Tuning the electrochemical swelling of polyelectrolyte multilayers toward nanoactuation

We discuss physicochemical determinants of electrochemical polyelectrolyte multilayer swelling that are relevant to actuator usage. We used electrochemical quartz crystal microbalance with dissipation monitoring (EC-QCM-D) and cyclic voltammetry to compare the electrochemical swelling of two types of ferrocyanide-containing polyelectrolyte multilayers, poly(l-glutamic acid)/poly(allylamine hydrochloride) (PGA/PAH), and carboxymethyl cellulose/poly(diallyldimethylammonium chloride) (CMC/PDDA). We showed that ferrocyanide oxidation causes the swelling of PGA/PAH multilayers whereas it results in the contraction of CMC/PDDA multilayers. This behavior can be attributed to the presence of a positive and a negative Donnan potential in the case of PGA/PAH and CMC/PDDA multilayers, respectively. Using multilayers consisting of PGA and poly(allylamine) ferrocene (PGA/PAH-FC), we applied EC-QCM-D and demonstrated potentiostatic thickness control with nanometer precision and showed that the multilayer's thickness depends linearly on the applied potential within a certain potential range.