Polyamorphism and the universal liquid–liquid critical point in the supercooled state

Abstract

The physics of critical phenomena is well established in systems as diverse as molecular fluids, crystalline alloys and magnetic materials. As the critical point is approached, the susceptibility increases anomalously and fluctuations give rise to dramatic opalescence. Evidence has recently emerged for the existence of a second critical point in the liquid state at supercooled temperatures, below which polyamorphic phases coexist differing in density but sharing the same composition. Whilst much attention has been paid to supercooled water, polyamorphic phases have been observed in many elemental and oxide liquids potentially offering routes to low-entropy glasses. Our recent direct observation of a polyamorphic phase transition in levitated molten yttria-alumina offers the first opportunity to study the associated critical point in a real supercooled system. In situ small-angle X-ray scattering records sharp rises in the average correlation length of density fluctuations and in the compressibility as the transition is approached. Both increases approximate to the universal power-law relations predicted by the three-dimensional Ising model in common with all critical point phenomena. The observation brings the second critical point predicted in liquids into line with other critical phenomena.

Bond orientational order in liquids: Towards a unified description of water-like anomalies, liquid-liquid transition, glass transition, and crystallization

“…As in the case of water, K T may also exhibit an anomalous increase, due to the increase in the number density of locally favoured structures, S, itself (not due to its fluctuations). Finally, it is worth noting that critical-like fluctuations and the steep increase in the susceptibility, which might be due to LLT, were recently reported for supercooled yttria-alumina melts [157,158,201,202].…”