Corrosion Of Iron Research Articles

Microscale chemical imaging to characterize and quantify corrosion processes at the metal-electrolyte interface

We introduce an experimental setup to chemically image corrosion processes at metal-electrolyte interfaces under stagnant, confined conditions—relevant in a wide range of situations. The setup is based on a glass capillary, in which precipitation of corrosion products in the interfacial aqueous phase can be monitored over time with optical microscopy, and chemically and structurally characterized with microscopic synchrotron-based techniques (X-ray fluorescence, X-ray diffraction, and X-ray absorption spectroscopy). Moreover, quantification of precipitates through X-ray transmission measurements provides in-situ corrosion rates. We illustrate this setup for iron corrosion in a pH 8 electrolyte, revealing the critical role of O2 and iron diffusion in governing the precipitation of ferrihydrite and its transformation to goethite. Corrosion and coupled reactive transport processes can thus be monitored and fundamentally investigated at the metal-electrolyte interface, with micrometer-scale resolution. This capillary setup has potential applications for in-situ corrosion studies of various metals and environments.

Spatial distribution of corrosion products from a bridge pier

AbstractThis paper studies the spatial distribution of corrosion by-products by a bridge pier within a conductive medium. An electrochemical impedance spectroscopy (EIS) technique was used to investigate an uncoated metallic bridge pier submerged in static distilled water. An equivalent circuit model, derived from EIS results, served as the foundation for the study. Further, the role of diffusion was analysed, considering its significance in characterising the transfer of particles from the pier into the surrounding water. This exploration revealed the complex interaction between the diffusion processes of various corrosion by-products as a function of distance. In addition, by evaluating the spatial distribution of iron (II) corrosion by-products and modelling nanoparticle diffusion, the research examined the impact of diffusion and concentration on corrosion particle transmission. The findings, analysed via Nyquist and Bode plots, demonstrate significant differences between theoretical and empirical diffusion coefficients. Results indicated that under natural corrosion conditions, the primary product of the corrosion reaction, iron (II), disperses into the medium when oxidation occurs. The elevated resistivity due to the presence of iron (II) underscores the diffusion effect, leading to corrosion product precipitation and reaching saturation level. Additionally, the results demonstrated ideal values for the diffusion coefficient, which are crucial for advanced corrosion modelling. The results emphasised the need for empirical data to improve corrosion prediction models and informed maintenance strategies for submerged structures.

The clogging effect of nanoscale zero valent iron corrosion in bicarbonate anaerobic water on porous media: A real-time pore-scale visualization

The corrosion-induced permeability changes of nanoscale zero-valent iron (NZVI) are one of the crucial factors constraining the successful application of NZVI in the remediation of contaminated groundwater. It is of great significance to study the dynamic evolution of corrosion products of NZVI after NZVI is injected into porous media and its influence on pore plugging effect from the pore scale. Micro computed tomography (Micro-CT) imaging technology, mineralogical characterization and theoretical calculations were used to understand the details of NZVI corrosion plugging porous media at the pore scale. This study reveals the factors of NZVI corrosion plugging porous media, namely, gas production (H2) in the early and middle stages of corrosion (before 90 days) and solid phase changes (NZVI volume increase and migration) in the later stages (after 90 days). The permeability loss rate of the porous media was 66.8%, 87.3%, 79.4%, and 53.6% at the corrosion times of 30, 60, 90, and 120 days, respectively. After 90 d of corrosion, the particle size of NZVI increases by 7.9%, and the secondary minerals formed by corrosion are mainly Fe3O4/γ-Fe2O3 and FeOOH. In addition, this study also found that the migration of NZVI after 90 d was due to its corrosion reducing the magnetic attraction between particles, dissociating into smaller particles or agglomerates under the action of fluid dynamics, resulting in its redistribution in the porous medium and causing blockage. This study clarifies that NZVI corrosion plays a vital influence in affecting the permeability and clogging of porous media, providing valuable guidance for optimizing NZVI-based remediation technologies.

Corrosion potential and theoretical studies of fabricated Schiff base for carbidic austempered ductile iron in 1M H2SO4 solution

In this body of work, a chemical known as 2-cyano-N-(4-morpholino benzyl dine) acetohydrazide (CMBAH) is explored for its ability to suppress the carbidic austempered ductile iron (CADI) corrosion in 1M H2SO4. Density functional theory was used in experiments and theoretical investigations to investigate the inhibiting impact. The corrosion of CADI alloys in 1M H2SO4 produced a corrosion resistance superior to that of CADI heat treatment (H.T.). As-cast carbidic ductile iron (CDI) 4 alloy with 1.5%t Cr-Nb has a corrosion rate (C.R.) of 11.69 mm/year, which drops to 5.31 mm/year at HT-275 °C and 6.13 mm/year at HT-375 °C. When describing the adsorption of inhibitors, the Langmuir adsorption isotherm is the most effective method. The findings of the Gads show that the inhibition was induced mainly by the physisorption on the surface CADI alloys. In addition to this, it was found that the results of the experiments and the hypotheses were largely harmonious with one another. The formation of protective layers on the CADI surfaces is also visible in the images captured by the SEM. In 1M H2SO4, these Schiff base inhibitors effectively prevent corrosion caused by CADI. However, the combination of inhibitors leads to a fine microstructure with ausferrite and narrow ferrite needles, promoting corrosion resistance. The CADI needles rated an upper ausferritic microstructure with wide ferrite needles.

Experimental Study on the Chlorine-Induced Corrosion and Blister Formation of Steel Pipes Coated with Modified Polyethylene Powder.

In this study, chlorine-induced corrosion and blister formation on steel pipes (SPs) coated with modified polyethylene powder (MPP) were evaluated through various tests, including chlorine exposure, wet immersion, and temperature gradient experiments. The results confirmed that the extent of corrosion and iron leaching varied with the coating type as expected. In batch leaching tests, no corrosion was observed on modified polyethylene-coated steel pipes (MPCSPs) within a chlorine concentration range of 0 mg/L to 10 mg/L; similarly, there were no significant changes in specimen weight or iron levels. In contrast, the control group with uncoated SPs exhibited significant iron leaching and corrosion, a trend consistent in sequential leaching experiments. SEM analysis after a month of chlorine exposure revealed no significant corrosion on MPCSPs, and SEM-EDX confirmed no major changes in the carbon bond structure, indicating resistance to high chlorine concentrations. Comparative analysis of wet immersion and temperature gradient tests between MPCSP and conventional epoxy-coated SP (ECSP) specimens revealed that MPCSPs did not develop blisters even after 100 days of immersion, whereas ECSPs began showing blisters as early as 50 days. In temperature gradient tests, MPCSPs showed no blisters after 100 days, while ECSPs exhibited severe internal coating layer blisters.

The beginning of iron corrosion - high-resolution visualization with 3D electron tomography

Understanding the genesis and early-phase reactions of iron corrosion is essential for the early detection, mitigation and prevention of metal degradation. In this work, high-resolution 3D tomography of metallic iron oxidation was acquired using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). In particular, dendritic capillaries (<0.5 nm) were observed during the initial oxidation of fresh nanoscale zero-valent iron due to the differential oxygen diffusion and iron atoms migration. This observation led to the proposal of a nanoscale “pothole” model for early-phase corrosion, wherein hollowing out of the metal nanoparticle and formation of nanovoids beneath the iron/oxide interface through Kirkendall effect. Coalescence of the nanocapillaries results in the ultimate collapse of metal structure and/or functional failure. Using nanoscale zero-valent iron as a research model, this work provides unprecedented insights into the nano- and atomic-scale mechanisms of iron oxidation, paving the way for advanced detection and prevention strategies for iron corrosion.

Tribological properties of YG8/steel friction pair in an aqueous lubrication system with an ionic liquid: Experimental results and molecular dynamics simulations

In this work, an ionic liquid (G-RIC) with excellent lubricating performance was successfully prepared, and the tribological properties as an additive in glycerol-water solutions were explored. The results indicated that 2.0 % additive content can reduced the friction coefficient to below 0.1, leading to a decline in the wear volume of 76 %. Gray cast iron corrosion tests revealed that the additive exhibited excellent corrosion resistance. Quantum chemical calculations revealed that the anion RIC has a low energy gap (ΔE = 0.034 Ha), which implies that it is more prone to undergoing tribochemical reactions with the metal substrate under frictional heat. The synergistic action of the liquid lubrication layer, adsorption film, and friction protective film created an interface that easily shears.

No signs of microbial-influenced corrosion of cast iron and copper in bentonite microcosms after 400 days

High-level radioactive waste needs to be safely stored for a long time in a deep geological repository by using a multi-barrier system. In this system, suitable barrier materials are selected that ideally show long-term stability to prevent early radionuclide release into the biosphere. In this study, different container matals (copper and cast iron) and pore water compositions (Opalinus Clay pore water and saline cap rock solution) were combined with Bavarian bentonite in static batch experiments to investigate microbial-influenced corrosion. The increasing concentration of iron and copper in the solution as well as detected corrosion products on the metal surface are indicative of anaerobic corrosion of the respective metals during an incubation of 400 days at 37 °C. However, although the intrinsic microbial bentonite community was stimulated with either lactate or H2, an acceleration of cast iron- and copper corrosion did not occur. Furthermore, neither corrosive bacteria nor conventional bacterial corrosion products, such as metal sulfides, were detected in any of the analyzed samples. The analyses of geochemical parameters (e.g. ferrous iron-, iron-, copper- and potassium concentrations as well as redox potentials) showed significant changes in some cast iron- and copper-containing setups, but these changes did not correlate with the microbial community structure in the respective microcosms, as confirmed by statistical analyses. Hence, the analyzed Bavarian bentonite (type B25) showed no significant contribution to cast iron and copper corrosion under the applied conditions after 400 days of incubation. From this perspective, bentonite B25 could be a suitable candidate as a geotechnical barrier in future repositories.

Deciphering microbial communities involved in marine steel corrosion using high-throughput amplicon sequencing.

To characterize the source and effects of bacterial communities on corrosion of intertidal structures, three different UK coastal sites were sampled for corrosion materials, sediment and seawater. Chemical analyses indicate the activity of sulfate-reducing microbes (SRBs) at 2 sites (Shoreham and Newhaven), but not at the third (Southend-on-Sea). Microbial communities in the deep sediment and corrosion samples are similar. The phylum Proteobacteria is dominant (40.4% of the total ASV), followed by Campilobacterota (11.3%), Desulfobacterota and Firmicutes (4%-5%). At lower taxonomic levels, corrosion causing bacteria, such as Shewanella sp. (6%), Colwellia sp. (7%) and Mariprofundus sp. (1%), are present. At Southend-on-sea, the relative abundance of Campilobacterota is higher compared to the other two sites. The mechanism of action of microorganisms at Shoreham and Newhaven involves biogenic sulfuric acid corrosion of iron by the combined action of SRBs and sulfur-oxidizing microbes. However, at Southend-on-sea, sulfur compounds are not implicated in corrosion, but SRBs and other electroactive microbes may play a role in which cathodic reactions (electrical MIC) and microbial enzymes (chemical MIC) are involved. To contribute to diagnosis of accelerated intertidal corrosion types, we developed a rapid identification method for SRBs using quantitative polymerase chain reaction high-resolution melt curve analysis of the dsrB gene.

Enhanced Cr(VI) removal and stabilization from bioleached wastewater by zero-valent iron coupled with hetero and autotrophic bacteria

Zero-valent iron (Fe0) usually suffers from organic acid complexation and ferrochrome layer passivation in Cr(VI) removal from bioleached wastewater of Cr slag. In this work, a synergetic system combined Fe0 and mixed hetero/autotrophic bacteria was established to reduce and stabilize Cr(VI) from bioleached wastewater. Due to bacterial consumption of organic acid and hydrogen, severe iron corrosion and structured-Fe(II) mineral generation (e.g., magnetite and green rust) occurred on biotic Fe0 surface in terms of solid-phase characterization, which was crucial for Cr(VI) adsorption and reduction. Therefore, compared with the abiotic Fe0 system, this integrated system exhibited a 6.1-fold increase in Cr(VI) removal, with heterotrophic reduction contributing 3.4-fold and abiotic part promoted by hydrogen-autotrophic bacteria enhancing 2.7-fold. After reaction, the Cr valence distribution and X-ray photoelectron spectroscopy indicated that most Cr(VI) was converted into immobilized products such as FexCr1-x(OH)3, Cr2O3, and FeCr2O4 by biotic Fe0. Reoxidation experiment revealed that these products exhibited superior stability to the immobilized products generated by Fe0 or bacteria. Additionally, organic acid concentration and Fe0 dosage showed significantly positive correlation with Cr(VI) removal within the range of biological adaptation, which emphasized that heterotrophic and autotrophic bacteria acted essential roles in Cr(VI) removal. This work highlighted the enhanced effect of heterotrophic and autotrophic activities on Cr(VI) reduction and stabilization by Fe0 and offered a promising approach for bioleached wastewater treatment.

Investigation of microstructure, corrosion and mechanical properties of iron and holmium modified Sn-3.0Ag0.5Cu solder alloy with ultrasonic treatment

This research investigated the microstructure, corrosion behavior and mechanical properties of iron and holmium modified Sn-3.0Ag-0.5Cu solder alloy with ultrasonic treatment. The results demonstrated that the distribution of the phases in the ultrasonically treated solder alloys became homogeneous and the microstructure of ultrasonically treated solder alloys were more refined. The average grain size of ultrasonically treated solder alloys was reduced from 206.7 μm to 184.1 μm. A significant increase in the tensile strength from 38.75 MPa to 47.38 MPa was found in the ultrasonically treated solder alloys. The polarization curves results indicated that the solder alloys treated with ultrasound possessed lower corrosion current density and the results of atomic force microscopy suggested that roughness of corrosion products morphology was reduced. Furthermore, the electrochemical impedance spectroscopy (EIS) results indicated that the ultrasonically treated solder alloys had larger diameter of the semicircular loops and higher total impedance values.

Unveiling the Mechanism and Kinetics of Pollutant Attenuation by Free Radicals Triggered from Goethite in Water Distribution Systems.

Investigating the fate of persistent organic pollutants in water distribution systems (WDSs) is of great significance for preventing human health risks. The role of iron corrosion scales in the migration and transformation of organics in such systems remains unclear. Herein, we determined that hydroxyl (•OH), chlorine, and chlorine oxide radicals are generated by Fenton-like reactions due to the coexistence of oxygen vacancy-related Fe(II) on goethite (a major constituent of iron corrosion scales) and hypochlorous acid (HClO, the main reactive chlorine species of residual chlorine at pH ∼ 7.0). •OH contributed mostly to the decomposition of atrazine (ATZ, model compound) more than other radicals, producing a series of relatively low-toxicity small molecular intermediates. A simplified kinetic model consisting of mass transfer of ATZ and HClO, •OH generation, and ATZ oxidation by •OH on the goethite surface was developed to simulate iron corrosion scale-triggered residual chlorine oxidation of organic compounds in a WDS. The model was validated by comparing the fitting results to the experimental data. Moreover, the model was comprehensively applicable to cases in which various inorganic ions (Ca2+, Na+, HCO3-, and SO42-) and natural organic matter were present. With further optimization, the model may be employed to predict the migration and accumulation of persistent organic pollutants under real environmental conditions in the WDSs.

Influence of riboflavin on the corrosion of X80 pipeline steel by Sulfate reducing bacteria

The sulfate reducing bacteria(SRB) is commonly attached to the surface of buried pipeline steel, and the electron shuttle in the corrosion medium can promote the release of electrons from iron oxidation through the bacterial cell wall into the cytoplasm to accelerate the corrosion of anode iron. This study investigated the impact of riboflavin (RF) as an endogenous electron shuttle on the corrosion behavior of X80 pipeline steel in SRB system. The findings indicated that while the type of corrosion products remains unchanged in samples under SRB+10 mg l−1 RF system, there was an expansion in both area and depth of corrosion pits on the sample surface, resulting in a corrosion loss rate approximately 3 times higher than that observed in SRB system. Furthermore, the polarization resistance (Rp) value of the sample in SRB system is about 2 ∼ 5 times that of the sample in SRB+10 mg l−1 RF system. Additionally, the corrosion current density of X80 pipeline steel samples soaked in SRB and SRB +10 mg l−1 RF system for 14 days is 9.31 × 10-6 A·cm−2 and 1.28 × 10−5 A·cm−2, and the addition of 10 mg l−1 RF increases the corrosion current density of SRB system by about 37.49%. These results indicated that the reaction resistance of SRB-induced MIC in X80 pipeline steel was significantly reduced due to the presence of RF.

A DFT study on substituent effects on iron corrosion inhibition capability of indole derivatives

A DFT study on substituent effects on iron corrosion inhibition capability of indole derivatives

Study of Corrsion System on Iron Artefacts through Neutronic Analysis

This study was conducted to confirm the possibility of using the corrosion products of iron artifacts and corrosion systems for non-destructive analysis using neutrons by applying the non-destructive analysis method and the destructive analysis method together to the analysis of the corrosion system of iron artifacts. As a result of transmission analysis, the shape of the artifact, the boundary between the metal layer and the corrosion layer, etc. could be confirmed, and through tomography, the shape, surface shape, and internal cross section of the artifact could be confirmed. It was confirmed that the corrosion thickness using the residual stress measurement method has a high reliability of less than 10% of an error compared to other analysis results, so it is highly likely to be used to measure the corrosion thickness. It was confirmed that the corrosion layer of the iron artifact analyzed this time was mainly Goethite among the types of DPL and was embedded with Magnetite/Maghemite. Since the neutron analysis can estimate the corrosion thickness non-destructive, it is highly likely to be used to study the corrosion rate of iron artifacts by burial environment through additional studies.

Effect of Copper and Nickel Content on the Corrosion Mechanisms in Ferritic Matrix Gray Cast Irons under Simulated Marine Environments

This article investigated the influence of copper (Cu) and nickel (Ni) on atmospheric corrosion in gray cast iron under simulated marine conditions. The goal was to compare the effect of Cu and Ni addition in castings with weathering steels. Selected alloys were cast, cut, prepared, and heat-treated for microstructure homogenization. Accelerated corrosion tests were conducted using a salt spray chamber. Corroded samples were analyzed for corrosion thickness and deposits using scanning electron microscopy, X-ray diffraction, and electrochemical techniques. The results indicate that alloying elements significantly affect corrosion processes. In the long-term, Cu had a greater impact on the corrosion mechanisms than Ni. Both Cu and Ni exhibited similar effects on the corrosion mechanisms in gray cast iron and weathering steels. In the initial and final stages, the behavior was comparable to that of weathering steels, but in the intermediate stage, it differed from the literature, suggesting the presence of an additional mechanism between these stages.

In-situ resistance mapping of surface corrosion of iron using contact-mode carbon fibre as potentiometric tip

Scanning Probe Microscopy (SPM) has recently gained significant attention from both scientists and engineers for its unique capability to investigate localized corrosion phenomena. This paper introduces a novel application of SPM that offers a unique in-situ means to quantitatively evaluate the resistance of a spontaneously formed oxide layer on the conductive surface of an uncoated iron sample. This approach involved rastering a thin carbon fibre on the iron sample immersed on a corrosive medium while maintaining direct contact between the tip of the carbon fibre and the studied surface. Depending on the resistance between the tip and the sample, the measured voltage proportionally varied between 0 and the potential of the potentiometric circuit formed by the iron sample, the electrolyte and the carbon fibre. Through the application of the voltage divider formula, the measured potential map was transformed into a resistance map. This process allowed us to render a visual representation of the resistance distribution across the surface of the iron sample, providing some insights into the properties of the oxide layer.

Atmospheric corrosion of iron under a single droplet: A new systematic multi-electrochemical approach

Utilizing a dedicated micro-sized three-electrode cell, this study systematically investigates early-stage electrochemical properties and corrosion behavior of pure iron under single droplets. Various volumes and NaCl concentrations were considered during the evaporation-driven shape and concentration evolution of single droplets. The measurements disclosed that reducing the droplet size from 5 µL to 1.5 µL at 0.01 M NaCl concentration, increased noise resistance (Rn) and polarization resistance (Rp) values. However, at 0.1 M and 0.2 M NaCl concentrations, reducing droplet size led to the domination of relatively high chloride ion concentration over oxygen diffusion, resulting in a very low Rn and Rp, and hence enhanced localized corrosion.

Innovative perspective for the cleaning of historical iron heritage: novel bio-organogel for the combined removal of undesired organic coatings and corrosion

An innovative green organogel was designed to simultaneously tackle inorganic compounds (i.e., iron corrosion) and organic substances (i.e., acrylic coatings) as undesired materials possibly present on the surface of altered indoor metal artworks. Poly-3-hydroxybutyrate (PHB), ethyl lactate (EL), and deferoxamine B (DFO) were employed in the formulation as thickening agent, organic solvent, and complexing agent, respectively, aiming to propose a sustainable and less harmful chemical cleaning method for metal care. The components were selected because they are bio-sourced, renewable, biodegradable, and non- or low-toxic materials. A multi-modal protocol of analysis was carried out to characterise the newly designed PHB-EL-DFO organogel. The cleaning performance of the novel formulation was assessed on mild steel mock-ups presenting both corrosion and organic coating to be removed. The conducted multi-analytical approach verified that the PHB-EL-DFO gel was able to tackle the two undesired materials simultaneously in an adjustable and easy-to-use way thanks to a modular application.

Elucidating microbial iron corrosion mechanisms with a hydrogenase-deficient strain of Desulfovibrio vulgaris.

Sulfate-reducing microorganisms extensively contribute to the corrosion of ferrous metal infrastructure. There is substantial debate over their corrosion mechanisms. We investigated Fe0 corrosion with Desulfovibrio vulgaris, the sulfate reducer most often employed in corrosion studies. Cultures were grown with both lactate and Fe0 as potential electron donors to replicate the common environmental condition in which organic substrates help fuel the growth of corrosive microbes. Fe0 was corroded in cultures of a D. vulgaris hydrogenase-deficient mutant with the 1:1 correspondence between Fe0 loss and H2 accumulation expected for Fe0 oxidation coupled to H+ reduction to H2. This result and the extent of sulfate reduction indicated that D. vulgaris was not capable of direct Fe0-to-microbe electron transfer even though it was provided with a supplementary energy source in the presence of abundant ferrous sulfide. Corrosion in the hydrogenase-deficient mutant cultures was greater than in sterile controls, demonstrating that H2 removal was not necessary for the enhanced corrosion observed in the presence of microbes. The parental H2-consuming strain corroded more Fe0 than the mutant strain, which could be attributed to H2 oxidation coupled to sulfate reduction, producing sulfide that further stimulated Fe0 oxidation. The results suggest that H2 consumption is not necessary for microbially enhanced corrosion, but H2 oxidation can indirectly promote corrosion by increasing sulfide generation from sulfate reduction. The finding that D. vulgaris was incapable of direct electron uptake from Fe0 reaffirms that direct metal-to-microbe electron transfer has yet to be rigorously described in sulfate-reducing microbes.