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Microscopic physical basis of the poromechanical behavior of cement-based materials

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Abstract

Contrary to other porous materials such as sandstones, bricks or porous glas, the inter-atomic bonding continuity of cement-based materials is far from obvious. When scrutinized at very microscopic level, continuity of the ionic-covalent bonding in the solid phase is almost everywhere interrupted by water molecules or liquid water films of variable thickness. Yet, concrete and cement pastes are able to withstand stresses of the same magnitude as rocks. The purpose of this paper to explore the possible reasons for such a high cohesion, in terms of inter-particle forces using general arguments and molecular simulation computations includingab initio quantum chemical methods applied toC-S-H. As it will be discussed, molecular simulation studies provide strong arguments for predicting that short-and medium-range attractive electrostatic forces are the essential components of the cohesion, ofC-S-H with, at short distance (sub-nm), a significant iono-covalent contribution involving strongly localized calcium ions and water molecules and, at larger distance (a few nm), ionic correlation forces involving hydrated and mobile calcium ions in liquid water films. Only a marginal contribution is expected from van der Waals attraction whereas capillary forces might contribute at a level comparable to that of correlation forces in unsaturated conditions. The parallel with clay-based earthen construction materials is part of the clue of this rationale.

Résumé

Contrairement à d'autres matériaux poreux comme les grès, les briques ou certains verres, les matériaux cimentaires ne possèdent pas un schéma simple de liaisons interatomiques. La continuité du réseau de liaisons iono-covalentes y est presque partout interrompue par des molécules d'eau ou des films d'eau d'épaisseur variable. Pourtant, le béton et les pâtes de ciment sont capables de supporter des contraintes du même ordre de grandeur que celles que supportent les roches. Nous avons analysé, les mécanismes de cette cohésion élevée en termes de forces interparticulaires, d'abord à l'aide d'arguments généraux, puis à l'aide de calculs de modélisation moléculaire, y compris des calculs de chimie quantique ab initio, appliqués aux C-S-H. Les résultats fournissent des arguments sérieux en faveur d'une cohésion principalement de type électrostatique avec, à très courte distance (sub-nm), une contribution iono-covalente impliquant des ions calcium et des molécules d'eau fortement localisées et, à plus grande distance (quelques nm), des forces de corrélation ionique dues à des ions calcium mobiles au sein de films d'eau liquide. Les forces de van der Waals n'auraient qu'une contribution marginale tandis que les forces capillaires pourraient avoir, en conditions fortement insaturées, une contribution comparable à celle des forces de corrélation ionique. La comparaison avec les argiles fournit un fil conducteur utile à cette analyse.

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Authors and Affiliations

  1. Centre de Recherche sur la Matière Divisée (CRMD), CNRS and Université d'Orléans, France

    A. Gmira & M. Zabat

  2. Centre de Recherche sur les Mécanismes de la Croissance Cristalline (CRMC2), CNRS, Luminy, France

    R. J. -M. Pellenq

  3. École Supérieure de Physique et Chimie Industrielles (ESPCI), Paris, France

    H. Van Damme

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Gmira, A., Zabat, M., Pellenq, R.J.M. et al. Microscopic physical basis of the poromechanical behavior of cement-based materials. Mat. Struct. 37, 3–14 (2004). https://doi.org/10.1007/BF02481622

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