Negative Enthalpy Variation Drives Rapid Recovery in Thermoplastic Elastomer

Abstract The mechanism behind the resilience of polymeric materials, typically attributed to the well‐established entropy elasticity, often ignores the contribution of enthalpy variation (ΔH), because it is based on the assumption of an ideal chain. However, this model does not fully account for the reduced resilience of thermoplastic polyurethane (TPU) during long‐range deformation, which is mainly caused by the dynamics of physical crosslink networks. Such reduction is undesirable for long‐range stretchable TPU considering its wide application range. Therefore, a negative ΔH effect is established in this work to facilitate instant recovery in long‐range stretchable TPU, achieved by constructing a reversible interim interface via strain‐induced phase separation. Consequently, the newly constructed dual soft segmental TPU shows resilience efficiency exceeding 95%, surpassing many synthetic high‐performance TPUs with typical efficiencies below 80%, and comparable to biomaterials. Moreover, a remarkable hysteresis loop with a ratio exceeding 50%, makes it a viable candidate for applications such as artificial ligaments or buffer belts. The research also clarifies structural factors influencing resilience, including the symmetry of the dual soft segments and the content of hard segments, offering valuable insights for the design of highly resilient long‐range stretchable elastomers.