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.     

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.     

Decalcification shrinkage of cement paste

Decalcification of cement paste in concrete is associated with several modes of chemical degradation including leaching, carbonation and sulfate attack. The primary aim of the current study was to investigate the effects of decalcification under saturated conditions on the dimensional stability of cement paste. Thin (0.8 mm) specimens of tricalcium silicate (C₃S) paste, white portland cement (WPC) paste, and WPC paste blended with 30% silica fume (WPC/30% SF) were decalcified by leaching in concentrated solutions of ammonium nitrate, a method that efficiently removes calcium from the solid while largely preserving silicate and other ions. All pastes were found to shrink significantly and irreversibly as a result of decalcification, particularly when the Ca/Si ratio of the C-S-H gel was reduced below ∼ 1.2. Since this composition coincides with the onset of structural changes in C-S-H such as an increase in silicate polymerization and a local densification into sheet-like morphologies, it is proposed that the observed shrinkage, here called decalcification shrinkage, is due initially to these structural changes in C-S-H at Ca/Si ∼ 1.2 and eventually to the decomposition of C-S-H into silica gel. In agreement with this reasoning, the blended cement paste exhibited greater decalcification shrinkage than the pure cement pastes due to its lower initial Ca/Si ratio for C-S-H gel. The similarities in the mechanisms of decalcification shrinkage and carbonation shrinkage are also discussed.     

Examining the relationship between the microstructure of calcium silicate hydrate and drying shrinkage of cement pastes

Cement paste undergoes a volumetric contraction called drying shrinkage when placed in a low relative humidity (RH) environment. Only a portion of this shrinkage is reversible upon rewetting. In order to understand better the mechanisms responsible for the irreversible portion of drying shrinkage, a quantitative comparison was made between shrinkage values and microstructural properties of cement pastes. Drying shrinkage, surface area and pore volume were manipulated using curing temperature and chemical admixtures. It was observed that total and irreversible drying shrinkage increase with surface area and pore volume as measured by nitrogen (1-40 nm pore radius range), when degree of hydration and water-to-cement ratio (w/c) are held constant (0.55 and 0.45, respectively).     

Desiccation shrinkage of cementitious materials as an aging, poroviscoelastic response

This paper describes and evaluates a new model that utilizes aging poroviscoelasticity for predicting the shrinkage of cementitious materials induced by loss of moisture from the pore structure (i.e. desiccation). The new model incorporates well-accepted mechanisms for desiccation shrinkage and accounts for the effect of changing concentrations of dissolved species in the pore fluid. Additionally, the model is used to interpret viscoelastic behavior during the drying process via comparisons of model predictions with measured shrinkage of hardened portland cement paste. It was found that while a poroelastic model under predicts the measured shrinkage, the poroviscoelastic model significantly over predicts the shrinkage unless intrinsic aging of the C–S–H gel is included in the model.     

Effect of Heat Treatment on the Pore Structure and Drying Shrinkage Behavior of Hydrated Cement Paste

The effect of a short heat treatment on hydrated cement paste has been investigated by measuring the weight and length changes of specimens as they undergo various combinations of heating, drying, and resaturation. Heating a cement paste to 60°C coarsens the capillary pore system, decreases the volume of mesopores, and increases the degree of polymerization of the silicates. In addition, the saturated weight of the paste is permanently decreased by a heat treatment. This weight loss can be explained by conversion of bound hydroxyl groups into liquid water during polymerization of the C-S-H gel phase. These experiments help reconcile and interpret published results describing the properties of cement cured at various temperatures, the effects of a short heat treatment on cement paste, and the thermal expansion behavior of saturated and dry cement paste.     

Basic creep,drying creep and shrinkage of a mature cement paste after a heat cycle

Cement paste that was heated in a saturated state at an age of 28 days exhibited reductions in basic creep and shrinkage and an increase in the extent of polymerisation of the hydrated silicates. This behaviour was similar to that of cement pastes heated at early ages. Drying creep was also reduced by the heat treatment, the reductions in drying creep being closely related to the reductions in shrinkage. Measured changes in properties that were related to the structure of the cement paste assisted interpretation of the present deformation and strength observations and of transitional thermal creep data reported in the literature.     

The effect of rate of drying on the drying creep of hardened cement paste

Tests were performed on miniature, thin-wallm hardened cement paste specimens; specimens under load were dried at various rates, re-wet and then unloaded. Deformation was monitored throughout. Appropriate control specimens for shrinkage/swelling, basic creep and weight change were also tested. Relationships between moisture loss, shrinkage and wetting creep were obtained. It was found that, like shrinkage, the magnitude of drying creep is independent of rate of drying. Also, drying creep bears a linear relationship to concomitant shrinkage over a wide range; similarly, wetting creep is linearly related to swelling. Drying creep and wetting creep are completely irrecoverable. Discussion centres about the significance of the results with respect to the prediction of creep strains when environmental conditions change; results suggest it may be possible to develop prediction equations which are not overly complicated.     

超细矿渣粉和偏高岭土对硫铝酸盐水泥早期收缩性能的影响

通过开展化学收缩、自收缩与干燥收缩试验,研究了超细矿渣粉和偏高岭土对硫铝酸盐水泥早期收缩性能的影响。结果表明,掺入超细矿渣粉与偏高岭土会增大水泥浆体的内部相对湿度,能有效抑制水泥浆体的化学收缩、自收缩与干燥收缩,且掺量越大,抑制效果越明显,根据水泥浆体的内部相对湿度能够大致判断其自收缩的变化规律。掺入超细矿渣粉与偏高岭土会加快硫铝酸盐水泥的早期水化,使化学收缩变化速率达到峰值的时间提前。当超细矿渣粉的掺量为20%(质量分数,下同)或偏高岭土的掺量为10%、20%时,与空白组相比水泥浆体的7 d自收缩分别减小了42.21%、35.89%和63.73%,7 d干燥收缩分别减小了24.89%、16.42%和30.87%。在相同掺量条件下,掺入偏高岭土的水泥浆体化学收缩、自收缩与干燥收缩显著小于掺入超细矿渣粉的水泥浆体。自收缩与线性化学收缩的比值随龄期的增长而减小,掺入超细矿渣粉与偏高岭土后,自收缩与线性化学收缩的比值进一步减小。     

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).     

大堆积密度骨料配制的混凝土的性能(英文)

当今世界对可持续发展的关注促进了低水泥用量混凝土建筑工程的产生。增加混凝土中骨料体系的堆积密度是降低水泥用量的一个策略。增加骨料体系的堆积密度可以降低填充骨料颗粒间隙所需要的水泥浆体的量。研究了大堆积密度骨料配制的混凝土。这些混凝土比普通的结构混凝土低15%～25%的水泥用量,当骨料体系级配合理时混凝土工作性好。水泥浆体体积的降低在明显改进混凝土干缩与徐变性能的同时,也会对其工作性产生不利影响。骨料含量不会显著影响不同配比混凝土的抗压强度和劈裂强度。     

Creep and relaxation of cement paste caused by stress‐induced dissolution of hydrated solid components

The creep and relaxation of cement paste caused by dissolving solid hydration products is evaluated in this work. According to the second law of thermodynamics, dissolution or precipitation of solid constituents may be altered by the change in stress/strain fields inside cement paste via alteration of the stress power or strain energy. Thus, it is hypothesized that stress‐induced dissolution can affect the overall creep/relaxation behavior of cement composites. A novel, fully coupled thermodynamic, mechanical, and microstructural model (TM²) that uses the finite element method was developed to predict the time‐evolving properties of cement paste under prescribed strains and to test the hypothesis. In the model, the strain energy was incorporated to accurately predict the effect of stress and strain fields on cement microstructure change. From the simulation results, depending on the stress/strain levels and the choice of the domain (over which the thermodynamic equilibrium is enforced), stress‐induced dissolution of solid constituents can lead to significant creep/relaxation.     

水泥浆体早期的自收缩和干燥收缩

水泥浆体早期(<7 d)收缩行为已受到越来越多的关注,利用波纹管法测量自收缩,通过测量不同水灰比净浆的自收缩和干燥收缩来评价早期收缩.试验结果表明,与其他方法相比,波纹管法能直接准确地测量早期自收缩.养护1 d后测量初长为基准测量自收缩会忽略水泥浆体早期很大一部分自收缩,初凝后10 min开始测量较为合理.由于很多工程中实际养护条件不足,以养护3 d初长为基准测得的干燥收缩不能准确反映真实的早期干燥收缩.     

Microstructural and bulk property changes in hardened cement paste during the first drying process

This paper reports the microstructural changes and resultant bulk physical property changes in hardened cement paste (hcp) during the first desorption process. The microstructural changes and solid-phase changes were evaluated by water vapor sorption, nitrogen sorption, ultrasonic velocity, and ²⁹Si and ²⁷Al nuclear magnetic resonance. Strength, Young's modulus, and drying shrinkage were also examined. The first drying process increased the volume of macropores and decreased the volume of mesopores and interlayer spaces. Furthermore, in the first drying process globule clusters were interconnected. During the first desorption, the strength increased for samples cured at 100% to 90% RH, decreased for 90% to 40% RH, and increased again for 40% to 11% RH. This behavior is explained by both microstructural changes in hcp and C–S–H globule densification. The drying shrinkage strains during rapid drying and slow drying were compared and the effects of the microstructural changes and evaporation were separated.     

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.     

Characterization of elastic and time-dependent deformations in high performance lightweight concrete by image analysis

Image analysis and strain mapping were used to examine the nature of elastic, creep and shrinkage strains in high performance lightweight concrete (HPLC). The strain maps showed non-uniform deformations related to microstructural features. Both average strain and non-uniformity increased with time under testing. Paste-rich regions exhibited higher creep plus shrinkage than the lightweight aggregate (LWA) particles examined herein; it is suggested that LWA could have a role in reducing deformations of the paste. Compared to normal weight high performance concrete (HPC), the paste and LWA in the HPLC exhibited more gradual spatial differences in elastic deformations, creep and shrinkage. It is proposed that this difference results from the lower stiffness of the LWA compared to granite used in the HPC. The results indicate that improvement in elastic property matching between the lightweight aggregate and high performance paste reduces stress concentrations at the aggregate/paste interface and contributes to reductions in deformations of HPLC compared to HPC.     

Constitutive Model for Predicting Ultimate Drying Shrinkage of Concrete

A constitutive model is derived from theory of elasticity for predicting ultimate drying shrinkage of concrete. The model was extended by incorporating the semiempirical composite model proposed by Hirsch and Dougill for predicting Young's modulus of concrete. Their composite model is the geometric mean of Paul's upper and lower limit boundaries of a two-phase composite. According to the shrinkage model the parameters needed for predicting ultimate drying shrinkage of concrete at any relative humidity of drying are the following: ultimate shrinkage of a paste of same water-to-cement (W/C; ratio and degree of hydration as the concrete, relative volume of aggregates and unhydrated cement, and the elastic properties of hydrated paste and the particles. The shrinkage model was tested on shrinkage results obtained in this study and by Pickett. Three different W/C ratios were covered together with a wide range in aggregate contents. Excellent agreement with the results was found.     

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.