Monte Carlo simulation of surfactant adsorption on hydrophilic surfaces

Monte Carlo simulations have been carried out to study the adsorption behavior of small flexible amphiphilic molecules on solid surfaces from aqueous solutions. A simple coarse-grained solvent-free off-lattice model, with a square-well pair potential and hard core excluded volume effect, has been used. Adsorption isotherms for weakly and strongly hydrophilic homogeneous surfaces have been determined. The adsorbed layer displays a coexistence region with an upper critical point. Below the critical temperature a densely packed patch coexists with a two-dimensional gas-analogous phase. Above the critical temperature, a percolating network forms at higher surfactant concentrations. Depending on the ratio between the strength of the hydrophobic effect and the adsorption energy, a large variety of associates has been observed. Monolayers, bilayers, admicelles, small clusters, and percolating networks as typical associate structures have been found. In the four-region model, which is extended by the coexistence region, a characteristic adsorbed layer structure for each region can be detected. Intermediate structure types have been produced by variation of the adsorption energy.