Segmental motion of entangled random coil polymers studied by pulsed gradient spin echo nuclear magnetic resonance

Pulsed gradient spin echo nuclear magnetic resonance (NMR) is used to inves tigate polymer mean-squared segmental displacements in semidilute solutions of high molar mass polystyrene in deuterio-toluene. Nine molar masses from 1 to 20 million daltons are studied at a fixed concentration of 5% w/v, an d a range of concentrations from 5% to 20% at fixed molar mass of 3 million daltons. The distance and time scales accessed are 20 to 1000 nm and 10 to 3000 ms, respectively. Evidence for intrachain spin diffusion is found and its effect corrected for. The time dependence of mean-squared segmental di splacements is fitted to the predictions of the Doi-Edwards model and tube disengagement times and tube diameters obtained. (C) 1998 American Institut e of Physics. [S0021-9606(98)50646-0].