Identifying the location and micellization of PEG-b-PCL multiblock copolymers in PLA/PCL blends via AFM nanoscale IR spectroscopy

The IR absorption mapping of two multiblock copolymers based on poly(ethylene glycol) and poly(ε-caprolactone) segments (PEG-b-PCL) in poly(acid lactic) and poly(ε-caprolactone) blends (PLA/PCL) was performed via AFM nanoscale IR spectroscopy. These copolymers, having the same number average molar masses ($\overline{M_n}$) but varying block sizes, were added into the blend in different amounts (1 and 5 wt%) using a co-rotating twin-screw extrusion. The results revealed that copolymers with smaller blocks are preferentially located near the interface when incorporated in small quantities. Increasing the copolymer content led to preferential diffusion into the PLA matrix. Compatibilization with the longer block-size copolymers also led to preferential diffusion in the PLA matrix, albeit with a tendency to form micelles. This hampers the overall mechanical properties of the blend, making the compatibilized blend more brittle than neat PLA. Compatibilization with the short block-size copolymers showed no micellization and improved the mechanical behavior of PLA/PCL.