Observation of banded spherulites in pure poly(l-lactide) and its miscible blends with amorphous polymers

Banded spherulites of pure poly(l-lactide) (PLLA) were observed via the 'crystallization after annealing' procedure, while only common spherulites were obtained via the 'direct isothermal crystallization' procedure. Wide angle X-ray diffraction revealed that the two types of spherulites had the same crystal lattice of α-modification. Atomic force microscopy demonstrated that the alternative negative and positive birefringent bands resulted from the alternative edge-on and flat-on lamellar orientations in the spherulites. Furthermore, the effect of thermal history on the spherulitic morphology was investigated in details. The PLLA samples melted for longer time or those with lower melting point were more likely to form banded spherulites. The possibility that the change of molecular weight was a determining factor of banding was excluded by the results on differently prepared samples with the same molecular weight. Therefore, we conclude that it was complete melting of the crystalline residues that favored formation of PLLA banded spherulites. Blending of PLLA with atactic poly(d,l-lactide) or poly[(R,S)-3-hydroxybutyrate], led to reduced band spacing. Effect of blending on the chain mobility, spherulite growth kinetics, supercooling and lamellar surface energy was quantitatively studied, which suggests that the blending-reduced band spacing cannot be attributed to the above factors. Therefore, there are other blending-relevant factors leading to the reduced band spacing.