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.
Quasielastic neutron scattering measurements and ab initio MD-simulations on single ion motions in molten NaF.
The ionic stochastic motions in the molten alkali halide NaF are investigated by quasielastic neutron scattering and first principles molecular dynamics simulation. Quasielastic neutron scattering was employed to extract the diffusion behavior of the sodium ions in the melt. An extensive first principles based simulation on a box of up to 512 particles has been performed to complement the experimental data. From that large box, a smaller 64-particle box has then been simulated over a runtime of 60 ps. A good agreement between calculated and neutron data on the level of spectral shape has been obtained. The obtained sodium diffusion coefficients agree very well. The simulation predicts a fluorine diffusion coefficient similar to the sodium one. Applying the Nernst-Einstein equation, a remarkable large cross correlation between both ions can be deduced. The velocity cross correlations demonstrate a positive correlation between the ions over a period of 0.1 ps. That strong correlation is evidence that the unlike ions do not move completely statistically independent and have a strong association over a short period of time.
Influence of pressure and fluidization velocity on the hydrodynamics of a fluidized bed containing horizontal tubes
Abstract An experimental investigation of the influence of horizontal tubes on the bubble behaviour and through-flow velocity of gas inside bubbles was carried out and the influence of pressure and fluidization velocity was studied. The visible bubble flow rate and the gas velocity through the bubbles were measured simultaneously in a pressurized fluidized bed, using capacitance and Pitot-static pressures probes respectively. Silica sand with a mean particle diameter of 0.7 mm was fluidized at pressures between 01. and 1.6 MPa, in a bed of 0.2 × 0.3 m cross-section. Six different horizontal tube configurations were used and comparisons were made with results obtained in the same bed operated without tubes. The results from the bed with tubes show that the influence of pressure and fluidization velocity is basically the same as in the bed without tubes; an increase in pressure and fluidization velocity increases the bubble activity. At low excess gas velocities, the influence of immersed tubes on the bubble behaviour is less pronounced than at high excess gas velocities. Measurements and visual observations show that a small tube pitch gives a more uniform distribution of the visible bubble flow over the bed cross-section. At a combination of high pressure, high excess gas velocity and a large tube pitch, a preferred bubble path was observed in the centre of the bed cross-section. The pressure probe measurements show that the through-flow velocity of gas inside the bubbles is in most cases higher when tubes are present in the bed. The through-flow velocity consistently decreases with increasing pressure in the bed without tubes. The tendency is largely the same at a low excess gas velocity when tubes are present, but at a high excess gas velocity the through-flow velocity first decreases and then increases as the pressure is increased.