Hysteretic Swelling/Deswelling of Polyelectrolyte Brushes and Bilayer Films in Response to Changes in pH and Salt Concentration

We use a quartz crystal microbalance with dissipation (QCM-D) to investigate the swelling/de-swelling and hysteresis in brushes of weakly ionizable polyanion poly(acrylic acid) (PAA) brushes and bilayers containing a PAA brush and a poly(ethylene imine) (PEI) overlayer. We show that for a long PAA chain (M(w) = 39 kDa), at low grafting density ([Formula: see text] < 0.05 chains/nm(2)) and at a pH value (=4.2) at which it is partially charged, in the low-salt “osmotic brush” regime, the brush height no longer increases with increased grafting density as is seen for shorter brushes and denser grafting, but shows a slight decrease in height, in qualitative agreement with predictions of scaling theory. In a cycle of stepped pH changes, we also show that at a low grafting density of [Formula: see text] = 0.023 chains/nm(2) and M(w) = 39 kDa, there is hysteresis in swelling over timescales of many minutes. For higher grafting densities [Formula: see text] = 0.87 chains/nm(2) and shorter chains (2 kDa), we see little or no measurable hysteresis, and, at intermediate chain length 14 kDa and grafting density [Formula: see text] = 0.06 chains/nm(2), hysteresis is observed at short timescales but is greatly reduced at longer timescales. These results are similarly observed when bilayers are made by adsorbing onto the PAA brush a layer of the polycation PEI. In addition, we also note hysteresis in swelling upon changes of salt concentration when pH is fixed. These results show the rich thermodynamics and kinetics of even monolayers and bilayers of polyelectrolyte films.