Abstract
Monolayers of a statistical copolymer with a poly(methacrylate) chain and hydrophilic and hydrophobic side groups are investigated at the air/water interface. The isotherms suggest a fluid and a frozen phase. With in-situ X-ray reflectivity the monolayer thickness is determined to be 2.5 nm or less. The shear viscosity in the fluid phase is extremely high yet can be described in the framework of the free area model. However, the parameter which characterizes the overlap of holes available for a diffusing monomer unit is a factor of 2 higher than expected, suggesting local diffusion barriers formed by nanosized clusters. In the glassy phase single-molecule fluorescence shows anomalous diffusion in an ≈140 nm cage (cf. ref 1), indicating that the clusters touch. The aggregates are mainly formed by the hydrophilic monomers, as both the X-ray data and the isotherms suggest.
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