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.
Coordination numbers and physical properties in molten salts and their mixtures.
Mixtures of trivalent metal halides with alkali halides are involved in many technologies but, from a more fundamental and general perspective, are worthy of study as interesting systems in which to examine the relationship between atomic-scale structure and physical properties. Here we examine the relationship between the viscosity and local and longer range structural measures in such mixtures where the trivalent metal cations span a significant size range and exhibit different behaviours in the dependence of their viscosity on the mixture composition. We characterise the structure and dynamics of the first coordination shell and the relationship between its structural relaxation time and the shear relaxation time of the mixture (the Maxwell relaxation time). We are then led to an examination of the structure of the networks which progressively form between the trivalent metal cations as their concentration increases in the mixtures. Here we find significant differences between small and larger cations, sufficient to explain the different behaviour of their viscosities. We draw attention to the similarities and differences of these networks with those which form in highly viscous, glass-forming materials like BeF2:LiF.
Traceability strategy for gear-pitch-measuring instruments: development and calibration of a multiball artifact
There is a strong demand to ensure the traceability of gear-measuring instruments (GMIs). We propose a multiball artifact (MBA) for the evaluation of pitch-measuring accuracy. The aim of the MBA is to transfer the minimum uncertainty from a calibrated value at the National Metrology Institute of Japan (NMIJ) to a measured value of GMIs at a shop floor. The MBA is composed of equally spaced high-accuracy balls around an axis. The pitch-measuring accuracy of GMIs is evaluated by measuring the angular pitch deviation of the balls instead of the angular pitch deviation of a gear. We calibrated the angular pitch deviation using a coordinate measuring instrument (CMM) at the NMIJ and adapting a multiple-orientation technique. We proposed a calibration strategy of the angular pitch deviation. The calibration value of the pitch deviation for the MBA at the NMIJ was obtained with a measurement uncertainty (U95) of 0.2 µm. We evaluated the pitch-measuring accuracy of a GMI using the calibrated MBA. Each value of U95 for the cumulative and single pitch deviations for the left and right flanks was less than or equal to 0.5 µm. The small uncertainty was transferred from the NMIJ to the GMI.