The deuteron NMR Hahn echo decay in polyethylene oxide melts

Abstract

The deuteron transverse relaxation properties of polyethylene oxide melts of four different molecular weights, covering the range from the onset of entanglements to the regime of fully entangled chains, are investigated using Hahn echo decays over an extensive time interval up to ten times the effective transverse spin relaxation time. The results are compared to predictions based on the Rouse and reptation formalisms, taking into account the dynamical heterogeneity of linear polymer chains produced by the end segments. The experimental results can be described qualitatively by a combination of both models, with the contribution of reptation dynamics increasing with growing chain length. The transition is continuous, rather than being characterized by sharp regime boundaries. Up to a molecular weight of 300.000 g/mol, the predicted limit of pure reptation dynamics is not yet reached. Quantitative deviations from the predicted decays as computed by numerical procedures become observable toward the long-time limit of the Hahn echo decays and are being discussed in terms of shortcomings of the available reptation theories.