Shape Memory Networks With Tunable Self‐Stiffening Kinetics Enabled by Polymer Melting‐Recrystallization

Shape memory polymers (SMPs) are deformable materials capable of recovering from a programmed temporary shape to a permanent shape under specific stimuli. However, shape recovery of SMPs is often accompanied by the evolution of materials from a stiff to soft state, leading to a significant decrease in strength/modulus and thereby impacting their practical applications. Although some attempts are made to pursue the SMPs with self-stiffening capability after shape recovery, the modulus increase ratio is much limited. Inspired by the recrystallization process of CaCO₃ during crab molting, a novel and universal strategy is developed to construct water-free self-stiffening SMPs by using a single thermal stimulus through harnessing the polymer melting-recrystallization. The shape recovery is achieved through the melting of polymer primary crystals, followed by the self-stiffening via polymer recrystallization at the same recovery temperature, in which the modulus increase rate and ratio can be programmed in a wide range. Additionally, conceptual applications of these self-stiffening SMPs as artificial stents with self-enhancing supporting function are successfully demonstrated. This work is believed to provide new insights for developing the advanced shape memory devices.