Tuneable material properties of Organosolv lignin biocomposites in response to heat and shear forces

Lignin as a renewable biomacromolecule is considered as a sustainable feedstock for the generation of bioplastics and bioplastic composites. However, during thermoplastic processing, high temperature and mechanical forces are known to promote destructive bond-cleavage in a vast majority of macromolecules due to overheating and internal friction between molecular constituents. This study demonstrates that several material properties (e.g. thermal stability, mechanical properties) of biocomposites with a high Organosolv lignin content (≥50 w%) can be tuned by carefully selecting thermal and mechanical energy input during compounding. Organosolv lignin obtained from ensiled grass was shown to undergo in-situ coupling reactions at temperatures below the main degradation point (<200 °C) resulting in an up to 6-fold increase in molecular weight (M_w). The results from Fourier Transform Infrared (FTIR) spectroscopy suggested the formation of ester bonds, which was ascribed to direct esterification reactions, which occur due to energy transfer in the melt phase. When subjecting the extracted lignin to prolonged compounding times, it was shown that higher coupling degrees resulted in a lignin biocomposite with increased stiffness and ultimate tensile stress of about 1800% and 40%, respectively. Temperature was shown to have the highest effect on coupling reactions, whereas the energy transfer by mechanical forces during compounding was lower and followed a non-linear behaviour. In tensile stress–strain curves, biocomposites with high energy input revealed a distinct yield point (16 MPa). Ultra-micro-hardness tests confirmed that the biocomposite became significantly stiffer in response to shear and thermal forces with a reduction in indentation creep C_it of 2.0% to a value of up to 8.5%. Organosolv lignin biocomposites obtained at higher specific energy input (EIN) through thermal energy input and shear forces showed an increased dynamic stiffness C_dyn up to 100%, which was observed by multiple step tests (MST).