Journal of Polymer Science Part B: Polymer Physics, Vol.54, No.16, 1573-1580, 2016
Molecular Mechanism Leading to Memory Effect of Mesomorphic Isotactic Polypropylene
In this study, memory effect of mesomorphic isotactic polypropylene (iPP) was investigated using polarized optical microscope and small-angle X-ray scattering. Differing from classical memory effect, mesomorphic iPP melt had a higher growth rate and a higher memory temperature. The relative growth rate increased with increasing crystallization temperature. Lauritzen-Hoffman plots indicated that the increased growth rate arose from reduced surface nucleation barrier. The highest memory temperature was estimated to be 185 degrees C, which was close to the equilibrium melting point of iPP crystal. Additionally, Small-angle X-ray scattering measurements showed that a liquid crystal layer might exist between lamellar and amorphous layers. Based on above results, a crystallization model was proposed. In the mesomorphic iPP melt, there exist aggregates structurally similar to beta phase except a-phase crystal residuals, which cannot act as nucleation sites or transform to b crystal through surface nucleation. The only way for the aggregate is to transform to a crystal during crystal growth. The aggregate decreases the surface nucleation barrier and promotes the helical growth, leading to higher growth rate. Only when the aggregate relaxes to polymer coils through thickening at a higher temperature, can the memory effect be erased. (C) 2016 Wiley Periodicals, Inc.
Keywords:activation energy;crystallization;growth rate;lamellar;memory effect;mesomorphic iPP;poly(propylene) (PP);SAXS;small-angle X-ray scattering;surface nucleation