Effects of entanglements on the crystallization and morphology of semicrystalline polymers

Crystallization of polymers from entangled melts generally leads to the formation of semicrystalline materials with a nanoscopic morphology consisting of stacks of alternating crystalline and amorphous layers. The factors controlling the thickness of the crystalline layers were extensively studied; however, there is no quantitative understanding of the thickness of the amorphous layers. We elucidate the effect of entanglements on the semicrystalline morphology by the use of a series of model blends of high-molecular weight polymers with unentangled oligomers leading to a reduced entanglement density in the melt as characterized by rheological measurements. Small-angle X-ray scattering experiments after isothermal crystallization reveal a reduced thickness of the amorphous layers, while the crystal thickness remains largely unaffected. We introduce a simple, yet quantitative model without adjustable parameters, according to which the measured thickness of the amorphous layers adjusts itself in such a way that the entanglement concentration reaches a specific maximum value. Furthermore, our model suggests an explanation for the large supercooling that is typically required for crystallization of polymers if entanglements cannot be dissolved during crystallization.