Structure and dynamics in yttrium-based molten rare earth alkali fluorides.
The transport properties of molten LiF-YF3 mixtures have been studied by pulsed field gradient nuclear magnetic resonance spectroscopy, potentiometric experiments, and molecular dynamics simulations. The calculated diffusion coefficients and electric conductivities compare very well with the measurements across a wide composition range. We then extract static (radial distribution functions, coordination numbers distributions) and dynamic (cage correlation functions) quantities from the simulations. Then, we discuss the interplay between the microscopic structure of the molten salts and their dynamic properties. It is often considered that variations in the diffusion coefficient of the anions are mainly driven by the evolution of its coordination with the metallic ion (Y(3+) here). We compare this system with fluorozirconate melts and demonstrate that the coordination number is a poor indicator of the evolution of the diffusion coefficient. Instead, we propose to use the ionic bonds lifetime. We show that the weak Y-F ionic bonds in LiF-YF3 do not induce the expected tendency of the fluoride diffusion coefficient to converge toward one of the yttrium cation when the content in YF3 increases. Implications on the validity of the Nernst-Einstein relation for estimating the electrical conductivity are discussed.
Molecular dynamics simulations of the local structures and transport coefficients of molten alkali chlorides.
Systematic results from molecular dynamics simulations of molten alkali chlorides (ACl) serials are presented in detail in this paper. The effects of temperature and cationic size on the structures and transport properties of molten salts have been investigated and analyzed. The local structures of molten ACl have been studied via the analysis of radial distribution functions and angular distribution functions. The coordination number of ACl decreases when ACl melts from solid and increases as cationic radius increases. Molten LiCl takes a distorted tetrahedral complex as the microconfiguration, while other melts have the tendency to keep the original local structure of the corresponding crystal. Temperature has no significant effect on the local structures of molten ACls. The results also show that the Tosi-Fumi potential predicts positive temperature dependences for self-diffusion coefficients and ionic conductivity, and negative temperature dependences for both viscosity and thermal conductivity of molten ACls. Ionic diffusivity decreases as cationic radius increases from LiCl to CsCl. The simulation results are in agreement with the experimental data available in the literature.
Analysis of the stress wave effect during coal breakage by a high-pressure abrasive air jet
In view of the defects of borehole collapse, inhibition of gas desorption and migration of gas existing in hydraulic fracturing and other hydraulic permeability–increasing measures for soft coal seams with low-permeability technology is proposed for coal breakage by a high-pressure abrasive gas jet for relieving pressure and increasing permeability. The comparative analysis of gas jet flow field structure between convergent nozzle and Laval nozzle has been given by numerical simulation. For Laval nozzle, the expansion wave and compression wave alternate and move forward steadily in gas jet and vanish when potential core length reaches maximum. So, the Laval nozzle can form more stable flow filed structure of gas jet and avoid shock wave in gas jet. Furthermore, a high-speed camera is adopted to analyze the jet structure and verify the conclusion of numerical simulation. Based on thermodynamic theory, this article calculates and analyzes the critical local sound velocity and pressure generated from the stress wave during the process of coal breakage by the gas jet. Furthermore, experimental coal breakage by a high-pressure abrasive gas jet is carried out. The high-pressure abrasive gas jet impacts the coal body as a quasi-static load and a dynamic load and forms corrosion pits on the surface of the coal body. Penetrating cracks are formed within the coal in the pattern of the loaded stress wave which leads to coal breakage. The effects of porosity and permeability on the propagation of the stress wave in coal are analyzed by establishing the dispersion equation for the spread of the stress wave in coal. The results show that porosity has a significant effect on wave velocity and that the attenuation of the stress wave is intensified with an increase in porosity. Moreover, the stress wave attenuation is more obvious at high frequency. The effect of permeability on the wave velocity is not significant at low frequencies. In contrast, at high frequency and relatively low permeability, the wave velocity increases with the permeability, and the attenuation of the wave velocity initially increases and then decreases. When the permeability is greater than 10−11 m2, the wave velocity is not affected by the permeability. However, the stress wave is not attenuated.