Slow dynamics in transient polyelectrolyte hydrogels formed by self-assembly of block copolymers

Transient polyelectrolyte hydrogels were formed by self-assembly of triblock copolyelectrolytes with a central hydrophilic block, poly(acrylic acid) (PAA), and two hydrophobic end blocks, poly(n-butyl acrylate(50%)-stat-acrylic acid(50%)) [P(nBA(50%)-stat-AA(50%))]. The relaxation of the concentration fluctuations was investigated by dynamic light scattering as a function of the concentration, the pH, the temperature, and the ionic strength. A relatively fast mode was observed at all polymer concentrations caused by cooperative diffusion of the polymers. Above the critical percolation concentration a second slow relaxation mode was observed caused by a linear displacement of small heterogeneities in the network with constant velocity. The relative amplitude of the slow mode was determined by the strength of the electrostatic repulsion. The velocity of the displacement in the transient network is shown to be directly correlated to the terminal relaxation time of the shear modulus and has the same Arrhenius temperature dependence. Both the velocity of the displacement and the mechanical relaxation strongly slow down with decreasing degree of ionization below 0.7 and increasing ionic strength above 0.5 M. A ballistic relaxation process has been reported earlier for colloidal gels, and the present study shows that it can also occur in polymeric networks.