Macromolecules, Vol.27, No.24, 7085-7089, 1994
The Polyelectrolyte Brush - Implications from Simulation Results on Polyelectrolytes in Solution
Simulation results as well as experimental data indicate that full stretching of flexible polyelectrolytes will not occur for experimentally realizable solution conditions. Using density-dependent swelling exponents nu(phi) as suggested by Stevens and Kremer (SK) from the results of a MD simulation study of fully ionized polyelectrolyte chains in solution without added salt, we present an Alexander-de Gennes-like scaling picture for the behavior of charged brushes. The brush height is found to become dependent on the grafting density as soon as internal stretching is incomplete, i.e., at nu(phi) < 1. Due to SK the maximum stretching occurring below a characteristic saturation density is given by nu(s) = 0.90. For polyelectrolyte brushes, however, even this maximum internal stretching cannot be reached because end-grafted chains do not overlap at the saturation density. Density-independent behavior with nu(sr) = 0.80 should be seen when the short length scale regime, predicted by SK, is reached at high grafting densities. At intermediate grafting densities the stretching exponent is continuously increased with reduced density. For the particular grafting technique used in the experiment, the grafting density itself becomes dependent on the chain length N. Hence, there appears a modified overall chain length dependence of the brush height.
Keywords:PARTIALLY IONIZED POLYELECTROLYTES;ELECTROSTATIC PERSISTENCE LENGTH;POLY-ELECTROLYTE;CONFORMATION;SOLVENT;CHAINS;LAYER