Correlating Melt Dynamics and Configurational Entropy Change With Topological Phases of AsxS100–x Glasses and the Crucial Role of Melt/Glass Homogenization

Abstract

Melt dynamics and glass Topological phases of especially dry and homogenized binary AsxS100-x melts/glasses are examined in Modulated-DSC, Raman scattering and volumetric experiments. In the S-rich glasses (12% 20 as x increases. Taken together, these results underscore that superstrong melts yield isostatically rigid glasses, while fragile ones form either Flexible or Stressed-rigid glasses upon cooling. The onset of the rigidity transition near = 2.22, instead of the usual value of = 2.40, is identified with presence of QT local structures in addition to Pyramidal As(S1/2)3 local structures in the glassy backbone, and with a small but finite fraction of polymeric Sn chains being decoupled from the backbone.