Surface Forces of Asymmetrically Grown Polyelectrolyte Multilayers: Searching for the Charges.

Surface forces are used to investigate the polymer conformation and the surface charge of polyelectrolyte multilayers. Films are prepared from strong polyelectrolytes with low and high linear charge density at 0.1 M NaCl, namely poly(diallyldimethylammonium) (PDADMA) and poly(styrenesulfonate) (PSS). The multilayer has two growth regimes: in the beginning, the film can contain as many positive as negative monomers. After about 15 deposited layer pairs, a linear growth regime characterized by an excess of cationic PDADMA monomers occurs. Independent of the film composition, at preparation conditions, the film surface is flat, uncharged and partially hydrophobic. Surface force measurements at decreased ionic strength provide insight. For PSS-terminated films electrostatic forces are found. At the beginning of multilayer formation, the surface charge density is negative. However, in the linear growth regime it is positive and low (one charge per 200-400 nm). This reversal of surface charge density of PSS-terminated films is attributed to excess PDADMA-monomers within the film. PDADMA terminated films show steric forces, chains protrude into the solution and form a pseudobrush, which scales as a polyelectrolyte brush with a low grafting density (1900 nm per chain). We suggest a model of polyelectrolyte multilayer formation: PDADMA with its low linear charge density adsorbs with weakly bound chains. Monovalent anions within the film compensate PDADMA monomer charges. When PSS adsorbs onto a PDADMA-terminated multilayer, PSS monomers replace monovalent anions. While electrostatic bonds are formed and dissolved within the polyelectrolyte multilayer, the surface charge density remains zero.