Autonomous Thermal-Oxidative Composition Inversion and Texture Tuning of Liquid Metal Surfaces

• Published in: ACS nano 2018-05, Vol.12 (5), p.4744-4753
• Main Authors: Cutinho, Joel, Chang, Boyce S, Oyola-Reynoso, Stephanie, Chen, Jiahao, Akhter, S. Sabrina, Tevis, Ian D, Bello, Nelson J, Martin, Andrew, Foster, Michelle C, Thuo, Martin M
• Format: Article
• Language: English
• ISSN: 1936-0851; 1936-086X
• DOI: 10.1021/acsnano.8b01438

Droplets capture an environment-dictated equilibrium state of a liquid material. Equilibrium, however, often necessitates nanoscale interface organization, especially with formation of a passivating layer. Herein, we demonstrate that this kinetics-driven organization may predispose a material to autonomous thermal-oxidative composition inversion (TOCI) and texture reconfiguration under felicitous choice of trigger. We exploit inherent structural complexity, differential reactivity, and metastability of the ultrathin (∼0.7–3 nm) passivating oxide layer on eutectic gallium–indium (EGaIn, 75.5% Ga, 24.5% In w/w) core–shell particles to illustrate this approach to surface engineering. Two tiers of texture can be produced after ca. 15 min of heating, with the first evolution showing crumpling, while the second is a particulate growth above the first uniform texture. The formation of tier 1 texture occurs primarily because of diffusion-driven oxide buildup, which, as expected, increases stiffness of the oxide layer. The surface of this tier is rich in Ga, akin to the ambient formed passivating oxide. Tier 2 occurs at higher temperature because of thermally triggered fracture of the now thick and stiff oxide shell. This process leads to inversion in composition of the surface oxide due to higher In content on the tier 2 features. At higher temperatures (≥800 °C), significant changes in composition lead to solidification of the remaining material. Volume change upon oxidation and solidification leads to a hollow structure with a textured surface and faceted core. Controlled thermal treatment of liquid EGaIn therefore leads to tunable surface roughness, composition inversion, increased stiffness in the oxide shell, or a porous solid structure. We infer that this tunability is due to the structure of the passivating oxide layer that is driven by differences in reactivity of Ga and In and requisite enrichment of the less reactive component at the metal–oxide interface.