Self-Assembly into Strands in Amphiphilic Polymer Brushes

The self-assembly of amphiphilic macromolecules end-grafted to a plane surface is studied using mean-field theory and computer simulations. Chain backbones are built from hydrophobic groups, whereas side groups are hydrophilic. The brush is immersed in a solvent, which can be good or poor, but on average is not far from θ conditions. It is demonstrated that the strong amphiphilicity of macromolecules at a monomer unit level leads to their self-assembly into a system of strands with a 2D hexagonal order in a cross-section parallel to the grafting plane. The structure period is determined by the length of side groups. In theory, this effect is explained by the orientation of strongly amphiphilic monomer units at a strand/solvent boundary that leads to an effective negative contribution to the surface tension. Computer simulations with molecular dynamics (MD) are used for a detailed study of the local brush structure. The aggregation number of strands grows with the increase of the grafting density and side group length.