Differential diffusion driven far-from-equilibrium shape-shifting of hydrogels

Far-from-equilibrium (FFE) conditions give rise to many unusual phenomena in nature. In contrast, synthetic shape-shifting materials typically rely on monotonic evolution between equilibrium states, limiting inherently the richness of the shape-shifting behaviors. Here we report an unanticipated shape-shifting behavior for a hydrogel that can be programmed to operate FFE-like behavior. During its temperature triggered shape-shifting event, the programmed stress induces uneven water diffusion, which pushes the hydrogel off the equilibrium based natural pathway. The resulting geometric change enhances the diffusion contrast in return, creating a self-amplifying sequence that drives the system into an FFE condition. Consequently, the hydrogel exhibits counterintuitive two opposite shape-shifting events under one single stimulation, at a speed accelerated by more than one order magnitude. Our discovery points to a future direction in creating FFE conditions to access otherwise unattainable shape-shifting behaviors, with potential implications for many engineering applications including soft robotics and medical devices.