Universal Polymer Dynamics Revealed by Field Cycling 1H NMR

Abstract

We apply fast field cycling 1H NMR to study segmental reorientation dynamics in melts of linear polybutadiene, polyisoprene, and polydimethylsiloxane in the high molecular weight limit. Measuring fully protonated as well as partially deuterated polymers, we show that in contrast to previous reports the relaxation behavior at low frequencies, for which polymer-specific contributions show up, is not universal but depends on the particular internuclear vectors of the 1H spin pairs in the monomer unit. Only after extracting the polymer specific contributions from the overall susceptibility spectra by accounting for the glassy contribution, the “polymer spectra” reveal universal behavior which can be described by two power law regimes: one attributed to free Rouse dynamics and one, at lower frequencies, to entanglement effects. Yet the predictions of the tube-reptation model are not observed.