The role of the amorphous phase in melting of linear UHMW-PE : implications for chain dynamics

In ultra-high molecular weight polyethylene (UHMW-PE), it is possible to obtain single chain forming single crystals, where chains are adjacently re-entrant. Depending on the heating rate, it is feasible to melt these crystals either by simple consecutive detachment of chain stems from the crystalline substrate or by cluster melting, where several chain stems are involved. The consecutive detachment of chain stems occurs at the melting point predicted from the Gibbs–Thomson equation, whereas the cluster melting at much higher temperatures. Melting by the consecutive detachment of chain stems from the crystal substrate and their diffusion in the melt ultimately result in a new melt state having a heterogeneous distribution of physical entanglements, which invokes differences in local mobility. With combined DSC, rheology and solid-state NMR studies, it is concluded that the disentangled domains present within the entangled matrix possess higher local mobility than the entangled domains, ultimately causing lower elastic modulus. The fraction of the entangled and disentangled domains is maintained at higher temperatures, leading to a thermodynamically non-equilibrium melt state. In contrast, in cluster melting, where several chain stems (initially disentangled) can simultaneously adopt the random coil state, entanglements that are formed are homogeneously distributed in the melt. The paper invokes the influence of the topological differences present in the amorphous phase of the semi-crystalline polymer on the melting kinetics of crystals. The reported findings have implications for the melting behaviour and the resulting melt state of polymers in general.