Abstract
Adsorption of weakly charged polyelectrolyte (PE) chains from dilute solution on an oppositely charged surface is studied using the self-consistent mean-field approach. The structure of the adsorbed polymer layer and its excess charge are analyzed in the most important asymptotic and intermediate regimes both analytically and numerically. Different regimes of surface charge compensation by PE chains including partial and full charge inversion are identified and discussed in terms of physical parameters like the magnitude of specific short-range interactions of PE segments with the surface, solvent quality and ionic strength. The effect of excluded-volume monomer interactions is considered quantitatively both in the marginally good and poor solvent regimes.
Highlights
Let us consider a dilute solution of polyelectrolyte (PE) chains
The results on charge inversion considered in this paper may provide some basis for understanding the structure of PE multilayers (PEMs),[3,11,12] but we do not claim a direct relevance of the adsorption results to PEMs
The adsorbed PE layer structure and charge compensation effect can be described in terms of the minimal set of the following reduced variables flexible PE chains: h = h/h0, reflecting a s~ex = sex/s, selpf-sffiffiffiimilar structure of 1= n 1⁄4 rD=h0, k~ 1⁄4 kh[0], B = B/B0, and C = C/C0, where h is the layer thickness, sex = fG À
Summary
Let us consider a dilute solution of polyelectrolyte (PE) chains. In the presence of an oppositely charged surface the PE chains tend to form an adsorbed layer on it. The latter quantity was analysed by Joanny[7] who developed a theory of polyelectrolyte adsorption from dilute solution on an oppositely charged surface based on a mean-field model rather similar to that adopted in ref. One aim of the present paper is to generalize the theory[7] and to analyse the solvent quality and surface interaction effects in more detail Another aim is to provide a more complete and quantitative analytical description of the charge inversion effect in the asymptotic regimes of low and high ionic strength and in other regimes. It was found[7] that the excess charge of the adsorbed layer, sex, is inversely proportional to the Debye length rD at low salt concentration This general relationship has not been fully justified and has been missing a proper prefactor.
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