DLVO Interactions between Particles and Rough Surfaces: An Extended Surface Element Integration Method.

The surface element integration (SEI) method is a computationally facile technique for calculating DLVO interactions between particles and surfaces. This method yields the exact total DLVO interaction between a particle and a flat surface; however, all surfaces have some degree roughness that profoundly affects the interaction. Previously, an ad hoc approximate method has been used to extend the SEI method to interactions between particles and surfaces with arbitrary morphology. Here we derive a more rigorous approximate method based on the fundamental scaling of DLVO interactions, which approaches the exact solution as the separation distance decreases regardless of the particle or surface morphology. We verify this method by comparison to the exact van der Waals energy when roughness is present on the particle and surface. The accuracy of this method at small separations makes it well-suited for the contexts of particle adhesion and deposition in which the length scale of interaction is on the order of angstroms and nanometers, respectively.

ab initio study of Mn-based systems for oxidative degradation.

Organic contaminants can be removed from water/wastewater by oxidative degradation using oxidants such as manganese oxides and/or aqueous manganese ions. The Mn species show a wide range of activity, which is related to the oxidation state of Mn. Here, we use ab initio molecular dynamics simulations to address Mn oxidation states in these systems. We first develop a correlation between Mn partial atomic charge and the oxidation state based on results of 31 simulations on known Mn aqueous complexes. The results collapse to a master curve; the dependence of partial atomic charge on oxidation state weakens with increasing oxidation state, which concurs with a previously proposed feedback effect. This correlation is then used to address oxidation states in Mn systems used as oxidants. Simulations of MnO2 polymorphs immersed in water give average oxidation states (AOS) in excellent agreement with experimental results, in that ß-MnO2 has the highest AOS, α-MnO2 has an intermediate AOS, and δ-MnO2 has the lowest AOS. Furthermore, the oxidation state varies substantially with the atom's environment, and these structures include Mn(III) and Mn(V) species that are expected to be active. In regard to the MnO4-/HSO3-/O2 system that has been shown to be a highly effective oxidant, we propose a novel Mn complex that could give rise to the oxidative activity, where Mn(III) is stabilized by sulfite and dissolved O2 ligands. Our simulations also show that the O2 would be activated to O22- in this complex under acidic conditions, and could lead to the formation of OH radicals that serve as oxidants.

Derjaguin-Landau-Verwey-Overbeek energy landscape of a Janus particle with a nonuniform cap.

A colloidal particle is often termed "Janus" when some portion of its surface is coated by a second material which has distinct properties from the native particle. The anisotropy of Janus particles enables unique behavior at interfaces. However, rigorous methodologies to predict Janus particle dynamics at interfaces are required to implement these particles in complex fluid applications. Previous work studying Janus particle dynamics does not consider van der Waals interactions and realistic, nonuniform coating morphology. Here we develop semianalytic equations to accurately calculate the potential landscape, including van der Waals interactions, of a Janus particle with nonuniform coating thickness above a solid boundary. The effects of both nonuniform coating thickness and van der Waals interactions significantly influence the potential landscape of the particle, particularly in high ionic strength solutions, where the particle samples positions very close to the solid boundary. The equations developed herein facilitate more simple, accurate, and less computationally expensive characterization of conservative interactions experienced by a confined Janus particle than previous methods.

Relative importance of electrostatic and van der Waals forces in particle adhesion to rough conducting surfaces.

It is commonly assumed that van der Waals forces dominate adhesion in dry systems and electrostatic forces are of second order importance and can be safely neglected. This is unambiguously the case for particles interacting with flat surfaces. However, all surfaces have some degree of roughness. Here we calculate the electrostatic and van der Waals contributions to adhesion for a polarizable particle contacting a rough conducting surface. For van der Waals forces, surface roughness can diminish the force by several orders of magnitude. In contrast, for electrostatic forces, surface roughness affects the force only slightly, and in some regimes it actually increases the force. Since van der Waals forces decrease far more strongly with surface roughness than electrostatic forces, surface roughness acts to increase the relative importance of electrostatic forces to adhesion. We find that for a particle contacting a rough conducting surface, electrostatic forces can be dominant for particle sizes as small as ∼1-10 µm.

Particle adhesion to rough surfaces.

While particle adhesion to smooth surfaces is well understood, real surfaces are not perfectly smooth, and the effects of surface roughness on adhesion are not easily characterized. We develop a theory for the effects of surface roughness on the strength of particle adhesion due to van der Waals forces, in the Derjaguin-Muller-Toporov (DMT)-type adhesion regime. We first address a well-defined rough surface created by embedding spheres in a smooth substrate, which had been previously examined experimentally. We derive an analytic expression for the adhesive force of particles to this well-defined surface, with the key distinction from the previous work being the inclusion of interactions from surface asperities not in direct contact with the particle. We show that our theory is in good agreement with experimental results in the DMT regime. Within appropriate limits, we extend our theory to general rough surfaces and verify the theory by comparing to the exact numerical results. We show that the interactions from surface asperities not in direct contact with the particle are the dominant contribution to the adhesive force under some conditions, and our theory predicts the experimental and numerical adhesion forces very accurately.