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Colloidal droplets are used in a variety of practical applications. Some ofthese applications require particles of different sizes. These include medicaldiagnostic methods, the creation of photonic crystals, the formation ofsupraparticles, and the production of membranes for biotechnology. A series ofearlier experiments had shown the possibility of particle separation near thecontact line, dependent upon their size. A mathematical model has beendeveloped to describe this process. Bi-dispersed colloidal droplets evaporatingon a hydrophilic substrate are taken into consideration. A particle monolayeris formed near the periphery of such droplets due to the small value of thecontact angle. The shape of the resulting deposit is associated with the coffeering effect. The model takes into account both particle diffusion and transferscaused by capillary flow due to liquid evaporation. Monte Carlo simulations ofsuch particle dynamics have been performed at several values of particleconcentration in the colloidal solution. The numerical results agree with theexperimental observations, in which small particles accumulate nearer to thecontact line than do the large particles. However, the particles do notactually reach the contact line, but accumulate at a small distance from it.The reason for this is the surface tension acting on the particles in areaswhere the thickness of the liquid layer is comparable to the particle size.Indeed, the same mechanism affects the observed separation of the small andlarge particles.

Monte Carlo simulation of particle size separation in evaporating bi-dispersed colloidal droplets on hydrophilic substrates