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低热密非晶冰的量热玻璃-液体转变的可逆性和同位素效应。

Reversibility and isotope effect of the calorimetric glass --> liquid transition of low-density amorphous ice.

机构信息

Institute of Physical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria.

出版信息

Phys Chem Chem Phys. 2010 Jan 21;12(3):708-12. doi: 10.1039/b917662d. Epub 2009 Nov 20.

DOI:10.1039/b917662d
PMID:20066356
Abstract

We here report differential scanning calorimetry (DSC) scans recorded by repeatedly heating the H(2)O (D(2)O) low density amorph (LDA) which was made by isothermal decompression of very high-density amorphous ice (VHDA) at 140 K from 1.1 to 0.006 GPa. These DSC scans show a glass --> liquid transition endotherm with an onset temperature (T(g)) of approximately 137 (140) K at a heating rate of 30 K min(-1) accompanied by an increase in heat capacity of approximately 1.7 (1.5) J K(-1) mol(-1). We establish the reversibility of this effect by thermally cycling between its glassy state below 137 K and its highly viscous liquid state at 149 K. All calorimetric signatures, including H/D isotope effect, are highly similar to the signatures in hyperquenched glassy water (HGW). We argue that the observation of almost identical calorimetric traces for HGW and LDA implies that there is no need to reassign HGWs T(g) to higher temperatures provided that the viscous liquid state connected to both LDA and HGW behaves as an ideally "strong" liquid in the Angell classification. We furthermore show that LDA prepared by isothermal decompression of VHDA is more crystallization-resistant than LDA made from high-density amorphous ice (HDA) by isobaric warming. We suggest that the former route via VHDA removes "nanocrystalline remnants" in LDA which are still present in the latter after pressure-amorphization of hexagonal ice to HDA at 77 K.

摘要

我们在这里报告了通过反复加热在 140 K 下从 1.1 到 0.006 GPa 对非常高密度非晶冰 (VHDA) 进行等静压分解而制得的 H(2)O(D(2)O)低密度非晶 (LDA) 记录的差示扫描量热法 (DSC) 扫描。这些 DSC 扫描显示出玻璃到液体的转变吸热峰,在 30 K min(-1) 的加热速率下,起始温度 (T(g)) 约为 137(140) K,比热增加约 1.7(1.5) J K(-1) mol(-1)。我们通过在 137 K 以下的玻璃态和 149 K 下的高粘性液态之间进行热循环来证明这种效应的可逆性。所有的量热学特征,包括 H/D 同位素效应,都与超快速冷却玻璃态水 (HGW) 非常相似。我们认为,对于 HGW 和 LDA,观察到几乎相同的量热痕迹表明,只要与 LDA 和 HGW 相连的粘性液态表现为 Angell 分类中的理想“强”液体,就没有必要将 HGW 的 T(g)重新分配到更高的温度。此外,我们还表明,通过 VHDA 等静压分解制备的 LDA 比通过等压升温从高密度非晶冰 (HDA) 制备的 LDA 更具抗结晶性。我们认为,前者通过 VHDA 去除了 LDA 中仍存在的“纳米晶残余物”,而后者在六角形冰在 77 K 加压非晶化为 HDA 后仍存在。

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