Toughening of poly(l-lactide) with poly(ε-caprolactone): Combined effects of matrix crystallization and impact modifier particle size

Enhancing matrix crystallization has been demonstrated to be an effective method to simultaneously improve the impact toughness and heat resistance of poly(l-lactide) (PLLA) modified with flexible polymers, such as poly(ε-caprolactone) (PCL). Unfortunately, increasing PLLA matrix crystallinity alone cannot guarantee the enhancement of impact toughness in most cases, so other structural parameters should be considered. In this work, taking PLLA/PCL (80/20) blend as an example, the combined roles of matrix crystallization and impact modifier particle size in the toughening have been investigated. PLLA matrix crystallinity was controlled by adding a highly effective nucleating agent and PCL particle size was tailored by varying processing conditions while maintaining constant interfacial adhesion. It is interesting to find that toughening is efficient only if matrix crystallinity and particle size are well matched. With the significant increase of matrix crystallinity, an evident decrease of optimum particle size for toughening PLLA has been identified for the first time. Therefore, suitable particle size is the precondition for highly crystalline matrix to work effectively in the toughening because only small particles (0.3–0.5 μm) are effective in trigger shear yielding mechanism of the matrix needed for good toughness, whereas relatively large particles (0.7–1.1 μm) are only capable of toughening amorphous matrix effectively by initiating multiple crazing of the matrix. Importantly, our findings can be used to well explain the reason for the different roles of matrix crystallization in the toughening of different PLLA blends reported in the literature. Furthermore, the heat resistance of the blend with a highly crystalline matrix is much better than that of the blend with an amorphous one as expected. This work could not only provide a new insight into the synergistic roles of matrix crystallization and modifier particle size in the toughening of PLLA but also set up a universal framework for designing high-performance PLLA products with both good impact toughness and high heat resistance.