Competitive adsorption of neutral comb polymers and sodium dodecyl sulfate at the air/water interface.

The interfacial behavior of aqueous solutions of four different neutral polymers in the presence of sodium dodecyl sulfate (SDS) has been investigated by surface tension measurements and ellipsometry. The polymers comprised linear poly(ethylene oxide) with low and high molecular masses (10(3) and 10(6) Dalton (Da), respectively), and two high molecular mass methacrylate-based comb polymers containing poly(ethylene oxide) side chains. The adsorption isotherms of SDS, determined by Gibbs analysis of surface tension data, are nearly the same in the presence of the high molecular mass linear polymer and the comb polymers. Analysis of the ellipsometric data reveals that while a single surface layer model is appropriate for films of polymer alone, a more sophisticated interfacial layer model is necessary for films of SDS alone. For the polymer/surfactant mixtures, a novel semiempirical approach is proposed to determine the surface excess of polymer, and hence quantify the interfacial composition, through analysis of data from the two techniques. The replacement of the polymer due to surfactant adsorption is much less pronounced for the high molecular mass linear polymer and for the comb polymers than for the low molecular mass linear polymer. This finding is rationalized by the significantly higher adsorption driving force of the larger polymer molecules as well as by their more amphiphilic structure in the case of the comb polymers.