Surface rheology of a polymer monolayer: effects of polymer chain length and compression rate

We study surface layers of a simple homopolymer poly(vinyl acetate) on the air-water interface as a function of the concentration and the polymer molecular weight. Our results suggest that there is an effect of the compression rate on both the structure of the layers and their rheological behavior, while the length of the chain influences only the rheology. At very low compression speeds, the surface layer of short chains does not exhibit the classical semi-dilute regime behavior, forming instead a solid phase. For fluid layers, we report on the dependence of surface viscosity upon the concentration, showing a first crossover, which happens close to the semi-dilute-concentrated regime boundary, from a scaling behavior with the concentration to an Eyring-like liquid. A second rheological transition happens at very high concentrations, near close packing, where the Newtonian liquid phase gives way to a soft solid phase.