Memory effect in isothermal crystallization of syndiotactic polypropylene - role of melt structure and dynamics?

The crystalline-memory effect on the crystallization of syndiotactic polypropylene is investigated by differential scanning calorimetry and solid-state NMR spectroscopy. The influence of several parameters in the thermal (pre-)treatment and the crystallization conditions is studied in detail. In agreement with previous reports, the power law behavior of the overall crystal growth rate is found to be remarkably different for melts with and without memory. This has previously been interpreted in terms of changes in the structure and/or the dynamics of the melt (disentangled state, local order), and a variety of NMR experiments is used to detect such potential changes. All our NMR results are identical for melts with and without memory, therefore excluding any large effect of the "memory" on melt structure or dynamics exceeding the percent level of the whole sample volume, and thus supporting more conventional interpretations in terms of persisting nuclei. Samples that were pre-crystallized at lower temperatures exhibit a larger memory effect, and the potential nuclei fraction is a non-equilibrium structure and is restricted to the 0.1% level if it is crystalline or highly ordered.