Nanoparticle adsorption dynamics at fluid interfaces

Understanding the dynamic adsorption of nanoparticles (NPs) at fluid interfaces is important for stabilizing emulsions and for the preparation of 2D NP-based materials. Here we show that the Ward-Tordai equations commonly employed to describe the dynamics of surfactant adsorption at a fluid interface combined with a Frumkin adsorption isotherm can be employed to model the diffusion-limited adsorption of NPs onto a fluid interface. In contrast to surfactants, an additional wetting equation of state (EOS) must be incorporated to characterize the dynamic interfacial tension during the adsorption of NPs to the oil-water interface. Our results show agreement between the model and experiments with NP area fractions <0.3. Slower dynamics are observed at larger area fractions, which are speculated to arise from polydispersity or re-organization at the interface. We show the model can be extended to the competitive adsorption between the NPs and a surface active species.