Disentangled Melt of Ultrahigh-Molecular-Weight Polyethylene: Fictitious or Real?

There are two opposing views on the role of the melting of low-entangled polyethylenes on the obtained entanglement density in the molten state and the time required for its equilibration, namely, instantaneous recovery to the equilibrium melt state upon melting (chain explosion) versus slow recovery (melt memory effect). A series of rheological studies have shown that slow heating of low-entangled nascent ultrahigh-molecular-weight polyethylene (UHMWPE) powders to temperatures above the equilibrium melting temperature causes the formation of "the disentangled nonequilibrium melt" due to consecutive detachment of chain stems from the edges of crystals keeping the largely intact low-entangled middle part of chains in the melt. Contrary to the rheology findings, studies of several mechanical properties of recrystallized UHMWPE have found that the equilibrium entanglement density is reached instantly upon the melting of low-entangled UHMWPE, suggesting a chain explosion mechanism. To obtain additional information that can help in understanding the melt memory phenomenon better, several UHMWPE samples are studied by H-1 NMR T-2 relaxometry. The NMR experiments are performed for melts prepared from UHMWPE powders with different entanglement densities that were molten using fast (similar to 10 K/min) and slow (similar to 0.2 K/min) heating rates. In all cases, the existence of "the disentangled nonequilibrium melt" was not observed. The results are explained by the chain explosion mechanism that leads to the equilibrium volume-average entanglement density, already at the final stage of melting. Cautious rheological experiments also do not detect "the disentangled nonequilibrium melt". Possible artifacts of previous rheological studies of disentangled UHMWPE melts are discussed. The conclusion of the present study is supported by a large number of previous investigations that are briefly reviewed. Is the disentangled melt state fictitious or real? The answer is yes and no. Chain explosion causes instantaneous equilibration of the volume-average entanglement density upon melting by the formation of local entanglements that play a major role in several volume-average properties, i.e., modulus, drawability, adhesion, segmental mobility, and some other properties. However, the uniform distribution of topological knots between chains is a slow process that is largely governed by chain reptation. The heterogeneity of the entanglement network as well as the impurities in UHMWPE can influence (1) the local nucleation phenomenon at crystallization that does not characterize the entanglement network and (2) deformation properties at ultimate strains. Therefore, the definition of melt memory and chain explosion should be specified to properties that are used for the characterization of low-entangled and equilibrium melt states.