Modeling the Electrostatics of Hollow Shell Suspensions: Ion Distribution, Pair Interactions, and Many-Body Effects

Yannick Hallez (1) , Martine Meireles (1)

1 LGC - Laboratoire de Génie Chimique

Electrostatic interactions play a key role in hollow shell suspensions as they determine their structure, stability,thermodynamics, and rheology and also the loading capacity of small charged species for nanoreservoir applications. In this work, fast, reliable modeling strategies aimed at predicting the electrostatics of hollow shells for one, two, and many colloids are proposed and validated. The electrostatic potential inside and outside a hollow shell with a finite thickness and a specific permittivity is determined analytically in the Debye-Hückel (DH) limit. An expression for the interaction potential between two such hollow shells is then derived and validated numerically. It follows a classical Yukawa form with an effective charge depending on the shell geometry, permittivity, and inner and outer surface charge densities. The predictions of the Ornstein-Zernike (OZ) equation with this pair potential to determine equations of state are then evaluated by comparison to results obtained with a Brownian dynamics algorithm coupled to the resolution of the linearized Poisson-Boltzmann and Laplace equations PB-BD simulations). The OZ equation based on the DLVO-like potential performs very well in the dilute regime as expected, but also quite well, and more surprisingly, in the concentrated regime in which full spheres exhibit significant many-body effects. These effects are shown to vanish for shells with small thickness and high permittivity. For highly charged hollow shells, we propose and validate a charge renormalization procedure. Finally, using PB-BD simulations, we show that the cell model predicts the ion distribution inside and outside hollow shells accurately in both electrostatically dilute and concentrated suspensions. We then determine the shell loading capacity as a function of salt concentration, volume fraction, and surface charge density for nanoreservoir applications such as drug delivery, sensing, or smart coatings.

Mots clés: Electrostatic; Interaction; Hollow; Shell; Cell model; Pair potential; Ornstein-Zernike; Poisson-Boltzmann; Equation of state

Domaines: Génie chimique; Génie des procédés

Yannick Hallez, Martine Meireles. Modeling the Electrostatics of Hollow Shell Suspensions: Ion Distribution, Pair Interactions, and Many-Body Effects. Langmuir, 2016, vol. 32 (n° 40), pp. 10430-10444. ⟨10.1021/acs.langmuir.6b02730⟩. ⟨hal-01390506⟩