Segmental Mobility, Interfacial Polymer, Crystallization and Conductivity Study in Polylactides Filled with Hybrid Lignin-CNT Particles

A newly developed series of polylactide (PLA)-based composites filled with hybrid lignin-carbon nanotube (CNTs) particles were studied using thermal and dielectric techniques. The low CNT content (up to 3 wt%) aimed to create conductive networks while enhancing particle-polymer adhesion. For comparison, PLA composites based on lignin and CNTs were also examined. Although infrared spectroscopy showed no significant interactions, calorimetry and dielectric spectroscopy revealed a rigid interfacial PLA layer exhibiting restricted mobility. The interfacial polymer amount was found to increase monotonically with the particle content. The hybrid-filled PLA composites exhibited electrical conductivity, whereas PLA/Lignin and PLA/CNTs remained insulators. The result was indicative of a synergistic effect between lignin and CNTs, leading to lowering of the percolation threshold to 3 wt%, being almost ideal for sustainable conductive printing inks. Despite the addition of lignin and CNTs at different loadings, the glass transition temperature of PLA (60 °C) decreased slightly (softer composites) by 1-2 K in the composites, while the melting temperature remained stable at ~175 °C, favoring efficient processing. Regarding crystallization, which is typically slow in PLA, the hybrid lignin/CNT particles promoted crystal nucleation without increasing the total crystallizable fraction. Overall, these findings highlight the potential of eco-friendly conductive PLA composites for new-generation applications, such as printed electronics.