Force-Dependent Fracture of Dynamic Polymer Networks: Sacrificial Bond Rupture and Dispersion-Induced Physical Crosslinking
- 1School of Chemistry and Chemical Engineering
- 2Shanghai Jiao Tong University
Abstract
We use coarse-grained molecular dynamics to investigate tensile fracture in dynamically crosslinked polymer networks, where both weak-linker and strong backbone bonds rupture according to Bell-model force-dependent probabilities. Competition between these pathways determines whether preferential weak-linker rupture relieves local stress, redistributes load, and protects the backbone. Lower linker activation energy or stretching stiffness promotes this sacrificial pathway, suppressing backbone rupture and delaying failure. Linker regeneration preserves connectivity but reloads the backbone, weakening sacrificial protection and reducing extensibility. Dispersion interactions between linker beads induce aggregation and physical crosslinking; moderate attraction reinforces the network, whereas stronger attraction suppresses weak-linker rupture, redirects load to the backbone, and causes embrittlement. Varying dynamic crosslinker content further tunes the balance between sacrificial weak-linker rupture and dispersion-induced reinforcement, with an intermediate content providing a favorable combination of stiffness, strength, and extensibility. These results identify force-dependent competition between weak and strong bonds as a unifying mechanism for polymer-network design.
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BibTeX
@misc{guo2026forcedependent,
title = {{Force-Dependent Fracture of Dynamic Polymer Networks: Sacrificial Bond Rupture and Dispersion-Induced Physical Crosslinking}},
author = {Wenjing Guo and Tao Zhang},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008249/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008249/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Force-Dependent Fracture of Dynamic Polymer Networks: Sacrificial Bond Rupture and Dispersion-Induced Physical Crosslinking
AU - Wenjing Guo
AU - Tao Zhang
PY - 2026
DA - 2026/09/03
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008249/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008249/v1
AB - We use coarse-grained molecular dynamics to investigate tensile fracture in dynamically crosslinked polymer networks, where both weak-linker and strong backbone bonds rupture according to Bell-model force-dependent probabilities. Competition between these pathways determines whether preferential weak-linker rupture relieves local stress, redistributes load, and protects the backbone. Lower linker activation energy or stretching stiffness promotes this sacrificial pathway, suppressing backbone rupture and delaying failure. Linker regeneration preserves connectivity but reloads the backbone, weakening sacrificial protection and reducing extensibility. Dispersion interactions between linker beads induce aggregation and physical crosslinking; moderate attraction reinforces the network, whereas stronger attraction suppresses weak-linker rupture, redirects load to the backbone, and causes embrittlement. Varying dynamic crosslinker content further tunes the balance between sacrificial weak-linker rupture and dispersion-induced reinforcement, with an intermediate content providing a favorable combination of stiffness, strength, and extensibility. These results identify force-dependent competition between weak and strong bonds as a unifying mechanism for polymer-network design.
ER -