Microstructure-based micromechanical prediction of elastic properties in hydrating cement paste

Elastic properties of hydrating cement paste can be successfully predicted by combination of the hydration model, percolation theory and micromechanical analysis. Reconstruction of hydrating microstructure is based on the 3D digital NIST model of cement hydration, which is enhanced for the prediction of two C-S-H types. Chemical phases in a percolated microstructure served as an input in a two-level analytical or one-level 3D FEM or FFT elastic homogenization. Special mesh generation for the percolated microstructure is discussed as well as its numerical implementation. Good results from FEM and FFT were found for the size of the representative volume element of 50 × 50 × 50 μm, considering water-to-cement ratio in the range from 0.25 to 0.5. While good predictions in well-hydrated cement pastes were obtained for both analytical and numerical approaches, numerical homogenization was found more accurate and versatile for the whole hydration time.     

Characterization by solid-state NMR and selective dissolution techniques of anhydrous and hydrated CEM V cement pastes

The long term behaviour of cement based materials is strongly dependent on the paste microstructure and also on the internal chemistry. A CEM V blended cement containing pulverised fly ash (PFA) and blastfurnace slag (BFS) has been studied in order to understand hydration processes which influence the paste microstructure. Solid-state NMR spectroscopy with complementary X-ray diffraction analysis and selective dissolution techniques have been used for the characterization of the various phases (C₃S, C₂S, C₃A and C₄AF) of the clinker and additives and then for estimation of the degree of hydration of these same phases. Their quantification after simulation of experimental ²⁹Si and ²⁷Al MAS NMR spectra has allowed us to follow the hydration of recent (28 days) and old (10 years) samples that constitutes a basis of experimental data for the prediction of hydration model.     

Influence of the porosity gradient in cement paste matrix on the mechanical behavior of mortar

This paper is devoted to the study of the influence of the microstructure of mortar on its mechanical behavior. For this purpose, mechanical tests have been carried out on mortars and a mathematical model, the (n + 1)-phase model, has been used to take into account three variable parameters of the microstructure of mortar (the thickness of the interfacial transition zone, the porosity gradient in the cement paste matrix and the nature of the constituents of the Interfacial Transition Zone) for some given parameters (volume fraction of aggregates, porosity of the mortar and mechanical behavior of the aggregates and the cement paste). By fitting some measured moduli to the model predictions, we can estimate in a non-destructive manner, the possible distribution of porosity within the Interfacial Transition Zone. Our results provide information on the data such micromechanical models can deal with in order to predict the elastic behavior of mortars.     

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.     

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.     

Microstructure of cement paste subject to early carbonation curing

Microstructure of Ordinary Portland Cement paste subjected to early age carbonation curing was studied to examine the effect of early carbonation on performance of paste at different ages. The study was intended to understand the mechanism of concrete carbonation at early age through the microstructure development of its cement paste. Early carbonation was carried out after 18-hour initial controlled air curing. The microstructure characterized by XRD, TGA, ²⁹Si NMR and SEM was correlated to strength gain, CO₂ uptake and pH change. It was found that early carbonation could accelerate early strength while allowing subsequent hydration. The short term carbonation created a microstructure with more strength-contributing solids than conventional hydration. Calcium hydroxide was converted to calcium carbonates, and calcium–silicate–hydrate became intermingled with carbonates, generating an amorphous calcium–silicate–hydrocarbonate binding phase. Carbonation modified C–S–H retained its original gel structure. The re-hydration procedure applied after carbonation was essential in increasing late strength and durability.     

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 gap-graded particle size distribution for blended cements: Analytical approach and experimental validation

To increase the packing density of blended cement paste, a gap-graded particle size distribution (PSD) was theoretically deduced and modified according to the wet density of actual paste. Then experiments were conducted to validate the hypothesis of improvement of the properties of blended cements by the gap-graded PSDs proposed. The experimental results show that the gap-graded PSD resulted in a decreased water requirement and an increased packing density of blended cement paste, and modified gap-graded PSDs gave further effects. The heat of hydration of gap-graded blended cement pastes released slowly in the first 24 h and increased rapidly afterward. The microstructure of gap-graded blended cements was much more homogeneous and denser than that of reference blended cement, therefore both early and late mechanical properties of low clinker gap-graded blended cements were improved significantly and even higher than those of Portland cement.     

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.     

Autogenous shrinkage in high-performance cement paste: An evaluation of basic mechanisms

In this paper, various mechanisms suggested to cause autogenous shrinkage are presented. The mechanisms are evaluated from the point of view of their soundness and applicability to quantitative modeling of autogenous shrinkage. The capillary tension approach is advantageous, because it has a sound mechanical and thermodynamical basis. Furthermore, this mechanism is easily applicable in a numerical model when dealing with a continuously changing microstructure. In order to test the numerical model, autogenous deformation and internal relative humidity (RH) of a Portland cement paste were measured during the first week of hardening. The isothermal heat evolution was also recorded to monitor the progress of hydration and the elastic modulus in compression was measured. RH change, degree of hydration and elastic modulus were used as input data for the calculation of autogenous deformation based on the capillary tension approach. Because a part of the RH drop in the cement paste is due to dissolved salts in the pore solution, a method is suggested to separate this effect from self-desiccation and to calculate the actual stress in the pore fluid associated with menisci formation.     

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.     

Elastic and creep properties of young cement paste,as determined from hourly repeated minute-long quasi-static tests

Cement pastes are highly creep active materials at early ages. We here characterize both the elastic stiffness and the creep properties of ordinary Portland cement pastes conditioned at 20 °C. Three different compositions are investigated, defined in terms of initial water-to-cement mass ratios amounting to 0.42, 0.45, and 0.50, respectively. Implementing a new early-age creep testing protocol, we perform a series of 168 three minute long uniaxial macroscopic creep tests on the aging materials, with one such test per hour and corresponding material ages spanning from 21 h to approximately eight days. In this way, it is guaranteed that the material microstructure remains virtually unaltered during each individual creep test, while subsequent creep tests refer to clearly different microstructures. In order to minimize material damage, the compressive loads are restricted to at most 15% of the uniaxial compressive strength reached at the time of testing. The loading protocol consists of quasi-instantaneous compressive loading and unloading steps as well as a three minute long holding period in between. Representing the measured compliances very precisely by means of a power-law expression including elastic and creep moduli, as well as a creep exponent, while requiring the elastic and creep strains to be compressive at all times, yields concavely increasing time evolutions of elastic and creep moduli, as well as slightly decreasing or quasi-constant evolutions of the creep exponent. Combination of these results with calorimetry-based evolutions of the degree of hydration yields linear elasticity-hydration degree and over-linear creep modulus-hydration degree relations, while the creep exponents (slightly) decrease with ongoing hydration. The herein quasi-statically determined elastic moduli agree very well with those determined ultrasonically on the same cement pastes. This impressively underlines the fundamental characteristics of elastic properties being related to an energy potential, independently of loading paths and corresponding strain rates.     

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.     

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.     

Application of synchrotron microtomography for pore structure characterization of deteriorated cementitious materials due to leaching

Deteriorated mortars and cement pastes (w/c = 0.50) were prepared by an accelerated leaching test using electrochemical migration technique. This technique enabled the reduction of the CaO/SiO₂ molar ratio to less than 2.0. Non-destructive three-dimensional imaging of the internal microstructure of the deteriorated cement matrix in hardened cement paste and mortar was performed using synchrotron X-ray computed microtomography at SPring-8, Japan. After image analysis at a spatial resolution of 0.5 μm/voxel the microtomographic images successfully visualized increased pore spaces in the deteriorated cement matrix with the effective porosity ranging from 0.31 to 0.38. In addition the diffusion tortuosity in the pore space derived from random walk simulation was also evaluated as a pore structure-transport parameter. Indications suggest that the deterioration of the cement matrix due primarily to the dissolution of portlandite decreases the diffusion tortuosity to a single digit as the degree of pore connectivity becomes larger at the submicron scale.     

Rehydration and microstructure of cement paste after heating at temperatures up to 300 °C

This paper is concerned with the evolution of the microstructure of cementitious materials subjected to high temperatures and subsequent resaturation in the particular context of long-term storage of radioactive wastes, where diffusive and convective properties are of primary importance. Experimental results obtained by mercury intrusion porosimetry (MIP) are presented concerning the evolution of the pore network of ordinary portland cement (OPC) paste heated at temperatures varying between 80 and 300 °C. The consequences of heating on the macroscopic properties of cement paste are evaluated by measures of the residual gas permeabilities, elastic moduli and Poisson's ratio, obtained by nondestructive methods. Resaturation by direct water absorption and water vapour sorption are used to estimate the reversibility of dehydration. The results provide some evidence of the self-healing capacity of resaturated cement paste after heating at temperatures up to 300 °C.     

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。     

A model investigation of the influence of particle shape on portland cement hydration

The NIST Virtual Cement and Concrete Testing Laboratory (VCCTL) is used to simulate the influence of particle shape on the hydration kinetics and setting of portland cement. Building on previous work in reconstructing particle shapes from real cements, real-shape particles are used to produce three-dimensional digitized cement paste microstructures, and the hydration of these microstructures is tracked using VCCTL. The degree of hydration and percolation of solids is monitored and compared to experimental data at several water-cement ratios. The simulations predict that shapes of particles influence cement hydration in two ways: the additional surface / volume ratio relative to spherical particles results in greater rates of hydration, and the anisometry in shape influences the degree of hydration at which the particles and hydration products percolate to form a stiff three-dimensional network.     

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.