Empowering PLA bioplastics: Elevating applications horizon through groundbreaking eco-innovative fibrillation, chain extension, and crosslinking techniques

Abstract

This comprehensive study introduces pioneering techniques in the toughening of polylactic acid (PLA) by incorporating thermoplastic polyurethane (TPU) nanofibrils, leveraging two distinct crosslinking methods to significantly enhance the material’s mechanical performance. Method 1 employs a silane/moisture crosslinking process, whereas Method 2 utilizes a tailored diisocyanate crosslinking approach, offering a more environmentally sustainable alternative. Molecular structural analysis was performed extensively by using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC), rheological assessments, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). Method 2 not only preserves TPU nanofibrils but also elevates the mechanical properties of PLA-TPU composites beyond the capabilities of Method 1. Notably, by leveraging the simultaneous crosslinking of TPU and chain extension of PLA with the tailored diisocyanate approach, we enhance PLA’s mechanical properties and energy absorption capabilities. These advancements are achieved without a high rubber content, which typically compromises strength/stiffness, thermomechanical stability, crystallization, and transparency of PLA. The resulting composites prepared via Method 2 display remarkable increases in tensile toughness, ranging from 30-60 MPa, and impact strength, achieving a span of 60–140 J/m. This is primarily due to the occurrence of a brittle-to-ductile transition (BDT) at only 3 wt% nanofibril TPU content while maintaining a high PLA modulus of 3 GPa. This critical balance between chain-extending and crosslinking reactions ensures the maintenance of PLA’s inherent strength/stiffness, crystallization, and optical clarity. The research presented here marks a significant shift in the development of tougher, more thermally stable, transparent, and sustainable polymer blends and composites. Method 2, with its tailored fiber size reduction (90–280 nm), and environmental consciousness, broadens the horizon of PLA’s applications.