Molecular dynamics study on the zeta potential and shear plane of montmorillonite in NaCl solutions

Abstract Zeta potential and the position of the shear plane are key physical properties characterizing the behavior of clay minerals in the colloidal system, and have been applied in many fields such as electroosmotic consolidation and electro-kinetic decontamination. In the past decades, numerous studies have been conducted on measuring and calculating the zeta potential. Nevertheless, few researchers have been reported to achieve a systematic understanding and predicting the zeta potential and the shear plane's position, especially for clay particles. This paper provided a molecular dynamics (MD)-based method to determine the zeta potential and shear layer thickness simultaneously to fill the gap. In the paper, the structure of the electrical double layer (EDL) was investigated for montmorillonite mesopore containing NaCl electrolyte in the concentration of 0.20–1.30 mol/L. The density profiles of ion species were well predicted by the Stern model, combining the Stern potential's determination. The calculated zeta potential based on the electroosmotic velocity profile in nonequilibrium molecular dynamics (NEMD) simulation was improved by introducing the slip length and was found to be closely comparable to the experimental values. Furthermore, the results confirmed that the shear plane cannot be observed from the electroosmotic velocity profile and self-diffusion coefficient of species in the MD simulation. The position of the zeta potential was determined by the Stern model and triple-layer model (TLM), showing a certain distance from the Stern plane. The zeta position was found that has a linear relationship with the Debye length and linearly depends on the ionic strength in the log scale, in agreement with previous investigations. The findings provided a systematic insight into the electrical double layer structure, zeta potential and shear plane for montmorillonite.