Observation of shish crystal growth into nondeformed melts

Thin films of isotactic polystyrene (iPS) were deformed on a carbon supported TEM grid at temperatures between 210 °C and 240 °C. The elongation of the supercooled polymer melt films is localized in a deformation zone due to the formation of cracks within the brittle carbon support film, whereas the adjoining areas stay in a relaxed state. Since the nucleation of fibrous (shish) crystals needs an orientation mechanism to align the molecular chains, their origin is located in the deformation zone. It is shown that the subsequent growth of the shish crystal can propagate into the relaxed melt although it has to surmount the adhesion to the carbon substrate. From these results the conclusion is drawn that the shish crystal growth can be an autocatalytic process, which induces a self-orientation of the molecules in the growth front of the crystal tip and does not necessarily need an external flow field.