NCMAS系统熔体结构和动力学性质压力效应的分子动力学研究

Molecular dynamics simulations were used to study the pressure dependence of the structure and the dynamic properties of forsterite melt (Mg_2SiO_4), diopside melt (CaMgSi_2O_6), anorthite melt (CaAl_2Si_2O_8), jadite melt (NaAlSi_2O_6) and albite melt (NaAlSi3O8) from 0 GPa to 25 GPa at about 2000 K and the following conclusions have been reached. Firstly, the ratio of NBO to T (NBO and T denote the content of non-bridging oxygen and the total content of Si~(4+) and Al~(3+) respectively) is closely related to the pressure and the composition of the melts. It decreases monotonously in forsterite, diopside and anorthite melts while increases at the initial stage and then decreases in jadite and albite melts with increasing pressure. At a fixed pressure, the shear viscosity of the melts decreases with increasing NBO/T and the variation rate is almost 150 times higher in fully polymerized melts than that in de-polymerized melts in comparison with anorthite melts. Secondly, it is generally accepted that the formation of the Si and A1 will promote the diffusion of the network-forming ions. The hypothesis is frequently employed to explain the emergence of the maximum self-diffusion coefficient of the network-forming ions in fully polymerized melts. However, I detected that the pressure corresponding to the peak of the self-diffusion coefficient of the network-forming ions is lower than that corresponding to the maximum content of Si and A1, and that there exists an approximately linear relationship between the self-diffusion coefficient of the ions and the breaking frequency of the bonds under a given pressure, which is different from the present understanding about the mechanism of self-diffusion. Thirdly, the relationship between the self-diffusion coefficient of Si~(4+), Al~(3+) and O~(2-) and the shear viscosity of the melts evolves from the Stokes-Einstein equation and Sutherland-Einstein equation to the Eyring equation with increasing pressure. And the key to obtain self-diffusion coefficient from shear viscosity under difference pressures is to determine A. in the Eyring equation. For Si~(4+) and O~(2-), this could be done using the linear relationship between A, and NBO% in anorthite melts. However, this method is inapplicable in other kinds of melts.