From microns to nanometers: morphology development in semicrystalline polymers by scanning force microscopy

In studies of spherulitic crystallization in polymers, many questions pertaining to the mechanism of the crystallization process have remained unanswered. A currently accepted view describes the development of spherulites from a framework of individual dominant lamellae that splay apart and branch (e.g., by a dislocation mechanism). This model, in addition, assumes that the space between the dominant lamellae is filled by subsidiary lamellae. In the center of a spherulitic entity, there is a hedritic core that occupies a relative volume that depends on the level of maturity of the spherulitic development. Typical hedritic views consist of lamellae that have a flat stack, or sheaflike, splaying appearance depending on the angle and depth of observation with respect to the central stack of lamellae. Visualization of the three-dimensional appearance of these hedrites by atomic force microscopy (AFM) and the observation of their growth in situ are the subjects of this article. First, we describe AFM studies of hedrites observed at etched surfaces of β-isotactic polypropylene (β-IPP). Evidence sup-porting splaying, branching via dislocations, and development of curved lamellae is presented. In the second part, we describe real-time hot-stage AFM in situ observations of the hedritic growth in poly(ethylene oxide) (PEO) and poly-(ε-caprolactone) (PCL)