Milling around glassy ice
Water ice has many crystalline phases, along with a few amorphous structures. The complex structural diagram is important to understand because of the widespread importance of ice. Rosu-Finsen et al. discovered a medium-density amorphous ice formed by ball milling hexagonal ice at low temperatures. The distinct density and structure helped to identify it as a new form of ice, opening up questions as to the stable amorphous structure of this important material. —BG
Abstract
Amorphous ices govern a range of cosmological processes and are potentially key materials for explaining the anomalies of liquid water. A substantial density gap between low-density and high-density amorphous ice with liquid water in the middle is a cornerstone of our current understanding of water. However, we show that ball milling “ordinary” ice Ih at low temperature gives a structurally distinct medium-density amorphous ice (MDA) within this density gap. These results raise the possibility that MDA is the true glassy state of liquid water or alternatively a heavily sheared crystalline state. Notably, the compression of MDA at low temperature leads to a sharp increase of its recrystallization enthalpy, highlighting that H2O can be a high-energy geophysical material.
Register and access this article for free
As a service to the community, this article is available for free.
Access the full article
View all access options to continue reading this article.
Supplementary Materials
This PDF file includes:
Other Supplementary Material for this manuscript includes the following:
- Download
- 79.94 MB
References and Notes
1
C. G. Salzmann, Advances in the experimental exploration of water’s phase diagram. J. Chem. Phys. 150, 060901 (2019).
2
M. Millot, F. Coppari, J. R. Rygg, A. Correa Barrios, S. Hamel, D. C. Swift, J. H. Eggert, Nanosecond X-ray diffraction of shock-compressed superionic water ice. Nature 569, 251–255 (2019).
3
R. Yamane, K. Komatsu, J. Gouchi, Y. Uwatoko, S. Machida, T. Hattori, H. Ito, H. Kagi, Experimental evidence for the existence of a second partially-ordered phase of ice VI. Nat. Commun. 12, 1129 (2021).
4
C. G. Salzmann, J. S. Loveday, A. Rosu-Finsen, C. L. Bull, Structure and nature of ice XIX. Nat. Commun. 12, 3162 (2021).
5
T. M. Gasser, A. V. Thoeny, A. D. Fortes, T. Loerting, Structural characterization of ice XIX as the second polymorph related to ice VI. Nat. Commun. 12, 1128 (2021).
6
V. B. Prakapenka, N. Holtgrewe, S. S. Lobanov, A. F. Goncharov, Structure and properties of two superionic ice phases. Nat. Phys. 17, 1233–1238 (2021).
7
T. Loerting, K. Winkel, M. Seidl, M. Bauer, C. Mitterdorfer, P. H. Handle, C. G. Salzmann, E. Mayer, J. L. Finney, D. T. Bowron, How many amorphous ices are there? Phys. Chem. Chem. Phys. 13, 8783–8794 (2011).
8
E. F. Burton, W. F. Oliver, The Crystal Structure of Ice at Low Temperatures. Proc. R. Soc. Lond. 153, 166–172 (1935).
9
O. Mishima, L. D. Calvert, E. Whalley, ‘Melting Ice’ I at 77 K and 10 kbar: A New Method of Making Amorphous Solids. Nature 310, 393–395 (1984).
10
O. Mishima, L. D. Calvert, E. Whalley, An Apparently First-order Transition Between Two Amorphous Phases of Ice Induced by Pressure. Nature 314, 76–78 (1985).
11
R. J. Nelmes, J. S. Loveday, T. Strässle, C. L. Bull, M. Guthrie, G. Hamel, S. Klotz, Annealed High-density Amorphous Ice Under Pressure. Nat. Phys. 2, 414–418 (2006).
12
T. Loerting, C. Salzmann, I. Kohl, E. Mayer, A. Hallbrucker, A Second Distinct Structural “State” of High-density Amorphous Ice at 77 K and 1 bar. Phys. Chem. Chem. Phys. 3, 5355–5357 (2001).
13
C. A. Tulk, C. J. Benmore, J. Urquidi, D. D. Klug, J. Neuefeind, B. Tomberli, P. A. Egelstaff, Structural studies of several distinct metastable forms of amorphous ice. Science 297, 1320–1323 (2002).
14
O. Mishima, Y. Suzuki, Propagation of the polyamorphic transition of ice and the liquid-liquid critical point. Nature 419, 599–603 (2002).
15
M. M. Koza, R. P. May, H. Schober, On the heterogeneous character of water’s amorphous polymorphism. J. Appl. Cryst. 40, s517–s521 (2007).
16
P. H. Poole, F. Sciortino, U. Essmann, H. E. Stanley, Phase Behavior of Metastable Water. Nature 360, 324–328 (1992).
17
O. Mishima, H. E. Stanley, Decompression-induced melting of ice IV and the liquid-liquid transition in water. Nature 392, 164–168 (1998).
18
J. S. Tse, D. D. Klug, C. A. Tulk, I. Swainson, E. C. Svensson, C.-K. Loong, V. Shpakov, V. R. Belosludov, R. V. Belosludov, Y. Kawazoe, The Mechanisms for Pressure-induced Amorphization of Ice Ih. Nature 400, 647–649 (1999).
19
H. Schober, M. M. Koza, A. Tölle, C. Masciovecchio, F. Sette, F. Fujara, Crystal-like high frequency phonons in the amorphous phases of solid water. Phys. Rev. Lett. 85, 4100–4103 (2000).
20
P. G. Debenedetti, Supercooled and glassy water. J. Phys. Condens. Matter 15, R1669–R1726 (2003).
21
B. Geil, M. M. Koza, F. Fujara, H. Schober, F. Natali, Absence of Fast Precursor Dynamics of Low-density Amorphous Ice around its Hypothetical Glass Transition Temperature. Phys. Chem. Chem. Phys. 6, 677–679 (2004).
22
D. T. Limmer, D. Chandler, Theory of amorphous ices. Proc. Natl. Acad. Sci. U.S.A. 111, 9413–9418 (2014).
23
J. J. Shephard, S. Ling, G. C. Sosso, A. Michaelides, B. Slater, C. G. Salzmann, Is High-Density Amorphous Ice Simply a “Derailed” State along the Ice I to Ice IV Pathway? J. Phys. Chem. Lett. 8, 1645–1650 (2017).
24
P. G. Debenedetti, F. Sciortino, G. H. Zerze, Second critical point in two realistic models of water. Science 369, 289–292 (2020).
25
C. A. Tulk, J. J. Molaison, A. R. Makhluf, C. E. Manning, D. D. Klug, Absence of amorphous forms when ice is compressed at low temperature. Nature 569, 542–545 (2019).
26
K. H. Kim, K. Amann-Winkel, N. Giovambattista, A. Späh, F. Perakis, H. Pathak, M. L. Parada, C. Yang, D. Mariedahl, T. Eklund, T. J. Lane, S. You, S. Jeong, M. Weston, J. H. Lee, I. Eom, M. Kim, J. Park, S. H. Chun, P. H. Poole, A. Nilsson, Experimental observation of the liquid-liquid transition in bulk supercooled water under pressure. Science 370, 978–982 (2020).
27
S. Kwok, Physics and Chemistry of the Interstellar Medium. (Univ. Science Books, 2007).
28
P. Baláž, M. Achimovičová, M. Baláž, P. Billik, Z. Cherkezova-Zheleva, J. M. Criado, F. Delogu, E. Dutková, E. Gaffet, F. J. Gotor, R. Kumar, I. Mitov, T. Rojac, M. Senna, A. Streletskii, K. Wieczorek-Ciurowa, Hallmarks of mechanochemistry: From nanoparticles to technology. Chem. Soc. Rev. 42, 7571–7637 (2013).
29
A. W. Weeber, H. Bakker, Amorphization by ball milling. A review. Physica B 153, 93–135 (1988).
30
M. Descamps, J. F. Willart, Perspectives on the amorphisation/milling relationship in pharmaceutical materials. Adv. Drug Deliv. Rev. 100, 51–66 (2016).
31
F. Delogu, G. Cocco, Weakness of the “hot spots” approach to the kinetics of mechanically induced phase transformations. J. Alloys Compd. 465, 540–546 (2008).
32
M. Descamps, J. F. Willart, E. Dudognon, V. Caron, Transformation of pharmaceutical compounds upon milling and comilling: The role of T(g). J. Pharm. Sci. 96, 1398–1407 (2007).
33
Materials and methods are available as supplementary materials.
34
T. L. Malkin, B. J. Murray, C. G. Salzmann, V. Molinero, S. J. Pickering, T. F. Whale, Stacking disorder in ice I. Phys. Chem. Chem. Phys. 17, 60–76 (2015).
35
F. Perakis, K. Amann-Winkel, F. Lehmkühler, M. Sprung, D. Mariedahl, J. A. Sellberg, H. Pathak, A. Späh, F. Cavalca, D. Schlesinger, A. Ricci, A. Jain, B. Massani, F. Aubree, C. J. Benmore, T. Loerting, G. Grübel, L. G. M. Pettersson, A. Nilsson, Diffusive dynamics during the high-to-low density transition in amorphous ice. Proc. Natl. Acad. Sci. U.S.A. 114, 8193–8198 (2017).
36
D. Mariedahl, F. Perakis, A. Späh, H. Pathak, K. H. Kim, C. Benmore, A. Nilsson, K. Amann-Winkel, X-ray studies of the transformation from high- to low-density amorphous water. Philos. Trans. R. Soc. A. 377, 20180164 (2019).
37
C. Mitterdorfer, M. Bauer, T. G. A. Youngs, D. T. Bowron, C. R. Hill, H. J. Fraser, J. L. Finney, T. Loerting, Small-angle neutron scattering study of micropore collapse in amorphous solid water. Phys. Chem. Chem. Phys. 16, 16013–16020 (2014).
38
J. L. F. Abascal, E. Sanz, R. García Fernández, C. Vega, A potential model for the study of ices and amorphous water: TIP4P/Ice. J. Chem. Phys. 122, 234511 (2005).
39
J. L. Finney, A. Hallbrucker, I. Kohl, A. K. Soper, D. T. Bowron, Structures of high and low density amorphous ice by neutron diffraction. Phys. Rev. Lett. 88, 225503 (2002).
40
N. Esmaeildoost, H. Pathak, A. Späh, T. J. Lane, K. H. Kim, C. Yang, K. Amann-Winkel, M. Ladd-Parada, F. Perakis, J. Koliyadu, A. R. Oggenfuss, P. J. M. Johnson, Y. Deng, S. Zerdane, R. Mankowsky, P. Beaud, H. T. Lemke, A. Nilsson, J. A. Sellberg, Anomalous temperature dependence of the experimental x-ray structure factor of supercooled water. J. Chem. Phys. 155, 214501 (2021).
41
O. Mishima, Reversible First-order Transition between Two H2O Amorphs at 0.2 GPa and 135 K. J. Chem. Phys. 100, 5910–5912 (1994).
42
H. Gleiter, Nanocrystalline materials. Prog. Mater. Sci. 33, 223–315 (1989).
43
A. Rosu-Finsen, M. Davies, A. Amon, H. Wu, A. Sella, A. Michaelides, C. Salzmann, Experimental data for research article “Medium-density amorphous ice”, Dryad (2023); https://doi.org/10.5061/dryad.7sqv9s4wk.
45
J. J. Shephard, B. Slater, P. Harvey, M. Hart, C. L. Bull, S. T. Bramwell, C. G. Salzmann, Doping-induced disappearance of ice II from water’s phase diagram. Nat. Phys. 14, 569–572 (2018).
46
A. B. Spierings, M. Schneider, R. Eggenberger, Comparison of density measurement techniques for additive manufactured metallic parts. Rapid Prototyping J. 17, 380–386 (2011).
47
K. Röttger, A. Endriss, J. Ihringer, S. Doyle, W. F. Kuhs, Lattice Constants and Thermal Expansion of H2O and D2O Ice Ih Between 10 and 265 K. Acta Crystallogr. B 50, 644–648 (1994).
48
B. Kamb, I. I. Ice, A Proton-Ordered Form of Ice. Acta Crystallogr. 17, 1437–1449 (1964).
49
E. Mayer, R. Pletzer, Astrophysical Implications of Amorphous Ice - a Microporous Solid. Nature 319, 298–301 (1986).
50
S. K. Talewar, S. O. Halukeerthi, R. Riedlaicher, J. J. Shephard, A. E. Clout, A. Rosu-Finsen, G. R. Williams, A. Langhoff, D. Johannsmann, C. G. Salzmann, Gaseous “nanoprobes” for detecting gas-trapping environments in macroscopic films of vapor-deposited amorphous ice. J. Chem. Phys. 151, 134505 (2019).
51
T. Loerting, K. Winkel, M. Seidl, M. Bauer, C. Mitterdorfer, P. H. Handle, C. G. Salzmann, E. Mayer, J. L. Finney, D. T. Bowron, How many amorphous ices are there?Phys. Chem. Chem. 13, 8783–8794 (2011).
52
A. Hallbrucker, E. Mayer, Calorimetric study of the vitrified liquid water to cubic ice phase transition. J. Phys. Chem. 91, 503–505 (1987).
53
O. Mishima, L. D. Calvert, E. Whalley, ‘Melting Ice’ I at 77 K and 10 kbar: A New Method of Making Amorphous Solids. Nature 310, 393–395 (1984).
54
T. Loerting, C. Salzmann, I. Kohl, E. Mayer, A. Hallbrucker, A Second Distinct Structural “State” of High-density Amorphous Ice at 77 K and 1 bar. Phys. Chem. Chem. 3, 5355–5357 (2001).
55
R. J. Nelmes, J. S. Loveday, T. Strässle, C. L. Bull, M. Guthrie, G. Hamel, S. Klotz, Annealed High-density Amorphous Ice Under Pressure. Nat. Phys. 2, 414–418 (2006).
56
T. L. Malkin, B. J. Murray, C. G. Salzmann, V. Molinero, S. J. Pickering, T. F. Whale, Stacking disorder in ice I. Phys. Chem. Chem. 17, 60–76 (2015).
57
C. G. Salzmann, B. J. Murray, J. J. Shephard, Extent of stacking disorder in diamond. Diamond Related Materials 59, 69–72 (2015).
58
J. L. F. Abascal, E. Sanz, R. García Fernández, C. Vega, A potential model for the study of ices and amorphous water: TIP4P/Ice. J. Chem. Phys. 122, 234511 (2005).
59
M. Matsumoto, T. Yagasaki, H. Tanaka, Novel Algorithm to Generate Hydrogen-Disordered Ice Structures. J. Chem. Inf. Model. 61, 2542–2546 (2021).
60
A. Hjorth Larsen, J. Jørgen Mortensen, J. Blomqvist, I. E. Castelli, R. Christensen, M. Dułak, J. Friis, M. N. Groves, B. Hammer, C. Hargus, E. D. Hermes, P. C. Jennings, P. Bjerre Jensen, J. Kermode, J. R. Kitchin, E. Leonhard Kolsbjerg, J. Kubal, K. Kaasbjerg, S. Lysgaard, J. Bergmann Maronsson, T. Maxson, T. Olsen, L. Pastewka, A. Peterson, C. Rostgaard, J. Schiøtz, O. Schütt, M. Strange, K. S. Thygesen, T. Vegge, L. Vilhelmsen, M. Walter, Z. Zeng, K. W. Jacobsen, The atomic simulation environment-a Python library for working with atoms. J. Phys. Condens. Matter 29, 273002 (2017).
61
S. Plimpton, Fast Parallel Algorithms for Short-Range Molecular Dynamics. J. Comput. Phys. 117, 1–19 (1995).
62
S. Le Roux, P. Jund, Ring statistics analysis of topological networks: New approach and application to amorphous GeS2 and SiO2 systems. Comput. Mater. Sci. 49, 70–83 (2010).
63
D. Mariedahl, F. Perakis, A. Späh, H. Pathak, K. H. Kim, C. Benmore, A. Nilsson, K. Amann-Winkel, X-ray studies of the transformation from high- to low-density amorphous water. Philos. Trans. R. Soc. A. 377, 20180164 (2019).
64
T. Li, D. Donadio, G. Russo, G. Galli, Homogeneous ice nucleation from supercooled water. Phys. Chem. Chem. 13, 19807–19813 (2011).
65
M. Bonomi, D. Branduardi, G. Bussi, C. Camilloni, D. Provasi, P. Raiteri, D. Donadio, F. Marinelli, F. Pietrucci, R. A. Broglia, M. Parrinello, PLUMED: A portable plugin for free-energy calculations with molecular dynamics. Comput. Phys. Commun. 180, 1961–1972 (2009).
66
G. A. Tribello, M. Bonomi, D. Branduardi, C. Camilloni, G. Bussi, PLUMED 2: New feathers for an old bird. Comput. Phys. Commun. 185, 604–613 (2014).
67
J. A. Sellberg, C. Huang, T. A. McQueen, N. D. Loh, H. Laksmono, D. Schlesinger, R. G. Sierra, D. Nordlund, C. Y. Hampton, D. Starodub, D. P. DePonte, M. Beye, C. Chen, A. V. Martin, A. Barty, K. T. Wikfeldt, T. M. Weiss, C. Caronna, J. Feldkamp, L. B. Skinner, M. M. Seibert, M. Messerschmidt, G. J. Williams, S. Boutet, L. G. M. Pettersson, M. J. Bogan, A. Nilsson, Ultrafast X-ray probing of water structure below the homogeneous ice nucleation temperature. Nature 510, 381–384 (2014).
68
H. Pathak, A. Späh, K. H. Kim, I. Tsironi, D. Mariedahl, M. Blanco, S. Huotari, V. Honkimäki, A. Nilsson, Intermediate range O-O correlations in supercooled water down to 235 K. J. Chem. Phys. 150, 224506 (2019).
69
C. Benmore, L. C. Gallington, E. Soignard, Intermediate range order in supercooled water. Mol. Phys. 117, 2470–2476 (2019).
70
N. Esmaeildoost, H. Pathak, A. Späh, T. J. Lane, K. H. Kim, C. Yang, K. Amann-Winkel, M. Ladd-Parada, F. Perakis, J. Koliyadu, A. R. Oggenfuss, P. J. M. Johnson, Y. Deng, S. Zerdane, R. Mankowsky, P. Beaud, H. T. Lemke, A. Nilsson, J. A. Sellberg, Anomalous temperature dependence of the experimental x-ray structure factor of supercooled water. J. Chem. Phys. 155, 214501 (2021).
71
C. R. Krüger, N. J. Mowry, G. Bongiovanni, M. Drabbels, U. J. Lorenz, Electron Diffraction of Water in No Man’s Land. arXiv:2211.04419 [physics.chem-ph] (2022).