Interfacial Thermodynamics of Polymeric Mesophases

Summary:A complete mechanical‐thermodynamical formulation for multicomponent nematic polymer‐isotropic fluid interfaces is derived, validated, and used to derive the structure and shape equations for these soft anisotropic polymer interfaces. The fundamental role of liquid crystalline order and long range effects in coupling bulk and interfacial effects, and in coupling thermodynamical/liquid crystalline order/geometrical variables is demonstrated, discussed, and validated. The Gibbs‐Duhem nemato‐thermodynamics equation emerges from an interfacial tension γ = γ(Θ, μ ,Q, ∇sQ,k) that depends on temperature (Θ), chemical potential (μ ), nematic tensor order parameterQ, surface gradients ofQ, and geometryk, and leads to new couplings in these enhanced phase spaces. The role of entropy and adsorption, and long range effects on interfacial shape and structure selection is revealed. For flat interfaces the preferred structure emerges from a competition between energy, entropy, and adsorption.