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At least 271 records · Page 15

Corrosion of Candidate Materials in Molten FLiBe Salt for Fluoride-Salt-Cooled High-Temperature Reactor (FHR)

Molten fluoride salts have attracted considerable attention because of their desirable thermophysical properties that lead to superior heat transfer. Recently, fluoride salts are being considered as coolants in the fluoride salt-cooled high temperature reactors (FHRs). The successes of the molten salt reactor experiment (MSRE) program in 1950's-70's at Oak Ridge National Laboratory (ORNL) has also driven the pursuit of molten salt nuclear reactor as one of the lead next generation nuclear reactor concepts. Unlike MSRE where the uranium fuel was dissolved in the molten fluoride salt, the FHR concept is expected to use molten salt (2LiF-BeF{sub 2}, FLiBe) only as coolant in conjunction with solid TRISO fuel particles immersed in the molten salt. One of the important challenges in FHR development is corrosion of structural materials in high-temperature molten 2LiF-BeF{sub 2} (FLiBe) salt. Currently, 316 stainless steel (nominal composition: Fe-12Ni-17Cr-2.5Mo-1Si-2Mn-0.03C) and Hastelloy N (nominal composition: Ni-7Cr-16Mo-5Fe-1Si-0.8Mn) are deemed as promising candidate alloys for the construction of some of the structural components of FHR. 316 stainless steel is ASME code certified for high temperatures (up to 760 deg. C) applications. Hastelloy N has been shown to have outstanding corrosion resistance in molten FLiBe but present code certification data limit the use of this alloy to only about 704 deg. C. Modifications of Hastelloy N with higher creep strength are presently being developed at ORNL. Other materials such graphite, SiC/SiCf and C/Cf composites, are also considered for structural applications in the FHR. The presence of these multiple materials in a molten FLiBe salt medium can further exacerbate and complicate corrosion effects. Therefore, it is necessary to understand the corrosion behavior of these materials in molten FLiBe salt. The corrosion behavior of Hastelloy N, 316 stainless steel, and CVD SiC and two types of SiC-SiC{sub f} composites have been tested in molten FLiBe salt at 700 deg. C. When tested in metal-lined crucibles both Hastelloy N and 316 stainless steel showed very good corrosion resistance. Samples tested in graphite crucibles showed greater propensity for corrosion and carburization was observed in the near surface regions of the alloys. CVD SiC showed outstanding corrosion resistance. However, the two SiC-SiC{sub f} composites exhibited corrosion attack implying that the manufacturing process may play a role in the corrosion of these composites. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Investigation of Corrosion Behavior of Ti/TiN Multilayers on Al7075 Deposited by High-Vacuum Magnetron Sputtering in 3.5% NaCl Solution

Although Al 7075 has many favorable mechanical properties such as the large strength-to-weight ratio, the relatively poor corrosion resistance has restricted industrial applications. In this work, Ti/TiN as hard multilayered and nanostructured coatings are deposited on the relatively soft Al 7075 structure by high-vacuum radio-frequency magnetron sputtering and the phase, structure, and morphology are investigated in details. The corrosion behavior is evaluated by electrochemical impedance spectroscopy in 3.5% NaCl at a pH of 7.5 for 1, 6, 12, 24, 36, 48, 60, and 72 h. At time points of 1, 6, 12, and 24 h, primary oxide layers and double layers are formed, but the corrosive medium penetrates the primary titanium nitride columnar structure. At longer time points of 24, 36, 48, 60, and 72 h, formation of stronger oxide and double layers leads to better corrosion resistance which is 14.8 times better than that observed from the uncoated substrate after immersion for 36 h. According to R{sub ct}, the corrosion resistances of the short and long immersion groups are 808.5-1984 and 808.5-1248 kΩ cm{sup 2}, respectively, thereby confirming the effectiveness of the Ti/TiN coating against corrosion in comparison with the corrosion resistance of 84.3 kΩ cm{sup 2} observed from the uncoated Al 7075. The smallest corrosion resistance of 808.5 kΩ cm{sup 2} observed at the time point of 24 h is 9.6 times that of the uncoated substrate. Graphical Abstract: A 1.4-µm-thick Ti/TiN hard nanostructured coating comprising six layers is deposited on the relatively soft Al 7075 substrate by high-vacuum radio-frequency magnetron sputtering at 100 °C. The first layer of the intermediate Ti layer cannot improve the corrosion resistance of the TiN super hard coating with a columnar structure. The second and third intermediate Ti layers play an important role in improving the corrosion resistance of Al 7075 by obstructing defects and coating damage from aggressive Cl{sup −} ions and penetration of water. The mechanism involves self-healing of defects by oxide formation and Warburg resistance by diffusion control. .

36 MATERIALS SCIENCE↗

Effects of blended cements and carbonation on chloride-induced corrosion propagation

Highlights: • Corrosion propagation of blended cements was investigated for 1 year. • Carbonated and non‑carbonated mortars were evaluated. • Galvanostatic pulse and ER sensors were used to monitor corrosion. • Mortar properties were correlated with corrosion rates and corrosion damage. • Relationships between mortar properties and corrosion behaviour were established. Supplementary cementitious materials are known to refine the pore structure of concrete and accelerate the carbonation progress. The combination of the two processes can have both beneficial and disadvantageous effects on corrosion, especially when chlorides are also involved. In this study the corrosion properties of multiple blended cements were evaluated in carbonated and non‑carbonated states, with chlorides introduced through cyclic ponding. The examination involved monitoring the propagation phase, determining the microstructural properties of cements, and assessing the final corrosion damage. The results showed that the steel in the blended cements initially had a relatively high corrosion activity, which later decreased compared to the OPC. This stabilisation was presumably due to the beneficial changes to the pore structure. Carbonation had a significant impact on the corrosion, with carbonated mortars revealing shallower damage over a larger surface area. This effect was more pronounced for blended cements that exhibited greater susceptibility to carbonation.

36 MATERIALS SCIENCE↗

Corrosion-induced microstructural developments in 316 stainless steel during exposure to molten Li 2 BeF 4 (FLiBe) salt

The microstructural evaluation and characterization of 316 stainless steel samples that were tested in molten Li 2 BeF 4 (FLiBe) salt were investigated in this study for evaluating its performance in high-temperature molten fluoride salts. Recently, 316 stainless steel and FLiBe salt are being actively considered as the main structural alloy and primary coolant of fluoride salt-cooled high-temperature reactor (FHR), a leading nuclear reactor concept for the next generation nuclear plants (NGNP). In support of the materials development for the FHR, high-temperature corrosion tests of 316 stainless steel in molten FLiBe salt at 700°C have been conducted in both bare graphite crucibles and 316 stainless steel-lined crucibles in an inert atmosphere for up to 3000 hours. The microstructure of the tested samples was comprehensively characterized using scanning electron microscopy (SEM) in conjunction with energy dispersive x-ray spectroscopy (EDS) and electron backscatter diffraction (EBSD), and scanning transmission electron microscopy (STEM) with EDS. In addition to the noticeable intergranular corrosion attack on surface, the corrosion in terms of the Cr depletion along high angle grain boundaries (15-180º) extended to 22µm in depth after 3000-hour exposure to molten FLiBe salt in graphite crucible. The coherent Σ3 grain boundary appeared high resistance to the Cr depletion. The substantial Cr depletion from the near-to-surface layer induced phase transformation from γ-martensite to α-ferrite phase (FeNi x ) during corrosion at 700ºC. Furthermore, the presence of graphite in the molten salt doubled the corrosion attack depth and led to the formation of round Mo2C, hexagonal Cr 7 C 3 and needle-like Al 4 C 3 phase within the alloy as deep as 50 µm after 3000-hour corrosion testing. Based on the microstructural analysis, the corrosion mechanisms of 316 stainless steel in molten FLiBe salt in different corrosion crucibles were illuminated through schematic diagrams. Additionally, a thermal diffusion controlled corrosion model was developed and validated by experimental data for predicting the long-term corrosion attack depth.

36 MATERIALS SCIENCE↗

Corrosion behaviors of friction welded dissimilar aluminum alloys

Highlights: • Corrosion properties of friction welded dissimilar aluminum alloys seem to be governed by the anode part in the weld. • Intense corrosion near the interface has the limited region due to insufficient ionic transport. • Self-formation of a micro-galvanic cell is a main reason for the inferior corrosion performance. - Abstract: Corrosion behaviors of the friction welded dissimilar aluminum alloys were investigated to understand how galvanic effect plays a role in altering corrosion properties of the dissimilar weld. From the fact that the weld had the similar OCP value to that of AA2017, it can be inferred that the corrosion characteristics of the weld is under the control of the AA2017 part in the weld and as a result, only the AA2017 part in the weld had experienced severe corrosion, leaving AA6063 under cathodic protection. Intense corrosion occurring near the interface implies that the area near the interface is placed under the effect of galvanic corrosion and there was the effective distance where the galvanic effect exerts an impact due to the increase in the resistance of the electrolyte with the distance from the interface. The disappearance of Warburg diffusion plot in Nyquist plots for the weld seemed to be the breakdown of the passivation layer related to the formation of the micro-galvanic cell, which in turn presented the shrinkage in the capacitance response, indicating that charge reactions in the form of corrosion occurred.

36 MATERIALS SCIENCE↗

Corrosion of 304 stainless steel in static liquid lithium under high vacuum

To study the compatibility especially the corrosion characteristic of structural material stainless steel (SS) with liquid lithium (Li) is an important factor for the simultaneous application of liquid Li and SS as a blanket material or potential plasma facing material (PFM) in future fusion devices. Here, the corrosion behaviors of 304SS exposed to liquid Li at 700 K for 1320 hr under high vacuum were investigated. After exposure to liquid Li, 304SS produces non-uniform corrosion which includes corrosion products and grain boundary corrosion. Compared with the corrosion behaviors at 600 K and 640 K, temperature plays an important role in the corrosion behaviors of 304SS in static liquid Li. The weight loss, corrosion depth and corrosion products of 304SS specimens increase with the corrosion temperature. In general, the compatibility between 304SS and static liquid Li is relatively good under the experimental conditions. And besides, it is unexpectedly found that the compatibility of copper with Li is not good.

304SS↗

Corrosion of alloys in a chloride molten salt (NaCl-LiCl) for solar thermal technologies

Next-generation solar power conversion systems in concentrating solar power (CSP) applications require high-temperature advanced fluids in the range of 600–800 °C. Current commercial CSP plants use molten nitrate salt mixtures as the heat transfer fluid and the thermal energy storage (TES) media while operating with multiple hours of energy capacity and at temperatures lower than 565 °C. At higher temperatures, the nitrates cannot be used because they decompose. Molten chloride salts are candidates for CSP applications because of their high decomposition temperatures and good thermal properties; but they can be corrosive to common alloys used in vessels, heat exchangers, and piping at these elevated temperatures. In this article, we present the results of the corrosion evaluations of several alloys in eutectic 34.42 wt% NaCl – 65.58 wt% LiCl at 650–700 °C in nitrogen atmosphere. Electrochemical evaluations were performed using open-circuit potential followed by a potentiodynamic polarization sweep. Corrosion rates were determined using Tafel slopes and Faraday's law. A temperature increase of as little as 50 °C more than doubled the corrosion rate of AISI stainless steel 310 and Incoloy 800H compared to the initial 650 °C test. These alloys exhibited localized corrosion. Inconel 625 was the most corrosion-resistant alloy with a corrosion rate of 2.80±0.38 mm/year. For TES applications, corrosion rates with magnitudes of a few millimeters per year are not acceptable because of economic considerations. Additionally, localized corrosion (intergranular or pitting) can be catastrophic. Furthermore, corrosion-mitigation approaches are required for advanced CSP plants to be commercially viable.

47 OTHER INSTRUMENTATION↗

Irradiation-Accelerated Corrosion of Reactor Core Materials. Final Report

This project aims to understand how radiation accelerates corrosion of reactor core materials. The combination of high temperature, chemically aggressive coolants, a high radiation flux and mechanical stress poses a major challenge for the life extension of current light water reactors, as well as the success of most all GenIV concepts. Of these four drivers, the combination of radiation and corrosion places the most severe demands on materials, for which an understanding of the fundamental science is simply absent. Only a few experiments have been conducted to understand how corrosion occurs under irradiation, yet the limited data indicates that the effect is large; irradiation causes order of magnitude increases in corrosion rates. Without a firm understanding of the mechanisms by which radiation and corrosion interact in film formation, growth, breakdown and repair, the extension of the current LWR fleet beyond 60 years and the success of advanced nuclear energy systems are questionable. The proposed work will address the process of irradiation-accelerated corrosion that is important to all current and advanced reactor designs, but remains very poorly understood. An improved understanding of the role of irradiation in the corrosion process will provide the community with the tools to develop predictive models for in-reactor corrosion, and to address specific, important forms of corrosion such as irradiation assisted stress corrosion cracking.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Reduction of Methane Leaks through Corrosion Mitigation Pre-treatments for Pipelines with Field Applied Coatings

Corrosion of buried, coated steel pipelines transporting natural gas is a significant source of methane emissions, from pipeline venting required for maintenance and repairs and from pipeline leaks and incidents. Corrosion of steel under field applied coatings is an important safety concern for the pipeline industry. This project investigates the application of a field applied alloy over girth welds to mitigate external corrosion of buried coated steel pipelines. Various metallic coating options were considered, which were required to meet several criteria: (1) it must resist corrosion under open-circuit or mild cathodic protection conditions, (2) it must protect the substrate steel, and (3) it must not negatively affect the adhesion of the field coating. Finite element models and lab testing were performed of alloy coating compositions to identify promising alloy types underneath disbonded coatings. Polarization curves of coating alloys were generated to provide the boundary conditions for the COMSOL model to compute potential and current distributions around coated areas. Sacrificial and corrosion-resistant metal alloy coatings were evaluated and optimized using corrosion modeling and laboratory electrochemical testing, where aluminum alloy 5356 (5% Mg) and steel alloy B9 (9% Cr) were selected. Corrosion test coupons were designed and fabricated using thermal spray aluminum 5356 and welded B9 steel overlays on API 5L grade X42 line pipe steel. The corrosion test coupons, with simulated pipe coating damage, were tested in a laboratory soil box and a field pipeline site in Texas for 3-months. Corrosion test coupons were then tested for 6-months at field pipeline sites in Texas and Tennessee to quantify corrosion rates and performance of the aluminum and steel alloys under polyethylene tape and 2-part epoxy coatings, various coating holidays, and with and without cathodic protection.

03 NATURAL GAS↗

Fe-Coated Optical Fiber for Distributed Corrosion Monitoring in Soil and Aqueous Environment

Natural gas pipeline corrosion represents a substantial cost and safety concern during normal operations. The effective and real-time monitoring of corrosion is important to detect and mitigate pipeline risks before corrosion-related catastrophic events happen. Here, we describe the use of iron (Fe) coated optical fiber sensors (OFS) for distributed corrosion monitoring where Fe acts as a corrosion proxy. By using an optical backscattering reflectometer (OBR), corrosion was monitored based on the increase in the backscattered intensity amplitude of the light being passed as Fe underwent corrosion. The Fe-coated OFSs were prepared with a film thickness between 25–225 nanometers (nm) by an electroless plating approach and corroded by a carbon dioxide (CO2)-saturated acidic electrolyte. The corrosion rate (CR) was approximately 2.5 millimeters (mm)/year for Fe with a film thickness of 30 nm and increased with film thickness. Backscattering-based CRs were supported by visible light transmission measurements, which have been previously demonstrated. Additionally, a correlation between the intermittent transmission and residual Fe film thickness during the corrosion of Fe was established. The corrosion sensor was also tested in soil at > 1 foot depth. Fe-coated OFS was loaded into a Draka cable, which provides mechanical support during fiber deployment and installation into either acidified soil, top-soil, or sandy soil (50/50).

corrosion↗

Corrosion of Containment Alloys in Molten Salt Reactors and the Prospect of Online Monitoring

The aim of this review is to communicate some essential knowledge of the underlying mechanism of the corrosion of structural containment alloys during molten salt reactor operation in the context of prospective online monitoring in future MSR installations. The formation of metal halide species and the progression of their concentration in the molten salt do reflect containment corrosion, tracing the depletion of alloying metals at the alloy salt interface will assure safe conditions during reactor operation. Even though the progress of alloying metal halides concentrations in the molten salt do strongly understate actual corrosion rates, their prospective 1 st order kinetics followed by near-linearly increase is attributed to homogeneous matrix corrosion. The service life of the structural containment alloy is derived from homogeneous matrix corrosion and near-surface void formation but less so from intergranular cracking (IGC) and pitting corrosion. Online monitoring of corrosion species is of particular interest for molten chloride systems since besides the expected formation of chromium chloride species CrCl 2 and CrCl 3 , other metal chloride species such as FeCl 2 , FeCl 3 , MoCl 2 , MnCl 2 and NiCl 2 will form, depending on the selected structural alloy. The metal chloride concentrations should follow, after an incubation period of about 10,000 hours, a linear projection with a positive slope and a steady increase of <1 ppm per day. During the incubation period metal concentration show 1 st order kinetics and increasing linearly with time. Ideally, a linear increase reflects homogeneous matrix corrosion, while a sharp increase in the metal chloride concentration could set a warning flag for potential material failure within the projected service life, e.g. as result of intergranular cracking or pitting corrosion. Continuous monitoring of metal chloride concentrations can therefore provide direct information about the mechanism of the ongoing corrosion scenario and offer valuable information for a timely warning of prospective material failure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Corrosion Testing of Carbon Steel Exposed to Sludge Heel Chemical Cleaning Solutions - 16109

As efforts continue to treat and dispose of millions of gallons of legacy radioactive materials from the production of nuclear weapons, non-compliant waste storage tanks will gradually be emptied of the bulk waste volume leaving heel materials requiring removal prior to tank closure. The waste heel slurries are distributed on the floor of large, million gallon tanks, which frequently contain numerous obstructions that limit the effectiveness of mechanical removal methods. As a result, chemical cleaning methods are needed for the effective removal of the heels as well as chemical scales that are present on the tank walls and other interior surfaces. Two tank cleaning technologies have already been implemented at the Savannah River Site (SRS): Low Temperature Aluminum Dissolution (LTAD) and Bulk Oxalic Acid Cleaning (BOAC). Recent chemical cleaning efforts on SRS Tank 12 were very successful with regard to bulk sludge heel (especially for Al, Fe, and U phases) and beta/gamma radionuclide removal. Although chemical cleaning using these technologies has been shown to be effective, no disposition path has been identified for oxalate added during BOAC, and insoluble oxalate salts are accumulating within the SRS tank farm and waste processing facilities (evaporators, etc.). Extensive sludge washing is also required to remove moderately soluble sodium oxalate salts prior to sludge vitrification in the SRS Defense Waste Processing Facility (DWPF). As a result, oxalate additions to the tank farm need to be minimized by the use of supplementary acids to assist sludge removal in OA or the use of other cleaning reagents or processing strategies. Previous SRNL testing revealed the importance of pH control for BOAC and recommended the use of a supplementary acid (dilute HNO{sub 3}) with OA to minimize oxalate additions. Primary drivers in SRS Tank Closure Performance Assessments, which evaluate the fate and impact of tank sludge residuals on a geological timescale, are the removal of alpha emitting radionuclides present at low concentrations such as Pu, Am, and Np, which are not highly soluble in currently utilized chemical cleaning reagents. Scoping studies conducted at SRNL revealed promising methods to dissolve the actinides within the HLW tank heels. Oxidation of the actinides with permanganate in either strong caustic (10 M NaOH) or dilute acidic (0.2 M HNO{sub 3}) solutions was shown to result in dissolution of oxy/hydroxide phases of these metals in the absence of major sludge phases. The waste tanks at SRS and Hanford are constructed of carbon steel. Carbon steel corrodes rapidly in most acidic and/or oxidizing environments. Previous electrochemical corrosion testing indicated that the corrosion rates in dilute HNO{sub 3} with OA may result in manageable corrosion rates, over short exposure periods. Additional corrosion testing was performed to provide data for the nitric acid/OA blend as well as the acid/permanganate and caustic permanganate based chemical cleaning solutions. Corrosion rates from the passive coupon tests for the nitric acid/oxalic acid blend were significantly greater than those observed previously with the electrochemical testing. This result may be due to simultaneous electrochemical and chemical dissolution of the steel. The corrosion rate data from the coupon tests in the nitric acid/oxalic acid blend were evaluated to determine the degree of potential structural damage. The corrosion rates, although relatively high, would not be expected to cause damage that would reduce the capacity of the tank primary wall if the process is completed within a month. The corrosivity of sodium permanganate in four proposed cleaning solutions, 1 nitric acid solution and 3 sodium hydroxide solutions, was studied by electrochemical methods at room temperature. The corrosion rates were significantly less aggressive than in the nitric acid/oxalic acid blend corrosion tests. Passive coupon tests needs to be performed in these solutions to ensure that chemical dissolution of the metal is not occurring simultaneously. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Corrosion Testing of TiN on Steel Substrates for use in Waste Packages

An outer shield barrier for spent nuclear fuel casks is being developed in order to improve dry cask performance under mechanical, chemical, and radiological burdens. The materials proposed for the outer shield barrier are titanium nitride (TiN), a composite oxide layer consisting of ZrO{sub 2}, TiO{sub 2}, and Al{sub 2}O{sub 3}, and a final layer of molybdenum disulfide (MoS{sub 2}). A proposed multilayer and multicomposite approach are being investigated in order to optimize the outer shield barriers performance. Spent nuclear fuel casks are frequently made, in part, of 304 and 316 stainless steels. These materials have been chosen as substrates to deposit single layer films of the proposed materials. In order to understand how these materials will behave layered and composited it is first necessary to understand how they perform individually. Several corrosion studies have been performed and analyzed for cyclic corrosion and static corrosion in different brine solutions and at different temperatures. The corrosion rate, over potential, activation enthalpy, and entropy of corrosion have been documented in previous publications. One of the main functions of the TiN coating is to serve as a corrosion barrier on the waste package. In this study we investigate pitting corrosion on thin layers of TiN through cyclic polarization testing and scanning electron microscopy. The corrosion protection of thin layers of TiN has been investigated on 304 and 316 stainless steels. Cyclic polarization testing has been used to this end. Corrosion rates have been calculated using tefel fits on data obtained from this testing and SEM images were used in conjunction with this data. Pitting is observed to occur even at the thickest deposition conditions tested. Although the corrosion rates decrease at these thicker values - sometimes dramatically - thicker layers will be deposited in the future to provide complete resistance to pitting. Deposition and testing of these layers is currently underway. (authors)

36 MATERIALS SCIENCE↗

Fe Thin Film-Coated Optics for Corrosion Monitoring: Optical and Electrochemical Studies

Corrosion proxy materials integrated with an optical sensing platform enable a real-time optical corrosion sensor for natural gas pipelines to prevent methane leaks and catastrophic events. Effects of CO 2 , pH, and film thickness on corrosion of Fe thin films (25, 50, 100 nm) were studied using optical and electrochemical methods in 3.5%wt. NaCl solutions at 30 °C. An increase in light transmission (T%) corresponded to corrosion of Fe thin films. CO 2 accelerated corrosion of Fe thin films due to the lower pH and the promoted corrosion reactions, resulting in a faster increase of T% than without CO 2 or at higher pH. While the corrosion rate increased with increasing film thickness, electrochemical corrosion of Fe thin films was in good agreement with that of bulk carbon steel, verifying that Fe thin films can serve as a representative corrosion proxy when integrated with the optical sensing platform.

36 MATERIALS SCIENCE↗

Results of stainless steel canister corrosion studies and environmental sample investigations

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-SO 4 , 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/m 2 . 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.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Corrosion of Structural Materials for Advanced Supercritical Carbon- Dioxide Brayton Cycle

The supercritical carbon-dioxide (referred to as SC-CO 2 hereon) Brayton cycle is being considered for power conversion systems for a number of nuclear reactor concepts, including the sodium fast reactor (SFR), fluoride saltcooled high temperature reactor (FHR), and high temperature gas reactor (HTGR), and several types of small modular reactors (SMR). The SC-CO 2 direct cycle gas fast reactor has also been recently proposed. The SC-CO 2 Brayton cycle (discussed in Chapter 1) provides higher efficiencies compared to the Rankine steam cycle due to less compression work stemming from higher SC-CO 2 densities, and allows for smaller components size, fewer components, and simpler cycle layout. For example, in the case of a SFR using a SC-CO 2 Brayton cycle instead of a steam cycle would also eliminate the possibility of sodium-water interactions. The SC-CO 2 cycle has a higher efficiency than the helium Brayton cycle, with the additional advantage of being able to operate at lower temperatures and higher pressures. In general, the SC-CO 2 Brayton cycle is well-suited for any type of nuclear reactor (including SMR) with core outlet temperature above ~ 500°C in either direct or indirect versions. In all the above applications, materials corrosion in high temperature SC-CO 2 is an important consideration, given their expected lifetimes of 20 years or longer. Our discussions with National Laboratories and private industry early on in this project indicated materials corrosion to be one of the significant gaps in the implementation of SC-CO 2 Brayton cycle. Corrosion can lead to a loss of effective load-bearing wall thickness of a component and can potentially lead to the generation of oxide particulate debris which can lead to three-body wear in turbomachinery components. Another environmental degradation effect that is rather unique to CO 2 environment is the possibility for simultaneous occurrence of carburization during oxidation of the material. Carburization can potentially lead to embrittlement of structural alloys in SC-CO 2 Brayton cycle. An important consideration in regards to corrosion is that the temperatures can vary widely across the various sections of the SC-CO 2 Brayton cycle, from room temperature to 750°C, with even higher temperatures being desirable for higher efficiencies. Thus the extent of corrosion and corrosion mechanisms in various components and SC-CO 2 Brayton cycle will be different, requiring a judicious selection of materials for different sections of the cycle. The goal of this project was to address materials corrosion-related challenges, identify appropriate materials, and advance the body of scientific knowledge in the area of high temperature SC-CO 2 corrosion. The focus was on corrosion of materials in SC-CO 2 environment in the temperature range of 450°C to 750°C at a pressure of 2900 psi for exposure duration for up to 1000 hours. The Table below lists the materials tested in the project. The materials were selected based on their high temperature strength, their code certification status, commercial availabilities, and their prior or current usage in the nuclear reactor industry. Additionally, pure Fe, Fe-12%Cr, and Ni-22%Cr were investigated as simple model materials to more clearly understand corrosion mechanisms. This first phase of the project involved testing in research grade SC-CO 2 (99.999% purity). Specially designed autoclaves with high fidelity temperature, pressure, and flow control capabilities were built or modified for this project.

36 MATERIALS SCIENCE↗

FY18 Status Report: SNL Research into Stress Corrosion Cracking of SNF Interim Storage Canisters

This progress report describes work done in FY18 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). The work focuses on stress corrosion cracking (SCC), the only mechanism 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. Work in FY18 continued several studies initiated in FY17 that are aimed at refining the understanding of the chemical and physical environment on canister surfaces, and evaluating the relationship between chemical and physical environment and the form and extent of corrosion that occurs. The SNL canister environment work focused on evaluating the stability of sea-salt deliquescent brines on the heated canister surface; an additional opportunity to analyze dusts sampled from an inservice spent nuclear fuel storage canister also arose. The SNL corrosion work focused predominantly on pitting corrosion, a necessary precursor for SCC, and process of pit-to-crack transition. SNL is collaborating with several university partners to investigate SCC crack growth experimentally, providing guidance for design and interpretation of experiments. The scope of these efforts targets near-marine Independent Spent Fuel Storage Installation environments which are generally considered to be most aggressive for pitting and SCC. Work to define the chemical and physical environment that could develop on storage canister surfaces in near-marine environments included experiments to evaluate the thermal stability of magnesium chloride brines, representative of the first brines to form when sea-salts deliquesce, with the specific goal of understanding and interpreting results of sea-salt and magnesium chloride corrosion experiments carried out under accelerated conditions. The experiments showed that magnesium chloride brines, and by extension, low RH sea-salt deliquescent brines, are not stable at elevated temperatures, losing chloride via degassing of HC1 and conversion to Mg-hydroxychlorides and carbonates. The experiments were carried out on an inert substrate to eliminate the effects of corrosion reactions, simulating brine stabilities in the absence of, or prior to, corrosion. Moreover, analysis of salts recovered from actively corroding metal samples shows that corrosion also supports or drives conversion of magnesium chloride or sea-salt brines to less deliquescent salts. This process has significant implications on corrosion, as the secondary phases are less deliquescent than magnesium chloride; the conversion reaction results in decreases in brine volume, and potentially results in brine dry-out. The deliquescence properties of these reaction products will be a topic of active research in FY19.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Hanford Double Shell Waste Tank Corrosion Studies (Final Report FY2019)

During fiscal year (FY) 2019, the Savannah River National Laboratory (SRNL) focused on four primary tasks for Hanford Double Shell Tanks (DSTs) corrosion studies. The first task, New Limits, was a continuation from the electrochemical work started in FY16, to expand electrochemical testing to elevated temperatures and elevated hydroxide concentrations and evaluate how these factors will influence pitting corrosion. Using the pitting factor (PF) equation, these new conditions were validated to provide a conservative estimate for the susceptibility of pitting corrosion on legacy carbon steel. The second task, Secondary Liner Corrosion, focused on Vapor Space Corrosion (VSC) and immersion testing studies using two commercially available vapor corrosion inhibitors (VCIs). For this FY, the VCI strategy was applied mid-experiment to determine performance on weathered coupons. The third task, Long-Term Open Circuit Potential (OCP) Drift, was performed using simplified simulated chemistries to evaluate change in pitting corrosion risk due to evolution of corrosion potential for mill-scale and freshly polished 600-grit surfaces. Finally, the fourth task, Microbiologically-Influenced Corrosion (MIC) studies, was focused on the study of leak detection pit (LDP) water sent from the Hanford tank farm for determination of bacteria that can be conducive to corrosion using commercially available kits: BART TM and MICkit® 5. In addition, this FY, a secondary task was added which was a continuation of the study of the Quartz-enhanced Photoacoustic Spectroscopy (QEPAS) system. Work was started but was ultimately not pursued. A summary of each task performed is presented below.

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