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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↗

Comparative Stress Corrosion Cracking and General Corrosion Resistance of Annealed and Hardened 440 C Stainless Steel - New Techniques in Stress Corrosion Testing

The corrosion and stress corrosion cracking (SCC) characteristics of annealed and hardened 440C stainless steel were evaluated in high humidity and 3.5-percent NaCl solution. Corrosion testing consisted of an evaluation of flat plates, with and without grease, in high humidity, as well as electrochemical testing in 3.5-percent NaCl. Stress corrosion testing consisted of conventional, constant strain, smooth bar testing in high humidity in addition to two relatively new techniques under evaluation at MSFC. These techniques involve either incremental or constant rate increases in the load applied to a precracked SE(B) specimen, monitoring the crack-opening-displacement response for indications of crack growth. The electrochemical corrosion testing demonstrated an order of magnitude greater general corrosion rate in the annealed 440C. All techniques for stress corrosion testing showed substantially better SCC resistance in the annealed material. The efficacy of the new techniques for stress corrosion testing was demonstrated both by the savings in time and the ability to better quantify SCC data.

Mendreck, M. J.↗

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.↗

Mechanism of Na2SO4-induced corrosion of molybdenum containing nickel-base superalloys at high temperatures. I - Corrosion in atmospheres containing O2 only. II - Corrosion in O2 + SO2 atmospheres

Kinetics of the Na2SO4-induced corrosion of the molybdenum-containing nickel-base superalloys, B-1900 and Udimet 700, coated with Na2MoO4, has been studied in oxygen atmosphere at temperatures ranging from 750 to 950 C. Because the gas turbine atmosphere always contains some SO2 and SO3, the effect of atmospheric SO2 content on corrosion of Udimet-700 has also been studied. It was found that in the O2 atmosphere the melt in the catastrophic corrosion phase consists of Na2MoO4 plus MoO3, with the onset of the catastrophic corrosion coinciding with the appearance of MoO3. In the presence of low levels of atmospheric SO2 (below 0.24 percent), the melt during catastrophic corrosion contains, in addition to Na2MoO4 and MoO3, some quantities of Na2SO4. At the levels of SO2 above 1 percent, no catastrophic corrosion was observed. At these SO2 levels, internal sulfidation appears to be the primary mode of degradation.

Misra, A. K.↗

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↗

Corrosion-Activated Micro-Containers for Environmentally Friendly Corrosion Protective Coatings

This work concerns the development of environmentally friendly encapsulation technology, specifically designed to incorporate corrosion indicators, inhibitors, and self-healing agents into a coating, in such a way that the delivery of the indicators and inhibitors is triggered by the corrosion process, and the delivery of self-healing agents is triggered by mechanical damage to the coating. Encapsulation of the active corrosion control ingredients allows the incorporation of desired autonomous corrosion control functions such as: early corrosion detection, hidden corrosion detection, corrosion inhibition, and self-healing of mechanical damage into a coating. The technology offers the versatility needed to include one or several corrosion control functions into the same coating.The development of the encapsulation technology has progressed from the initial proof-of-concept work, in which a corrosion indicator was encapsulated into an oil-core (hydrophobic) microcapsule and shown to be delivered autonomously, under simulated corrosion conditions, to a sophisticated portfolio of micro carriers (organic, inorganic, and hybrid) that can be used to deliver a wide range of active corrosion ingredients at a rate that can be adjusted to offer immediate as well as long-term corrosion control. The micro carriers have been incorporated into different coating formulas to test and optimize the autonomous corrosion detection, inhibition, and self-healing functions of the coatings. This paper provides an overview of progress made to date and highlights recent technical developments, such as improved corrosion detection sensitivity, inhibitor test results in various types of coatings, and highly effective self-healing coatings based on green chemistry. The NASA Kennedy Space Centers Corrosion Technology Lab at the Kennedy Space Center in Florida, U.S.A. has been developing multifunctional smart coatings based on the microencapsulation of environmentally friendly corrosion indicators, inhibitors and self-healing agents. This allows the incorporation of autonomous corrosion control functionalities, such as corrosion detection and inhibition as well as the self-healing of mechanical damage, into coatings. This paper presents technical details on the characterization of inhibitor-containing particles and their corrosion inhibitive effects using electrochemical and mass loss methods.Three organic environmentally friendly corrosion inhibitors were encapsulated in organic microparticles that are compatible with desired coatings. The release of the inhibitors from the microparticles in basic solution was studied. Fast release, for immediate corrosion protection, as well as long-term release for continued protection, was observed.The inhibition efficacy of the inhibitors, incorporated directly and in microparticles, on carbon steel was evaluated. Polarization curves and mass loss measurements showed that, in the case of 2MBT, its corrosion inhibition effectiveness was greater when it was delivered from microparticles.

Corrosion Control↗

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↗

NASA's Corrosion Technology Laboratory at the Kennedy Space Center: Anticipating, Managing, and Preventing Corrosion

Corrosion is the degradation of a material that results from its interaction with the environment. The marine environment at NASAs Kennedy Space Center (KSC) has been documented by ASM International (formerly American Society for Metals) as the most corrosive in the United States. With the introduction of the Space Shuttle in 1981, the already highly corrosive conditions at the launch pads were rendered even more severe by the 70 tons of highly corrosive hydrochloric acid that were generated by the solid rocket boosters. Numerous failures at the launch pads are caused by corrosion.The structural integrity of ground infrastructure and flight hardware is critical to the success, safety, cost, and sustainability of space missions. As a result of fifty years of experience with launch and ground operations in a natural marine environment that is highly corrosive, NASAs Corrosion Technology Laboratory at KSC is a major source of corrosion control expertise in the launch and other environments. Throughout its history, the Laboratory has evolved from what started as an atmospheric exposure facility near NASAs launch pads into a world-wide recognized capability that provides technical innovations and engineering services in all areas of corrosion for NASA and external customers.This presentation will provide a historical overview of the role of NASAs Corrosion Technology in anticipating, managing, and preventing corrosion. One important challenge in managing and preventing corrosion involves the detrimental impact on humans and the environment of what have been very effective corrosion control strategies. This challenge has motivated the development of new corrosion control technologies that are more effective and environmentally friendly. Strategies for improved corrosion protection and durability can have a huge impact on the economic sustainability of human spaceflight operations.

Corrosion↗

NASA's Corrosion Technology Laboratory at the Kennedy Space Center: Anticipating, Managing, and Preventing Corrosion

The marine environment at NASAs Kennedy Space Center (KSC) has been documented by ASM International (formerly American Society for Metals) as the most corrosive in North America. With the introduction of the Space Shuttle in 1981, the already highly corrosive conditions at the launch pads were rendered even more severe by the highly corrosive hydrochloric acid (HCl) generated by the solid rocket boosters (SRBs). Numerous failures at the launch pads are caused by corrosion. The structural integrity of ground infrastructure and flight hardware is critical to the success, safety, cost, and sustainability of space missions. NASA has over fifty years of experience dealing with unexpected failures caused by corrosion and has developed expertise in corrosion control in the launch and other environments. The Corrosion Technology Laboratory at KSC evolved, from what started as an atmospheric exposure test site near NASAs launch pads, into a capability that provides technical innovations and engineering services in all areas of corrosion for NASA, external partners, and customers.This paper provides a chronological overview of NASAs role in anticipating, managing, and preventing corrosion in highly corrosive environments. One important challenge in managing and preventing corrosion involves the detrimental impact on humans and the environment of what have been very effective corrosion control strategies. This challenge has motivated the development of new corrosion control technologies that are more effective and environmentally friendly. Strategies for improved corrosion protection and durability can have a huge impact on the economic sustainability of human spaceflight operations.

Corrosion Control↗

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↗

Corrosion on Mars: An Investigation of Corrosion Mechanisms Under Relevant Simulated Martian Environments

This one-year project was selected by NASA's Science Innovation Fund in FY17 to address Corrosion on Mars which is a problem that has not been addressed before. Corrosion resistance is one of the most important properties in selecting materials for landed spacecraft and structures that will support surface operations for the human exploration of Mars. Currently, the selection of materials is done by assuming that the corrosion behavior of a material on Mars will be the same as that on Earth. This is understandable given that there is no data regarding the corrosion resistance of materials in the Mars environment. However, given that corrosion is defined as the degradation of a metal that results from its chemical interaction with the environment, it cannot be assumed that corrosion is going to be the same in both environments since they are significantly different. The goal of this research is to develop a systematic approach to understand corrosion of spacecraft materials on Mars by conducting a literature search of available data, relevant to corrosion in the Mars environment, and by performing preliminary laboratory experiments under relevant simulated Martian conditions. This project was motivated by the newly found evidence for the presence of transient liquid brines on Mars that coincided with the suggestion, by a team of researchers, that some of the structural degradation observed on Curiosity's wheels may be caused by corrosive interactions with the brines, while the most significant damage was attributed to rock scratching. An extensive literature search on data relevant to Mars corrosion confirmed the need for further investigation of the interaction between materials used for spacecraft and structures designed to support long-term surface operations on Mars. Simple preliminary experiments, designed to look at the interaction between an aerospace aluminum alloy (AA7075-T73) and the gases present in the Mars atmosphere, at 20degC and a pressure of 700 Pa, showed that there is an interaction between the small amount of oxygen present in the Mars gas and the alloy when there is a scratch that removes the protective aluminum oxide film. Further studies are needed to consider many other important components of the Mars environment that can affect this interaction such as: the effect of oxidants, the effect of radiation on their oxidizing properties and the possible catalytic effects of the clays present in the Martian regolith. The results of this one-year project provide strong justification for further investigation of the corrosion mechanism of materials relevant to long-term surface operations in support of future human exploration missions on Mars.

Perchlorates↗

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↗