Nanoparticle adhesion at liquid interfaces

Nanoparticle adhesion at liquid interfaces plays an important role in drug delivery, dust removal, the adsorption of aerosols, and controlled self-assembly. However, quantitative measurements of capillary interactions at the nanoscale are challenging, with most existing results at the micrometre to millimetre scale. Here, we combine atomic force microscopy (AFM) and computational simulations to investigate the adhesion and removal of nanoparticles from liquid interfaces as a function of the particles' geometry and wettability. Experimentally, AFM tips with controlled conical geometries are used to mimic the nano-asperities on natural nanoparticles interacting with silicone oil, a model liquid for many engineering applications including liquid-infused surfaces. Computationally, continuum modelling with the Surface Evolver software allows us to visualise the interface configuration and predict the expected force profile from energy minimisation. Quantitative agreement between the experimental measurements and the computational simulations validates the use of continuum thermodynamics concepts down to the nanoscale. We demonstrate that the adhesion of the nanoparticles is primarily controlled by surface tension, with minimum line tension contribution. The particle geometry is the main factor affecting the length of the capillary bridge before rupture. Both the particle geometry and liquid contact angle determine the shape of the adhesion force profile upon removal of the particle from the interface. We further extend our simulations to explore more complex geometries, rationalising the results from experiments with imperfect AFM tips. Our results could help towards the design of smart interfaces, for example, able to attract or repel specific particles based on their shape and chemistry.