SANS from Salt-Free Aqueous Solutions of Hydrophilic and Highly Charged Star-Branched Polyelectrolytes

Abstract : Scattering functions of sodium sulfonated polystyrene (NaPSS) star-branched polyelectrolytes with high sulfonation degrees were measured from their salt-free aqueous solutions, using the Small Angle Neutron Scattering (SANS) technique. Whatever the concentration c, they display two maxima. The first, of abscissa q 1 *, is related to a position order between star cores and scales as q 1 * 9 c 1/3. The second, of abscissa q 2 *, is also observed in the scattering function of a semi-dilute solution of NaPSS linear polyelectrolytes. In the dilute regime (c < c*, non-overlapping stars), peak abscissa does not depend on concentration c and is just an intramolecular characteristic associated with the electrostatic repulsion between arms of the same star. In the semi-dilute regime, due to the star interpenetration, the scattering function – through the peak position, reflects repulsion between arms of the same star or of different stars. The c threshold between these distinct c-dependencies of q 2 * in the dilute and semi-dilute regimes is estimated as c*. Just as simple is the measurement of the geometrical radius R of the star obtained from the q 1 * value at c* through the relation 2R = 2π/q 1 *. By considering NaPSS stars of the same functionality with different degrees of polymerization per arm N a , we find R scaling linearly with N a , suggesting an elongated average conformation of the arms. This is in agreement with theoretical predictions and simulations. Meanwhile the value of q 2 * measured in the dilute regime does not allow any inhomogeneous counterion distribution inside the stars to be revealed.
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François Boué, Jérôme Combet, Bruno Demé, Martine Heinrich, Jean-Georges Zilliox, et al.. SANS from Salt-Free Aqueous Solutions of Hydrophilic and Highly Charged Star-Branched Polyelectrolytes. Polymers, MDPI, 2016, 8 (6), pp.228. ⟨10.3390/polym8060228⟩. ⟨hal-01386366⟩

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