Corrosion Film Research Articles

Corrosion Evaluation and Mechanism Research of AISI 8630 Steel in Offshore Oil and Gas Environments.

In this study, we optimized the traditional composition of AISI 8630 steel and evaluated its corrosion resistance through a series of tests. We conducted corrosion tests in a 3.5% NaCl solution and performed a 720 h fixed-load tensile test in accordance with the NACE TM-0177-2016 standard to assess sulfide stress corrosion cracking (SSCC). To analyze the corrosion products and the structure of the corrosion film, we employed X-ray diffraction and transmission electron microscopy. The corrosion rate, characteristics of the corrosion products, structure of the corrosion film, and corrosion resistance mechanism of the material were investigated. The results indicate that the optimized AISI 8630 material demonstrates excellent corrosion resistance. After 720 h of exposure, the primary corrosion products were identified as chromium oxide, copper sulfide, iron oxide, and iron-nickel sulfide. The corrosion film exhibited a three-layer structure: the innermost layer with a thickness of 200-300 nm contained higher concentrations of alloying elements and formed a dense, cohesive rust layer that hindered the diffusion of oxygen and chloride ions, thus enhancing corrosion resistance. The middle layer was thicker and less rich in alloying elements, while the outer layer, approximately 300-400 nm thick, was relatively loose.

New insights into the influence mechanism of carbides on the localized corrosion of N80 carbon steel: Experiments and first-principles study

Carbides significantly influenced the corrosion behavior of N80 carbon steel. The specific types of carbides and their adsorption behavior at the interface with the steel matrix were particularly complex. This study comprehensively evaluated the impact of carbides on the localized corrosion of N80 steel using both computational and experimental techniques. The findings revealed that the predominant carbides in the steel were Fe3C, with a potential difference of approximately 65.3 mV greater than that of the steel matrix, leading to preferential dissolution of the steel matrix. The corrosion film that formed on the steel surface was loose and porous, enriched with Cl-, and insufficient to effectively prevent the penetration of corrosive media. The work function relationship between Fe3C and the steel matrix was Fe < Fe3C, and O exhibited a higher adsorption energy on the Fe surface than on the Fe3C surface. This resulted in a strong galvanic coupling corrosion effect between Fe3C and the steel matrix. Fe3C, acting as the cathodic phase in the galvanic corrosion process, accelerated the adsorption of O2 on the steel surface, which in turn led to significant dissolution of the steel matrix. This process facilitated the nucleation of pits, ultimately resulting in the formation of stable pits on the surface.

The corrosion behavior and passive film properties of the cast and annealed AlCoCrFeNi2.1 eutectic high-entropy alloy in sulfuric acid solution

The effect of microstructure on the corrosion behavior and film properties of strengthened AlCoCrFeNi2.1 eutectic high-entropy alloy (EHEA) was investigated. Annealing of the 80 % cold-rolled AlCoCrFeNi2.1 EHEA at 650–1200 ℃ effectively improved the stable passive region to 930 mV, and decreased the passive current density by 25 % to 3.5 μA/cm2 compared with the cast alloy in 0.1 M H2SO4 solution. The improved corrosion resistance of the annealed AlCoCrFeNi2.1 EHEA was attributed to the increasing oxides proportion and thickness of passive film and the reduced composition difference between FCC and B2 phases. The B2 phase in lamellae suffered the severest corrosion.

Localized Corrosion Behavior and Corrosion Microstructure of LZ91 and LAZ931 Mg Alloys

LZ91 (Mg-9 wt%Li-1 wt%Zn) and LAZ931 (Mg-9 wt%Li-3 wt%Al-1 wt%Zn) alloys are emerging ultra-lightweight Mg alloys, which can be used in applications that require weight reduction. Although LZ91 alloy has found some success in the 3C industry, the relatively inferior mechanical strength limits its widespread application. To improve the mechanical properties, Al was added to LZ91 alloy to form LAZ931 alloy. However, both LZ91 and LAZ931 alloys are primarily composed of a dual-phase structure with α (HCP) and β (BCC) phases, which form a microgalvanic couple in the corrosion environment. Furthermore, adding Al introduces additional secondary phases, such as AlLi and MgLi2Al, which complicate the corrosion behavior and mechanism. Therefore, this study investigates the corrosion behavior and microstructure of LZ91 and LAZ931 Mg alloys in 3.5 wt% NaCl solution and the relationships to the phase distribution in the alloy substrates.By in situ optical microscope (OM) observations and open circuit potential (OCP) monitoring, localized corrosion initiates on the LAZ931 alloy earlier than on the LZ91 alloy. The early initiation and propagation of localized corrosion on the LAZ931 alloy result in worse corrosion resistances and faster corrosion rates measured by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves. By scanning Kelvin probe force microscopy (SKPFM), the Li-rich β phase is more active than the Mg-rich α phase. However, interestingly, localized corrosion was found to preferentially propagate inside the α phase, which seems to contradict the SKPFM measurements. The preferential propagation of localized corrosion in the α phase could be related to the difference in the surface corrosion film thicknesses on the α and β phases before localized corrosion propagation. The localized corrosion behavior and corrosion microstructure of the alloys will be discussed based on electrochemical measurements and site-specific microstructure characterizations. Figure 1

Developing and Testing Standards to Assess Atmospheric Corrosion of Silver Witness Coupons

Silver witness coupons are used to assess the corrosivity and chemistry of an ambient environment. The formation of silver corrosion products such as silver chloride is highly dependent on local conditions. However, the mechanisms that are responsible for these corrosion products are not well-understood, and there is a lack of standards used to compare and assess the quality of observations.The goal of this study is to synthesize silver corrosion film standards with known thickness and morphology. Compounds of interest include silver chloride, silver oxide, silver sulfide, silver sulfite, and silver sulfate. These compounds were generated electrochemically by oxidizing the silver in the presence of the anion of interest (chloride, sulfite, or sulfate), chemically by submerging the silver in a solution containing the anion, and chemically by dipping the silver in molten silver salts. The surface chemistry of these films was then analyzed using galvanostatic reduction, x-ray diffraction, x-ray photon spectroscopy, Raman spectroscopy, and energy dispersion spectroscopy. The films generated from each method were compared against each other to determine the optimal film thickness and morphology. In the future, these results will be compared against the surface chemistry of silver films formed by testing in laboratory chambers or by exposure in field environments. Figure 1

Performance of a Ship-Based Cupronickel Alloy in Exposure Conditions of Arabian Seawater-A Comparative Study.

Cupronickel-based alloys are widely known for their excellent resistance against aqueous corrosion, however, they can be susceptible to corrosion at accelerated rates and premature failure when exposed to a polluted or brackish seawater medium, even for short-term exposure durations. This unfamiliar corrosion behavior may be a result of the formation of an unprotected corrosion film during the early exposure durations. The paper investigates the corrosion phenomenon in cupronickel 90/10 alloy, by exposing the coupons in two different seawater compositions in the Arabian Sea region. Corrosion losses were investigated on the experimental coupons in a submerged position, for a maximum exposure duration of 150 days, using the conventional weight loss method and a new dimensional metrology-based measurement technique. Additionally, in this research the tubes of a marine heat exchanger having similar material that failed prematurely during operation in the Arabian Sea were also investigated for corrosion losses, followed by the characterization of the corrosion deposits using following analytical techniques: SEM, EDS, XRD and Raman Scattering. The experimental results showed significantly higher corrosion losses on coupons exposed to seawater site rich in pollutants and nutrients including dissolved inorganic nitrogenous compounds, compared to those subjected to a natural seawater solution in corrosion tanks maintained in a controlled environment.

Engineering battery corrosion films by tuning electrical double layer composition

Engineering battery corrosion films by tuning electrical double layer composition

Spatially Resolved Components in Battery Corrosion Films by 4D STEM

Spatially Resolved Components in Battery Corrosion Films by 4D STEM

Effect of ultrasonic assisted-ECAP processing on the microstructure, mechanical properties, and fluoride-induced corrosion performance of pure titanium

The influence of the ultrasonic assisted equal channel angular pressing (UA-ECAP) process on the microstructural characteristics, mechanical properties, and fluoride-induced corrosion behavior of grade 2 commercially pure titanium (CP-Ti) is investigated. The UA-ECAP process, particularly in the first pass, induces the formation of twins and slip bands. Continued slip band activity leads to non-equilibrium structures and ultrafine grains in subsequent passes. Mechanical properties analyses show hardness progression from 147 HV (annealed state) to 233 HV (3-pass UA-ECAPed) and yield strength increase from 465 MPa to 765 MPa with elongation reduction from 24.6 % to 16.6 %. Fluoride-induced corrosion of various samples in 1 wt% HF solution is investigated through electrochemical and immersion tests. After 28 days of immersion, the 3-pass UA-ECAPed sample exhibits a corrosion rate around half that of the annealed one and lower than other UA-ECAPed samples. Microscopic observations of corroded samples reveal the 3-pass UA-ECAPed sample's film is denser and more uniform, as compared with the other samples. Glow discharge optical emission spectroscopy (GDOES) confirms the corrosion films on all samples consist of an outer region rich in oxygen/fluorine and an inner region rich in oxygen; however, the film exists on the 3-pass UA-ECAPed sample exhibits over twice thicker than other samples and with higher contribution of oxygen in it as well. A proposed physical model is provided to explain the 3-pass ECAP sample's enhanced corrosion resistance.

Synergistic effect of temperature, concentration and solution flow on corrosion and passive film of austenitic SS 304L and 316L in concentrated sulfuric acid

The synergistic effect of temperature, sulfuric acid concentration and solution flow on the corrosion behavior and passive film properties of austenitic SS 304L and 316L have been investigated in concentrated sulfuric acid. Design of experiment was used and electrochemical techniques were employed. It was found that investigated parameters synergistically affect the corrosion behavior and passive film properties. Surface films formed at high concentrations are less defective and increasing temperature and solution flow introduced more defects; however, the passive film repairs itself. Increasing the temperature and solution flow resulted in higher passive film coverage and cracking of the passive film, respectively.

Corrosion Behavior of Cu-Ni-Fe-Mn-Cr Alloy in 3.5 wt% NaCl Solution

A novel Cu-10Ni-1.7Fe-0.5Mn-0.2Cr alloy was fabricated and exposed to a neutral 3.5 wt% NaCl solution for various days. The corrosion performance, corrosion film, and corrosion mode of the alloy were investigated in detail. The results suggested that the average corrosion rate reduced from 0.082 mm/a for 1-d immersion sample to 0.037 mm/a for 30-d immersion sample. The reduction in corrosion rate was mainly attributed to the progressive thickness and densification of the corrosion film, leading to increasing the resistance of the corrosion film with the prolonged exposure time. Low-valent oxides and chlorinated compounds were generated over the 1-d immersion sample surface, while high-valent oxides and hydroxide compounds were developed over the 30-d immersion sample surface. The mature corrosion film typically composed of Cu2O, CuO, Cu2(OH)3Cl, γ-FeOOH, MnO2, and Cr2O3. Eventually, the alloys suffered from selective corrosion and intergranular corrosion after a long exposure time in NaCl solution.

Salinity effect on corrosion inhibition of 2-mercaptopyrimidine as an inhibitor in CO2-containing solution

In this work, the effects of Cl-, Ca2+, and Mg2+ on the corrosion inhibition performance of 2-mercaptopyrimidine (2-MP) were investigated. The analysis reveals a marked reduction in the inhibition efficiency of 2-MP, from 91.24 % to 76.29 %, as the NaCl content in the solution rises from 1 wt% to 20 wt%. UV–visible absorption spectroscopy and quartz crystal microbalance measurements indicate that the desorption of 2-MP worsens with an increasing content of corrosive ions. Molecular dynamics simulations reveal the inhibitor desorption mechanism. This work enhances understanding of ion effects on corrosion inhibition and film degradation in high salinity environments.

Mitigating segregation and synergistically improving corrosion resistance via Ca-Y microalloying in twin-roll cast Mg-Al-Mn dilute alloys

This study investigates Ca-Y microalloying to address macro-segregation and enhance corrosion resistance in twin-roll cast Mg-Al-Mn alloys. Ca-Y microalloying alleviates macro-segregation by transforming Al-Al pairs into Al-Ca pairs and refines eutectic Al2Ca via heterogeneous nucleation. In 3.5 wt% NaCl solution, Ca-Y microalloying promotes the formation of protective Al2O3, Y2O3, and Ca-oxides on the eutectic Al2Ca, thus reducing pitting corrosion. More importantly, Ca-Y microalloying prevents the formation of Al-poor regions, which are prone to micro-galvanic corrosion and oxide film degradation. Overall, Ca-Y microalloying significantly improves corrosion resistance via a synergistic effect in refining the eutectic Al2Ca phase and decreasing Al-solute segregation.

Microstructure evolution and corrosion behavior of TIG welded joint of a new Mg[sbnd]Gd[sbnd]Nd[sbnd]Zn[sbnd]Zr alloy during post-weld heat treatment

The corrosion behavior of the tungsten inert gas (TIG) welded Mg3Nd3Gd0.2Zn0.5Zr alloy with different post-weld heat treatments was systematically investigated. The results show that the corrosion resistance of the sand-cast base material (BM) was inferior to that of the fusion zone (FZ), which was attributed to the larger grain size and exacerbated galvanic corrosion caused by coarser Mg3(Nd, Gd) eutectic phases and numerous β precipitates. It is found that post-weld solid-solution (T4) treatment could significantly enhance the corrosion resistance of the joint due to the dissolution of the cathodic second phases and the denser protective film abundant in RE oxides generated in corrosive solution. The precipitation of nanosized phases and ZnZr clusters would slightly increase the susceptibility to localized corrosion of the peak-aged (T6) joint. As the main corrosion products, MgO and Mg(OH)2 are distributed throughout the whole corrosion film, while RE oxides and RE hydroxides are mainly distributed in the inner layer, which can be explained by inward oxidation and replacement reactions between RE elements and MgO/Mg(OH)2. Based on the composition and structure of the corrosion product film, a physical model has been proposed for depicting the microstructure evolution associated with the corresponding corrosion behavior of the joints. This work could promote the applications of welded MgRE alloy joint in some corrosion environments.

Accelerated corrosion of 70/30 copper-nickel alloys in sulfide-polluted seawater environment by sulfide

The effect of sulfides on the pitting corrosion behavior and film chemistry of 70/30 copper-nickel alloys in aerated seawater was investigated. Sulfides in seawater prevent the formation of protective oxides on the surface of the alloy and alter the morphology and composition of the corrosion products. It results in the corrosion product film consisting of the double layer structure of the loose and porous sulfide-containing outer layer and the dense inner layer. This double-layer structure of the corrosion product film can't alleviate corrosion, but instead accelerates the development of pitting corrosion. The statistical analysis method is used to study the corrosion process of 70/30 copper-nickel alloy in sulfide-containing environment. This work records the trend of pitting corrosion towards the horizontal and longitudinal directions.

Microstructure of corrosion product film formed on aged WE43 alloy

A dense three-layer corrosion product film was formed on aged WE43 alloy in 3.5 wt.% NaCl solution. The microstructure of the film was analyzed in detail by TEM. The three-layer corrosion product film is composed of RE2O3, MgO layer doped with RE2O3 and Mg(OH)2 layer doped with RE2O3 from the inside to the outside. A large amount of rare earth oxide particles formed both by the outward oxidation of rare earth precipitates and rare earth elements, are the main reason for the formation of the corrosion film. The RE2O3 has the preferential orientation with ( 2-11) plane and [231] direction parallel to (002) plane and [ 1-1-0] direction of MgO, respectively. Thus, the rare earth oxide particles can fill the gap of porous MgO layer, and improve the compactness of the film. The inner RE2O3 layer and mixed layer of MgO and RE2O3 play an important role in the formation of the film. The compact inner film can prevent the corrosion medium from reacting with the Mg matrix.

Effects of micro-alloying Ag on microstructure, mechanical properties and corrosion behavior of extruded Mg-2Zn-0.2Ca-xAg alloys

The present work investigates effects of micro-alloying Ag on the microstructure, mechanical properties and corrosion behavior of as-extruded Mg-2Zn-0.2Ca alloys. The addition of Ag, up to 0.5 wt%, induce limited difference on microstructural characteristics such as slightly coarser microstructures due to the enhanced dynamic recrystallization process and the presence of refined precipitates. The tensile properties of the alloy were not significantly changed by Ag addition, i.e., all the alloys exhibited exceptional elongation of ∼30%, moderate tensile yield strength and ultimate strength of ∼140 MPa and ∼240 MPa, respectively. The corrosion performance of the alloys was progressively deteriorated with increasing Ag content i.e., the corrosion rate increased from 0.40 ± 0.23 mm/y for Mg-2Zn-0.2Ca alloy to 3.27 ± 0.24 mm/y for the Mg-2Zn-0.2Ca-0.5Ag alloy. The compromised corrosion performance was attributed to a large electrode potential difference between the nobler Ca2Mg6Zn3 phase and the α-Mg matrix as well as a less protective corrosion film, by increasing Ag addition.

New insights into the inhibition mechanism of carboxylate species on magnesium surface

The microstructure and composition of corrosion film deposited on pure Mg were systematically investigated, and for the first time DFT was used to reveal the adsorption behavior of carboxylates on the surface of corrosion layer rather than the metallic Mg. Presence of carboxylate inhibitor dramatically modified composition of the corrosion film and bonded directly with Mg atoms in the outermost MgO based corrosion layer by means of carboxyl. The bonded Mg atoms were lifted by 0.8 – 1.1 Å from their original position when abundant inhibitors started to act as complexing agent, leading to deteriorated inhibition effect.

Investigating the effect of Cr content on the microstructure and electrochemical measurement of low alloy steel

In this study, the effect of Cr content on microstructure and electrochemical measurement of low alloy steel in 3.5 wt% NaCl solution was investigated using scanning electron microscope (SEM), X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical workstation, and the CCT curves of the samples were calculated using JMatPro software. The results showed that the augmentation of Cr content inhibits the formation of ferrite and promotes the development of cementite in low alloy steels. And the reduction of Ar3 (the temperature at which austenite transforms to ferrite) and the increase in Ar1 (the temperature at which ferrite transforms to pearlite) also contribute to the expansion of the pearlite area. The XRD results show that the samples primarily consist of Fe-Cr solid solution with a body-centered cubic structure. As the Cr content increases, the peaks corresponding to the (110), (200), and (211) planes gradually enhance which means the improvement in the crystallinity of the samples. The improvement in the crystallinity can result in a decrease of grain size. Due to the suitable ratio of cementite to pearlite and the synergistic effect of grain size refinement, the Cr2 sample exhibits the best tensile property when the Cr content is 0.970 wt%. Cr(OH)3 and Cr2O3 with protective effects are generated in the corrosion film on the surface of Cr-containing low-alloy steels. And Cr also promotes the transformation of γ-FeOOH to α-FeOOH in the corrosion film because of the atomic radius of Cr3+ being smaller than that of Fe3+. These substances enhance the ability of the corrosion film to block corrosive media and protect the matrix. The results of the electrochemical measurement showed that the increasing Cr content from 0.970 to 4.657 wt% resulted in the enhancement of steel's corrosion resistance. The Cr4 sample exhibits the best corrosion resistance when the Cr content is 4.657 wt%.

Correlation between the micro-shot peening coverage and surface microstructural evolution and fluoride-induced corrosion behavior in Monel 400 alloy

This study examines the influence of micro-shot peening (MSP) on Monel 400 alloy, focusing on surface microstructural evolution and fluoride-induced corrosion behavior compared to its solution annealed (SAed) counterpart. MSP treatments were conducted at various surface coverages (100%, 200%, 500%, 1000%, 1500%, and 2000%). Characterization encompassed microhardness, surface roughness, grazing incidence x-ray diffraction (GI-XRD), field emission scanning electron microscopy (FE-SEM) with electron backscatter diffraction (EBSD), and transmission electron microscopy (TEM). With increasing the MSP coverage to 2000%, the surface crystallite size decreased from approximately ∼30 µm in the SAed sample to 60 nm. TEM analysis emphasized dislocation slip and formation of dislocation structures as the primary mechanisms for the grain refinement. However, the 2000% coverage exhibited microcrack formation, compromising its hydrofluoric (HF) corrosion resistance. Electrochemical tests revealed severe localized corrosion in all MSP-treated samples except the 1500% coverage, which exhibited a minimum passive current density of 0.2–1.0 µA/cm2. Inductively coupled plasma optical emission spectroscopy (ICP-OES) of immersion solutions showed lower copper and nickel ion concentrations (<150 ppm) in the 1500% MSP-treated sample, indicating its enhanced corrosion resistance. X-ray photoelectron spectroscopy (XPS) identified NiO, NiF2, CuO, CuF2, and Cu(OH)2 phases in SAed and 1500% MSPed samples, with a higher concentration of copper oxide (CuO) in the corrosion film of the 1500% MSP-treated sample, contributing to its superior corrosion resistance.