Consequences of water between two hydrophobic surfaces on adhesion and wetting

The contact of two hydrophobic surfaces in water is of importance in biology, catalysis, material science, and geology. A tenet of hydrophobic attraction is the release of an ordered water layer, leading to a dry contact between two hydrophobic surfaces. Although the water-free contact has been inferred from numerous experimental and theoretical studies, this has not been directly measured. Here, we use surface sensitive sum frequency generation spectroscopy to directly probe the contact interface between hydrophobic poly(dimethylsiloxane) (PDMS) and two hydrophobic surfaces (a self-assembled monolayer, OTS, and a polymer coating, PVNODC). We show that the interfacial structures for OTS and PVNODC are identical in dry contact but that they differ dramatically in wet contact. In water, the PVNODC surface partially rearranges at grain boundaries, trapping water at the contact interface leading to a 50% reduction in adhesion energy compared to OTS-PDMS contact. The Young-Dupré equation, used extensively to calculate the thermodynamic work of adhesion, predicts no differences between the adhesion energy for these two hydrophobic surfaces, indicating a failure of this well-known equation when there is a heterogeneous contact. This study exemplifies the importance of interstitial water in controlling adhesion and wetting.