Thermoplastic Blend Exhibiting Shape Memory-Assisted Self-Healing Functionality

Here, we report on a polymer blend consisting of a soft thermoplastic polyurethane (TPU) elastomer and a low melting temperature thermoplastic healing agent (polycaprolactone, PCL). In this study, polymer blends containing up to 60 wt % PCL were prepared and the resulting mechanical, thermal, shape memory, and self-healing properties were studied. These immiscible polymers exhibit two well-separated transitions attributable to the melting of PCL and TPU hard segments. This viscoelastic behavior engendered shape memory capability at moderate processing temperatures (∼90 °C) and melt processability at elevated temperatures (>160 °C). The reversible plasticity shape memory (RPSM) effect was also characterized: when subjected to 125% strain at room temperature and subsequently heated to 90 °C, the samples nearly fully recovered to their original length. Moreover, upon heating to above PCL's melting temperature, the flow of PCL into an undeformed crack was shown to fill the crack void, thus promoting self-repair. Through the action of mild heating (90 °C/30 min), fracture surfaces are brought into intimate contact through the action of the RPSM effect and subsequently healed through the redistribution of molten PCL. The shape memory-assisted self-healing efficiency was evaluated by comparing the tensile force restoration after healing of a highly deformed, notched sample to its behavior prior to notching. It was observed that blends containing up to 30 wt % PCL showed nearly complete restoration of properties. In contrast, pure TPU showed only about 5% healing efficiency because of the absence of the PCL healing agent. Blends containing 50 and 60 wt % PCL likewise did not exhibit appreciable restoration of properties, and this was attributed to their propensity to neck during crack opening and poor mechanical properties at elevated temperatures. Blends may serve as a self-healing replacement for pure TPU in existing applications (e.g., automotive and sporting goods) or as a self-healing shape memory polymer in advanced products in soft robotic, biomedical, and microelectronic applications.