Morphologies of miscible PCL/PVC blends confined in ultrathin films

Morphologies of ultrathin films (10–60 nm) of miscible poly(ε-caprolactone)/poly(vinyl chloride) (PCL/PVC) blends have been investigated under isothermal crystallization conditions by real time atomic force microscopy, and electron diffraction techniques. It was found that the morphology and growth rate of PCL/PVC blends strongly depend on the blend composition, crystallization temperature and film thickness. At a film thickness of 30 nm, the truncated lozenge-shape morphology of pure PCL crystals, found when the growth rate is slow, bent with increasing PVC content to form S-shaped or inverted S-shaped crystals, the curvature increasing by lowering the crystallization temperature. Electron diffraction patterns reveal that these crystals are flat-on single crystals with the PCL molecular chains (c axis) in the blends slightly tilted with respect to the lamella normal, while the b direction of the crystal lattice, corresponding to the fast growing direction of the growth front, follows a S line. Upon decreasing the film thickness (<30 nm), the S-shaped or inverted S-shaped crystals transform into four-branch dendritic lamellae.