Influence of molecular weight on crystallization rate of oriented, glassy nylon 6

Differential scanning calorimetry and wide angle X‐ray diffractometry were used to investigate the effects of molecular weight and molecular weight distribution on the crystallization kinetics of oriented, glassy nylon 6. The samples had number average molecular weights ranging from 10,000 to 42,000 and polydispersity indices ranging from 2.0 to 3.1. Noncrystalline films were prepared by quenching molten films between plattens chilled with liquid nitrogen. These films were drawn 4X and 5‐1/3X, and the resultant uniaxial orientation was observed to enhance markedly the room temperature crystallization kinetics. Although macroscopic deformation can be assumed to be affine at the molecular level, it is hypothesized that wholechain molecular relaxation occurs at rates inversely proportional to the square of molecular weight, thereby creating a distribution of extension ratios which reflect the actual molecular weight distribution. Thus, the crystallization rate and the degree of crystallinity depend on the fraction of high molecular weight molecules present in the sample. Given two samples with the same molecular weight, the one with the broader distribution crystallizes more rapidly. Similarly, samples having the larger molecular weight crystallize to a greater extent when two samples have the same molecular weight distribution.