Water-Based Polyurethane Dispersions: A Detailed Analysis of the Particle Charge Using Soft and Hard Particle Model

Water-based polyurethane dispersions (PUDs) show a characteristic dependency of the electrophoretic mobility on the electrolyte concentration, which can be investigated by hard and soft particle models. For this purpose, additional information can be obtained by determining particle charges and electrostatic potentials. PUDs with different contents of an intrinsic ionic stabilizer and various polyol components were synthesized according to the acetone process. The particle charge was characterized by potentiometric acid-base titration, and the data of the titration curve were fitted assuming multiple functional groups with adaptable acid strengths. To investigate the electrostatic potentials, electrophoretic mobilities were measured as a function of electrolyte concentration and analyzed by soft and hard particle theory. Acid-base titration experiments indicated that not all detected ionic groups are located on the surface but are partly arranged inside the polymer particle, as evidenced by a significant decrease of the corresponding effective dissociation constant. The evaluation of the titration data and the electrokinetic experiments showed that the soft particle model of Ohshima is not suitable to reflect the actual particle charge. In contrast, the hard particle model can describe the measured electrophoretic mobility of the dispersions very well if the relaxation effect is taken into account. The dependency of the corresponding zeta potentials on the electrolyte concentration can be excellently modeled assuming a constant surface potential ψ₀ and distance of the shear plane x_s. Reasonable results are obtained for both parameters with only minor differences between the PUD series. Nonetheless, the electrokinetic surface charge densities calculated with respect to the surface potential are lower than expected from the titration results. Although our results indicate a more complex charge distribution in a peripheral layer, the hard particle model currently shows the best description of the electrokinetic behavior of the PUDs.