Journal of Polymer Science Part B: Polymer Physics, Vol.38, No.1, 222-233, 2000
A new proposal for polymer dynamics in steady shearing flows
Beginning with a recently proposed expression for the drag force on a single macromolecule pulled with constant velocity through a fluid of long-entangled molecules (V. R. Mhetar and L. A. Archer, Macromolecules 1998, 31, 6639), we investigate the effect of entanglement loss on polymer dynamics in steady shearing flows. At steady-state, a balance between the elastic restoring force and viscous drag acting on entangled polymer segments reveals a critical molecular strain gamma(m,c) beyond which the drag force exerted on polymer molecules by their neighbors is insufficient to support arbitrarily small orientation angles. Specifically, we find that in fast steady shear flows tau(d)(-1) < (gamma) over dot < tau(Rouse)(-1), polymer orientation in the shear plane approaches a limiting angle chi(c) approximate to atau(1/(1 + gamma(m,c))) beyond which flow becomes incapable of producing further molecular alignment. Shear flow experiments using a series of concentrated polystyrene/diethyl phthalate solutions with fixed entanglement spacing, but variable polymer molecular weight 0.94 X 10(6) less than or equal to <(M-omega)over bar> less than or equal to 5.48 X 10(6), reveal a limiting steady-state orientation angle between 6 degrees and 9 degrees over a range of shear rates; confirming the theoretical result. Orientation angle undershoots observed during start-up of fast steady shearing flows are also explained in terms of a transient imbalance of elastic restoring force and viscous drag on oriented polymer molecules. Our findings suggest that the Doi-Edwards affine orientation tensor (Q) is not universal, but rather depends on deformation type and deformation history through a balance of elastic force and viscous drag on polymer molecules.
Keywords:polymer dynamics;steady shear flow;orientation angle;Doi-Edwards theory;entanglement loss;partial retraction;convected constraint release;viscous drag