Molecular dynamics simulations of displacement cascades in LiAlO2 and LiAl5O8 ceramics.

Molecular dynamics was employed to investigate the radiation damage due to collision cascades in LiAlO2 and LiAl5O8, the latter being a secondary phase formed in the former during irradiation. Atomic displacement cascades were simulated by initiating primary knock-on atoms (PKA) with energy values = 5, 10 and 15 keV and the damage was quantified by the number of Frenkel pairs formed for each species: Li, Al and O. The primary challenges of modeling an ionic system with and without a core-shell model for oxygen atoms were addressed and new findings on the radiation resistance of these ceramics are presented. The working of a variable timestep function and the kinetics in the background of the simulations have been elaborated to highlight the novelty of the simulation approach. More importantly, the key results indicated that LiAlO2 experiences much more radiation damage than LiAl5O8, where the number of Li Frenkel pairs in LiAlO2 was 3-5 times higher than in LiAl5O8 while the number of Frenkel pairs for Al and O in LiAlO2 are ~ 2 times higher than in LiAl5O8. The primary reason is high displacement threshold energies (Ed) in LiAl5O8 for Li cations. The greater Ed for Li imparts higher resistance to damage during the collision cascade and thus inhibits amorphization in LiAl5O8. The presented results suggest that LiAl5O8 is likely to maintain structural integrity better than LiAlO2 in the irradiation conditions studied in this work.

Influence of ambient gas on self-reversal in Li transitions relevant to isotopic analysis.

Laser induced breakdown spectroscopy is a promising, rapid analysis method for the detection and quantification of Li and its isotopes needed in geochemical, nuclear, and energy storage applications. However, spectral broadening in laser produced plasmas, presence of fine and hyperfine structures, and self-reversal effects make Li isotopic analysis via laser induced breakdown spectroscopy challenging. The present study explores the influence of Ar, N2, and He ambient gases over the pressure range of 0.05 - 100 Torr on line broadening and self-reversal of the Li I transition with the greatest isotopic shift in the VIS spectral region (i.e., ≈670.8 nm, ≈15.8 pm isotopic shift). We perform spatially and temporally resolved optical emission spectroscopy of plasmas produced via laser ablation of LiAlO2 substrates. Our results show that the self-reversal and linewidth is reduced at lower pressures for all gases, and using optimized plasma conditions with chemometric methods, the 6Li/7Li isotopic ratios can be predicted.

Probing the Radial Chemistry of Getter Components in Light Water Reactors via Controlled Electrochemical Dissolution.

Getters are among the key functional components in the tritium-producing burnable absorber rods (TPBARs) of light water reactors (LWRs) and are used to capture the released tritium gas. They are nickel-plated zircaloy-4 tubes that, upon exposure to irradiation or tritium in the light water reactors, undergo alteration in structure, chemical composition, and chemistry. Understanding the radial tritium distribution is key to gaining insight into the evolution of new chemistry upon irradiation to predict getter performance. The holy grail is to develop a method akin to selectively peeling off the layers of an onion in an effort to get a radial map of elements and particularly tritium across the getter. Toward this goal, the overall aim of this work is to establish a correlative technique that can be used to determine radial tritium distribution across getters. To this end, this work specifically focuses on the validation of a correlative method for controlled radial dissolution of nickel-plated getters. Here, pristine getters as well as getters loaded with different mass ratios of hydrogen and deuterium are used as the nonradioactive surrogates of tritium, the idea being that the methodology can be readily extended to tritiated getter components. Here, the surface nickel layers as well as the bulk zirconium layers are sequentially dissolved in a controlled, uniform way using voltage-assisted electrochemical dissolution techniques. The dissolution is complemented by periodic elemental analysis of the electrolyte solution during and post dissolution. This is complemented by microscopic analyses on the exposed surfaces to provide a correlative technique for a complete picture of the radial distribution of various elements across the getter.

An electrochemical technique for controlled dissolution of zirconium based components of light water reactors.

Zircaloy-4 (Zr-4) based liners and getters are the principle functional components of Tritium-Producing Burnable Absorber Rods (TPBARs) in light water nuclear reactors where they reduce tritiated water into tritium gas. Upon tritium exposure, zirconium tritide is formed, which changes the chemical composition, structure and morphology of these materials. Their thermodynamic properties are affected by (i) the hydride phase identity, (ii) radial and spatial tritide/hydride (T/H) distribution, and (iii) the changes in structure and morphology of the material upon T/H-migration, and their comprehensive knowledge is needed to predict performance of these materials. This work demonstrates that controlled potential electrochemistry techniques to be highly efficient for controlled oxidative radial dissolution of Zr-4 based liners (both unloaded and loaded with hydride/deuteride as chemical surrogates for tritium). The electrodissolution is further combined with microscopic techniques to accurately determine the distribution of hydride phases. This work demonstrates a reliable technique for radially etching the liners after irradiation to provide insight into the radial and spatial distribution of tritium within the TPBAR, improving the fundamental understanding of tritium transport and providing a basis for validating predictive models.