Optical evidence for adsorption of charged inverse micelles in a Stern layer

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Understanding the properties and behavior of nonpolar liquids containing surfactant and colloidal particles is essential for applications such as electrophoretic ink displays and liquid toner printing. Charged inverse micelles, formed from aggregated surfactant molecules, and their effect on the electrophoretic motion of colloidal particles have been investigated in quite some detail over the past years. However, the interactions of charged inverse micelles at the electrode interfaces are still not well understood. In some surfactant systems the charged inverse micelles bounce off the electrodes, while in other systems they are quickly adsorbed to the electrodes upon contact. In this work a fluorocarbon solvent doped with a fluorosurfactant is investigated in which the adsorption of charged inverse micelles to the electrode occurs slowly, leading to long-term charging phenomena. We propose a physical model and an equivalent electrical model based on adsorption and desorption of inverse micelles into a Stern layer with finite thickness. We compare two limiting cases of this model: the ‘adsorption/desorption’ limit and the ‘Stern layer adsorption’ limit. Both limits are compatible with electrical measurements. The ‘Stern layer adsorption’ limit additionally explains the optical measurements, because these measurements indicate that the diffuse double layer vanishes over time when a polarizing voltage step is applied. The obtained value for the Stern layer thickness and the proportionality between the charging time constant and the surfactant concentration are also compatible with the ‘Stern layer adsorption’ limit.