화학공학소재연구정보센터
Journal of Chemical Physics, Vol.116, No.22, 10020-10029, 2002
Molecular weight dependence of segmental alignment in a sheared polymer melt: A deuterium nuclear magnetic resonance investigation
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 S-XX (velocity), S-YY (velocity gradient), and S-ZZ (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.