materials Article Building and Breaking Bonds by Homogenous Nucleation in Glass-Forming Melts Leading to Transitions in Three Liquid States Robert F. Tournier 1,* and Michael I. Ojovan 2,3 1 LNCMI-EMFL, CNRS, Université Grenoble Alpes, INSA-T, UPS, 38042 Grenoble, France 2 Department of Materials, Imperial College London, London SW7 2AZ, UK;
[email protected] 3 Department of Radiochemistry, Lomonosov Moscow State University, 119991 Moscow, Russia * Correspondence:
[email protected] Abstract: The thermal history of melts leads to three liquid states above the melting temperatures Tm containing clusters—bound colloids with two opposite values of enthalpy +D"lg × DHm and −D"lg × DHm and zero. All colloid bonds disconnect at Tn+ > Tm and give rise in congruent materials, through a first-order transition at TLL = Tn+, forming a homogeneous liquid, containing tiny superatoms, built by short-range order. In non-congruent materials, (Tn+) and (TLL) are separated, Tn+ being the temperature of a second order and TLL the temperature of a first-order phase transition. (Tn+) and (TLL) are predicted from the knowledge of solidus and liquidus temperatures using non- classical homogenous nucleation. The first-order transition at TLL gives rise by cooling to a new liquid state containing colloids. Each colloid is a superatom, melted by homogeneous disintegration of nuclei instead of surface melting, and with a Gibbs free energy equal to that of a liquid droplet containing the same magic atom number. Internal and external bond number of colloids increases at Tn+ or from Tn+ to Tg. These liquid enthalpies reveal the natural presence of colloid–colloid bonding and antibonding in glass-forming melts.