Multiscale Structure and Microscopic Deformation Mechanisms of Gel-Spun Ultrahigh-Molecular-Weight Polyethylene Fibers

We investigate the molecular features of high-performance gel-spun ultrahigh-molecular-weight polyethylene UHMWPE fibers (SK75, invented and manufactured by DSM) and propose a multiscale structural model that describes the organization of molecules from the unit cell to the filament level, based on X-ray diffraction in static and dynamic conditions (during tensile testing). The model emphasizes the discontinuous nature of the crystalline phase, which is embedded in a percolating amorphous phase and connected by tie molecules running through the amorphous phase. The tie molecules play a critical role in the tensile properties (e.g., Young's modulus and sonic modulus) of the material. We analyze the micromechanics of the material during tensile deformation and show that, in the elastic regime, the stress-transfer mechanisms (e.g., tie molecules) are so efficient to realize a homogeneous stress distribution through the various length scales (from filament level to unit cell level). Plastic deformation of filaments begins with shear break-up of crystals that triggers or is triggered by an unusual, not well explored, deformation mode of the orthorhombic unit cell (contraction of the a-axis with simultaneous expansion of the b-axis). We also show that the morphological model with discontinuous crystalline phase provides a logical base for the interpretation of the sonic modulus of UHMWPE fibers. Realignment of molecules in the noncrystalline regions of the material can explain the remarkable increase of the sonic modulus measured during tensile tests.