Interaction between Nearly Hard Colloidal Spheres at an Oil-Water Interface

Abstract

We show that the interaction potential between sterically stabilized, nearly hard-sphere [poly(methylmethacrylate)-poly(lauryl methacrylate) (PMMA-PLMA)] colloids at a water-oil interface has a negligible unscreened-dipole contribution, suggesting that models previously developed for charged particles at liquid interfaces are not necessarily applicable to sterically stabilized particles. Interparticle potentials, $U(r)$, are extracted from radial distribution functions [$g(r)$, measured by fluorescence microscopy] via Ornstein-Zernike inversion and via a reverse Monte Carlo scheme. The results are then validated by particle tracking in a blinking optical trap. Using a Bayesian model comparison, we find that our PMMA-PLMA data is better described by a screened monopole only rather than a functional form having a screened monopole plus an unscreened dipole term. We postulate that the long range repulsion we observe arises mainly through interactions between neutral holes on a charged interface, i.e., the charge of the liquid interface cannot, in general, be ignored. In agreement with this interpretation, we find that the interaction can be tuned by varying salt concentration in the aqueous phase. Inspired by recent theoretical work on point charges at dielectric interfaces, which we explain is relevant here, we show that a screened $\frac{1}{r^2}$ term can also be used to fit our data. Finally, we present measurements for poly(methyl methacrylate)-poly(12-hydroxystearic acid) (PMMA-PHSA) particles at a water-oil interface. These suggest that, for PMMA-PHSA particles, there is an additional contribution to the interaction potential. This is in line with our optical-tweezer measurements for PMMA-PHSA colloids in bulk oil, which indicate that they are slightly charged.