Simulating the Shape-Memory Behavior of Amorphous Switching Domains of Poly(L-lactide) by Molecular Dynamics

Abstract

The thermally induced shape-memory effect of polymers is typically characterized by cyclic uniaxial thermomechanical tests. Here, a molecular-dynamics (MD) simulation approach of such a cyclic uniaxial thermomechanical test is presented for amorphous switching domains of poly(L-lactide) (PLLA). Uniaxial deformation of the constructed PLLA models is simulated with a Parinello–Rahman scheme, as well as a pragmatic geometrical approach. We are able to describe two subsequent test cycles using the presented simulation approach. The obtained simulated shape-memory properties in both test cycles are similar and independent of the applied deformation protocols. The simulated PLLA shows high shape fixity ratios (Rf ≥ 94%), but only a moderate shape recovery ratio is obtained (Rr ≥ 30%). Finally, the structural changes during the simulated test are characterized by analysis of the changes in the dihedral angle distributions.