How Polyelectrolyte Adsorption Depends on History: A Combined Fourier Transform Infrared Spectroscopy in Attenuated Total Reflection and Surface Forces Study

We present a systematic study of how adsorption history affects the thickness, surface forces, and interfacial rheology of a model cationic polymer. The polymer was quaternized poly-4-vinylpyridine, QPVP (weight-average degree of polymerization nw ) 325 and 98% quaternized with ethyl bromide). The main comparisons concerned one-step adsorption from solution at a variable salt concentration up to 0.5 M NaCl, versus two-step adsorption (initial adsorption from buffer solution without added salt, then NaCl added later). The aqueous solutions were buffered at pH ) 9.2 such that the surfaces (mica in the case of surfaces forces (SFA) experiments, oxidized silicon in the case of in situ infrared (FTIR-ATR) experiments) in each case carried a large negative charge. The SFA and FTIR-ATR experiments gave consistent estimates of the amount of polymer adsorbed, confirming the expectation that adsorption should be driven by electrostatic attraction to the surface of large opposite charge. The adsorbed amount showed little dependence on path, validating the common assumption of equilibration in this respect. However the layer thickness measured by surface forces, the shear nanorheology response at a given surface force, and the dichroism of pendant side groups of the polymer all showed a pronounced dependence on the path to reach the adsorbed state. We interpret the measurements to suggest that two-step adsorption produces an inhomogeneous layer comprised of a dense layer of segments closest to the solid surface and a sparse outer layer. In particular, two-step adsorption produced thicker layers and a greater tendency to decouple shear forces from those that resist compression in the normal direction, thereby lessening the shear forces at a given level of normal force.