Surface Nanopatterns of Two Types of Banded Spherulites in Poly(nonamethylene terephthalate) Thin Films

Surface nanopatterns of dual ring-banded spherulites in poly(nonamethylene terephthalate) (PNT) were investigated using polarized optical microscopy (POM) and atomic force microscopy (AFM). The surface morphology differs between narrow-spaced single ring bands versus widely spaced double ring bands in spherulites, labeled Type-1 and Type-2, respectively. Ridge and valley consist of two discrete species ranging from nano- to micrometer-sized crystals shaped and oriented differently. Ridges of Type-1 and Type-2 spherulites apparently differ in shapes of the crystal plates. AFM height profile analysis reveals that the ridge of Type-2 ring-banded spherulite is higher than that of Type-1 spherulites. The crystal packing on the ridges and valley of these two types of ring-banded was further compared using high-magnification AFM phase imaging. There exists a transition zone in going from the ridge and valley regions in the Type-2 ring-banded spherulites crystallized at T c = 75–85 °C; the crystals on the transition zone change gradually in sizes and orientation from those in the ridge to valley. By contrast, Type-1 ring-banded spherulite does not have this kind of transition zone, meaning that crystals in the ridges abruptly submerge into valley in Type-1 ring-banded spherulites. Details of packing of nanosize crystals in forming ridge and valleys of these two ring band types are discussed.