Supercooled nano-droplets of water confined in hydrophobic rubber

Hydrophobic elastomers are capable of absorbing a small amount of water that forms droplets around hydrophilic sites. These systems allow the study of confinement effects by a hydrophobic environment on the dynamics and thermodynamic behaviour of water molecules. The freezing-melting properties and the dynamics of water inside nano-droplets in butyl rubber are affected, as revealed by differential scanning calorimetry (DSC) and deuterium nuclear magnetic resonance (²H-NMR). Upon cooling down, all water crystalizes with a bimodal droplet population (d_a = 3.4 nm and d_b = 4.4 nm) in a temperature range associated with the droplet size distribution. However, the melting temperature is not shifted according to the Gibbs-Thomson equation. The relative decrease of the ²H-NMR longitudinal magnetization is not a single exponential and, by inverse Laplace transformation, it was deduced to be bimodal in agreement with the DSC measurements (T_1,a ∼ 10 ms and T_1,b ∼ 200 ms). The deduced correlation time of molecular reorientation is longer than that of bulk water and the behaviour with temperature follows the Vogel-Fulcher-Tammann (VFT) equations with a changing fragility as the droplet size is reduced when reducing hydration.