Attractive interaction and bridging transition between neutral colloidal particles due to preferential adsorption in...

We examine the solvent-mediated interaction between two neutral colloidal particles due to preferential adsorption in a near-critical binary mixture. We take into account the renormalization effect due to the critical fluctuations using the recent local functional theory [J. Chem. Phys. 136, 114704 (2012)]. We calculate the free energy and the force between two colloidal particles as functions of the temperature T, the composition far from the colloidal particles c(∞), and the colloid separation ℓ. The interaction is much enhanced when the component favored by the colloid surfaces is poor in the reservoir. For such off-critical compositions, we find a surface of a first-order bridging transition ℓ=ℓ(cx)(T,c(∞)) in the T-c(∞)-ℓ space in a universal, scaled form, across which a discontinuous change occurs between separated and bridged states. This surface starts from the bulk coexistence surface (CX) and ends at a bridging critical line where ℓ is determined by T as ℓ=ℓ(c)(T). On approaching the critical line, the discontinuity vanishes and the derivatives of the force with respect to T and ℓ both diverge. Furthermore, bridged states continuously change into separated states if c(∞) (or T) is varied from a value on CX to a value far from CX with ℓ kept smaller than ℓ(c)(T).