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Volume measurements by displacement of a piston into the ice-containing vessel yield misleading information when performed over a long period, because: (i) contraction of the components of the high pressure assembly, when the assembly as a whole slowly cools, appears as a change in volume, and (ii) the indium metal used for isolating ice from the pressure vessel gradually creeps into the space between the piston and cylinder, and this too appears as a change in volume. Both occurrences falsify the results.
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Because of the thermal and pressure inertia of the large and massive high pressure assembly, its operation in vacuum, and its extremely slow depressurization and cooling, neither in situ diffraction measurements could be made on the samples, nor could the sample be recovered for ex situ measurements at ambient pressure.
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Transformation of ice Ih to a high pressure crystalline ice or a mixture of crystalline ices at this pressure has usually not been observed (Refs. 1-7, 14-16, and 19). But when such a crystallization has been observed it has occurred implosively with a sudden decrease in pressure and increase in κ (Refs. 17 and 20). This did not occur here.
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The pressure was auto-restored in our experiments. This means that a decrease in volume on amorphization of ice Ih at a pressure p decreased its value to p′ and the amorphization stopped. When the pressure was restored to p, more ice Ih amorphized, and the pressure again decreased to p′, and so on. This is expected to continue until all ice Ih is amorphized, as occurs on thermodynamic melting and a first-order phase transformation. But here amorphization remained incomplete, and κ decreased with t even when the sample was kept subsequently at a higher p. Also, amorphization at a fixed p and T is not to be seen in the same manner as a phase transformation at ambient pressure, because the volume, κ and p all decrease in our experiment at GPa pressure, but p does not decrease during phase transformation at ambient pressure.
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In one dilatometric study on a 1-1.5 mm thick sample of ice Ih at 77 K amorphization of ice Ih to "HDA" has been found to occur first slowly and then abruptly, reaching completion at ∼1.06 GPa (Ref. 14). But we now know that when the sample is kept at a fixed pressure far above the onset pressure for a short period, the plot of the piston displacement against pressure in the amorphization range of both ice Ih and cubic ice would be vertical, suggesting a relatively abrupt decrease. A recent study has, for example, shown such a vertical decrease in Fig. 1 in Ref. 16, where κ of the sample kept for 1 h or more makes amorphization appear as if it is occurring abruptly. It is worth noting that the rate of pressurization in the earlier study (Ref. 14) had not been controlled, and that an unknown period of time was allowed between pressure-increase steps which leads to this behavior. This is also apparent in the plot for ice Ih at 115 K in Fig. 1.
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