Stepwise collapse of highly overlapping electrical double layers

When two charged surfaces and their accompanying electrical double layers (EDLs) approach each other in an electrolyte solution, the EDLs first begin to overlap and finally collapse under confinement. During this collapse we can observe repulsive forces and film-thickness transitions, which contain valuable information about different structural elements present at the interface. Sensing and discriminating these transitions by size and frequency of occurrence is possible via direct force measurements. Changing salt concentration or pH provide additional means to shift chemical potentials and interfacial populations, and therefore also to shift the relative stability of these structural elements. We provide new evidence that the previously observed oscillatory surface force appearing at the final stages of collapse of the EDL is initially due to layering transitions between hydrated ions, which then develop into smaller transitions between highly confined adsorbed ion states.