Chloride-induced Stress Corrosion Cracking Research Articles

The effect of microstructure of an advanced duplex stainless steel on the pitting corrosion and chloride-induced stress corrosion cracking resistance

The effect of austenite morphology on the corrosion resistance of a newly-developed advanced duplex stainless steel (ADCS) was evaluated by electrochemical and chloride-induced stress corrosion cracking (CISCC) tests. By properly controlling heat treatment conditions, equiaxed (EQ) and elongated (EL) austenites were formed in ferrite matrix. ADCS-EQ exhibited higher pitting potential than ADCS-EL, primarily owing to less phase boundary. Meanwhile, ADCS-EL showed better CISCC resistance than ADCS-EQ, as the elongated austenite inhibited selective dissolution. Overall, the CISCC resistance of ADCS was more affected by austenite morphology and orientation, and would not be in accordance with pitting corrosion resistance.

Analysis, Assessment, and Mitigation of Stress Corrosion Cracking in Austenitic Stainless Steels in the Oil and Gas Sector: A Review

This comprehensive review examines the phenomena of stress corrosion cracking (SCC) and chloride-induced stress corrosion cracking (Cl-SCC) in materials commonly used in the oil and gas industry, with a focus on austenitic stainless steels. The study reveals that SCC initiation can occur at temperatures as low as 20 °C, while Cl-SCC propagation rates significantly increase above 60 °C, reaching up to 0.1 mm/day in environments with high chloride concentrations. Experimental methods such as Slow Strain Rate Tests (SSRTs), Small Punch Tests (SPTs), and Constant-Load Tests (CLTs) were employed to quantify the impacts of temperature, chloride concentration, and pH on SCC susceptibility. The results highlight the critical role of these factors in determining the susceptibility of materials to SCC. The review emphasizes the importance of implementing various mitigation strategies to prevent SCC, including the use of corrosion-resistant alloys, protective coatings, cathodic protection, and corrosion inhibitors. Additionally, regular monitoring using advanced sensor technologies capable of detecting early signs of SCC is crucial for preventing the onset of SCC. The study concludes with practical recommendations for enhancing infrastructure resilience through meticulous material selection, comprehensive environmental monitoring, and proactive maintenance strategies, aimed at safeguarding operational integrity and ensuring environmental compliance. The review underscores the significance of considering the interplay between mechanical stresses and corrosive environments in the selection and application of materials in the oil and gas industry. Low pH levels and high temperatures facilitate the rapid progression of SCC, with experimental results indicating that stainless steel forms passive films with more defects under these conditions, reducing corrosion resistance. This interplay highlights the need for a comprehensive understanding of the complex interactions between materials, environments, and mechanical stresses to ensure the long-term integrity of critical infrastructure.

Metallurgical failure investigation of small bore piping (SBP) in a diesel hydrotreating unit (DHT) of an oil refinery

Abstract Hydrocarbon leaks were repeatedly found in the client’s refinery. Because of the recurring nature of this failure, the operator approached the authors’ laboratory to get a second opinion on the metallurgical root cause of the failure. It was known from the customer that corrosive species, such as ammonium chloride salt precipitates, are present in the subject diesel hydrotreating unit (DHT). From the findings obtained in the investigation that is the subject of this contribution, the conclusion of the original metallurgical root cause analysis (RCA), namely that the subject piping failed by transgranular chloride-induced stress corrosion cracking (Cl-SCC), could be verified and is indeed correct. The metallurgical root cause of the small bore piping (SBP) failure is chloride-induced SCC. The morphology of the cracking is very distinct and is clearly consistent with transgranular Cl-SCC. A material change to the nickel-base material Alloy 625, already considered by the client, since this alloy is believed to be immune to chloride-induced SCC, would be a good, even though expensive solution. It should be emphasized that there are no metallic materials completely resistant to SCC. If the environment is harsh enough, except for some titanium alloys, i. e., if the source of the chloride ions cannot be eliminated, which is likely the case here, a regular inspection and replacement of these SBP systems might have to be considered. It should further be emphasized that a chloride concentration below 50 ppm is by no means any guarantee for the avoidance of SCC, since chlorides can concentrate in crevices, corrosion pits and such, i. e., the local concentration is what matters, not the local.

The impact of loading rate on chloride induced stress corrosion cracking of 304L stainless steel

Abstract The influence of applied loading rate (dK/dt) on stress corrosion cracking (SCC) behavior in annealed 304L stainless steel immersed in 4.7 M MgCl2 solution was assessed at varying temperatures from 23 °C to 70 °C. Measured crack growth rates obtained under rising K loading (dK/dt > 0) are compared to those obtained during static K testing. A rising K-based loading protocol was found to yield more conservative crack growth rates across all temperatures, with the variation in crack growth rates (and therefore the dependence in loading rate) decreasing with increasing environmental severity.

A Study on the Propagation of Chloride-Induced Stress Corrosion Cracking for Austenitic Stainless Steel at Corrosion Environment

Austenitic stainless steels have been widely used in the petrochemical industry, nuclear power plants and the ship industry due to their high toughness and corrosion resistance. However, these materials are susceptible to environmentally-assisted degradation, such as chloride-induced stress corrosion cracking (CISCC). In this respect, this study investigated CISCC crack propagation rate for austenitic stainless steels, such as type 304L and type 316L, in the corrosion environment. Considering the environment of the spent nuclear fuel canister used in the dry storage system, the test chamber is always maintained at 3.5% NaCl and related humidity (RH) 95% at 60℃. For initiation of CISCC, a test procedure, which has nine pre-cracking procedures for a CT specimen, is suggested. In a test procedure, crack transitioning, which induces the environmental corrosion crack, is observed after mechanical precracking. To determine the CISCC crack length corresponding to each test step, the direct current potential drop (DCPD) method is measured in real-time. In addition, the CISCC crack observed after final fracture is measured using optical microscopy in order to improve the accuracy of the measured crack length. In the test results, CISCC crack resistance of type 316L is better than that of type 304L. Finally, the test results show that the CISCC crack propagation rate is 2.784E-11 m/s for type 304L and is 9.93E-11 m/s for type 316L.

Chloride-Induced Stress Corrosion Cracking of Friction Stir-Welded 304L Stainless Steel: Effect of Microstructure and Temperature

Dry storage canisters of used nuclear fuels are fabricated using SUS 304L stainless steel. Chloride-induced stress corrosion cracking (CISCC) is one of the major failure modes of dry storage canisters. The cracked canisters can be repaired by friction stir welding (FSW), a low-heat input ‘solid-phase’ welding process. It is important to evaluate the ClSCC resistance of the friction stir welded material. Stress corrosion cracking (SCC) studies were carried out on mill-annealed base materials and friction stir welded 304L stainless U-bend specimens in 3.5% NaCl + 5 N H2SO4 solution at room temperature and boiling MgCl2 solution at 155 °C. The engineering stress on the outer fiber of the FSW U-bend specimen was ~60% higher than that of the base metal (BM). In spite of the higher stress level of the FSW, both materials (FSW and BM) showed almost similar SCC failure times in the two different test solutions. The SCC occurred in the thermo-mechanically affected zone (TMAZ) of the FSW specimens in the 3.5% NaCl + 5 N H2SO4 solution at room temperature, while the stirred zone (SZ) was relatively crack-free. The failure occurred at the stirred zone when tested in the boiling MgCl2 solution. Hydrogen reduction was the cathodic reaction in the boiling MgCl2 solution, which promoted hydrogen-assisted cracking of the heavily deformed stirred zone. The emergence of the slip step followed by passive film rupture and dissolution of the slip step could be the SCC events in the 3.5% NaCl + 5 N H2SO4 solution at room temperature. However, the slip step height was not sufficient to cause passivity breakdown in the fine-grained SZ. Therefore, the SCC occurred in the partially recrystallized softer TMAZ. Overall, the friction-stirred 304L showed higher tolerance to ClSCC than the 304L base metal.

Turbulent Particle Flow in Spent Nuclear Fuel Storage Systems

Deposition models are being developed with the commercial computational fluid dynamics software STAR-CCM+ to evaluate particulate deposition on spent nuclear fuel (SNF) canisters. The primary particulate of concern is chloride salts, which are dispersed in the atmosphere and then deposited onto the canisters. During dry storage, the primary degradation process is likely to be chloride-induced stress corrosion cracking (CISCC) at the heat-affected zones of the canister welds. It is known that stainless steel canisters are susceptible to CISCC; however, the rate of chloride deposition onto the canisters is poorly known, based on sparse field data from a small number of sites. This paper describes work looking at various approaches to modeling turbulence, such as Reynolds-averaged Navier Stokes (RANS) and large eddy simulation (LES), and its impact on particle flow and deposition within a ventilated SNF storage system. The deposition rate is determined for a vertical canister system and a horizontal canister system. LES has the potential to simulate turbulent flows more accurately versus RANS, but is much more computationally expensive. A k-omega version of the RANS turbulence model was used for this study. The computational efficient RANS steady-state model predicted a similar canister deposition result as the LES simulation for a vertical canister storage system. For a horizontal storage system, the RANS steady-state model predicted more particles depositing on the canister than the LES simulation, providing a conservative estimation for particle deposition. A wall correction factor was added to the RANS model to dampen the turbulence fluctuation normal to a surface that left undamped, leads to the RANS model overpredicting deposition along a surface for smaller particles. This work was done to further development of deposition models that could be used to plan and inform SNF canister aging management programs with predictive models for the timing and occurrence of canister CISCC. This work is part of a larger effort tasked with understanding the likelihood of canister degradation due to CISCC. These models are still under development, and testing is needed for validation. However, these models are being presented now to demonstrate to canister vendors, utilities, regulators, and stakeholders the value of this type of modeling.

Chloride-induced stress corrosion cracking in Austenitic steels for SNF storage canisters - Recent understanding and advances in mitigation and repair

Chloride-induced stress corrosion cracking (CISCC) is a critical threat to stainless steel (SS) spent nuclear fuel (SNF) and radioactive materials storage canisters currently in service worldwide. In the past decade, extensive research has been conducted to understand fundamental mechanisms of CISCC, as well as to develop effective repair and mitigation methods to prevent catastrophic failure of the SNF canisters from CISCC. This review article aims to: (1) summarize recent progress from fundamental studies of CISCC in SS, and (2) present state-of-the-art developments in CISCC mitigation and repair techniques that may be especially well-suited for SNF storage applications, including cold spray (CS), friction stir welding (FSW), friction surfacing (FS), laser shock peening (LSP), and ultrasonic nanocrystal surface modification (UNSM). Knowledge gaps in current understanding of CISCC and roadmaps for deployment of the repair techniques are also discussed.

Computation of Particulate Deposition on Dry Storage Canisters

This paper provides an overview of ongoing work aimed at developing spent nuclear fuel (SNF) canister deposition models. Currently, it is known that stainless steel canisters are susceptible to chloride-induced stress corrosion cracking (CISCC). However, the rate of CISCC degradation and the likelihood that it could lead to a through-wall crack is unknown. While it is currently unknown if there is a threshold chloride surface concentration for CISCC initiation, it can be assumed that the onset and progress of material degradation will depend on the local contaminant concentration, the properties of the contaminant species, and the synergistic effects when multiple contaminants are present. This study uses well-developed computational fluid dynamics and particle tracking tools and applies them to SNF storage to determine the rate of deposition on canisters. Understanding the rate of deposition on SNF canisters could be important for making canister aging management predictions. This study is a part of an ongoing effort funded by the U.S. Department of Energy, Office of Nuclear Energy, Office of Spent Fuel and Waste Science and Technology, which is tasked with doing research relevant to enhancing the technical basis for ensuring the safe extended storage and subsequent transport of SNF. This work is being presented to demonstrate a potentially useful technique for SNF canister vendors, utilities, regulators, and stakeholders to utilize and further develop for their own designs and site-specific studies.

Study of Mechanical Properties, Microstructure, and Residual Stresses of AISI 304/304L Stainless Steel Submerged Arc Weld for Spent Fuel Dry Storage Systems

The confinement boundaries of spent nuclear fuel (SNF) canisters are typically fusion welded. Welded microstructures, strain hardening, and residual stresses combined with a chemically aggressive, chloride-rich environment led to concerns that the welded canister may be susceptible to chloride-induced stress corrosion cracking (CISCC). A comprehensive understanding of the modification of stainless steel (SS) metallurgical and mechanical properties by fusion welding could accelerate the predictive analysis of CISCC susceptibility. This paper describes a submerged arc welding (SAW) procedure that was developed and qualified on 12.7 mm (0.5 in.) thick AISI 304/304L SS to produce joints in a way similar to actual SNF canister manufacturing. This procedure has the potential to reduce the production cost and weld CISCC susceptibility by using fewer welding passes and lower heat input than current industrial applications. Global and local mechanical behaviors and properties, as well as residual stress distributions on the welded joint, were studied. The results indicate that hardness values in the fusion zone (FZ) and heat-affected zone (HAZ) are slightly higher than that of the base metal. Strain localization was presented in the HAZ before the tensile stress reached its maximum value, and then it shifted to the FZ. The specimen finally broke in the FZ. High tensile residual stresses exhibited in the FZ and the nearby HAZ suggest the highest CISCC-susceptible spots. The maximum tensile residual stresses were along the welding direction, indicating that if cracks occur, they would be perpendicular to the welding direction. This study involved developing and qualifying a SAW procedure for SNF canister production. The new procedure yielded cost savings (SAW working efficiency increased by about 80%), improved mechanical properties, and presented moderate residual stresses. Analysis revealed that the welded joint’s low-stress and high-stress damage assessments may be affected by shifts in the strain localization spot under loading.

Development of a duplex stainless steel for dry storage canister with improved chloride-induced stress corrosion cracking resistance

The chloride-induced stress corrosion cracking (CISCC) is one of the major integrity concerns in dry storage canisters made of austenitic stainless steels (ASSs). In this study, an advanced duplex stainless steel (DSS) with a composition of Fe–19Cr–4Ni-2.5Mo-4.5Mn (ADCS) was developed and its performance was compared with that of commercial ASS and DSS alloys. The chemical composition of ADCS was determined to obtain greater pitting and CISCC resistance as well as a proper combination of strength and ductility. Then, the thermomechanical processing (TMP) condition was applied, which resulted in higher strength than ASSs (304L SS and 316L SS) and better ductility than DSSs (2101 LDSS and 2205 DSS). The potentiodynamic polarization and electrochemical impedance spectra (EIS) results represented the better pitting corrosion resistance of ADCS compared to 304L SS and 316L SS by forming a better passive layer. The CISCC tests using four-point loaded specimens showed that cracks were initiated at 24 h for 304L SS and 144 h for 316L SS, while crack was not found until 1008 h for ADCS. Overall, the developed alloy, ADCS, showed better combination of CISCC resistance and mechanical properties as dry storage canister materials than commercial alloys.

Stress Corrosion Cracking of Austenitic Stainless Steels in Environments Relevant to Spent Nuclear Fuel Storage

Localized corrosion and stress corrosion cracking (SCC) are potential degradation mechanisms for stainless steels (SS) during exposure to corrosive environments. When localized corrosion features are subject to stresses (either external or residual), a crack can nucleate and grow. One potential scenario under which chloride-induced SCC may pose a risk is the interim storage of spent nuclear fuels (SNF) in SS canisters. In the U.S., these SS canisters are located at interim spent fuel storage installations across the country. As canisters cool over time, dust deposition can lead to the formation of corrosive brines, which form by various salt compositions. Initial studies have shown significant influences of environment on corrosion severity and morphology, which may in turn influence crack nucleation and growth. Recent, compositional analysis of salts on the surface of interim SNF SS storage canisters has been carried out with representative brine mixing formulations developed for laboratory exposures. This presentation evaluates the corrosivity, specifically in-situ crack growth rates influenced by the electrochemical environment of the prepared brines as compared to saturated salts and other seawater surrogate brines. The crack growth rates, in-situ electrochemical measurements, as well as fractography will be discussed in terms of testing methodologies and potential risks for canister degradation. SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525. This document is SAND2023-02249A.

Effects of environmental parameters on chloride-induced stress corrosion cracking behavior of austenitic stainless steel welds for dry storage canister application

This study investigated the chloride-induced stress corrosion cracking (CISCC) behavior expected to occur in welds of austenitic stainless steel, which are considered candidate materials for dry storage containers for spent nuclear fuel. The behavior was studied by varying temperature, relative humidity (RH), and chloride concentration. 304L-ER308L welded plates were processed into U-bend specimens and exposed to a cyclic corrosion chamber for 12 weeks. The CISCC behavior was then analyzed using electron microscopy. A previous study by the authors confirmed that CISCC occurred in ER308L at 60 °C, 30% RH, and 0.6 M NaCl via selective corrosion of δ-ferrite. When the temperature was lowered from 60 °C to 50 °C, CISCC still occurred. However, when the humidity was reduced to 20% RH, CISCC did not happen. This can be attributed to the retardation of the deliquescence of NaCl at lower humidity, which was insufficient to promote CISCC. Furthermore, increased chloride concentration to 1.0 M resulted in the absence of CISCC and widespread surface corrosion with severe pitting corrosion because of the increase in thin film thickness.

Synchrotron X-ray fluorescence imaging study on chloride-induced stress corrosion cracking behavior of austenitic stainless steel welds via selective corrosion of δ-ferrite

Chloride-induced stress corrosion cracking (CISCC) is a degradation of austenitic stainless steels by Cl-containing media, residual stress, and materials susceptibility. In this study, synchrotron X-ray fluorescence imaging and electron microscopy were utilized to investigate the CISCC mechanism in austenitic stainless steel welds 304 L-ER308L and 316 L-ER316L. Specimens were exposed to 60 °C and 30% relative humidity conditions for 3 months and their microstructure and chemistry were analyzed. Since δ-ferrite is composed of ferrite formers especially Cr and acts as a sink for impurities, selective corrosion of δ-ferrite results in pitting corrosion and CISCC propagation.

Novel photocatalytic coating for corrosion mitigation in 304LSS of dry storage canisters

Type 304L stainless steel (304LSS) is one of the candidate canister materials for storing radioactive spent fuels, usually near seashore environments along with nuclear power plants. During the prolonged exposure of dry storage canisters to saline environments, they are highly susceptible to chloride induced stress corrosion cracking. Failure of a dry storage canister not only would release radioactive isotopes into the environment, but would also lead to a costly replacement of the cracked canister. The objective of this study is to develop a multilayered titanium dioxide (TiO2) composite coating on a 304LSS substrate. With ultraviolet (UV) illumination, this coating would act as a barrier and simultaneously offer cathodic protection against corrosion in the substrate alloy. The composite coating consists of a plain amorphous TiO2 coating over another cerium-doped (Ce-doped) TiO2 coating. Electronic currents generated by photo-catalytic reaction of the amorphous TiO2 coating under UV illumination were measured. Photo-electrochemical analyses and surface morphology observations were conducted to evaluate the performance of the Ce-doped coatings on corrosion mitigation. Optimal amounts of cerium doping that offered better photo-cathodic protection were also explored. Results indicated that the Ce-doped TiO2 coating exhibited a better performance on photo-cathodic protection for 304L stainless steel in aerated 3.5% NaCl solutions than the one without cerium doping. The underlying Ce-doped TiO2 coating was effectively charged during UV illumination, and it was able to continuously release electrons even after the UV was switched off, thus providing uninterrupted photo-cathodic protection for the coated 304L stainless steel substrate.

Stress Corrosion Cracking Mechanisms of UNS S32205 Duplex Stainless Steel in Carbonated Solution Induced by Chlorides

Herein, the chloride-induced stress corrosion cracking (SCC) mechanisms of UNS S32205 duplex stainless steel (DSS) reinforcing bars in alkaline and carbonated solutions are studied. Electrochemical monitoring and mechanical properties were tested using linear polarization resistance and electrochemical impedance spectroscopy, coupled with the slow strain rate tensile test (SSRT) to evaluate the SCC behavior and unravel the pit-to-crack mechanisms. Pit initiation and crack morphology were identified by fractographic analysis, which revealed the transgranular (TG) SCC mechanism. HCO3− acidification enhanced the anodic dissolution kinetics, thus promoting a premature pit-to-crack transition, seen by the decrease in the maximum phase angle in the Bode plot at low frequencies (≈ 1 Hz) for the carbonated solution. The crack propagation rate for the carbonated solution increased by over 100% compared to the alkaline solution, coinciding with the lower phase angle from the Bode plots, as well as with the lower charge transfer resistance. Pit initiation was found at the TiN nonmetallic inclusion inside the ferrite phase cleavage facet, which developed TG-SCC.

Effect of Laser Shock Peening on the Stress Corrosion Cracking of 304L Stainless Steel

Storage canisters used in nuclear power plants operating in seaside areas—where the salt content in the atmosphere is high—may be susceptible to chloride-induced stress corrosion cracking (CISCC). Chloride-induced stress corrosion cracking is one of the ways in which dry storage canisters made of stainless steel can degrade. Stress corrosion cracking depends on the microstructure and residual stress, and it is therefore very important to improve the surface properties of materials. Laser shock peening both greatly deforms the material surface and refines grains, and it generates compressive residual stress in the deep part from the surface of the material. This study focused on the effect of laser shock peening on the stress corrosion cracking of 304L stainless steel. The laser shock peening was found to induce compressive residual stress from the surface to a 1 mm depth, and the SCC properties were evaluated by a U-bend test. The results showed that the SCC resistance of laser-peened 304L stainless steel in a chloride environment was enhanced, and that it was closely related to grain size, the pitting potential of the cross section, and residual stress.

A review on pitting corrosion and environmentally assisted cracking on duplex stainless steel

Duplex stainless steel is widely used in the petrochemical, maritime, and food industries. However, duplex stainless steel has the problem of corrosion failures during use. This topic has not been comprehensively and academically reviewed. These factors motivate the authors to review the developments in the corrosion research of duplex stainless steel. The review found that the primary reasons for the failure of duplex stainless steels are pitting corrosion and chloride-induced stress corrosion cracking. After being submerged in water, the evolution of the passive film on the duplex stainless steel can be loosely classified into three stages: nucleation, rapid growth, and stable growth stages. Instead of dramatic rupture, the passive film rupture process is a continuous metal oxidation process. Environmental factors scarcely affect the double-layer structure of the passive film, but they affect the film's overall thickness, oxide ratio, and defect concentration. The six mechanisms of alloying elements on pitting corrosion are summarized as stabilization, ineffective, soluble precipitates, soluble inclusions, insoluble inclusions, and wrapping mechanisms. In environments containing chlorides, ferrite undergoes pitting corrosion more easily than austenite. However, the pitting corrosion resistance reverses when sufficiently large deformation is used. The mechanisms of pitting corrosion induced by precipitates include the Cr-depletion, microgalvanic, and high-stress field theories. Chloride-induced cracks always initiate in the corrosion pits and blunt when encountering austenite. Phase boundaries are both strong hydrogen traps and rapid hydrogen diffusion pathways during hydrogen-induced stress cracking.

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.

Effect of cold deformation on the stress corrosion cracking resistance of a high-strength stainless steel

The resistance to chloride-induced stress corrosion cracking was investigated on a high-strength CrNiMnMoN austenitic stainless steel in the hot-rolled and in different cold-drawn states. The resistance against chloride-induced stress corrosion cracking was determined by slow strain rate tests in different chloride containing solutions at elevated temperatures. A fracture analysis was carried out using scanning electron microscopy. Improved resistance is obtained by the formation of deformation-induced twins. In addition, synchrotron X-ray diffraction measurements show full austenite stability during all cold-drawing steps.Graphical abstract