Radiation-Induced Long-Lived Transients and Metal Particle Formation in Solid KCl–MgCl2 Mixtures

Ramos-Ballesteros, Alejandro; Gakhar, Ruchi; Woods, Michael E.; Horne, Gregory P.; Iwamatsu, Kazuhiro; Wishart, James F.; Pimblott, Simon M.; LaVerne, Jay A.

doi:10.1021/acs.jpcc.2c01725

Radiation-Induced Long-Lived Transients and Metal Particle Formation in Solid KCl–MgCl₂ Mixtures

Journal Article · Mon Jun 06 04:00:00 EDT 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c01725· OSTI ID:1870397

^[1]; ^[2]; ^[2]; ^[2]; Iwamatsu, Kazuhiro ^[3]; ^[3]; ^[2]; ^[1]

Univ. of Notre Dame, IN (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Here, the electron paramagnetic resonance and diffuse reflectance-optical absorption spectra of room-temperature γ-irradiated KCl–MgCl₂ binary solid salt mixtures (98:2 mol % and 2:98 mol %) and the eutectic (68:32 mol %) are reported. Additionally, powder X-ray diffraction of the pristine salts and thermal annealing studies of the irradiated salts were performed to evaluate the radiolysis product stability, annihilation, and association in metallic particles. The main long-lived transient species detected in 98:2 mol % KCl–MgCl₂ salts were perturbed F-centers, that is, trapped electrons (e_t^–) in the vicinity of Mg ions (λ_max at 561 nm), and the radiolytic reduction of Mg²⁺ to Mg⁺ and Mg⁰. Thermal annealing promoted the diffusion of defects to yield polycations (Mg_n⁺). On the other hand, irradiation of 2:98 mol % KCl/MgCl₂ salts showed the formation of cationic and neutral Mg dimers (Mg₂⁺ and Mg₂) and trimers as well as centers with a rhombic powder pattern apparently consisting of an electron shared between three Mg²⁺ nuclei associated with an anion vacancy (ν_a⁺–Mg₃⁵⁺). Trapped electrons (e_t^–) (F-centers) were not observed in the irradiated eutectic mixture; instead, Mg₂, Mg⁰, and Cl₃^– were observed. It was observed that the higher temperature for thermal ionization of radiation-reduced Mg species decreased the extent of electron recombination reactions and the disproportionation of Cl₃^– compared to the pure KCl but enhanced the aggregation of Mg into larger metallic microstructures (metallic particles).

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; AC07-05ID14517; FC02-04ER15533

OSTI ID:: 1870397

Alternate ID(s):: OSTI ID: 1889137
OSTI ID: 1897116

Report Number(s):: BNL-223031-2022-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 23 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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