Posted by This study employs a multiscale simulation approach to investigate the underlying mechanisms of reversible cross-linking behavior in polymer materials, spanning from the molecular to the continuum scale. At the molecular scale, all-atom molecular dynamics simulations revealed host–guest interactions in the reversible cross-linking system and quantified the energy barriers associated with the reversible association and dissociation of supramolecular crosslinks. These results elucidate the intrinsic mechanisms of dynamic crosslinking and energy dissipation. At the continuum scale, finite element analysis was conducted to examine interfacial adhesion mechanisms, focusing on the effects of interface thickness, stress distribution, and overall toughness. Among the studied host-guest pairs, β-cyclodextrin–adamantane (βCD–Ad) formed the most stable configuration, consistent with experimental results. Additionally, two stable interaction sites were identified above and below the center of the cyclic molecule, which are critical for achieving both high toughness and effective reversible cross-linking. The finite element results further demonstrate that the mechanical properties of the host-guest interface significantly influence both the macroscopic mechanical response and healing behavior. With increasing interface thickness, the effective Young’s modulus increases, indicating greater interfacial stiffness, whereas the maximum stress peaks at intermediate thickness then slightly declines, likely due to reduced modulus compatibility and localized stress concentrations.
Chao Luo, Kenji Yamaoka, Yoshinori Takashima, Yasutomo Uetsuji (2026) Multiscale mechanistic analysis of reversible cross-linking polymers based on host–guest interactions from molecular to continuum simulations. Journal of Molecular Structure 1355, 145020.
https://doi.org/10.1016/j.molstruc.2025.145020.