Glass transition in hyperquenched water?

Kohl, Ingrid; Bachmann, L.; Mayer, Erwin; Hallbrucker, Andreas; Loerting, Thomas

doi:10.1038/nature03707

Cited by 73 publications

(98 citation statements)

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“…However, our study reveals that both HDL and LDL can be observed experimentally, and in terms of fragility, the transformation from HDL to LDL involves a dynamic crossover from a less strong to a very strong liquid. This finding settles a long-standing question in understanding water, in which LDL near 140 K was postulated to be "strong" (8,(52)(53)(54)(55), "not strong" (56), "not fragile" (9,11,57), or "the strongest liquid yet identified" (58). In fact, our temperature-dependent dielectric and heating-rate-dependent calorimetric data classify LDL as a "superstrong" liquid (59), which shows the lowest steepness index m 1 = 14 ± 1 of all liquids.…”

Section: Discussionmentioning

confidence: 83%

“…The occurrence of water's ambient pressure glass transition at T g,1 = 136 ± 2 K (4-6) has been discussed controversially for almost five decades mainly because its calorimetric signature is very feeble (7). Even though the question about the nature of this transition has not been settled ultimately, recent work interprets this signature to be consistent with a glass-toliquid transition and places deeply supercooled water into the category of "strong" liquids (8)(9)(10)(11). Lately, it has become clear that water's high-density phase exhibits a glass transition at pressures ≥0.1 GPa, which has also been interpreted in terms of a glass-to-liquid transition (12)(13)(14)(15).…”

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confidence: 99%

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Water’s second glass transition

Amann‐Winkel

Gainaru

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et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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The glassy states of water are of common interest as the majority of H 2 O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water's calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules. This "double T g scenario" is related to the coexistence of two liquid phases. The calorimetric signature of the second glass transition is much less feeble, with a heat capacity increase at T g,2 about five times as large as at T g,1 . By using broadband-dielectric spectroscopy we resolve loss peaks yielding relaxation times near 100 s at 126 K for low-density amorphous ice and at 110 K for high-density amorphous ice as signatures of these two distinct glass transitions. Temperature-dependent dielectric data and heating-rate-dependent calorimetric data allow us to construct the relaxation map for the two distinct phases of water and to extract fragility indices m = 14 for the low-density and m = 20-25 for the high-density liquid. Thus, low-density liquid is classified as the strongest of all liquids known ("superstrong"), and also high-density liquid is classified as a strong liquid.

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Section: Discussionmentioning

confidence: 83%

mentioning

confidence: 99%

Water’s second glass transition

Amann‐Winkel

Gainaru

Handle

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

270

301

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“…In these cases, crystallization interferes at a temperature about 14 K above T g and the C p increases in this range are ð1.9 AE 0.2Þ J mol −1 K −1 (2) and ð1.6 AE 0.2Þ J mol −1 K −1 (3) for the glassliquid transition of ASW and HGW, respectively. † (In a later study (17), a smaller value of 0.7 J mol −1 K −1 was reported for HGW.) Thus, the heat capacity rise for HDA is larger.…”

Section: Resultsmentioning

confidence: 99%

Glass–liquid transition of water at high pressure

Andersson

2011

Proc. Natl. Acad. Sci. U.S.A.

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The knowledge of the existence of liquid water under extreme conditions and its concomitant properties are important in many fields of science. Glassy water has previously been prepared by hyperquenching micron-sized droplets of liquid water and vapor deposition on a cold substrate (ASW), and its transformation to an ultraviscous liquid form has been reported on heating. A densified amorphous solid form of water, high-density amorphous ice (HDA), has also been made by collapsing the structure of ice at pressures above 1 GPa and temperatures below approximately 140 K, but a corresponding liquid phase has not been detected. Here we report results of heat capacity C p and thermal conductivity, in situ, measurements, which are consistent with a reversible transition from annealed HDA to ultraviscous high-density liquid water at 1 GPa and 140 K. On heating of HDA, the C p increases abruptly by ð3.4 AE 0.2Þ J mol −1 K −1 before crystallization starts at ð153 AE 1Þ K. This is larger than the C p rise at the glass to liquid transition of annealed ASW at 1 atm, which suggests the existence of liquid water under these extreme conditions. glass transition | pressure-induced amorphization | relaxation U nlike most liquids that vitrify by normal supercooling, water vitrifies only by hyperquenching of its micron-size droplets, and its porous amorphous state is made by vapor deposition (1-3). Pure bulk water densified by high pressure also does not vitrify on normal cooling; instead it freezes to proton-disordered high-density ices. However, in 1984 Mishima et al. (4) discovered a path to obtain a high-density amorphous ice (HDA) by pressurization of hexagonal ice, ice Ih, to approximately 1.5 GPa at 77 K. This amorphous form is characterized by the absence of Bragg peaks, but it is heterogeneous on a mesoscopic length scale (5). On heating at high pressures above approximately 0.5 GPa (6), it relaxes, homogenizes, and densifies before crystallization, and the ultimately densified form has been referred to as very highdensity amorphous ice (vHDA) (7). There are thus a multiplicity of amorphous states with densities in between HDA and vHDA, which are produced by isothermal pressurization of ice Ih at temperatures below approximately 140 K, and these are here generically referred to as HDA.States of water at extreme pressure and temperature conditions are important for, for example, understanding of tectonics in large bodies of the outer solar system where ice is one of the rock-forming minerals (8), and for water's phase diagram and properties (9), but it is not known whether HDA transforms to glassy and liquid states on heating. This work reports a unique high-pressure, in situ, heat capacity C p study of HDA just below its crystallization point where a glass to liquid transition may occur. It is here shown that HDA exhibits a glass transition with a heat capacity rise larger than that for amorphous solid water and hyperquenched water at 1 atm, which suggests a thermodynamic path between the annealed state of HDA and liquid wa...

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“…Water molecules have been reported to gain rotational freedom at the glass transition (Fisher & Devlin, 1995) and to exhibit translational diffusion just above, at 150 K (Smith & Kay, 1999). However, the existence of ultraviscous water in the temperature range between 136 and 150 K remains controversial (Kohl et al, 2005;Yue & Angell, 2004) and a direct transformation from the glassy to the crystalline state at 150-160 K has been proposed (Velikov et al, 2001). In any case, liquid bulk water cannot be studied experimentally at temperatures between 150 and 235 K, the so-called 'no man's land' (Mishima & Stanley, 1998).…”

Section: Temperature-dependent Behaviour Of Protein Crystalsmentioning

confidence: 99%

Temperature-dependent macromolecular X-ray crystallography

Weik

Colletier

2010

Acta Crystallogr D Biol Crystallogr

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X-ray crystallography provides structural details of biological macromolecules. Whereas routine data are collected close to 100 K in order to mitigate radiation damage, more exotic temperature-controlled experiments in a broader temperature range from 15 K to room temperature can provide both dynamical and structural insights. Here, the dynamical behaviour of crystalline macromolecules and their surrounding solvent as a function of cryo-temperature is reviewed. Experimental strategies of kinetic crystallography are discussed that have allowed the generation and trapping of macromolecular intermediate states by combining reaction initiation in the crystalline state with appropriate temperature profiles. A particular focus is on recruiting X-ray-induced changes for reaction initiation, thus unveiling useful aspects of radiation damage, which otherwise has to be minimized in macromolecular crystallography.

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Glass transition in hyperquenched water?

Cited by 73 publications

References 9 publications

Water’s second glass transition

Water’s second glass transition

Glass–liquid transition of water at high pressure

Temperature-dependent macromolecular X-ray crystallography

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