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水的多晶型转变以及压力下冰的非晶化

Water's polyamorphic transitions and amorphization of ice under pressure.

作者信息

Johari G P, Andersson Ove

机构信息

Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario L8S 4L7, Canada.

出版信息

J Chem Phys. 2004 Apr 1;120(13):6207-13. doi: 10.1063/1.1651063.

Abstract

Transformations of water's high density amorph (HDA) to low density amorph (LDA) and of LDA's to cubic ice (Ic) have been studied by in situ thermal conductivity kappa measurements at high pressures. The HDA to LDA transformation is unobservable at p of 0.07 GPa, indicating that, for a fixed heating rate, an increase in pressure increases the temperature of HDA to LDA transformation and decreases that of LDA to ice Ic, causing thereby the two transformations to merge, and HDA appears to convert directly to ice Ic. Thus either LDA forms but converts extremely rapidly to ice Ic, or LDA does not form. At a fixed p and T, in the range of pressure amorphization of hexagonal ice, kappa continues to decrease with time. Therefore, the amorphization of ice Ih is kinetically controlled. When HDA at 1 GPa was heated from 130 to 157 K and densified to very HDA, its kappa increased by 3%. Our findings and a scrutiny of earlier reports show that a reversible transition between HDA and LDA does not occur at approximately 135 K and approximately 0.2 GPa. Since there is no unique HDA, it is difficult to justify the conjecture for a second critical point for water.

摘要

通过在高压下原位测量热导率κ,研究了水的高密度非晶态(HDA)向低密度非晶态(LDA)的转变以及LDA向立方冰(Ic)的转变。在0.07 GPa的压力下,HDA向LDA的转变不可观测,这表明,对于固定的加热速率,压力增加会提高HDA向LDA转变的温度,降低LDA向冰Ic转变的温度,从而导致这两种转变合并,HDA似乎直接转变为冰Ic。因此,要么LDA形成但极其迅速地转变为冰Ic,要么LDA不形成。在固定的压力和温度下,在六方冰的压力非晶化范围内,κ随时间持续降低。因此,冰Ih的非晶化受动力学控制。当1 GPa下的HDA从130 K加热到157 K并致密化为非常高密度的HDA时,其κ增加了3%。我们的发现以及对早期报告的仔细审查表明,在大约135 K和大约0.2 GPa时,HDA和LDA之间不会发生可逆转变。由于不存在唯一的HDA,因此很难证明关于水的第二个临界点的猜想是合理的。

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