Molecular weight dependence of segmental alignment in a sheared polymer melt: A deuterium nuclear magnetic resonance investigation

Abstract

H 2 NMR quadrupole interaction spectroscopy has been used to measure the molecular weight dependence of poly(dimethylsiloxane) chain deformation under shear in a cylindrical Couette cell while NMR velocimetry has been used to directly measure shear rates. The signals were acquired from a perdeuterated benzene probe molecule, which provides a motionally averaged sampling of the entire segmental ensemble. We have measured the dependence on shear rate of the SXX (velocity), SYY (velocity gradient), and SZZ (vorticity) elements of the segmented alignment tensor, fitting the data using the standard Doi–Edwards theory and modified to allow for convected constraint release. Our results suggest that the tube disengagement times scale as molecular weight to the power 3.5±0.1, consistent with the usual 3.4 power law. Our velocimetry measurements indicate a reproducible and consistent slip occurring at high molecular weights (>1 M Dalton), a phenomenon which is independently observed in a lower than expected chain deformation.