Superstrong nature of covalently bonded glass-forming liquids at select compositions.

Variation of fragility (m) of specially homogenized Ge(x)Se(100-x) melts is established from complex specific heat measurements and shows that m(x) has a global minimum at an extremely low value (m = 14.8(0.5)) in the 21.5% < x < 23% range of Ge. Outside of that compositional range, m(x) then increases first rapidly and then slowly to about m = 25-30. By directly mapping melt stoichiometry as a function of reaction time at a fixed temperature T > Tg, we observe a slowdown of melt-homogenization by the super-strong melt compositions, 21.5% < x < 23%. This range furthermore appears to be correlated to the one observed between the flexible and stressed rigid phase in network glasses. These spectacular features underscore the crucial role played by topology and rigidity in the properties of network-forming liquids and glasses which are highlighted when fragility is represented as a function of variables tracking the effect of rigidity. Finally, we investigate the fragility-glass transition temperature relationship, and find that reported scaling laws do not apply in the flexible phase, while being valid for intermediate and stressed rigid compositions.