Localized Corrosion Mechanism Research Articles

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.

Electrochemical characterization of localized corrosion mechanism of ALD Al2O3-coated copper for microelectronic application

To achieve performance and reliability in microelectronics devices, copper interconnections must be protected from aggressive environment during the manufacturing process and throughout the life of the devices. Atomic Layer Deposition Al2O3 thin films has been used as a compatible layer with key integration process steps, as well as being corrosion-resistant in neutral media. However, electrochemical tests in aggressive environment have revealed that the alumina prematurely failed to protect copper from localized corrosion. In this study, local and global electrochemical techniques have been employed to evaluate the reactivity of copper at multiple scales and to elucidate the underlying corrosion mechanisms.

A highly sensitive, long-time stable Ag/AgCl ultra-micro sensor for in situ monitoring chloride ions inside the crevice using SECM

Tracking the variation of Cl− timely within the crevice is of great significance for comprehending the dynamic mechanism of crevice corrosion. The reported chloride ion selective electrodes are difficult to realize the long-time Cl− detection inside the confined crevice, due to their millimeter size or a relative limited lifespan. For this purpose, an Ag/AgCl ultra-micro sensor (UMS) with a radius of 12.5 μm was fabricated and optimized using laser drawing and electrodeposition techniques. Results show the AgCl film's structure is significantly impacted by the deposited current density, and further affects the linear response, life span and stability of Ag/AgCl UMS. The UMS prepared at current density of 0.1 mA/cm2 for 2 h shows a rapid response (several seconds), excellent stability and reproducibility, strong acid/alkali tolerance, sufficient linearity (R2 > 0.99), and long lifespan (86 days). Moreover, combined with the potentiometric mode of scanning electrochemical microscope (SECM), the Ag/AgCl UMS was successfully applied to monitor the in-situ radial Cl− concentration in micro-regions inside a 100 μm gap of stainless steel. The findings demonstrated that there was obvious radial difference in Cl− concentration inside the crevice, where the fastest rise in Cl− concentration was at the opening. The proposed method which combines the UMS with SECM has attractive practical applications for microzone Cl− monitoring in real time inside crevice. It may further promote the study of other localized corrosion mechanism and the development of microzone ions detection method.

Corrosion behaviour of electropolished magnesium materials

Although magnesium and its alloys are promising candidates as biodegradable implant materials, the tendency for localised corrosion mechanism in physiological environment limit their biomedical application. Electropolishing is an attractive strategy for improving the corrosion behaviour of metals, but it is still largely unexplored in magnesium materials. In this study, the characterisation of electropolished surfaces of AM50 and pure magnesium was performed, focussing on their in vitro degradation behaviour in cell medium. Corrosion rates were evaluated using potentiodynamic polarisation. The surface morphology before and after the onset of corrosion was investigated by scanning electron microscopy and confocal laser scanning microscopy. The presented electropolishing process led to improved surface performances, observable by significantly lower corrosion rates (0.08 mm·year−1 in Dulbecco's modified Eagle's medium), lower arithmetical mean height (0.05 µm), lower water contact angle (25–35°) and lower micro hardness (35–50 HV 0.1) compared to mechanically and chemically treated surfaces. MgO/Mg(OH)2 could be detected on electropolished surfaces. The localised corrosion mode could be reduced, but not entirely prevented. Electropolishing shows great potential as post-treatment of magnesium-based components, but detailed tests of the long-term corrosion behaviour are an important area of future research.

A mechanistic study on localized corrosion of sandwich multi-layered aluminium sheet in 3.5 wt.% NaCl solution

Multi-layered aluminium sheets are quickly gaining wide applications in several industries. However, a complete understanding of how the macro- and microstructures of composite influence the corrosion behavior is still far from being achieved. In this work, the electrochemical behavior of a 4343/3003/7072 aluminum alloy (AA) composite in 3.5 wt.% NaCl solution was investigated using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and scanning electron microscopy (SEM). The evolution of corrosion morphologies was analyzed from cross-sectional and plane directions, and the localized corrosion mechanism was discussed. Due to the galvanic effect existed in the cross-section, the corrosion resistance of the cross-section was higher than that of the plane surface. From the cross-section, the AA3003 was protected as the cathode and the adjacent AA4343 and AA7072 acted as anodes. Localized corrosion mainly initiated around Al-Si-Mn-Fe and Si-rich phases.

Understanding localized corrosion mechanism of 90/10 copper-nickel alloy in flowing NaCl solution induced by partial coverage of corrosion products films

The galvanic effect induced by partial coverage of corrosion products films is studied for 90/10 copper-nickel alloy in flowing NaCl solution using electrochemical and surface analytical methods, aiming at understanding the localized corrosion mechanism. The results show that small-area bare samples act as cathode with polarity reversal and anode after coupled to statically and dynamically pre-filmed samples for 240 h, respectively. The latter indicates higher localized corrosion risk, especially at high flow velocities of 3.3 m/s and 4.2 m/s. The localized corrosion mechanisms are explained based on evolution of corrosion products films during coupling.

Unraveling the effect of sulfide-oxide complex inclusions on the localized corrosion mechanism for carbon steel

The localized corrosion induced by (Ca, Mn)S-(Al, Mg)O complex inclusions was investigated. It revealed that MgO·Al2O3 served as cores and MnS·CaS as shells in the carbon steel. MnS and CaS acted as an anodic phase in the galvanic corrosion formed with steel matrix, while MgO and Al2O3 had no galvanic couple effect with MnS and CaS. MnS was the most preferentially dissolved and triggered localized corrosion, which expanded in the order of CaS-Fe-MgO·Al2O3. The driving force for sulfides and steel matrix dissolution was the effect of galvanic couple, and high local plastic deformation caused by oxides, respectively.

Gas liquid-carried flow accelerates MIC by sulfate reducing bacteria biofilm

The corrosion and perforation leakage of shale gas pipelines can lead to serious environmental damage. By tracking the water and gas components throughout the shale gas production cycle, the main factors that affect corrosion in shale gas pipelines have been identified: carbon dioxide, dissolved oxygen, sulfate-reducing bacteria, and chloride ions. The study focused on understanding the development mechanism of localized corrosion of L360N steel within the upward shale gas gathering pipeline, particularly under the combined influence of sulfate-reducing bacteria and flowing conditions. SRB could form a biofilm on the surface of the steel. Through the Dissimilatory Sulfate Reduction (DSR) process, the metabolites reacted with Fe2+ to produce FeS. The corrosion rate of L360N steel was observed to be higher when exposed to gas-liquid flow compared to static conditions. In the flowing state, the boundary layer within the upward pipeline exhibited backflow tendencies, causing a portion of the corrosion products and biofilm to peel off. This exposure revealed a local surface, acting as an anode. As a result, corrosion pits were further deepened due to microscopic eddy currents, indicating that zero net liquid flow accelerated the corrosion process.

In-situ electrochemical testing and fluid dynamics simulation of pipeline defects under flow accelerated corrosion

The pipeline defects of flow accelerated corrosion (FAC) on the corrosion behaviors and localized corrosion mechanisms on different locations of the depressions and the welded joint with weld reinforcements were investigated using wire beam electrode (WBE) techniques and fluid dynamics simulations. The results revealed that the swirling vortex inside the depression and the local jet impact by the fluid separation in the weld reinforcement can accelerate the localized corrosion. Also, the depressed upper and trailing edge regions and the weld toes on both sides of the weld reinforcement experience considerable pressure fluctuations, enhancing interfacial mass transfer processes and inducing cavitation for severe localized corrosion failure. Furthermore, the galvanic corrosion strength factor (g) indicated an enhanced susceptibility of localized corrosion in depression and welded joints with weld reinforcement.

Localized Corrosion Mechanism of Q125 Casing Steel in Residual Acid Solution during Oil Reservoir Acidizing

This paper aims to investigate the localized corrosion mechanism of Q125 casing steel in residual acid solution with Mannich base type inhibitors during oil reservoir acidizing process. The corrosion behavior of Q125 casing steel in fresh acid (20% HCl) and residual acid solution (pH 1.0 and pH 3.0 HCl) with and without 3-(4-chlorophenylimino)-1-(piperidine-1-ylmethyl) indolin-2-one (Mannich base type, Mb) inhibitor was studied by electrochemical test, weight loss, and surface analysis. The morphology and composition of corrosion products were analyzed by SEM/EDS and XPS; the local corrosion rate of casing steel with or without inhibitor was obtained by 3D profilometry. It was determined that the inhibitor had higher inhibition efficiency in fresh acid conditions than in residual acid conditions. Under the condition of residual acid, the decrease in inhibitor molecular coverage on the substrate surface promotes the occurrence of local corrosion. Pitting corrosion was detected in the residual acid solution containing Mannich base inhibitor, which may be related to the fact that FeCO3 hinders the adsorption of inhibitor molecules on the substrate surface.

Localized corrosion of 304 stainless steel triggered by embedded MnS

The present work investigated the localized corrosion of 304 stainless steel triggered by MnS in 3.5 wt% NaCl solution via multi-analytical approaches including in-situ and ex-situ techniques. The results suggested that the dissolution of MnS starts from boundary areas and directly releases elemental sulfur. The reoccurrence and disappearance of elemental sulfur during MnS dissolution indicated that sulfur was continuously consumed and converted. Copper-containing compounds were found deposited on residual MnS in the corrosion pit, whilst a thin Cr2O3 film covered the pit and thickened over time. Based on the evidence obtained, a more comprehensive MnS-induced localized corrosion mechanism was proposed.

Quantitative Evaluation of the Ability of Accelerated Tests to Simulate On-Road Corrosion Morphology of Automotive Aluminum Alloys

Three wrought automotive Al-Mg-Si alloys (6xxx-series) were exposed to an on-road service environment and in six standard laboratory-accelerated exposure tests. Optical micrographs of all these exposures were obtained and the resulting corrosion morphology was quantified using fractal dimension analysis and corrosion boundary length-to-area ratios. Additionally, the images were also used to train a convolutional neural network (CNN)-based pattern recognition algorithm, which was then used to quantitatively identify which accelerated test was the closest match to the field exposures. Overall, no single accelerated test could fully capture the on-road results or ubiquitously be the most appropriate test regardless of alloy and temper. However, results from fractal dimension and length-to-area ratio analyses identified that among the tests studied, those with acidified electrolytes are more appropriate for matching on-road corrosion morphology. The CNN algorithm output also agreed with this finding, indicating that the results from tests with acidified electrolytes correlated to field morphology with a confidence >70% for most of the images tested, thus showing the utility of these methods in providing quantitative bases for morphology comparison. Assessed in the context of literature evidence for localized corrosion mechanisms in 6xxx-series alloys, these results also indicated that pH may play an influential role in how corrosion morphology develops in these alloys upon exposure to a complex on-road environment.

Quantitative 3D Characterization for Kinetics of Corrosion Initiation and Propagation in Additively Manufactured Austenitic Stainless Steel.

In situ X-ray computed tomography (X-ray CT) is used to investigate the effects of characteristic microstructural features on the pitting initiation and propagation in austenitic stainless steel specimens prepared with laser powder bed fusion (LPBF) additive manufacturing. In situ X-ray CT in probing the mechanism and kinetics of localized corrosion is demonstrated by immersing two LPBF specimens with different porosities in an aggressive ferric chloride solution for the evaluation of corrosion. X-ray CT images are acquired from the specimens after every 8hours of immersion over an extended period of time (216hours). Corrosion pit growth is then quantitatively analyzed with a data-constrained modeling method. The pitting growth mechanism of LPBF stainless steel is found to be different from that of conventional stainless steels. More specifically, the mechanism of corrosion pit initiation is closely correlated with the original lack of fusion porosity (LOF) distribution on the surface of the specimens and preferential pit propagation through the LOF pores inside the specimens. Pit growth kinetics are derived from pit volume changes determined through 3D data analysis. The pit growth kinetics in LPBF specimens are found to vary in the initial pit formation, competitive pit propagation, and the dominant pit growth stages.

Effect of Testing Conditions, Gauge, and Temper on Stress Corrosion Cracking of AA7xxx Aluminum Aerospace Plate Alloys

The European Aviation Safety Agency’s recent safety information bulletin (SIB 2018-04R2) describes a brittle intergranular cracking phenomenon in 7xxx aluminum alloys and recommends testing conditions. These testing conditions are severe compared with expectations regarding, temperature, humidity, and stress in aerostructures. In this study, strong increases in time to failure of smooth specimens tested in humid air were observed when reducing either temperature or stress to levels closer to what is representative of in-service conditions. The cracking morphologies after testing in hot, humid air were identical to those described in the literature for in-service occurrences of stress corrosion cracking (SCC), including the observation of crack arrest markings consistent with a mechanism of alternate local corrosion and crack propagation by hydrogen embrittlement. The differences between such fracture surfaces and those observed in the industry standard SCC screening test, which uses a chloride-containing solution to accelerate initiation and propagation, can be attributed to the pitting of the crack surface in a chloride-containing solution in the wake of the propagating crack. The performances of 7xxx-T7 aluminum plates SCC testing in either hot, humid air or a chloride-containing aqueous solution have been compared as a function of thickness, over-aging treatment, and composition. There is a strong effect of plate thickness in both tests, with substantial decreases in initiation time and lifetime for thinner plates. The effect of plate gauge is such that “legacy” materials (such as 7010-T7651, 7050-T7651, and 7050-T7451) passing the SIB 2018-04R2 test at high thicknesses, fail at lower gauges, yet have been flying for nearly 50 y. An increase in SCC performance with increased overaging is observed in both tests. As a consequence, comparisons of SCC performance of alloy compositions should be made wherever possible at identical plate thickness and for aging treatments that result in comparable strengths. When this is done, high Zn concentration 7449-T76++ (7449-T7651 with additional aging) shows a slightly worse strength-SCC balance than 7010-T7651 and 7050-T7651. The observed trends in SCC performance in the two tests are consistent, suggesting that similar repeated initiation and propagation mechanisms are responsible for cracking in humid air and in aqueous NaCl environments.

Localized Corrosion Mechanisms – a Bayesian Reasoning Perspective

The mechanisms for localized corrosion proposed over the last several decades are fall into two two major categories: (1) defect generation in the passive film of the open surface leading to breakdown and enhanced local dissolution and (2) the maintenance of a local electrolyte chemistry that promotes continued localized corrosion. A qualitative argument was proposed by Frankel et al. [1] to bridge the gap between passive film and local chemistry mechanisms. They suggest that passive film breakdown was more important for alloy-environment situations where pit initiation was more difficult, whereas local chemistry was more relevant for situations where pit initiation was more facile. Another difficulty arises when modeling the effect of local chemistry on stabilization of local corrosion. Is it the formation of critical pH, critical metal-anion complexes, or metal-anion salt film that is responsible for the stabilization of localized corrosion? These effects are interrelated because high concentration of metal cations can lead to acidification and salt film formation. Specific experimental techniques may bias conclusions with respect to one mechanism or another. Furthermore, uncertainties exist in the data used to validate models as conditions assumed in the models may be difficult to access. It is convenient under these circumstances to take a probabilistic approach based on Bayesian network (BN) to assess the likelihood of validity of a causal mechanism [2]. In this presentation, the importance of local acidity versus metal-salt formation on localized corrosion is examined through a Bayesian network model. The Bayesian network consists of nodes connected through cause-effect relationships characterized by conditional probabilities. The network computes the marginal probability of an event given causal events. Conversely, given an evidence, the preceding causes are evaluated using Bayes theorem. Thus, BN provides a probabilistic framework for cause-effect evaluations based on experimental evidence. Results from the literature and recent experiments are presented to illustrate the approach. Limitations of the approach are also presented. Frankel, G.S., T. Li, and J.R. Scully, Localized Corrosion: Passive Film Breakdown vs Pit Growth Stability. J. of The Electrochemical Society, 2017. 164(4): p. C180-C181.Pearl, J., Causality. 2009: Cambridge university press.

Passive Film Structure and Corrosion Initiation in Al Alloys with Far-from-Equilibrium Compositions and Microstructures

Al alloys with far-from-equilibrium compositions and microstructures are reported to possess high corrosion resistance and strength. These alloys produced are by non-equilibrium processing techniques such as high-energy ball milling, sputtering, and ion implantation. Depending on the processing techniques and conditions, the microstructure of the alloys could be heterogeneous. For example, alloys produced by high-energy ball milling and subsequent consolidation comprise a matrix with high solid solubility of the solute and uniformly distributed secondary phases. Such a heterogeneous microstructure is expected to influence the passive film composition and localized corrosion mechanisms. In the present study, passive film composition on the ball-milled alloys was studied using a combination of scanning transmission electron microscope, X-ray photoelectron spectroscopy, and secondary ion mass spectrometry (SIMS). Additionally, pits and regions near pits were investigated which helped in understanding factors causing pit initiation and repassivation.

Light Metal Alloys Local Reactivity, from AFM Based Scanning Kelvin Probe Force Microscopy (AFM-SKPFM) to Scanning Electrochemical Nanocapillary (SEN)

Materials surface heterogeneities obviously plays a crucial role in reactivity issues and generate various types of detrimental localized corrosion attacks. In corrosion science, a first question to be addressed is how these various materials microstructure affect oxidation / passivation and localized corrosion initiation mechanisms. A methodology for microscale characterization of initial stage of surface reactions has been developed based on the Atomic Force Microscopy (AFM) Scanning Kelvin Probe Force Microscopy (AFM-SKPFM). In very early work, potential mapping with micrometer lateral resolution (lateral detection limit of materials surface heterogeneities is better but the signal has to be deconvoluted) allowed to clearly identify "cathodic" and anodic sites on Al- alloys [1]. Careful potential calibration and surface conditioning with solution exposure generating the formation of an electrochemical double layer allow obtaining local thermodynamic information closely linked to "practical electrochemical potential series" measured in bulk solution conditions. This contribution will start by revisiting some "historical" examples of AFM-SKPFM characterization (a tribute to Jerry Frankel's activities) of aluminum and magnesium alloys [1,2]. These materials surfaces will further be used to show how reaction kinetic information on corrosion processes can be obtained with similar lateral resolution by means of the newly developed Scanning Electrochemical Nanocapillary (SEN) technique. After introducing the SEN technique and methodology, the presentation will focus on showing how the combination of these two approaches allows refining the local corrosion mechanism assessment of heterogeneous materials. The SEN technique is very versatile and allows various types of electrochemical measurements to be performed with constant tracking of the topography. The technique is based on a nanocapillary glass tip (< 100 nm) excited laterally by a piezoelectric element. A control of the capillary vibration damping when approaching the surface and a feedback loop (like the tapping mode in AFM) allows a very precise control of the approach and electrolyte contact on the surface. The glass capillary filled with the electrolyte of interest integrates a reference and Pt counter electrodes to perform electrochemical measurements exposing only the area of interest to aggressive electrolytes. Using its "hopping" mode (a scan with electrochemical characterization of successive individual nanoscale areas), corrosion initiation susceptibility can be addressed. This will be illustrated through the surface reactivity study of model Al-Cu-Mg microscale intermetallics and Mg-based alloys, using SEN OCP linescans. In addition information about extend of the attack can be subsequently retrieved from SEM observations. Using the precise positioning ability of the SEN setup with X, Y and Z direction piezos, potentiodynamic polarization measurements can furthermore be performed on selected area of interest. The example of an Mg-Fe composite material will be used to discuss its local electrochemical behavior.After the presentation of the SEN characterization results, additional aspects of the measured potential by AFM-SKPFM will also be discussed as adsorbed species, especially strong dipolar molecules, can significantly contribute to the measured signal [3]. Modification of the AFM-SKPFM setup towards atmospheric corrosion investigation will finally be presented. This environmental AFM/SKPFM bridges the gap between the full electrochemical local characterizations that can be offered by the SEN technique and an "electrochemical reaction" diagnostic obtained by SKPFM in thin water layer. The example of a very reactive WC-Co composite will be presented to demonstrate the reactivity issue, galvanic coupling controlling local dissolution processes [4].AcknowledgementsGerald Frankel for the great time I spent at Ohio State University in the Fontana Corrosion Center developing the AFM-based SKPFM methodology. Empa for internal project financial support of the SEN instrument.

Electrochemical Study of Pitting Corrosion of Corrosion Resistant Alloys in Supercritical CO2 Environment

Various types of corrosion resistance alloys such as 13 Cr, Super 13 Cr, and duplex stainless steels are typically used in oil and gas and CO2 capture and storage applications, especially the injection section, where the pipeline could be exposed to aqueous phase and the risk of localized corrosion is of high concern. The composition of these materials is engineered to provide high corrosion-resistant properties. The operating conditions in the above-mentioned applications can include high CO2 pressure and high temperature leading to the “so-called” supercritical CO2 condition. Under the supercritical CO2 conditions, the pH of the aqueous phase in the system can be as low as pH ~ 3 buffered by the dissolved CO2. The environment can also contain high salinity, and therefore, the passive layer on the stainless steel might be locally damaged resulting in pitting corrosion. While there are numerous studies available on the localized corrosion of different stainless steels in chloride-containing aqueous environment, the number of studies in supercritical CO2 conditions is limited. The objective of this work is to understand the effect of supercritical CO2 on the localized corrosion mechanism of corrosion resistant alloys.Three different types of corrosion resistant alloys (13 Cr, Super 13 Cr, and duplex stainless steel) are studied under CO2 pressure (0 to 14 MPa) and at high temperature (150˚C) in 5 wt.% NaCl solution. The experiments are conducted in a high-pressure autoclave system at a consistent initial pH for comparison. The electrochemical behavior and the pitting corrosion are studied using cyclic potentiodynamic polarization and potentiostatic measurements. The surface of each specimen is investigated using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) before and after the electrochemical experiments to characterize the microstructural and localized corrosion features, respectively. All the tested materials show passive behavior under the conditions of the current study, however the pitting potential decreased in this order: duplex, Super 13 Cr and 13 Cr stainless steel.

Study on the local corrosion behaviour and mechanism of bogie steel welded joints

The local corrosion behaviour and mechanism of welded joints were studied. The results show that the corrosion was caused by the distribution of microstructure defects in different areas of the weld. In the early stage, the potential difference between the base metal and the heat affected zone was less than 50 mV, so there would be no galvanic effect. As the corrosion progressed, the potential difference increased gradually, and the maximum value exceeded 160 mV. During this period, the corrosion rate was mainly affected by galvanic effect, and the order was weld seam > base metal > heat affected zone.

New insights on the initial local corrosion of composite Al7Cu2Fe/Al20Cu2Mn3 intermetallic particles in 2024-T351 aluminum alloy

The very initial stage of local corrosion in composite Al7Cu2Fe/Al20Cu2Mn3 intermetallic particles (IMPs) was studied on a FIB site-specific specimen. It is confirmed by quasi in-situ TEM observation that the regions with long-range ordered (LRO) structure embedded in Al7Cu2Fe are the initial local corrosion sites. Besides, the de-alloying of LRO regions at Al7Cu2Fe/Al20Cu2Mn3 interface would highly increase the local potential difference and the galvanic driving force to trigger anodic dissolution of the Al20Cu2Mn3 phase. It provides new insights into the initiation and propagation mechanism of localized corrosion in composite IMPs.