Electrochemically addressed cross-links in polyelectrolyte multilayers: cyclic duravoltammetry

In situ nanoindentation was performed on a multilayer of poly(acrylic acid) and a high molecular weight, pendant chain polyviologen under controlled electrochemical potential. The modulus of the thin film of polyelectrolyte complex was reversibly modulated, by about an order of magnitude, upon changing the state of charge within the material using the electrochemically active and addressable viologen repeat units. The applied potential, under aqueous conditions, is believed to control the extent of cross-link formation. Simultaneous quartz crystal microbalance measurements revealed the flux of ions into or out of the multilayer during redox cycling. Apparent film modulus also depends on the identity of the last layer.