Water’s second glass transition

Amann‐Winkel, Katrin; Gainaru, C.; Handle, Philip H.; Seidl, Markus; Nelson, Helge; Böhmer, Roland; Loerting, Thomas

doi:10.1073/pnas.1311718110

Cited by 265 publications

(349 citation statements)

References 58 publications

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“…This is consistent with, although not proof of, a liquid-like component arising from the LDA state. This is also consistent with previous reports that LDA ice undergoes a glass-to-liquid transition before transforming to a crystalline ice state (10,11,14). Similar crack healing and molecular rearrangements are observed during the HDA to LDA conversion.…”

Section: Discussionsupporting

confidence: 92%

“…The glass-to-liquid transition in these polyamorphic forms of ice is the focus of theories proposed to explain anomalous properties of supercooled water (4)(5)(6)(7)(8). Although supporting experimental evidence exists (9)(10)(11)(12)(13)(14)(15), it remains controversial as the direct observation of a glass-to-liquid transition has been stymied by rapid crystallization below the homogeneous nucleation temperature (∼235 K at 0.1 MPa).…”

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confidence: 99%

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Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

Kim

Täte

Grüner

2015

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

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Observation of theorized glass-to-liquid transitions between lowdensity amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-toliquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-toliquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water.glass-to-liquid transition | high-density amorphous ice | low-density amorphous ice | quenched HDA | first-order phase transition W ater has glassy states, including low-density amorphous (LDA) and high-density amorphous (HDA) ice (1-3). The glass-to-liquid transition in these polyamorphic forms of ice is the focus of theories proposed to explain anomalous properties of supercooled water (4-8). Although supporting experimental evidence exists (9-15), it remains controversial as the direct observation of a glass-to-liquid transition has been stymied by rapid crystallization below the homogeneous nucleation temperature (∼235 K at 0.1 MPa).In general, glasses are nonergodic, noncrystalline solids, in which atoms are fixed to their initial positions for macroscopically long periods of time (16). As is well known, when stress is applied, glasses can be cracked. Above the glass transition temperature, T g , the ergodic liquid is restored, and the stress-induced cracks in glasses can be healed by the diffusive motions of liquids. Indeed, it has been shown that the crack-healing process is reproducible and correlated with the glass transition temperatures, independent of liquid fragility (17, 18). ResultsBulk Water. In this study, crack healing is used to probe the molecular mobility in cryogenic transitions between glassy states of water or between glassy and crystalline states. Cracks do not heal for a sample held within any particular cryogenic solid state, indicating a low mobility in each of these states. Crack healing observed during phase transformations requires a high molecular mobility and is suggestive of an intermediate glass-to-liquid transition in the pathway between solid states. Fig. 1 shows the paths in a schematic phase diagram of water that were used to form and probe LDA and HDA ice. To facilitate vitrification of the bulk state of water, either NaK tartrate [sodium potassium tartrate, 0.9 M; mole fraction (moles salt/total moles) of 0.016 or hydration number R (moles H 2 O/moles salt) of 62] or NaCl (sodium chloride, 1.5 M; m...

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Section: Discussionsupporting

confidence: 92%

mentioning

confidence: 99%

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

Kim

Täte

Grüner

2015

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

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“…The confused state of debate is reminiscent of the notorious case of vitreous water, where hyperquenched glass studies also indicate high T g values [36][37][38], while work on glasses formed by other routes [39,40], or extrapolated from binary solutions [41,42], yield much lower values. In any case it appears that covalency of interaction, and the related average bond density, can no longer be the dominant consideration for GST glasses.…”

Section: Discussionmentioning

confidence: 99%

Glass Transitions, Semiconductor-Metal Transitions, and Fragilities in Ge−V−Te ( V=As , Sb) Liquid Alloys: The Difference One Element Can Make

Wei¹,

Coleman²,

Lucas³

et al. 2017

Phys. Rev. Applied

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Glass transition temperatures (T g ) and liquid fragilities are measured along a line of constant Ge content in the system Ge-As-Te, and contrasted with the lack of glass-forming ability in the twin system Ge-Sb-Te at the same Ge content. The one composition established as free of crystal contamination in the latter system shows a behavior opposite to that of more covalent system.Comparison of T g vs bond density in the three systems Ge-As-chalcogen differing in chalcogen i.e. S, Se, or Te, shows that as the chalcogen becomes more metallic, i.e. in the order S = 2.3.When the more metallic Sb replaces As at greater than 2.3, incipient metallicity rather than directional bond covalency apparently gains control of the physics. This leads us to an examination of the electronic conductivity and, then, semiconductor-to-metal (SC-M) transitions, with their associated thermodynamic manifestations, in relevant liquid alloys. The thermodynamic components, as seen previously, control liquid fragility and cause fragile-tostrong transitions during cooling. We tentatively conclude that liquid state behavior in phase change materials (PCMs) is controlled by liquid-liquid (SC-M) transitions that have become submerged below the liquidus surface. In the case of the Ge-Te binary, a crude extrapolation to GeTe stoichiometry indicates that the SC-M transition lies about 20% below the melting point, suggesting a parallel with the intensely researched "hidden liquid-liquid (LL) transition", in supercooled water. In the water case, superfast crystallization initiates in the high fragility domain some 4% above the T LL which is located at ~15% below the (ambient pressure) melting point.

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“…with aðT Þ = 8e 2 0 R 2 e 2 ðT Þϕ 2 ðT Þ σðTÞ > 0, [6] where R is the radius of the capillary, « is the relative dielectric permittivity of water, ϕ is the electric potential of the capillary surface, and σ is the electrical conductivity of the fluid. The viscosity deduced with usual Poiseuille flow formulas is thus overestimated.…”

Section: Methodsmentioning

confidence: 99%

“…10 7 K · s −1 (3). As a consequence, many questions about supercooled and glassy water and its glass-liquid transition remain open (4)(5)(6)(7).…”

mentioning

confidence: 99%

Viscosity of deeply supercooled water and its coupling to molecular diffusion

Dehaoui

Issenmann

Caupin

2015

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

195

220

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The viscosity of a liquid measures its resistance to flow, with consequences for hydraulic machinery, locomotion of microorganisms, and flow of blood in vessels and sap in trees. Viscosity increases dramatically upon cooling, until dynamical arrest when a glassy state is reached. Water is a notoriously poor glassformer, and the supercooled liquid crystallizes easily, making the measurement of its viscosity a challenging task. Here we report viscosity of water supercooled close to the limit of homogeneous crystallization. Our values contradict earlier data. A single power law reproduces the 50-fold variation of viscosity up to the boiling point. Our results allow us to test the Stokes-Einstein and Stokes-Einstein-Debye relations that link viscosity, a macroscopic property, to the molecular translational and rotational diffusion, respectively. In molecular glassformers or liquid metals, the violation of the Stokes-Einstein relation signals the onset of spatially heterogeneous dynamics and collective motions. Although the viscosity of water strongly decouples from translational motion, a scaling with rotational motion remains, similar to canonical glassformers.supercooled water | viscosity | Stokes-Einstein relations W ater, considered as a potential glassformer, has been a longlasting topic of intense activity. Its possible liquid-glass transition was reported 50 years ago to be in the vicinity of 140 K (1, 2). However, ice nucleation hinders the access to this transition from the liquid side. Bypassing crystallization requires hyperquenching the liquid at tremendous cooling rates, ca. 10 7 K · s −1 (3). As a consequence, many questions about supercooled and glassy water and its glass-liquid transition remain open (4-7).As an example, crystallization of water is accompanied by one of the largest known relative changes in sound velocity, which has been attributed to the relaxation effects of the hydrogen bond network (8, 9). Indeed, whereas the sound velocity is around 1,400 m · s −1 in liquid water at 273 K, it reaches around 3,300 m · s −1 in ice at 273 K and a similar value in the known amorphous phases of ice at 80 K (10). Such a large jump is usually the signature of a strong glass, i.e., one in which relaxation times or viscosity follow an Arrhenius law upon cooling. However, pioneering measurements on bulk supercooled water by NMR (11) and quasi-elastic neutron scattering (12), as well as recent ones by optical Kerr effect (8, 9), reveal a large super-Arrhenius behavior between 340 and 240 K, similar to what is observed in fragile glassformers (13,14). The temperature dependence of the relaxation time is well described by a power law (8, 9), as expected from mode-coupling theory (15, 16), which usually applies well to liquids with a small change of sound velocity upon vitrification. Based on these and other observations, it has been hypothesized that supercooled water experiences a fragile-tostrong transition (17). This idea has motivated experimental efforts to measure dynamic properties of supercooled wate...

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Water’s second glass transition

Cited by 265 publications

References 58 publications

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

Glass Transitions, Semiconductor-Metal Transitions, and Fragilities in Ge−V−Te ( V=As , Sb) Liquid Alloys: The Difference One Element Can Make

Viscosity of deeply supercooled water and its coupling to molecular diffusion

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