NMR spin–spin relaxation in solid and molten polyethylene structures

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Abstract
The NMR spin‐spin relaxation (T2) spectra of high‐density polyethylene (PE) has been investigated over a wide range of temperatures, both in the solid and molten states. Previous work in these laboratories has shown that the T2 relaxation spectrum of molten polyethylene differs from that of other polymers studied in that (a) it cannot be decomposed into two relaxation spectra (T2S and T2L) and (b) there is some evidence of a memory effect. This paper attempts to elucidate these observations, and compare them with the spin‐spin relaxation of polyethylene at lower temperatures. In the solid state, the T2 decay comprises both a Gaussian distribution for the crystalline region, and an exponential decay for the amorphous component. The effects of crystallization conditions and of temperature were determined. In the molten state the T2 decay is more complex, but can be resolved into three exponentials. The longest (T2L) component arises as expected from the most mobile, low molecular weight fraction. The T2S component is due to an entangled but mobile network, as in other polymers. In addition, a short relaxation component T2X is observed, which is influenced by previous crystallinity and the processing history of the material, and is ascribed to some vestigial degree of structure in the molten phase.