How Surface Make-Up and Receding Electrokinetics Determine the Sign and Magnitude of Electrification at Water-Hydrophobe Interfaces?

Abstract

It has been widely reported that as water contacts hydrophobic materials such as air or hydrocarbons (liquid or solid), the interfaces acquire a negative charge. It is not entirely clear whether this occurs due to the nature of water, or the hydrophobe, or purely the interface. Here, we probe the effects of surface chemistry and the speed of liquid-solid contact formation and separation on electrification. Glass capillaries grafted with mixed self-assembled monolayers of octadecyltrichlorosilane (ODTS) and (3-aminopropy)triethoxysilane (APTES) were exploited. Water was drawn inside these capillaries from an electroneutral reservoir, and the excess charge carried by the pendant droplets, if any, was quantified using an electrometer with a 100 fC resolution. Depending on the APTES content, the surface charge density at the water-hydrophobe interface ranged from negative (for ODTS) to near-neutral (for APTES 2-sec-exposure followed by ODTS) to positive APTES(5s)-ODTS. Next, we probed the charge (Q) contributions of the following steps on the electrification: (i) Contact (Q_1^n): as a dry capillary enters the water reservoir; (ii) Liquid uptake (Q_2^n): as water is uptaken; (iii) Capillary lift (Q_3^n): the filled capillary is removed from the reservoir; and (iv) Liquid release (Q_4^n): releasing the liquid back into the reservoir. This revealed that the electrification during water uptake (Q_2^n) varied with the rate of release during the previous cycle (Q_4^(n-1)), and it did not depend on the uptake rate. We explain these findings based on the electrical double layer theory, electrokinetics, and charge conservation, advancing the current understanding of electrification.