Building and Breaking Bonds by Homogenous Nucleation in Glass-Forming Melts Leading to Transitions in Three Liquid States

The thermal history of melts leads to three liquid states above the melting temperatures T_m containing clusters—bound colloids with two opposite values of enthalpy +Δε_lg × ΔH_m and −Δε_lg × ΔH_m and zero. All colloid bonds disconnect at T_n+ > T_m and give rise in congruent materials, through a first-order transition at T_LL = T_n+, forming a homogeneous liquid, containing tiny superatoms, built by short-range order. In non-congruent materials, (T_n+) and (T_LL) are separated, T_n+ being the temperature of a second order and T_LL the temperature of a first-order phase transition. (T_n+) and (T_LL) are predicted from the knowledge of solidus and liquidus temperatures using non-classical homogenous nucleation. The first-order transition at T_LL 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 T_n+ or from T_n+ to T_g. These liquid enthalpies reveal the natural presence of colloid–colloid bonding and antibonding in glass-forming melts. The Mpemba effect and its inverse exist in all melts and is due to the presence of these three liquid states.