The Isothermal Melting Kinetics of Ultra-High Molecular Weight Polyethylene Crystals

The isothermal melting behaviors of ultra-high molecular weight polyethylene (UHMWPE) with different entangled states (i.e., nascent and melt-crystallized samples) are studied. For two kinds of UHMWPE samples, the result shows that the relative content of survived crystals (X_s) exponentially decreases with time and reaches a constant value. It is suggested that such a melting behavior is related to the observed nonlinear growth of crystals induced by the kinetically rejected entanglements accumulated at the growth front. Additionally, the exponential decay of X_s with time provides a characteristic melting time (τ) for the melting process. Compared to the melt-crystallized UHMWPE, the τ value of nascent UHMWPE is generally longer even in a higher temperature range, which is mainly because the former has a larger entanglement density difference. Furthermore, these observations demonstrate that UHMWPEs with different entangled states have an analogous melting mechanism since they exhibit a similar melting activation energy (≈1300 kJ mol⁻¹).