Vapor Sorption-Desorption Phenomena of HD and GB Simulants from Polyurethane Thin Films on Aluminum Oxide via a Quartz Crystal Microbalance.

Protection and decontamination of surfaces after exposure to chemical warfare agents (CWAs) are of considerable interest to the homeland defense and battlespace operation communities. In this work, polyurethane was spin-coated onto aluminum oxide quartz crystal microbalance (QCM) sensors. Polyurethane film thickness was varied by altering the concentration of the polymer/chloroform solution used for spin-coating. Atomic force microscopy confirmed the formation of smooth, homogeneous films on the QCM sensor surface. Aluminum oxide QCM sensors coated with polyurethane were exposed to saturated vapors of dichloropentane (DCP), a mustard gas (HD) simulant, and dimethyl methylphosphonate (DMMP), a sarin gas (GB) simulant, and the mass uptake, diffusion coefficient, volume fraction, and partition coefficient of the simulant in the film were determined from QCM data. Results showed that both DCP and DMMP readily sorbed into the films although the mass uptake of DCP was greater than that of DMMP owing to DCP's higher vapor pressure. Additionally, the CWA simulant uptake increased with polyurethane film thickness. Sorption diffusion coefficients were 1 × 10-13 cm2/s and 1 × 10-12 cm2/s for DCP and DMMP vapor, respectively. Simulant desorption was also measured and showed that some DMMP remained in the film/substrate system, while DCP sorption was fully reversible. Reversible desorption for both CWA simulants was relatively quick and independent over the range of film thicknesses studied, with average desorption diffusion coefficients of 2 × 10-9 cm2/s and 1 × 10-11 cm2/s for DCP and DMMP, respectively. Collectively, this study is expected to inform protection and decontamination strategies of equipment and structures upon exposure to CWAs.

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.