Yue Yuanzheng, Angell C Austen
Section of Chemistry, Department of Life Sciences, Aalborg University, DK-9000 Aalborg, Denmark.
Nature. 2004 Feb 19;427(6976):717-20. doi: 10.1038/nature02295.
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 decades. For the last 20 years, the existence of a glass transition at 136 K (ref. 3) has been widely accepted, but the transition exhibits qualities difficult to reconcile with our current knowledge of glass transitions. 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 conclusion that the glass transition of water cannot be probed directly.
对于那些在很宽温度范围内都能保持液态的物质(“良好玻璃形成体”)来说,形成玻璃是正常现象;如果冷却速度足够快,能够绕过结晶过程,那么大多数液体都可以被诱导形成玻璃。在重新加热但仍低于熔点的过程中,良好玻璃形成体在突然转变为过冷液体时会表现出玻璃化转变,而其他物质则直接从玻璃态转变为晶态。水在结晶之前是否会出现玻璃化转变,在过去五十多年里一直备受争议。在过去20年中,136K时存在玻璃化转变(参考文献3)这一观点已被广泛接受,但该转变所表现出的特性难以与我们目前对玻璃化转变的认识相协调。在此,我们报告了对超淬火无机玻璃的详细量热表征,这些玻璃在加热时,在达到其玻璃化转变温度之前不会结晶。我们将我们的结果与玻璃态水的行为进行比较,发现诸如归因于水的玻璃化转变的小吸热效应,只是在较高温度下发生的真正玻璃化转变的一个“影子”,从而证实了水的玻璃化转变无法直接探测的结论。