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Horne, Gregory P.

Publications and source records attributed to Horne, Gregory P..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Correction: Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ′, N ′-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

Correction for ‘Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ′, N ′-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation’ by Gregory P. Horne et al. , Phys. Chem. Chem. Phys. , 2023, 25 , 16404–16413, https://doi.org/10.1039/D3CP01119D.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Comprehensive Synthesis and Structural Trends in Tetramethyl Diglycolamide (TMDGA) Nitrate Complexes with Lanthanides and Americium

Complexes of N,N,N',N'-tetramethyl diglycolamide (TMDGA), a hydrophilic diglycolamide (DGA) proposed as an aqueous phase holdback reagent, have been crystallized for the majority of the lanthanide series (excluding promethium), yttrium, and americium to deepen our structural understanding of trivalent metal ion (M 3+ ) DGA coordination compounds in the presence of nitrate counter-anions. The presented collection of 16 complexes with accompanying single-crystal structures, taking formulas [M(TMDGA) 3 ][M(NO 3 ) 6 ] (M = La, Ce, Pr, Nd, Sm, Am), [M(TMDGA) 3 ][M(NO 3 ) 5 (H 2 O)] 1–x [M(NO 3 ) 4 (H 2 O) 2 ] x (NO 3 ) 1+x (M = Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), [M(TMDGA) 3 ] 2 [M(NO 3 ) 4 (H 2 O) 2 ] 0.75 [M(NO 3 ) 5 (H 2 O)] 1.25 (NO 3 ) 2.75 ·H 2 O (M = Lu), and [M(TMDGA) 3 ][M(NO 3 ) 5 (H 2 O)](NO 3 )·CH 3 OH (M = Y) were all synthesized via solvent diffusion of reaction mixtures containing the metal nitrate M(NO 3 ) 3 ·nH 2 O and TMDGA. Single-crystal X-ray diffraction analyses of these new structures show that each TMDGA complex comprises of three TMDGA ligands coordinating the metal ion via carbonyl and etheric oxygen atoms forming [M(TMDGA) 3 ] 3+ cations. Spectroscopy measurements under high pressure displayed notable differences in the f → f transition shifting between that of Nd(III) and Am(III). Shifting of transitions by 2.0 nm were observed in Nd up to 8.50 ± 0.09 GPa, while Am saw shifting between 11.0 to 13.5 nm at pressures up to 20.06 ± 1.90 GPa. The local geometry in these complexes is a distorted spherical capped square antiprism (CSAPR-9) except for of the yttrium complex, which exhibits a distorted spherical tricapped trigonal prismatic (TCTPR-9) geometry. Further, the anions that form concomitantly with the TMDGA complexes are composed of hexanitrato species for the early lanthanide ions (lanthanum to samarium); whereas the remaining smaller lanthanides did not possess sufficiently large ionic radii to coordinate six bidentate nitrate anions, instead, one or two nitrate anions are situated in the outer sphere. The systematic progression of changes in the anionic environments of these complexes outlines the changing coordination habits afforded by the lanthanide contraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Identification and time evolution of thionyl chloride (SOCl 2 ) radiolysis products

In this study, innovative solutions are needed to reduce the amount of high-level waste generated by used nuclear fuel recycling strategies to support the widespread adoption of sustainable nuclear fission energy technologies. To this end, a new sulfur chloride-based process has been developed to recycle zirconium alloy-based materials, which make up a significant fraction of high-level radioactive waste. To support the continued development of this process, we present new data on the potential reaction pathways over time of the products arising from the gamma and electron beam radiolysis of neat thionyl chloride (SOCl 2 ). Interrogation of the gamma irradiated liquid by Raman spectroscopy provided more conclusive identification of the SOCl 2 degradation products, specifically sulfur dichloride (SCl 2 ), molecular chlorine (Cl 2 ), sulfur dioxide (SO 2 ), and sulfuryl chloride (SO 2 Cl 2 ). In comparison, the high dose rate (~10 7 Gy s -1 ) electron beam irradiations formed significantly more degradation products. For both cobalt-60 gamma and electron beam irradiations, the observed degradation products were found to evolve as a function of time post-irradiation via the same reaction pathways, with indication of a solvent regeneration mechanism. These findings are fortuitous for process development, as such a mechanism would be beneficial for process longevity and cost effectiveness.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Effect of f -element complexation on the radiolysis of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])

A systematic study of the impact on the chemical reactivity of the oxidising n-dodecane radical cation (RH˙ + ) with f-element complexed 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) has been undertaken utilizing time-resolved electron pulse radiolysis/transient absorption spectroscopy and high-level quantum mechanical calculations. Lanthanide ion complexed species, [Ln((HEH[EHP]) 2 ) 3 ], exhibited vastly increased reactivity (over 10× faster) in comparison to the non-complexed ligand in n-dodecane solvent, whose rate coefficient was k = (4.66 ± 0.22) × 10 9 M -1 s -1 . Similar reactivity enhancement was also observed for the corresponding americium ion complex, k = (5.58 ± 0.30) × 10 10 M -1 s -1 . The vastly increased reactivity of these f-element complexes was not due to simple increased diffusion-control of these reactions; rather, enhanced hole transfer mechanisms for the complexes were calculated to become energetically more favourable. Interestingly, the observed reactivity trend with lanthanide ion size was not linear; instead, the rate coefficients showed an initial increase (Lu to Yb) followed by a decrease (Tm to Ho), followed by another increase (Dy to La). This behaviour was excellently predicted by the calculated reaction volumes of these complexes. In conclusion, complementary cobalt-60 gamma irradiations for select lanthanide complexes demonstrated that the measured kinetic differences translated to increased ligand degradation at steady-state timescales, affording ~38% increase in ligand loss of a 1:1 [La((HEH[EHP]) 2 ) 3 ]: HEH[EHP] ratio system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Radiolytic evaluation of a new technetium redox control reagent for advanced used nuclear fuel separations

Technetium is a problematic radioisotope for used nuclear fuel (UNF) and subsequent waste management owing to its high environmental mobility and coextraction in reprocessing technologies as the pertechnetate anion (TcO 4 - ). Consequently, several strategies are under development to control the transport of this radioisotope. A proposed approach is to use diaminoguanidine (DAG) for TcO 4 - and transuranic ion redox control. Although the initial DAG molecule is ultimately consumed in the redox process, its susceptibility to radiolysis is currently unknown under envisioned UNF reprocessing conditions, which is a critical knowledge gap for evaluating its overall suitability for this role. To this end, we report the impacts of steady-state gamma irradiation on the rate of DAG radiolysis in water, aqueous 2.0 M nitric acid (HNO 3 ), and in a biphasic solvent system composed of aqueous 2.0 M HNO 3 in contact with 1.5 M N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA) dissolved in n-dodecane. In addition, we report chemical kinetics for the reaction of DAG with key transients arising from electron pulse radiolysis, specifically the hydrated electron (e aq - ), hydrogen atom (H ˙ ), and hydroxyl ( ˙ OH) and nitrate (NO 3 ˙ ) radicals. The DAG molecule exhibited significant reactivity with the ˙ OH and NO 3 ˙ radicals, indicating that oxidation would be the predominant degradation pathway in radiation environments. This is consistent with its role as a reducing agent. Steady-state gamma irradiations demonstrated that DAG is readily degraded within a few hundred kilogray, the rate of which was found to increase upon going from water to HNO 3 containing solutions and solvents systems. This was attributed to a thermal reaction between DAG and the predominant HNO 3 radiolysis product, nitrous acid (HNO 2 ), k(DAG + HNO 2 ) = 5480 ± 85 M -1 s -1 . Although no evidence was found for the radiolysis of DAG altering the radiation chemistry of the contacted DEHiBA/n-dodecane phase in the investigated biphasic system, the utility of DAG as a redox control reagent will likely be limited by significant competition with its degradation by HNO 2 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Chemical Kinetics for the Oxidation of Californium(III) Ions with Select Radiation-Induced Inorganic Radicals (Cl 2 •– and SO 4 •– )

Despite the availability of transuranic elements increasing in recent years, our understanding of their most basic and inherent radiation chemistry is limited and yet essential for accurate interpretation of their physical and chemical properties. Here, in this work, we explore the transient interactions between trivalent californium ions (Cf 3+ ) and select inorganic radicals arising from the radiolytic decomposition of common anions and functional group constituents, specifically the dichlorine (Cl 2 •- ) and sulfate (SO 4 •- ) radical anions. Chemical kinetics, as measured by integrated electron pulse radiolysis and transient absorption spectroscopy techniques, are presented for the reactions of these two oxidizing radicals with Cf 3+ ions. The derived and ionic strength corrected second-order rate coefficients (k) for these radiation-induced processes are k(Cf 3+ + Cl 2 •- ) = (8.28 ± 0.61) × 10 5 M -1 s -1 and k(Cf 3+ + SO 4 •- ) = (9.50 ± 0.43) × 10 8 M -1 s -1 under ambient temperature conditions (22 ± 1 °C).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

High temperature gamma radiation-induced chromium redox chemistry via in situ spectroscopic measurements

Chromium ions can make their way into the primary coolant of nuclear power reactors from the corrosion of stainless-steel reactor components, decreasing the material's corrosion resistance and resulting in increased transport of further corrosion products. Despite these potential effects, the radiation-induced redox speciation of chromium ions in aqueous solution is not well understood, especially at the elevated temperatures experienced by reactor coolants. Here, in the present work, we report new experimental results demonstrating that in aerated aqueous solution, the radiolytic oxidation of Cr(III) to Cr(VI) occurs at pH 4, while the reduction of Cr(VI) to Cr(III) occurs at pH 2. The oxidation of Cr(III) is primarily attributed to the reaction of the hydroxyl radical (˙OH) with the Cr(OH) 2+ species, while the reduction of Cr(VI) is attributed to reactions involving the hydrated electron (e aq - ) and hydrogen atom (H˙). Additionally, the steady-state equilibrium yield of Cr(VI) from the gamma irradiation of pH 4 Cr(III) solutions decreased with increasing temperature (over a range of 37–195 °C). This observation indicates that the activation energy of the Cr(VI) reduction reactions is higher than that for the Cr(III) oxidation reactions, such that it becomes relatively more favorable at higher temperatures. Overall, these data are important for the development of complementary multiscale models for the prediction of metal ion speciation in high temperature radiation environments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ', N '-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

The impact of trivalent lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the n-dodecane radical cation (RH˙+) has been measured by electron pulse radiolysis and evaluated by quantum mechanical calculations. Additionally, Arrhenius parameters were determined for the reaction of the non-complexed TODGA ligand with the RH˙ + from 10–40 °C, giving the activation energy (E a = 17.43 ± 1.64 kJ mol –1 ) and pre-exponential factor (A = (2.36 ± 0.05) × 10 13 M –1 s –1 ). The complexation of Nd(III), Gd(III), and Yb(III) ions by TODGA yielded [LnIII(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3× faster) with the RH˙ + , relative to the non-complexed ligand: k([Ln III (TODGA) 3 (NO 3 ) 3 ] + RH˙ + ) = (8.99 ± 0.93) × 10 10 , (2.88 ± 0.40) × 10 10 , and (1.53 ± 0.34) × 10 10 M –1 s –1 , for Nd(III), Gd(III), and Yb(III) ions, respectively. The rate coefficient enhancement measured for these complexes exhibited a dependence on atomic number, decreasing as the lanthanide series was traversed. Preliminary reaction free energy calculations—based on a model [Ln III (TOGDA)] 3+ complex system—indicate that both electron/hole and proton transfer reactions are energetically unfavorable for complexed TODGA. Furthermore, complementary average local ionization energy calculations showed that the most reactive region of model N,N,N',N'-tetraethyl diglycolamide (TEDGA) complexes, [Ln III (TEGDA) 3 (NO 3 ) 3 ], toward electrophilic attack is for the coordinated nitrate (NO 3 – ) counter anions. Furthermore, it is possible that radical reactions with the complexed NO 3 – counter anions dominate the differences in rates seen for the [Ln III (TODGA) 3 (NO 3 ) 3 ] complexes, and are likely responsible for the reported radioprotection in the presence of TODGA complexes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Impact of iodide ions on the speciation of radiolytic transients in molten LiCl–KCl eutectic salt mixtures

The fate of fission-product iodine is critical for the deployment of next generation molten salt reactor technologies, owing to its volatility and biological impacts if it were to be released into the environment. To date, little is known on how ionizing radiation fields influence the redox chemistry, speciation, and transport of iodine in high temperature molten salts. Here we employ picosecond electron pulse irradiation techniques to elucidate for the first time the impact of iodide ions (I – ) on the speciation and chemical kinetics of the primary radiation-induced transient radicals generated in molten chloride salt mixtures (e S – and Cl 2 ˙– ) as a function of temperature (400–700 °C). In the presence of I – ions (≥ 1 wt% KI in LiCl–KCl eutectic), we find that the transient spectrum following the electron pulse is composed of at least three overlapping species: the e S – and the Cl 2 ˙– and ICl ˙– radical anions, for which a deconvoluted spectrum of the latter is reported here for the first time in molten salts. This new transient spectrum was consistent with gas phase density functional theory calculations. The lifetime of the e S – was unaffected by the addition of I – ions. The newly observed interhalogen radical anion, ICl˙ – , exhibited a lifetime on the order of microseconds over the investigated temperature range. The associated chemical kinetics indicate that the predominate mechanism of ICl˙ – decay is via reaction with the Cl 2 ˙– radical anion. The iodine containing product of this reaction is expected to be ICl 2 – , which will have implications for the transport of fission-product iodine in MSR technologies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Radiolytic Evaluation of 3,4,3-LI(1,2-HOPO) in Aqueous Solutions

We report the octadentate hydroxypyridinone ligand 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO) has been identified as a promising candidate for both chelation and f-element separation technologies, two applications that require optimal performance in radiation environments. However, the radiation robustness of HOPO is currently unknown. Here, we employ a combination of time-resolved (electron pulse) and steady-state (alpha self-radiolysis) irradiation techniques to elucidate the basic chemistry of HOPO and its f-element complexes in aqueous radiation environments. Chemical kinetics were measured for the reaction of HOPO and its Nd(III) ion complex ([Nd III (HOPO)] - ) with key aqueous radiation-induced radical transients (eaq - , H · atom, and · OH and NO 3 · radicals). The reaction of HOPO with eaq - is believed to proceed via reduction of the hydroxypyridinone moiety, while transient adduct spectra indicate that reactions with the H · atom and · OH and NO 3 · radicals proceeded by addition to HOPO's hydroxypyridinone rings, potentially allowing for the generation of an extensive suite of addition products. Complementary steady-state 241 Am(III)-HOPO complex ([ 241 Am III (HOPO)] - ) irradiations showed the gradual release of 241 Am(III) ions with increasing alpha dose up to 100 kGy, although complete ligand destruction was not observed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Milestone 1.2.12: The Fate of Oxygen Radical Species in Corroded Aluminum Alloys under Irradiation

The U.S. Department of Energy tasked Idaho National Laboratory to evaluate the feasibility of extended dry storage of aluminum-clad spent nuclear fuel (ASNF) in heliumbackfilled canisters. A significant research effort has been devoted to determining the amount of radiation-induced molecular hydrogen (H 2 ) generation from corrosion layers that would be present on the fuel assembly surfaces. However, limited attention has been directed to the oxygen radical species that are concurrently generated in these H 2 producing radiation environments. This report collates and summarizes the available experimental and computational studies on the fate of these reactive oxygen radicals during the irradiation of aluminum oxyhydroxide and hydroxide polymorphs typically formed on ASNF. Based on this review, it is determined that radiation-induced oxygen-centered radicals do not react to give molecular oxygen gas (O 2 ), but rather remain trapped in the aluminum corrosion layers in their original crystal lattice positions. Overall, O 2 generation will not be a concern for extended storage of ASNF in helium-backfilled canisters. That is, no O 2 contribution to pressurization of sealed dry storage systems or creation of a flammable atmosphere is anticipated.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Radiolytic evaluation of select sulfur chlorides (S 2 Cl 2 and SOCl 2 ) for advanced low temperature chlorination of zirconium-based used nuclear fuel cladding

New sulfur chloride compounds—sulfur monochloride (S 2 Cl 2 ) and thionyl chloride (SOCl 2 )—have been proposed as alternative chlorinating agents for the chemical decladding of zirconium-based used nuclear fuel cladding materials. However, the radiation stability of these compounds has not been thoroughly evaluated, despite envisioned process conditions involving intense, multi-component radiation fields. Knowledge of the radiation chemistry of these sulfur chlorides is essential for the development and optimization of alternative chlorination technologies. To this end, we present preliminary findings on the gamma radiolysis of neat S 2 Cl 2 and SOCl 2 at ambient temperature up to ~ 34 MGy. In this study, Raman spectroscopy and density functional theory calculations were used to identify the Raman-active degradation products from S 2 Cl 2 and SOCl 2 radiolysis. Both sulfur chloride compounds exhibited significant radiation resistance, with respect to changes in the Raman signatures of the parent compounds and the ingrowth of Raman-active degradation products. For S 2 Cl 2 , molecular chlorine (Cl 2 ) was directly identified as the predominant degradation product, which was completely consumed at higher absorbed doses (> 9 MGy). Similarly, the main degradation product from SOCl 2 radiolysis was also Cl 2 , although in this system it continued to grow in with dose over the entire dose range. Further, an “S=O” containing degradation product(s) was also identified as a compliment to Cl 2 . Overall, the perceived radiation resistance of these sulfur chloride compounds makes them suitable for inclusion in a used nuclear fuel chemical decladding process, especially as radiolytically formed Cl 2 can be used to reform the parent compounds, thereby increasing the longevity of the solvents used.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Gamma Radiation-Induced Degradation of Acetohydroxamic Acid (AHA) in Aqueous Nitrate and Nitric Acid Solutions Evaluated by Multiscale Modelling

Acetohydroxamic acid (AHA) has been proposed for inclusion in advanced, single-cycle, used nuclear fuel reprocessing solvent systems for the reduction and complexation of plutonium and neptunium ions. For this application, a detailed description of the degradation of AHA in dilute aqueous nitric acid is required. To this end, we present a comprehensive, multiscale computer model for the coupled radiolytic and hydrolytic degradation of AHA in aqueous sodium nitrate and nitric acid solutions. Rate coefficients for the reactions of AHA and HA with the oxidizing nitrate radical were measured for the first time using pulsed electron radiolysis and used as inputs in the kinetic model. The computer model results are validated by comparison to experimental data from steady state gamma irradiations, for which the agreement is excellent. Here, the presented model accurately predicts the yields of the major degradation products of AHA: acetic acid, hydroxylamine, nitrous oxide, and molecular hydrogen.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Radiolytic Gas Production from Aluminum Coupons (Alloy 1100 and 6061) in Helium Environments—Assessing the Extended Storage of Aluminum Clad Spent Nuclear Fuel

Corrosion of aluminium alloy clad nuclear fuel, during reactor operation and under subsequent wet storage conditions, promotes the formation of aluminium hydroxide and oxyhydroxide layers. These hydrated mineral phases and the chemisorbed and physisorbed waters on their surfaces are susceptible to radiation-induced processes that yield molecular hydrogen gas (H 2 ), which has the potential to complicate the long-term storage and disposal of aluminium clad nuclear fuel through flammable and explosive gas mixture formation, alloy embrittlement, and pressurization. Here, we present a systematic study of the radiolytic formation of H 2 from aluminium alloy 1100 (AA1100) and 6061 (AA6061) coupons in “dry” (~0% relative humidity) and “wet” (50% relative humidity) helium environments. Cobalt-60 gamma irradiation of both aluminium alloy types promoted the formation of H 2 , which increased linearly up to ~2 MGy, and afforded G-values of 1.1 ± 0.1 and 2.9 ± 0.1 for “dry” and “wet” AA1100, and 2.7 ± 0.1 and 1.7 ± 0.1 for “dry” and “wet” AA6061. The negative correlation of H 2 production with relative humidity for AA6061 is in stark contrast to AA1100 and is attributed to differences in the extent of corrosion and varying amounts of adsorbed water in the two alloys, as characterized using optical profilometry, scanning electron microscopy, Raman spectroscopy, and X-ray diffraction techniques.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Milestone 1.2.11: H 2 Production from Surrogate Non-Native Corrosion Plumes on Aluminum 6061-T6 Fuel Cladding Surrogates

Thick, localized, “non-native” corrosion plumes have been identified on Advanced Test Reactor fuel elements, raising concern on their impact on the radiolytic formation of molecular hydrogen gas (H 2 ) from aluminum-clad spent nuclear fuel (ASNF) under proposed extended (> 50 years) dry storage conditions. Here, we report our findings on H 2 generation from the gamma irradiation (up to 52 MGy) of surrogate “non-native” corrosion plume coupons: ambient-temperature-corroded (~350 days in water) aluminum alloy 6061 (AA6061) coupons in helium gas environments with ~0% added relative humidity. Additionally, we provide a comparison of proposed ASNF drying techniques— vacuum drying only, vacuum drying + 100 °C for 4 hr, and vacuum drying + 220 °C for 4 hr—on the yield of H 2 from these surrogate systems. The presented data indicates that similar amounts of H 2 (~2 × 10–3 µmol J–1) are formed from gamma irradiated AA6061 coupons corroded under different temperature regimes, i.e., ambient/350 days vs. 90 C/30 days. These findings validate current, complimentary modelling predictions based on high-temperature-corrosion irradiation data only. Further, the application of a heat treatment procedure (100 and 220 °C), in conjunction with vacuum drying, accelerated the rate at which a steady-state H 2 yield was attained, in comparison to vacuum only, due to the removal of H 2 precursors in the form of adsorbed waters. Interestingly, within the confidence limits of our measurements, negligible difference in total H 2 yield was found between the two investigated heat treatment procedures.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Radiation-induced reaction kinetics of Zn 2+ with e S - and Cl 2 ˙ - in Molten LiCl–KCl eutectic at 400–600 °C

We report molten chloride salts are currently under consideration as combined coolant and liquid fuel for next-generation molten salt nuclear reactors. Unlike complementary light-water reactor technologies, the radiation science underpinning molten salts is in its infancy, and thus requires a fundamental mechanistic investigation to elucidate the radiation-driven chemistry within molten salt reactors. Here we present an electron pulse radiolysis kinetics study into the behaviour of the primary radiolytic species generated in molten chloride systems, i.e., the solvated electron (e S - ) and di-chlorine radical anion (Cl 2 ˙- ). We examine the reaction of e S - with Zn 2+ from 400–600 °C (E a = 30.31 ± 0.09 kJ mol -1 ), and the kinetics and decay mechanisms of Cl 2 ˙- in molten lithium chloride-potassium chloride (LiCl–KCl) eutectic. In the absence of Zn 2+ , the lifetime of e S - was found to be dictated by residual impurities in ostensibly “pure” salts, and thus the observed decay is dependent on sample history rather than being an intrinsic property of the salt. The decay of Cl 2 ˙- is complex, owing to the competition of Cl 2 ˙- disproportionation with several other chemical pathways, one of which involves reduction by radiolytically-produced Zn + species. Overall, the reported findings demonstrate the richness and complexity of chemistry involving the interactions of ionizing radiation with molten salts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Milestone 1.2.10: Steady-state H 2 “roll over” point data for aluminum alloys 1100 and 6061

Extended (> 50 years) dry storage is being evaluated by the U.S. Department of Energy (DOE) for the disposition of ~ 18 metric tons of aluminum-clad spent nuclear fuel (ASNF). Transition of the current ASNF inventory into dry storage—using the standard DOE canister—necessitates a rigorous, predictive understanding of the long-term physical and chemical factors that may influence the integrity of the proposed storage canister, including radiolytic molecular hydrogen (H 2 ) generation. Current model predictions employ initial radiolytic yields of H 2 , the values of which change as the cladding’s H 2 -precursor inventory is depleted and H 2 itself becomes progressively more involved in radiolytic and surface dissociation processes. Consequently, the absorbed radiation dose that this steady-state H 2 yield corresponds to is essential for the evaluation and improvement of model predictions. Here, we report our findings on the long-term generation of H 2 from the gamma irradiation (≤ 36 MGy) of corroded AA1100 and AA6061 coupons in helium environments at ambient temperature and ~ 50% RH. Our findings show that AA1100 systems reached steady-state by ~ 36 MGy, while higher doses were necessary for AA6061 systems. This discrepancy was attributed to the AA6061 coupons developing a thicker corrosion layer that led to the trapping of H 2 and its precursors, and potentially additional chemistries, ultimately delaying the depletion of H 2 precursors and the system’s “roll over” point. Further, current model predictions—based on previous AA1100 data—do not show steady-state attainment until above 120 MGy, which is not the case for the AA1100 data collected here. Consequently, the new alloy dependent data presented here are important for the continued improvement of predictive computer models for evaluating the feasibility of extended storage of ASNF in helium backfilled canisters.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗