Formation of tethered nanolayers: Three regimes of kinetics

An investigation of the kinetics of tethering of amine functional-ended polystyrene from good solvent to the surface of a solid substrate showed three distinct regimes of kinetics rather than the two predicted by theory. The first regime was fast and appeared to be controlled by diffusion through the solvent, as predicted by theory. The second regime was slow and appeared to be linear in the natural logarithm of time, as predicted by theory. The third regime, not predicted by theory, was one of accelerated tethering (termed by us "layer-assisted tethering"). The third regime, observed for different solvents, different molecular weights, and different temperatures, ended when saturation was reached. We suggest herein an explanation for the observed acceleration.