Lamellae evolution of stereocomplex-type poly(lactic acid)/organically-modified layered zinc phenylphosphonate nanocomposites induced by isothermal crystallization

Abstract

Stereocomplex-type poly(lactic acid) (SC-PLA)/oleylamine-modified layered zinc phenylphosphonate (SC-PLA/m-PPZn) nanocomposites are successfully fabricated using a solution mixing process. Wide-angle X-ray diffraction (WAXD) analysis reveals that the structural arrangement of the oleylamine-modified PPZn exhibits a large interlayer spacing of 30.3 Å. In addition, we investigate the temperature effect on the real-time structural arrangement of PPZn and m-PPZn. The results indicated that the lattice expansion of m-PPZn with increasing temperature leads to an increase in the interlayer spacing from 30.3 to 37.1 Å as the temperature increases from 30 to 150 °C. The interlayer spacing decreases slightly as the temperature further increases to 210 °C. This behavior might be attributed to interlayer oleylamine elimination, which results in hydrogen bonding destruction between the hydroxide sheets and water molecules. As the temperature reaches 240 °C, the in situ WAXD patterns show the coexistence of m-PPZn and PPZn. However, the layered structures of m-PPZn at 300 °C are almost the same as those of PPZn, after the complete degradation temperature of oleylamine. The morphology of the SC-PLA/m-PPZn nanocomposites characterized using WAXD and transmission electron microscopy (TEM) demonstrates that most partial delamination layered materials are randomly dispersed in the SC-PLA matrix. Small-angle X-ray scattering reveals that higher crystal layer thickness and lower surface free energy is achieved in 0.25 wt% SC-PLA/m-PPZn nanocomposites. These results indicate that the introduction of 0.25 wt% m-PPZn into SC-PLA reduces the surface free energy, thereby increasing the polymer chain mobility.