Shape-Memory Behavior of Polylactide/Silica Ionic Hybrids

Commercial polylactide (PLA) was converted and endowed with shape-memory properties by synthesizing ionic hybrids based on blends of PLA with imidazolium-terminated PLA and poly[s-caprolactone-co-Dplactide] (P[CL-co-LA]) and surface modified silica nanoparticles. The electrostatic interactions assist with the silica nanoparticle dispersion in the polymer matrix. Since nanoparticle dispersion in polymers is a perennial challenge and has prevented nanocomposites from reaching their full potential in terms of performance we expect this new design will be exploited in other polymers systems to synthesize well-dispersed nano composites. Rheological measurements of the ionic hybrids are consistent with the formation of a network. The ionic hybrids are also much more deformable compared to the neat PIA. More importantly, they exhibit shape-memory behavior with fixity ratio R-f approximate to 100% and recovery ratio R-r = 79%, for the blend containing 25 wt % im-PLA and 25 wt % im-P[CL-co-LA] and 5 wt % of SiO2-SO3Na. Dielectric spectroscopy and dynamic mechanical analysis show a second, low-frequency relaxation attributed to strongly immobilized polymer chains on silica due to electrostatic interactions. Creep compliance tests further suggest that the ionic interactions prevent permanent slippage in the hybrids which is most likely responsible for the significant shape-memory behavior observed.