Charging and Aggregation Properties of Carboxyl Latex Particles: Experiments versus DLVO Theory

Carboxyl latex particles of two different sizes were used to study the early stages of aggregation in dilute colloidal suspensions. The charging behavior as a function of solution pH was characterized in acid−base titration and electrophoresis experiments at fixed ionic strength; absolute aggregation rate constants were measured by combined static and dynamic light scattering as a function of pH and ionic strength. Up to an ionic strength of 10 mM in a KCl solution, the classical DLVO theory of colloidal stability is seen to work quantitatively. At higher ionic strength, however, well-known discrepancies between theory and experiment are observed. An analysis of the theoretical pair interaction energy suggests that quantitative agreement can be achieved when the energy barrier for reaction-limited aggregation lies at surface separations of at least 1−2 nm. This result is consistent with recent measurements of colloidal forces and interaction energies, as well as with earlier aggregation and deposition studies typically carried out in the unfavorable situation of barriers at subnanometer distances. The theoretical discussion further considers the appropriate choice of a Hamaker constant, the effect of nonlinearity in the Poisson−Boltzmann equation on stability predictions, as well as the role of charge regulation and the error introduced by the Derjaguin approximation.