Self-assembly of mono- and poly-dispersed nanoparticles on emulsion droplets: antagonistic synergistic effects as a function of particle size.

In this work, using Dissipative Particle Dynamics simulations, we provide fundamental insights into the self-assembly of nanoparticles (NPs) on droplet surfaces in an oil-in-water emulsion. We highlight the effect of particle size on the arrangement of NPs for different interparticle interactions. NPs of two different sizes were considered. In general, when the NP-NP interaction is changed from repulsive to attractive, a transition in the NP arrangement occurs from weekly-connected networks to clusters of NPs separated by particle-free domains. When NP-NP interactions are strongly attractive, NPs yield small 3D aggregates on the droplet surface. These arrangements seem to agree with experimental observations reported in the literature. In addition, our simulations suggest that small NPs are able to diffuse more easily on the droplet surface, which leads to prompt self-organisation, while large NPs are more likely to form metastable structures, perhaps because of slow mobility and strong adsorption to the interface. Our analysis suggests that thermal fluctuations could provide the activation energy for the small NPs to escape local minima in the free energy landscape. The results obtained for systems containing NPs of two sizes provide evidence of size segregation on the droplet surface, which could be useful when NP self-assemblies are used, for example, to template supra-molecular materials. However, analysis of the simulated trajectories suggests that the results depend strongly on the initial configuration, as the larger NPs seem to impose barriers for the small NPs to adsorb and diffuse on the droplet surface.