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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 19 records

Near-Field Corrosion Interactions between Glass and Corrosion Resistant Alloys

This study explores the corrosion interactions between model nuclear waste glass materials and corrosion resistant alloys, under conditions that simulate the near field of a nuclear waste repository. The interactions between the corrosion of stainless steel (SS) 316, alloy G30, or alloy 625, and international simple glass or soda-lime silica glass are systematically studied. The dissimilar materials were exposed in close proximity to each other in different electrolytes at 90 oC. After exposure, the glass surface exposed near metals showed different regimes of corrosion, with distinct surface morphologies and chemistries that were likely affected by the local environment created by the localized corrosion of metals. Surface and solution analyses showed that the corrosion rate of glass was enhanced by the presence of metals. Infrared spectroscopy data suggested the local build-up of stresses in the contact area of glass, which may lead to the mechanical instability of the glass alteration layer. On the other hand, the effect of glass on metal corrosion is strongly dependent on the leaching solution. In electrolytes containing abundant aggressive anions such as Cl-, glass seems to suppress the localized corrosion of SS by the precipitation of a Si-rich surface film that protects the SS substrate from solutions. However, in less aggressive electrolytes, the corrosion rate of SS was increased by the presence of glass corrosion products. Overall, our study showed that the hidden and localized damage on glass in contact with metals may enhance the release of incorporated radionuclides compared to typical uniform glass corrosion. Therefore, more attention should be paid to the corrosion interactions between metals and glass under repository conditions.

Guo, Xiaolei↗

Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments

During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.

Zhen-Wu, Bi Yun↗

Corrosion proxy material integrated sensor devices for distributed sensing of early corrosion onset and corrosion quantification

Embodiments relate to methods, systems and apparatus for detecting corrosion using a detector apparatus with a host component. The method includes a detector apparatus. The detector apparatus includes an energy source; a corrosion proxy thin film that corrodes at a rate where the normalized change of mass of the film over time is greater than the normalized change of mass of the bulk material of the host component in a harsh environment; and the detector, wherein the detector is capable of detecting a change in energy due to corrosion of the corrosion proxy thin film. The method includes exposing the host component and the corrosion proxy thin film to the harsh environment; and detecting a change in energy using the detector due to corrosion of the corrosion proxy thin film.

Ohodnicki, Jr., Paul R.↗

Corrosion properties of powder bed fusion additively manufactured 17-4 PH stainless steel

The corrosion susceptibility of a laser powder bed fusion (LPBF) additively manufactured alloy, UNS S17400 (17-4 PH), was explored compared to conventional wrought material. Microstructural characteristics were characterized and related to corrosion behavior in quiescent, aqueous 0.6 M NaCl solutions. Electrochemical measurements demonstrated that the LPBF 17-4 PH alloy exhibited a reduced passivity range and active corrosion compared to its conventional wrought counterpart. Lastly, a micro-electrochemical cell was employed to further understand the effects of the local scale and attributed the reduced corrosion resistance of the LPBF material to pores with diameters ≥ 50 µm.

36 MATERIALS SCIENCE↗

Oxidative Corrosion of the UO 2 (001) Surface by Nonclassical Diffusion

Uranium oxide is central to every stage of the nuclear fuel cycle, from mining through fuel fabrication and use, to waste disposal and environmental cleanup. Its chemical and mechanical stability are intricately linked to the concentration of interstitial O atoms within the structure and the oxidation state of U. We have previously shown that during corrosion of the UO2 (111) surface under either 1 atm O2 gas or oxygenated water at room temperature, oxygen interstitials diffuse into the substrate to form a superlattice with three-layer periodicity. In the current study, we present results from surface x-ray scattering that reveal the structure of the oxygen diffusion profile beneath the (001) surface. The first few layers below the surface oscillate strongly in their surface-normal lattice parameters, suggesting preferential interstitial occupation of every other layer below the surface, which is geometrically consistent with the interstitial network that forms below the oxidized (111) surface. Deeper layers are heavily contracted and indicate that the oxidation front penetrates ~52 Å below the (001) surface after 21 days of dry O2 gas exposure at ambient pressure and temperature. X-ray photoelectron spectroscopy indicates U is present as U(IV), U(V), and U(VI).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

In Situ Transmission Electron Microscopy of High-Temperature Inconel-625 Corrosion by Molten Chloride Salts

This paper describes an approach to monitor high temperature molten chloride (MgCl 2 -NaCl-KCl) salt corrosion of Inconel-625 alloy in real time at high spatial resolution. The approach is based on a micro-environmental-cell assembly integrated into a transmission-electron-microscope goniometer to examine in situ the salt-alloy interface during corrosion, employing real time electron diffraction and imaging. It establishes procedures to minimize incorporation of H 2 O or O 2 from atmosphere in the chloride salts during sample fabrication and corrosion, which is critical to understanding the fundamental corrosion mechanisms. A clustering algorithm and a 2D Gaussian fit function are used to determine diffraction spot intensities in in situ diffraction patterns, to quantify alloy corrosion. This facilitates quantitative observation of the evolution of individual grains, in contrast to conventional macroscopic corrosion rate quantification. The isothermal corrosion rate of Inconel-625 in an anhydrous, unoxidized salt-stack is 220 ± 30 μm year -1 at 700 °C and 350 ± 20 μm year -1 at 800 °C. However, the corrosion rate at 700 °C increases five-fold to 1000 ± 170 μm year -1 when the salt stack is air-exposed, indicating the dominant effects of hydrated or oxidized impurities on corrosion acceleration. Furthermore, real time imaging of the microstructure evolution suggests that corrosion is initiated at grain boundaries.

14 SOLAR ENERGY↗

Monitoring reinforcement corrosion and corrosion-induced cracking by X-ray microcomputed tomography method

X-ray microcomputed tomography (X-ray μCT) method is proposed to trace steel corrosion and corrosion-induced cracking in cement paste. Experimental results show it can track the time-dependent development of steel corrosion and corrosion products, as well as the subsequent initiation and propagation of corrosion-induced cracks. Furthermore, the information of corrosion pits, corrosion products, and corrosion-induced cracks can be clearly obtained from the whole specimen by this novel method. Additionally, SEM/EDS results agree closely with image analyses by X-ray μCT. This method provides a new angle to investigate the reinforcement corrosion process and can help to improve the numerical analysis of corrosion-induced damage in reinforced concrete structures. - Highlights: • Reinforcement corrosion and corrosion-induced cracking is traced by X-ray μCT method. • The development of corrosion products can be determined as a function of time and space. • Subsequent initiation and propagation of corrosion-induced cracks can be monitored. • The time-dependent corrosion process can be quantitative analyzed by X-ray μCT measurement.

36 MATERIALS SCIENCE↗

Technical Note: Characterization of Corrosion Films Formed on Austenitic Stainless Steel in Supercritical CO 2 Containing H 2 O and O 2

Future technologies require structural alloys resistant to corrosion in supercritical CO 2 (sCO 2 ) fluids containing impurities such as H 2 O and O 2 . Traditional pipeline steels are potentially unsuitable for these environments and more corrosion resistant alloys such as stainless steels might be required. Little is known about the corrosion products formed on, and hence the processes which control corrosion of, stainless steels in impure sCO 2 environments. In this study, austenitic stainless steel 347H (UNS S34709) was exposed to sCO 2 containing H 2 O and O 2 at 8 MPa and 50°C or 250°C, and separately to the aqueous phase in equilibrium with the sCO 2 at 50°C, to simulate conditions expected in sCO 2 -based power cycles and carbon capture and storage pipelines. Only thin (< 20 nm) surface films formed after 500 h resulting in small mass changes and corrosion rates < 10 –4 mm/y, suggesting the material resists significant degradation in these environments. X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the corrosion films in detail. Here, the exposure to the aqueous phase resulted in a thin (< 5 nm) Cr-oxide and/or -hydroxide passive film, while exposure to sCO 2 phases resulted in a multilayer Fe-rich oxide structure characteristic of a gas-phase oxidation process.

36 MATERIALS SCIENCE↗

Evolution of Metastable Phases During Mg Metal Corrosion: An In Situ Cryogenic X-ray Photoelectron Spectroscopy Study

Magnesium and its alloys are potential structural materials candidates for a wide variety of applications due to their high strength-to-weight ratio. However, ductility and poor corrosion resistance under ambient environmental conditions are the bottleneck for industrial deployment. Designing passivation layers and/or corrosion resistant alloys requires fundamental understanding of the corrosion process. The traditional ex-situ spectroscopic measurements of polycrystalline metal surface with ubiquitous surface impurities and grain boundaries only provided an indistinct view of the corrosion process. To clearly distinguish the mechanism and sequence of corrosion process, we employed in-situ cryo-based x-ray photoelectron spectroscopy (XPS) measurements on Mg single crystal surface exposed to aqueous salt solution. Clean Mg (0001) surfaces were exposed to pure D2O and NaCl aqueous solution (5 wt% NaCl+95 wt% D2O). The interfacial reactions were studied using multimodal analysis including XPS, x-ray diffraction (XRD) and scanning electron microscopy (SEM). In contrast to previous studies, our experiments demonstrated the formation of magnesium chloride hydroxide hydrate during aqueous salt corrosion processes. Evidence of metastable ClO* radicals were also found during the initial aqueous salt solution exposure.

Shutthanandan, Vaithiyalingam↗

Electrochemical mechanisms of leakage-current-enhanced delamination and corrosion in Si photovoltaic modules

This paper analyzes the mechanisms for corrosion and delamination observed in Si photovoltaic modules subjected to high temperature and humidity with a negative-ground bias testing. Based on the thermodynamic data, the ionic component of the leakage current causes reduction reactions of water on the cathodic metallization, producing hydrogen gas and hydroxide ions. Ag fingers are strong catalysts for this reduction reaction compared to other materials used in solar cells and can be the initiation sites of corrosion and delamination caused by the electrochemical reactions. The produced hydrogen gas accumulates inside the module potentially producing a high gas pressure that can promote delamination, which is often preferentially initiated on metallization where the adhesion strength is lower [1], [2], [3]. The local basicity near the metal surface increases due to the hydroxide ion generation. Thus, the environment inside the encapsulant can be alkaline despite the presence of acetic acid decomposition products from the encapsulant. Corrosion of materials such as Si used in solar cells occurs and the extent depends on their corrosion resistance to the alkaline solution. This suggests that corrosion and delamination are interactive and promote the formation and propagation of one another.

14 SOLAR ENERGY↗

Effects of surface initial condition on aqueous corrosion of glass-A study with a model nuclear waste glass

Being a nonequilibrium material, the structure of glass varies with the sample history. Thus, the initial surface condition of a glass can vary with the preparation condition and have a large impact on its reactivity. This paper shows that the aqueous corrosion behavior of international simple glass (ISG) varies depending on the initial surface state. The ISG glass samples were prepared as-polished-only and polished-then-annealed and they were immersed in aqueous solution saturated with soluble SiO 2 at 30°C (modeling a mild condition) and at 90°C (modeling a severe condition). Molecular dynamics simulations were performed to obtain coordination numbers of network formers of ISG to assist oxygen speciation calculations. The surface structures of as-prepared and corroded ISG samples were analyzed using various imaging and spectroscopic techniques. Among these analyses, only the oxygen speciation with x-ray photoelectron spectroscopy showed discernable differences between two uncorroded surfaces with different preparation histories; all other methods could not differentiate the surface preparation history before aqueous corrosion. Such minor difference in chemical structures was found to have a profound impact on corrosion behaviors in the mild condition. In the harsh condition, the surface history dependence was not as drastic as the corrosion in the mild condition. The analysis results of the corroded surfaces suggested that the thickness and structure of the alteration layer formed on ISG in aqueous corrosion can vary with the initial surface state.

nuclear, defects, corrosion↗

Effects of Radiation-Induced Defects on Corrosion

The next generation of nuclear reactors will expose materials to conditions that, in some cases, are even more extreme than those in current fission reactors, inevitably leading to new materials science challenges. Radiation-induced damage and corrosion are two key phenomena that must be understood both independently and synergistically, but their interactions are often convoluted. In the light water reactor community, a tremendous amount of work has been done to illuminate irradiation-corrosion effects, and similar efforts are under way for heavy liquid metal and molten salt environments. While certain effects, such as radiolysis and irradiation-assisted stress corrosion cracking, are reasonably well established, the basic science of how irradiation-induced defects in the base material and the corrosion layer influence the corrosion process still presents many unanswered questions. In this review, we summarize the work that has been done to understand these coupled extremes, highlight the complex nature of this problem, and identify key knowledge gaps.

36 MATERIALS SCIENCE↗

Self-accelerated corrosion of nuclear waste forms at material interfaces

The US plan for high-level nuclear waste includes the immobilization of long-lived radionuclides in glass or ceramic waste forms in stainless-steel canisters for disposal in deep geological repositories. Here we report that, under simulated repository conditions, corrosion could be significantly accelerated at the interfaces of different barrier materials, which has not been considered in the current safety and performance assessment models. Severe localized corrosion was found at the interfaces between stainless steel and a model nuclear waste glass and between stainless steel and a ceramic waste form. The accelerated corrosion can be attributed to changes of solution chemistry and local acidity/alkalinity within a confined space, which significantly alter the corrosion of both the waste-form materials and the metallic canisters. The corrosion that is accelerated by the interface interaction between dissimilar materials could profoundly impact the service life of the nuclear waste packages, which, therefore, should be carefully considered when evaluating the performance of waste forms and their packages. Moreover, compatible barriers should be selected to further optimize the performance of the geological repository system.

Guo, Xiaolei↗

Accelerating effects of galvanic corrosion and dissimilar materials on the corrosion of 316H in NaCl-MgCl2 salt

Corrosion of materials presents a significant challenge for the long-term operation of molten salt reactors. This study aims to identify the most effective techniques for evaluating the corrosion performance of materials in molten salts, with a focus on the effects of galvanic corrosion and dissimilar materials. A reliable testing methodology for assessing material corrosion in molten chloride salts has been successfully developed. The corrosion of Alloy 316H in molten NaCl-MgCl2 salt was found to be significantly accelerated by galvanic corrosion. Additionally, the presence of dissimilar materials resulted in a slight increase in the corrosion rate of Alloy 316H in NaCl-MgCl2 salt. Microstructural characterization was utilized to understand the corrosion behavior of test samples under different conditions. Common trends observed across samples include chromium depletion and iron enrichment near corroded surfaces. Molybdenum enrichment along grain boundaries and corrosion surfaces was also frequently noted.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hydro-chemo-mechanical phase field formulation for corrosion induced cracking in reinforced concrete

Steel corrosion induced cracking in reinforced concrete structures is often caused by volumetric straining at the steel-concrete interface. This volumetric strain is mainly controlled by the rate of generation of corrosion product, which depends on the diffusion of Cl{sup −} and dissolved O{sub 2} as well as the chemical reaction at the steel-concrete interface. While many numerical modeling techniques have been proposed to tackle this complex phenomenon, most have been limited to using staggered solution schemes, where the diffusion, chemical reaction, mechanical strain, and crack fields are solved for separately. Unfortunately, such approaches introduce numerical errors that can lead to unrealistic predictions. Therefore, a coupled solution, is needed to remove the formulation induced errors and understand this complex phenomenon. To provide a unifying solution framework for corrosion induced cracking in reinforced concrete, a phase field formulation is presented and implemented with FEM algorithms. The governing equations are derived from the system's free energy and Fick's law of diffusion. The proposed formulation was first validated in 1D by comparing the modeling results with the semi-analytical solution approximated via Laurent series to avoid singularities in the complex domain. 2D plane strain solutions to the embedded rebar undergoing corrosion induced cracking with pre-cracks are also presented and compared with the approximated solutions from linear elastic fracture mechanics theory (LEFM). The modeling of crack propagation enabled by the proposed formulation is also presented along with parametric studies to reveal the roles of the fracture toughness and permeability of the concrete on the corrosion induced cracking. A case study was also conducted on H-pile steel with concrete jackets to demonstrate the feasibility of modeling corrosion induced fracture in reinforced concrete structures with complex steel-concrete interfaces.

36 MATERIALS SCIENCE↗

Revisiting the effects of molybdenum and tungsten alloying on corrosion behavior of nickel-chromium alloys in aqueous corrosion

Minor alloying additions such as molybdenum (Mo) have major effects on the localized corrosion resistance of corrosion resistant alloys containing chromium. However, progress in alloy development is mostly based upon empirical observations, where any mechanistic insights are largely relegated to the latter stages of localized corrosion (i.e., stabilization and propagation) that are more readily accessible experimentally. For instance, it is well understood that Mo and tungsten (W) affect repassivation of local active, as well as widespread transpassive, corrosion sites and Mo surface enrichment during corrosion is well-documented. In this paper, a comprehensive examination of the functions and mechanism by which selected Mo and W operate to improve the passivity and resistance to breakdown during the initial stages of localized corrosion of the most common Ni-based solid solution alloys is presented. Furthermore, it is shown that Mo and W exert considerable influence on many stages of corrosion, including both passivation and film breakdown, re-enforcing old and introducing more recent ideas in this comprehensive review of the current state of corrosion research on Ni-Cr-(Mo + W) alloys.

36 MATERIALS SCIENCE↗