In Situ Analysis of Melt-Drawing Behavior of Ultrahigh Molecular Weight Polyethylene Films with Different Molecular Weights: Roles of Entanglements on Oriented Crystallization

Ultrahigh molecular weight polyethylene (UHMW-PE) films having different molecular weights (MWs) were melt-drawn at 150 °C. The stress–strain curve for higher-MW film exhibits higher stress on the characteristic plateau region and a subsequent steeper increase of stress due to strain hardening. Structural changes during such melt-drawing were analyzed using in situ wide-angle X-ray diffraction measurements. Hexagonal crystallization occurs at the beginning of the plateau region, independent of the sample MW. Once this hexagonal reflection intensity is saturated, it remains constant even at the later stage of draw. In contrast, orthorhombic reflection intensities gradually increase with increasing draw strain. Both of these oriented crystallizations into plateau hexagonal and increasing orthorhombic forms are accelerated with increasing MW. Correspondingly, the higher amount of extended chain crystals (ECCs) was confirmed from morphological observation for the resultant melt-drawn films of the higher-MW sample. Deep entanglements can effectively transmit the applied stress; thus, the oriented amorphous melts induce rapid hexagonal crystallization with disentangling shallow entanglements, which subsequently transforms into orthorhombic form. Such hexagonal crystallization plays the role of a thermodynamic pathway for growing such ECCs, where the stable orthorhombic form gradually accumulates with increasing draw strain