Molecular dynamics simulation and non-isothermal crystallization kinetics of polyamide 4 and different bio-based polyamide blends

Abstract

The effects of the structural units and blending ratio on the crystallization behavior of blends of polyamide 4 (PA4) with polyamide 56 (PA56) and polyamide 11 (PA11) were studied using molecular dynamics simulations and non-isothermal crystallization kinetics. The simulation results show that the crystallinity of PA4/PA56 blends (B4/56) with a PA56 content of 30–50% was 3.5–10.8% lower than that of B4/56 with a PA56 content of 20%, and the crystallinity of PA4/PA11 blends (B4/11) decreased by 9.5% as PA11 content increased from 20% to 50%. The experimental results show that both B4/56 and B4/11 form PA4- and PA56-rich (PA11-rich) phases through crystallization-induced phase separation. The interplanar spacing of the PA4-rich phase of B4/56 changed relative to that of PA4, indicating that some PA56 entered the PA4-rich phase unit cell. As the PA56 content increased from 20% to 50%, the crystallinity of B4/56 decreased by 11.2%, and the crystallization-induced phase separation grew distinct. The B4/56 with a higher PA4 content crystallized more easily. As the PA11 content increased from 20% to 50%, the crystallinity of B4/11 decreased by 12.5%, and PA11 barely participated in the crystallization of the PA4-rich phase. The blending ratio had no significant effect on the crystallization rate and crystal-growth degree of B4/11, and the non-isothermal crystallization activation energy of B4/11 was significantly higher than that of B4/56, indicating that the crystallization ability of the B4/11 blend system is worse. This study provides a theoretical basis for the design and performance regulation of PA4-based polyamide blends.