Transition in the Acid-Base Component of Surface Free Energy of Ice upon the Premelting of its Second Molecular Bilayer

Abstract

Molecular disordering of the ice surface occurs below the bulk melting temperature of 273 K, termed surface premelting. The top-most molecular layer begins gradually premelting at 200 K, and has been linked to its low coefficient of friction through an increase in molecular mobility. The second molecular bilayer premelts around 257 K, but no study has linked this transition to a change in any macroscopic phenomena. Here, we show that the thermodynamic work of adhesion between polydimethylsiloxane (PDMS) and ice changes abruptly at 257.0 $\pm$ 0.1 K. Surface-sensitive sum frequency generation spectroscopy shows that there are no molecular level changes at the PDMS surface or the ice-PDMS interface near the transition in adhesion, indicating that the transition arises from changes of the ice surface. Using existing contact angle data in the literature, we show that this transition is due to a decrease in the acid-base component of the surface free energy of ice by 17 $\pm$ 2 mJ/m$^2$ at 257.0 $\pm$ 0.1 K. The change in surface energy provides a possible explanation for a variety of unexplained phenomena seen across the literature including ice adhesion, friction, and the morphology of snowflakes.