Interfacial aspects of polymer brushes prepared on conductive substrates by aryl diazonium salt surface-initiated ATRP

This article describes the use of aryl diazonium salts to attach halogenated functional groups that initiate atom transfer radical polymerization (ATRP) at the surface of conductive substrates. The interest of this procedure lies in the fact that aryl diazonium salts permit the grafting of high‐density initiators within a few minutes of electrochemical surface treatment, and subsequently promote the growth of very compact polymer chains. Several brominated aryl groups were tested for surface‐initiating ATRP of styrene and methacrylates. The chemical structure of the polymer brushes was characterized by high‐resolution XPS. Particularly, it is shown that grafting of poly(tert‐butyl methacrylate), PtBMA, from the surface of glassy carbon plates followed by hydrolysis resulted in carboxylated, tethered chains that were characterized in terms of hydrophilicity and propensity to uptake silver cations. Copyright © 2008 John Wiley & Sons, Ltd.