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.

Poly(lactic acid) (PLA) is a widely used biobased polyester which can be derived from renewable resources. Due to its excellent properties, it has already been adopted in various industrial sectors. While PLA is compostable, its degradation to the environment is very slow, necessitating the development of efficient recycling methods. This study focuses on the chemical recycling via microwave-assisted alkaline hydrolysis of PLA and its copolymers with poly(ethylene azelate) (PEAz), aiming to recover both carboxylic acid monomers: lactic acid and azelaic acid. Moreover, our method tunes the degradation of PLA via the synthesis of the novel aliphatic PLA-based copolyesters, targeting engineering-like applications, specifically in the field of printed electronics. Various process parameters were analyzed, including the temperature and the duration of the experiments as well as different phase transfer catalysts. Complete degradation was achieved at low temperatures (110–125 °C) and short times (12–15 min) for the PLA-based copolyesters, offering significant environmental benefits, as considerably less energy is consumed compared to chemical conventional methods. So, by changing the composition of the copolyesters through the incorporation of PEAz blocky segments, the ester bonds became more susceptible to hydrolysis under alkaline conditions assisted with microwave irradiation. Additionally, enzymatic hydrolysis was also studied in parallel for comparative purposes, revealing low degradation rates, thus establishing the microwave-assisted alkaline hydrolysis as a solid and reliable method for tuning the degradation of PLA-based materials.

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.

A depth study of optical, isothermal crystallization and mechanical properties was conducted on a series of poly(lactic acid) (PLA) nanocomposites based on lignin/multi-walled carbon nanotubes (MWCNTs) hybrid nanomaterial. The preparation was performed via solution casting followed by melt mixing. For comparison reasons, a group of PLA/lignin polymeric materials were prepared. Infrared spectroscopy (FTIR) did not reveal any significant impact on the main peaks of the nanocomposites by the incorporation of the additives. The optical properties were strongly affected by the content of the additive, as long as the thermal transitions parameters as evaluated from the differential scanning calorimetry (DSC) show important differences between cold and melt crystallization. X-ray diffraction (XRD) showed the semicrystalline behavior of the materials, while during isothermal crystallization experiments, the hybrid conductive nanomaterial acted as nucleation agent by promoting crystallization. Under evaluation of the mechanical properties, Young’s modulus tensile parameter increased significantly while the content of the hybrid nanomaterial increased, and the bending experiments of the materials with low content of the additives did not break. Thus, these substrates could be promising candidates for engineering applications, such as printed electronics.

The synthesis of two series of poly(lactic acid) (PLA)-based polymer nanocomposites (PNCs) filled with small amounts (0.5 and 1%) of Ag and Cu nanoparticles (NPs) was performed. Moreover, two methods for the PNC synthesis were performed, namely, ‘conventional mixing techniques’ and ‘in situ ring opening polymerization (ROP)’. The latter method was employed for the first time; moreover, it was found to be more effective in achieving very good NP dispersion in the polymer matrix as well as the formation of interfacial polymer–NP interactions. The in situ ROP for PLA/Cu was not productive due to the oxidation of Cu NPs being faster than the initiation of ROP. The presence of NPs resulted in suppression of the glass transition temperature, T_g (23–60 °C), with the effects being by far stronger in the case of ROP-based PNCs, e.g., exhibiting T_g decrease by tens of K. Due to that surprising result, the ROP-based PLA/Ag PNCs exhibited elevated ionic conductivity phenomena (at room temperature). This can be exploited in specific applications, e.g., mimicking the facilitated small molecules permeation. The effects of NPs on crystallinity (2–39%) were found opposite between the two series. Crystallinity was facilitated/suppressed in the mixing/ROP -based PNCs, respectively. The local and segmental molecular mobility map was constructed for these systems for the first time. Combining the overall data, a concluding scenario was employed, that involved the densification of the polymer close to the NPs’ surface and the free volume increase away from them. Finally, an exceptional effect was observed in PLA + 0.5% Ag (ROP). The crystallization involvement resulted in a severe suppression of T_g (−25 °C).