Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates that the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the "buckling failure" of the square-ice-nanotube columns, which is dominated by the lateral pressure.