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Scaling behavior of thin films on chemically heterogeneous walls
Alexandr Malijevský1, Andrew O Parry2, Martin Pospíšil3
1Department of Physical Chemistry, University of Chemical Technology Prague, Praha 6, 166 28, Czech Republic and Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v. v. i., 165 02 Prague 6, Czech Republic.
Abstract:
We study the adsorption of a fluid in the grand canonical ensemble occurring at a planar heterogeneous wall which is decorated with a chemical stripe of width L. We suppose that the material of the stripe strongly preferentially adsorbs the liquid in contrast to the outer material which is only partially wet. This competition leads to the nucleation of a droplet of liquid on the stripe, the height h_{m} and shape of which (at bulk two-phase coexistence) has been predicted previously using mesoscopic interfacial Hamiltonian theory. We test these predictions using a microscopic Fundamental Measure Density Functional Theory which incorporates short-ranged fluid-fluid and fully long-ranged wall-fluid interactions. Our model functional accurately describes packing effects not captured by the interfacial Hamiltonian but still we show that there is excellent agreement with the predictions h_{m}≈L^{1/2} and for the scaled circular shape of the drop even for L as small as 50 molecular diameters. For smaller stripes the droplet height is considerably lower than that predicted by the mesoscopic interfacial theory. Phase transitions for droplet configurations occurring on substrates with multiple stripes are also discussed.
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