Thermal conductivity of model zeolites: molecular dynamics simulation study

Abstract

The thermal conductivity of model zeolites was investigated using non-equilibrium molecular dynamics calculations. This type of calculation was found to overestimate the thermal conductivity of low-density silica polymorphs. A better reproduction of the experimental results was found for zeolites, and this was related to the lower phonon mean free path. The thermal conductivity of framework silicates was shown to be determined primarily by the vibrations of the continuous oxygen sublattice. Thus, the most drastic suppression of the heat transfer was related to alterations of the O-O distances; for example, a sixfold reduction in thermal conductivity compared to that of siliceous LTA zeolite was found for LTA-A1PO₄. Framework cations were shown to affect the heat transfer by changing the vibrational modes of the structural building units of the framework and non-framework counter-cations, by disturbing the oxygen sublattice locally and acting as Rayleigh and resonant scatterers. A model assuming the heat transfer to be due only to non-dispersive acoustic phonons failed to reproduce the dependence of the thermal conductivity on the mass of the cations and the unit-cell dimension, thus suggesting a more sophisticated mechanism of heat transfer to be operative in framework materials. The effect of non-framework non-ionic species on the thermal conductivity was shown to be determined by their effect on the characteristics of the oxygen framework vibrations. Thus, repulsive interactions between the oxygen sublattice and Xe₈ clusters, reducing the anisotropy and anharmonicity of the oxygen vibrations, give rise to enhanced heat transfer in LTA-SiO₂ at ambient conditions.