A Monte-Carlo study of equilibrium polymers in a shear flow

We use an off-lattice microscopic model for solutions of equilibrium polymers (EP) in a lamellar shear flow generated by means of a self-consistent external field between parallel hard walls. The individual conformations of the chains are found to elongate in flow direction and shrink perpendicular to it while the average polymer length decreases with increasing shear rate. The Molecular Weight Distribution of the chain lengths retains largely its exponential form in dense solutions whereas in dilute solutions it changes from a power-exponential Schwartz distribution to a purely exponential one upon an increase of the shear rate. With growing shear rate the system becomes increasingly inhomogeneous so that a characteristic variation of the total monomer density, the diffusion coefficient, and the center-of-mass distribution of polymer chains of different contour length with the velocity of flow is observed. At higher temperature, as the average chain length decreases significantly, the system is shown to undergo an order-disorder transition into a state of nematic liquid crystalline order with an easy direction parallel to the hard walls. The influence of shear flow on this state is briefly examined. Received 22 October 1998 and Received in final form 12 April 1999