Thermal conductivity in modified oxide glasses is governed by modal phase changes

Abstract

The thermal conductivity of glasses is well-known to be significantly harder to theoretically describe compared to crystalline materials. Because of this fact, the fundamental understanding of thermal conductivity in glasses remain extremely poor when moving beyond the case of simple glasses, e.g., glassy SiO$_2$, and into so-called 'modified' oxide glasses, that is, glasses where other oxides (e.g. alkali oxides) have been added to break up the network and alter e.g. elastic and thermal properties. This lack of knowledge is apparent despite how modified glasses comprise the far majority of known glasses. In the present work we study an archetypical series of sodium silicate ($x\text{Na}_2\text{O}\text{-}(100\text{-}x)\text{SiO}_2$) glasses. Analyses of modal contributions reveal how increasing Na$_2$O content induces increasing vibrational localization with a change of vibrations to be less ordered, and a related general decrease in modal contributions to thermal conductivity. We find the vibrational phases (acoustic vs. optical) of sodium vibrations to be relatively disordered compared to the network-forming silicon and oxygen species, explaining how increasing Na$_2$O content decreases thermal conductivity. Our work sheds new light on the fundamentals of glassy heat transfer as well as the interplay between thermal conduction and modal characteristics in glasses.