Dislocation mechanism for transformation between cubic ice Ic and hexagonal ice Ih

Abstract

Cubic ice Ic is metastable, yet can form by the freezing of supercooled water, vapour deposition at low temperatures and by depressurizing high-pressure forms of ice. Its structure differs from that of common hexagonal ice Ih in the order its molecular layers are stacked. This stacking order, however, typically has considerable disorder; that is, not purely cubic, but alternating in hexagonal and cubic layers. In time, stacking-disordered ice gradually decreases in cubicity (fraction having cubic structure), transforming to hexagonal ice. But, how does this disorder originate and how does it transform to hexagonal ice? Here we use numerical data on dislocations in hexagonal ice Ih to show that (1) stacking-disordered ice (or Ic) can be viewed as fine-grained polycrystalline ice with a high density of extended dislocations, each a widely extended stacking fault bounded by partial dislocations, and (2) the transformation from ice Ic to Ih is caused by the reaction and motion of these partial dislocations. Moreover, the stacking disorder may be in either a higher stored energy state consisting of a sub-boundary network arrangement of partial dislocations bounding stacking faults, or a lower stored energy state consisting of a grain structure with a high density of stacking faults, but without bounding partial dislocations. Each state transforms to Ih differently, with a duration to fully transform that strongly depends on temperature and crystal grain size. The results are consistent with the observed transformation rates, transformation temperatures and wide range in heat of transformation.