A new phase of solid superionic ice has been created for the first time in the laboratory. By heating a tiny sample of ultrapure water while compressing it to extreme pressures, physicists at the French Alternative Energies and Atomic Energy Commission (CEA) succeeded in forming an ice phase that features a hexagonal close-packed (hcp) structure and liquid-like hydrogen diffusing through a solid lattice of oxygen atoms. This demonstration could help us better understand the structure of ice giant planets such as Uranus and Neptune, which may harbour this form of ice deep within their interiors.
Unlike water’s familiar liquid, vapour and ice phases, superionic ice can only exist when water is subjected to tens or even hundreds of GPa of pressure at temperatures above 1000-2000 K. Under these conditions, theory predicts that hydrogen ions (protons) diffuse so readily through empty sites in water’s oxygen lattice that the material’s ionic conductivity may exceed 100 Siemens per centimetre, making it almost as conductive as metals. The melting temperature of this form of ice is also extremely high, reaching several thousand kelvin as new ice structures develop that feature a close-packed oxygen lattice.
Diamond anvil cells and X-ray diffraction spectra
To create super-high pressures in the laboratory, researchers typically use diamond anvil cells, which are tiny cavities in which samples are tightly compressed between the tips of two opposing diamond surfaces. In the new work, a CEA team led by physicists Alexis Forestier and Gunnar Weck added two high-thermal-conductivity cup-shaped discs made of boron-doped diamond to the diamond anvil surfaces. This set-up enabled them to apply pressure while heating their 12 micron-sized sample uniformly with lasers, thereby avoiding the large temperature gradients that complicate measurements in conventional diamond anvil cells.
Forestier, Weck and colleagues heated their sample of ultrapure water from 300 to 2630 K while applying pressures between 80 and 229 GPa. Thanks to the Extremely Brilliant Source’s sub-micron beam – part of the ID27 beamline at the European Synchrotron Research Facility in Grenoble – they were able to obtain high-quality X-ray diffraction spectra despite the small size of their sample. According to the CEA researchers, these spectra clearly showed a new hexagonal close-packed (hcp) phase of superionic ice emerging alongside a previously observed face-centred cubic (fcc) phase across a pressure range of 130-200 GPa and temperatures above 1800 K.
A link to Uranus and Neptune
The discovery brings the total number of superionic phases of water to three, with the other being the body-centred cubic phase first observed in 2016. But that’s not all. Forestier, Weck and colleagues say that their results, which they report in Physical Review Letters, could also help explain the magnetic fields of Uranus and Neptune.
Unlike the Earth’s magnetic field, these fields are skewed and off-centre with respect to the planets’ axis of rotation. These properties have led scientists to hypothesize that instead of being generated by the motion of molten iron in the planet’s core (as on Earth), the magnetic fields of Uranus and Neptune could arise from conductive superionic warm dense ice (composed of water, ammonia and methane) in the planets’ outer third.
“The experimental observation of this new hcp superionic phase now provides a rationale for incorporating its mechanical properties and ionic conductivity into these models of planetary interiors,” Forestier says. “Indeed, this phase can coexist with the fcc superionic phase and become more stable at higher pressures (above 150–200 GPa), and so probably exist deeper within the inner shell of these ice giants.”
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The researchers’ next step will be to precisely define regions of the phase diagram where pressure and temperature are stable; map out the transition lines between the different phases (molecular and superionic); and understand how the new hcp phase behaves as it melts. This will help confirm whether these phases are stable and present within Uranus and Neptune, Forestier tells Physics World.
“We also want to obtain more direct experimental signatures of superionic behaviour, beyond the thermal expansion we observed,” Weck adds. “Brillouin spectroscopy measurements, for example, could reveal anomalies in the speed of sound, strengthening the evidence for proton diffusion.”