Phase separation of a model binary polymer solution in an external field

Physics – Condensed Matter – Soft Condensed Matter

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Scientific paper

The phase separation of a simple binary mixture of incompatible linear polymers in solution is investigated using an extension of the sedimentation equilibrium method, whereby the osmotic pressure of the mixture is extracted from the density profiles of the inhomogeneous mixture in a gravitational field. In Monte-Carlo simulations the field can be tuned to induce significant inhomogeneity, while keeping the density profiles sufficiently smooth for the macroscopic condition of hydrostatic equilibrium to remain applicable. The method is applied here for a simplified model of ideal, but mutually avoiding polymers, which readily phase separate at relatively low densities. The Monte-Carlo data are interpreted with the help of an approximate bulk phase diagram calculated from a simple, second order virial coefficient theory. By deriving effective potentials between polymer centres of mass, the binary mixture of polymers is coarse-grained to a ``soft colloid'' picture reminiscent of the Widom-Rowlinson model for incompatible atomic mixtures. This approach significantly speeds up the simulations, and accurately reproduces the behaviour of the full monomer resolved model.

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