The Effect of Thermal History on the Fast Crystallization of Poly(l-Lactide) with Soluble-Type Nucleators and Shear...

The N₁,N₁'-(ethane-1,2-diyl)bis(N₂-phenyloxalamide) (OXA) is a soluble-type nucleator with a dissolving temperature of 230 °C in poly(l-lactic acid) (PLLA) matrix. The effect of thermal history and shear flow on the crystallization behavior of the PLLA/OXA samples was investigated by rheometry, polarized optical microscopy (POM), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and scanning electron microscopy (SEM). The crystallization process of the PLLA/OXA-240 sample (i.e., pre-melted at 240 °C) was significantly promoted by applying a shear flow, e.g., the onset crystallization time (t_onset) of the PLLA at 155 °C was reduced from 1600 to 200 s after shearing at 0.4 rad/s for even as short as 1.0 s, while the crystallinity (X_c) was increased to 40%. Moreover, the t_onset of the PLLA/OXA-240 sample is 60%⁻80% lower than that of the PLLA/OXA-200 sample (i.e., pre-melted at 200 °C) with a total shear angle of 2 rad, indicating a much higher crystallization rate of the PLLA/OXA-240 sample. A better organization and uniformity of OXA fibrils can be obtained due to a complete pre-dissolution in the PLLA matrix followed by shear and oscillation treatments. The well dispersed OXA fibrils and flow-induced chain orientation are mainly responsible for the fast crystallization of the PLLA/OXA-240 samples. In addition, the shear flow created some disordered α'-form crystals in the PLLA/OXA samples regardless of the thermal history (200 or 240 °C).