Direct imaging of a first-order liquid-liquid phase transition in undercooled molten Pd[sbnd]Ni[sbnd]P alloys and its thermodynamic implications

Abstract

Polyamorphic transition is the transition between two amorphous states or two liquid states (LLT) at a fixed composition of a substance. Experience in LLT is limited. Besides, its nature remains largely unknown as it occurs under the experimental conditions of high pressure/temperature (P/T) or high undercooling. In this study, we found that some undercooled PdNiP melts undergo a LLT. Contrary to all earlier studies, PdNiP specimens that contain the structural changes that occur at different stages of the LLT can be prepared for electron microscopy. HRTEM (high resolution transmission electron microscope) establishes that it is a first-order phase transition. From thermodynamics, a first-order phase change is accompanied by a latent heat. Here it was measured by a DSC (differential scanning calorimeter). A first-order LLT has important thermodynamic implications. First, it reconfirms that a liquid has different kinds of short-range-orders (SROs). Second, the first-order LLT implies that the SROs of a liquid are divided into distinct groups, each containing either a SRO or a number of different SROs, but not all. Physically, each group represents a real liquid. Third, the SRO(s) in a group can be assigned an independent Gibbs free energy, GSRO(P, T, c=composition) and the thermodynamics of the liquids can be described in terms of these GSRO.