Free energy of semiflexible polymers and structure of interfaces

The free energy of semiflexible polymers is calculated as a functional of the compositional scalar order parameter phi and the orientational order parameter of second-rank tensor S-ij on the basis of a microscopic model of wormlike chains with variable segment lengths. Mie use a density functional theory and a gradient expansion to evaluate the entropic part of the free energy, which is given in a power series of Q(ij) = S-ij/phi. The interaction term of the free energy is derived with a random phase approximation. For the rigid rod limit, the nematic-isotropic transition point is given by N omega phi = 4.05141, N and omega being the degree of polymerization and the anisotropic interaction parameter, respectively, and the degree of ordering at the transition point is 0.33448. We also find that the contour length of polymer chains becomes larger in a nematic phase than in an isotropic phase. Interface profiles are obtained numerically for some typical cases. In the neighborhood of isotropic-isotropic interfaces, polymer chains tend to align parallel to the interface on the polymer-rich side and perpendicular on the poor side. When an isotropic region and a nematic region coexist, orientational order parallel to the interface is preferred in the nematic region.