Morphological and kinetic analyses of regime transition for poly[(S)-lactide] crystal growth.

Regime transitions of poly[(S)-lactide] (PLA) crystal growth from the melt were investigated by studying the morphological changes and carrying out kinetic analysis using microscopic techniques. PLA thin films with an average layer thickness of 100 nm were isothermally crystallized at a given crystallization temperature after melting at 220 degrees C. Following isothermal crystallization at a temperature below 145 degrees C, uniform two-dimensional spherulites having stacked flat-on lamellar texture were developed throughout the PLA thin films. On the basis of electron diffraction analysis for two-dimensional spherulites of PLA, it was found that the average growth direction of an individual lamellar crystal was parallel to the crystallographic b axis. At temperatures above 150 degrees C, hexagonal lamellar crystals were formed from the melt. Electron diffractograms of these lamellae showed that the crystal had orthogonal packing of PLA molecules and a truncated-lozenge-shaped growth behavior. The growth surfaces of the hexagonal crystal were parallel to either the crystallographic (110) or the (100) plane. The PLA crystal growth rate along the b axis direction was evaluated at various crystallization temperatures of the thin films. Kinetic analysis of crystal growth in the PLA thin film demonstrated that the regime transitions of PLA crystal growth, from regime III to regime II and from regime II to regime I, occur at around 120 and 147 degrees C, respectively. The transition from regime II to regime I induced morphological changes in the crystalline aggregates whereby spherulitic aggregates transformed into hexagonal lamellar stacking. As for the transition between regimes II and III, no obvious morphological change in the spherulitic crystal aggregates was observed.