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At least 19 records

Determining Drying Conditions to Mitigate Hanford Double Shell Storage Tank Underside Corrosion — Phase 1

The Hanford Site in Washington State has legacy radiological waste that is being retrieved from single shell tanks (SSTs) and transferred to newer, double shell tanks (DSTs) for eventual closure of the SSTs. The waste is maintained in the DSTs until eventual immobilization can be performed at the Waste Treatment and Immobilization Plant (WTP), currently under construction. Until full immobilization is complete, extended service of the DSTs must be ensured by mitigating corrosion of the steel tank walls and buried steel pipelines. A Pit Air Supply System has been developed to mitigate corrosion of the leak detection pits connected to the concrete foundations of the DSTs. The objectives for the present study are: (i) to corrode steel specimens in an electrolytic simulant to form artificial pits with specific pit depths, and (ii) to determine the temperature and humidity levels that will mitigate further pit growth. Experimental work and results will be presented to evaluate conditions associated with the PASS system and predict corrosion rates when the PASS is operating.

Atmospheric Corrosion↗

Coupled neutronics, thermochemistry, corrosion modeling and sensitivity analyses for isotopic evolution in molten salt reactors

This study presents a computational methodology for analyzing isotopic evolution and associated uncertainties in molten salt reactors (MSRs), focusing on both fluoride- and chloride-based fuel salts. The primary goal is to enhance the understanding of isotopic behavior in MSRs and provide data to support future experimental efforts. The methodology integrates transport-coupled depletion calculations using OpenMC, equilibrium thermodynamics modeling with Thermochimica, and a corrosion model. Sensitivity analyses are performed to evaluate the impact of power density, air ingress, and humidity content on isotopic evolution in MSR concepts. This study examines representative F- and Cl-based MSR designs, highlighting the dominant influence of power density on isotopic composition, which significantly affects isotope production and depletion rates, accounting for approximately 76% of the observed variance in element concentration. Air ingress and humidity content also affect the redox potential, solubility of heavier elements, and corrosion rates, thereby altering the expected isotopic evolution in the reactor. On average, air ingress accounts for around 17% of the variance in element concentrations, while humidity explains the remaining 7%. These variances differ significantly from element to element, depending on the element’s role in depletion, redox potential evolution, and galvanic corrosion. The findings indicate that power density, air ingress, and humidity content are all critical factors for optimizing reactor design and operational strategies. Furthermore, the study provides expected ranges for key impurities in the fuel salt, which are crucial for guiding future experimental studies and refining MSR designs. Finally, this study demonstrates the importance of modeling depletion coupled with the evolution of redox potential and chemical interactions in MSR fuel salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Deliquescence of eutectic LiCl-KCl diluted with NaCl for interim waste salt storage

Molten eutectic LiCl-KCl salt is a widely used electrolyte for electrorefining uranium from spent nuclear fuel. Due to the hygroscopic nature of this salt, careful handling and storage of solidified waste electrorefiner (ER) salt is required to avoid deliquescence and corrosion of container materials. This study investigated a potential processing path for reducing the deliquescence through dilution with NaCl. The hydration behavior of LiCl-KCl salts diluted with NaCl was evaluated in terms of mass gain due to mass of water absorption, visual evidence of deliquescence, and visual evidence of corrosion to stainless steel containers in a humid air environment. Pure eutectic LiCl-KCl exhibited a 50 mass% increase due to water absorption and showed signs of deliquescence after 24 hours. 89 mass% NaCl was required in order to prevent deliquescence. Dilution with 89% NaCl was also found to protect corrosion to stainless steel crucibles. Corrosion, thus, appears to require deliquescence. While NaCl dilution greatly decreases steady state hydration and eliminated deliquescence, storage volume is increased ~10x.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mechanistic modeling of copper corrosions in data center environments

Air-side economizers are increasingly used to take advantage of “free-cooling” in data centers with the intent of reducing the carbon footprint of buildings. However, they can introduce outdoor pollutants to indoor environment of data centers and cause corrosion damage to the information technology equipment. Here, to evaluate the reliability of information technology equipment under various thermal and air-pollution conditions, a mechanistic model based on multi-ion transport and chemical reactions was developed. The model was used to predict Cu corrosion caused by Cl2-containing pollutant mixtures. It also accounted for the effects of temperature (25 °C and 28 °C), relative humidity (50%, 75%, and 95%), and synergism. It also identified higher air temperature as a corrosion barrier and higher relative humidity as a corrosion accelerator, which agreed well with the experimental results. The average root mean square error of the prediction was 13.7 Å. The model can be used to evaluate the thermal guideline for data centers design and operation when Cl2 is present based on pre-established acceptable risk of corrosion in data centers’ environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deliquescence of Eutectic LiCl-KCl Diluted with NaCl for Interim Waste Salt Storage

Molten eutectic LiCl-KCl salt is a widely used electrolyte for electrorefining uranium from spent nuclear fuel. Due to the hygroscopic nature of this salt, such operations must be performed under controlled atmospheric conditions, and waste salts require careful storage to avoid deliquescence and corrosion of container materials. This study investigated a potential processing path for reducing the degree of deliquescence through dilution to varying extents with NaCl. Here, the hydration behavior of LiCl-KCl salts diluted with NaCl was evaluated in terms of mass gain due to water absorption, degree of deliquescence (including first appearances of standing water), and evidence of corrosion to stainless steel containers in a humid air environment (40°C, 20% relative humidity). In this humid air environment, pure eutectic LiCl-KCl exhibited a 50 mass % increase due to water absorption and showed evidence of standing water after 24 h. Waste salt diluted with NaCl required loadings of 89 mass % NaCl in order to prevent deliquescence and exhibited a 3 mass % increase due to water absorption. After periodic observation for 48 h, standing water was observed near all ingots with the exception of the 89 mass % NaCl samples. Dilution with 89% NaCl was also found to reduce evidence of corrosion when stored in stainless steel crucibles. While dilution with NaCl greatly decreases steady-state hydration, the storage volume is increased ~10× through this procedure.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electrochemical Measurement of Atmospheric Corrosion

Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

DeArmond, Anna H.↗

The effect of heat treatment and test parameters on the aqueous stress corrosion cracking of D6AC steel

The crack growth behavior of D6AC steel as a function of stress intensity, stress and corrosion history and test technique, under sustained load in natural seawater, 3.3 percent NaCl solution, distilled water, and high humidity air was investigated. Reported investigations of D6AC were considered with emphasis on thermal treatment, specimen configuration, fracture toughness, crack-growth rates, initiation period, threshold, and the extension of corrosion fatigue data to sustained load conditions. Stress history effects were found to be most important in that they controlled incubation period, initial crack growth rates, and apparent threshold.

Gilbreath, W. P.↗

NARAC Meteorological Monitoring Tower Maintenance Report: Submarine Base Group Two, Sub Base New London NEWLBASE2 Tower

Comments: The roof-based tower is located on Building 17 on Naval Submarine Base New London. Tower installation date is unknown. A second GFCI outlet in-line with the standard GFCI in the logger enclosure is mounted on conduit out of the tower base pedestal. The roof surface has been replaced and is now safe to walk on. The tower was not climbed during this maintenance visit. After the maintenance visit in 2018, the tower was deemed unsafe to climb due to age, corrosion, and deterioration of the tower components. The wind, air temperature, and relative humidity sensors located on the upper part of the tower require climbing of the tower for servicing and could not be accessed for inspection and maintenance. The tower is scheduled for replacement in FY2023. Tasks to be Completed: Tower system replacement / relocation. Consider replacement or bypassing of the suspect precipitation gauge signal connector.

99 GENERAL AND MISCELLANEOUS↗

Life-Prediction Parameters of Sapphire Determined for the Design of a Space Station Combustion Facility Window

To characterize the stress corrosion parameters and predict the life of a sapphire window being considered for use in the International Space Station's Fluids and Combustion Facility, researchers at the NASA Glenn Research Center conducted stress corrosion tests, fracture toughness tests, and reliability analyses, as shown in the figures. Standardized test methods, developed and updated by the author under the auspices of American Society for Testing and Materials, were employed. One interesting finding is that sapphire exhibits a susceptibility to stress corrosion in water similar to that of glass. In addition to generating the stress corrosion parameters and fracture toughness data, closed-form expressions for the variances of the crack growth parameters were derived. The expressions allow confidence bands to be easily placed on life predictions of ceramic components. Brittle materials such as sapphire and quartz are required for windows in a variety of applications such as the Fluids and Combustion Facility. To minimize the launch weight of such facilities, researchers must design the windows to be as lightweight as possible. The safe use of lightweight, brittle windows in structural applications is limited by two factors: low fracture toughness and slow crack growth, or stress corrosion. Stress corrosion of these and other optical materials can occur in relatively common environments, such as humid air. Access to the data has been requested by designers for use in the life prediction of a Northrop Grumman F16 instrument window and a Jet Propulsion Laboratory instrument window. One Space Act Agreement has been formed. Future work includes the measurement of the life of subscale windows.

Salem, Jonathan A.↗

Milestone 1.2.13: Preliminary Measurements of Radiolytic Nitric Acid Formation to Support Predictive Model Validation

Predictive computational models have been developed to support the technical basis for extended dry storage of aluminum-clad spent nuclear fuel (ASNF) in helium-backfilled cannisters. To date, these models have been optimized on a variety of irradiation experiments designed to elucidate the radiation-induced formation of molecular hydrogen gas, a radiolysis product that is potentially problematic for the safe storage of ASNF. However, the yield of nitric acid (HNO3) has not been determined, despite conservative predictions of its formation (300–4000 ppm) in 1% residual air environments irradiated in contact with ASNF. HNO3, another problematic radiolysis product, can lead to enhanced corrosion and potentially compromise storage canister integrity. Thus, to support the validation of predictive computer models, we report the measurement and quantification of HNO3 from the gamma irradiation of aluminum alloy coupons in humid air.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

An experimental study on dehumidification and regeneration performance of a new nonporous membrane-based heat and mass exchanger using an ionic liquid desiccant

As a promising alternative to inefficient vapor-compression-based air conditioning, liquid desiccant dehumidification uses a liquid desiccant in contact with the humid air absorbing the moisture. However, it has not gained much market share due to the issues related to the carryover, corrosion, fouling, and crystallization of liquid desiccant. The research has developed a new membrane-based exchanger, which uses a non-corrosive ionic liquid desiccant and nonporous tubular membranes to address these issues. As the second generation of the prototype, the new exchanger was tested at various operating conditions. According to the experimental data, when it is used in the dehumidification loop, the new membrane-based exchanger achieves a specific vapor transportation rate of 778.6 g/(h–m 2 ) and an average water vapor flux of 0.316 g/(h-m 2 -Pa), which is a significant improvement compared with the previous designs using nonporous membranes. It also achieved a comparable or even better dehumidification performance compared with the dehumidifiers that use porous membrane and conventional liquid desiccants. However, the regeneration performance is not as good as its dehumidification. It is mainly caused by the high operating temperature required in the regeneration loop. The experimental data and findings provide first-hand experimental data and enhance the understanding of advanced membrane-based ionic liquid desiccant systems.

42 ENGINEERING↗

Characterization of Cracking and Crack Growth Properties of the C5A Aircraft Tie-Box Forging

Detailed destructive examinations were conducted to characterize the integrity and material properties of two aluminum alloy (7075-T6) horizontal stabilizer tie box forgings removed.from US. Air Force C5A and C5B transport aircraft. The C5B tie box forging was,found to contain no evidence of cracking. Thirteen cracks were found in the CSA,forging. All but one of the cracks observed in the C5A component were located along the top cap region (one crack was located in the bottom cap region). The cracks in the C5A component initiated at fastener holes and propagated along a highly tunneled intergranular crack path. The tunneled crack growth configuration is a likelv result of surface compressive stress produced during peening of the .forging suijace. The tie box forging ,fatigue crack growth, fracture and stress corrosion cracking (SCC) properties were characterized. Reported herein are the results of laboratory air ,fatigue crack growth tests and 95% relative humidity SCC tests conducted using specimens machined from the C5A ,forging. SCC test results revealed that the C5A ,forging material was susceptible to intergranular environmental assisted cracking: the C5A forging material exhibited a SCC crack-tip stress-intensity factor threshold of less than 6 MPadn. Fracture toughness tests revealed that the C5A forging material exhibited a fracture toughness that was 25% less than the C5B forging. The C5A forging exhibited rapid laboratory air fatigue crack growth rates having a threshold crack-tip stress-intensity factor range of less than 0.8 MPa sup m. Detailed fractographic examinations revealed that the ,fatigue crack intergranular growth crack path was similar to the cracking observed in the C5A tie box forging. Because both fatigue crack propagation and SCC exhibit similar intergranular crack path behavior, the damage mechanism resulting in multi-site cracking of tie box forgings cannot be determined unless local cyclic stresses can be quantified.

Piascik, Robert S.↗

Review and Summary of Corrosion Behavior for Aluminum-Clad Spent Nuclear Fuel in Dry Storage

A description of the corrosion behavior of aluminum alloys used for cladding on aluminum-based, aluminum-clad nuclear fuel used in research reactors under potential dry storage conditions has been compiled. An evaluation is made of potential additional corrosion with water postulated to not be removed during drying. The relative humidity (RH) produced by typical dryness criteria for industrial spent nuclear fuel drying is expected to be low, particularly at high temperatures (17% RH at 20°C and lower at higher temperatures). Existing corrosion data suggests that negligible vapor-phase corrosion of aluminum is expected at such low humidity, even for nominally bare aluminum surfaces. That is, the predicted relative humidity from free water (e.g., 17% RH) is below the “critical” relative humidity (~40% RH at room temperature), below which no significant corrosion is observed for bare aluminum. Furthermore, reported room-temperature corrosion rates are very low even under saturated (100% RH) water vapor. Existing results showing significant vapor-phase corrosion corresponded specifically to conditions of high temper ed with high relative humidity. A relatively large reservoir of (chemically bound) water exists in the aluminum (oxy)hydroxide films on the SNF cladding surface. The estimated total could saturate the gas even at relatively high temperature if fully released; however, its release as molecular water is expected to only be plausible if the temperature during storage exceeds both the drying temperature and the threshold for thermal decomposition of the trihydroxides (~220°C). Therefore, the combination of high temperature and high relative humidity that could drive significant corrosion is considered implausible during sealed dry storage following an appropriate drying process, to include >220°C drying for canisters that may approach or exceed this temperature during storage. Vapor-phase testing of aluminum samples with an adherent (oxy)hydroxide layer, prepared in liquid water to resemble those on actual aluminum-clad spent nuclear fuel (ASNF), did not observe evidence of additional corrosion even at combined high-temperature (up to 180°C) and high-humidity (up to 100% RH) conditions. Instead, small net mass losses were observed for most specimens and attributed to dehydration of the samples, which had been air-dried only prior to testing. ASNF being moved to dry storage is expected to have an existing (oxy)hydroxide film, suggesting that the cladding will be less prone to additional corrosion than bare aluminum metal. If significant corrosion did occur during sealed storage, the overall extent and impact is expected to be small. Corrosion post-closure of a canister would not alter the total amount of hydrogen in the canister, so it would have no effect on the maximum H 2 release already assessed in existing bounding calculations. In addition, the total amount of water in a 25-µm dense bayerite film would consume a only ~8 µm additional aluminum metal on average, if fully consumed by oxidizing aluminum metal to Al 2 O 3 . These conclusions are consistent with ASNF-in-canister simulations to date, which included a reaction pathway for corrosion using kinetics from previous literature and believed to be conservative and predicted very low rates of corrosion.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Revealing the growth kinetics of atmospheric corrosion pitting in aluminum via in situ microtomography

Abstract Understanding the mechanistic relationship between the environment, microstructure, and local kinetics of atmospheric corrosion damage remains a central challenge. To address this challenge, this study used laboratory-based X-ray tomography to directly observe attack in-operando over an extended period, enabling insights into the evolving growth kinetics and morphology of individual pits over months of exposure. Damage progression associated with nine pits in a 99.9% pure aluminum wire exposed to chloride salts in humid air was characterized. Most pits grew at a nominally linear rate up until pit death, which occurred within 12–24 h of nucleation. Exceptions to this were observed, with three pits exhibiting bimodal growth kinetics and growing for 40 or more hours. This was explained by secondary droplets that formed near the pits, increasing the cathode area. A corrosion-driven drying mechanism likely contributed to pit death in both cases. Pits first grew into the material followed by lateral expansion.

36 MATERIALS SCIENCE↗

Falling-film thermosyphons: Application to water harvesting from humid gas streams

Water harvesting from humid gas streams is central to fresh-water production, desalination, and particulate removal from combustion gas streams. Two-phase thermosyphons are well suited for these applications due to their very low thermal resistance, but have several operating limits at the high heat flows required for such applications. This work introduces the falling-film thermosyphon for large-scale condensation applications. Working fluid is pumped to the top of the evaporator to provide the evaporating liquid film on the inner tube wall, rather than by vapor condensation. The flooding, dry-out and pool-boiling limits are eliminated, resulting in significantly higher maximum heat fluxes for the same physical evaporator size. Furthermore, the condenser no longer needs to be located vertically above the evaporator, which allows for a standard steam condenser to be used. A model for the condensation process in humid air was developed that estimates the fluid and heat transfer and is confirmed experimentally. Further benefits include the use of a high-thermal-conductivity polymer material for the evaporator section to minimize corrosion, and the ability to impose a temperature boundary condition on the evaporator, which is made possible due to the elimination of a liquid pool.

42 ENGINEERING↗

Probing the hydrolytic degradation of UF 4 in humid air

This manuscript describes the chemical transformations that occur during hydrolysis of uranium tetrafluoride (UF 4 ) due to its storage in humid air (85% and 50% relative humidity) at ambient temperatures. This hydrolysis was previously reported to proceed slowly or not at all (depending on the percent relative humidity); however, previous reports relied primarily on X-ray diffraction methods to probe uranium speciation. Here, we employ a battery of physiochemical probing techniques to explore potential hydrolysis, including Raman spectroscopy, powder X-ray diffraction, 19 F nuclear magnetic resonance spectroscopy, scanning electron microscopy, and focused ion beam microscopy with energy-dispersive X-ray spectroscopy. Of these, only Raman spectroscopy proved to be particularly useful at observing chemical changes to UF 4 . It was found that anhydrous UF 4 slightly oxidizes over the course of thirteen days to Schoepite-like uranium complexes and possibly UO 3 . In contrast, UF 4 exposed to 50% relative humidity slightly decomposes into UO 2 F 2 , Schoepite-like uranium complexes, and possibly a high order uranium oxide that eluded chemical assignment (U x O y ). Despite the rich chemical speciation observed in our Raman spectroscopy measurements, X-ray diffraction and 19 F NMR measurements on the same material showed no changes. Microscopy measurements suggest that the observed reactions between UF 4 and water occur primarily on the surface of UF 4 particulates via a method that is visually similar to surface corrosion of metals. Therefore, we postulate that NMR spectroscopy and X-ray diffraction, which are well-suited for bulk analysis, are less suited than Raman spectroscopy to observe the surface-based reactions that occur to UF 4 when exposed to humid air. Considering the importance of UF 4 in the production of nuclear fuel and weapons, the results presented herein are widely applicable to numerous nuclear science fields where uranium detection and speciation in humid environments is of value, including nuclear nonproliferation and nuclear forensics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiation-induced molecular hydrogen gas generation in the presence of aluminum alloy 1100

The United States government currently manages nearly 13 metric tons of aluminum-clad spent nuclear fuel (SNF) without a long-term storage solution, so a fundamental understanding of corrosion processes occurring on aluminum alloy surfaces is of utmost importance to plan for extended (>50 years) interim dry storage of aluminum-clad SNF. While thermal and chemical corrosion processes are well characterized for aluminum, radiation effects are not. To help understand the impacts of radiation on aluminum-clad SNF, here the radiation-induced molecular hydrogen gas (H 2 ) generation from pristine and pre-corroded aluminum alloy 1100 (Al-1100) coupons have been studied. Corrosion of coupons was achieved by submerging coupons in water at 95 °C for 29 days, yielding a ~5 μm boehmite/bayerite oxide film. Pre-corroded coupons were exposed to cobalt-60 gamma radiation to absorbed doses of up to 1.0 MGy under a variety of conditions: cover-gas composition (argon, nitrogen, or air), relative humidity (0, 50, and 100%), and temperature (ambient, 100, and 200 °C). Post-irradiation measurements demonstrated that the yield of H 2 was directly attributable to the presence of the Al-1100 coupons and their physisorbed water with dependence on absorbed gamma dose, relative humidity, and cover-gas composition. No H 2 was quantified in the presence of air, while both nitrogen and argon environments afforded higher H 2 yields with increasing relative humidities. This was attributed to the greater availability of adsorbed water for radiolytic processes. Irradiation of pre-corroded Al-1100 coupons at different temperatures under 0% relative humidity argon conditions yielded statistically equivalent H 2 yields for ambient temperatures and 100 °C. However, irradiation at 200 °C promoted a 3 to 4-fold increase in the yield of H 2 , possibly due to the transformation of bayerite to boehmite and/or improved efficiency of H • and H 2 release from oxide surfaces.

36 MATERIALS SCIENCE↗