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At least 451 records · Page 25

Direct observation of pitting corrosion evolutions on carbon steel surfaces at the nano-to-micro- scales

The Cl¯-induced corrosion of metals and alloys is of relevance to a wide range of engineered materials, structures, and systems. Because of the challenges in studying pitting corrosion in a quantitative and statistically significant manner, its kinetics remain poorly understood. Herein, by direct, nano- to micro-scale observations using vertical scanning interferometry (VSI), we examine the temporal evolution of pitting corrosion on AISI 1045 carbon steel over large surface areas in Cl¯-free, and Cl¯-enriched solutions. Special focus is paid to examine the nucleation and growth of pits, and the associated formation of roughened regions on steel surfaces. By statistical analysis of hundreds of individual pits, three stages of pitting corrosion, namely, induction, propagation, and saturation, are quantitatively distinguished. By quantifying the kinetics of these processes, we contextualize our current understanding of electrochemical corrosion within a framework that considers spatial dynamics and morphology evolutions. In the presence of Cl¯ ions, corrosion is highly accelerated due to multiple autocatalytic factors including destabilization of protective surface oxide films and preservation of aggressive microenvironments within the pits, both of which promote continued pit nucleation and growth. Furthermore these findings offer new insights into predicting and modeling steel corrosion processes in mid-pH aqueous environments

36 MATERIALS SCIENCE↗

Impact of aqueous solution pH on network structure of corrosion–induced surface layers of boroaluminosilicate glass

Understanding of the long-term stability of vitrified nuclear waste glass is critical to its safe storage, but knowledge gaps remain regarding the corrosion mechanism, especially with respect to surface alteration layers whose presence changes the observed corrosion rates. Here, we report the aqueous corrosion of a model boroaluminosilicate glass at ground water relevant pHs as investigated by vibrational spectroscopy to understand the network structure of the alteration layer that we hypothesize controls the corrosion rates. Both specular reflection infrared spectroscopy and infrared variable angle spectroscopic ellipsometry were used to elucidate details of the structure of the alteration layers formed at pH 7 and pH 9. After 2312 days, the thickness of the alteration layer is found to be ~2000 nm for corrosion at pH 7 and ~300 nm for corrosion at pH 9. Here, the interpretation of the vibrational spectra suggests that alteration layers formed at pH 7 and pH 9 both exhibit a porous network with "silica-like" structures, but with differences in the bond lengths and bond angles in the glass network. Moreover, the relative abundance of the hydrous species within the porous network appears to be dependent on pH. Additionally, the spectroscopic data suggest that the B and Ca trapped in the alteration layer during the secondary corrosion of the pH 9 pre-corroded sample in pH 3 solution are hydrated within the nano-porous layer and not bound to the silicate network. However, the precise chemical form remains to be determined. Based on these findings, we propose that the combination of the network structure of the alteration layer and the relative abundance of hydrous species within the alteration layer act to control the transport of ionic species dissolved from the reaction front to the aqueous solution outside the glass.

36 MATERIALS SCIENCE↗

Accelerating FEM-Based Corrosion Predictions Using Machine Learning

Atmospheric corrosion of metallic parts is a widespread materials degradation phenomena that is challenging to predict given its dependence on many factors (e.g. environmental, physiochemical, and part geometry). For materials with long expected service lives, accurately predicting the degree to which corrosion will degrade part performance is especially difficult due to the stochastic nature of corrosion damage spread across years or decades of service. The Finite Element Method (FEM) is a computational technique capable of providing accurate estimates of corrosion rate by numerically solving complex differential Eqs. characterizing this phenomena. Nevertheless, given the iterative nature of FEM and the computational expense required to solve these complex equations, FEM is ill-equipped for an efficient exploration of the design space to identify factors that accelerate or deter corrosion, despite its accuracy. In this work, a machine learning based surrogate model capable of providing accurate predictions of corrosion with significant computational savings is introduced. Specifically, this work leverages AdaBoosted Decision trees to provide an accurate estimate of corrosion current per width given different values of temperature, water layer thickness, molarity of the solution, and the length of the cathode for a galvanic couple of aluminum and stainless steel.

36 MATERIALS SCIENCE↗

Evaluating Corrosion Effects on the Stainless Steel Components of the SAVY-4000/Hagan Nuclear Material Storage Containers

Surveillance of vented, stainless-steel Hagan and SAVY-4000 storage containers with some plutonium materials has revealed evidence of corrosion inside the container. There are ~3000 items stored in Hagan containers and ~600 items currently stored in SAVY-4000 containers at TA -55. The Hagan is made of 304L steel, while the SAVY-4000 is made of 316L and should be less susceptible to corrosion. Given the relatively thin body wall of these containers (nominally 0.762 millimeters), it is essential to understand the effects of corrosion on the lifetime of the containers to ensure worker safety. Studies are being conducted on both container types to determine the relative susceptibility of the two containers to corrosion. This paper describes the potential cause of corrosion, the extent of corrosion, and types of corrosion observed, along with the results of accelerated aging experiments. The combined results of the surveillance and lifetime extension studies establish a technical basis for extending the design life of the stainless steel components of the SAVY-4000 container from 5 years to 15 years.

36 MATERIALS SCIENCE↗

Hanford Tank Waste Disposition Integrated Flowsheet: Corrosion Specification Development Final Report

The Savannah River National Laboratory has developed a corrosion model to facilitate implementation of Hanford’s Direct Feed Low Activity Waste flowsheet. The focus was specifically on secondary effluent waste stream compositions from the Hanford Waste Treatment and Immobilization Plant’s melter off-gas treatment system returned to the Hanford Tank Farms (return stream.) The return stream compositions were predicted to contain components at relative concentrations that are significantly more corrosive toward the carbon steel waste tanks, specifically halide and sulfate anions, than the current waste compositions in the tank farms. Electrochemical tests were performed, utilizing a statistically designed matrix, to determine the corrosion chemistry limits that will mitigate pitting in the return stream. The current corrosion chemistry specifications for the Hanford Tank Farms do not mitigate for the halide concentrations that will be expected in the return stream. The model requires a 10:1 nitrite to total halide ratio, for stream compositions at a minimum of pH 10 and a maximum temperature of 40°C. The final specification may use other corrosion data that is being generated for the DST chemistry control limits to delineate between the effect of fluoride and chloride. This test program has employed statistically designed test matrices and electrochemical test methods to validate the corrosion model specifically at boundary regions to optimize corrosion control specifications.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of a Corrosion Monitoring System for Advanced Molten Salt Reactors

Molten salt reactors (MSRs) have been identified as one of several possible next-generation advanced reactor designs that could replace the aging fleet. There are many inherent advantages to MSRs, including higher power density, lower pressure, low stored energy, and prompt negative temperature reactivity coefficient Ezell et al. [2018]. However, there are challenges related to the operating temperatures, as well as, the corrosive salts attacking the structural materials. During the Molten Salt Reactor Experiment (MSRE), which was operated at Oak Ridge National Laboratory (ORNL) (Ignatiev et al. [2014], Forsberg et al. [2007], Forsberg et al. [2008], Delpech et al. [2009], Serp et al. [2014], Ignatiev and Surenkov [2017]) corrosion was monitored by sampling the salt for chromium. However, this type of monitoring does not identify the location of corrosion. In FY18, ORNL developed a novel in-situ corrosion sensor that could be placed on the outside of the structure to monitor changes in magnetic susceptibility of salt-wetted alloys as corrosion occurs Holcomb et al. [2019]. Initial testing with this novel sensor demonstrated a correlation between the change in signal output from the sensor to the various levels of pre-corroded test specimens. However, all initial testing was performed at room temperatures, which is not realistic for the harsh MSR environment. Based on this research, FY19 funding allowed for development of a high-temperature version of the sensor to be installed at various locations on the reactor infrastructure. The high-temperature sensor can operate at up to 750°C and can monitor development of corrosion inside the pipe. This sensor measures the increase in magnetic susceptibility that occurs as chromium dissolves from the inner surface of the pipe, when paramagnetic structural alloys become ferromagnetic with the loss of chromium. This report will discuss the development of corrosion monitoring sensor and the testing with results of corroded specimens at increasing temperatures.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

SNF Interim Storage Canister Corrosion and Surface Environment Investigations (FY2020 Status Report)

This progress report describes work performed during FY20 at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of spent nuclear fuel (SNF). Of particular concern is stress corrosion cracking (SCC), by which a through-wall crack could potentially form in a canister outer wall over time intervals that are shorter than possible dry storage times. Work in FY20 further defined our understanding of the potential chemical and physical environment present on canister surfaces, evaluated the relationship between the environment and the resultant corrosion that occurs, and initiated crack growth rate testing under relevant environmental conditions. In FY20, work to define dry storage canister surface environments included several tasks. First, collection of dust deposition specimens from independent spent fuel storage installation (ISFSI) site locations helped to establish a more complete understanding of the potential chemical environment formed on the canister. Second, the predicted evolution of canister surface relative humidity RH) values was estimated using ISFSI site weather data and the horizontal canister thermal model used by the SNL probabilistic SCC model. These calculations determined that for typical ISFSI weather conditions, seasalt deliquescence to produce MgCl2-rich brines could occur in less than 20 years at the coolest locations on the canister surface, and, even after nearly 300 years, conditions for NaCl deliquescence (75% RH) are not reached. This work illustrates the importance of understanding the stability of MgCl2-rich brines on the heated canister surface, and the potential impact of brine composition on corrosion processes, including pitting and stress corrosion cracking. In an additional study, the description of the canister surface environment was refined in order to define more realistic corrosion testing environments including diurnal cycles, soluble salt chemistries, and inert mineral particles. The potential impacts of these phenomena on canister corrosion are being evaluated experimentally. Finally, work over the past few years to evaluate the stability of magnesium chloride brines continued in FY20. MgCl2 degassing experiments were carried out, confirming that MgCl2 brines slowly degas HCl on heated surfaces, converting to less deliquescent magnesium hydroxychloride phases and potentially leading to brine dryout.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Corrosion of U233-Doped Uranium Oxide using Microfluidics Methods

The aim of work this year has been to investigate the role of alpha (α)-radiation and hydrogen (H 2 ) on the corrosion of uranium oxide (UO 2 ) using a microfluidic device. The microfluidic device, termed the Particle-Attached Microfluidic Electrochemical Cell, (PAMEC), enables monitoring of the UO 2 electrochemical corrosion potential (E corr ) under different environments, including de-aerated conditions and in the presence of dissolved H 2 . The Si 3 N 4 window allows us to study morphological and chemical changes under an electron microscope. We have previously demonstrated that the PAMEC matches the results from bulk electrochemical tests with UO 2 [1]. We used the high specific activity uranium (U) isotope, 233 U, (t 1/2 = 160,000 years) incorporated into UO 2 , to generate a localized a-field. The objective of the experiments were to mimic the radiation environment that would be experience at the surface of aged spent nuclear fuel (SNF) during long-term geologic disposal under anoxic conditions. Wittman et al. [2] predicted that in the presence of a pure a-radiation field and under H 2 conditions, the concentration of the radiolytic oxidant H 2 O 2 would be suppressed or even eliminated. In a UO 2 corrosion experiment this would be exhibited through a lowering of the measured UO 2 corrosion potential compared to identical conditions in the absence of dissolved H 2 . We found that the predictions of Wittman and co-workers were supported and that the corrosion potential of the 233 U-doped UO 2 in solution lowered with presence of H 2 gas and increased in the absence of H 2 , when under anoxic conditions. The PAMEC experiments indicate that H 2 O 2 has been eliminated in a solution sparged with H 2 while exposed to an a-radiation field. The corrosion potential of the a-doped 233 U(10%)- 238 UO 2 in a solution sparged with Ar/H 2 matched the corrosion potential of 238 UO 2 in solution sparged with air. This clearly demonstrated that the H 2 O 2 had been eliminated and that the only oxidant present was O 2 in this system in complete agreement with the modeling results of Wittman et al. These results point to the need to improve the Fuel Matrix Degradation (FMD) Process Model training data set that is being used in the FMD surrogate model that is being developed for the repository program. The incorporation of realistic radiation chemistry will improve the scientific basis for the FMD Model.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multiscale Development and Validation of the Stainless Steel Alloy Corrosion (SStAC) Tool for High Temperature Engine Materials

The goal of this project was to create a simulation tool to assist in part design, reducing costs by eliminating the need for conservative material selection, and enabling alloy optimization to improve corrosion resistance. Thus, it helps decrease costs for existing engines and assists in the material and engine design for the engines of the future. To meet our stated goal, we developed the Stainless-Steel Alloy Corrosion (SStAC) tool, which: (1) Models corrosion of engine valves fabricated from 21-2N valve steel in an engine environment at temperatures up to 800 °C. (2) Runs in 1D for a fast estimate of the corrosion rate, and in 2D or 3D for more detailed simulations that represent any part geometry and predict the precise location and rate of corrosion and its impact on the mechanical and thermal behavior. (3) Was implemented using the open-source Multiphysics Object Oriented Simulation Environment (MOOSE). (4) Couples the corrosion model with mechanics and thermal transport models. The SStAC tool can predict the corrosion rate of 21-2N engine valves with less than 10% error.

36 MATERIALS SCIENCE↗

Property Measurements of LiF-NaF-KF Molten Salts Doped with Corrosion Products and Oxygen

Measurements of thermophysical properties of molten salts are needed for modeling and simulation activities that support the development of molten salt reactor (MSR) technologies. Properties of interest including transition temperatures, phase behavior, heat capacity, density, volumetric thermal expansion, surface tension, viscosity, thermal diffusivity, thermal conductivity, and vapor pressure are being performed at Argonne. Results of these property measurements are suitable for use in evaluating reactor performance during startup and the early operating life of the reactor. Ingressions of oxygen and moisture into the fuel salt are expected to occur at different times during the operating life of the reactor due to system leaks, maintenance, and refueling activities. The presence of these environmental contaminants induces corrosion of structural materials. The introduction of corrosion-derived species, oxygen and moisture is expected to affect the physical and chemical properties of the salt and operation of the reactor. Previous work performed at Argonne evaluated the effects of fission product dopants on the thermal properties of eutectic LiF-NaF-KF (FLiNaK). Properties of FLiNaK are commonly used to represent those of fluoride-bearing fuel salts. Metallic corrosion products such as chromium and nickel ions together with dissolved oxygen are expected to affect system redox differently than the accumulation of fission products. Work summarized in this report was performed to measure the effects of corrosion products and dissolved oxygen on the phase transitions, and specific heat capacity of FLiNaK. Thermophysical property measurements were made using four salts that were prepared by doping aliquots of a eutectic mixture of FLiNaK with surrogate corrosion products. Controlled additions of CrF 3 and NiF 2 were used as surrogates for corrosion product contamination anticipated during extended reactor operations in which fuel salt is in contact with steel reactor components. Controlled additions of UF 4 from two sources containing known amounts of UO 2 at different concentrations were used to represent oxygen contamination. The phase transitions and specific heat capacities of the four salts were measured by using differential scanning calorimetry. Measurements were made at temperatures spanning the range of 500−900 °C, which is the expected operating range of MSRs. Measured property values were compared to values measured previously with eutectic FLiNaK without dopants. Differences between property values measured for the doped and non-doped salts were compared with the uncertainties of the measurements to determine the significance of the effect of corrosion products and oxygen on salt properties.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Accelerated corrosion testing of cold spray coatings on 304L in chloride environments

Cold spray is an advanced metal manufacturing technique applied across many fields for a wide range of functions. Low heat input and compressive stresses induced into the substrate by the cold spray process makes it a promising choice for protective corrosion resistant coatings. One potential application for cold spray is as a protective coating against corrosion for spent nuclear fuel (SNF) interim dry storage canisters. As these canisters are currently stored at interim storage locations longer than originally intended, chloride induced stress corrosion cracking has been identified as a high priority knowledge gap, specifically with respect to prolonging or extending canister lifetimes ( Teague et al., 2019 ). The high deployability of cold spray, for which nozzles have been developed for application in constrained spaces, in conjunction with beneficial properties inherent to cold spray makes this a good candidate for a corrosion protection coating on SNF canisters. This work explores a pathway to rapidly down-select cold spray coatings for canisters by focusing on the corrosion properties. Specifically, this study examines the corrosion protection abilities of nickel and nickel-based alloy cold spray coatings on 304 L stainless steel in chloride rich environments through electrochemical scans and ferric chloride pitting tests (ASTM G48 Method A). It was shown that the porosity of the coating, the processing gas, material selection, and deformation in the substrate all impact the corrosion behavior of cold spray coatings and are areas where optimization could reduce potential materials degradation, enabling enhanced coatings development.

Karasz, Erin K.↗

Evaluation of Corrosion and Its Impact on the Mechanical Performance of Al–Steel Joints

Aluminum–steel joints are increasingly used in the automotive industry to meet the requirements for energy saving and emission reduction. Among various joining technologies, self-pierce riveting (SPR) and resistance spot welding (RSW) are two well-established technologies for fabricating dissimilar joints with stable and high mechanical performance. However, corrosion will occur in these joints inevitably due to different electrochemical properties, which can degrade the surface quality and the mechanical performance, such as strength. This paper presents a method of understanding the corrosion mechanisms in joining aluminum and steel. For this understanding, a hybrid method combining experimental observations, mechanical properties identification, and analytical approaches was used to assess the evolution of the impact of corrosion on the joining performance, such as traction separation curves. The study was conducted on common combinations used in the vehicles, e.g., a 1.2 mm thickness aluminum alloy (AA 6022) and 2.0 mm thickness hot deep galvanized steel (HDG HSLA 340) joined by SPR and RSW. After the fabrication of these joints, accelerated cyclic corrosion tests of up to 104 cycles were performed, which reproduced the environmental conditions to which a vehicle was exposed. By investigating the microstructural evolution within the joints, the corrosion mechanisms of SPR and RSW joints were revealed, including the initiation and propagation. Moreover, the intrinsic impact of the corrosion on the mechanical performance, including the strength, axial stiffness, and crashworthiness, was analyzed by performing a lap-shear test. It showed that as corrosion proceeds, the fracture modes and mechanical performance are affected significantly.

Chemistry↗

Modeling the Impact of Grain Size on Corrosion Behavior of Ni-Based Alloys in Molten Chloride Salt via Cellular Automata

Molten chloride salts hold significant promise as both thermal transfer and storage media for next-generation concentrated solar power (CSP) systems. However, molten chlorides pose a considerable corrosion risk to structural materials, particularly Ni-based alloys. One approach to enhancing corrosion resistance is through the optimization of grain structure; however, it remains uncertain whether increasing or decreasing grain size enhances corrosion resistance. A cellular automata (CA) program was developed to evaluate the interplay between grain size and corrosion in Ni-based alloy. Our CA program tracks alloy composition, surface roughness, and thickness loss via a graphical user interface, displaying corrosion and diffusion status, and multiple user input cards for tuning the simulation. CA simulations of Inconel 625 indicate enhanced corrosion resistance with increased grain size, with passivating oxides offering limited protection. Additionally, the temporal evolution of alloy surface roughness demonstrates notable fluctuations, with abrupt increases attributed to corrosion along vertical grain boundaries and sudden decreases to grain detachment from the protective film.

Materials Science↗

Susceptibility to hot corrosion of four nickel-base superalloys, NASA-TRW VIA, B-1900, 713C and IN-738

The susceptibility to hot corrosion of four nickel-base, cast superalloys has been studied at 900 and 1000 C. The test consisted of coating alloy samples with known amounts of Na2SO4 and oxidizing the coated samples isothermally in 1 atmosphere of slowly flowing oxygen, the weight-gain being monitored on a sensitive recording microbalance. Susceptibility to hot corrosion decreased in the order of decreasing molybdenum content of the alloys. Preoxidation of samples before hot-corrosion testing markedly increased the induction period observed prior to the inception of hot corrosion for all alloys tested. X-ray diffraction analyses of the oxide scales were made. All samples that underwent hot corrosion showed the presence of a (Ni,Co)MoO4 layer near the alloy-oxide interface. Several specimens displayed resistance to hot corrosion and these showed NaTaO3 as a prominent feature in their oxide scale. Our results may be interpreted as indicating that molybdenum in an alloy is detrimental, with respect to hot corrosion, while tantalum is beneficial.

Stearns, C. A.↗

Effect of sodium, potassium, magnesium, calcium, and chlorine on the high temperature corrosion of IN-100, U-700, IN-792, and Mar M-509

The effects of potential impurities such as Na, K, Mg, Ca, and Cl, in coal-derived liquid fuels on accelerated corrosion of IN-100, U-700, IN-792, and Mar M-509 were investigated using a Mach 0.3 burner rig for times to 200 hours in one hour cycles. These impurities were injected in combination as aqueous solutions into the combustor. Other variables were time, temperature, and fuel-to-air ratio. The experimental matrix was a central composite fractional fractorial design divided into blocks to allow modification of the design as data was gathered. The extent of corrosion was determined by metal consumption. The time exponent was near 1.0 for the least corrosion resistant alloys, U-700 and IN-100; near 0.8 for the moderately resistant IN-792; and close to Mar M-509, the most corrosion resistant alloy. As anticipated, corrosion rapidly increased with increasing temperature as well as Na and K concentrations, while corrosion decreased somewhat as the Ca concentration increased for all alloys. Mg was beneficial for the Ni-base alloys but had little effect on the Co-base alloy. Surprisingly, the effect of increasing Cl was to decrease the corrosion of all alloys. Little interaction among the dopants was noted.

Lowell, C. E.↗

Atmospheric corrosion model and monitor for low cost solar arrays

An atmospheric corrosion model and corrosion monitoring system has been developed for low cost solar arrays (LSA). The corrosion model predicts that corrosion rate is the product of the surface condensation probability of water vapor and the diffusion controlled corrosion current. This corrosion model is verified by simultaneous monitoring of weather conditions and corrosion rates at the solar array test site at Mead, Nebraska.

Kaelble, D. H.↗

Interaction of sulfuric acid corrosion and mechanical wear of iron

Friction and wear experiments were conducted with elemental iron sliding on aluminum oxide in aerated sulfuric acid at concentrations ranging from very dilute (0.00007 N; i.e., 4 ppm) to very concentrated (96 percent acid). Load and reciprocating sliding speed were kept constant. With the most dilute acid concentration of 0.00007 to 0.0002 N, a complex corrosion product formed that was friable and often increased friction and wear. At slightly higher concentrations of 0.001 N, metal losses were essentially by wear alone. Because no buildup of corrosion products occurred, this acid concentration became the standard from which to separate metal loss from direct corrosion and mechanical wear losses. When the acid concentration was increased to 5 percent (1 N), the well-established high corrosion rate of iron in sulfuric acid strongly dominated the total wear loss. This strong corrosion increased to 30 percent acid and decreased somewhat to 50 percent acid in accordance with expectations. However, the low corrosion of iron expected at acid concentrations of 65 to 96 percent was not observed in the wear area. It was apparent that the normal passivating film was being worn away and a galvanic cell established that rapidly attacked the wear area. Under the conditions where direct corrosion losses were highest, the coefficient of friction was the lowest.

Rengstorff, G. W. P.↗

Interaction of sulfuric acid corrosion and mechanical wear of iron

Friction and wear experiment were conducted with elemental iron sliding on aluminum oxide in aerated sulfuric acid at concentrations ranging from very dilute (0.00007 N; i.e., 4 ppm) to very concentrated (96 percent acid). Load and reciprocating sliding speed were kept constant. With the most dilute acid concentration of 0.00007 to 0.0002 N, a complex corrosion product formed that was friable and often increased friction and wear. At slightly higher concentrations of 0.001 N, metal losses were essentially by wear alone. Because no buildup of corrosion products occurred, this acid concentration became the standard from which to separate metal loss from direct corrosion and mechanical wear losses. When the acid concentration was increased to 5 percent (1 N), the well-established high corrosion rate of iron in sulfuric acid strongly dominated the total wear loss. This strong corrosion increased to 30 percent acid and decreased somewhat to 50 percent acid in accordance with expectations. However, the low corrosion of iron expected at acid concentrations of 65 to 96 percent was not observed in the wear area. It was apparent that the normal passivating film was being worn away and a galvanic cell established that rapidly attacked the wear area. Under the conditions where direct corrosion losses were highest, the coefficient of friction was the lowest.

Rengstorff, G. W. P.↗