No abstract

The effect of solvent conditions on the growth of polyelectrolyte (PE) multilayer films comprising poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate sodium salt) (PSS) on planar substrates was investigated by means of surface plasmon resonance spectroscopy (SPRS), quartz crystal microbalance (QCM), and atomic force microscopy techniques. The solvent quality was varied by the addition of ethanol to the PE solutions used for deposition of the layers, thus tuning the relative strength of electrostatic and secondary intermolecular and intramolecular interactions. Experiments were performed with PE solutions both without added electrolyte and containing 0.5 M NaCl. Decreasing the solvent quality (i.e., increasing the amount of ethanol in the adsorption solution) resulted in a marked increase of both the multilayer film thickness and mass loading, as determined from the SPRS spectra and QCM frequency shifts, respectively. With the solution composition approaching the precipitation point, thick PAH/PSS films were formed due to the screening of the electrostatic intra- and interchain repulsions and enhanced hydrophobic interactions between the polyelectrolyte chains. However, the films formed from water/ethanol mixtures remained stable upon subsequent exposure to water or salt-containing solutions: no significant film desorption occurred after up to 24 h of exposure to water or 0.5 M NaCl solutions. In addition, the effect of postdeposition exposure to water/ethanol mixtures was investigated for PE multilayers assembled from aqueous solutions. In this case, the optical thickness of the films was determined during exposure to water/ethanol mixtures, and instead of swelling, the polyelectrolyte films collapse to the surface as a result of the unfavorable segment-solvent interactions.

A noninterferometric surface force apparatus has been used to measure interactions between glass spheres in dilute aqueous polyvinylamine solutions at two different salt concentrations. Close to the substrate charge neutralization point, an attractive interaction is present mainly because of bridging of the extending polymer tails. Additional adsorption leads to an overcompensation of the glass negative surface charge, and the interaction at this point is dominated by a long-range double-layer repulsion. The results from fitting the Derjaguin−Landau−Verwey−Overbeek theory to the measured force curves demonstrate that the degree of overcompensation increases with polyelectrolyte concentration and increasing ionic strength of the solution (addition of indifferent electrolyte). An increase in ionic strength results in the screening of the electrostatic forces which leads to:  (i) a reduced free energy cost of creating a charged interface, (ii) a decreased repulsion between protonated amine groups along the polymer backbone and a corresponding increased chain flexibility, (iii) a reduced electrostatic attraction between the polyelectrolyte and the surface. The first effect is apparently is the most important in the present case.

The adsorption behavior of bottle-brush polymers with different charge/PEO ratio on silica was studied using optical reflectometry and QCM-D. The results obtained under different solution conditions clearly demonstrate the existence of two distinct adsorption mechanisms depending on the ratio of charge/PEO. In the case of low-charge density brush polymers (0-10 mol %), the adsorption occurs predominantly through the PEO side chains. However, the presence of a small amount of charge along the backbone (as low as 2 mol %) increases the adsorption significantly above that of the uncharged bottle-brush polymer in pure water. As the charge density of the brush polymers is increased to 25 mol % or larger the adsorption occurs predominantly through electrostatic interactions. The adsorbed layer structure was studied by measuring the layer dissipation using QCM-D. The adsorbed layer formed by the uncharged brush polymer dissipates only a small amount of energy that indicates that the brush lie along the surface, the scenario in which the maximum number of PEO side chains interact with the surface. The adsorbed layers formed by the low-charge density brush polymers (2-10 mol %) in water are more extended, which results in large energy dissipation, whereas those formed by the high-charge density brush polymers (50-100 mol %) have their backbone relatively flat on the surface and the energy dissipation is again low.