Direct Measurement of Curvature-Dependent Surface Tension in a Capillary-Condensed Alcohol Nanomeniscus

TL;DR

This study directly measures how surface tension varies with curvature at the nanoscale in alcohol nanomenisci, revealing significant increases at high curvature and implications for nucleation processes.

Contribution

It provides the first direct experimental evidence of curvature-dependent surface tension at the nanometer scale using atomic force microscopy.

Findings

Surface tension doubles at a radius of ~ -0.46 nm for ethanol and n-propanol.

Larger negative curvature correlates with higher surface tension.

Facilitated nucleation observed at ~ 1 nm scale.

Abstract

Surface tension is a key parameter for understanding nucleation from the very initial stage of phase transformation. Although surface tension has been predicted to vary with the curvature of the liquid-vapor interface, particularly at the large curvature of, e.g., the subnanometric critical nucleus, experimental study still remains challenging due to inaccessibility to such a small cluster. Here, by directly measuring the critical size of a single capillary-condensed nanomeniscus using atomic force microscopy, we address the curvature dependence of surface tension of alcohols and observe the surface tension is doubled for ethanol and n-propanol with the radius-of-curvature of ~ -0.46 nm. We also find that the interface of larger negative (positive) curvature exhibits the larger (smaller) surface tension, which evidently governs nucleation at ~ 1 nm scale, indicating more facilitated nucleation than normally expected. Such well characterized curvature effects contribute to better understanding and accurate analysis of nucleation occurring in various fields including material science and atmospheric science.