Facet-Dependent Charge Density of Serpentine: Nanoscopic Implications for Aggregation and Entrainment of Fine Particles

Deciphering the facet-dependent surface properties of clay minerals holds vital significance in both fundamental research and practical engineering applications. To date, the anisotropic local charge density of serpentine surfaces still remains elusive, and thus, the interaction energies and associated aggregate structures between different crystal planes of serpentine cannot be quantitatively determined. In this work, different crystal planes of serpentine (i.e., SiO basal, MgOH basal, and edge) were selectively exposed, and their surface potentials and charge densities were determined using atomic force microscopy (AFM) force measurements coupled with Derjaguin-Landau-Verwey-Overbeek (DLVO) theory fitting. The SiO and edge planes consistently exhibited a permanently negative surface charge, whereas the point of zero charge (PZC) on the MgOH plane was estimated to be pH 9.0-11.0. Based on the interaction energy calculation between different serpentine planes, the aggregation structures of serpentine were predicted. Combined with scanning electron microscopy observation of freeze-dried samples, SiO-MgOH and MgOH-edge associations were found to dominate the aggregate structures at pH ≤ 9.0, thereby resulting in a stacking or "card-houses" structures. In contrast, all of the plane associations exhibited the repulsive interaction energy at pH 11.0, which led to a completely dispersed system, ultimately causing the most severe fine particle entrainment during froth flotation. Our work provides quantitative clarification of facet-dependent surface properties and aggregate structures of serpentine under different pH conditions, which will help improve the fundamental understanding of colloidal behaviors of clay minerals.