Hysteresis is observed in sorption-induced swelling in various soft nanoporous polymers. The associated coupling mechanism responsible for the observed sorption-induced swelling and associated hysteresis needs to be unraveled. Here we report a microscopic scenario for the molecular mechanism responsible for hysteresis in sorption-induced swelling in natural polymers such as cellulose using atom-scale simulation; moisture content and swelling exhibit hysteresis upon ad- and desorption but not swelling versus moisture content. Different hydrogen bond networks are examined; cellulose swells to form water–cellulose bonds upon adsorption but these bonds do not break upon desorption at the same chemical potential. These findings, which are supported by mechanical testing and cellulose textural assessment upon sorption, shed light on experimental observations for wood and other related materials.

Highlights: 1. Coupling mechanism of sorption and deformation is reviewed by molecular simulations. 2. Poromechanics model is developed based on the coupling mechanism at nanoscale. 3. Different types of sorption isotherms exhibited by different adsorbent-adsorbate systems are quantitatively explained by the developed model. 4. Influences of material properties on the coupled behavior of sorption and deformation are characterized.

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This paper aims at providing a methodological framework for investigating wood polymers using atomistic modeling, namely, molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations. Atomistic simulations are used to mimic water adsorption and desorption in amorphous polymers, make observations on swelling, mechanical softening, and on hysteresis. This hygromechanical behavior, as observed in particular from the breaking and reforming of hydrogen bonds, is related to the behavior of more complex polymeric composites. Wood is a hierarchical material, where the origin of wood-moisture relationships lies at the nanoporous material scale. As water molecules are adsorbed into the hydrophilic matrix in the cell walls, the induced fluid–solid interaction forces result in swelling of these cell walls. The interaction of the composite polymeric material, that is the layer S2 of the wood cell wall, with water is known to rearrange its internal material structure, which makes it moisture sensitive, influencing its physical properties. In-depth studies of the coupled effects of water sorption on hygric and mechanical properties of different polymeric components can be performed with atomistic modeling. The paper covers the main components of knowledge and good practice for such simulations.