Multifunctional polyurethane shape memory polymers (PU-SMPs) have been of increasing interest in various applications. Here we report structure characterization, detailed methodology, and obtained results on the identification of functional properties of a thermoset PU-SMP (MP4510) with glass transition temperature of 45 °C. The stable, chemically crosslinked network of this thermoset PU-SMP results in excellent shape memory behavior. Moreover, the proximity of the activation temperature range of this smart polymer to room and body temperature enables the PU-SMP to be used in more critical industrial applications, namely fast-response actuators. The thermomechanical behavior of a shape memory polymer determines the engineering applications of the material. Therefore, investigation of the shape memory behavior of this class of commercial PU-SMP is of particular importance. The conducted structural characterization confirms its shape memory properties. The shape fixity and shape recovery properties were determined by a modified experimental approach, considering the polymer’s sensitivity to external conditions, i.e., the temperature and humidity variations. Three thermomechanical cycles were considered and the methodology used is described in detail. The obtained shape fixity ratio of the PU-SMP was approximately 98% and did not change significantly in the subsequent cycles of the thermomechanical loading due to the stability of chemical crosslinks in the thermoset materials structure. The shape recovery was found to be approximately 90% in the first cycle and reached a value higher than 99% in the third cycle. The results confirm the effect of the thermomechanical training on the improvement of the PU-SMP shape recovery after the first thermomechanical cycle as well as the effect of thermoset material stability on the repeatability of the shape memory parameters quantities.

Thermoresponsive shape memory polymers (SMPs) with the remarkable ability to remember a temporary shape and recover their original one using temperature have been gaining more and more attention in a wide range of applications. Traditionally, SMPs are investigated using a method named often “hot-programming”, since they are heated above their glass transition temperature (T_g) and after that, reshaped and cooled below T_g to achieve and fix the desired configuration. Upon reheating, these materials return to their original shape. However, the heating of SMPs above their T_g during a thermomechanical cycle to trigger a change in their shape creates a temperature gradient within the material structure and causes significant thermal expansion of the polymer sample resulting in a reduction in its shape recovery property. These phenomena, in turn, limit the application fields of SMPs, in which fast actuation, dimensional stability and low thermal expansion coefficient are crucial. This paper aims at a comprehensive experimental investigation of thermoplastic polyurethane shape memory polymer (PU-SMP) using the cold programming approach, in which the deformation of the SMP into the programmed shape is conducted at temperatures below T_g. The PU-SMP glass transition temperature equals approximately 65 °C. Structural, mechanical and thermomechanical characterization was performed, and the results on the identification of functional properties of PU-SMPs in quite a large strain range beyond yield limit were obtained. The average shape fixity ratio of the PU-SMP at room temperature programming was found to be approximately 90%, while the average shape fixity ratio at 45 °C (T_g − 20 °C) was approximately 97%. Whereas, the average shape recovery ratio was 93% at room temperature programming and it was equal to approximately 90% at 45 °C. However, the results obtained using the traditional method, the so-called hot programming at 65 °C, indicate a higher shape fixity value of 98%, but a lower shape recovery of 90%. Thus, the obtained results confirmed good shape memory properties of the PU-SMPs at a large strain range at various temperatures. Furthermore, the experiments conducted at both temperatures below T_g demonstrated that cold programming can be successfully applied to PU-SMPs with a relatively high T_g. Knowledge of the PU-SMP shape memory and shape fixity properties, estimated without risk of material degradation, caused by heating above T_g, makes them attractive for various applications, e.g., in electronic components, aircraft or aerospace structures.