Equilibrium and kinetic properties of triblock copolymers at hydrophobic surfaces

The adsorption of a series of (ethylene oxide-tetrahydrofuran-ethylene oxide), EOn/2THFmEOn/2, triblock copolymers has been studied at the water/hydrophobic silica interface by time-resolved ellipsometry. The copolymers form monolayers with the middle tetrahydrofuran block anchoring at the surface and the ethylene oxide groups either anchoring at the surface or protruding into the aqueous phase. The degree of anchoring of the EO chains depends critically on the surface coverage. The copolymer isotherms are generally rather well described by the conventional Langmuir expression, and the plateau surface area per polymer molecule increases linearly with the molecular weight. However, the plateau thickness exhibits a more complex behavior. At low coverages, the adsorbed layer thickness is small, and both THF and EO chains form trains at the surface. As the surface coverage increases, however, the EO chains are increasingly forced away from the surface, and the mean thickness of the adsorbed layer exhibits a relatively strong linear dependence on the surface excess. At higher coverages, closer to the adsorption plateau, a weaker dependence is observed. The thickness increase is in this latter region due to the increasing steric repulsion between protruding EO chains. Outside the adsorbed layer, we also found support for the existence of a depletion layer. We show further that there are three regimes in the kinetics of adsorption. In the first (low surface coverage), the process is diffusion controlled and the rate is proportional to the concentration difference between the bulk solution and the subsurface located just outside the adsorbed layer. In the second regime (intermediate coverages and adsorption times), the kinetics ark governed by the rate of displacement of anchored EO chains by THF chains of adsorbing copolymers. In the third regime (high surface coverages), the adsorption slows down markedly due to the energy barrier caused by presence of the relatively dense brush of adsorbed EO chains. In this regime, the surface excess varies proportionally with log t, which was also observed to be the case during the desorption process.