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Polymers 2016, 8(6), 228; doi:10.3390/polym8060228

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

1
Laboratoire Léon Brillouin (CEA-CNRS), CE Saclay, 91191 Gif-sur-Yvette Cedex, France
2
Génie Microbiologique et Procédés Alimentaires, INRA-AgroParisTech-UPSay, 1 rue Lucien Brétignières, 78850 Thiverval-Grignon, France
3
Institut Charles Sadron (CNRS-UdS), 23 rue du Loess, BP 84047, 67034 Strasbourg Cedex 2, France
4
Institut Laue Langevin, BP 156, 38042 Grenoble Cedex 9, France
5
Institut de Chimie (UdS), 1 rue Blaise Pascal, BP 296R8, 67008 Strasbourg Cedex, France
We dedicate this paper to Jean-Georges Zilliox, deceased.
*
Author to whom correspondence should be addressed.
Academic Editor: Christine Wandrey
Received: 29 February 2016 / Revised: 14 May 2016 / Accepted: 23 May 2016 / Published: 8 June 2016
(This article belongs to the Collection Polyelectrolytes)
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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 q1*, is related to a position order between star cores and scales as q1* ∝ c1/3. The second, of abscissa q2*, 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 q2* 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 q1* value at c* through the relation 2R = 2π/q1*. By considering NaPSS stars of the same functionality with different degrees of polymerization per arm Na, we find R scaling linearly with Na, suggesting an elongated average conformation of the arms. This is in agreement with theoretical predictions and simulations. Meanwhile the value of q2* measured in the dilute regime does not allow any inhomogeneous counterion distribution inside the stars to be revealed. View Full-Text
Keywords: electrostatics; polyelectrolytes; star polymers; Small Angle Neutron Scattering; scattering peak; Debye length; scaling laws; counterions; condensation; semi-dilute; interpenetration; overlap concentration electrostatics; polyelectrolytes; star polymers; Small Angle Neutron Scattering; scattering peak; Debye length; scaling laws; counterions; condensation; semi-dilute; interpenetration; overlap concentration
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Boué, F.; Combet, J.; Demé, B.; Heinrich, M.; Zilliox, J.-G.; Rawiso, M. SANS from Salt-Free Aqueous Solutions of Hydrophilic and Highly Charged Star-Branched Polyelectrolytes. Polymers 2016, 8, 228.

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