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Free energy of colloidal particles at the surface of sessile drops
The influence of finite system size on the free energy of a spherical
particle floating at the surface of a sessile droplet is studied both
analytically and numerically. In the special case that the contact angle at the
substrate equals a capillary analogue of the method of images is
applied in order to calculate small deformations of the droplet shape if an
external force is applied to the particle. The type of boundary conditions for
the droplet shape at the substrate determines the sign of the capillary
monopole associated with the image particle. Therefore, the free energy of the
particle, which is proportional to the interaction energy of the original
particle with its image, can be of either sign, too. The analytic solutions,
given by the Green's function of the capillary equation, are constructed such
that the condition of the forces acting on the droplet being balanced and of
the volume constraint are fulfilled. Besides the known phenomena of attraction
of a particle to a free contact line and repulsion from a pinned one, we
observe a local free energy minimum for the particle being located at the drop
apex or at an intermediate angle, respectively. This peculiarity can be traced
back to a non-monotonic behavior of the Green's function, which reflects the
interplay between the deformations of the droplet shape and the volume
constraint.Comment: 24 pages, 19 figure