Adsorption characteristics of brush polyelectrolytes on silicon oxynitride revealed by dual polarization interferometry

Adsorption properties of bottle-brush polyelectrolytes have been investigated using dual polarization interferometry (DPI), which provides real time monitoring of adsorbed layer thickness and refractive index. The adsorption on silicon oxynitride was carried out from aqueous solution with no added inorganic salt, and the adsorbed polyelectrolyte layer was subsequently rinsed with NaCl solutions of increasing concentration. The bottle-brush polyelectrolytes investigated in this study have different ratios of permanent cationic charged segments and uncharged PEO side chains. Both the cationic groups and the PEO side chains have affinity for silica-like surfaces, and thus contribute to the adsorption process that becomes rather complex. Adsorption properties in water, responses to changes in ionic strength of the surrounding medium, adsorption kinetics and the layer structure are all strongly dependent on the ratio between backbone charges and side chains. The results are interpreted in terms of competitive adsorption of segments with different chemical nature. The adsorption kinetics is relatively fast, taking only tens to hundreds of seconds when adsorbed from dilute 100 ppm solutions. The DPI technique was found to be suitable for studying such rapid adsorption processes, including determination of the initial adsorption kinetics. We expect that the effects observed in this study are of general importance for synthetic and biological polymers carrying segments of different nature.

As a result of our investigation we present the illustrations shown in (a–c) describing the structural evolution of the adsorbed layers formed by high charge density PEO45MEMA:METAC-X polymers (50 ⩽ X ⩽ 75) where the molecules are adsorbed preferentially parallel to the surface. The structural evolution of the layers formed by low charge density PEO45MEMA:METAC-X (10 ⩽ X ⩽ 25) is illustrated in (d–f). These polymers initially adsorb preferentially parallel to the surface whereas the final layer structure is more extended.Figure optionsDownload high-quality image (71 K)Download as PowerPoint slide