Effect of flow on solutions of rod-coil block co-polymers

Abstract

An elongational flow field is imposed on a solution of block copolymers consisting of semirigid macromolecules with rigid, rodlike sequences of units in combination with random coil (flexible) units. The problem is formulated according to the lattice treatment of Matheson and Flory. In this formulation, the system consists of rigid blocks whose lengths and locations are fixed by the structure within each macromolecule. These blocks are separated by random coiled units. An excess free energy other than the equilibrium Gibbs free energy of the quiescent solution has to be considered due to the flow field that tends to align the rods. This excess free energy is calculated from the potential energy of rods when a steady-state, homogeneous and irrotational flow field is applied to the solution. The effects of composition, polymer-solvent interaction, size of the co-polymer and flow rates are investigated. Depending on the size and number of rods, some of the chains studied exhibit a biphasic region at equilibrium that shifts to lower concentrations with increasing flow. Longer chains with shorter rods that are isotropic at equilibrium, exhibit a biphasic region at finite values of flow. The degree of orientation increases sharply when the system is biphasic. For larger flows, the orientation function is very close to unity which is perfect orientation. (C) 2005 Elsevier Ltd. All rights reserved.