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At least 217 records · Page 12

Corrosion Behavior of Pipeline Steel with Different Microstructures Under AC Interference in Acid Soil Simulation Solution

Corrosion behavior of X65 pipeline steels with different microstructures under alternating current (AC) interference was investigated in acid soil simulation solution by potentiodynamic polarization curve, potentiostatic polarization curve and immersion test. The results show that superimposed AC causes a sharp increase in corrosion current density of X65 steel. With the increase in i{sub AC}, the corrosion current densities of steels with various microstructures increase, especially at high i{sub AC}. Hot-rolled steel mainly experiences uniform corrosion, with very slight pit corrosion. Serious corrosion degrees with intensive corrosion pits can be observed on the surfaces of normalized and quenched microstructure steels. The annealed steel exhibits the feature of non-uniform corrosion with some pitting. The steels with various microstructures applied with AC have different corrosion resistance. The normalized steel shows the worst corrosion resistance, then the quenched microstructure, and the hot-rolled steel displays the optimum corrosion resistance. The difference in the microstructure can result in difference in corrosion degree and occurrence position of pitting corrosion of X65 steel. The normalized microstructure composed of polygonal ferrite and a large amount of pearlite and bainite is the most susceptible to AC corrosion.

36 MATERIALS SCIENCE↗

Research on the Corrosion Behavior of X70 Pipeline Steel Under Coupling Effect of AC + DC and Stress

The coupling effect of stray AC (alternating current) + DC (direct current) and tensile stress-induced X70 pipeline corrosion is complicated with its mechanism uncovered. In this work, the corrosion behavior of X70 pipeline steel under three different corrosion (including an individual AC corrosion, mixed AC + 150 MPa tensile stress corrosion, coupling effect of AC + a 30 A/m{sup 2} DC interference and 150 MPa tensile stress corrosion) conditions in Dagang soil simulated solution was investigated by COMSOL Multiphysics software simulation, electrochemical tests, scanning electron microscope and other techniques. The results indicated that with the increase in AC density, the open-circuit potential of the X70 steel samples was negatively shifted and corrosion rate increased in three different corrosion conditions. The corrosion rates of X70 steel samples under individual AC interference were almost unchanged when 150.9 MPa tensile stress was applied. When applying 30 A/m{sup 2} DC interference, the corrosion rate of X70 steel increases significantly. Therefore, the factors affecting corrosion performance of X70 pipeline steel were DC > AC > stress. Under individual AC interference, uniform corrosion occurred on the X70 steel at an AC current density of less than 30 A/m{sup 2}, while the pitting corrosion occurred at an AC current density of greater than 100 A/m{sup 2}. The application of tensile stress and DC had a certain inhibitory effect on pitting corrosion.

36 MATERIALS SCIENCE↗

Corrosion behavior in high heat input welded heat-affected zone of Ni-free high-nitrogen Fe–18Cr–10Mn–N austenitic stainless steel

The pitting corrosion and interphase corrosion behaviors in high heat input welded heat-affected zone (HAZ) of a metastable high-nitrogen Fe–18Cr–10Mn–N austenitic stainless steel were explored through electrochemical tests. The HAZs were simulated using Gleeble simulator with high heat input welding condition of 300 kJ/cm and the peak temperature of the HAZs was changed from 1200 °C to 1350 °C, aiming to examine the effect of δ-ferrite formation on corrosion behavior. The electrochemical test results show that both pitting corrosion resistance and interphase corrosion resistance were seriously deteriorated by δ-ferrite formation in the HAZ and their aspects were different with increasing δ-ferrite fraction. The pitting corrosion resistance was decreased by the formation of Cr-depleted zone along δ-ferrite/austenite (γ) interphase resulting from δ-ferrite formation; however it didn't depend on δ-ferrite fraction. The interphase corrosion resistance depends on the total amount of Cr-depleted zone as well as ferrite area and thus continuously decreased with increasing δ-ferrite fraction. The different effects of δ-ferrite fraction on pitting corrosion and interphase corrosion were carefully discussed in terms of alloying elements partitioning in the HAZ based on thermodynamic consideration. - Highlights: • Corrosion behavior in the weld HAZ of high-nitrogen austenitic alloy was studied. • Cr{sub 2}N particle was not precipitated in high heat input welded HAZ of tested alloy. • Pitting corrosion and interphase corrosion show a different behavior. • Pitting corrosion resistance was affected by whether or not δ-ferrite forms. • Interphase corrosion resistance was affected by the total amount of δ-ferrite.

36 MATERIALS SCIENCE↗

Environmentally Friendly Coating Technology for Autonomous Corrosion Control

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.

Coatings↗

Corrosion Behavior of AZ31 Magnesium Alloy Produced by Continuous Variable Cross Section Direct Extrusion

In order to study the corrosion behavior of magnesium alloys of high performance in the simulated seawater by continuous variable cross section direct extrusion (CVCDE), an electrochemical method and weight loss method were used to study the difference between AZ31 magnesium alloys produced by CVCDE with different numbers of interim dies to examine the electrochemical corrosion behavior and corrosion rate at 3.5 wt.% NaCl solution in this paper. Scanning electron microscopy and x-ray diffraction were used to analyze the morphology of corrosion surfaces and the composition of the corrosion products of samples soaked for different times. The results show that after CVCDE with different numbers of interim dies, the size of the microstructure is refined gradually, and the grain orientation is also different; with the increase in the number of interim dies, the thermodynamic corrosion tendencies are different, and the corrosion resistance of samples extruded by conventional extrusion is relatively good; the charge transfer and material transfer process are the two main factors affecting the corrosion rate, which determines the direction of the electrochemical reaction; the corrosion form of the sample extruded by CVCDE is the local corrosion which is the filiform corrosion and pitting corrosion, and the corrosion product is mainly water-insoluble Mg(OH){sub 2}.

36 MATERIALS SCIENCE↗

A Multi-Scale Computational Platform for Predictive Modeling of Corrosion in Al-Steel Joints (Final Report)

The research team proposed to develop innovative multi-scale models to predict corrosion and the resulting mechanical performances in aluminum-steel joints. The methods of joining considered are resistance spot welding, self-piercing riveting, and rivet-welding, all suitable for mass production applications. The multi-scale models integrate high throughput first-principle calculations based on density functional theory (DFT), high throughput calculation of phase diagrams (CALPHAD) modeling, and finite element method (FEM) simulations. These models are to be validated through laboratory experiments. Furthermore, the models are available as open source so as to enable scientists and engineers in the community to adapt and contribute to the development and application. The approaches rely on the research team’s extensive experience on the prediction of properties of individual phases at finite temperatures and variable compositions through DFT calculations, and our broad expertise on dissimilar material joining and their corrosion. The proposed computational framework enables high throughput computations for improved predictions of corrosion and the associated mechanical performance in dissimilar material joints, resulting in significant reduction in computational time needed by the current state-of-the-art methods. With the participation of researchers from three universities, an auto manufacturer, two manufacturing technology/equipment suppliers, and a software developer/vendor, the interdisciplinary research team applies the technical development on both phase-based modeling and laboratory experiments into the automobile body joining processes for validation and technology demonstration. The global cost of corrosion was estimated at about 3.4% of the global GDP in 2013. By using available corrosion control practices, it is estimated a saving between 15-35% of the cost of corrosion. In the U.S., more than $276 billion is spent repairing corrosion damage. Prediction of the corrosion and its impact on performance of the dissimilar material joints is critical for reducing the massive number of the current corrosion-based recalls for automobiles. Thus, the project goal is to develop models to enable predictive maintenance and end-of-life planning of multi-metal joints with risk of corrosion under different conditions such as exposure to high temperatures in summer and salt solutions in winter, quantified through its pH. An academia-industry consortium led by the University of Michigan and including Pennsylvania State University, University of Illinois Urbana-Champaign, University of Georgia, General Motors Company, Livermore Software Technology Corporation, and Optimal Process Technologies, LLC. created multi-scale models for prediction of corrosion in aluminum-steel joint structures such of them used in vehicle subassemblies – chassis and transmission systems. Starting from the first principle calculations, the team developed mathematical and data-driven models to predict the metallic components, which are formed during joining of two metals, for example aluminum and steel - a lightweight multilateral system which is currently used in more than 60% car bodies. These models were used for simulating chemical reactions that are happening when the joining metallic components are exposed to high temperatures and different pH values. The team was able to predict how the corrosion installs on the metallic components and how they lead to a sudden failure of components in cars. Newly developed machine learning algorithms combining Science, Technology, Engineering and Math disciplines, advanced finite element simulation and experimental validations have been integrated in a platform for prediction of the corrosion evolution and prediction the failure of joints under mechanical loadings and fatigue. Moreover, based on machine learning and inverse analysis, the team proposed solutions for designing new metallic alloys less susceptible to corrosion when joining multi-material assembles. An average of 4% error compared with experiments was achieved for the most common joints that are used in vehicle subassemblies.

36 MATERIALS SCIENCE↗

Review and Summary of Corrosion Behavior for Aluminum-Clad Spent Nuclear Fuel in Dry Storage

A description of the corrosion behavior of aluminum alloys used for cladding on aluminum-based, aluminum-clad nuclear fuel used in research reactors under potential dry storage conditions has been compiled. An evaluation is made of potential additional corrosion with water postulated to not be removed during drying. The relative humidity (RH) produced by typical dryness criteria for industrial spent nuclear fuel drying is expected to be low, particularly at high temperatures (17% RH at 20°C and lower at higher temperatures). Existing corrosion data suggests that negligible vapor-phase corrosion of aluminum is expected at such low humidity, even for nominally bare aluminum surfaces. That is, the predicted relative humidity from free water (e.g., 17% RH) is below the “critical” relative humidity (~40% RH at room temperature), below which no significant corrosion is observed for bare aluminum. Furthermore, reported room-temperature corrosion rates are very low even under saturated (100% RH) water vapor. Existing results showing significant vapor-phase corrosion corresponded specifically to conditions of high temper ed with high relative humidity. A relatively large reservoir of (chemically bound) water exists in the aluminum (oxy)hydroxide films on the SNF cladding surface. The estimated total could saturate the gas even at relatively high temperature if fully released; however, its release as molecular water is expected to only be plausible if the temperature during storage exceeds both the drying temperature and the threshold for thermal decomposition of the trihydroxides (~220°C). Therefore, the combination of high temperature and high relative humidity that could drive significant corrosion is considered implausible during sealed dry storage following an appropriate drying process, to include >220°C drying for canisters that may approach or exceed this temperature during storage. Vapor-phase testing of aluminum samples with an adherent (oxy)hydroxide layer, prepared in liquid water to resemble those on actual aluminum-clad spent nuclear fuel (ASNF), did not observe evidence of additional corrosion even at combined high-temperature (up to 180°C) and high-humidity (up to 100% RH) conditions. Instead, small net mass losses were observed for most specimens and attributed to dehydration of the samples, which had been air-dried only prior to testing. ASNF being moved to dry storage is expected to have an existing (oxy)hydroxide film, suggesting that the cladding will be less prone to additional corrosion than bare aluminum metal. If significant corrosion did occur during sealed storage, the overall extent and impact is expected to be small. Corrosion post-closure of a canister would not alter the total amount of hydrogen in the canister, so it would have no effect on the maximum H 2 release already assessed in existing bounding calculations. In addition, the total amount of water in a 25-µm dense bayerite film would consume a only ~8 µm additional aluminum metal on average, if fully consumed by oxidizing aluminum metal to Al 2 O 3 . These conclusions are consistent with ASNF-in-canister simulations to date, which included a reaction pathway for corrosion using kinetics from previous literature and believed to be conservative and predicted very low rates of corrosion.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Corrosion of Zinc Cold Spray Coatings in a Wet Sweet and Sour Gas Environment

Internal corrosion is a problem for steel pipelines transporting natural gas or CO 2 containing water and partial pressures of H 2 S higher than 0.3 kPa (0.05 psi). This work aims to mitigate internal corrosion in steel pipelines transporting natural gas containing H 2 S using cold spray coatings. Two types of the cold spray binary metallic coatings (zinc chromium [ZnCr]. zinc niobium [ZnNb]) were studied using electrochemical techniques: potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The corrosion resistance of cold spray coatings (ZnCr, ZnNb) was evaluated in an environment containing 4 bar CO 2 pressure, simulating the partial pressures found in gas transmission lines over a solution of 3.5 wt% NaCl heated to 40°C. A concentration of 0.003 M Na 2 S 2 O 3 ·5H 2 O, corresponding to H 2 S partial pressures around 0.079 bar (1.146 psi), was used to simulate sour conditions. Postcorrosion surface characterization was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive x-ray spectroscope (EDS) and x-ray diffraction analysis. The data showed that the presence of 0.003 M Na 2 S 2 O 3 ·5H 2 O shifted the corrosion potential to more anodic values and decreased the corrosion current density. Both coatings showed similar behavior after 1 h of exposure in the CO 2 /H 2 S environment, indicating that similar electrochemical reactions were occurring on ZnNb and ZnCr. SEM images and EDS surface analyses for specimens showed a significant change in the surface chemical composition of carbon steel coated with ZnNb and ZnCr after 24 h of immersion. In the presence of thiosulfate (under sour conditions), the formation of corrosion product layers (ZnCO 3 and ZnS) on top of ZnNb and ZnCr coatings increased their corrosion resistance, which helped to reduce their corrosion by a factor of 2. Under a sweet environment, the corrosion rates for steel coated with cold spray coatings after 14 d of exposure are lower than that for galvanized steel by a factor of 5 due to the ZnCO 3 layer formed on top of the coatings. The ZnCO 3 layer formed on the steel surface acts as a physical barrier against corrosion by blocking the diffusion of corrosive species to the surface. No localized attack was observed. ZnCr Cold spray coating with defect showed promising corrosion protection against CO 2 corrosion (sweet corrosion) after 14 d of exposure to a CO 2 environment. Here, the scratch on the coating simulated damage created in service, and it was deep enough to expose the substrate material (steel). The formation of zinc oxide (ZnO) and zinc carbonate (ZnCO 3 ) on the scratch confirmed the cathodic protection of the steel by ZnCr and ZnNb coatings.

36 MATERIALS SCIENCE↗

Assessment of the Corrosion Risks to a Double Shell Tank During the Selective Removal of a Cesium-rich Supernate Layer - 20227

The Direct Feed Low Activity Waste (DF-LAW) activity will provide the initial feed to the Waste Treatment and Immobilization Plant at the Hanford Tank Farm facility. Feed preparation for DF-LAW will be carried out in multiple double shell waste tanks (DST) utilizing the Tank Side Cesium Removal (TSCR) process. Tank AP-106 will be an integral part of the TSCR process and hence key to the DFLAW activity. Prior to being utilized for this purpose, the Cs-137 concentration levels in the AP-106 supernate must be reduced significantly. The AP-106 re-purposing process manages normal waste tank addition procedures such that waste acceptance criteria objectives for Cs-137 removal are achieved. As this process was being developed, several concerns regarding tank integrity during and after repurposing of Tank AP-106, and the associated tanks (i.e., AP-102, AN-101, and AP-108), were addressed. The potential corrosion degradation mechanisms identified based on process knowledge included: general and pitting corrosion, caustic stress corrosion cracking, concentration cell corrosion, and microbiologically induced corrosion (MIC). A systematic approach was undertaken to assess the risk of corrosion during the AP-106 re-purposing process. The assessment considered the initial and present condition of the tank, the service history of the tank, the environmental conditions created in each tank during each stage of the process, process timing, and corrosion testing and modeling that approximated tank conditions. Based on this information, recommendations were provided to minimize the exposure of the tank to corrosive conditions. These recommendations included time limits for each stage of the process, staging of corrosion inhibitor solutions should process delays occur, and waste sampling with potential chemistry adjustments at defined steps in the process. Additionally, recommendations for post-process supernate chemistry adjustments and tank inspections were put forth. The greatest risk for this process occurs during the manipulation of large quantities of Columbia River water (i.e., greater than 450,000 gallons) within AP-106, the associated tanks and the supporting infrastructure (i.e., transfer line piping). This risk becomes more pronounced if there is a process upset and the tank walls remain exposed to a corrosive condition longer than intended. As long as the river water is blended into the supernate in a timely fashion, and the waste is adjusted appropriately with corrosion inhibitors, corrosion may be minimized and the final condition of the supernate in AP-106 and the associated tanks is expected to be in compliance with corrosion chemistry requirements. Contingency plans will be made to minimize the impact of a process upset. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electrochemical metrics for corrosion resistant alloys

Abstract Corrosion is an electrochemical phenomenon. It can occur via different modes of attack, each having its own mechanisms, and therefore there are multiple metrics for evaluating corrosion resistance. In corrosion resistant alloys (CRAs), the rate of localized corrosion can exceed that of uniform corrosion by orders of magnitude. Therefore, instead of uniform corrosion rate, more complex electrochemical parameters are required to capture the salient features of corrosion phenomena. Here, we collect a database with an emphasis on metrics related to localized corrosion. The six sections of the database include data on various metal alloys with measurements of (1) pitting potential, E pit , (2) repassivation potential, E rp , (3) crevice corrosion potential, E crev , (4) pitting temperature, T pit , (5) crevice corrosion temperature, T crev , and (6) corrosion potential, E corr , corrosion current density, i corr , passivation current density, i pass , and corrosion rate. The experimental data were collected from 85 publications and include Al- and Fe-based alloys, high entropy alloys (HEAs), and a Ni-Cr-Mo ternary system. This dataset could be used in the design of highly corrosion resistant alloys.

36 MATERIALS SCIENCE↗

Launch Pad Coatings for Smart Corrosion Control

Corrosion is the degradation of a material as a result of its interaction with the environment. The environment at the KSC launch pads has been documented by ASM International (formerly American Society for Metals) as the most corrosive in the US. The 70 tons of highly corrosive hydrochloric acid that are generated by the solid rocket boosters during a launch exacerbate the corrosiveness of the environment at the pads. Numerous failures at the pads are caused by the pitting of stainless steels, rebar corrosion, and the degradation of concrete. Corrosion control of launch pad structures relies on the use of coatings selected from the qualified products list (QPL) of the NASA Standard 5008A for Protective Coating of Carbon Steel, Stainless Steel, and Aluminum on Launch Structures, Facilities, and Ground Support Equipment. This standard was developed to establish uniform engineering practices and methods and to ensure the inclusion of essential criteria in the coating of ground support equipment (GSE) and facilities used by or for NASA. This standard is applicable to GSE and facilities that support space vehicle or payload programs or projects and to critical facilities at all NASA locations worldwide. Environmental regulation changes have dramatically reduced the production, handling, use, and availability of conventional protective coatings for application to KSC launch structures and ground support equipment. Current attrition rate of qualified KSC coatings will drastically limit the number of commercial off the shelf (COTS) products available for the Constellation Program (CxP) ground operations (GO). CxP GO identified corrosion detection and control technologies as a critical, initial capability technology need for ground processing of Ares I and Ares V to meet Constellation Architecture Requirements Document (CARD) CxP 70000 operability requirements for reduced ground processing complexity, streamlined integrated testing, and operations phase affordability. Researchers at NASA's Corrosion Technology Laboratory at KSC are developing a smart, environmentally friendly coating system for early corrosion detection, inhibition, and self healing of mechanical damage without external intervention. This smart coating will detect and respond actively to corrosion and mechanical damage such as abrasion and scratches, in a functional and predictable manner, and will be capable of adapting its properties dynamically. This coating is being developed using corrosion sensitive microcapsules that deliver the contents of their core (corrosion inhibiting compounds, corrosion indicators, and self healing agents) on demand when corrosion or mechanical damage to the coating occurs.

Calle, Luz M.↗

Discerning the effect of various irradiation modes on the corrosion of Zircaloy-4

Using proton irradiation, this study investigates the individual influence of several factors on the corrosion kinetics of Zircaloy-4 in a hydrogenated water environment simulating a Pressurized Water Reactor (PWR). Using both simultaneous irradiation-corrosion and autoclave corrosion, we separately examine: (i) the effect of pre-irradiation on modifying the structure of the material, (ii) the impact of irradiation on creating defects in the growing oxide layer during corrosion, and (iii) the influence of irradiation on increasing the corrosion potential through radiolysis during corrosion. To replicate neutron-irradiated microstructure, two proton pre-irradiation schedules were employed: Schedule 1 (isothermal irradiation at 350 °C to 5 dpa) to simulate high-temperature PWR conditions, and Schedule 2 (two-step process: irradiation to 2.5 dpa at -10 °C followed by 2.5 dpa at 350 °C) to simulate lower temperature PWR and Boiling Water Reactor (BWR) conditions. Long-term autoclave corrosion testing over 360 days at 320 °C revealed no significant difference between unirradiated samples and those pre-irradiated according to either schedule, with all samples exhibiting sub-cubic kinetics within the pre-transition regime. Irradiated samples underwent Simultaneous Irradiation Corrosion (SIC) tests, corroding in 320 °C water while being irradiated with protons. Corrosion was found to accelerate in all SIC-tested samples relative to autoclave conditions, with the greatest increase observed in non-pre-irradiated samples. Pre-irradiation with either schedule resulted in a slower corrosion rate compared to non-pre-irradiated regions under SIC conditions. The degree of radiolysis observed in the SIC tests surpassed typical PWR conditions, approaching levels found in BWRs. Radiolysis products were identified as the primary contributors to accelerated corrosion, corroborated by radiolysis bar tests. Furthermore, these findings underscore the intricate interactions between irradiation, corrosion, and water chemistry in determining Zircaloy-4 corrosion kinetics within nuclear reactor environments.

Pressurized Water Reactor↗

Progress in Understanding the Origins of Excellent Corrosion Resistance in Metallic Alloys: From Binary Polycrystalline Alloys to Metallic Glasses and High Entropy Alloys

Some of the factors responsible for good corrosion resistance of select polycrystalline and emerging alloys in chloride solutions are discussed with a goal of providing some perspectives on the current status and future directions. Traditional metallic glass alloys, single phase high entropy alloys (HEAs), early metallic glasses, and high entropy metallic glasses are all emerging corrosion-resistant alloys (CRAs) that utilize traditional strategies for improved corrosion resistance as well as take advantage of some other novel beneficial attributes. These materials enjoy many degrees of freedom as far as choice of both composition and structure, providing great flexibility in the pursuit of superior corrosion resistance. The new materials depart from classical solvent-solute type polycrystalline binary or ternary alloys. Thus, such emerging materials provide significant opportunities to achieve even greater improvements in corrosion resistance in harsh environments. Several examples of the unique corrosion properties of selected materials in the context of modern theories of corrosion are discussed herein. Discussion is restricted to solid-solution binary or ternary polycrystalline alloys, several metallic glass alloys, and single phase HEAs. A common feature of many CRAs is that composition and microstructure often affect both passivity and resistance to localized corrosion that can be divided into initiation, stabilization, and propagation stages. Enormous complexities in protective oxide structures and chemistries and the large number of combinatorial possibilities in newer materials such as HEAs preclude trial-and-error approaches and perhaps even combinatorial experimental design. Computational materials methodologies will be required in the search for new corrosion-resistant alloys in these material classes. The search must consider the best scientific insights available regarding how major and minor alloy additions, as well as various microstructural attributes, contribute to corrosion mitigation. Additional scientific insights, as they emerge, will enable choices beyond the reliance on high concentrations of alloying elements that are known to affect passivity breakdown and pit stabilization. A challenge is to connect the “basic attributes” of an alloy with its properties. The strength of this connection will likely require new scientific principles enabling deep multiphysics insights in order to link feature(s) such as composition and metallurgical phases to the desired corrosion properties. Application of data informatics will likely also play a role given the plethora of variables that are important in corrosion and the difficulty in assessing all relationships. Here, the opportunity exists to accelerate the design of emerging materials for high corrosion resistance.

36 MATERIALS SCIENCE↗

Corrosion Monitoring in an Irradiated/Used Fuel Dry Storage Container - 19193

A corrosion monitoring system was developed to monitor the corrosion behaviour of steel components embedded in the high density concrete of a Dry Storage Container (DSC). The DSC is a free-standing reinforced concrete container, with an inner carbon-steel liner and an outer carbon-steel shell, for the storage, on-site transfer and off-site transportation of irradiated Candu fuel. Normally, uncontaminated concrete is benign with regards to embedded steel components because high alkalinity in the concrete leads to formation of a passive film on the steel surface, which prevents excessive metal loss. However, corrosion of steel in concrete may be promoted by one or more of local concentration of chloride ions or local loss of alkalinity. For the DSC, it is recognized that the above mechanism(s) are unlikely, however, if any did exist, the corrosion mechanisms that could then occur would include corrosion of carbon steel components and stress corrosion cracking of 304L stainless steel components. In order to confirm that these unlikely events are not occurring, Ontario Power Generation has undertaken a project to investigate the corrosion behaviour of metallic components embedded in the DSC's high density concrete. A corrosion monitoring system that can be installed within the concrete space of a DSC was designed and installed to monitor changes in temperature, corrosion potential, corrosion rate, and electrochemical noise. The corrosion monitoring system was commissioned in July 2012, followed by the commencement of monitoring and measurements. The corrosion data, collected for the three years from year 2012 to 2015, were analyzed. It was concluded that the corrosion rates of both carbon steel and stainless steel within the DSC are very low and consistent with the intended minimum operational life of the DSC. The monitoring system as a whole has allowed a systematic and long term judgement regarding the conditions within the DSCs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Stainless steel corrosion by molten nitrates : analysis and lessons learned.

A secondary containment vessel, made of stainless 316, failed due to severe nitrate salt corrosion. Corrosion was in the form of pitting was observed during high temperature, chemical stability experiments. Optical microscopy, scanning electron microscopy and energy dispersive spectroscopy were all used to diagnose the cause of the failure. Failure was caused by potassium oxide that crept into the gap between the primary vessel (alumina) and the stainless steel vessel. Molten nitrate solar salt (89% KNO{sub 3}, 11% NaNO{sub 3} by weight) was used during chemical stability experiments, with an oxygen cover gas, at a salt temperature of 350-700 C. Nitrate salt was primarily contained in an alumina vessel; however salt crept into the gap between the alumina and 316 stainless steel. Corrosion occurred over a period of approximately 2000 hours, with the end result of full wall penetration through the stainless steel vessel; see Figures 1 and 2 for images of the corrosion damage to the vessel. Wall thickness was 0.0625 inches, which, based on previous data, should have been adequate to avoid corrosion-induced failure while in direct contact with salt temperature at 677 C (0.081-inch/year). Salt temperatures exceeding 650 C lasted for approximately 14 days. However, previous corrosion data was performed with air as the cover gas. High temperature combined with an oxygen cover gas obviously drove corrosion rates to a much higher value. Corrosion resulted in the form of uniform pitting. Based on SEM and EDS data, pits contained primarily potassium oxide and potassium chromate, reinforcing the link between oxides and severe corrosion. In addition to the pitting corrosion, a large blister formed on the side wall, which was mainly composed of potassium, chromium and oxygen. All data indicated that corrosion initiated internally and moved outward. There was no evidence of intergranular corrosion nor were there any indication of fast pathways along grain boundaries. Much of the pitting occurred near welds; however this was the hottest region in the chamber. Pitting was observed up to two inches above the weld, indicating independence from weld effects.

36 MATERIALS SCIENCE↗

Corrosion in Supercritical Carbon Dioxide: Materials, Environmental Purity, Surface Treatments, and Flow Issues (Project No. 10-872)

The supercritical CO 2 Brayton cycle is gaining importance for power conversion in the Generation IV fast reactor system because of its high conversion efficiencies. When used in conjunction with a sodium fast reactor, the supercritical CO 2 cycle offers additional safety advantages by eliminating potential sodium-water interactions that may occur in a steam cycle. In power conversion systems for Generation IV fast reactors, supercritical CO 2 temperatures could be in the range of 30°C to 650°C, depending on the specific component in the system. Materials corrosion primarily at high temperatures will be an important issue. Therefore, the corrosion performance limits for materials at various temperatures must be established. The proposed research will have four objectives centered on addressing corrosion issues in a high-temperature supercritical CO 2 environment: Task 1: Evaluation of corrosion performance of candidate alloys in high-purity supercritical CO 2 : The following alloys will be tested: Ferritic-martensitic Steels NF616 and HCM12A, austenitic alloys Incoloy 800H and 347 stainless steel, and two advanced concept alloys, AFA (alumina forming austenitic) steel and MA754. Supercritical CO 2 testing will be performed at 450°C, 550°C, and 650°C at a pressure of 20 MPa, in a test facility that is already in place at the proposing university. High purity CO 2 (99.9998%) will be used for these tests. Task 2: Investigation of the effects of CO, H 2 O, and O 2 impurities in supercritical CO 2 on corrosion: Impurities that will inevitably present in the CO 2 will play a critical role in dictating the extent of corrosion and corrosion mechanisms. These effects must be understood to identify the level of CO 2 chemistry control needed to maintain sufficient levels of purity to manage corrosion. The individual effects of important impurities CO, H 2 O, and O 2 will be investigated by adding them separately to high purity CO 2 . Task 3: Evaluation of surface treatments on the corrosion performance of alloys in supercritical CO 2 : Surface treatments can be very beneficial in improving corrosion resistance. Shot peening and yttrium and aluminum surface treatments will be investigated. Shot peening refines the surface grain sizes and promotes protective Cr-oxide layer formation. Both yttrium and aluminum form highly stable oxide layers (Y 2 O 3 and Al 2 O 3 ), which can get incorporated in the growing Fe-oxide layer to form an impervious complex oxide to enhance corrosion resistance. Task 4: Study of flow-assisted corrosion of select alloys in supercritical CO 2 under a selected set of test conditions: To study the effects of flow-assisted corrosion, tests will be conducted in a supercritical CO 2 flow loop. An existing facility used for supercritical water flow studies at the proposing university will be modified for use in this task. The system is capable of flow velocities up to 10 m/s and can operate at temperatures and pressures of up to 650°C and 20 MPa, respectively. All above tasks will be performed in conjunction with detailed materials characterization and analysis using scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS), x-ray diffraction (XRD), Auger electron spectroscopy (AES) techniques, and weight change measurements. Inlet and outlet gas compositions will be monitored using gas chromatography-mass spectrometry (GCMS).

36 MATERIALS SCIENCE↗

Development of Preliminary VERA-CS Crud Induced Localized Corrosion Modeling Capability

The objective of this milestone was to develop a crud-induced localized corrosion (CILC) screening capability in VERA-CS using existing codes and capabilities that had been developed in the Consortium for Advanced Simulation of Light Water Reactors (CASL) as part of the efforts to resolve the crud challenge problem. The milestone work focused on improving existing CASL software and implementing clad corrosion modeling into VERA-CS. Clad corrosion modeling was implemented by creating an application interface (API) in the Cicada software so that its clad heat transfer and corrosion models could be used in VERA-CS. Cicada was coupled to the subchannel code CTF for solving crud and corrosion growth. Additionally, a clad corrosion model was added directly to CTF to serve as an alternate approach. The rod thermal hydraulic reconstruction (ROTHCON) process, which is used for capturing computational fluid dynamics (CFD)-predicted rod-surface heat and turbulence behavior that can impact crud-induced power shift (CIPS) and CILC prediction, was also implemented into VERA-CS. Usability improvements were made to this feature, which was developed over several previous milestones, so that the VERA-CS user can link spacer grids in a VERA-CS model to an applicable pregenerated spacer grid data file if available. Several assessments were performed to demonstrate the proper functioning of the new capability. Sensitivity studies were performed to demonstrate the effect of crud lithium content, oxide thermal conductivity, Cicada mesh refinement, and ROTHCON coupling mesh refinement on predicted amounts of crud and oxide growth. A full-scale demonstration was performed by running Seabrook Cycle 5 with the CILC capability. Some general observations were made from the assessments. It was observed that predicted corrosion thickness is less than anticipated for CILC cases, so further work is needed to better understand and improve the corrosion modeling. Refining the coupling mesh in the ROTHCON process leads to increased corrosion and crud thickness, which can affect where crud and corrosion grow, how thick it gets, and how many rods experience crud and corrosion growth. Results indicate that applying the ROTHCON process and refining the coupling mesh leads to only a slight increase in total core maximum crud and corrosion thickness, but it leads to a significant increase in the number of rods with a maximum thickness that surpasses a set threshold value (i.e., more rods grow thicker corrosion and crud). Computational performance of the simulation is degraded by a factor of 5{6 with high coupling mesh refinement. The impact of the ROTHCON coupling mesh refinement on total core crud mass is less significant; however, using the ROTHCON process with CFD-generated data over the Yao{Hochreiter{Leech (YHL) model in CTF leads to significantly different amounts of total core crud mass. Future work on the CILC screening capability will include model improvement and validation, development and testing of a CILC-risk screening criteria, and performance improvements.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

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. Effective monitoring of corrosion is important to detect and mitigate pipeline risks before corrosion-related catastrophic events happen. Here, we describe the use of Fe-coated optical fiber sensors (OFS) for distributed corrosion monitoring where Fe acts as a corrosion proxy. By using an optical backscatterring reflectometer (OBR), corrosion was monitored based on the increase in backscattered intensity amplitude of the light being passed as Fe undergoes corrosion. The Fe-coated OFSs were prepared with a film thickness between 25-225 nm by an electroless plating approach and corroded by a CO2-saturated acidic electrolyte. The corrosion rate was approximately 2.5 mm/yr for Fe with a film thickness of 30 nm and increased with film thickness. Backscattering-based corrosion rates 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 corrosion of Fe was established. Corrosion was measurable out to > 100 m which is a significant improvement over our previous work showing corrosion sensing at < 10 m. The corrosion sensor was also tested in soil at >1 ft 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.

aqueous environment↗