Weak polyelectrolyte brushes: re-entrant swelling and self-organization

We have studied the combined influence of pH and ionic strength on the properties of brushes of a weak polyion, poly(acrylic acid), in conditions of grafting density close to the mushroom-brush crossover. By combining atomic force microscopy AFM and quartz crystal microbalance, we show that at low ionic strengths the conformational change of grafted polyions is non-monotonic with increasing pH due to the counterintuitive variation of the ionization degree. Thus, reentrant swelling of the polymer chains is observed with increasing pH. This effect is more important at low polymer grafting densities, when it is accompanied by in-plane heterogeneous distribution at intermediate pH values. In addition, we observed self-assembly on the polymer brush (formation of holes and islands) at pH values below pK(a), due to the short-range attractive interaction between uncharged grafted chains. The sensitivity of the ionization of grafted chains to the physicochemical environment was also studied by measuring the interaction force between a silica tip and polymer brushes by atomic force microscopy. The dependence of the ionization of polyions on the presence of the tip points toward important charge regulation effects, in particular at pH values corresponding to partial ionization of the polyion.