Nucleation, Development and Healing of Micro-Cracks in Shape Memory Polyurethane Subjected to Subsequent Tension Cycles.

Thermoresponsive shape memory polymers (SMPs) have garnered increasing interest for their exceptional ability to retain a temporary shape and recover the original configuration through temperature changes, making them promising in various applications. The SMP shape change and recovery that happen due to a combination of mechanical loading and appropriate temperatures are related to its particular microstructure. The deformation process leads to the formation and growth of micro-cracks in the SMP structure, whereas the subsequent heating over its glass transition temperature T g leads to the recovery of its original shape and properties. These processes also affect the SMP microstructure. In addition to the observed macroscopic shape recovery, the healing of micro-crazes and micro-cracks that have nucleated and developed during the loading occurs. Therefore, our study delves into the microscopic aspect, specifically addressing the healing of micro-cracks in the cyclic loading process. The proposed research concerns a thermoplastic polyurethane shape memory polymer (PU-SMP) MM4520 with a T g of 45 °C. The objective of the study is to investigate the effect of the number of tensile loading-unloading cycles and thermal shape recovery on the evolution of the PU-SMP microstructure. To this end, comprehensive research starting from structural characterization of the initial state and at various stages of the PU-SMP mechanical loading was conducted. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) were used. Moreover, the shape memory behavior in the thermomechanical loading program was investigated. The obtained average shape fixity value was 99%, while the shape recovery was 92%, which confirmed good shape memory properties of the PU-SMP. Our findings reveal that even during a single loading-unloading tension cycle, crazes and cracks nucleate on the surface of the PU-SMP specimen, whereas the subsequent temperature-induced shape recovery process carried out at the temperature above T g enables the healing of micro-cracks. Interestingly, the surface of the specimen after three and five loading-unloading cycles did not exhibit crazes and cracks, although some traces of cracks were visible. The traces disappeared after exposing the material to heating at T g + 20 °C (65 °C) for 30 min. The crack closure phenomenon during deformation, even without heating over T g , occurred within three and five subsequent cycles of loading-unloading. Notably, in the case of eight loading-unloading cycles, cracks appeared on the surface of the PU-SMP and were healed only after thermal recovery at the particular temperature over T g . Upon reaching a critical number of cycles, the proper amount of energy required for crack propagation was attained, resulting in wide-open cracks on the material's surface. It is worth noting that WAXS analysis did not indicate strong signs of typical highly ordered structures in the PU-SMP specimens in their initial state and after the loading history; however, some orientation after the cyclic deformation was observed.