Are Contact Angle Measurements Useful for Oxide-Coated Liquid Metals?

This work establishes that static contact angles for gallium-based liquid metals have no utility despite the continued and common use of such angles in the literature. In the presence of oxygen, these metals rapidly form a thin (similar to 1-3 nm) surface oxide skin that adheres to many surfaces and mechanically impedes its flow. This property is problematic for contact angle measurements, which presume the ability of liquids to flow freely to adopt shapes that minimize the interfacial energy. We show here that advancing angles for a metal are always high (>140 degrees)-even on substrates to which it adheres-because the solid native oxide must rupture in tension to advance the contact line. The advancing angle for the metal depends subtly on the substrate surface chemistry but does not vary strongly with hydrophobicity of the substrate. During receding measurements, the metal droplet initially sags as the liquid withdraws from the sac formed by the skin and thus the contact area with the substrate initially increases despite its volumetric recession. The oxide pins at the perimeter of the deflated sac on all the surfaces are tested, except for certain rough surfaces. With additional withdrawal of the liquid metal, the pinned angle gets smaller until eventually the oxide sac collapses. Thus, static contact angles can be manipulated mechanically from 0 degrees to >140 degrees due to hysteresis and are therefore uninformative. We also provide recommendations and best practices for wetting experiments, which may find use in applications that use these alloys such as soft electronics, composites, and microfluidics.

Automated summary

This study shows that static contact angles for gallium-based liquid metals are not practical due to the formation of a surface oxide skin that affects the measurements. The contact angles exhibit hysteresis and are sensitive to the substrate surface chemistry, with the ability to be mechanically manipulated.