Controlling stereocomplex crystal morphology in poly(lactide) through chain alignment

The incorporation of poly(d-lactide) (PDLA) to form stereocomplex crystallites (SCs) within a poly(l-lactide) (PLLA) matrix is among the most effective strategies in overcoming PLLA's numerous drawbacks. However, high concentrations of PDLA (>3 wt%) are required to improve PLLA's crystallization kinetics and melt strength, which is undesirable owing to PDLA's high cost. In this study, we use chain alignment as a levier to tune stereocomplex superstructure morphology to overcome these limitations. Herein, PLLA/PDLA blends were manufactured using an environmentally friendly and low-cost single step spunbond fibrillation process, yielding microfibers stretched to diameters of 5-20 μm. During this stretching process, PLLA and PDLA chains are aligned along the flow direction. SCs subsequently formed in situ upon heating, dramatically improving crystallization kinetics, melt elasticity, and tensile performance compared with neat PLLA and non-stretched blend analogues, even with low PDLA content (<3 wt%). These improvements were attributed to topological variations in SC superstructures caused by alignment of PLLA and PDLA chains. The application of chain alignment in tuning SC superstructure morphology is ubiquitous in fibrillation processes.