Fracture of dual crosslink gels with permanent and transient crosslinks: Effect of the relaxation time of the transient crosslinks
Résumé
We investigate the fracture properties of poly(acrylamide-co-1-vinylimidazole) dual crosslink hydrogels (P(AAm-co-VIm)-M 2+ gels) containing a small fraction of covalent bonds and a majority of dynamic bonds based on metal coordination bonds (Ni 2+ or Zn 2+). Unlike a previous study on a different dual crosslink hydrogel system having slower dynamic bonds based on poly(vinylalcohol) and borate ions (PVA-Borax gels), the presence of these faster dynamic coordination bonds has two main effects: They significantly toughen the P(AAm-co-VIm)-M 2+ gels even at high stretch rates, where the dynamic bonds should in principle behave as covalent bonds at the crack tip, and they toughen the gels at very low stretch rates, where the dynamic bonds are invisible during the loading stage. We propose two additional molecular mechanisms to rationalize this behavior of P(AAm-co-VIm)-M 2+ gels: we hypothesize that fast exchanging dynamic bonds remain slow compared to the characteristic time of bond scission and are therefore able to share the load upon covalent bond scission even at low loading rates. We also argue of the existence of longer-lived clusters of dynamic bonds that introduce a stretch rate dependent strain hardening in uniaxial tension and stabilize and increase the size of the dissipative zone at the crack tip, thereby introducing a strain dependent dissipative mechanism.
Domaines
Matière Molle [cond-mat.soft]Origine | Fichiers produits par l'(les) auteur(s) |
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