First-order transitions in glasses and melts induced by solid superclusters nucleated and melted by homogeneous nucleation instead of surface melting

• Published in: Chemical physics 2019-08, Vol.524, p.40-54
• Main Author: Tournier, Robert F.
• Format: Article
• Language: English
• Subjects: Physics
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2019.02.006

[Display omitted] Ethylbenzene enthalpy Δεig × ΔHm below Tm = 178.1 K. Undercooled Phase 3 enthalpy coefficient Δεig versus (T − 178.1)2/178.12 in a two-liquid model; Δεig × ΔHm being the enthalpy difference between those of Liquid 1 and Liquid 2. Phase 3 undergoes a first-order transition at TK2 = 104.7 K in the absence of glass transition at Tg = 114.5 K and its enthalpy coefficient cannot be lower than (−0.17855). An underlying first-order transition limits the relaxation enthalpy and fixes the first-order transition temperatures of ultrastable glasses. Phase 3 undergoes other first-order transitions at higher temperatures associated glacial, superheated and supercooled phases in various substances. •A renewed nucleation equation & a two-liquid model predict all sharp transitions.•The liquids 1 & 2 give rise to glass and ordered liquid Phase 3 below and above Tg.•Liquid Phase 3 is “ordered” up to Tn+ > Tm and nucleated by cooling at a new Tn+