How entanglements determine the morphology of semicrystalline polymers*

Crystallization of polymers from entangled melts generally leads to the formation of semicrystalline materials with a nanoscopic lamellar morphology. Controlling this structure is key to the rational design, application and possible re-use of thermoplastic materials, but there is no consensus yet on the factors that control the thickness of the amorphous layers. We elucidate the effect of entanglements on the morphology in a series of model blends of high-molecular-weight polymers with unentangled oligomers leading to a reduced entanglement density as characterized by rheological measurements in the melt. Small-angle X-ray scattering experiments after isothermal crystallization reveal a reduced thickness of the amorphous layers, while the crystal thickness remains largely unaffected. A simple yet quantitative model without adjustable parameter is suggested, 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.