This progress report describes work being done at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of spent nuclear fuel (SNF). Of particular concern is stress corrosion cracking (SCC), by which a through-wall crack could potentially form in a canister outer wall over time intervals that are shorter than possible dry storage times. In order for SCC to occur, three criteria must be met. A corrosive environment must be present on the canister surface, the metal must susceptible to SCC, and sufficient tensile stress to support SCC must be present through the entire thickness of the canister wall. SNL is currently evaluating the potential for each of these criteria to be met.
This report documents the mockup specifications and manufacturing processes; the initial cutting of the mockup into three cylindrical pieces for testing and the measured strain changes that occurred during the cutting process; and the planned weld residual stress characterization activities and the status of those activities.
Long-term corrosion experiments have been performed on Alloy 22 (UNS N06022), in a series of heated brines formulated to represent evaporatively concentrated ground water, to evaluate the long-term corrosion performance of the material. These solutions included 0.5 M NaCl, in addition to two simulated concentrated ground water solutions. Under conditions where Alloy 22 was anticipated to be passive, the corrosion rate was found to be vanishingly small (i.e., below the resolution of the weight-loss technique used to quantify corrosion in this study). However, under low pH conditions where Alloy 22 was anticipated to be active, or more specifically, where the chromium oxide passive film was not thermodynamically stable, the corrosion rate was appreciable. Furthermore, under such conditions the corrosion rate was observed to be a strong function of temperature, with an activation energy of 72.9±1.8 kJ/mol. Time of Flight-Secondary Ion Mass Spectroscopy analysis of the oxide layer revealed that, while sulfur was present within the oxide for all test conditions, no accumulation was observed at or near the metal/oxide interface. These observations confirm that inhibition of passive film formation via sulfur accumulation does not occur during the corrosion of Alloy 22.
This progress report describes work being done at Sandia national Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of used nuclear fuel. The work involves both characterization of the potential physical and chemical environment on the surface of the storage canisters and how it might evolve through time, and testing to evaluate performance of the canister materials under anticipated storage conditions.
In July, 2014, the Electric Power Research Institute and industry partners sampled dust on the surface of an unused canister that had been stored in an overpack at the Hope Creek Nuclear Generating Station for approximately one year. The foreign material exclusion (FME) cover that had been on the top of the canister during storage, and a second recently-removed FME cover, were also sampled. This report summarizes the results of analyses of dust samples collected from the unused Hope Creek canister and the FME covers. Both wet and dry samples of the dust/salts were collected, using SaltSmart(TM) sensors and Scotch-Brite(TM) abrasive pads, respectively. The SaltSmart(TM) samples were leached and the leachate analyzed chemically to determine the composition and surface load per unit area of soluble salts present on the canister surface. The dry pad samples were analyzed by X-ray fluorescence and by scanning electron microscopy to determine dust texture and mineralogy; and by leaching and chemical analysis to deter mine soluble salt compositions. The analyses showed that the dominant particles on the canister surface were stainless steel particles, generated during manufacturing of the canister. Sparse environmentally - derived silicates and aluminosilicates were also present. Salt phases were sparse, and consisted of mostly of sulfates with rare nitrates and chlorides. On the FME covers, the dusts were mostly silicates/aluminosilicates; the soluble salts were consistent with those on the canister surface, and were dominantly sulfates. It should be noted that the FME covers were w ashed by rain prior to sampling, which had an unknown effect of the measured salt loads and compositions. Sulfate salts dominated the assemblages on the canister and FME surfaces, and included Ca-SO4 , but also Na-SO4, K-SO4, and Na-Al-SO4. It is likely that these salts were formed by particle - gas conversion reactions, either prior to, or after, deposition. These reactions involve reaction of carbonate, chloride, or nitrate salts with at mospheric SO2, sulfuric acid, or a mmonium sulfate to form sulfate minerals. The Na-Al-SO4 phase is unusual, and may have formed by reaction of Na-Al containing phases in aluminum smelter emissions with SO2 , also present in smelter emissions. An aluminum smelter is located in Camden, NJ, 40 miles NE of the Hope Creek Site.
This progress report describes work being done at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of used nuclear fuel. The work involves both characterization of the potential physical and chemical environment on the surface of the storage canisters and how it might evolve through time, and testing to evaluate performance of the canister materials under anticipated storage conditions. To evaluate the potential environment on the surface of the canisters, SNL is working with the Electric Power Research Institute (EPRI) to collect and analyze dust samples from the surface of in-service SNF storage canisters. In FY 13, SNL analyzed samples from the Calvert Cliffs Independent Spent Fuel Storage Installation (ISFSI); here, results are presented for samples collected from two additional near-marine ISFSI sites, Hope Creek NJ, and Diablo Canyon CA. The Hope Creek site is located on the shores of the Delaware River within the tidal zone; the water is brackish and wave action is normally minor. The Diablo Canyon site is located on a rocky Pacific Ocean shoreline with breaking waves. Two types of samples were collected: SaltSmart™ samples, which leach the soluble salts from a known surface area of the canister, and dry pad samples, which collected a surface salt and dust using a swipe method with a mildly abrasive ScotchBrite™ pad. The dry samples were used to characterize the mineralogy and texture of the soluble and insoluble components in the dust via microanalytical techniques, including mapping X-ray Fluorescence spectroscopy and Scanning Electron Microscopy. For both Hope Creek and Diablo Canyon canisters, dust loadings were much higher on the flat upper surfaces of the canisters than on the vertical sides. Maximum dust sizes collected at both sites were slightly larger than 20 μm, but Phragmites grass seeds ~1 mm in size, were observed on the tops of the Hope Creek canisters. At both sites, the surface dust could be divided into fractions generated by manufacturing processes and by natural processes. The fraction from manufacturing processes consisted of variably-oxidized angular and spherical particles of stainless steel and iron, generated by machining and welding/cutting processes, respectively. Dust from natural sources consisted largely of detrital quartz and aluminosilicates (feldspars and clays) at both sites. At Hope Creek, soluble salts were dominated by sulfates and nitrates, mostly of calcium. Chloride was a trace component and the only chloride mineral observed by SEM was NaCl. Chloride surface loads measured by the Saltsmart™ sensors were very low, less than 60 mg m–2 on the canister top, and less than 10 mg m–2 on the canister sides. At Diablo Canyon, sea-salt aggregates of NaCl and Mg-SO4, with minor K and Ca, were abundant in the dust, in some cases dominating the observed dust assemblage. Measured Saltsmart™ chloride surface loads were very low (<5 mg m–2); however, high canister surface temperatures damaged the Saltsmart™ sensors, and, in view of the SEM observations of abundant sea-salts on the package surfaces, the measured surface loads may not be valid. Moreover, the more heavily-loaded canister tops at Diablo Canyon were not sampled with the Saltsmart™ sensors. The observed low surface loads do not preclude chloride-induced stress corrosion cracking (CISCC) at either site, because (1) the measured data may not be valid for the Diablo Canyon canisters; (2) the surface coverage was not complete (for instance, the 45º offset between the outlet and inlet vents means that near-inlet areas, likely to have heavier dust and salt loads, were not sampled); and (3) CISCC has been experimentally been observed at salt loads as low as 5-8 mg/m2. Experimental efforts at SNL to assess corrosion of interim storage canister materials include three tasks in FY14. First, a full-diameter canister mockup, made using materials and techniques identical to those used to make interim storage canisters, was designed and ordered from Ranor Inc., a cask vendor for Areva/TN. The mockup will be delivered prior to the end of FY14, and will be used for evaluating weld residual stresses and degrees of sensitization for typical interim storage canister welds. Following weld characterization, the mockup will be sectioned and provided to participating organizations for corrosion testing purposes. A test plan is being developed for these efforts. In a second task, experimental work was carried out to evaluate crevice corrosion of 304SS in the presence of limited reactants, as would be present on a dustcovered storage canister. This work tests the theory that limited salt loads will limit corrosion penetration over time, and is a continuation of work carried out in FY13. Laser confocal microscopy was utilized to assess the volume and depth of corrosion pits formed during the crevice corrosion tests. Results indicate that for the duration of the current experiments (100 days), no stifling of corrosion occurred due to limitations in the amount of reactants present at three different salt loadings. Finally, work has been carried out this year perfecting an instrument for depositing sea-salts onto metal surfaces for atmospheric corrosion testing purposes. The system uses an X-Y plotter system with a commercial airbrush, and deposition is monitored with a quartz crystal microbalance. The system is capable of depositing very even salt loadings, even at very low total deposition rates.
This document identifies materials and material mitigation processes that might be used in new designs for standardized canisters for storage, transportation, and disposal of spent nuclear fuel. It also addresses potential corrosion issues with existing dual-purpose canisters (DPCs) that could be addressed in new canister designs. The major potential corrosion risk during storage is stress corrosion cracking of the weld regions on the 304 SS/316 SS canister shell due to deliquescence of chloride salts on the surface. Two approaches are proposed to alleviate this potential risk. First, the existing canister materials (304 and 316 SS) could be used, but the welds mitigated to relieve residual stresses and/or sensitization. Alternatively, more corrosion-resistant steels such as super-austenitic or duplex stainless steels, could be used. Experimental testing is needed to verify that these alternatives would successfully reduce the risk of stress corrosion cracking during fuel storage. For disposal in a geologic repository, the canister will be enclosed in a corrosion-resistant or corrosion-allowance overpack that will provide barrier capability and mechanical strength. The canister shell will no longer have a barrier function and its containment integrity can be ignored. The basket and neutron absorbers within the canister have the important role of limiting the possibility of post-closure criticality. The time period for corrosion is much longer in the post-closure period, and one major unanswered question is whether the basket materials will corrode slowly enough to maintain structural integrity for at least 10,000 years. Whereas there is extensive literature on stainless steels, this evaluation recommends testing of 304 and 316 SS, and more corrosion-resistant steels such as super-austenitic, duplex, and super-duplex stainless steels, at repository-relevant physical and chemical conditions. Both general and localized corrosion testing methods would be used to establish corrosion rates and component lifetimes. Finally, it is unlikely that the aluminum-based neutron absorber materials that are commonly used in existing DPCs would survive for 10,000 years in disposal environments, because the aluminum will act as a sacrificial anode for the steel. We recommend additional testing of borated and Gd-bearing stainless steels, to establish general and localized corrosion resistance in repository-relevant environmental conditions.
This progress report describes work being done at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of used nuclear fuel. The work involves both characterization of the potential physical and chemical environment on the surface of the storage canisters and how it might evolve through time, and testing to evaluate performance of the canister materials under anticipated storage conditions.
Potentially corrosive environments may form on the surface of spent nuclear fuel dry storage canisters by deliquescence of deposited dusts. To assess this, samples of dust were collected from in-service dry storage canisters at two near-marine sites, the Hope Creek and Diablo Canyon storage installations, and have been characterized with respect to mineralogy, chemistry, and texture. At both sites, terrestrially-derived silicate minerals, including quartz, feldspars, micas, and clays, comprise the largest fraction of the dust. Also significant at both sites were particles of iron and iron-chromium metal and oxides generated by the manufacturing process. Soluble salt phases were minor component of the Hope Creek dusts, and were compositionally similar to inland salt aerosols, rich in calcium, sulfate, and nitrate. At Diablo Canyon, however, sea-salt aerosols, occurring as aggregates of NaCl and Mg-sulfate, were a major component of the dust samples. The seasalt aerosols commonly occurred as hollow spheres, which may have formed by evaporation of suspended aerosol seawater droplets, possibly while rising through the heated annulus between the canister and the overpack. The differences in salt composition and abundance for the two sites are attributed to differences in proximity to the open ocean and wave action. The Diablo Canyon facility is on the shores of the Pacific Ocean, while the Hope Creek facility is on the shores of the Delaware River, several miles from the open ocean.
A primary concern with dry storage of spent nuclear fuel is chloride-induced stress corrosion cracking, caused by deliquescence of salts deposited on the stainless steel canisters. However, limited access through the ventilated overpacks and high surface radiation fields impede direct examination of cask surfaces for CISCC, or sampling of surface deposits. Predictive models for CISCC must be able to predict the occurrence of a corrosive chemical environment (a chloride-rich brine formed by dust deliquescence) at specific locations (e.g. weld zones) on the canister surface. The presence of a deliquescent brine is controlled by the relative humidity (RH), which is a function of absolute humidity and cask surface temperature. This requires a thermal model that includes the canister and overpack design, canister-specific waste heat load, and passive cooling by ventilation. Brine compositions vary with initially-deposited salt assemblage, reactions with atmospheric gases, temperature, and the relative rates of salt deposition and reaction; predicting brine composition requires site-specific compositional data for atmospheric aerosols and acid gases. Aerosol particle transport through the overpack and deposition onto the canister must also be assessed. Initial field data show complex variability in the amount and composition of deposited salts as a function of canister surface location.
For the interim storage of used nuclear fuel, the storage casks/containers will be exposed to conditions under which considerable dust and/or atmospheric aerosols may be deposited on the surface. These dust layers may contain a sizeable portion of water soluble salts, particularly in marine environments where many interim storage systems are located. These soluble salts will deliquesce if sufficient moisture is present, resulting in the formation of potentially corrosive brine on the material surface. Experimental results have illustrated that some stainless steels, such as 304SS (a common material of construction for interim storage containers) can and will undergo localized corrosion in elevated temperature conditions where a chloride rich brine has formed on the surface. Results presented here illustrate that it is possible that stifling of localized attack will result when limited reactant is present, but additional analysis is necessary before a definite conclusion can be made.
Once sufficiently cool, spent nuclear fuel is stored in dry storage cask systems, most commonly consisting of welded stainless steel containers enclosed in ventilated concrete or steel overpacks. As the United States does not currently have a viable disposal pathway for SNF, these containers may be required to perform their waste isolation function for many decades beyond their original design criteria. Failure by stress corrosion cracking due to deliquescence of deposited salt aerosols is a major concern. Parameters controlling deliquescence include the temperature and RH at the waste package surface, and the composition of deposited salts. The timing and duration of deliquescence under in situ conditions is poorly defined, because of uncertainties in thermal history, the large variability in temperatures over the storage container surface, and uncertainties in the composition of deposited salts. Storage installations in near-marine environments are of greatest concern because of exposure to significant quantities of chloride-rich sea salt aerosols. Published stainless steel corrosion studies with sea salt and sea salt components suggest that conditions conducive to localized corrosion initiation and propagation may exist on the surface of SNF storage containers in such environments at some point in their extended service life, and furthermore, that stress corrosion cracking may occur over a broad range of potentially relevant conditions. However, the studies were carried out with heavy salt loads and limited gas flow, which may limit the beneficial effects of brine/atmosphere exchange (e.g., acid degassing, CO2 exchange, degassing and thermal decomposition of ammonium phases). Gas exchange with the atmosphere will modify brine pH and chloride content, and will modify the deliquescent salt assemblage through precipitation of Ca and Mg carbonates, potentially limiting brine volumes or resulting in dryout. Nitrate-rich inland salt aerosols are considered less corrosive, but may have higher levels of potentially reactive pollutants. Moreover, the compositions of inland salt deposits on hot storage containers may have greater uncertainty, as ammonium- and nitrate-rich salt assemblages are subject to thermal decomposition and potential reactions with organics. For both inland and near-marine sites, little information is available on the dust/salt deposition rates, or the quantity of salt present on existing storage container surfaces. A sampling program for in situ dust deposits on current storage containers will provide critical compositional data for new stress corrosion cracking studies, and will allow evaluation of the applicability of existing studies of stainless steel stress corrosion cracking under conditions of dust deliquescence.