Quantifying and controlling the cation uptake upon hydrated ionic liquid-induced swelling of polyelectrolyte multilayers.

Controlling the uptake of specific ions in polyelectrolyte multilayers is of interest for various fields of application. Here, we quantify the amount of cation of an ionic liquid, namely 1,3-bis(cyanomethyl)imidazolium chloride, incorporated into polyelectrolyte multilayers upon contact with an ionic liquid solution. The ion partition equilibrium is determined depending on concentration in solution, employing attenuated total reflection infrared spectroscopy. Generating an excess charge in multilayers by post-preparative manipulation of their charge balance, one can control the incorporated amount. Three multilayer systems are assembled for this purpose, i.e., PSS/PDADMAC, PSS/PAH and PAA/PDADMAC, employing poly(styrene sulfonate) (PSS), poly(diallyldimethylammonium chloride) (PDADMAC), poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA). The charge balance of the latter two films is manipulated by an external pH stimulus generating an excess positive or negative internal charge, respectively. The concentration of cations in PEM amounts to 30% to 100% of the bulk concentration and scales as PAA/PDADMAC > PSS/PDADMAC > PSS/PAH. Thus, post-preparative pH treatment may be a future tool to create ion-conductive polymer gel films with a desired concentration of small cations.