Liquid metals (LMs) are immiscible in many common electrolytic
solutions and, when immersed in them, establish phase boundaries that
display intriguing interfacial characteristics. The application of
a cathodic potential to such interfaces may trigger phase separation
of solute elements out of the LMs. Here, we investigate this possibility
in two of the most researched and industrially used eutectic ternary
LMs of Galinstan (Ga-In-Sn) and Field’s metal (FM, In–Bi–Sn).
We observe that upon surface perturbation by an applied electric potential,
solute elements compete to segregate out of the LM alloys according
to their energy levels. The nature of the electrolytic solutions plays
a key role in the separation process as they dictate whether solute
metals are expelled selectively in their pure form or as binary compounds.
For example, in a phosphate-based aqueous electrolyte, nano-sized
Sn-based entities are selectively expelled from Galinstan, while only
Bi-based structures leave the surface of FM. In contrast, in a non-aqueous
electrolyte, nano-sized binary compounds of Sn–In and Bi–Sn
are separated from the surfaces of Galinstan and FM, respectively.
We show that selectivity in the surface separation process, achieved
by the alteration of the electrolytic solutions, is due to the interplay
between the electrodynamic interactions and the electrocapillary effect.
This study presents two key findings: (a) it is essential to carefully
consider the possibility of component separation in electrochemical
systems based on LMs and (b) it demonstrates interfacial metallurgical
pathways to process alloys for refining metals into specific purities,
component ratios, and dimensions.