Tunable shape transformation of freezing liquid water marbles.

Liquid water marbles coated with fumed silica nanoparticles exhibit various shape transformations upon freezing which are dependent on the hydrophobicity of the nanoparticles. The shape can be recovered during re-melting. For marbles coated with the most hydrophobic particles, a vertically prolonged morphology with a pointed protrusion on the top is formed on freezing. For marbles coated with less hydrophobic particles, a lateral expanded flying saucer-shaped morphology is formed. The different responses to freezing result from the different heterogeneous nucleation sites owing to the different positions of the particles at the air-water interface. If the particles are more immersed in water, ice embryos tend to form in the concave cavities between the particles. The volume expansion of water caused by freezing and continuous nucleation lead to continuous lateral stretching of the particle network coating the droplet surface and ultimately to the horizontally inflated shape of the marble. If the particles are more exposed to air, nucleation occurs on the convex surface of the particles, similar to that of a bare water droplet on a hydrophobic substrate.