Franz-Josef Ulm

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.

A realistic molecular model of cement hydrates

Despite decades of studies of calcium-silicate-hydrate (C-S-H), the structurally complex binder phase of concrete, the interplay between chemical composition and density remains essentially unexplored. Together these characteristics of C-S-H define and modulate the physical and mechanical properties of this “liquid stone” gel phase. With the recent determination of the calcium/silicon (C/S = 1.7) ratio and the density of the C-S-H particle (2.6 g/cm3) by neutron scattering measurements, there is new urgency to the challenge of explaining these essential properties. Here we propose a molecular model of C-S-H based on a bottom-up atomistic simulation approach that considers only the chemical specificity of the system as the overriding constraint. By allowing for short silica chains distributed as monomers, dimers, and pentamers, this C-S-H archetype of a molecular description of interacting CaO, SiO2, and H2O units provides not only realistic values of the C/S ratio and the density computed by grand canonical Monte Carlo simulation of water adsorption at 300 K. The model, with a chemical composition of (CaO)1.65(SiO2)(H2O)1.75, also predicts other essential structural features and fundamental physical properties amenable to experimental validation, which suggest that the C-S-H gel structure includes both glass-like short-range order and crystalline features of the mineral tobermorite. Additionally, we probe the mechanical stiffness, strength, and hydrolytic shear response of our molecular model, as compared to experimentally measured properties of C-S-H. The latter results illustrate the prospect of treating cement on equal footing with metals and ceramics in the current application of mechanism-based models and multiscale simulations to study inelastic deformation and cracking.

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

Abstract 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 Poissons 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 Poissons 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.

On the use of nanoindentation for cementitious materials

Recent progress in experimental and theoretical nanomechanics opens new venues in materials science for the nano-engineering of cement-based composites. In particular, as new experimental techniques such as nanoindentation provide unprecedented access to micromechanical properties of materials, it becomes possible to identify the mechanical effects of the elementary chemical components of cement-based materials at the scale where physical chemistry meets mechanics, including the properties of the four clinker phases, of portlandite, and of the C-S-H gel. In this paper, we review some recent results obtained by nanoindentation, which reveal that the C-S-H gel exists “mechanically” in two different forms, a lowdensity form and a high-density form, which have different mean stiffness and hardness values and different volume fractions. While the volume fractions of the two phases depend on mix proportions, the mean stiffness and hardness values do not change from one cement-based material to another; instead they are intrinsic properties of the C-S-H gel.RésuméLes récents progrès en “nanomécanique”, aussi bien sur le plan théorique qu’expérimental, ouvrent de nouvelles perspectives en science des matériaux pour la nano-ingénierie des composites à base de ciment. Grace à de nouvelles techniques expérimentales telles que la ‘nanoindentation’, qui permet d’avoir un accès sans précédent aux propriétés micromécaniques des matériaux, il devient notamment possible d’identifier les effets mécaniques des composants chimiques élémentaires à l’échelle où la chimie rejoint la mécanique; cela inclut les propriétés des quatre phases de clinkers, de la portlandite et du gel de C-S-H. Dans le présent article, nous analysons quelques résultats récents obtenus par nanoindentation; ces résultats révèlent que le gel de C-S-H existe “mécaniquement” sous deux formes différentes, l’une à faible densité et l’autre à forte densité. La valeur moyenne du module d’élasticité, de la dureté, ainsi que la fraction volumique de ces deux formes sont différentes. Alors que la fraction volumique des deux phases dépend de la formulation du mélange, les valeurs moyennes du module d’élasticité et de la dureté sont identiques d’un composite à l’autre; il s’agit de propriétés intrinsèques du gel de C-S-H.

Nanogranular origin of concrete creep

Concrete, the solid that forms at room temperature from mixing Portland cement with water, sand, and aggregates, suffers from time-dependent deformation under load. This creep occurs at a rate that deteriorates the durability and truncates the lifespan of concrete structures. However, despite decades of research, the origin of concrete creep remains unknown. Here, we measure the in situ creep behavior of calcium–silicate–hydrates (C–S–H), the nano-meter sized particles that form the fundamental building block of Portland cement concrete. We show that C–S–H exhibits a logarithmic creep that depends only on the packing of 3 structurally distinct but compositionally similar C–S–H forms: low density, high density, ultra-high density. We demonstrate that the creep rate (≈1/t) is likely due to the rearrangement of nanoscale particles around limit packing densities following the free-volume dynamics theory of granular physics. These findings could lead to a new basis for nanoengineering concrete materials and structures with minimal creep rates monitored by packing density distributions of nanoscale particles, and predicted by nanoscale creep measurements in some minute time, which are as exact as macroscopic creep tests carried out over years.

Combinatorial molecular optimization of cement hydrates.

Despite its ubiquitous presence in the built environment, concrete’s molecular-level properties are only recently being explored using experimental and simulation studies. Increasing societal concerns about concrete’s environmental footprint have provided strong motivation to develop new concrete with greater specific stiffness or strength (for structures with less material). Herein, a combinatorial approach is described to optimize properties of cement hydrates. The method entails screening a computationally generated database of atomic structures of calcium-silicate-hydrate, the binding phase of concrete, against a set of three defect attributes: calcium-to-silicon ratio as compositional index and two correlation distances describing medium-range silicon-oxygen and calcium-oxygen environments. Although structural and mechanical properties correlate well with calcium-to-silicon ratio, the cross-correlation between all three defect attributes reveals an indentation modulus-to-hardness ratio extremum, analogous to identifying optimum network connectivity in glass rheology. We also comment on implications of the present findings for a novel route to optimize the nanoscale mechanical properties of cement hydrate.

Confined water dissociation in microporous defective silicates: mechanism, dipole distribution, and impact on substrate properties.

Interest in microporous materials has risen in recent years, as they offer a confined environment that is optimal to enhance chemical reactions. Calcium silicate hydrate (C-S-H) gel, the main component of cement, presents a layered structure with sub-nanometer-size disordered pores filled with water and cations. The size of the pores and the hydrophilicity of the environment make C-S-H gel an excellent system to study the possibility of confined water reactions. To investigate it, we have performed molecular dynamics simulations using the ReaxFF force field. The results show that water does dissociate to form hydroxyl groups. We have analyzed the water dissociation mechanism, as well as the changes in the structure and water affinity of the C-S-H matrix and water polarization, comparing the results with the behavior of water in a defective zeolite. Finally, we establish a relationship between water dissociation in C-S-H gel and the increase of hardness due to a transformation from a two- to a three-dimensional structure.

Creep and shrinkage of concrete: physical origins and practical measurements ☆

Subcommittee 4 of RILEM TC 107-CSP has established recommendations for shrinkage and creep tests. These recommendations are based on physical and mechanical analysis of these tests, to ensure that they provide reproducible and objective results. However, the complete specification of these tests must also make it possible to respond to diversified needs: in particular, industrial users (contractors, suppliers of materials, etc.) are increasingly led to request such tests, and the type of experimental data they expect can be quite different from what is expected by people who draft regulations or develop numerical models. This paper therefore presents, in a first part, thinking about these needs, which are found to be highly varied and rapidly evolving. In a second part, we review the importance of the scale effect that makes it tricky to attempt any extrapolation of the available experimental results in two directions (to the long-term and to large thickness). In the absence of a satisfactory explanation of this scale effect, a practical method is proposed that can be used to get round this difficulty experimentally and to deal with certain engineering problems.

Couplings in early-age concrete: From material modeling to structural design

Abstract Couplings in early-age concrete are the cross-effects between the hydration reaction, temperature evolution and deformation which can lead to cracking. They involve complex chemo-physical mechanism that operate over a broad range of scales, from nanometer to meter. This paper explores these thermo-chemo-mechanical cross-effects from the macroscale of engineering material modeling (the typical scale of laboratory test specimens) to the level of structural design. Set within the framework of chemoplasticity, the cross-effects in the constitutive model are derived from Maxwell-symmetries, and characterize the autogeneous shrinkage, hydrate heat and strength growth due to the chemo-mechanical, thermo-chemical and chemo-plastic couplings. These couplings at a material level can be determined from standard material tests, provided that the order of coupling is known. This is shown by considering adiabatic calorimetric experiments and isothermal strength growth tests, which lead to identify an intrinsic kinetics function that characterizes the macroscopic hydration kinetics of concrete. Finally, an example of application of the model to large-scale finite element analysis of concrete structures is presented, which clearly shows the consequences of thermo-chemo-mechanical couplings for the engineering design of concrete structures at early ages.

Subcontinuum mass transport of condensed hydrocarbons in nanoporous media

Although hydrocarbon production from unconventional reservoirs, the so-called shale gas, has exploded recently, reliable predictions of resource availability and extraction are missing because conventional tools fail to account for their ultra-low permeability and complexity. Here, we use molecular simulation and statistical mechanics to show that continuum description—Darcys law—fails to predict transport in shales nanoporous matrix (kerogen). The non-Darcy behaviour arises from strong adsorption in kerogen and the breakdown of hydrodynamics at the nanoscale, which contradict the assumption of viscous flow. Despite this complexity, all permeances collapse on a master curve with an unexpected dependence on alkane length. We rationalize this non-hydrodynamic behaviour using a molecular description capturing the scaling of permeance with alkane length and density. These results, which stress the need for a change of paradigm from classical descriptions to nanofluidic transport, have implications for shale gas but more generally for transport in nanoporous media.