Adhesion property profiles of supported thin polymer films

Polymer coatings are frequently utilized to control and modify substrate properties. The performance of the coatings is often determined by the first polymer layers between the substrate and the bulk polymer material, which are termed interphase. Standard methods have failed to completely characterize this interphase, because its properties change significantly over a few nanometers. Here we determine the spatially resolved adhesion properties of the interphase in polyelectrolyte multilayers (PEMs) by desorbing a single polymer covalently bound to an atomic force microscope cantilever tip from PEMs with varying thickness. We show that the adhesion properties of the first few layers (up to three double layers) is dominated by the surface potential of the substrate, while thicker PEMs are controlled by cohesion in between the PEM polymers. For cohesion, the local film conformation is the crucial parameter. This finding is generalized by utilizing oligoelectrolyte multilayer (OEM) as coatings and both hydrophilic and hydrophobic polymers as polymeric force sensors.