Non-Isothermal Crystallization Kinetics of PBSu/Biochar Composites Studied by Isoconversional and Model Fitting Methods

Polymers (Basel). 2023 Mar 23;15(7):1603. doi: 10.3390/polym15071603.

Abstract

Non-isothermal crystallization of Poly(butylene succinate) (PBSu)/biochar composites was studied at various constant cooling rates using differential scanning calorimetry. The analysis of the kinetics data revealed that the overall crystallization rate and activation energy of the PBSu polymer were significantly influenced by the addition of biochar. Specifically, the PBSu/5% biochar composite with a higher filler content was more effective as a nucleation agent in the polymer matrix, as indicated by the nucleation activity (ψ) value of 0.45. The activation energy of the PBSu/5% biochar composite was found to be higher than that of the other compositions, while the nucleation activity of the PBSu/biochar composites decreased as the biochar content increased. The Avrami equation, which is commonly used to describe the kinetics of crystallization, was found to be limited in accurately predicting the non-isothermal crystallization behavior of PBSu and PBSu/biochar composites. Although the Nakamura/Hoffman-Lauritzen model performed well overall, it may not have accurately predicted the crystallization rate at the end of the process due to the possibility of secondary crystallization. Finally, the combination of the Šesták-Berggren model with the Hoffman-Lauritzen theory was found to accurately predict the crystallization behavior of the PBSu/biochar composites, indicating a complex crystallization mechanism involving both nucleation and growth. The Kg parameter of neat PBSu was found to be 0.7099 K2, while the melting temperature and glass transition temperature of neat PBSu were found to be 114.91 °C and 35 °C, respectively, very close to the measured values. The Avrami nucleation dimension n was found to 2.65 for PBSu/5% biochar composite indicating that the crystallization process is complex in the composites.

Keywords: Nakamura/Hoffman–Lauritzen model; biochar; non-isothermal crystallization kinetics; poly(butylene succinate); Šesták–Berggren/Hoffman–Lauritzen model.