Investigation of the thermal conductivity of SiO2 glass using molecular dynamics simulations

Abstract A recent study showed that generating local crystalline paths within a glassy matrix provides only a moderate increase in thermal conductivity until the path fills most of the total volume. It was indicated that percolation theory governs the thermal conductivity in such crystalline‐implanted glass composites. In this study, we use computer simulations to investigate the effect of partial vitrification by breaking structural order of silica crystals by local vitrification. Such locally vitrified crystal structures are made by the bond‐transposition method, where the extent of vitrification can be tuned. Also, we test melt‐quenching of three SiO 2 crystalline structures (α‐quartz, coesite, and stishovite) to make silica glasses with different densities. The cooling rates and pressures were varied during the melting process in order to obtain glass structures with varied degrees of order. Our results show that the thermal conductivity of silica glasses calculated using Green–Kubo relation decreases rapidly as soon as the crystallinity is disturbed by bond transition or generated local glassy phase. This implies the phonon mean free path rapidly shrinks with even a small number of scatterers, regardless of the original polymorph. Through the investigation of the pressure effect, a strong proportional relation between the thermal conductivity and the density is found among all silica samples. Such correlation can be accounted by assuming a constant integral term in the Green–Kubo relation without the volume scaling, which is reasonable based on a weak dependence of κV on the density of silica glass except with a slight increase at low quench pressures. We hypothesize that when the quench pressure increases moderately, an increase of characteristic ring size tends to generate a more flexible SiO 2 structure which results more phonon scattering. Green–Kubo modal analysis further shows that the contribution from modes at low frequencies is suppressed when SiO 2 is melt‐quenched at higher pressure and vice versa.