1 research outputs found
Phase behavior and structure of model colloid-polymer mixtures confined between two parallel planar walls
Using Gibbs ensemble Monte Carlo simulations and density functional theory we
investigate the fluid-fluid demixing transition in inhomogeneous
colloid-polymer mixtures confined between two parallel plates with separation
distances between one and ten colloid diameters covering the complete range
from quasi two-dimensional to bulk-like behavior. We use the
Asakura-Oosawa-Vrij model in which colloid-colloid and colloid-polymer
interactions are hard-sphere like, whilst the pair potential between polymers
vanishes. Two different types of confinement induced by a pair of parallel
walls are considered, namely either through two hard walls or through two
semi-permeable walls that repel colloids but allow polymers to freely
penetrate. For hard (semi-permeable) walls we find that the capillary binodal
is shifted towards higher (lower) polymer fugacities and lower (higher) colloid
fugacities as compared to the bulk binodal; this implies capillary condensation
(evaporation) of the colloidal liquid phase in the slit. A macroscopic
treatment is provided by a novel symmetric Kelvin equation for general binary
mixtures, based on the proximity in chemical potentials of statepoints at
capillary coexistence and the reference bulk coexistence. Results for capillary
binodals compare well with those obtained from the classic version of the
Kelvin equation due to Evans and Marini Bettolo Marconi [J. Chem. Phys. 86,
7138 (1987)], and are quantitatively accurate away from the fluid-fluid
critical point, even at small wall separations. For hard walls the density
profiles of polymers and colloids inside the slit display oscillations due to
packing effects for all statepoints. For semi-permeable walls either similar
structuring or flat profiles are found, depending on the statepoint considered.Comment: 15 pages, 13 figure