Thermodynamic heat-transfer phenomena in nanostructured glassy substances: a comparative study on g-As₅Se₉₅ and g-As₅₅Se₄₅

Nanostructurization-driven responses in calorimetric heat-transfer phenomena are compared for glassy arsenoselenides at different levels of their molecular network organization, namely in high-polymerized g-As5Se95 and low-polymerized g-As55Se45, employing multifrequency temperature-modulated DSC-TOPEM (R) method complemented with Raman scattering microspectroscopy. It is shown that high-polymerized network composed of AsSe3 pyramids interlinked by Se chains with small number of Se-8 molecular units decoupled from this network prevails in melt-quenched and nanomilling-derived g-As5Se95. Transition to more polymerized network due to incorporation of destroyed Se-8 molecules into glass backbone occurs in this glass under nanostructurization. As a result, nanostructurization-driven calorimetric response in g-As5Se95 dominates by size-induced glass-transition temperature depression. The low-polymerized structure of g-As55Se45 is built of As-Se network enriched with tetra-arsenic selenide molecular units decoupled from this network. Molecular-to-network transition owing to nanomilling-driven destruction of these cage molecules and their incorporation into newly polymerized glass-forming backbone occurs in g-As55Se45 resulting in strong increase in calorimetric glass-transition temperature.