Enhancement of depletion forces by electrostatic depletant repulsion

A large variety of engaging phenomena stems from the occurrence of short-ranged attractive depletion forces. Yet, so far, most experimental studies have been interpreted on the basis of the simple Asakura–Oosawa model, where the depletion agent can be regarded as ideal. Here, conversely, we focus on a system where strong electrostatic coupling is present in the suspension. Specifically, from measurements of equilibrium sedimentation profiles, we obtain an equation of states for a colloidal system where depletion forces are tuned by the addition of a surfactant. At fixed colloid volume fraction, colloidal aggregation takes place when the surfactant concentration reaches a critical value which rises for increasing ionic strength. Screening repulsive electrostatic interactions inhibits the depletion mechanism and weakens the effective colloid-colloid attraction. The metastable coexistence curve displays the universal scaling behavior predicted for short-ranged potentials. The experimental data are compared with the theoretical predictions of a simple model which includes only electrostatic interactions. The effective depletion force on the colloids is evaluated by using the hypernetted-chain equation of liquid state theory at different salt concentrations. This model provides a convincing interpretation of the observed enhancement of the depletion mechanism by Coulomb repulsion.