Tailored One-Way and Two-Way Shape Memory Capabilities of Poly(ε-Caprolactone)-Based Systems for Biomedical Applications

This paper investigates the shape memory capabilities of semicrystalline networks, focusing the attention on poly(epsilon-caprolactone) (PCL) systems, a class of materials that allows to satisfy important requirements for their applications as biomedical devices, such as the good biocompatibility, the fast recovery of large "temporary" shape configurations, and the easy tailoring of the transformation temperatures. The materials were prepared with various crosslink densities and crosslinking methodologies; in particular, beside a thermal crosslinking based on reactive methacrylic end groups, a novel type of covalently crosslinked semicrystalline systems was prepared by a sol-gel approach from alkoxysilane-terminated PCL precursors, so as to avoid potentially toxic additives typically used for free-radical thermal curing. The materials were subjected to biological tests, to study their ability in sustaining cell adhesion and proliferation, and to thermal characterizations, to evaluate the possibility to tailor their melting and crystallization temperatures. The one-way shape memory (i.e., the possibility to set the material in a given configuration and to recover its pristine shape) and the two-way shape memory response (i.e., the triggered change between two distinguished shapes on the application of an on-off stimulus) were studied by applying optimized thermo-mechanical cyclic histories. The ability to fix the applied shape and to recover the original one on the application of heating (i.e., the one-way effect) was evaluated on tensile bars; further, to investigate a potential application as self-expandable stents, isothermal shape memory experiments were carried out also on tubular specimens, previously folded in a temporary compact configuration. The two-way response was studied through the application of a constant load and of a heating/cooling cycle from above melting to below the crystallization temperature, leading to a reversible elongation/contraction effect, involving maximum strain changes up to about 80%, whose extent may be controlled through the crosslink density.