Mechanisms of multi-shape memory effects and associated energy release in shape memory polymers

Shape memory polymers have attracted increasing research interest due to their capability of fixing a temporary shape and associated deformation energy then releasing them later on demand. Recently, it has been reported that polymers with a broad thermomechanical transition temperature range can demonstrate a multi-shape memory effect (m-SME), where shape recovery and energy release occur in a stepped manner during free recovery. This paper investigated the underlying physical mechanisms for these observed shape memory behaviors and the associated energy storage and release by using a theoretical modeling approach. A multibranch model, which is similar to the generalized standard linear solid model of viscoelasticity, was used for a quantitative analysis. In this model, individual nonequilibrium branches represent different relaxation modes of polymer chains with different relaxation times. As the temperature was increased in a staged manner, for a given temperature, different numbers of branches (or relaxation modes) became shape memory active or inactive, leading to the observed m-SME. For energy release during free recovery, under a tensile deformation of the SMP, stored energy in individual nonequilibrium branches was first transferred into a compressive deformation energy, then gradually declined to zero. Energy release during recovery was a complicated process due to the involvement of multiple relaxation modes.