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14) is higher than this binodal value Interfacial Phenomena in Thin Polymer Films: Phase Coexistence and Segregation 37 Fig. a Composition-depth f(z) profiles near the surface (at z=0) of a binary mixture at bulk concentration f1 at lower (T®Tw–) and upper (T®Tw+) limit of the first order wetting transition point Tw. b,c Cahn constructions with trajectories –2kÑf plotted for profiles f(z) with decreasing (solid lines) and increasing (dashed lines) slopes. Surface boundary condition (Eq. 26) is met at points (marked by ●) where surface energy derivative (–dfs/df)s (dotted line) intersects trajectories –2kÑf at concentrations reached at the surface.

For polymer blends the profile f(z) minimizing Eq. (33) was found [191], however, to be flat only at a 10–1 nm deep surface region and to be otherwise indistinguishable from the contour f(z) solving the standard expression (Eq. 24) for identical surface tension difference Dg assumed (related to fs with Eq. 34). Self-consistent mean filed calculations [174] lead to similar conclusions. Therefore, while long range surface forces are nowadays believed to be in charge of wetting dynamics [160, 192] (related to surface segregation phenomena), the computationally much simpler short-range fs approximation is used instead, with an equal confidence, to calculate the equilibrium profiles f(z).

The basic criterion for the critical wetting – 0

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