Response of a Permanently Charged Polyelectrolyte Brush to External Ions: The Aspects of Structure and Dynamics

Structure and dynamics inside permanently charged polyelectrolyte brushes, sodium polystyrene sulfonate brushes, during their response to the introduction of external ions (NaCl) are investigated by neutron reflectivity and dielectric spectroscopy. Neutron reflectivity measurements show that the segmental density of the inner part of the brushes decreases and that of the outer part increases when the salt level is tuned from the salt-free condition to a moderate level (<10^-2 M)-the brushes swell further compared with the salt-free condition. This is attributed to the breakup of the multiplets formed by dipole-dipole pairs, and by this process, the previously constrained chain segments by the multiplets are released. Dielectric spectroscopy discovers a giant dipole by the charge separation of the adsorbed counterions and the PSS^- chains, induced by electric field. The dynamics of the induced giant dipole is accelerated with the increase of external salt, as a result of the charge regularization by elevated salt level. At high-enough salt level, the screening effect reduces the electrostatic repulsion between the neighboring chains and makes the brushes shrink.