Water Content of Polyelectrolyte Multilayer Films Measured by Quartz Crystal Microbalance and Deuterium Oxide Exchange.

Water content of natural and synthetic, thin, polymer films is of considerable interest to a variety of fields because it governs properties such as ion conductivity, rigidity, porosity, and mechanical strength. Measuring thin film water content typically requires either complicated and expensive instrumentation or use of multiple instrumental techniques. However, because a quartz crystal microbalance (QCM) is sensitive to changes in mass and viscosity, deuterated solvent exchange has emerged as a simple, single-instrument, in situ method to quantify thin film water content. Relatively few studies, though, have employed this technique to measure water content of polyelectrolyte multilayers formed by layer-by-layer (LbL) assembly. In this work, poly (allyl amine) (PAH) and poly (styrene sulfonate) (PSS) films of up to nine layers were formed and the water content for each layer was measured via QCM with deuterium oxide exchange. The well-characterized nature of PAH/PSS films facilitated comparisons of the technique used in this work to other instrumental methods. Water content results showed good agreement with the literature and good precision for hydrated films thicker than 20 nm. Collectively, this work highlights the utility, repeatability, and limitations of this deuterated exchange technique in measuring the solvent content of thin films.