The structures and phase transitions occurring during the compression of polystyrene−poly(ethylene oxide) (PS−PEO) diblock copolymer monolayers at the air−water interface have been studied by surface pressure isotherms, neutron reflectivity, and Brewster angle microscopy. At low coverage, the EO monomers adsorb at the air−water interface, but the PEO layer is not purely bidimensional. At high coverage, the EO−interface interaction becomes repulsive. A brush structure has been observed with differences between the long and the short PEO chains attributed to the difference in the accessible range of surface concentration. For the longest chain, the PEO concentration profiles exhibit a superposition of a depletion layer near the interface and discontinuous profile characteristics of a two-phase brush described by the “n-cluster” theory. For the shortest chains, the profiles are “pseudoparabolic”. Finally, Brewster angle microscopy shows that, for the long chains, the transition between the adsorbed and the brush structures is first order.

We have studied both experimentally and theoretically the surface pressure isotherms of copolymers of polystyrene-polyethyleneoxide (PS-PEO) at the air-water interface. The SCMF (single chain mean-field) theory provides a very good agreement with the experiments for the entire range of surface densities and shows that the adsorption energy per PEO monomer at the air-water interface is about one kBT . In addition, the chain density profile has been calculated for a variety of surface densities, from the dilute to the very dense ones. The SCMF approach has been complemented by a mean-field approach in the low density regime, where the PEO chains act as a two-dimensional layer. Both theoretical calculations agree with the experiments in this region.

We report the first direct evidence for the formation of circular surface micelles (hemimicelles) on the surface of water. These highly monodisperse 30 nm hemimicelles, made from a semifluorinated alkane deposited as a Langmuir monolayer, form organized hexagonal arrays as determined by small-angle X-ray diffraction conducted directly on the water surface at grazing incidence.