On the structural polydispersity of random copolymers adsorbed at interfaces: comparison of surface and bulk distributions

Synthesis of random copolymers leads to a structurally polydispersed distribution of polymer chains, where one of the constituent monomers prefers residing on the interface, while the others have a tendency for remaining in the bulk. Previous studies have demonstrated the very strong dependence of the level of adsorption with the degree of blockiness and number of adsorbing residues of the chains. Using self-consistent field calculations, we obtain the distribution of the adsorbed copolymers and compare this with the bulk distribution of such chains. In our study, the whole range of structurally polydisperse chains in the distribution derived for a given random copolymer are simultaneously present and can compete with each other for adsorption. We show that the distribution of chains on the surface is grossly different to that in the bulk and is largely dominated by those rare chains at the tail end of the latter distribution.