Pit Initiation Research Articles

Corrosion-life prediction model for 316L stainless steel under electronic special gases containing trace moisture employed in semiconductor manufacturing industry

Special gases with trace moisture cause the formation of dynamic acidic microdroplets (DMD), which results in corrosion of semiconductor manufacturing devices. In this study, a predictive model for corrosion damage in 316L stainless steel (SS) was developed by combining the DMD process and the pitting initiation model. The DMD process was modeled using the BET model to describe the moisture-to-solution conversion. The pitting initiation model was reconstructed by incorporating the Sridhar model, temporal corrosion model, and Macdonald model. Finally, the predicted results were validated by various experimental data, indicating that the prediction model was accurate and highly reliable.

Role of Niobium on the Passivation Mechanisms of TiHfZrNb High-Entropy Alloys in Hanks' Simulated Body Fluid.

A family of TiHfZrNb high-entropy alloys has been considered novel biomaterials for high-performance, small-sized implants. The present work evaluates the role of niobium on passivation kinetics and electrochemical characteristics of passive film on TiHfZrNb alloys formed in Hanks' simulated body fluid by analyzing electrochemical data with three analytical models. Results confirm that higher niobium content in the alloys reinforces the compactness of the passive film by favoring the dominance of film formation and thickening mechanism over the dissolution mechanism. Higher niobium content enhances the passivation kinetics to rapidly form the first layer, and total surface coverage reinforces the capacitive-resistant behavior of the film by enrichment with niobium oxides and reduces the point defect density and their mobility across the film, lowering pitting initiation susceptibility. With the high resistance to dissolution and rapid repassivation ability in the aggressive Hanks' simulated body fluid, the TiHfZrNb alloys confirm their great potential as new materials for biomedical implants and warrant further biocompatibility testing.

Linear dependence of potential drop at the passive film/solution interface on film-formation potential and pH: Combining first-principles calculations with experiments

Potential drop at the oxide film/solution interface plays a critical part in numerous electrochemical processes, especially for the passivated metal-electrolyte system, affecting the passive film breakdown and the pitting initiation. There are still some controversies over the dependence of potential drop at the passive film/solution interface (φf/s) on potential and pH of electrolyte. Herein, we develop a model presenting the linear dependence of φf/s on both potential and pH, as represented by φf/s=φf/s(V=0,pH=0)0+αV+βpH. By analyzing the surface charge (i.e., point of zero charge, pHpzc) and performing first-principles calculations, we provide the insights into the effect of potential and pH on the φf/s, and into the linear relation between φf/s with pH beyond the Nernst relation that is attributed to the role of point defects in pHpzc of passive film on iron. In addition, two methods, e.g., a combination of Mott-Schottky measurement with first-principles, contact angle titration, are suggested to determine the values of α, β and φf/s(V=0,pH=0)0, respectively. The study of passivity of iron in borate buffer solutions validates our model.

Early Stages of Crack Nucleation Mechanism in Fe39Mn20Co20Cr15Si5Al1 High-Entropy Alloy during Stress Corrosion Cracking Phenomenon: Pit Initiation and Growth

Early Stages of Crack Nucleation Mechanism in Fe39Mn20Co20Cr15Si5Al1 High-Entropy Alloy during Stress Corrosion Cracking Phenomenon: Pit Initiation and Growth

Insight into the long-term corrosion evolution of borated stainless steels in the wet storage environment for spent nuclear fuel

Long-term corrosion evolution of boron-containing stainless-steel (BSS) in simulated environment of spent nuclear fuel wet storage is investigated. Corrosion evolution goes through three phases of rising, stabilization and declining, which corresponds to five electrochemical processes. As B content increases, the initiation and stable growth of pits are promoted by decreased Crox3+ and increased inhomogeneity of passive film and enhanced micro-galvanic effect, resulting in reduced |Z|10mHz value and the duration of the second stage. Due to reduced grain sizes, the corrosion resistance of hot-rolled BSS is substantially improved with homogeneous passive film, higher Crox3+ in it and weaker micro-galvanic effect.

Al2O3-MnS Inclusions and Pitting Corrosion in the Weld Heat-Affected Zone

Manganese sulfide inclusions have been identified as a key factor contributing to the degradation of pitting corrosion resistance in both carbon and stainless steels. However, the precise reasons behind the differential reactivity of various sulfides, with some serving as active sites for pitting while others remain inactive, are not yet fully understood. The effect of debonding occurring at the interface between these inclusions and the steel matrix in relation to pitting corrosion has not been extensively investigated. In this study, an examination of a service-exposed pipeline girth weld was conducted. Immersion testing in blowdown water and multiscale characterization techniques investigated the inclusion-matrix interface debonding within the heat-affected zone. Our findings suggest that interfacial debonding is more likely at the Al2O3- MnS cluster interface. This observation offers a rationale for the selective reactivity of sulfides that form clusters with oxides, highlighting the likelihood that only sulfides clustering with oxides act as active pitting initiation sites.

Pit initiation in quenching and partitioning processed martensitic stainless steels

The present article investigates the influence of chemical composition and phase fractions on the corrosion behaviour of industrially produced quenching and partitioning (Q&P) martensitic stainless steels. Localised corrosion was analysed by scanning Kelvin probe force microscopy (SKPFM) and scanning electrochemical microscopy (SECM) in 3.5 wt.% NaCl solution. SKPFM revealed a Volta-potential difference of around 40 mV between inclusions and the matrix, which is larger than the Volta potential variations within the matrix. This difference in surface potential is a driving force for selective dissolution (corrosion initiation) at inclusions and inclusion/matrix interfaces. SECM detected early pitting initiation, particularly in alloys containing MnS and TiN inclusions. Results suggest that pitting initiation and propagation occur at those specific regions. This study emphasised that irrespective of chemical composition and phase fraction, localised corrosion initiation in Q&P-processed martensitic stainless steels is predominantly governed by the presence of inclusions.

CCDC32 stabilizes clathrin-coated pits and drives their invagination.

Clathrin-mediated endocytosis (CME) happens via the initiation, stabilization, and invagination of clathrin-coated pits (CCPs). In this study, we used a combination of quantitative live cell imaging, ultrastructure electron microscopy and biochemical experiments to show that CCDC32, a poorly studied and functional ambiguous protein, acts as an important endocytic accessory protein that regulates CCP stabilization and invagination. Specifically, CCDC32 exerts this function via its interactions with AP2, and the coiled-coil domain of CCDC32 and the α-appendage domain (AD) of AP2 are essential in mediating CCDC32-AP2 interactions. Importantly, we demonstrate that clinically observed loss-of-function mutations in CCDC32 lose AP2 interaction capacity and inhibit CME, resulting in the development of cardio-facio-neuro-developmental syndrome (CFNDS).

Effect of dissolved oxygen on corrosion behavior and mechanism of X70 pipeline steel in simulated low temperature bentonite-containing alkaline chloride environment

Effect of dissolved oxygen (DO) on the corrosion behavior of X70 pipeline steel in low temperature bentonite-containing alkaline chloride environments was comprehensively investigated. The cathodic reduction reaction is inhibited and corrosion current density gradually descent as the DO decreases, resulting in a significant improvement in the corrosion resistance of X70 pipeline steel. The content of Fe3O4 and α-FeOOH in the corrosion products film increases, refinement of rust grains and crack decreases effectively suppressing the penetration of corrosive substances. Pitting initiates within ferrite grains and at phase interface, while reducing the DO can restrain the chemical dissolution of MnS to retard the pit initiation.

Pitting corrosion characteristics of sintered Type 316 L stainless steel: relationship between pores and MnS

In Type 316 L stainless steel fabricated from gas-atomized powder via spark plasma sintering, lack-of-fusion pores and MnS inclusions were identified as possible pitting initiation sites. Through potentiodynamic polarization with different working electrode areas, the distribution density of the identified pit initiation sites was compared with that of sites found on wrought Type 316 L stainless steel. Surface observations of the sintered Type 316 L after polarization suggest that pitting corrosion was initiated at a location where both MnS and pores existed. By reducing the porosity and removing MnS, the roles of pores and MnS inclusions in the initiation of pitting corrosion were investigated.

Accelerated corrosion tests of a contact pair austenitic stainless steel – titanium alloy

The results of accelerated corrosion tests of a pair of austenitic stainless steel — titanium alloy under conditions of elevated temperatures and high concentrations of corrosive agents are presented, conditions for the developing the mechanism of local corrosion being the same. The proposed approach included provoking the appearance of microstress concentrators by three-point loading of test samples with subsequent forced development of local types of corrosion through simultaneous exposure to an increased concentration of corrosive agents and temperatures at a fixed exposure in an autoclave. The results of modeling the corrosion process in a titanium alloy being in contact with stainless steel are assessed proceeding from the data obtained from metallographic studies of the state of surface layers of the metal and the morphology of corrosion products on prepared sections of the surface of templates cut from the samples under study. We considred a pair of steel 08Kh18N10T — titanium alloy VT-5. It is shown that the contact of samples under conditions of accelerated corrosion tests does not lead to a significant development of local types of corrosion of the titanium alloy. On the contrary, analysis of the state of the surface layers of the samples of stainless steel revealed the presence of deep corrosion pits, triggering the intergranular corrosion. In this case, corrosion of austenitic steel, both in the presence and in the absence of contact with titanium, proceeded in three stages: the initiation and fusion of pitting; formation of knife corrosion ulcers; propagation of intergranular cracks into the depth of steel. The proposed methodology of corrosion testing can be used to predict the possible nature of the development of metal corrosion under operating conditions that form local zones of static stresses in structural materials, and for prompt response to extend the design life of the equipment at thermal and nuclear power facilities.

Selective Initiation of Corrosion Pits in Stainless Steel Using Scanning Electrochemical Cell Microscopy.

Scanning electrochemical cell microscopy is a useful technique for determining variations in corrosion behavior across a surface. However, the numerous options for experimental parameters and little understanding of their effect on the corroding system render comparisons of results between studies difficult. Herein, we explore changes in corrosion behavior of two martensitic stainless steels, a cast CA6NM and a wrought S41500, as a result of the chosen experimental parameters, including scan rate, approach potential, surface oil immersion, and tip aperture diameter. The study demonstrates that these experimental parameters can be controlled to probe oxide passivation kinetics and single pitting events by changing the surface state and cathodic currents. We measured the pitting and repassivation kinetics of a single pit and determined the compositional change of the Al2O3 inclusion site initiation point. Hundreds of data points were measured within 17 h of experimental time on the stainless steel samples, allowing statistical averages of corrosion and pitting values. This work will open new avenues for fine-tuning various corrosion aspects at the microscale, thereby contributing to a deeper understanding of the corrosion processes and mechanisms of diverse materials.

Effects of Process-Induced Defects on the Corrosion of Additively Manufactured Stainless Steel 304L

This study investigates the impact of process-induced defects such as gas pores, lack of fusions, and surface roughness on corrosion behavior of stainless steel 304L (SS304L) fabricated by laser powder bed fusion additive manufacturing. Specimens are printed with optimized process parameters but selected from different locations on the build plate. Parallel and perpendicular surfaces to the build direction are investigated and compared with corrosion properties of wrought SS304L in 5 wt% NaCl. The results reveal significant difference in corrosion behavior among specimens due to variations in their defect features. Pitting potential, pit initiation, and growth rates are found to be influenced by specimen location on the build plate. The specimen located in downstream of the shielding gas flow shows the least corrosion resistance. While no clear trends are observed between some corrosion properties and defect features, other properties show strong correlations. For example, no trend is observed for the corrosion properties in relation to pore average area fraction. However, strong correlations are observed for the corrosion properties as functions of defects maximum area. Corrosion properties linearly deteriorate as the defects maximum area increases. Roughness shows a mixed relationship with pitting potential. Comprehensive discussions on all these effects are presented.

Influence of Chloride Ion Concentration on Corrosion Behavior of WC–MgO Composite

The influence of chloride ion (Cl−) concentration on the corrosion mechanism of WC–MgO composites has been studied in this work. The results suggest that the corrosion resistance of WC–MgO composite decreases first and then increases with the increase in Cl− concentration. Solution conductivity and dissolved oxygen content are the main influence factors. The solution conductivity determines the charge transfer process, and the dissolved oxygen determines the cathodic oxygen absorption reaction. The corrosion characteristic is typical pitting corrosion. Meanwhile, the corrosion mechanism contains an oxidation process of the WC matrix and the dissolution destruction of the MgO toughening phase. The formation of the WO3 corrosion layer hinders the general corrosion to protect the inner material. However, the dissolution of MgO induces the initiation of pitting. The local alkaline caused by MgO dissolution promotes the dissolution of the WC matrix, which leads to the expansion of pitting.

Stainless steel selection tool for water application: pitting engineering diagrams

Introduction: This work systematically investigates the effect of chloride level, temperature, and the water system’s oxidative power on the pitting corrosion performance of stainless steels in pH-neutral environments.Methods: Two test programs were set to a) develop a robust method for constructing the pitting engineering diagrams and b) construct the pitting engineering diagrams based on the obtained method from the first test program. The various electrochemical techniques were selected to assess and understand factors that affect the corrosion behavior of stainless steel. Extensive testing was performed with short-term electrochemical measurements and long-term immersion tests.Results and Discussion: The obtained results demonstrate that the electrochemical methods are sufficient to define pitting diagrams showing the boundaries between pitting and no pitting as a function of chloride concentration, temperature, and the water system’s oxidation potential. The laboratory long-term electrochemical test results correspond the best to real applications and clearly underline the importance of an induction time for pit initiation. Accordingly, two sets of pitting engineering diagrams were constructed based on the water system’s oxidation potential. Measurements at the applied potential of 150 mV vs. saturated calomel electrode (SCE) correspond to applications in sterile tap water, whereas the applied potential of 400 mV vs. SCE corresponds to slightly chlorinated water or water with some biological activity. Pitting engineering diagrams were proved to be very useful tools to aid material selection in water application. However, it is important to realize that additional factors, such as different surface conditions and the presence of other environmental species, crevice design, or weld will affect the exact position of the boundaries between pitting and no pitting.

The combined effect of carbon starvation and exogenous riboflavin accelerated the Pseudomonas aeruginosa-induced nickel corrosion

The primary objective of this study is to elucidate the synergistic effect of an exogenous redox mediator and carbon starvation on the microbiologically influenced corrosion (MIC) of metal nickel (Ni) by nitrate reducing Pseudomonas aeruginosa. Carbon source (CS) starvation markedly accelerates Ni MIC by P. aeruginosa. Moreover, the addition of exogenous riboflavin significantly decreases the corrosion resistance of Ni. The MIC rate of Ni (based on corrosion loss volume) is ranked as: 10 % CS level + riboflavin > 100 % CS level + riboflavin > 10 % CS level > 100 % CS level. Notably, starved P. aeruginosa biofilm demonstrates greater aggressiveness in contributing to the initiation of surface pitting on Ni. Under CS deficiency (10 % CS level) in the presence of riboflavin, the deepest Ni pits reach a maximum depth of 11.2 μm, and the corrosion current density (icorr) peak at approximately 1.35 × 10−5 A·cm−2, representing a 2.6-fold increase compared to the full-strength media (5.25 × 10−6 A·cm−2). For the 10 % CS and 100 % CS media, the addition of exogenous riboflavin increases the Ni MIC rate by 3.5-fold and 2.9-fold, respectively. Riboflavin has been found to significantly accelerate corrosion, with its augmentation effect on Ni MIC increasing as the CS level decreases. Overall, riboflavin promotes electron transfer from Ni to P. aeruginosa, thus accelerating Ni MIC.

Enhanced localized corrosion resistance of Ni-based alloy 625 processed by directed energy deposition additive manufacturing

We report a significant improvement in localized corrosion resistance of Ni-based alloy 625 processed by directed energy deposition (DED) in 7.6 mol/L LiCl at 50 °C. Disparities observed in polarization behavior between DED and wrought alloy 625 are analyzed through compositional and microstructural differences. The exceptional localized corrosion resistance of the DED alloy likely stems from the refinement of secondary phases resultant from the DED process. The prototypical precipitates larger than ≈1 μm in the wrought material, primarily Nb,Ti-enriched face centered cubic nitrides with the stoichiometry of MN where M = Nb, Ti, Cr, served as pit initiation sites and likely degraded the corrosion resistance.

Role of MnS in the intergranular corrosion and depassivation of sensitized Type 304 stainless steel

During polarization in 1 M NaCl (pH 5.4), intergranular corrosion of sensitized re-sulfurized Type 304 stainless steel occurred after pit initiation at MnS inclusions. Intergranular corrosion occurred when the pitting corrosion reached a Cr-depleted region along the sensitized grain boundaries. During depassivation under open-circuit conditions in 1 M NaCl (pH 1.0), MnS dissolution occurred as the first step, and the second step was the initiation of intergranular corrosion. Finally, dissolution of the steel matrix occurred. The role of MnS in the initiation of intergranular corrosion and depassivation of sensitized steel is discussed.

Effect of Sn addition on microstructure, hardness and corrosion behavior of CoCrFeNiSnx high entropy alloys in chloride environment

The microstructure, hardness and corrosion behavior of CoCrFeNiSnx (x = 0, 0.1, 0.5 and 1.0) HEAs were investigated in this work. The increase of the Sn addition resulted in the improvement of hardness (reached 424.9 HV) which attributed to the increase of the Ni3Sn2 phase with higher hardness. Adding Sn with molar ratio of 0.1 promoted the pitting initiation due to the potential difference between the two phases. CoCrFeNiSn0.5 and CoCrFeNiSn1.0 exhibited enhanced corrosion resistance compared to the alloy without Sn, which ascribed to the increase in cathode area (Ni3Sn2 phase) leading to a decrease in pitting sensitivity of FCC phase.

Visualization and Location Determination of Pit Initiation Sites in Martensitic Stainless Steel during Corrosion-Fatigue Cyclic Plastic Deformation

Low-carbon martensitic stainless steels, such as 13%Cr4%Ni, are widely used in manufacturing hydraulic turbine runners. High tensile strength steel, such as cast CA6NM or wrought S41500 martensitic stainless steel, has an acceptable resistance to corrosion and cavitation, and reduces the weight and cost while offering a more efficient design. During operation, the combined effect of cyclic loading (fatigue) and corrosion reduces the fatigue strength and can initiate cracks at localized corrosion surface defects.In this study, we determined the bulk and localized corrosion behavior of wrought (S41500) and cast (CA6NM) 13%Cr4%Ni stainless steel before and after plastic deformation.Susceptibility to pitting corrosion was studied using open circuit potential and potentiodynamic polarization measurements in 0.020 M NaCl. Localized corrosion behavior was studied using a scanning droplet cell (SDC) and oil immersed scanning electrochemical cell microscopy (OI-SECCM). The bulk and localized electrochemical measurements after different surface preparation methods (mechanical polishing, followed by etching or electro-etching in different media) were compared.The surface defects including micro-voids and inclusions of different types were characterized. The location of pit initiation was then determined using scanning electron microscopy and profilometry imaging. A three-electrode microcell with a working electrode of 1 mm² was designed and hyphenated with optical microscope to allow in situ tracking of pit initiation and growth. Chronopotentiometry and chronoamperometry controlled pit initiation, while optical microscopy demonstrated dynamic release of corrosion products and measured oxide repassivation kinetics.Finally, the in situ technique was developed further to include a microtensiometer fatigue apparatus to study the synergy effect between corrosion and fatigue. Location of pit initiation was compared with and without plastic deformation. Videos of pit initiation and growth will be presented.