Colloidal aggregate micromechanics in the presence of divalent ions

Colloidal gels exhibit rheological properties, such as a yield stress and elasticity, which arise from the manner in which stress is transmitted through the microstructure. Insight into the mechanisms of stress transmission is critical in developing a full understanding of the mechanics of these materials. Paramount to this is a thorough knowledge of the interparticle interactions. In this work, we use optical trapping to study interactions between poly(methyl methacrylate) (PMMA) particles in adhesive contact by measuring the bending elasticity of directly assembled colloidal aggregates under various physicochemical conditions. The simplified geometry of the aggregate enables us determine the single-bond rigidity, which can then be related to the work of adhesion, W(SL), through the Johnson-Kendall-Roberts (JKR) theory of adhesion. We find that W(SL) is independent of ionic strength in flocculating monovalent salt solutions. However, more complex behavior is observed for divalent salts. Using zeta-potential measurements, we show that divalent cations adsorb to the particle surface. This results in the formation of ionic bridges between particles in adhesive contact. A model of the aggregate micromechanics that considers the divalent ion contribution to the surface energy provides a direct link between the interfacial properties of the particles, nanoscale contact interactions between particles, and the bulk gel modulus.