We explore the conditions under which colloids can be stabilized by the addition of smaller particles. The largest repulsive barriers between colloids occur when the added particles repel each other with soft interactions, leading to an accumulation near the colloid surfaces. At lower densities these layers of mobile particles (nanoparticle halos) result in stabilization, but when too many are added, the interactions become attractive again. We systematically study these effects--accumulation repulsion, reentrant attraction, and bridging--by accurate integral equation techniques.
The effect of varying wall-particle and particle-particle interactions on the density profiles near a single wall and the solvation forces between two walls immersed in a fluid of particles is investigated by grand canonical Monte Carlo simulations. Attractive and repulsive particle-particle and particle-wall interactions are modeled by a versatile hard-core Yukawa form. These simulation results are compared to theoretical calculations using the hypernetted chain integral equation technique, as well as with fundamental measure density functional theory (DFT), where particle-particle interactions are either treated as a first order perturbation using the radial distribution function or else with a DFT based on the direct-correlation function. All three theoretical approaches reproduce the main trends fairly well, but exhibit inconsistent accuracy, particularly for attractive particle-particle interactions. We show that the wall-particle and particle-particle attractions can couple together to induce a nonlinear enhancement of the adsorption and a related "repulsion through attraction" effect for the effective wall-wall forces. We also investigate the phenomenon of bridging, where an attractive wall-particle interaction induces strongly attractive solvation forces.
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