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Cubic ice Ic without stacking defects obtained from ice XVII

Nature Materials volume 19, pages 663–668 (2020)Cite this article

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Abstract

Amongst the more than 18 different forms of water ice, only the common hexagonal phase and the cubic phase are present in nature on Earth. Nonetheless, it is now widely recognized that all samples of ‘cubic ice’ discovered so far do not have a fully cubic crystal structure but instead are stacking-disordered forms of ice I (namely, ice Isd), which contain both hexagonal and cubic stacking sequences of hydrogen-bonded water molecules. Here, we describe a method to obtain large quantities of cubic ice Ic with high structural purity. Cubic ice Ic is formed by heating a powder of D2O ice XVII obtained from annealing of pristine C0 hydrate samples under dynamic vacuum. Neutron diffraction experiments performed on two different instruments and Raman spectroscopy measurements confirm the structural purity of the cubic ice, Ic. These findings contribute to a better understanding of ice I polymorphism and the existence of the two natural ice forms.

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Fig. 1: Pictorial representation of the atomic positions of ice Isd.
Fig. 2: Diffraction studies report cubic ice formation.
Fig. 3: Density of ice XVII and ice Ic as a function of temperature.
Fig. 4: Transformation of ice Ic into ice Ih.
Fig. 5: Raman characterization of the transition from ice XVII to ice Ic.

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Data availability

The neutron diffraction data that support the findings of this study are available at the DOIs reported in refs. 46,49,50. All other data are available within the article and its supplementary files and from the corresponding authors on reasonable request.

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Acknowledgements

Neutron beam time at ISIS and ILL is gratefully acknowledged, on the basis of the agreement of the CNR (Italy) with STFC (UK) and ILL (France) concerning collaboration in scientific research. L.U. and M.Celli acknowledge the PRIN project ZAPPING, no. 2015HK93L7, granted by the Italian Ministero dell’Istruzione, dell’Università e della Ricerca supporting their research in high-pressure materials science. L.U., M.Celli and L.d.R. acknowledge support from the Fondazione Cassa di Risparmio di Firenze under the contract ICEXVII. ISIS Pressure and Furnaces section and the Electronics section were vital for setting up with gas-handling system and in-situ sample heating for the HRPD experiment. Technical support by A. Donati (IFAC-CNR) for setting up of the high-pressure autoclave for the synthesis of the samples is gratefully acknowledged.

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Authors and Affiliations

  1. Consiglio Nazionale delle Ricerche, Istituto di Fisica Applicata ‘Nello Carrara’, Sesto Fiorentino, Italy

    Leonardo del Rosso, Milva Celli, Francesco Grazzi & Lorenzo Ulivi

  2. Dipartimento di Scienza dei Materiali, Università di Milano Bicocca, Milano, Italy

    Michele Catti

  3. Institut Laue-Langevin (ILL), Grenoble, France

    Thomas C. Hansen

  4. ISIS Neutron and Muon Facility, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Chilton, UK

    A. Dominic Fortes

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  1. Leonardo del Rosso
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Contributions

This work is the result of a common effort to which all authors contributed. In particular, L.d.R. and M.Celli synthesized the samples. M.Celli, L.d.R. and L.U. carried out the Raman experiment. M.Catti, L.d.R., L.U. and T.C.H. carried out the experiment at ILL. L.d.R., F.G. and A.D.F. carried out the experiment at ISIS, RAL. M.Celli and L.U. performed the Raman data analysis. M.Catti, L.d.R., F.G. and A.D.F. performed the diffraction data analysis. L.U., L.d.R. and M.Celli wrote the manuscript. All the authors read and corrected the manuscript.

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Correspondence to Leonardo del Rosso or Lorenzo Ulivi.

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del Rosso, L., Celli, M., Grazzi, F. et al. Cubic ice Ic without stacking defects obtained from ice XVII. Nat. Mater. 19, 663–668 (2020). https://doi.org/10.1038/s41563-020-0606-y

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