Flow birefringence of disordered block copolymer melts

Abstract

The birefringence relaxation after a step strain S(t), and the oscillatory flow birefringence S* are calculated for disordered block copolymer melts, on the basis of four models for the chain dynamics: the Rouse model, the Doi-Edwards reptation model, the reptation model with constraint release, and the reptation model with orientational coupling. All the calculations are performed in the mechanically-uniform limit, i.e., the average subchain length and friction coefficient are independent of block. The net birefringence is assumed to contain no form contribution, and the approach of Kuhn and Gruen is employed in the computation of the intrinsic birefringence. The most important feature of the results is that the stress-optic relation does not apply in general for block copolymers; therefore, unique information about chain relaxation mechanisms can be obtained from measurements of flow birefringence. It is shown that the phase angle of S* can be particularly sensitive to the lengths and chain locations of the various blocks, with the most striking effects occurring when two (or more) blocks have optical anisotropies of opposite sign. In contrast, in the mechanically-uniform limit the viscoelastic properties are independent of block length and location.