title: Effect of interfacial ion structuring on range and magnitude of electric double layer, hydration, and adhesive interactions between mica surfaces in 0.05-3 M Li⁺ and Cs⁺ electrolyte solutions.
abstract: Ions and water structuring at charged-solid/electrolyte interfaces and forces arising from interfacial structuring in solutions above 100 mM concentrations dominate structure and functionality in many physiological, geological, and technological systems. In these concentrations, electrolyte structuring occurs within the range of molecular dimensions. Here, we quantitatively measure and describe electric double layer (EDL) and adhesive interactions at mica-interfaces in aqueous CsCl and LiCl solutions with concentrations ranging from 50 mM to 3 M. Complementarily, using atomic force microscopy and surface forces apparatus experiments we characterize concentration-dependent stark differences in the inner and outer EDL force profiles, and discuss differences between the used methods. From 50 mM to 1 M concentrations, interactions forces measured in CsCl-solutions exhibit strong hydration repulsions, but no diffuse EDL-repulsions beyond the Stern layer. In confinement the weakly hydrated Cs(+) ions condensate into the mica-lattice screening the entire surface charge within the Stern layer. In contrast, strongly hydrated Li(+) ions only partially compensate the surface charge within the Stern layer, leading to the formation of a diffuse outer double layer with DLVO behavior. Both LiCl and CsCl solutions exhibit oscillatory ion-hydration forces at surface separations from 2.2 nm to 4-8 Å. Below 4-8 Å the force profiles are dominated in both cases by forces originating from water and/or ion confinement at the solid/electrolyte/solid interface. Adhesive minima and their location vary strongly with the electrolyte and its concentration due to specific ion correlations across the interface, while dispersion forces between the surfaces are overpowered. Highly concentrated 3 M solutions exhibit solidification of the inner EDL structure and an unexpected formation of additional diffuse EDL forces with an increasing range, as recently measured in ionic liquids. Our results may have important implications for understanding and modeling of interaction forces present in static and dynamic systems under physiological and high salt conditions.
authors.affiliation: Department of Interface Chemistry and Surface Engineering, Max-Planck Institut für Eisenforschung GmbH , Max-Planck-Straße 1, D-40237, Düsseldorf, Germany.
authors.forename: Theodoros
authors.initials: T
authors.lastname: Baimpos
authors.forename: Buddha R
authors.initials: BR
authors.lastname: Shrestha
authors.forename: Sangeetha
authors.initials: S
authors.lastname: Raman
authors.forename: Markus
authors.initials: M
authors.lastname: Valtiner
mesh_terms: D000538:Aluminum Silicates / Q000737:chemistry*; D002586:Cesium / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D004573:Electrolytes / Q000737:chemistry*; D018021:Lithium Chloride / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D000538:Aluminum Silicates; D002712:Chlorides; D004573:Electrolytes; D002586:Cesium; D018021:Lithium Chloride; C028019:cesium chloride; C011934:mica