Formation of Ordered Ice Nanotubes Inside Carbon Nanotubes

Abstract

Following their discovery, carbon nanotubes have attracted interest not only for their unusual electrical and me-chanical properties, but also because their hollow interior can serve as a nanometre-sized capillary, mould, or template in material fabrication. The ability to en¬capsulate a material in a nanotube also offers new possibili¬ties for investigating dimensionally confined phase transi¬tions . Particularly intriguing is the conjecture that matter within the narrow confines of a carbon nanotube might ex¬hibit a solid–liquid critical point beyond which the distinc¬tion between solid and liquid phases disappears. This unusual feature, which cannot occur in bulk material, would allow for the direct and continuous transformation of liquid matter into a solid. Here we report simulations of the behavior of water encapsulated in carbon nanotubes that suggest the existence of a variety of new ice phases not seen in bulk ice, and of a solid–liquid critical point. Using carbon nanotubes with diameters ranging from 1.1 nm to 1.4 nm and applied axial pressures of 50 MPa to 500 MPa, we find that water can exhibit a first-or¬der freezing transition to hexagonal and heptagonal ice nano¬tubes, and a continuous phase transformation into solid-like square or pentagonal ice nanotubes