title: Ice-like water supports hydration forces and eases sliding friction.
abstract: The nature of interfacial water is critical in several natural processes, including the aggregation of lipids into the bilayer, protein folding, lubrication of synovial joints, and underwater gecko adhesion. The nanometer-thin water layer trapped between two surfaces has been identified to have properties that are very different from those of bulk water, but the molecular cause of such discrepancy is often undetermined. Using surface-sensitive sum frequency generation (SFG) spectroscopy, we discover a strongly coordinated water layer confined between two charged surfaces, formed by the adsorption of a cationic surfactant on the hydrophobic surfaces. By varying the adsorbed surfactant coverage and hence the surface charge density, we observe a progressively evolving water structure that minimizes the sliding friction only beyond the surfactant concentration needed for monolayer formation. At complete surfactant coverage, the strongly coordinated confined water results in hydration forces, sustains confinement and sliding pressures, and reduces dynamic friction. Observing SFG signals requires breakdown in centrosymmetry, and the SFG signal from two oppositely oriented surfactant monolayers cancels out due to symmetry. Surprisingly, we observe the SFG signal for the water confined between the two charged surfactant monolayers, suggesting that this interfacial water layer is noncentrosymmetric. The structure of molecules under confinement and its macroscopic manifestation on adhesion and friction have significance in many complicated interfacial processes prevalent in biology, chemistry, and engineering.
authors: Department of Polymer Science, University of Akron, Akron, OH 44325, USA.
authors: Nishad
authors: 0000-0003-0780-8718
authors: N
authors: Dhopatkar
authors: Department of Polymer Science, University of Akron, Akron, OH 44325, USA.
authors: Adrian P
authors: AP
authors: Defante
authors: Department of Polymer Science, University of Akron, Akron, OH 44325, USA.
authors: Ali
authors: A
authors: Dhinojwala
mesh_terms: D004738:Engineering; D057927:Hydrophobic and Hydrophilic Interactions; D007053:Ice / Q000032:analysis*; D055585:Physical Phenomena; D011312:Pressure; D013499:Surface Properties; D014867:Water / Q000737:chemistry*
chemical_list: D007053:Ice; D014867:Water
keywords: coordinated water; friction, surfactants; hydration forces; sum frequency generation