Abstract
A series of poly(lactic acid) (PLA)/biochar (BC) bio-composites filled with low amounts (1-5 wt%) of BC were prepared and characterized. The synthesis involved the in situ ring-opening polymerization (ROP) of lactide in the presence of two different types of BC named SWP550 and SWP700, having been produced by pyrolysis of softwood pellets at two different temperatures, 550 and 700 °C, respectively. The bio-composites were characterized by complementary techniques. The successful synthesis of PLA and PLA/BC bio-composites was directly demonstrated by the formation of new bonds, most probably between PLA and BC. Indirect evidence for that was obtained by the systematic molar mass reduction in the presence of BC. BC was found by transmission electron microscopy (TEM) micrographs to be well dispersed at the nanosize level, indicating that in situ polymerization is a technique quite efficient for producing bio-composites with finely dispersed BC additive. The molecular dynamics mapping is performed here via dielectric spectroscopy, moreover, for the first time in these PLA/BC systems. The strong PLA/BC interactions (due to the grafting) led to a systematic deceleration of segmental mobility (elevation of the T(g)) in the bio-composites despite the opposite effect expected by the decrease in molar mass with the BC content increasing. In addition, the same interactions and chain-length reduction are responsible for the slight suppression of the PLA's crystallizability. The effects are slightly stronger for SWP700 as compared to SWP550. The crystal structure is rather similar between the unfilled matrix and the bio-composites, whereas, based on the overall data, the semicrystalline morphology is expected to be tighter in the bio-composites. The thermal stability and decomposition kinetics were also thoroughly studied. All materials exhibit good resistance to thermal degradation. Additionally, the mechanical properties of bio-composites were evaluated by tensile testing and found slightly enhanced at low biochar contents and decreasing thereafter due to the low molecular weight of bio-composites with the larger BC contents.