Prigogine-Defay ratio of glassy freezing scales with liquid fragility

Abstract

A detailed study of published experimental data for a variety of materials on the incremental variation of heat capacity, thermal expansion, and compressibility at glassy freezing reveals a striking dependence of the Prigogine-Defay ratio R on the fragility index m. At high m, R approaches values of ~1, the Ehrenfest expectation for 2nd order continuous phase transitions, while R reaches values > 20 for low fragilities. We explain this correlation by the degree of separation of the glassy freezing temperature from a hidden phase transition into an ideal low-temperature glass.

Manuscript 11 pages, 2 figures and Supplemental Material 6 pages, 1 figure, 1 table

References in corpus (11)

• Theoretical perspective on the glass transition and amorphous materials
• Glassy Aging Dynamics
• Thermal expansion and the glass transition
• Modern computational studies of the glass transition
• Temperature development of glassy alpha-relaxation dynamics determined by broadband dielectric spectroscopy
• Ionic conductivity of deep eutectic solvents: The role of orientational dynamics and glassy freezing
• Insights into glass formation and glass transition in supercooled liquids, by study of related phenomena in crystals
• Broadband dielectric spectroscopy on benzophenone: alpha relaxation, beta relaxation, and mode coupling theory
• Single-order-parameter description of glass-forming liquids: A one-frequency test
• Unified percolation scenario for the $\alpha$ and $\beta$ processes in simple glass formers
• Universal correlations between the fragility and interparticle repulsion of glass-forming liquids