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Scattering Functions of Flexible Polyelectrolytes in the Presence of Mixed Valence Counterions:  Condensation and Scaling

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    Article

    Scattering Functions of Flexible Polyelectrolytes in the Presence of Mixed Valence Counterions:  Condensation and Scaling
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    Institut Charles Sadron (CNRS-ULP), 6 rue Boussingault, 67083 Strasbourg Cedex, France
    Laboratoire Léon Brillouin (CEA-CNRS), CE Saclay, 91191 Gif-sur-Yvette Cedex, France
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    Macromolecules

    Cite this: Macromolecules 2005, 38, 17, 7456–7469
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    https://doi.org/10.1021/ma0479722
    Published July 21, 2005
    Copyright © 2005 American Chemical Society
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    Abstract

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    We have investigated by small-angle X-ray and neutron scattering the structure of salt-free aqueous solutions of sulfonated polystyrene with variable fractions of monovalent (sodium, Na) and divalent (calcium, Ca) counterions. We follow the variation of the position of the maximum in the scattered intensity, q*, as a function of the concentration, c, and the fraction of Ca counterions. A relevant parameter is the degree of condensation of Na and Ca counterions in the different mixtures. We survey the literature and check that, in the case of monovalent counterions, the variation of q* with c can be described by the scaling theory of Dobrynin, Colby, and Rubinstein, provided the counterion condensation is included according to the Manning−Oosawa approach. Scattering data from mixed valence systems are still in agreement with this scaling model at lower concentrations, except for pure CaPSS2 aqueous solutions. For increasing concentration, a discrepancy is enhanced that extends toward higher Ca fractions. This indicates that counterion condensation is not the only process. Another possible one is a retraction of the macroions due to divalent counterions that induce bridging-type correlations between monomers, as already observed on the form factors of CaPSS2 and NaPSS plus added CaCl2 salt. Such a retraction modifies the scaling, in particular, via a change in the overlap concentration c*. Furthermore, it is noticeable that q* measurements have to be handle with care. We show that misinterpretation of the characteristic maximum in the small-angle scattering of polyelectrolyte solutions may occur, especially at high concentration, if the contribution of the condensed counterions to the total scattering function is predominant.

    Copyright © 2005 American Chemical Society

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     Corresponding author:  Tel +33 3 88 41 40 96; Fax +33 03 88 41 40 99; e-mail [email protected].

    Cited By

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    This article is cited by 33 publications.

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    Macromolecules

    Cite this: Macromolecules 2005, 38, 17, 7456–7469
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ma0479722
    Published July 21, 2005
    Copyright © 2005 American Chemical Society
    Request reuse permissions

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