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Hysteresis from Multiscale Porosity: Modeling Water Sorption and Shrinkage in Cement Paste

Matthew B. Pinson

Enrico Masoero

Patrick A. Bonnaud

Hegoi Manzano

Qing Ji

Sidney Yip

Jeffrey J. Thomas

Martin Z. Bazant

Krystyn J. Van Vliet

Hamlin M. Jennings*

  • Department of Physics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

  • School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne NE1 7RU, United Kingdom

  • New Industry Creation Hatchery Center, Tohoku University, Sendai 980-8578, Japan

  • Molecular Spectroscopy Laboratory, Universidad del Paìs Vasco/EHU, 48080 Bilbao, Spain

  • Inspur Group, State Key Laboratory of High-End Server & Storage Technology, Jinan, Shangdong 250101, People’s Republic of China

  • Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

  • Schlumberger-Doll Research, Cambridge, Massachusetts 02139, USA

  • Department of Chemical Engineering and Department of Mathematics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

  • Department of Materials Science and Engineering and Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

  • Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

  • *Corresponding author. hmj@mit.edu
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Phys. Rev. Applied 3, 064009 – Published 17 June, 2015

DOI: https://doi.org/10.1103/PhysRevApplied.3.064009

Abstract

Cement paste has a complex distribution of pores and molecular-scale spaces. This distribution controls the hysteresis of water sorption isotherms and associated bulk dimensional changes (shrinkage). We focus on two locations of evaporable water within the fine structure of pastes, each having unique properties, and we present applied physics models that capture the hysteresis by dividing drying and rewetting into two related regimes based on relative humidity (RH). We show that a continuum model, incorporating a pore-blocking mechanism for desorption and equilibrium thermodynamics for adsorption, explains well the sorption hysteresis for a paste that remains above approximately 20% RH. In addition, we show with molecular models and experiments that water in spaces of ≲1  nm width evaporates below approximately 20% RH but reenters throughout the entire RH range. This water is responsible for a drying shrinkage hysteresis similar to that of clays but opposite in direction to typical mesoporous glass. Combining the models of these two regimes allows the entire drying and rewetting hysteresis to be reproduced accurately and provides parameters to predict the corresponding dimensional changes. The resulting model can improve the engineering predictions of long-term drying shrinkage accounting also for the history dependence of strain induced by hysteresis. Alternative strategies for quantitative analyses of the microstructure of cement paste based on this mesoscale physical model of water content within porous spaces are discussed.

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Phys. Rev. Applied 3, 064009– Published 17 June, 2015
  • Received 2 September 2014

© 2015 American Physical Society

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