Surface phase separation in complex mixed adsorbing systems: an interface-bulk coupling effect

The interfacial thermodynamics and structure of ternary mixtures of the type A+B+solvent are investigated. According to the Gibbs phase rule, the coupling between the bulk phase and the interfacial region-which is related to the reversibility of the adsorption of the corresponding species-is a determinant as to whether phase separation can be observed at the interface. For an n-component adsorbing solution, at least one of the species has to adsorb irreversibly over the experimental time scales in order not to fix more intensive variables than those required to observe surface phase separation. We present results for a lattice model planar interface consisting of the ternary mixture A+B+solvent. The solvent molecules and the type A molecules have fixed chemical potentials at the interface since they are equilibrated with a bulk solution. In contrast, the type B molecules are irreversibly adsorbed at the interface and do not equilibrate with the bulk. Mean-field theory is compared with Monte Carlo simulation. Interestingly, the spinodal line in the interaction-composition plane shows a reentrant on the B-rich phase side. We discuss the implications of these results for surface phase separation of adsorbing mixtures of proteins and low-molecular-weight surfactants.