Enhancing nucleation and controlling crystal orientation by rubbing/scratching the surface of a thin polymer film

We used the tip of an atomic force microscope (AFM) in the contact mode to scratch/rub the surface of a glassy polymer thin film, i.e., isotactic polystyrene (i-PS) at room temperature. After subsequent isothermal crystallization, an extremely high nucleation density of edge-on crystals within the rubbed region or at the edge of the scratched area was observed. Furthermore, a transition from edge-on to flat-on lamellae occurred beyond a certain distance from the edge of the scratched region. Our results demonstrate that both, soft rubbing or hard scratching, allow to lower the nucleation barrier for polymer crystallization and to control the orientation of the resulting crystalline lamellae. The role of scratching/rubbing on chain deformation and its relation to nucleation and crystal orientation in polymer thin films is discussed.