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Being able to predict and tune the colloidal stability of nanoparticles isessential for a wide range of applications, yet our ability to do so iscurrently poor due to a lack of understanding of how they interact with oneanother. Here, we show that the agglomeration of apolar particles is dominatedby either the core or the ligand shell, depending on the particle size andmaterials. We do this by using Small-Angle X-ray Scattering and moleculardynamics simulations to characterize the interaction between hexadecanethiolpassivated gold nanoparticles in decane solvent. For smaller particles, theagglomeration temperature and interparticle spacing are determined by orderingof the ligand shell into bundles of aligned ligands that attract one anotherand interlock. In contrast, the agglomeration of larger particles is driven byvan der Waals attraction between the gold cores, which eventually becomesstrong enough to compress the ligand shell. Our results provide a microscopicdescription of the forces that determine the colloidal stability of apolarnanoparticles and explain why classical colloid theory fails.

On the colloidal stability of apolar nanoparticles: The role of particle size and ligand shell structure