Macromolecules, Vol.28, No.18, 6078-6083, 1995
Polymer-Solutions Under Electric-Fields - Ellipsoidal Correlation Holes
An electric field, epsilon, shifts the phase equilibria in polymeric solutions and distorts anisotropically concentration fluctuations in the vicinity of the coexistence curve. I present a statistical theory of birefringent binary polymeric solutions. An explicit form for the structure factor in terms of the molecular anisotropic polarizabilities of the statistical segments, upsilon(A) and upsilon(B), is given. For polymers A (containing N-A segments) in a monomeric solvent B, it is predicted that in the critical point the anisotropic corrections to the light scattering intensity scales as N(A)(1/2)upsilon(A) epsilon(2). When upsilon(A) > 0 and upsilon(B) < 0, for polymer A (N-A) plus polymer B (NB) solution the resulting anisotropy turns out to be dependent solely on the sign of the combination N(A)(-1/2)upsilon(A) + N(B)(-1/2)upsilon(B). The theory provides a microscopic argumentation on why an electric field suppresses the separation and why the phase equilibria shift is proportional to on. We also predict diamond- and pillowlike forms of the isointensity contours.