Engineering topics

Wilbanks, Joseph Richard

Publications and source records attributed to Wilbanks, Joseph Richard.

8 records

DOE OSTI2024

Milestone 1.2.16. Reconciling the Impacts of Thermal Pretreatment on Radiation-Induced H2 Generation from Aluminum-Clad Spent Nuclear Fuel Surrogate Materials

To support the technical basis for the extended dry storage of aluminum-clad spent nuclear fuel (ASNF), thermal pretreatment procedures to minimize the radiation-induced generation of molecular hydrogen (H2) have been investigated. The aim of thermal pretreatment is to eliminate the residual adsorbed water content on the ASNF’s corrosion layers, precursors for H2 generation. To date, irradiation studies in this area have found conflicting results for the effectiveness of thermal pretreatment procedures. The aim of this study was to reconcile those differences. However, the presented results, which utilized a modified in situ thermal pretreatment procedure, afforded H2 yield data that further indicates that thermal pretreatment does not significantly reduce the radiation-induced yield of H2 from gamma irradiated ASNF surrogate materials. Assessment of the differences between thermal pretreatment studies suggests that stainless-steel—present in the irradiation setup of studies that demonstrated a reduction in the yield of H2 with thermal pretreatment—may afford not only unanticipated interfacial chemistry, but also the formation and radiolytic contribution of iron oxides to the chemistry underpinning the formation of H2 in these systems. Given the Department of Energy Standard Canister—proposed for the extended dry storage of ASNF—is predominantly composed of stainless-steel, the potential contribution of stainless-steel and its corrosion layers to radiolytic H2 production should be further investigated. This research was funded by the U.S. Department of Environmental Management, Office of Technology Development, under contract DE-AC07-05ID14517.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2024

Influence of metal ion complexation on the radiolytic longevity of butyramide extractants under direct dissolution conditions

The direct dissolution of volox-treated used nuclear fuel (UNF) into an organic solution—comprised of diluent and specialized extractants—poses a promising alternative to the traditional liquid-liquid solvent extraction approach to reprocessing UNF. However, moving to direct dissolution removes the presence of a concentrated nitric acid aqueous phase, which has been shown to significantly influence the radiolytic longevity of extractants in liquid-liquid solvent extraction flowsheets. With this in mind, and given the limited knowledge of radiation effects under direct dissolution conditions, we present a time-resolved and dose accumulation study on the impact of direct dissolution conditions on the radiolytic longevity of two candidate butyramide extractants—N,N-di-(2-ethylhexyl) butyramide (DEHBA) and N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA)—in pre-equilibrated n-dodecane solvent in the presence and absence of process relevant metal ions, uranium and rhenium. Rhenium, and by extension technetium, extraction had little impact (=10%) on the overall radiolytic stability of these ligands, despite observed increases in chemical kinetic reactivity (>2×) of the corresponding complexes with the n-dodecane radical cation. Uranium-loading on the other hand, significantly improved the lifetime of both ligands (>30%) under gamma irradiation, with a greater stabilization observed for DEHBA over DEHiBA. This draft manuscript has been prepared in fulfillment of NTRD-MRWFD-2024 M3FT-24IN030101115.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2024

Dodecane Radiolysis Yields by Time-Resolved and Steady-State Methods

Liquid organic molecules are present as solvents, complexing ligands, and additives in both used nuclear fuel reprocessing solvent systems and in their subsequent nuclear waste streams. Under these extreme environments, these organic molecules are constantly exposed to ionizing radiation which promotes their radiolysis, forming a variety of short-lived, highly energetic, excited state and radical species.1-4 Here, we demonstrate new experimental results for the steady-state and time-resolved irradiations of dodecane (C12H26), a long chain, liquid, aliphatic hydrocarbon that is the prototypical solvent used for benchtop studies of aqueous-organic solvent extraction systems. When ionizing radiation interacts with neat dodecane, the energy transfer can result in molecular ionization, to give the dodecane radical cation (C12H26+•) and the solvated electron (eS–), and molecular electronic excitation (C12H26*), which rapidly produces transient carbon-centered radical fragments (CxHy•) and hydrogen atoms (H•).1-4 Studies on the initial yields of the ionization and excitation products were performed using time-resolved picosecond electron pulse radiolysis with the use of molecular probes. Using steady-state cobalt-60 gamma irradiations, the suite of products formed by dodecane radiolysis in aerated and deaerated solutions was determined. Then, using iodine as an alkyl radical scavenger, the loss of molecular iodine with dose was quantified, and by correlating with the molecular hydrogen yields of the system, the initial yields of the various carbon-centered radicals were also determined. Finally, the rates of reactions of the C12H26+• and eS– with ligands proposed for use in spent nuclear fuel reprocessing were studied as a function of temperature from 10 – 40 °C.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

DOE OSTI2023

Class-based separations of mixed solid–liquid systems with condensable solvent washing and extraction: The dilemma of pizza box recycling

As primary feedstocks deplete across the world, raw material extraction becomes increasingly expensive. Awareness of the environmental impact of primary extraction has motivated the development of energy- and reagent-efficient methods for material reuse. This work confronts an emblematic challenge of modern recycling: the soiled pizza box. While the fibers constituting corrugated cardboard are generally recyclable, pizza contaminants such as sauces and oils complicate their reuse, resulting in municipal prohibitions on the recycling of used pizza boxes in cardboard recycling streams and a representative of 275 kg/year per US household of food waste that is directed to landfill. This challenge is common to many materials, and engineering strategies must be developed to tackle complex/mixed feedstocks. To address the mixed composition of the pizza box (and similar materials), an environmentally benign, non-toxic organic solvent is applied to remove and fractionate components from mixed materials. The solvent employed in this process, dimethyl ether (DME), is a condensable hygroscopic gas, which facilitates its removal and recovery for reuse. Further, the results of this study indicate that 1) DME is capable of solubilizing and extracting components from soiled cardboard and other materials, (resulting in cardboard drier than new/unused cardboard) facilitating its recycling, and 2) the DME-soluble components of the system phase separate into aqueous and fatty acid/oil fractions (potentially ~27.5 kg/year per US household). Condensable solvent-driven washing and extraction enable the efficient separation of multiple intermediate product streams, suggesting a pathway to enable technology development necessary for achieving clean production in a circular economy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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

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↗

DOE OSTI2021

Milestone 1.2.9: Radiolytic Gas Generation Measurements from Helium Backfilled Samples of AA1100 and AA6061 Coupons

Nearly 18 metric tons of aluminum-clad spent nuclear fuel (ASNF) is safely managed by the U.S. Department of Energy (DOE). These assemblies are currently in interim storage, with the intention of extended storage (>50 years) until final disposal. Strategies for the continued safe storage of this material are under evaluation, of which a key criterion is the extent of molecular hydrogen gas (H2) formation from the radiolysis of hydrated (oxy)hydroxide aluminum corrosion layers arising from in-reactor and wet storage conditions. Radiation-induced H2 formation has the potential to compromise cladding and storage canister integrity, in addition to promoting the formation of unfavorable gaseous environments. Consequently, understanding this radiation-induced phenomenon is essential for the development of predictive modeling capabilities to support technical considerations and the identification of radiation related challenges for the extended storage of ASNF. Here, we report radiolytic H2 yields (G-values, G(H2)) from the gamma irradiation of ‘pristine’ and pre-corroded aluminum coupons in helium (He) environments as a function of alloy composition (AA1100 and AA6061), relative humidity, and absorbed gamma dose. Measured yields were lower than corresponding values reported for argon environments, a positive result for proposed extended dry storage strategies that would employ helium as a backfill gas. Interestingly, the presented G(H2)He values are comparable to those previously measured in nitrogen environments, suggesting a He mediated H2 inhibition process, attributed here to Penning ionization.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗