Among various parameters that influence the formation of polyelectrolyte complexes and multilayers, special emphasis should be placed on ion-specific and solvent effects. In our study, we systematically examined the above-mentioned effects on poly(diallyldimethylammonium chloride) (PDADMACl)-sodium poly(4-styrenesulfonate) (NaPSS) complexation in solution and at the surface by means of dynamic light scattering, ellipsometry and atomic force microscopy measurements. As solvents, we used water and water/ethanol mixture. The obtained results confirm the importance of ion-specific and solvent effects on complexes prepared in solution, as well as on multilayers built up on a silica surface. The experiments in mixed solvent solution showed that at a higher ethanol mole fraction, the decrease in monomer titrant to titrand ratio, at which the increase in the size of complexes is observed, takes place. The difference between chloride and bromide ions was more pronounced at a higher mole fraction of ethanol and in the case of positive complex formation, suggesting that the larger amount of bromide ions could be condensed to the polycation chain. These findings are in accordance with the results we obtained for polyelectrolyte multilayers and could be helpful for designing polyelectrolyte multilayers with tuned properties needed for various applications, primarily in the field of biomedicine.

The study was carried out with the aim of establishing how the outcomes of polyelectrolyte multilayer formation can be predicted on the basis of the results of complexation studies in solution and vice versa .

In this study, the surface properties of Ti/TiO₂ substrate before and after the adsorption of polyelectrolytes were investigated. As model polyelectrolytes, strongly charged polycation poly(diallyldimethylammonium) (PDADMA) and strongly charged polyanion poly(4-styrenesulfonate) (PSS) were used. Initially, the bare titanium substrate was characterized by means of ellipsometry, atomic force microscopy (AFM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and measurements of inner surface potential using crystal electrode (CrE). It was shown that the substrate surface is very smooth with the roughness of 3.5 nm and oxide layer thickness of 3.8 nm. After the adsorption of PDADMA and PSS, polyelectrolyte-coated titanium surface was examined using the above-mentioned methods under the same conditions. It was found that both PDADMA cations and PSS anions form a stable polymeric nanofilm on Ti/TiO₂ surface that partially covers the surface, without significant impact on the surface roughness. The corrosion protection effectiveness values indicate that the corrosion properties were greatly enhanced upon polyion adsorption and polyelectrolyte coating formation on the flat TiO₂ surface. The obtained results were additionally confirmed by inner surface potential measurements. According to the methods employed, PDADMA nanofilm modification offers enhanced corrosion protection to the underlying titanium material in sodium chloride electrolyte solution.