Reversible Shape-Memory Effect in Cross-Linked Linear Poly(ε-caprolactone) under Stress and Stress-Free Conditions

The effect of cross-link density on the reversible shape-memory effect (SME) under constant load was systematically studied in cross-linked linear poly(e-caprolactone) (PCL). A remarkable reversible SME under stress-free conditions was observed in PCL with the highest achieved cross-link density. Thermal properties as well as morphology, size, and orientation of the nanocrystalline structure formed in covalent networks of PCL under load were compared with those in PCL crystallized under stress-free conditions. As shown, the oriented growth of crystals is the origin of both the reversible SME under and without load. Furthermore, a significant rise of crystallinity and crystal thickness was detected in PCL crystallized under constant load. The fitting curves of the temperature-dependent strain as well as the quantities of crystallinity, type of crystalline structure, size, and orientation of the crystals got by modeling the reversible SME in PCL under stress well correspond to their values obtained experimentally.