Nanosilk-Grafted Poly(lactic acid) Films: Influence of Cross-Linking on Rheology and Thermal Stability

This article reports a novel fabrication of branched cum cross-linked poly(lactic acid) (PLA) with nanosilk fibroin with graft chain topology by reactive extrusion process. It could be possible by the addition of a small amount of radical initiator (dicumyl peroxide (DCP)). Grafting of silk nanocrystals (SNCs) on PLA macromolecules that provides remarkable improvement in the rheological and thermal properties of the latter are confirmed by 1 H NMR and Fourier transform infrared investigation. Significant improvement is observed in zero shear viscosities, and the crossover point shifts to lower frequencies as compared to the branched and cross-linked PLA system. Along with SNC grafting, the crystallization process is also enhanced and stable crystals appeared during cooling, which results in a single melting peak. The rate of crystallization of PLA has been improved although the percentage crystallinity reduces with DCP content, as higher grafting and cross-linking restricts the chain segmental motion, which is critical for crystallization process. Furthermore, SNC grafting increases the reprocessability performance of PLA and provides higher rheological properties as compared to the branched and cross-linked PLA at all reprocessing cycles.