[en] It has been observed that the hydration of cement paste stops when the relative humidity drops below about 80%. A thermodynamic analysis shows that the capillary pressure exerted at that RH shifts the solubility of tricalcium silicate, so that it is in equilibrium with water. This is a reflection of the chemical shrinkage in this system: according to Le Chatelier's principle, since the volume of the products is less than that of the reactants, a negative (capillary) pressure opposes the reaction.

[en] An approach rooted in fundamental, mechanistic models of concrete materials offers the only viable path for handling the enormous number of variables that are being introduced as new materials are added to the design space, and as new properties are mandated for a sustainable infrastructure. These models must begin at the smallest length scales relevant for concrete properties; in some cases this is the scale of electron interactions among atoms and ions. But concrete has complex chemical and structural properties that are manifested at greater length and time scales, so atomic scale models must ultimately be integrated with new models that capture behavior at mesoscopic and macroscopic scales. We refer to this methodology as the 'bottom-up' approach because it proceeds from the smallest length scales. We describe this kind of modeling approach, include some recent results, and suggest some principles for collaboratively integrating multi-scale models.

[en] To test the ability of the Virtual Cement and Concrete Testing Laboratory (VCCTL) software to predict cement hydration properties, characterization of mineralogy and phase distribution is necessary. Compositional and textural characteristics of Cement and Concrete Reference Laboratory (CCRL) cements 151 and 152 were determined via scanning electron microscopy (SEM) analysis followed by computer modeling of hydration properties. The general procedure to evaluate a cement is as follows: (1) two-dimensional SEM backscattered electron and X-ray microanalysis images of the cement are obtained, along with a measured particle size distribution (PSD); (2) based on analysis of these images and the measured PSD, three-dimensional microstructures of various water-to-cement ratios are created and hydrated using VCCTL, and (3) the model predictions for degree of hydration under saturated conditions, heat of hydration (ASTM C186), setting time (ASTM C191), and strength development of mortar cubes (ASTM C109) are compared to experimental measurements either performed at NIST or at the participating CCRL proficiency sample evaluation laboratories. For both cements, generally good agreement is observed between the model predictions and the experimental data

[en] A recently described stochastic reaction-transport model on three-dimensional lattices is parallelized and is used to simulate the time-dependent structural and chemical evolution in multicomponent reactive systems. The model, called HydratiCA, uses probabilistic rules to simulate the kinetics of diffusion, homogeneous reactions and heterogeneous phenomena such as solid nucleation, growth and dissolution in complex three-dimensional systems. The algorithms require information only from each lattice site and its immediate neighbors, and this localization enables the parallelized model to exhibit near-linear scaling up to several hundred processors. Although applicable to a wide range of material systems, including sedimentary rock beds, reacting colloids and biochemical systems, validation is performed here on two minerals that are commonly found in Portland cement paste, calcium hydroxide and ettringite, by comparing their simulated dissolution or precipitation rates far from equilibrium to standard rate equations, and also by comparing simulated equilibrium states to thermodynamic calculations, as a function of temperature and pH. Finally, we demonstrate how HydratiCA can be used to investigate microstructure characteristics, such as spatial correlations between different condensed phases, in more complex microstructures

[en] When cementitious materials are dried, internal stresses are generated that lead to desiccation shrinkage, a portion of which is irreversible. Previous research has indicated that, while a cementitious composite is subjected to a state of stress, dissolution of cement grains and precipitation of hydrates can yield irreversible creep strains, and it is hypothesized that the same process can lead to irreversible shrinkage during drying. To evaluate this hypothesis, a computationally implemented model integrating a microstructural evolution model with a finite element calculation routine was utilized. This computationally implemented model is capable of predicting the magnitude of shrinkage deformation of cement paste during drying conditions as a result of cement grain dissolution and hydrate precipitation. From the simulation results, the mechanism of cement grain dissolution and hydrate precipitation can lead to significant shrinkage behavior of cement paste, and it is also a potential mechanism resulting in the irreversible component of desiccation shrinkage at early ages (e.g., while the hydration rate is significant). The predicted irreversible shrinkage decreases with the age at which drying is initiated as a result of the decreasing hydration reaction rate.

[en] A recent microstructural model of near-surface external sulfate attack on cement paste is modified to incorporate diffusive ionic transport between the surface and interior of a macroscopic specimen that has been hydrated for 100 d prior to exposure to sulfates. The model estimates the driving force for local expansive growth of the ${\mathrm{A}\mathrm{l}}_2{\mathrm{O}}_3-<!--\; ???\; -->{\mathrm{F}\mathrm{e}}_2{\mathrm{O}}_3$-tri (AFt) phase in terms of crystallization pressure, and the strain and stress fields are tracked within the microstructure with micrometer-scale resolution using a linear elastic finite element model. Damage induced by expansion modifies both the local effective transport properties and linear elastic properties of the local microstructure at different depths, and thereby potentially alters the rates of sulfate ingress and expansion. Therefore, the progress of phase transformations and expansion from the surface to the interior of the porous material is dictated by the rate of ingress of concentration fronts of both sulfate ions and pH, which do not necessarily coincide. The model is used to relate microscopic changes in the structure of cement paste, induced by ingress of sodium sulfate solutions of different concentrations, to the macroscopic expansion, and the results are compared with previous models and published experimental data. The model demonstrates what has previously been assumed in sulfate-attack models, namely that volumetric expansion of macroscopic paste samples in the early stages of sulfate attack is a linear function of the mass of AFt phase precipitated. In addition, the model captures the main features of the evolution of local elastic and transport properties within a macroscopic paste sample, showing an apparently parabolic dependence on depth of the local Young’s modulus and local formation factor. (paper)

[en] Efforts to model and simulate the highly complex cement hydration process over the past 40 years are reviewed, covering different modeling approaches such as single particle models, mathematical nucleation and growth models, and vector and lattice-based approaches to simulating microstructure development. Particular attention is given to promising developments that have taken place in the past few years. Recent applications of molecular-scale simulation methods to understanding the structure and formation of calcium-silicate-hydrate phases, and to understanding the process of dissolution of cement minerals in water are also discussed, as these topics are highly relevant to the future development of more complete and fundamental hydration models.

[en] Disagreements about the mechanisms of cement hydration remain despite the fact that portland cement has been studied extensively for over 100 years. One reason for this is that direct observation of the change in microstructure and chemistry are challenging for many experimental techniques. This paper presents results from synchrotron nano X-ray tomography and fluorescence imaging. The data show unprecedented direct observations of small collections of C₃S particles before and after different periods of hydration in 15 mmol/L lime solution. X-ray absorption contrast is used to make three dimensional maps of the changes of these materials with time. The chemical compositions of hydration products are then identified with X-ray fluorescence mapping and scanning electron microscopy. These experiments are used to provide insight into the rate and morphology of the microstructure formation.

[en] The reasons for the start and end of the induction period of cement hydration remain a topic of controversy. One long-standing hypothesis is that a thin metastable hydrate forming on the surface of cement grains significantly reduces the particle dissolution rate; the eventual disappearance of this layer re-establishes higher dissolution rates at the beginning of the acceleration period. However, the importance, or even the existence, of this metastable layer has been questioned because it cannot be directly detected in most experiments. In this work, a combined analysis using nano-tomography and nano-X-ray fluorescence makes the direct imaging of early hydration products possible. These novel X-ray imaging techniques provide quantitative measurements of 3D structure, chemical composition, and mass density of the hydration products during the induction period. This work does not observe a low density product on the surface of the particle, but does provide insights into the formation of etch pits and the subsequent hydration products that fill them.