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At least 19 records

Effect of substrate orientation and anisotropic strength on corrosion pits

The complexities of pitting corrosion and its associated pit morphologies are critical for predicting and preventing pit-related failure in materials. With the advances in computational tools, modeling of pitting corrosion has lately gained momentum. We recently developed a phase field model for 3-D pit morphology, and in the current work, the model is utilized to gain insight into the role of substrate orientation and anisotropic strength on crystallographic pits. The influence of these parameters on pit morphology and corrosion metrics such as pit volume, current, pit area, current density, and pit depth are studied. The crystallographic pit morphology changes with substrate orientation but not significantly with anisotropic strength. Finally, the anisotropic strength strongly influences the corrosion metrics whereas most corrosion metrics remain unaffected by substrate orientation.

36 MATERIALS SCIENCE↗

Pitting Corrosion in 316L Stainless Steel Fabricated by Laser Powder Bed Fusion Additive Manufacturing: A Review and Perspective

Abstract 316L stainless steel (316L SS) is a flagship material for structural applications in corrosive environments, having been extensively studied for decades for its favorable balance between mechanical and corrosion properties. More recently, 316L SS has also proven to have excellent printability when parts are produced with additive manufacturing techniques, notably laser powder bed fusion (LPBF). Because of the harsh thermo-mechanical cycles experienced during rapid solidification and cooling, LPBF processing tends to generate unique microstructures. Strong heterogeneities can be found inside grains, including trapped elements, nano-inclusions, and a high density of dislocations that form the so-called cellular structure. Interestingly, LPBF 316L SS not only exhibits better mechanical properties than its conventionally processed counterpart, but it also usually offers much higher resistance to pitting in chloride solutions. Unfortunately, the complexity of the LPBF microstructures, in addition to process-induced defects, such as porosity and surface roughness, have slowed progress toward linking specific microstructural features to corrosion susceptibility and complicated the development of calibrated simulations of pitting phenomena. The first part of this article is dedicated to an in-depth review of the microstructures found in LPBF 316L SS and their potential effects on the corrosion properties, with an emphasis on pitting resistance. The second part offers a perspective of some relevant modeling techniques available to simulate the corrosion of LPBF 316L SS, including current challenges that should be overcome.

Voisin, T. (ORCID:0000000287462659)↗

Automated Image Segmentation and Processing Pipeline Applied to X–Ray Computed Tomography Studies of Pitting Corrosion in Aluminum Wires

Understanding pitting corrosion is critical, yet its kinetics and morphology remain challenging to study from X-ray computed tomography (XCT) due to manual segmentation barriers. To address this, an automated pipeline leveraging deep learning for efficient large-scale XCT analysis is developed, revealing new corrosion insights. The pipeline enables pit segmentation, 3D reconstruction, statistical characterization, and a topological transformation for visualization. Here, the pipeline is applied to 87 648 XCT images capturing commercial purity aluminum (1100 Al) wire exposed to sodium chloride (NaCl) salt particles over a period of 122 h. The pipeline achieves complete feature extraction and statistical quantification across the entire XCT dataset, leveraging distributed computing environment for high efficiency. Global growth kinetics such as high-level stepwise sigmoidal volume loss patterns and granular individual pit developments are both captured for 36 detected pits. By combining automation, computer vision, and extensive XCT datasets, this research accelerates precise corrosion assessment to enable materials science discoveries at scale.

36 MATERIALS SCIENCE↗

Simulation of Fatigue Crack Initiation at Corrosion Pits With EDM Notches

Uniaxial fatigue tests were conducted to compare the fatigue life of laboratory produced corrosion pits, similar to those observed in the shuttle main landing gear wheel bolt-hole, and an electro-discharged-machined (EDM) flaw. EDM Jaws are used to simulate corrosion pits during shuttle wheel (dynamometer) testing. The aluminum alloy, (AA 7050) laboratory fatigue tests were conducted to simulate the local stress level contained in the wheel bolt-hole. Under this high local stress condition, the EDM notch produced a fatigue life similar to test specimens containing corrosion pits of similar size. Based on the laboratory fatigue test results, the EDM Jaw (semi-circular disc shaped) produces a local stress state similar to corrosion pits and can be used to simulate a corrosion pit during the shuttle wheel dynamometer tests.

Smith, Stephen W.↗

Critical role of slags in pitting corrosion of additively manufactured stainless steel in simulated seawater

Abstract Pitting corrosion in seawater is one of the most difficult forms of corrosion to identify and control. A workhorse material for marine applications, 316L stainless steel (316L SS) is known to balance resistance to pitting with good mechanical properties. The advent of additive manufacturing (AM), particularly laser powder bed fusion (LPBF), has prompted numerous microstructural and mechanical investigations of LPBF 316L SS; however, the origins of pitting corrosion on as-built surfaces is unknown, despite their utmost importance for certification of LPBF 316L SS prior to fielding. Here, we show that Mn-rich silicate slags are responsible for pitting of the as-built LPBF material in sodium chloride due to their introduction of deleterious defects such as cracks or surface oxide heterogeneities. In addition, we explain how slags are formed in the liquid metal and deposited at the as-built surfaces using high-fidelity melt pool simulations. Our work uncovers how LPBF changes surface oxides due to rapid solidification and high-temperature oxidation, leading to fundamentally different pitting corrosion mechanisms.

36 MATERIALS SCIENCE↗

The Effects of Hot Corrosion Pits on the Fatigue Resistance of a Disk Superalloy

The effects of hot corrosion pits on low cycle fatigue life and failure modes of the disk superalloy ME3 were investigated. Low cycle fatigue specimens were subjected to hot corrosion exposures producing pits, then tested at low and high temperatures. Fatigue lives and failure initiation points were compared to those of specimens without corrosion pits. Several tests were interrupted to estimate the fraction of fatigue life that fatigue cracks initiated at pits. Corrosion pits significantly reduced fatigue life by 60 to 98 percent. Fatigue cracks initiated at a very small fraction of life for high temperature tests, but initiated at higher fractions in tests at low temperature. Critical pit sizes required to promote fatigue cracking were estimated, based on measurements of pits initiating cracks on fracture surfaces.

Gabb, Timothy P.↗

Influence of Realistic, Cyclic Atmospheric Cycles on the Pitting Corrosion of Austenitic Stainless Steels

Pitting corrosion was evaluated on stainless steels 304H, 304, and 316L the surfaces of which had ASTM seawater printed on them as a function of surface roughness after exposure to an exemplar realistic atmospheric diurnal cycle for up to one year. Methods to evaluate pitting damage included optical imaging, scanning electron microscopy imaging, profilometry analysis, and polarization scans. The developed cyclic exposure environment did not significantly influence pitting morphology nor depth in comparison to prior static exposure environments. Cross-hatching was observed in a majority of pits for all material compositions with the roughest surface finish (#4 finish) and in all surface finishes for the 304H composition. Evidence is provided that cross-hatched pit morphologies are caused by slip bands produced during the grinding process for the #4 finish or by material processing. Additionally, micro-cracking was observed in pits formed on samples with the #4 surface finish and was greatly reduced or absent for pits formed on samples with smooth surface finishes. This suggests that both a low RH leading to an MgCl 2 -dominated environment and a rough surface containing significant residual stress are necessary for micro-cracking. Finally, the use of various characterization techniques and cross sectioning was employed to both qualitatively and quantitatively assess pitting damage across all SS compositions and surface finishes.

36 MATERIALS SCIENCE↗

Phase Field Modeling of Crystallographic Corrosion Pits

The modeling of corrosion to understand and predict corrosion behavior is a topical issue. Here, a 3D phase field model is developed to simulate the pit morphology, primarily focusing on crystallographic pits. A crystallographic function is employed to incorporate different corrosion rates for different crystallographic planes. The model is benchmarked and validated against an analytical solution for a simple case. 3D crystallographic pits in a single crystal are simulated and the effect of substrate orientation on the pit morphology is studied. The crystallographic pit morphology changes significantly with the substrate orientation and these morphologies have a symmetry consistent with the substrate orientation. This first 3D phase field model of crystallographic pits will help in predicting the intricate shapes of pits, thereby, pushing the frontiers of pitting corrosion modeling.

36 MATERIALS SCIENCE↗

Influence of Heat Input and Cold Wire Feeding Rate on Pitting Corrosion Resistance of Submerged Arc Welding Duplex Stainless Steel Welds

Welding thermal cycles may severely impair duplex stainless steel (DSS) performance, especially local pitting resistance and toughness. The restricted welding energy between 0.5 and 2.5 kJ mm{sup −1} represents a limiting factor for productivity increase in DSS welding, and the addition of cold wire is an interesting alternative to increase the welding deposition rate without adding extra heat. The aim of this work is to evaluate the influence of the cold wire feeding rate (CW) and heat input (HI) on pitting corrosion behavior of DSS UNS S32304 bead-on-plate welds obtained by submerged arc welding (SAW). Cyclic potentiodynamic polarization was carried out in transverse weld sections using 1 mol L{sup −1} NaCl solution at room temperature. Most pitting corrosion spots were located on the heat-affected zone (HAZ), and the pitting potentials were lower than the base metal due to higher ferrite fractions and the presence of chromium nitrides. Considering the same CW, the HI increasing reduced E{sub pit} for 1.6, 1.9, 2.2 kJ mm{sup −1}, but increased E{sub pit} for 2.7 kJ mm{sup −1}, due to a balance between the HAZ width and the austenite fraction.

36 MATERIALS SCIENCE↗

Pitting Corrosion of 10Ni8CrMoV High-Strength Steel Induced by a Potential Perturbation

Pitting corrosion of high-strength steel 10Ni8CrMoV under square wave polarization (SWP) in simulated deep-sea environment is investigated and the possible mechanism is proposed. The results show that potential perturbation generates periodic intensification effect on both anodic and cathodic processes by frequently breaking the electrode equilibrium state. The intensity of periodic intensification effect essentially depends on the concentration gradient of Fe{sup 2+} cations at the steel/solution interface which acts as the forced electrochemical oscillator. The concentration gradient and the resulting concentration polarization effect increase periodically with the increase in SWP potential range. The morphology observation of the pitting and electric charge calculation indicate that the periodic intensification effect can promote the initiation and growth of pits by enhancing the anodic dissolution even under cathodic protection, but it is ineffective below the hydrogen evolution potential. The decrease in either upper or lower potential can mitigate anodic dissolution. Through the statistical analysis of pitting size, it is found that the wide potential range tends to activate the metastable pitting formed under hydrostatic pressure, forming densely distributed pitting. Meanwhile, it is more favorable to the formation of fully grown pits with high size dispersion degree when the proportion of electric charge in the anodic process is higher.

36 MATERIALS SCIENCE↗

Phase-field model of pitting corrosion kinetics in metallic materials

This study presents a thermodynamically consistent phase field model for the quantitative prediction of the pitting corrosion kinetics in metallic materials. An order parameter is introduced to represent the metal’s physical state at each point in the entire domain. The free energy of the metal-electrolyte system is defined in terms of its metal ion concentration and the order parameter. The mass transport in the electrolyte and the electrochemical reactions in the electrolyte/metal interface are taken into consideration in the model to simulate metal corrosion in a corrosive environment. The governing equations for mass transport and the order parameter are solved in such a manner that the system’s free energy is reduced as a result of diffusion and migration processes, and the distribution of electrostatic potential is governed by Poisson’s equation. A calibration study is performed to couple the kinetic interface parameter with the corrosion current density, which results in a direct relationship between overpotential and the kinetic interface parameter. A comparative study is performed to validate the phase field model against the experimental results. Several case studies are also examined to understand the corrosion behavior of closely located pits, stressed material, ceramic particles-reinforced steel, and crystallographic orientation dependence.

36 MATERIALS SCIENCE↗

A space-time adaptive finite element method with exponential time integrator for the phase field model of pitting corrosion

In this paper we propose a space-time adaptive finite element method for the phase field model of pitting corrosion, which is a parabolic partial differential equation system consisting of a phase variable and a concentration variable. A major challenge in solving this phase field model is that the problem is very stiff, which makes the time step size extremely small for standard temporal discretizations. Another difficulty is that a high spatial resolution is required to capture the steep gradients within the diffused interface, which results in very large number of degrees of freedom for uniform meshes. To overcome the stiffness of this model, we combine the Rosenbrock–Euler exponential integrator with Crank–Nicolson scheme for the temporal discretization. Moreover, by exploiting the fact that the speed of the corroding interface decreases with time, we derive an adaptive time stepping formula. For the spatial approximation, we propose a simple and efficient strategy to generate adaptive meshes that reduces the computational cost significantly. Thus, the proposed method utilizes local adaptivity and mesh refinement for efficient simulation of the corrosive dissolution over long times in heterogeneous media with complex microstructures. We also present an extensive set of numerical experiments in both two and three dimensional spaces to demonstrate efficiency and robustness of the proposed method.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Understanding the efficacy of concentrated interstitial carbon in enhancing the pitting corrosion resistance of stainless steel

By introducing a high fraction of interstitial carbon through low temperature carburization, the pitting corrosion resistance of austenitic stainless steel can be significantly improved. Previous work attributed this to strengthening of the passive film by carbon. Here, however, we present a paradigm shift by showing that carbon actually weakens the passive film but strengthens the bonding within the alloy by forming localized (covalent) bonds with the metal atoms (Fe, Cr, Ni). Accordingly, the enhancement in pitting resistance is a result of carbon reducing the metal dissolution rate in a local pit environment by many orders of magnitude, which extremely decreases the growth stability of a pit and prevents it from transitioning into stable growth. Electronic structure calculations confirm that carbon bonds to the metal atoms and that the metal–carbon bonds are 1.4 to 2.0 times stronger than the metal–metal bonds. These results suggest a new strategy for the design of corrosion resistant alloys, namely surface engineering by infusion of concentrated interstitials that form strong bonds with the matrix atoms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Pitting Corrosion on Wrought and Additively Manufactured 316L Stainless Steel in Atmospheric Environments

Additive manufacturing of metal components enables rapid fabrication of complex geometries. However, metal additive manufacturing also introduces new morphological and microstructural characteristics which might be detrimental to component performance. Here we report the pitting corrosion properties of wrought and additively manufactured 316L stainless steel after atmospheric exposure to coastal environments and laboratory-created environments. Qualitative visualization in combination with quantitative analysis of resulting pits provided an in-depth understanding of pitting differences between wrought and additively manufactured 316L stainless steel and between coastal and laboratory-based exposure. Optical and scanning electron microscopy were utilized for visualization, while white light interferometry measured pits across approximately 5mm x 5mm areas on each sample. Post-processing of the interferometry data enables quantification of pitting attack for each sample in terms of both pit depth and pit volume. The pitting analysis introduced herein offers a new technique to compare pitting attack between different manufacturing processes and materials.

36 MATERIALS SCIENCE↗

Corrosion pitting of SiC by molten salts

The corrosion of SiC by thin films of Na2CO3 and Na2SO4 at 1000 C is characterized by a severe pitting attack of the SiC substrate. A range of different Si and SiC substrates were examined to isolate the factors critical to pitting. Two types of pitting attack are identified: attack at structural discontinuities and a crater-like attack. The crater-like pits are correlated with bubble formation during oxidation of the SiC. It appears that bubbles create unprotected regions, which are susceptible to enhanced attack and, hence, pit formation.

Jacobson, N. S.↗

Waste Chemistry Envelope for the Determination of Pitting Corrosion Susceptibility - 19554

Liquid radioactive wastes at the Hanford and Savannah River sites are stored in large underground carbon steel tanks. The high-level wastes are processed in several of the tanks and then transferred by piping to other site facilities for further processing before they are stabilized in a vitrified or grout waste form. Based on waste removal and processing schedules, many of the tanks, will be required to be in service for times exceeding the initial intended life (i.e., greater than 60 years). Until the waste is removed from storage, transferred, and processed, the materials and structures of the tanks must maintain a confinement function by providing a barrier to the environment and by maintaining acceptable structural stability during design basis events, which include loadings from both normal service and abnormal (e.g., earthquake) conditions. Administrative programs are in place to mitigate potential corrosion mechanisms and thereby maintain the structural and leak integrity functions of these waste tanks throughout their intended service life. Waste chemistry and temperature control are the means by which corrosion degradation of the waste tanks is minimized. Chemistry controls are based on in-situ coupon tests, waste tank experience, and laboratory testing. These requirements comprise the technical standards for corrosion control. The standards are utilized then as guidelines for operational procedures. The present waste chemistry controls for the Hanford DSTs were established in the 1980's in response to tank failures caused by stress corrosion cracking (SCC) at the DOE Savannah River Site (SRS). Portions of the SRS chemistry limits, which were developed at the Savannah River National Laboratory (SRNL) were coupled with corrosion testing results from Pacific Northwest National Laboratories (PNNL) and adopted for corrosion control of the double-shell tank (DST) waste at the Hanford Site. Since that time, the temperatures of the waste in the DSTs have decreased to less than 50 deg. C in most cases as the radioactive material has decayed. As a consequence, new chemistry controls were formulated for SCC in 2010. This testing however, did not address that potential for pitting in the supernatant and at the liquid-air interface. Indeed, initial tests indicated that the inhibitor requirements for SCC would be insufficient for the prevention of pitting. In addition to lower waste temperatures, future retrieval and process changes may impact the DST waste chemistry. Initial projections suggest that the waste chemistry of the DSTs may shift to a broader range of pH and higher aggressive anion concentrations (e.g., chloride, sulfate, etc.) than the wastes that are presently stored. Additionally, processes within the vitrification facility may result in streams that are returned to the tank farm for evaporation. These streams may also contain high concentrations of aggressive species. SRNL investigated the propensity for pitting of the carbon steel waste tanks at current and projected DST waste chemistries. A statistically designed series of tests provided a pitting factor that relates the ratio of the inhibitor species to the aggressive species and the probability of observing pitting. An acceptable pitting factor was determined and was utilized for the development of a new chemistry envelope. The new chemistry envelope was compared to the envelope that was established for SCC and was determined to be bounding. Validation of the new chemistry envelope was performed via model simulations and comparison with historical experimental results and approaches to establishing chemistry envelopes. The new chemistry envelope will eventually be part of an overall assessment of the condition of the tanks and any changes made to the overall structural integrity program for the Hanford DSTs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Revealing the growth kinetics of atmospheric corrosion pitting in aluminum via in situ microtomography

Abstract Understanding the mechanistic relationship between the environment, microstructure, and local kinetics of atmospheric corrosion damage remains a central challenge. To address this challenge, this study used laboratory-based X-ray tomography to directly observe attack in-operando over an extended period, enabling insights into the evolving growth kinetics and morphology of individual pits over months of exposure. Damage progression associated with nine pits in a 99.9% pure aluminum wire exposed to chloride salts in humid air was characterized. Most pits grew at a nominally linear rate up until pit death, which occurred within 12–24 h of nucleation. Exceptions to this were observed, with three pits exhibiting bimodal growth kinetics and growing for 40 or more hours. This was explained by secondary droplets that formed near the pits, increasing the cathode area. A corrosion-driven drying mechanism likely contributed to pit death in both cases. Pits first grew into the material followed by lateral expansion.

36 MATERIALS SCIENCE↗