Melting and crystallization of UHMWPE skived film

Commercial skived film from ultra-high molecular-weight polyethylene (UHMWPE) with considerable uniaxial orientation of lamellae is studied by ultra-small-angle X-ray scattering (USAXS) and wide-angle X-ray scattering (WAXS) during melting and crystallization in order to identify its mechanisms of crystallization. For the analysis of the nanostructure two-dimensional USAXS patterns are analyzed by means of the multidimensional chord distribution function (CDF) method. WAXS shows that crystallization is always isotropic and fast. WAXS reflections are observed before—under certain processing conditions—the SAXS pattern becomes anisotropic. Thus crystallization is decoupled from a slower process of oriented nanostructure formation (nanoforming). If nanoforming is performed isothermally at 105 °C, the evolving nanodomain layers obtain some preferential orientation, as long as the orientation of the melt has not previously been erased by melt-annealing at temperatures of 140 °C or above. Crystallization at temperatures ≥110 °C followed by quenching leads to isotropic nanostructure. Although crystallization is always observed early in the WAXS patterns, the USAXS patterns exhibit only weak discrete scattering during isothermal treatment at temperatures of 110 °C and higher. At 105 °C anisotropic isothermal nanoforming starts after 1.5 min. The melting of the original material resembles an inverted random car-parking mechanism. Only next-neighbor correlations are observed among the crystalline layers. The average nanodomain layer thickness is only slightly increasing (26–30 nm), whereas the long period increase is strong (from 60 nm to 140 nm).