Akimichi Oda

Precursors in stereo-complex crystals of poly(l-lactic acid)/poly(d-lactic acid) blends under shear flow

To improve the mechanical and the thermal performance of poly(lactic acid) materials, this work focuses on the formation of stereo-complex crystals by blending poly(l-lactic acid) (PLLA) with poly(d-lactic acid) (PDLA). The resulting structure was analyzed using time-resolved in situ X-ray scattering, optical microscopy, differential scanning calorimetry and viscoelastic measurements. The objective of this study is to investigate the effect of shear flow imposed prior to crystallization on higher-order structure formation and acceleration of stereo-complex crystal growth of PLLA and PDLA blends using a wide spatial scale analysis and viscoelastic measurements. Density fluctuations of 100 nm scale were observed prior to nucleation by in situ simultaneous wide- and small-angle X-ray scattering measurements. These density fluctuations grew with time and the intensity increased with increasing shear rate. Furthermore, the results revealed that the PLLA and PDLA chains were only partially interpenetrated; consequently, stereo-complex crystals could grow only in the mixed PLLA/PDLA phase. The correlation length of density fluctuation prior to nucleation was strongly dependent on the mixed phases.

Isothermal Crystallization Process of Poly(l-lactic acid)/Poly(d-lactic acid) Blends after Rapid Cooling from the Melt

We observed the crystallization process in poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) blends using in situ simultaneous small- and wide-angle X-ray scattering measurements with a high-speed temperature control cell. In situ X-ray scattering measurements revealed that density fluctuations larger than the long spacing periods grew during crystallization above 130 °C. In particular, the time evolution of the density fluctuations has a strong dependence on the crystallization temperature. The density fluctuations will promote the crystal nucleation and growth processes of the stereocomplex and increase with increasing crystallization temperature, which is strongly correlated with the complexation of PLLA and PDLA chains. On the other hand, below 120 °C, the kinetics of stereocomplex formation might be hindered by the decreased mobility, and no density fluctuations were observed in the case of homo crystal growth of PLLA or PDLA.