In Situ Polymerization as an Effective Method, Compared to Melt Mixing, for Synthesis of Flexible Poly(lactic acid) Nanocomposites Based on Metal Nanoparticles

A comprehensive investigation was conducted focusing on two series of poly(lactic acid) (PLA)-based nanocomposites filled with small amounts (0.5 and 1.0%) of metal (Ag/Cu) nanoparticles (NPs). Our work aimed to synthesize PLA/Ag nanocomposites via in situ ring-opening polymerization (ROP), and for comparison purposes, the same materials were also prepared via solution casting followed by melt mixing. PLA/Cu nanocomposites were also prepared via melt extrusion. Gel permeation chromatography (GPC) and intrinsic viscosity measurements [η] showed that the incorporation of Ag nanoparticles (AgNPs) resulted in a decrease in the molecular weight of the PLA matrix, indicating a direct effect of the AgNPs on its macromolecular structure. Fourier-transform infrared spectroscopy (FTIR) revealed no significant changes in the characteristic peaks of the nanocomposites, except for an in situ sample containing 1.0 wt% of AgNPs, where slight interactions in the C=O region were detected. Differential scanning calorimetry (DSC) analysis confirmed the semi-crystalline nature of the materials. Glass transition temperature was strongly affected by the presence of NPs in the case of the in situ-based samples. Melt crystallized studies suggested potential indirect polymer–NP interactions, while isothermal melt crystallization experiments confirmed the nucleation ability of the NPs. The mechanical performance was assessed via tensile and flexural measurements, revealing that the in situ-based samples exhibited remarkable flexibility. Moreover, during the three-point bending tests, none of the in situ nanocomposite samples broke. In this context, next-generation PLA-based nanocomposites have been proposed for advanced applications, including flexible printed electronics.