Study of Film Structure and Adsorption Kinetics of Polyelectrolyte Multilayer Films: Effect of pH and Polymer Concentration

The alternate adsorption of polycation poly(allylamine hydrochloride)(PAH) and the sodium salt of the polymeric dye poly{1-[p-(3′-carboxy-4′-hydroxyphenylazo)benzenesulfonamido]-1,2-ethandiyl}(PCBS) on quartz crystals coated with silica was studied to understand the structural properties and adsorption kinetics of these films using a combination of quartz crystal microbalance with dissipation monitoring (QCM-D), absorbance, and ellipsometry measurements. In-situ deposition of the polycation PAH on QCM crystals was monitored, followed by rinsing with water and then deposition of the polyanion PCBS. The effects of polymer concentration and pH on film structure, composition and adsorption kinetics were probed. The polymers were adsorbed at neutral pH conditions and at elevated pH conditions where PAH was essentially uncharged to obtain much thicker films. The change in the resonant frequency, Δf, of the QCM-D showed a linear decrease with the number of bilayers, a finding consistent with absorbance and ellipsometric thickness measurements which showed linear growth of film thickness. By using the Δf ratios of PCBS to PAH, the molar ratios of repeat units of PCBS to PAH in the bilayer films as determined by QCM-D were ∼1:1 at polyelectrolyte concentrations 5−10 mM repeat unit, indicating complete dissociation of the ionic groups. The frequency and dissipation data from the QCM-D experiments were analyzed with the Voigt model to estimate the thickness of the hydrated films which were then compared with thicknesses of dry films measured by ellipsometry. This led to estimates of the water content of the films to be ∼45 wt %. In addition to the QCM-D, some films were also characterized by a QCM which measures only the first harmonic without dissipation monitoring. For the deposition conditions studied, the deposited mass values measured by the QCM’s first harmonic were similar to the results obtained using higher harmonics from QCM-D, indicating that the self-assembled polyelectrolyte films were rigid.