Giant Decrease in Interfacial Energy of Liquid Metals by Native Oxides

Native oxides form on the surface of many metals. Here, using gallium-based liquid metal alloys, Johnson-Kendall-Roberts (JKR) measurements are employed to show that native oxide dramatically lower the tension of the metal interface from 724 to 10 mN m-1. Like conventional surfactants, the oxide has asymmetry between the composition of its internal and external interfaces. Yet, in comparison to conventional surfactants, oxides are an order of magnitude more effective at lowering tension and do not need to be added externally to the liquid (i.e., oxides form naturally on metals). This surfactant-like asymmetry explains the adhesion of oxide-coated metals to surfaces. The resulting low interfacial energy between the metal and the interior of the oxide helps stabilize non-spherical liquid metal structures. In addition, at small enough macroscopic contact angles, the finite tension of the liquid within the oxide can drive fluid instabilities that are useful for separating the oxide from the metal to form oxide-encased bubbles or deposit thin oxide films (1-5 nm) on surfaces. Since oxides form on many metals, this work can have implications for a wide range of metals and metal oxides in addition to explaining the physical behavior of liquid metal. The native oxide of liquid metal (LM) lowers the interfacial energy from 700mN/m (bare metal) to similar to 10 mN/m due to the anisotropy of the oxide: metallophilic inward-facing, and hydrophilic outward-facing interfaces. This decrease helps explain the unusual interfacial behavior of LM, such as adhesion to surfaces and dewetting of the metal from the oxide, including from an oxide-encased air bubble. image