Bergman R, Swenson J
Department of Experimental Physics, Chalmers University of Technology, Goteborg, Sweden.
Nature. 2000 Jan 20;403(6767):283-6. doi: 10.1038/35002027.
As with most liquids, it is possible to supercool water; this generally involves cooling the liquid below its melting temperature (avoiding crystallization) until it eventually forms a glass. The viscosity and related relaxation times (tau) of glass-forming liquids typically show non-Arrhenius temperature (T) dependencies. Liquids with highly non-Arrhenius behaviour in the supercooled region are termed 'fragile'. In contrast, liquids whose behaviour is close to the Arrhenius law (In tau infinity 1/T) are termed 'strong'. A unique 'fragile-strong' transition around 228 K has been proposed for supercooled water; however, experimental studies of bulk supercooled water in this temperature range are generally hampered because crystallization occurs. Here we use broad-band dielectric spectroscopy to study the relaxation dynamics of supercooled water in a wide temperature range, including the usually inaccessible temperature region. This is possible because the supercooled water is held within a layered vermiculite clay-the geometrical confinement and presence of intercalated sodium ions prevent most of the water from crystallizing. We find a relaxational process with an Arrhenius temperature dependence, consistent with the proposed strong nature of deeply supercooled bulk water. Because water that is less supercooled has been established as highly fragile, our results support the existence of a fragile-strong transition.
与大多数液体一样,水也可能被过冷;这通常涉及将液体冷却到其熔点以下(避免结晶),直到它最终形成玻璃态。形成玻璃的液体的粘度和相关弛豫时间(τ)通常表现出非阿伦尼乌斯温度(T)依赖性。在过冷区域具有高度非阿伦尼乌斯行为的液体被称为“易碎的”。相比之下,行为接近阿伦尼乌斯定律(lnτ∝1/T)的液体被称为“强的”。有人提出过冷水在228 K左右存在独特的“易碎-强”转变;然而,在这个温度范围内对大量过冷水的实验研究通常受到阻碍,因为会发生结晶。在这里,我们使用宽带介电谱来研究过冷水在很宽温度范围内的弛豫动力学,包括通常无法达到的温度区域。这是可行的,因为过冷水被保存在层状蛭石粘土中——几何限制和嵌入的钠离子的存在阻止了大部分水结晶。我们发现了一个具有阿伦尼乌斯温度依赖性的弛豫过程,这与所提出的深度过冷的大量水的强性质一致。由于欠过冷的水已被确定为高度易碎,我们的结果支持了易碎-强转变的存在。