Ice Nanotubes Research Articles

Phase Transition in Confined Water Inside Carbon Nanotubes

In materials confined within nanometer channels in single-walled carbon nanotube (SWNT) bundles, interesting properties which are not observed in bulk materials are expected. In the present paper, we report an X-ray diffraction (XRD) study on water adsorption in SWNT bundles. It was found that a substantial amount of water is absorbed inside SWNTs at room temperature (RT). The desorption-adsorption of water molecules occurred reversibly above RT. We found that the liquid-like water is transformed into a new solid form, i.e., ice nanotubes, at 235 K.

How does water freeze inside carbon nanotubes?

Phase behavior of quasi-one-dimensional water confined inside a carbon nanotube is studied in the thermodynamic space of temperature, pressure, and diameter of the cylindrical container. Four kinds of solid-like ordered structures—ice nanotubes—form spontaneously from liquid-like disordered phases at low temperatures. In the model system that comprises of TIP4P water molecules interacting with each other via short-range Lennard–Jones and long-range Coulomb site–site potentials under a periodic boundary condition in the axial direction, the phase change occurs either discontinuously or continuously depending on the path in the thermodynamic space. That the isotherms for a given diameter are found to be similar to those around the liquid–gas critical point of fluids suggests existence of a phase boundary terminated by a critical point. The apparently-complex phase behavior is accounted for by noting that the phase boundaries are layered surfaces in the three-dimensional thermodynamic space and some of the surfaces are terminated by critical lines.

Formation of ordered ice nanotubes inside carbon nanotubes.

Following their discovery, carbon nanotubes have attracted interest not only for their unusual electrical and mechanical properties, but also because their hollow interior can serve as a nanometre-sized capillary, mould or template in material fabrication. The ability to encapsulate a material in a nanotube also offers new possibilities for investigating dimensionally confined phase transitions. Particularly intriguing is the conjecture that matter within the narrow confines of a carbon nanotube might exhibit a solid-liquid critical point beyond which the distinction 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 behaviour 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-order freezing transition to hexagonal and heptagonal ice nanotubes, and a continuous phase transformation into solid-like square or pentagonal ice nanotubes.

Ice nanotube: What does the unit cell look like?

It is discovered that for an n-gonal ice nanotube built from stacking a single type of n-gonal rings of water, the unit cell consists of two stacked n-gonal rings. In one ring the O–H bonds of water molecules line up clockwise whereas in the other ring the O-H bonds line up counterclockwise. Among the n-gonal ice nanotubes examined, the pentagonal or hexagonal ice nanotube appears to be the most stable.