first three days. This change is in good agreement with that of a chemical reaction that was reported by measurements of the heat that is evolved during hydration. The free water is taken into C-S-H and is transformed to hydrated water by the hydration process. When hydration proceeds, the relaxation processes due to the orientation of the hydrated water in C-S-H occur at ∼100 MHz and 1 MHz.