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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

The Sporadic History of Rubidium and its Role in Corrosion of Steel Related to Nuclear Material Storage

The influence of rubidium (Rb), both in its metallic and oxidized states, on the corrosion resistance of steels has direct relevance to the storage of radioactive Kr-85 containing nuclear materials. Kr-85 undergoes a ß-decay to generate stable, metallic Rb. The literature to date is sparse, contained primarily in company reports and divisive as to whether Rb metal, or its oxides, can lead to corrosion of steel materials. In both the direct storage of Kr-85 and used nuclear fuel that will contain Kr-85, if Rb is corrosive then continual decay of the Kr-85 will generate an increasingly corrosive environment for the steel canister it is stored in. This review was written to consolidate the known data to date on Rb corrosion of steels to identify consistencies, contradictions and remaining gaps in our understanding of the Rb : steel system.

krypton, corrosion, steel, Rubidium↗

Pitting Corrosion in 316L Stainless Steel Fabricated by Laser Powder Bed Fusion Additive Manufacturing: A Review and Perspective

Abstract 316L stainless steel (316L SS) is a flagship material for structural applications in corrosive environments, having been extensively studied for decades for its favorable balance between mechanical and corrosion properties. More recently, 316L SS has also proven to have excellent printability when parts are produced with additive manufacturing techniques, notably laser powder bed fusion (LPBF). Because of the harsh thermo-mechanical cycles experienced during rapid solidification and cooling, LPBF processing tends to generate unique microstructures. Strong heterogeneities can be found inside grains, including trapped elements, nano-inclusions, and a high density of dislocations that form the so-called cellular structure. Interestingly, LPBF 316L SS not only exhibits better mechanical properties than its conventionally processed counterpart, but it also usually offers much higher resistance to pitting in chloride solutions. Unfortunately, the complexity of the LPBF microstructures, in addition to process-induced defects, such as porosity and surface roughness, have slowed progress toward linking specific microstructural features to corrosion susceptibility and complicated the development of calibrated simulations of pitting phenomena. The first part of this article is dedicated to an in-depth review of the microstructures found in LPBF 316L SS and their potential effects on the corrosion properties, with an emphasis on pitting resistance. The second part offers a perspective of some relevant modeling techniques available to simulate the corrosion of LPBF 316L SS, including current challenges that should be overcome.

Voisin, T. (ORCID:0000000287462659)↗

Mechanistic insights into selective oxidation and corrosion of multi-principal element alloys from high resolution and in situ microscopy

Multiple principal elements alloys (MPEAs) have drawn significant recent interest from the metallurgical research community. These novel alloys have the potential to replace traditional alloys with a range of tailored mechanical properties, corrosion resistance, and radiation tolerance enabled by complex compositions. The broad alloy design space of MPEAs presents a great opportunity to discover new forms of oxidation and corrosion resistance in extreme environments that break away from conventional corrosion resistant alloy design criteria. However, understanding the oxidation and corrosion response of MPEAs can be a challenging task due the complex composition, structural, and chemical state changes occurring in the corrosion product and at its interface with the base alloy. This perspective discusses the utility of high resolution and in situ microscopy techniques for revealing unique aspects of MPEA oxidation behavior at the near-atomic level. Challenges of studying these alloys and several open questions are presented.

Kautz, Elizabeth J.↗

Laboratory Accelerated Cyclic Corrosion Testing and On-Road Corrosion Testing of AA6××× Coupled to Carbon Fiber-Reinforced Plastics

Structures made from a combination of aluminum alloy (AA) and carbon fiber-reinforced plastic (CFRP) are susceptible to galvanic corrosion of the AA in harsh atmospheric conditions, such as might exist for closure panels in automotive applications. It is important to understand the galvanic corrosion behavior of these materials under laboratory conditions as that might allow prediction of performance in real environments. This work tested specially designed AA6×××-CFRP coupons, including AA6111 and AA6022, connected to CFRP made from two different carbon fiber fabrics (twill and random) with the aim of understanding the corrosion behaviors in a laboratory cyclic exposure chamber and during on-road exposure. The extent of corrosion was assessed by galvanic current measurements, optical profilometry, cross-sectional area analysis, and microscopic analysis. Based on the results, it was determined that the corrosion susceptibilities and morphologies observed in CFRP/AA couples tested in an environmental chamber for 12 weeks were in correspondence with those of the coupons subjected to on-road testing for 1 y in Columbus, OH.

Materials Science↗

Real time numerical computation of corrosion rates from corrosion sensors

A method for determining a corrosion rate includes receiving an input signal including corrosion data from a sensor. A signal-to-noise ratio (SNR) and a type of noise is determined from the input signal. A corrosion rate computation method is selected based on the SNR and the type of noise. The corrosion rate is determined, using a processor, based on a selected corrosion rate computation method.

36 MATERIALS SCIENCE↗

Geometric Optimization of an Electrochemical Purification Cell to Prevent Corrosion in CSP Plants During Operation

When exposed to moisture or oxygen, molten chloride salts produce corrosive impurities which degrade containment alloys. This can significantly decrease the lifetime and increase costs of molten-salt-based systems. To overcome this barrier, we designed and modeled an electrochemical purification cell to remove the corrosive impurity MgOH+. Various reactor architectures, including continuous stirred tank reactors (CSTRs) and plug flow reactors (PFRs) were investigated. Steady-state thermoelectric properties were evaluated using analytical methods, allowing assessment of the effects of structure and design parameters such as flow rate, cell length, and cross-sectional area of molten salt. The results suggest that our design could most effectively increase reliability and decrease costs of molten-chloride-salt-based systems by protecting them during continuous operation using an annular plug flow reactor.

analytical modeling↗

Multielectrode Array Sensors to Enable Long-Duration Corrosion Monitoring and Control of Concentrating Solar Power Systems

Molten mixtures of MgCl2-KCl-NaCl are promising heat transfer fluid (HTF) candidates for the next generation of concentrating solar power systems (Gen3 CSP), because of their low cost, high decomposition temperature, and favorable heat transfer characteristics. However, if the chemistry of the salts is not properly controlled, molten chlorides can cause corrosion of high-temperature metal alloys, such as Inconel (R), in CSP systems. Here we demonstrate a corrosion monitoring system that can be used to monitor the health of the structural alloys over long durations. The monitoring system includes a multielectrode array voltammetry sensor that measures the redox potential of molten MgCl2-KCl-NaCl mixture as well as the presence of corrosion products and impurities. The sensors have been successfully operated in static molten salt environments for long durations, and are capable of detecting corrosion products, such as Cr2+ and Fe2+, quantitatively at low concentrations (i.e., approximately 100 ppm) with less than 4% error.

Concentrated solar power↗

Purification of Lithium-Ion Battery Black Mass through Tailored Alkaline Corrosion

Obtaining high-purity material outputs is crucial to the viability of novel process aimed at direct recycling of lithium-ion batteries. Metallic impurities in recycled cathodes have been shown to inhibit performance, thereby threatening mainstream acceptance of recycled battery products. Thus, shredded black mass (BM) must be purified to remove metallic contaminants, and specifically Al and Cu originating from the electrode current collectors. We herein explore a process to ionize solid copper and aluminum to ionic form based on tailored alkaline chemistry, without incurring damage to the target cathode material (Li(NixMnyCo1-x-y)O2; NMC). Al and Cu corrosion may be enhanced through the addition of chloride salt, elevated temperatures, and the use of ultrasonication - all of which disrupt the formation of passivating films on the metallic surface, and thereby increase corrosion rate. We demonstrate optimized parameters for Al and Cu corrosion both from a kinetic and overall process cost perspective. Further, we analyze the impact of these conditions on the structural (XRD, SEM), chemical (EDS, ICP), and electrochemical (impedance, cycling, dQ/dV) properties of NMC, and suggest that the present purification method does not significantly disrupt NMC performance. Finally, we present preliminary results from a promising bench-scale demonstration of this purification process applied to a simulated black mass.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗

High temperature oxidation of corrosion resistant alloys from machine learning

Parabolic rate constants, k p , were collected from published reports and calculated from corrosion product data (sample mass gain or corrosion product thickness) and tabulated for 75 alloys exposed to temperatures between ~800 and 2000 K (~500–1700 °C; 900–3000°F). Data were collected for environments including lab air, ambient and supercritical carbon dioxide, supercritical water, and steam. Materials studied include low- and high-Cr ferritic and austenitic steels, nickel superalloys, and aluminide materials. A combination of Arrhenius analysis, simple linear regression, supervised and unsupervised machine learning methods were used to investigate the relations between composition and oxidation kinetics. The supervised machine learning techniques produced the lowest mean standard errors. The most significant elements controlling oxidation kinetics were Ni, Cr, Al, and Fe, with Mo and Co composition also found to be significant features. The activation energies produced from the machine learning analysis were in the correct distributions for the diffusion constants for the oxide scales expected to dominate in each class.

Materials Science↗

Rapid Predictions of Part Lifetimes in Corrosive Environments, Corrosion

Corrosion challenges persist throughout SNL’s mission areas. The primary difficulty lies in the fact that corrosion typically manifests as isolated, rare events, making preemptive identification exceedingly difficult. Our current strategy for addressing corrosion issues, such as anomalies and SFIs, is similarly isolated and reactive. This method is costly, time-consuming, heavily dependent on a limited number of experts, and offers minimal understanding of the overall damage distribution within the stockpile. This technical challenge is not unique to corrosion but is also prevalent in other material aging phenomena, such as tin-whisker growth in lead-free solder and fatigue failure of springs.

36 MATERIALS SCIENCE↗

Corrosion Research Survey: Corrosion-Surface Roughness Correlation on Carbon and Stainless Steels

Concerning the SAVY 4000 container LANL inspection acceptance of Ra (surface roughness) and its correlation to subsequent surface corrosion, a problem statement has been identified. The problem statement is as follows: When the 316L container has been subjected to accommodating materials producing high wattage, along with materials that eventually produce HCL (hydrochloric acid) will a higher or lower Ra on the inner surface of the SAVY 4000 container influence the rate or the amount of corrosion? In an effort to address this concern, a literature review covering more fundamental studies that examine the influence of roughness on corrosion in metals are surveyed. The scope is kept relevant to the less dynamic storage conditions that a SAVY container may be exposed to.

36 MATERIALS SCIENCE↗

Corrosion Testing Proposal -1: Assessment of the Corrosion of Stainless Steel Subjected to an Aqueous Solution of Hydrochloric Acid

This corrosion-test proposal outlines the methods to promote rapid pitting corrosion on various pitting resistant stainless steels under controlled conditions. This study can be performed in-whole or in- part as the Corrosion Working Group (CWG) leadership of the Los Alamos National Laboratory (LANL) deems pertinent. This proposal is in response to CWG’s need to understand the mechanisms and the possible detrimental failure of the 316L SAVY (an acronym that represents the first initial of the four co-developers, Stone, Anderson, Veirs, Yarbro) 4000 container design currently in service. This detrimental failure evolved from a question that the CWG arrived to by consensus as “What is the critical pit depth that would comprise the design wall-strength of the SAVY-4000?”

36 MATERIALS SCIENCE↗

Corrosion-Resistant Coatings on Spent Nuclear Fuel Canisters to Mitigate and Repair Potential Stress Corrosion Cracking (FY22 Status)

This report summarizes the activities performed by Sandia National Laboratories in FY22 to identify and test coating materials for the prevention, mitigation, and/or repair of potential chloride-induced stress corrosion cracking in spent nuclear fuel dry storage canisters. This work continues efforts by Sandia National Laboratories that are summarized in previous reports in FY20 and FY21 on the same topic. The previous work detailed the specific coating properties desired for application and implementation to spent nuclear fuel canisters (FY20) and identified several potential coatings for evaluation (FY21). In FY22, Sandia National Laboratories, in collaboration with four industry partners through a Memorandum of Understanding, started evaluating the physical, mechanical, and corrosion-resistance properties of 6 different coating systems (11 total coating variants) to develop a baseline understanding of the viability of each coating type for use to prevent, mitigate, and/or repair potential stress corrosion on cracking on spent nuclear fuel canisters. This collaborative R&D program leverages the analytical and laboratory capabilities at Sandia National Laboratories and the material design and synthesis capabilities of the industry collaborators. The coating systems include organic (polyetherketoneketone, modified polyimide/polyurea, modified phenolic resin), organic/inorganic ceramic hybrids (silane-based polyurethane hybrid and a quasi-ceramic sol-gel polyurethane hybrid), and hybrid systems in conjuncture with a Zn-rich primer. These coatings were applied to stainless steel coupons (the same coupons were supplied to all vendors by SNL for direct comparison) and have undergone several physical, mechanical, and electrochemical tests. The results and implications of these tests are summarized in this report. These analyses will be used to identify the most effective coatings for potential use on spent nuclear fuel dry storage canisters, and also to identify specific needs for further optimization of coating technologies for their application on spent nuclear fuel canisters. In FY22, Sandia National Laboratories performed baseline testing and atmospheric exposure tests of the coating samples supplied by the vendors in accordance with the scope of work defined in the Memorandum of Understanding. In FY23, Sandia National Laboratories will continue evaluating coating performance with a focus on thermal and radiolytic stability.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Optimizing the Operational Parameters of an Electrochemical Purification Cell for Corrosion Mitigation in CSP Plants During Operation: Preprint

To make concentrating solar power (CSP) cost-competitive, the next generation of CSP plants will increase efficiency by operating at a higher temperature, which will require a new thermal energy storage material. One option for the thermal energy storage material is a ternary chloride salt that is stable at the temperatures required, but reacts easily with the atmosphere to form MgOHCl, a corrosive impurity. If left unchecked, this impurity will corrode the containment alloys, potentially leading to dangerous spills. We are working to design an electrochemical purification cell to remove MgOHCl from the molten chloride salt during CSP plant operation. In this paper, we use predictive modeling to assess the rate at which purification must occur. Additionally, we analyze possible process flow pathways for the molten chloride salts. Ultimately, we determine that implementation of a single reactor through which all chloride salts flow is the most efficient design to reduce impurity concentration below 0.1 mol % impurity.

concentrating solar power↗

Cold Spray Deposition of 304L Stainless Steel to Mitigate Chloride-Induced Stress Corrosion Cracking in Canisters for Used Nuclear Fuel Storage

A feasibility study of the cold spray deposition process of 304L stainless steel on 304L stainless steel substrates as a mitigation method for chloride-induced stress corrosion cracking (CISCC) has been investigated under various substrate conditions. The study is aimed at the application of this technology to mitigate CISCC that may potentially occur in or nearthe fusion welded regions of stainless steel canisters in Dry Cask Storage System (DCSS) for used nuclear fuels. Spherical gas-atomized 304L stainless steel powder, in the size range of 25 µm to 44 µm, was used as a feedstock powder for the cold spray process. The powder was deposited on four types of 304L substrates with various surface conditions: as-polished, oxidized, cold-rolled, plates with prototypical CISCC. The effects of cold spray parameters on quality of cold spray coatings were investigated. Thickness, porosity, and phases in the as-deposited materials were evaluated using scanning electron microscopy (SEM) and X-ray diffraction (XRD), and correlated with microhardness and adhesion strength measured via micro-indentation and ASTM C633 pulling test, respectively. XRD analysis of the coatings was also conducted to examine the effects of cold spray condition on residual stress state in the coating. Detailed cross-sectional examination of coating/substrate interfaces was performed with transmission electron microscopy (TEM) equipped with energy dispersive spectroscopy (EDS). Dense and continuous coatings with good adhesion strength and hardness were produced for the various substrate conditions by adjusting cold spray parameters. The results demonstrate that cold spray stainless steel coating is a viable option to provide a physical barrier against CISCC in fusion weld regions of stainless steel in corrosive chloride salt-bearing environments.

Dry Cask Storage Systems, cold spray, 304L stainle↗

Surface-Activated Corrosion in Tin–Lead Halide Perovskite Solar Cells

Mixed tin–lead halide perovskite solar cells have promising power conversion efficiencies, but long-term stability is still a challenge. Here, we examine the stability of a 60:40 tin–lead perovskite to better understand diminished device performance upon thermal treatment, both in ambient and inert atmosphere. Operando X-ray diffraction shows a stable bulk structure of the perovskite absorber, leading to the hypothesis that surface chemistry dominates the degradation mechanism. X-ray photoelectron spectroscopy reveals two new observations post-thermal annealing that accompany previously reported Sn 4+ evolution: (i) the formation of I 3 – intermediates preceding I 2 loss at the surface and (ii) evidence of under-coordinated tin and lead surface sites (Sn δ<2+ and Pb δ<2+ , respectively) in inert and ambient conditions. These two species indicate an activated corrosion (i.e., both oxidation and reduction) process at the surface as a possible chemical pathway for degradation, which is expected to be accelerated under operando voltage and light biases.

14 SOLAR ENERGY↗

Corrosion-Resistant Coatings on Spent Nuclear Fuel Canisters to Mitigate and Repair Potential Stress Corrosion Cracking (FY23 Status)

This report summarizes the activities performed by Sandia National Laboratories in FY23 to identify and test coating materials for the prevention, mitigation, and/or repair of potential chloride-induced stress corrosion cracking in spent nuclear fuel dry storage canisters. This work continues efforts by Sandia National Laboratories that are summarized in previous reports from FY20 through FY22 on the same topic. In FY23, Sandia National Laboratories, in collaboration with five industry partners through a memorandum of understanding, evaluated the physical, mechanical, and corrosion-resistance properties of eight different coating systems. The evaluation included thermal and radiation environments relevant to various time periods of storage for spent nuclear fuel canisters. The coating systems include polymeric (polyetherketoneketone, modified polyimide/polyurea, modified phenolic resin, epoxy), organic/inorganic ceramic hybrids (silane-based polyurethane hybrid and a quasi-ceramic sol-gel polyurethane hybrid), and coatings utilizing a Zn-rich primer applied to stainless steel coupons. The results and implications of these tests are summarized in this report. These analyses will be used to identify the most effective coatings for potential use on spent nuclear fuel dry storage canisters and to identify specific needs for further optimization of coating technologies for application on spent nuclear fuel canisters.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗