Coarse-Grained Molecular Dynamics Simulation of Self-Assembly and Surface Adsorption of Ionic Surfactants Using an Implicit Water Model

We perform coarse-grained molecular dynamics simulations for sodium dodecyl sulfate (SDS) surfactant using a modification of the Dry Martini force field (Arnarez et al. 2014) with implicit water. After inclusion of particle mesh Ewald (PME) electrostatics, an artificially high dielectric constant for water (ε_r = 150), and reparameterization, we obtain structural and thermodynamic properties of SDS micelles that are close to those obtained from the standard Martini force field with explicit water, which in turn match those of atomistic simulations. The gains in computational efficiency obtained by removing explicit water allow direct simulations of the self-assembly of SDS in solution. We observe surfactant exchange among micelles and micelle fission and fusion and obtain realistic, equilibrated micelle size distributions at modest computational cost, as well as a transition to cylindrical micelles at high surfactant concentration or with added salt. We further apply this parametrized force field to study the adsorption of SDS onto hydrophobic surfaces and calculate the adsorption kinetics and equilibrium adsorption isotherm. The greatly increased speed of computation of surfactant self-assembly made possible by this Dry Martini method should allow future simulation of competitive adsorption of multiple surfactant species to surfaces, as well as simulation of micellar shape transitions

Modeling the Adsorption of Rheology Modifiers onto Latex Particles Using Coarse-Grained Molecular Dynamics (CG-MD) and Self-Consistent Field Theory (SCFT)

We model the adsorption of hydrophobically ethoxylated urethane (HEUR) thickeners onto two hydrophobic surfaces separated by a 50 nm gallery using coarse-grained molecular dynamics (CG-MD) with implicit solvent and three-dimensional self-consistent field theory (SCFT) with explicit solvent. The CG-MD simulations can be readily extended to encompass very long HEUR chains (up to 540 EO groups) but cannot with current computer speed simulate adsorption of HEURs with hydrophobes longer than 12 carbons (C12). The SCFT method can readily simulate HEURs with longer, C16, hydrophobes but has a greater challenge simulating very long EO chains. For HEURs with 180 EO units and C8 and C12 hydrophobes, both methods can be applied, allowing a combination of the two methods to span much of the parameter space of interest to experimentalists. It is demonstrated that depending on the hydrophobe strength and the HEUR concentration, HEUR chains can adsorb to the surfaces directly or indirectly (as adsorbed micelles or admicelles). We show that for hydrophobes as large or larger than C12 micellization and subsequent adsorption of the micelles play an important role in accurate prediction of adsorption isotherms and the structure of adsorbed layers and that micelles in solution form nodes that allow two or more HEUR chains to bridge the gallery between the two surfaces. The study suggests the need to investigate the influence of admicelles on the effective steric interaction potential, which, in turn, will influence both colloidal stability and rheology of HEUR thickened latex paints