Interfacial Irreversibly and Loosely Adsorbed Layers Abide by Different Evolution Dynamics.

Within the interfacial region of the substrate, polymer chains can form the inner irreversibly adsorbed and outer loosely adsorbed layers upon annealing. Owing to their different constrained environments, the evolution dynamics of the two layers are supposedly different. To trace such evolution dynamics, we thus resorted to sum frequency generation (SFG) vibrational spectroscopy, using polystyrene (PS) with a series of molar masses on sapphire substrates. By plotting the integrated SFG intensity as a function of the annealing time, we found that the inner irreversibly adsorbed layer had two segmental evolution processes (replacement and local structural relaxation), and the outer loosely adsorbed layer had the monotonical evolution dynamics (structural relaxation), with both evolving toward the dissipation of the interfacial molecular order of the backbones. A critical evolution time was defined for the inner irreversibly adsorbed layer, and a characteristic relaxation time was defined for the outer loosely adsorbed layer. With respect to the molar mass, phenomenologically, both the critical evolution time and the characteristic relaxation time show an asymptotic increase. In summary, this SFG investigation provides the first-hand experimental data on understanding the structural evolution dynamics of the interfacial adsorbed polymer chains, which would gradually split up into the irreversibly adsorbed layer and loosely adsorbed layer upon annealing.