Amorphous ice

Amorphous ice

Amorphous ice is an amorphous solid form of water, meaning it consists of water molecules that are randomly arranged like the atoms of common glass. Everyday ice is a polycrystalline material. Amorphous ice is distinguished by its lack of long-range order. Amorphous ice is produced by cooling liquid water very quickly (around 1,000,000 K/s), so the molecules don't have enough time to form a crystal lattice.

Just as there are many different crystalline forms of ice (currently fifteen known), there are also different forms of amorphous ice, distinguished principally by their densities.

Formation techniques

The key to producing amorphous ice is the rate of cooling. The liquid water must be cooled to its glass transition temperature (about 136 K or -137 deg C) in a matter of milliseconds to prevent the spontaneous nucleation of crystals. This is analogous to the production of ice cream, which must also be frozen quickly to prevent the growth of crystals in the mixture. The difference is that pure water forms crystals much more readily than the heterogeneous mixture of ingredients in ice cream, so amorphous water is more difficult to produce, requiring a physics lab rather than an ice cream churn.

Pressure is another important factor in the formation of amorphous ice, and changes in pressure may cause one form to convert into another.

Chemicals known as cryoprotectants can be added to water, to lower its freezing point (like an antifreeze) and increase viscosity, which inhibits formation of crystals. Vitrification without addition of cryoprotectants can be achieved by very rapid cooling. These techniques are used in biology for cryopreservation of cells and tissues.


Low-density amorphous ice

Low-density amorphous ice, also called LDA, vapor-deposited amorphous water ice, amorphous solid water (ASW) or hyperquenched glassy water (HGW), is usually formed in the laboratory by a slow accumulation of water vapor molecules (physical vapor deposition) onto a very smooth metal crystal surface under 120 K. In outer space it is expected to be formed in a similar manner on a variety of cold substrates, such as dust particles. It is expected to be common in the subsurface of exterior planets and comets. [ [ Estimation of water-glass transition temperature based on hyperquenched glassy water experiments] from Science (requires registration).]

Melting past its glass transition temperature (Tg) between 120 and 140 K, LDA is more viscous than normal water. Recent studies have shown the viscous liquid stays in this alternative form of liquid water up to somewhere between 140 and 210 K, a temperature range that is also inhabited by ice Ic [ [ Liquid water in the domain of cubic crystalline ice Ic] from AIP.] . LDA has a density of 0.94 g/cm³, less dense than the densest water (1.00 g/cm³ at 277 K), but denser than ordinary ice (ice Ih).

Hyperquenched glassy water (HGW) is formed by spraying a fine mist of water droplets into a liquid such as propane around 80 K or by hyperquenching fine micrometer-sized droplets on a sample-holder kept at liquid nitrogen temperature , 77K, in a vacuum. Cooling rates above 104 K/sec are required to prevent crystallization of the droplets. At liquid nitrogen temperature, 77K, HGW is kinetically stable and can be stored for many years.

High-density amorphous ice

High-density amorphous ice (HDA) can be formed by compressing ice Ih at temperatures below ~140K. At 77 K, HDA forms from ordinary natural ice at around 1.6 GPa [O. Mishima and LD Calvert, and E. Whalley, Nature 310, 393 (1984)] and from LDA at around 0.5 GPa [O. Mishima, LD Calvert, and E. Whalley, Nature 314, 76 (1985).] (approximately 5,000 atm). At 77 K it can be recovered back to ambient pressure and kept indefinitely. At ambient pressure HDA has a density of 1.17 g/cm³ [O. Mishima and LD Calvert, and E. Whalley, Nature 310, 393 (1984)] .

Very-high-density amorphous ice

Very-high-density amorphous ice (VHDA), was discovered in 1996 by Mishima who observed that HDA became denser if warmed to 160 K at pressures between 1 and 2 GPa and has a density of 1.26 g/cm³ at ambient pressure [ O.Mishima, Nature, 384, 6069 pp 546-549 (1996). ] . More recently, workers at the University of Innsbruck have suggested that this denser amorphous ice was a third amorphous form of water, distinct from HDA, and called it VHDA [Loerting, T., Salzmann, C., Kohl, I., Mayer, E., Hallbrucker, A., A 2nd distinct structural state of HDA at 77 K and 1 bar, PhysChemChemPhys 3:5355-5357. (2001).]


Amorphous ice is used in some scientific experiments, especially in electron cryomicroscopy of biomolecules. [Dubochet, J., M. Adrian, J. J. Chang, J. C. Homo, J. Lepault, A. W. McDowell, and P. Schultz. Cryo-electron microscopy of vitrified specimens. Q. Rev. Biophys. 21:129-228. (1988).] The individual molecules can be preserved for imaging in a state close to what they are in liquid water.


External links

* [ Discussion of amorphous ice] at LSBU's website.
* [ Journal of Physics article]
* [ Glass transition in hyperquenched water] from Nature (requires registration)
* [ Glassy Water] from Science, on phase diagrams of water (requires registration)
* [ AIP accounting discovery of VHDA]
* [ HDA in space]
* [ Computerized illustrations of molecular structure of HDA]
* [ Structure of amorphous ice]

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