Bulk and interfacial glass transitions of water

Fast scanning calorimetry (FSC) was employed to investigate glass softening dynamics in bulk-like and ultrathin glassy water films. Bulk-like water samples were prepared by vapor-deposition on the surface of a tungsten filament near 140 K where vapor-deposition results in low enthalpy glassy water films. The vapor-deposition approach was also used to grow multiple nanoscale (approximately 50 nm thick) water films alternated with benzene and methanoic films of similar dimensions. When heated from cryogenic temperatures, the ultrathin water films underwent a well manifested glass softening transition at temperatures 20 K below the onset of crystallization. However, no such transition was observed in bulk-like samples prior to their crystallization. These results indicate that thin-film water demonstrates glass softening dynamics that are dramatically distinct from those of the bulk phase. We attribute these differences to water's interfacial glass transition, which occurs at temperatures tens of degrees lower than that in the bulk. Implications of these findings for past studies of glass softening dynamics in various glassy water samples are discussed.