Fatigue fracture phenomenon that violates Lake-Thomas model in amorphous hydrogels with dynamic covalent crosslinks
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Hydrogels composed of three-dimensional amorphous polymer networks are widely used as soft and stretchable components in emerging devices and machines, as diverse as soft robotics, hydrogel ionotronics, hydrogel bioelectronics, tissue adhesives, and artificial organs. However, existing amorphous hydrogels are susceptible to fatigue fracture [1]. In this talk, we describe amorphous hydrogels with dynamic covalent bonds that can resist fatigue fracture [2]. The proposed hypothesis is verified by performing fatigue tests for polyacrylamide hydrogels crosslinked by covalent C–C bonds and by dynamic covalent siloxane bonds, with N, N’-methylenebis-acrylamide (MBAA) and silanes as the crosslinkers, respectively. Experiment results show that the fatigue threshold of MBAA-crosslinked hydrogels is 12.7 J/m2, much lower than the toughness, 70.2 J/m2, and comparable to the Lake–Thomas prediction, 11.17 J/m2. By contrast, the silane-crosslinked hydrogels achieve a fatigue threshold of 68.7 J/m2, surprisingly close to the toughness, 86.2 J/m2, which is reported for the first time in hydrogels with dynamic covalent bonds. The violation of the Lake–Thomas mechanism is due to the dynamic nature of siloxane bonds. Self-healing tests, self-recovery tests, and fatigue tests for silane-crosslinked hydrogels with different pH values are further performed to examine the bond dynamics. We discuss the importance of dynamic covalent bonds in synthesizing fatigue-free hydrogels by constructing a fatigue threshold-toughness Ashby plot. This work paves alternative avenues towards anti-fatigue soft materials with amorphous polymer networks.