Kinetics and structural studies of the atmospheric corrosion of carbon steels in Panama

The corrosion of a carbon steel was studied in different atmospheres at sites in the Republic of Panama. The weight loss (corrosion penetration) suffered by the carbon steel is related to time by a bilogarithmic law. Mössbauer spectroscopy indicated the rust was composed of non-stoichiometric magnetite (Fe_3-xO₄), maghemite (γ-Fe₂O₃), goethite (α-FeOOH) of intermediate particle size, lepidocrocite (γ-FeOOH) and superparamagnetic particles. Magnetite formation is related to the alternating dry--wet cycles. Goethite is related to corrosion penetration by a saturation type of behavior, following a Langmuir type of relationship. Goethite in rust protects steel against further atmospheric corrosion.     

Characterization of corrosion products formed on the surface of carbon steel by Raman spectroscopy

Corrosion of carbon steel in seashore salty soils containing 10, 20, and 34 wt% (saturated) water was investigated. The corrosion rate was measured and corrosion products were analyzed using Raman spectroscopy. It was found that carbon steel in the soil with 10 wt% water content had the largest corrosion rate and the corrosion was dominated by localized corrosion. The corrosion rate drops dramatically and turns to be general corrosion with increase of water content. The corrosion products in the soil with 20 and 34 wt% water content are mainly composed of α‐FeOOH, while in the soil with 10 wt% water content, the products show a delaminated structure of two layers with the inner layer mainly consisting of α‐FeOOH and the outer layer composed of Fe₂O₃ and Fe₃O₄. Copyright © 2008 John Wiley & Sons, Ltd.     

Improvement of the corrosion behavior of low carbon steel by laser surface alloying

In the present study, an integrated layer of iron aluminides of FeAl and Fe₃Al was formed on the surface of a low carbon steel sheet by a two-step process. The first step was hot dipping of the steel in a molten aluminum pool and secondly laser surface processing using a pulsed Nd:YAG laser. The corrosion resistance of the coated specimens was evaluated by activation polarization and Tafel methods. The results show that laser processing of the aluminized steel leads to a considerable increase in its corrosion resistance compared to both uncoated and merely aluminized materials.     

Synergistic effect between 4-(2-pyridylazo) resorcin and chloride ion on the corrosion of cold rolled steel in 0.5 M sulfuric acid

The corrosion inhibition of 1-(2-pyridylazo)-2-naphthol (PAR) on the corrosion of cold rolled steel in 0.5 M sulfuric acid (H₂SO₄) was studied using weight loss method and potentiodynamic polarization method. Results obtained revealed that together with chloride ion, PAR is an effective corrosion inhibitor for steel corrosion in sulfuric acid. It was found that for steel corrosion inhibition in the presence of single PAR in sulfuric acid the Temkin adsorption isotherm may be used to explain the adsorption phenomenon. For the mixture of PAR and NaCl used as corrosion inhibitor, however, the Langmuir adsorption isotherm can be used to satisfactorily elucidate the adsorption of mixture of PAR and NaCl. Potentiodynamic polarization studies showed that single PAR mainly acts as a cathodic inhibitor for the corrosion of steel in 0.5 M sulfuric acid. The mixture of PAR and chloride ion, however, acts as a mixed type inhibitor that mainly inhibits cathodic reaction of the steel corrosion in sulfuric acid. By means of electrochemical polarization tests, a desorption potential at ca. −370 mV was observed for the adsorption of mixture of PAR and chloride ion, when potential reaches this value, adsorbed inhibitor molecule heavily departs from the steel surface. For the mixture of PAR and chloride ion, thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy were obtained from experimental data of the temperature studies of the inhibition process at four temperatures ranging from 30 to 45 °C, the kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, and the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The most suitable range of inhibitor concentration was discussed. The inhibitive action was satisfactorily explained by using both thermodynamic and kinetic models. Synergism between chloride ion and PAR was proposed. The results obtained from weight loss and potentiodynamic polarization were in good agreement.     

Investigation of the inhibitive effect of triphenyltin 2-thiophene carboxylate on corrosion of steel in 2 M H3PO4 solutions

A new organic compound was synthesised and tested as corrosion inhibitor of steel in phosphoric acid medium using gravimetric, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that the inhibitor studied is a good cathodic inhibitor. EIS results show that the change in the impedance parameters (R_T and C_dl) with concentration of triphenyltin 2-thiophene carboxylate (TTC) is indicative of the adsorption of molecules leading to the formation of a protective layer on the surface of steel. The effect of the temperature on the steel corrosion in 2 M H₃PO₄ and with addition of various concentrations of TTC in the range of temperature 298-348 K was studied. The associated apparent activation corrosion energy has been determined.     

Raman and IR spectroscopy study of corrosion products on the surface of the hot‐dip galvanized steel with alkaline mud adhesion

The corrosion products formed on hot‐dip galvanized steel sheets for the automobile application with adhesion of alkaline mud containing different Cl⁻ ion contents are investigated by means of Raman and infrared (IR) spectroscopy. Results show that the Cl⁻ ion content in alkaline mud has great influence on the corrosion behavior of the galvanized steel. The Cl⁻ ions are responsible for the formation of the Zn₅Cl₂(OH)₈· H₂O layer on the surface of the steel at the early stage of corrosion. The rest of the Cl⁻ ions then penetrate and interrupt corrosion product layer resulting in pitting corrosion. Subsequently, the red corrosion product of α‐FeOOH (shaped as needle‐like structure) is formed, which then transforms into black rust of Fe₃O₄ (having a shape of slim needle). It is interesting to find out that pitting depth is inversely proportional to the Cl⁻ ion content. However, corrosion rate decreases with the increase of the Cl⁻ ions in mud. Copyright © 2009 John Wiley & Sons, Ltd.     

A CEMS Study of the Corrosion of Carbon Steel After Surface Laser Irradiation

The corrosion resistance of laser-irradiated carbon steel surfaces against SO₂-polluted atmospheres has been investigated by means of weight gain measurements and CEMS. The results show that the laser-irradiated samples present a higher corrosion resistance than the non-irradiated steel. The corrosion products are found to be superparamagnetic α-FeOOH and an amorphous Fe³⁺ oxyhydroxide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Microstructure and corrosion resistance of the layers formed on the surface of precipitation hardenable plastic mold steel by plasma-nitriding

Plasma-nitriding is used to improve the wear resistance and corrosion resistance of plastic mold steels by modifying the surface layers of these steels. In this study, a precipitation hardenable plastic mold steel (NAK80) was plasma-nitrided at 470, 500, and 530 °C for 4, 8, and 12 h under 25% N₂ + 75% H₂ atmosphere in an industrial nitriding facility. The microstructures of the base material and nitrided layers as well as the core hardness were examined, and various phases present were determined by X-ray diffraction. The corrosion behaviors were evaluated using anodic polarization tests and salt fog spray tests in 3.5% NaCl solution.The results had shown that plasma-nitriding does not cause the core to soften by overaging. Nitriding and aging could be achieved simultaneously in the same treatment cycle. Plasma-nitriding of NAK80 mold steel produced a nitrided layer composed of an outer compound layer constituting a mixture of ?-nitride and γ′-nitride and an adjacent nitrogen diffusion layer on the steel surface. The amount of ?-nitride and total nitrides increased with an increase in nitriding temperature and nitriding time. Corrosion study revealed that plasma-nitriding significantly improved the corrosion resistance in terms of corrosion potential, corrosion and pitting current density, and corrosion rate. This improvement was found to be directly related to the increase in the amount of ?-nitride at the surface, indicating the amount of ?-nitride controlling the corrosion resistance.     

Inhibition of steel corrosion in 2 M H3PO4 by artemisia oil

Artemisia oil (Ar) is extracted from artemisia herba alba collected in Ain es-sefra-Algeria, and tested as corrosion inhibitor of steel in 2 M H₃PO₄ using weight loss measurements, electrochemical polarisation and EIS methods. The naturally oil reduces the corrosion rate. The inhibition efficiency was found to increase with oil content to attain 79% at 6 g/l. Ar acts as a cathodic inhibitor. The effect of temperature on the corrosion behaviour of steel indicates that inhibition efficiency of the natural substance decreases with the rise of temperature. The adsorption isotherm of natural product on the steel has been determined.     

Analysis of EIS characteristics of CO2 corrosion of well tube steels with corrosion scales

The electrochemical impedance spectroscopy (EIS) was used to study the characteristics of CO₂ corrosion of N80 and 4Cr steels with corrosion scales. The results indicated that CO₂ corrosion scale on tube steel could prevent the rate of mass transfer remarkably, corrosion rate was controlled by ions diffusion in corrosion scale, which led to finite length diffusion impedance occurred in electrochemical impedance spectra. Additionally, pitting of N80 steel could lead to additional capacitive reactance in impedance spectrum. The ion diffusion coefficient in corrosion scale and porosity of corrosion scale could be calculated by Warburg impedance coefficient, the results shown that the value of H⁺ diffusion coefficient in N80 and 4Cr corrosion scale is (3.46 and 1.76) × 10⁻¹⁰ m² s⁻¹, respectively. The protective ability of 4Cr corrosion scale was better than that of N80 corrosion scale.     

Enhanced corrosion resistance of mild steel in normal sulfuric acid medium by 2,5-bis(n-thienyl)-1,3,4-thiadiazoles: Electrochemical, X-ray photoelectron spectroscopy and theoretical studies

The inhibitive action of some thiadiazole derivatives, namely 2,5-bis(2-thienyl)-1,3,4-thiadiazole (2-TTH) and 2,5-bis(3-thienyl)-1,3,4-thiadiazole (3-TTH) against the corrosion of mild steel in 0.5 M H₂SO₄ solution has been investigated using weight loss measurements, Tafel polarisation and electrochemical impedance spectroscopy (EIS) techniques. The experimental results obtained revealed that these compounds inhibited the steel corrosion in acid solution. The protection efficiency increased with increasing inhibitors concentration and the ability of the molecule to adsorb on the steel surface was dependent on the position of the sulphur atom on the thienyl substituent. Inhibition efficiency values obtained from various methods employed were in reasonable agreement. Potentiodynamic polarisation studies clearly showed that 2-TTH and 3-TTH acted as mixed inhibitors. Adsorption of these inhibitors on steel surface obeyed to Langmuir adsorption isotherm. X-ray photoelectron spectroscopy and the thermodynamic data of adsorption showed that inhibition of steel corrosion in normal sulphuric solution by n-TTH is due to the formation of a chemisorbed film on the steel surface. Molecular modelling was used to gain some insight, about structural and electronic effects in relation to the inhibiting efficiencies.     

Electrochemical recycling of cell phone Li-ion batteries: application as corrosion protector of AISI 430 stainless steel in artificial seawater

This article aims to present a new alternative to waste management of spent Li-ion batteries from cell phones. In this sense, the proposed is recycling the cobalt from Li-ion cathode by electrodeposition and apply it as corrosion protector of AISI 430 stainless steel. Thus, two greatest environmental problems can be solved, producing a low-cost and high-corrosion-resistant stainless steel. The cobalt electrodeposition bath came from acid dissolution of spent Li-ion cathode with chemical formula LiCoO₂. The charge efficiency for cobalt electrodeposition in ?1.0 V and pH = 3 reaches 95 %. A protective layer of Co₃O₄ was successfully obtained by treatment of AISI 430 stainless steel with cobalt electrodeposited at 800 °C for 200 h in air atmosphere. The corrosion current of AISI 430 stainless steel in artificial seawater was reduced from 30 to 0.76 μA cm^?2. The treatment proposed produces a AISI 430 stainless steel with double of corrosion resistance and half of cost if compared with AISI 304 stainless steel.     

Conversion electron Mössbauer spectroscopy study of growth and nature of corrosion products on mild steel exposed to different environments

In this study, conversion electron Mössbauer spectroscopy (CEMS) has been utilized for identifying the nature of initial corrosion products formed on the surface of steel under different environments and measurement of relative thickness of corrosion products formed. CEMS studies on mild steel exposed under different environments, viz. mild steel sprayed with (1) distilled water (2) 3% NaCl and (3) mild steel exposed to SO₂ were carried out. The initial stable product of corrosion is found to be γ-FeOOH, which will transform into other oxyhydroxides and oxides, depending on environments. The mechanisms for the corrosion processes occurring under different conditions are also discussed.     

Effect of surface nanocrystallization induced by fast multiple rotation rolling on hardness and corrosion behavior of 316L stainless steel

A nanostructured layer was fabricated by using fast multiple rotation rolling (FMRR) on the surface of 316L stainless steel. The microstructure in the surface was characterized by transmission electron microscopy and X-ray diffraction. The effects of FMRR on the microhardness, surface roughness and corrosion behavior of the stainless steel were investigated by microhardness measurements, surface roughness measurements, potentiodynamic polarization curves and pitting corrosion tests. The surface morphologies of pitting corrosion specimens were characterized by scanning electron microscopy. The results show that FMRR can cause surface nanocrystallization with the grain size ranges from 6 to 24 nm in the top surface layer of the sample. The microhardness of FMRR specimen in the top surface layer remarkably increases from 190 to 530 HV. However, the surface roughness slightly rises after FMRR treatment. The potentiodynamic polarization curves and pitting corrosion tests indicated that the FMRR treated 316L stainless steel with a surface nanocrystallized layer reduced the corrosion resistance in a 3.5% NaCl solution and enhanced the pitting corrosion rate in a FeCl₃ solution. Possible reasons leading to the decrease in corrosion resistance were discussed.     

Indoor atmospheric corrosion of conventional weathering steels in the tropical atmosphere of Panama

One year indoor atmospheric corrosion examinations have been carried out on two conventional weathering steels for a year, at two test sites, Tocumen and Sherman Breakwater in Panama. They are environmentally classified by ISO 9223 as S₁P₀ τ ₄ and S₃P₀ τ ₅, respectively. In this humid-tropical marine climate corrosion rates are rather high, especially at Sherman Breakwater test site, mainly due to the high deposition of chloride, among other environmental conditions. Our results indicate that indoor corrosion is highly determined by the time of wetness and chloride ions. A-588 weathering steel corroded at a generally lower rate than COR-420 weathering steel. Rust characterization was performed by XRD, FTIR, and Mössbauer spectroscopy. Lepidocrocite, goethite, maghemite and akaganeite were found as corrosion products. Akaganeite is only detected when high chlorides deposition rates are obtained, and no washing effect occurs. This phase, together with maghemite, is obtained when there is greater aggressiveness in the environment.     

Corrosion behaviour of AISI 304 stainless steel with Cu coatings in H2SO4

The work addresses the influence of cementation and electrodeposition of copper coatings on the corrosion resistance of AISI 304 stainless steel immersed in 30 wt.% H₂SO₄ at temperatures of 25 and 50 °C. Corrosion process was evaluated by gravimetric tests, DC measurements and electrochemical impedance spectroscopy (EIS). The specimen surfaces were analysed by scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. The corrosion performance of AISI 304 stainless steel in sulphuric acid solution was greatly improved by copper coatings. The amount of copper deposited by the cementation process was sufficient to protect the stainless steel of corrosion. A greater amount of copper obtained by electrodeposition treatments does not supply further improvement in the corrosion behaviour. The improved corrosion resistance is related to copper dissolution at the initial stages of immersion tests and the presence of Cu²⁺ in the solution, which makes the medium more oxidizing, increasing the stability of the passive layer. In addition, the presence of copper at the surface reduces the overpotential of cathodic reaction, enabling the transition from an active region to the passive one.     

Exceptionally high cavitation erosion and corrosion resistance of a high entropy alloy

Cavitation erosion and corrosion of structural materials are serious concerns for marine and offshore industries. Durability and performance of marine components are severely impaired due to degradation from erosion and corrosion. Utilization of advanced structural materials can play a vital role in limiting such degradation. High entropy alloys (HEAs) are a relatively new class of advanced structural materials with exceptional properties. In the present work, we report on the cavitation erosion behavior of Al_0.1CoCrFeNi HEA in two different media: distilled water with and without 3.5 wt% NaCl. For comparison, conventionally used stainless steel SS316L was also evaluated in identical test conditions. Despite lower hardness and yield strength, the HEA showed significantly longer incubation period and lower erosion-corrosion rate (nearly 1/4th) compared to SS316L steel. Enhanced erosion resistance of HEA was attributed to its high work-hardening behavior and stable passivation film on the surface. The Al_0.1CoCrFeNi HEA showed lower corrosion current density, high pitting resistance and protection potential compared to SS316L steel. Further, HEA showed no evidence of intergranular corrosion likely due to the absence of secondary precipitates. Although, the degradation mechanisms (formation of pits and fatigue cracks) were similar for both the materials, the damage severity was found to be much higher for SS316L steel compared to HEA.     

Identification of Green Rust Compounds in the Aqueous Corrosion Processes of Steels; the Case of Microbially Induced Corrosion and Use of 78 K CEMS

Fe(II)-Fe(III) hydroxy-sulphate Green Rust 2, GR2(SO₄ ^–), is obtained by microbially induced corrosion of steel. Transmission Mössbauer spectroscopy (TMS) was used to characterise the corrosion products of steel sheet piles under the biofilm at low sea-water level in a harbour. To understand the process, iron coupons maintained in aqueous solutions of 4 M NaCl and 0.1 M NaHCO₃ of pH 7.4 were studied by X ray diffraction and conversion electron Mössbauer spectroscopy (CEMS) at 78 K. The Fe(II)-Fe(III) hydroxy-carbonate, GR1(CO₃ ^–), covers the surface, as predicted by the E_h-pH diagram.     

Synergistic effect of iodide ions on the corrosion inhibition of steel in 0.5 M H2SO4 by new chalcone derivatives

The effect of addition of 4′,4-dihydroxychalcone (P₁), 4-aminochalcone (P₂) and 4-bromo, 4′-methoxychalcone (P₃) on the corrosion of steel in 0.5 M sulphuric acid has been studied by weight loss measurements, potentiodynamic and EIS measurements. We investigate the synergistic effect of iodide ions on the corrosion inhibition of steel in the presence of chalcone derivatives. The corrosion rates of the steel decrease with the increase of the chalcones concentration, while the inhibition efficiencies increase. The addition of iodide ions enhances the inhibition efficiency considerably. The presence of iodide ions increases the degree of surface coverage. The synergism parameters S_Θ and S_I, calculated from surface coverage and the values of inhibition efficiency, in the case of chalcone derivatives are found to be larger than unity. The enhanced inhibition efficiency in the presence of iodide ions is only due to synergism and there is a definite contribution from the inhibitors molecules. E (%) obtained from the various methods is in good agreement. Polarisation measurements show also that the compounds act as cathodic inhibitors.     

Influence of Cu and Ni on the morphology and composition of the rust layer of steels exposed to industrial environment

Four samples of steels with alloying elements were exposed to an industrial environment during 1,955 days, aiming to elucidate the effect of the alloying elements Cu and Ni on the resistance of weathering steels to corrosion processes. The samples were characterized with optical microscopy, scanning electron microscopy (SEM), powder X-ray diffraction (XRD), saturation magnetization measurements and with energy dispersive (EDS), infrared, Mössbauer and Raman spectroscopies. All the steels originated orange and dark corrosion layers; their thicknesses were determined from the SEM images. EDS data of such rust layers showed that the alloying element content decreases from the steel core towards the outer part of the rust layer. Moreover, in the dark rust layer some light-gray regions were identified in the W and Cu-alloy steel, where relatively higher Cr and Cu contents were found. XRD patterns, infrared, Raman and Mössbauer spectra (298, 110 and 4 K) indicated that the corrosion products are qualitatively the same, containing lepidocrocite (γFeOOH; hereinafter, it may be referred to as simply L), goethite (αFeOOH; G), feroxyhite (δ′FeOOH; F), hematite (αFe₂O₃; H) and magnetite (Fe₃O₄; M) in all samples; this composition does not depend upon the steel type, but their relative concentrations is related to the alloying element. Mössbauer data reveal the presence of (super)paramagnetic iron oxides in the corrosion products. Saturation magnetization measurements suggest that feroxyhite may be an occurring ferrimagnetic phase in the rust layer.