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最佳面朝前:冰水界面处的晶面竞争

Best face forward: crystal-face competition at the ice-water interface.

作者信息

Shultz Mary Jane, Bisson Patrick J, Brumberg Alexandra

机构信息

Laboratory for Water and Surface Studies, Tufts University , 62 Talbot Avenue, Medford, Massachusetts 02155, United States.

出版信息

J Phys Chem B. 2014 Jul 17;118(28):7972-80. doi: 10.1021/jp500956w. Epub 2014 May 13.

Abstract

The ice-water interface plays an important role in determining the outcome of both biological and environmental processes. Under ambient pressure, the most stable form of ice is hexagonal ice (Ih). Experimentally probing the surface free energy between each of the major faces of Ih ice and the liquid is both experimentally and theoretically challenging. The basis for the challenge is the near-equality of the surface free energy for the major faces along with the tendency of water to supercool. As a result, morphology from crystallization initiated below 0 °C is kinetically controlled. The reported work circumvents supercooling consequences by providing a polycrystalline seed, followed by isothermal, equilibrium growth. Natural selection among seeded faces results in a single crystal. A record of the growth front is preserved in the frozen boule. Crystal orientation at the front is revealed by examining the boule cross section with two techniques: (1) viewing between crossed polarizers to locate the optical axis and (2) etching to distinguish the primary-prism face from the secondary-prism face. Results suggest that the most stable ice-water interface at 0 °C is the secondary-prism face, followed by the primary-prism face. The basal face that imparts the characteristic hexagonal shape to snowflakes is a distant third. The results contrast with those from freezing the vapor where the basal and primary-prism faces have comparable free energy followed by the secondary-prism face.

摘要

冰水界面在决定生物和环境过程的结果方面起着重要作用。在常压下,冰最稳定的形式是六方冰(Ih)。通过实验探究Ih冰各主要晶面与液体之间的表面自由能,在实验和理论上都具有挑战性。造成这种挑战的原因是主要晶面的表面自由能近乎相等,以及水容易过冷的倾向。因此,在0°C以下开始结晶形成的形态是由动力学控制的。所报道的工作通过提供多晶籽晶,然后进行等温平衡生长,规避了过冷的影响。籽晶晶面之间的自然选择会形成单晶。生长前沿的记录保存在冷冻的晶锭中。通过两种技术检查晶锭横截面来揭示前沿的晶体取向:(1)在正交偏振器之间观察以确定光轴;(2)蚀刻以区分主棱柱面和次棱柱面。结果表明,0°C时最稳定的冰水界面是次棱柱面,其次是主棱柱面。赋予雪花特征六边形形状的基面则远排在第三位。这些结果与通过冷冻蒸汽得到的结果形成对比,在冷冻蒸汽的情况下,基面和主棱柱面具有相当的自由能,其次是次棱柱面。

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