Effect of Salt on Dynamic Mechanical Behaviors of Polyampholyte Hydrogels

Understanding the dynamic mechanical behaviors of tough hydrogels with ionic dynamic bonds in saline solution is crucial for applications, particularly in the biomedical field. In this work, using polyampholyte hydrogels, dually crosslinked with a primary network from covalent crosslinkers and/or trapped entanglements, and a dynamic network from ionic bonds, as a model system, we investigate the salt effect on rheological response and mechanical behaviors. Through a systematic study on one gel without a chemical crosslinker and one gel with a chemical crosslinker, we demonstrate that the salt effect on mechanical properties, including small-strain moduli, large deformation energy dissipation, and fracture stretch ratio, can be effectively converted into frequency or strain rate dependences following the time-salt superposition principle. Accordingly, we access a wide range of observation time scales from 10-11 to 102 rad/s at room temperature, covering three regimes: (I) the high-frequency plateau regime from the dynamic and primary networks, (II) the viscoelastic regime from sticky Rouse motion of ionic associations, and (III) the low-frequency plateau regime from the primary network. Moreover, we disclose an in-depth understanding of the entanglement's behavior in the long-timescale regime III. This work not only provides a guide to biological applications of hydrogels in saline environments but also gives important insights into the toughening mechanism via dynamic bonds in other systems with dually crosslinked structures.