Inclusion/Exclusion Behaviors of Small Molecules during Crystallization of Polymers in Miscible PLLA/TAIC Blend

In this work, PLLA/TAIC has been taken as a model system to investigate the inclusion and exclusion of small molecules during the crystallization of polymers in their miscible blend. Our results indicate that it is the growth rate and diameter of PLLA spherulites that dominate the localization of TAIC. On the one hand, crystallization temperature plays an important role. Crystallization at higher temperature corresponds to higher growth rates and a greater diameter of PLLA spherulites. The former improves the ability of PLLA crystals to trap TAIC while the latter leads to a lower volume fraction of space among neighboring PLLA spherulites. The combination of the two contributes to the enhanced inclusion behaviors. On the other hand, when compared to melt crystallization, cold crystallization results in much smaller spherulites (from higher nucleation density) and sufficient space among spherulites, which accounts for the enrichment of TAIC in interspherulitic regions and for its enhanced exclusion. In the adopted polymer–small molecule blend, TAIC can enrich in interspherulitic regions even in its miscible blend with PLLA, which can be attributed to its stronger diffusion ability.