Reconstruction of the Interface of Oxidatively Functionalized Polyethylene (PE-CO2H) and Derivatives on Heating. Revision.

Oxidation of low-density polyethylene film with aqueous chromic acid results in a material PE-CO2H having hydrophilic carboxylic acid and ketone groups in a thin oxidatively-functionalized interface. This interface is indefinitely stable at room temperature. On heating in vacuum, it rapidly becomes hydrophobic and similar in it wettability to unfunctionalized polyethylene film. The progression of the contact angle with water from the initial value 55 to the final value 103 follows kinetics that suggest that the polar functional groups disappear from the interface by diffusion. The magnitude of the apparent diffusion constant derived from these studies can be described approximately by an Arrhenius equation over a significant portion of the temperature range explored, with an Arrehnius activation energy of diffusion of approx kcalmol. Comparison of the properties of interfaces composed of carboxylic acid groups with those containing other species demonstrates that the structure of the interfacial groups also significantly influences the rate of reconstruction .