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Interfacial Thermodynamics of Polymeric Mesophases
Author(s) -
Rey Alejandro D.
Publication year - 2004
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200400030
Subject(s) - liquid crystal , thermodynamics , surface tension , isotropy , anisotropy , polymer , adsorption , materials science , gibbs free energy , surface energy , gibbs isotherm , entropy (arrow of time) , chemistry , physics , optics , optoelectronics , composite material
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 i s , Q , ∇ s Q , k ) that depends on temperature (Θ), chemical potential (μ i s ), nematic tensor order parameter Q , surface gradients of Q , and geometry k , 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.