Scaling Behavior and Segment Concentration Profile of Densely Grafted Polymer Brushes Swollen in Vapor

The scaling of the thickness, h_s, of a densely grafted polymer brush of chain length N and grafting density σ swollen in vapor agrees quantitatively with the scaling reported by Kuhl et al. for densely grafted brushes swollen in liquid. Deep in the brush, next to the substrate, the shape of the segment concentration profile is the same whether the brush is swollen by liquid or by vapor. Differences in the segment concentration profile are manifested primarily in the swollen brush interface with the surrounding fluid. The interface of the polymer brush swollen in vapor is much more abrupt than that of the same brush swollen in liquid. This has implications for the compressibility of the swollen brush surface and for fluctuations at that surface.