Clarifying the glass-transition behaviour of water by comparison with hyperquenched inorganic glasses

Abstract

The formation of glasses is normal for substances that remain liquid over a wide temperature range (the ‘good glassformers’) and can be induced for most liquids if cooling is fast enough to bypass crystallization. During reheating but still below the melting point, good glassformers exhibit glass transitions as they abruptly transform into supercooled liquids, whereas other substances transform directly from the glassy to the crystalline state. Whether water exhibits a glass transition before crystallization has been much debated over five decades1,2,3,4,5,6. For the last 20 years, the existence of a glass transition at 136 K (ref. 3) has been widely accepted2,3,4, but the transition exhibits qualities difficult to reconcile with our current knowledge of glass transitions2,5,6. Here we report detailed calorimetric characterizations of hyperquenched inorganic glasses that, when heated, do not crystallize before reaching their glass transition temperatures. We compare our results to the behaviour of glassy water and find that small endothermic effects, such as the one attributed to the glass transition of water, are only a ‘shadow’ of the real glass transition occurring at higher temperatures, thus substantiating the conclusion6 that the glass transition of water cannot be probed directly.

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Figure 1: DSC upscans of hyperquenched and annealed HQGs.
Figure 2: Comparison of DSC upscans of aged, hyperquenched mineral glass with the equivalent water DSC upscans for HQGW and ASW.
Figure 3: Effect of Ta on shadow glass transitions.

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Acknowledgements

We are grateful for the support of Rockwool International, Denmark, Department of Production, Aalborg University, Denmark (to Y.-Z.Y.) and for a Solid State Chemistry grant from the National Science Foundation (C.A.A.). We thank S.L. Jensen for help with samples.

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Correspondence to C. Austen Angell.

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Yue, Y., Angell, C. Clarifying the glass-transition behaviour of water by comparison with hyperquenched inorganic glasses. Nature 427, 717–720 (2004). https://doi.org/10.1038/nature02295

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