Transport of Flexible, Oil-Soluble Diblock and BAB Triblock Copolymers to Oil/Water Interfaces.

The connection between block copolymer architecture and adsorption at fluid/fluid interfaces is poorly understood. We characterize the interfacial properties of a well-defined series of polyethylene oxide/polydimethyl siloxane (PDMS) diblock and BAB triblock copolymers at the dodecane/water interface. They are oil-soluble and quite flexible because of their hydrophobic PDMS block. Rather than relying on equilibrium interfacial measurements for which it is difficult to mitigate experimental uncertainty during adsorption, we combine measurements of steady-state adsorption, dilatational rheology, and adsorption/desorption dynamics. Steady-state interfacial pressure is insensitive to interfacial curvature and mostly agrees with theory. Adsorption does not occur in the diffusive limit as is the case for many aqueous, small-molecule surfactants. Dilatational rheology reveals differences in behavior between the diblocks and triblocks, and all interfaces possess elasticities below the thermodynamic limit. Desorption dynamics show that material exchange between the interface and the neighboring fluid occurs too slowly to relax dilatational stresses. The mechanism of relaxation occurs at the interface, likely from the reorientation of adsorbed chains.