The changing topography of corroding mild steel surfaces in seawater

The corrosion of mild steel exposed to marine immersion conditions typically is not uniform although it is often idealized as such. Anodic regions and micro-pits develop very quickly after first exposure and eventually there is the development of shallow broad pits. This transition of the surface topography and the processes involved are still not completely understood. The present paper presents a number of images typical of the sequential evolution of the surface topology of mild steel corroding in sub-tropical coastal seawater. The sequence consists of the development of anodic areas, development of small pits and shallow broad pits, the apparent coalescence of small pits into larger localized corrosion and eventually the appearance of stepped or benched, perhaps irregular-shaped broad or macro-pits. This sequence is typical of that which has been observed many times and this suggests it is reasonable to infer a generic sequence that describes the changing surface of corroding mild steel in seawater. It will assist in developing a better understanding of the evolution of corrosion processes for mild steel in seawater and assist in identifying the various controlling processes.     

The heterogeneous electrochemical characteristics of mild steel in the presence of local glucose oxidase—A study by the wire beam electrode method

The influence of glucose oxidase (GOD) activity on the heterogeneous electrochemistry at artificial biofilm/mild steel interface was first characterized by the wire beam electrode (WBE) method. Potential/current distribution maps show that a cathodic zone can be formed at the GOD capsule site. The cathodic zone is gradually weakened due to the gluconic acid production in seawater. When GOD capsule is confined on rusted WBE surfaces, the formerly formed anodic zone is gradually changed into cathodic zone, in the presence of glucose. The novel device developed in our laboratory demonstrates powerful applications in heterogeneous electrochemistry measurements at the biofilm/mild steel interfaces.     

Heterogeneous corrosion of mild steel under SRB-biofilm characterised by electrochemical mapping technique

Heterogeneous corrosion of mild steel under sulphate reducing bacteria (SRB)-biofilm was characterised by wire beam electrode (WBE) technique and electrochemical impedance spectrum. The potential/current distributions of the WBE under SRB-biofilm showed that the potential maps could not indicate the localised corrosion of steels beneath biofilm due to the fact that all wire electrodes were short-circuited by the highly conductive sulphide precipitates embedded in SRB-biofilm. Instead, the galvanic current maps may give a good indication. The characteristic of super-capacitance (0.21 F/cm²) of SRB-biofilm was attributed to the huge specific surface area of conductive pore walls inside biofilm.     

Corrosion performance of conducting polymer coatings applied on mild steel

Conducting polypyrrole electrodes were obtained by galvanostatic electropolymerisation on mild steel electrodes from an aqueous solution. The electrochemical response of the coated electrodes in doped and in undoped state was compared with bare mild steel electrodes. The undoped polypyrrole coated electrode offered a noticeable enhancement of protection against corrosion processes.     

Corrosion inhibition of mild steel in hydrochloric acid solution by Schiff base furoin thiosemicarbazone

A heterocyclic Schiff base furoin thiosemicarbazone was tested for its corrosion inhibition towards mild steel in 1 M HCl solution using weight loss, Tafel polarization and electrochemical impedance spectroscopy techniques. Furoin thiosemicarbazone revealed good corrosion inhibition efficiency even at low concentrations towards mild steel in HCl medium. Comparison of corrosion inhibition efficiency of Schiff base and its parent amine and effect of temperature on inhibition efficiency were also investigated. The adsorption of furoin thiosemicarbazone on mild steel surface obeys Langmuir isotherm.     

Corrosion inhibition of mild steel by ethylamino imidazoline derivative in CO2-saturated solution

The corrosion inhibition and adsorption behaviour of 2-undecyl-1-ethylamino imidazoline (2UEI) on N80 mild steel in CO₂-saturated 3% NaCl solutions was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy techniques and SEM observation. Inhibitor efficiency increased with increase in 2UEI concentration. Temperature studies revealed an increase in inhibition efficiency with rise in temperature and corrosion activation energies decreased in the presence of 2UEI. A mechanism of chemical adsorption of 2UEI on the metal’s surface is proposed. The adsorption characteristics of the inhibitor were approximated by Temkin isotherm. The inhibition efficiency of 2UEI was enhanced in the presence of iodide ions.     

The effects of water pollution on the immersion corrosion of mild and low alloy steels

The short-term immersion corrosion of mild and low alloy steels in seawaters is known to be proportional to the concentration of dissolved oxygen (DO) in the bulk water. Longer-term corrosion is a function of the activity of sulphate-reducing bacteria and is influenced by the concentration of nutrients in the bulk water. These influences are examined in more detail for the corrosion of steels in the brackish waters of the River Thames and for several immersion corrosion sites on the Eastern Australian seaboard and in the North Sea. The published data sources were supplemented with plausible assumptions about environmental conditions. New interpretations of the data are provided based on the previously published model for immersion corrosion. For waters with negligible salinity and sulphate levels early corrosion loss was shown to depend on the dissolved oxygen content of the waters, and later corrosion loss was a direct function of nitrogenous nutrient (pollution) levels. This also applies to longer-term corrosion.     

Corrosion behaviour in alkaline medium of zinc phosphate coated steel obtained by cathodic electrochemical treatment

The present work evaluated the ability of zinc phosphate coating, obtained by cathodic electrochemical treatment, to protect mild steel rebar against the localized attack generated by chloride ions in alkaline medium. The corrosion behaviour of coated steel was assessed by open circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopy. The chemical composition and the morphology of the coated surfaces were evaluated by X-ray diffraction and scanning electron microscopy. Cathodically phosphated mild steel rebar have been studied in alkaline solution with and without chloride simulating the concrete pore solution. For these conditions, the results showed that the slow dissolution of the coating generates the formation of calcium hydroxyzincate (Ca(Zn(OH)₃)₂·2H₂O). After a long immersion time in alkaline solution with and without Cl⁻, the coating is dense and provides an effective corrosion resistance compared to mild steel rebar.     

Corrosion of vertical mild steel strips in seawater

This paper describes the corrosion loss profiles of 1 m long vertical steel strips attached to a raft and exposed for 1 year in calm natural seawater on the Australian eastern seaboard. The upper parts of the strips were exposed to the atmosphere and the lower parts immersed to depths varying from 0.3 to 0.9 m. It was found that, irrespective of the precise ratio of atmospheric/immersion exposure, corrosion in the splash zone was much higher than that at the waterline and in the atmosphere. There was also significant corrosion in the immersion zone, immediately below the waterline, consistent with classical observations. Above the water line there was only moderate variability in corrosion between the strips but there was much greater variability in corrosion loss for the parts of the strips fully immersed. Mass loss observations are compared with observations of the corrosion and pitting patterns observed in the various zones. Potential reasons for these observations are considered. The observations have implications for explaining aspects of accelerated low water corrosion (ALWC).     

Stainless steel ennoblement in freshwater: From exposure tests to mechanisms

This work confirms the systematic character of the open circuit potential (OCP) ennoblement for stainless steels immersed in natural freshwater, and highlights the mechanism(s) responsible for this evolution. To achieve these results, electrochemical measurements and analysis/observations of the surface were realized in situ during exposure tests in the river Seine on two exposition sites using an original immersion device. Electrochemical results show that on both immersion sites a new oxidizing compound is produced close to the surface and that its reduction, occurring at potentials higher than the initial OCP value, leads systematically to the ennoblement phenomenon. Surface analysis, electrochemical and chemical tests show that the oxidizing compound is not the same on both sites: on one site hydrogen peroxide is produced within the biofilm, while on the second one oxidized manganese is deposited on the surface. Thus the two mechanisms mentioned in the literature can occur on stainless steels immersed in the same water and lead to similar evolutions of the electrochemical behaviour. These two mechanisms are not specific of a type of water and seem to be complementary rather than opposed. They are both based on enzymatic processes.     

Corrosion inhibition of mild steel by plant extract in dilute HCl medium

The inhibition effect of Zenthoxylum alatum plant extract on the corrosion of mild steel in 5% and 15% aqueous hydrochloric acid solution has been investigated by weight loss and electrochemical impedance spectroscopy (EIS). The corrosion inhibition efficiency increases on increasing plant extract concentration till 2400 ppm. The effect of temperature on the corrosion behaviour of mild steel in 5% and 15% HCl with addition of plant extract was studied in the temperature range 50-80 °C. Surface analysis (SEM, XPS and FT-IR) was also carried out to establish the corrosion inhibitive property of this plant extract in HCl solution. Plant extract is able to reduce the corrosion of steel more effectively in 5% HCl than in 15% HCl. The adsorption of this plant extract on the mild steel surface obeys the Langmuir adsorption isotherm.     

Corrosion inhibition of mild steel in hydrochloric acid solution by some double Schiff bases

The inhibition effect of four double Schiff bases on the corrosion of mild steel in 2 M HCl has been studied by polarization, electrochemical impedance spectroscopy (EIS) and weight loss measurements. The inhibitors were adsorbed on the steel surface according to the Langmuir adsorption isotherm model. From the adsorption isotherm, some thermodynamic data for the adsorption process were calculated and discussed. Kinetic parameters activation such as E_a, ΔH∗, ΔS∗ were evaluated from the effect of temperature on corrosion and inhibition processes. Quantum chemical calculations have been performed and several quantum chemical indices were calculated and correlated with the corresponding inhibition efficiencies.     

Influence of Desulfovibrio sp. biofilm on SAE 1018 carbon steel corrosion in synthetic marine medium

This work assessed the effect of an enriched culture medium and synthetic seawater on the growth and production of exopolymeric substances (EPS) of a Desulfovibrio sp. strain, isolated from a Mexican oil well. The EPS (mainly consisting of proteins) growth was only achieved after exposing sulfate-reducing bacteria to culture media under dissimilative conditions that predominantly promoted the growth of the biofilm and a small concentration of microorganisms. Once this EPS film was obtained, the evolution of SAE 1018 carbon steel/biofilm/synthetic seawater (VNNS medium) interface was further studied using electrochemical impedance spectroscopy technique (EIS). This study revealed strong adhesion of the biofilm during the formation of iron sulfide (pirrotite) on carbon steel surface. The biofilm inhibits the accelerated damage of the steel for some time exhibiting impedance values of 30 000 Ω. However, at longer times the chemical environment around the biofilm, as a result of microbial metabolism, may become quite corrosive to steel.     

Corrosion control of mild steel using 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole in normal hydrochloric acid medium

The inhibition performance of the 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT) on mild steel in normal hydrochloric acid medium (1 M HCl) at 30 °C was tested by weight loss, potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. This organic compound inhibits the acidic corrosion even at very low concentration, reaching a value of inhibition efficiency up to 98% at a concentration of 3 × 10⁻⁴ M. The results obtained from the different corrosion evaluation techniques are in good agreement. Polarisation curves indicate that 4-MAT is a mixed inhibitor, affecting both cathodic and anodic corrosion currents. Data, obtained from EIS measurements, were analyzed to model the corrosion inhibition process through appropriate equivalent circuit model, a constant phase element (CPE) has been used. The adsorption of 4-MAT on the steel surface, in 1 M HCl solution, obeys to Langmuir’s isotherm with a very high negative value of the free energy of adsorption ΔG°_ads (chemisorption). X-ray photoelectron spectroscopy (XPS) was carried out to establish the mechanism of corrosion inhibition of mild steel in 1 M HCl medium in the presence of 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT).     

The effect of molybdate concentration and hydrodynamic effect on mild steel corrosion inhibition in simulated cooling water

The effects of two important factors namely concentration and hydrodynamics on the inhibition efficiency of molybdate were investigated using potentiodynamic polarization and electrochemical impedance spectroscopy tests. Results showed that molybdate was capable of inhibiting the corrosion of mild steel in simulated cooling water. The inhibition efficiency of molybdate was increased with increasing both its concentration and water circulation velocity. These two factors seem to promote the adsorption of molybdate and oxygen ions on the metal surface, leading to the formation of a protective layer with a greater charge transfer resistance and lower permeability. A model is also proposed which facilitates the probable mechanism of inhibition.     

Temperature effect on mild steel corrosion in acid media in presence of azoles

The inhibiting properties of four azoles (indole, benzimidazole, benzotriazole, benzothiazole) were investigated in case of mild steel corrosion in 1 M HCl. The effect of temperature was followed. Impedance spectroscopy, polarization resistance, gravimetric and polarization curves methods were applied. An adequate structural model of the interface in inhibitors presence is offered and the values of the corresponding parameters are calculated. The apparent activation energy of the process taking place in an inhibitor presence was determined on the ground of five temperature values in the range from 20 °C to 60 °C using the data obtained by two independent methods. Comparative investigations were carried out in 1 M H₂SO₄ aiming to elucidate the effect of the acid’s anion. The generalization of the data obtained provided to make conclusions concerning the mechanism of the inhibitors’ adsorption.     

Correlation between corrosion rate and AE signal in an acidic environment for mild steel

The AE method is an effective technique for inspecting corrosion damage of mild steel, such as tank bottom floors. However, the correlation between AE signals and corrosion behaviour for mild steel has not yet been fully clarified. In the present study, the authors considered that the corrosion regions of bottom floors become a strong acid environment by Cl⁻, as reported in a previous study. Thus, the polarization resistance for the test pieces of mild steel was measured with an AC impedance method under a strong acid environment. It was clear that the polarization resistance indicated the corrosion rate for a test piece of mild steel in the experiments. While measuring the AE signals, the corrosion rate was monitored with a test piece. As a result, the AE signal showed good correlation with the corrosion rates of the test pieces. The corrosion behaviour of the test pieces was then discussed with the corrosion potential measured during the experiments. Furthermore, the cathode current was changed to control the generated hydrogen gas volume. The volume of the hydrogen gas generated from the cathode reaction was correlated to the AE signals.     

Effect of hexamethylpararosaniline chloride (crystal violet) on mild steel corrosion in acidic media

The corrosion inhibition of mild steel in 0.5 M H₂SO₄ and 1 M HCl by hexamethylpararosaniline chloride (HMPC) was investigated using the gravimetric technique in the temperature range 303–333 K. The results indicate that HPMC inhibited the corrosion reaction in both acid media at all temperatures and inhibition efficiency increased with HMPC concentration. The inhibiting action is attributed to general adsorption of protonated and molecular HPMC species on the corroding metal surface. Adsorption followed a modified Langmuir isotherm and the Temkin isotherm, with very high negative values of the free energy of adsorption (). An increase in temperature reduced the inhibition efficiency of HPMC in 0.5 M H₂SO₄ but increased efficiency in 1 M HCl. Activation parameters such as activation energy (E_a), activation enthalpy (ΔH^∗) and activation entropy (ΔS^∗) as well as the adsorption heat (Q_ads) were evaluated from the effect of temperature on corrosion and inhibition processes.     

Corrosion inhibition of mild steel in acidic medium by some sulfa drugs compounds

The inhibiting effect of four sulfa drugs compounds (e.g. sulfaguanidine, sulfamethazine, sulfamethoxazole and sulfadiazine) on mild steel corrosion in 1.0 M HCl solutions were evaluated using both galvanostatic polarization and weight loss techniques. All the examined sulfa drug compounds reduce the corrosion of mild steel. Among the compounds studied, sulfadiazine exhibited the best inhibition efficiency and sulfaguanidine the lowest. The inhibition efficiency goes through a maximum for sulfaguanidine while it increases continuously with concentration to a limit with sulfadiazine, sulfamethoxazole and sulfamethazine respectively. Galvanostatic polarization measurements indicate that all the examined compounds are of mixed inhibitor type with predominant cathodic effectiveness. Moreover, the results revealed a better performance for these compounds as corrosion inhibitors in HCl than in H₂SO₄ solutions. Also, the corrosion inhibition mechanism is discussed.