Real Time Development of Structure in Partially Molten State Stretching of Polypropylene as Detected by Spectral Birefringence Technique: Effect of Isotacticity

The uniaxial deformation behavior of three polypropylene films with isotacticity indices varying from 43 to 95 was investigated in the partially molten state using real time, true stress, true strain, and birefringence measurement system. These polymers generally exhibit three regime stress‐birefringence behaviors during stretching. The unmelted crystalline regions act as physical junctions. If the films contain crystallinity that is too low (less than ca. 10%) the Regime I disappears. Under these conditions, the films were found to exhibit large linearity in strain and stress optical behavior. If, however, too low a deformation rate is employed, these relationships become non‐linear.

The increase of isotacticity increases the magnitude of the birefringence at all deformation levels primarily as a result of the increase in crystallinity that helps in establishing a long‐range physical network. This increase in the long‐range connectivity was found to promote not only the orientation in crystalline domains but also in the amorphous domains. The increased long‐range connectivity in high isotacticity films was also found to result in destruction of local initial structures that generate a large fraction of the oriented amorphous chain regions. This translates into larger stress decrease and birefringence increase changes during the holding stage where the oriented amorphous chains undergo complex relaxation/oriented crystallization processes.