Novel tunable super-tough materials from biodegradable polymer blends: nano-structuring through reactive extrusion†
Structuring blends on sub-micrometer scales, especially nano-scales, has a higher potential for improving their thermomechanical properties. Here, we propose a design strategy to fabricate compatible nano-blends by manipulating the reactions between two biodegradable polymers, e.g. polybutylene succinate (PBS) and polybutylene adipate terephthalate (PBAT), with extremely low free radical contents through reactive extrusion processing. Observed by transmission electron microscopy (TEM) and atomic force microscopy (AFM), it is found that PBAT is tightly surrounded by large amounts of PBS–PBAT co-polymers and dispersed in a PBS matrix with a particle size of less than 100 nm. We show how impact strength and polymer moduli can be improved simultaneously by decreasing the small amount of dispersed phase into nano-scale (droplet or lamina structures). With 5 wt% PBAT content in the PBS–PBAT blend, the notched impact strength of PBS is increased 1200% and the Young's modulus is increased 15%. Through in situ rheological monitoring and Fourier-transform infrared spectroscopy (FTIR) studies, the reason why nano-blends can be formed in such a low amount of peroxide is illustrated. Our investigation most significantly indicates the transformation of the partially compatible PBS–PBAT micro-blend into a fully compatible PBS–PBAT through nano-structuring. This work addresses the importance of reaction rate and mechanism in favoring the formation of co-polymers rather than homo-polymer crosslinking or self-decomposition in polymer blend modification via reactive extrusion design.