Electrochemical studies of packed iron powder electrodes: Effects of common constituents of natural waters on corrosion potential

Using a powder disk electrode (PDE) made with micron-sized, high purity iron metal we investigated how the corrosion of this material is affected by solution conditions that are relevant to the degradation of contaminants in environmental remediation applications. Changes in corrosion potential (E_corr) with time showed that low pH, high concentrations of chloride, and natural organic matter led to breakdown of the passive film. Bicarbonate caused E_corr to decline rapidly into the active potential region, but then E_corr rose back into the passive region over 10s of hours. The rate of decline in E_corr was greatest at higher pHs, suggesting a specific effect of rather than a general effect of pH.     

Reproducibility of corrosion parameters for the acidic dissolution of pure iron: potentiostatic polarisation

Polarisation curves were determined potentiostatically for pure polycrystalline iron corroding in oxygen-free 0.5 M H₂SO₄. Four different working electrode pre-treatments (abrasion/polishing, pre-polarisation and time to establish E_corr) were employed and the reproducibility of E_corr and calculated corrosion parameters (i_corr, Tafel slopes and i₀) for each treatment was determined. Electrode pre-treatment effects changes in working electrode catalytic activity with subsequent variation in the reproducibility of polarisation curves and measured and calculated corrosion parameters. A method incorporating abrasion/polishing followed by anodic/cathodic pre-polarisation resulted in general in improved parameter reproducibility and cathodic and anodic Tafel slopes close to those predicted by the reaction mechanisms.     

Effect of Immersion Time and Cooling Mode on the Electrochemical Behavior of Hot-Dip Galvanized Steel in Sulfuric Acid Medium

In this work, we investigated the influence of galvanizing immersion time and cooling modes environments on the electrochemical corrosion behavior of hot-dip galvanized steel, in 1 M sulfuric acid electrolyte at room temperature using potentiodynamic polarization technique. In addition, the evolution of thickness, structure and microstructure of zinc coatings for different immersion times and two cooling modes (air and water) is characterized, respectively, by using of Elcometer scan probe, x-ray diffraction and metallography analysis. The analysis of the behavior of steel and galvanized steel, vis-a-vis corrosion, by means of corrosion characteristic parameters as anodic (β _a) and cathodic (β _c) Tafel slopes, corrosion potential (E _corr), corrosion current density (i _corr), corrosion rate (CR) and polarization resistance (R _p), reveals that the galvanized steel has anticorrosion properties much better than that of steel. More the immersion time increases, more the zinc coatings thickness increases, and more these properties become better. The comparison between the two cooling modes shows that the coatings of zinc produced by hot-dip galvanization and air-cooled provides a much better protection to steel against corrosion than those cooled by quenching in water which exhibit a brittle corrosive behavior due to the presence of cracks.     

The corrosion behaviour of SS 41 steel in formic and acetic acids

The corrosion behaviour of SS 41 steel in formic acid and acetic acid was investigated by measuring the corrosion weight loss, the polarization curve and the impedance at the steel-solution interface. It was found that the corrosion rates of the steel in formic acid and acetic acid are markedly dependent on acid concentration and temperature. The corrosion rates in acetic acid are smaller than those in formic acid. The corrosion potential E_corr against pH of formic acid and acetic acid solutions shows a linear relationship.     

Corrosion characterization of new tin-silver binary alloys in nitric acid solutions

Electrochemical techniques were used to characterize the corrosion behavior of four new binary alloys xSn-Ag (x = 26, 50, 70 and 96.5 wt%) alloys and their individual metal components in nitric acid solutions. The experimental data were collected by using open-circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Over the concentration range studied (0.075-4.5 M), each of the two corrosion parameters (E_corr and i_corr) shows a regular dependency on both the alloy composition and the solution concentration. In general, for all studied samples, especially pure Ag and those with lower Sn contents (26 and 50 wt%), increasing the acid concentration increases i_corr, meanwhile causes a shift of the corresponding E_corr towards more positive values. This is probably due to the increase in the effect of cathodic depolarizer as the nitric acid concentration is increased. EIS results at the free corrosion potential confirmed well this behavior, where at concentrations ?1.5 M the thickness of the surface film increases while its resistance decreases with increasing tin wt%, indicating formation of less protective thicker film. However, at higher concentrations all samples exhibit identical behavior.     

Effect of plasma nitriding of electroplated chromium coatings on the corrosion protection C45 mild steel

Plasma nitriding is a promising posttreatment technique to create a nitride layer on electroplated chromium coatings for improving their corrosion resistance. In the present study, the effects of plasma nitriding on the corrosion properties of electroplated chromium/C45 mild steel were investigated using electrochemical characterization. The chromium plated samples were nitrided using a pulsed direct current glow discharge in an NH₃ atmosphere. The polarization curve measurement results showed that the plasma nitrided samples exhibited more positive corrosion potentials (E_corr), smaller corrosion currents (I_corr), and evident passivation when compared with unnitrided chromium plating/substrate system. The high value of E_corr and low value of I_corr imply an improvement of the corrosion resistance of the coating/substrate system after plasma nitriding.     

Action of chelators on solid iron in phosphate-containing aqueous solutions

To study the effect of strong iron-ligands on steel corrosion, mild steel electrodes were immersed in solutions containing 20 mM phosphate buffer (pH=7.2) and between 0.01 mM and 1 M of either the iron(II)-chelators 2,2^′-bipyridine or FerroZine, or the iron(III)-chelators citrate or acetylacetonate. Resulting surface reactions were investigated by quantifying the electrochemical potential (E), the electrochemical polarization resistance (R_p), the corrosion current (I_corr) and the release of iron into solution. The surface was further analyzed by scanning electron microscopy (SEM/SEM-EDAX) and atomic force microscopy. Concentrations of 0.1 mM of any of the chelators led to slight, temporary changes in E, I_corr and R_p. Concentrations of 10 mM resulted in characteristic changes of E, which were the same for all chelators and in the precipitation of FePO₄ in the case of citrate and acetylacetonate, or vivianite [Fe₃(PO₄)₂ · 8H₂O] in the case of bipyridine and FerroZine. Concentrations of 1 mM of both iron(III)-chelators led to a temporary drop of E similar to that found with 0.1 mM chelator. With iron(II)-chelators, E dropped to about −500 mV before oscillating for several days. The amplitudes of the oscillations were up to 200 mV with periods of 30 and 20-25 min for bipyridine and FerroZine, respectively.     

Corrosion fatigue behaviour of nitrogen-implanted steel in water

The corrosion fatigue behaviour of nitrogen implanted iron in neutral solutions has been investigated utilizing the oscillating cantilever beam method, by means of electrochemical (E_corr vs. time plots, R_p measurements) and S. E. M. techniques. The calculated corrosion rate under stagnant conditions is lowered for the implanted iron at all nitrogen doses with respect to untreated iron. The surface oxide layers achieve enhanced protecting capacity. Consequently under a cyclic load of 25.4 kg mm^?2, at a frequency of 16.6 Hz, cracks nucleation is delayed. The time to breaking of implanted specimens is considerably lower in our experimental conditions compared to untreated iron. The increase in the crack growth rate is consistent with the detrimental action of structural damage following implantation. The fracture morphology is also discussed.     

Inhibitory effect of some amino acids on corrosion of Pb-Ca-Sn alloy in sulfuric acid solution

The present article describes the inhibition effect of amino acids cysteine (Cys), methionine (Met) and alanine (Ala), towards the corrosion of lead-alloy (Pb-Ca-Sn) in H₂SO₄ solution by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), weight loss measurement and scanning electron microscopy (SEM) methods. The influence of inhibitor concentration, temperature and time on inhibitory behavior of the amino acids was investigated. The corrosion data including corrosion current density (I_corr), corrosion potential (E_corr) and charge transfer resistance (R_ct) were determined from Tafel plots and EIS. Recording impedance spectra showed that the charge transfer resistance is increased by increasing adsorption time. The SEM micrographs revealed that the corroded surface area is decreased in the presence of amino acids. Meanwhile, the inhibition efficiency (IE) was found to be depending on the type of amino acid and its concentration. The IE for 0.1 M Cys in 0.5 M H₂SO₄ is greater than 96%. Adsorption isotherms were fitted by Langmuir isotherm.     

Influence of flow on the corrosion inhibition of St52-3 type steel by potassium hydrogen-phosphate

Influence of hydrodynamic conditions on the corrosion of St52-3 type steel rotating disc electrode, RDE, in 3.5% NaCl and its corrosion inhibition using K₂HPO₄ have been studied. Results showed that by rotating the electrode in blank and inhibited solutions, corrosion current density, i_corr, increased, corrosion potential, E_corr, shifted toward more positive values and charge transfer resistance, R_ct, decreased. The inhibition efficiencies increased with electrode rotation rate. This increase was attributed to the enhanced mass transport of inhibitor molecules toward the metal surface and formation of more protective films. Little decrease of efficiencies at higher rotation speeds was probably because of the separation of protective films due to high shear stresses.     

Electrochemical behavior of anodized Mg alloy AZ91D in chloride containing aqueous solution

Electrochemical behavior in aerated 3.5 wt.% NaCl solution of Mg alloy AZ91D anodized or not has been investigated by using electrochemical impedance spectroscopy, potentiodynamic polarization and E_corr-t curve. Their microstructures before and after corrosion have been examined under scanning electron microscope. Testing results from E_corr-t and polarization curves indicate that the corrosion behavior of Mg alloy makes significant, characteristic changes due to anodization. Impedance spectra obtained show a regular evolution with exposure time revealing the development of corrosion damage. SEM micrographs confirm that there are pores, defects and microcracks in anodic film which determine the existence of film-vulnerable regions. Electrochemical data are combined with micrographs to explain protection mechanism of anodic film and corrosion mechanism of Mg alloy.     

Acid-acid function of Eichhornia crassipes roots as inhibitor for mild steel in 0.5 M H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solution

The inhibitory potential of an acid extract of Eichhornia crassipes constituents on corrosion of mild steel in 0.5 M H₂SO₄ solution was the basis of this study. Acid extract of the root was employed to create the same type of environment for acidic cleaning and pickling. The roots of Eichhornia crassipes (water hyacinth) were sun-dried and pulverized into powdered form. Acid extraction was carried out by weighing 10 g of the pulverized roots into a beaker containing 1000 mL of 0.5 M H₂SO₄, placed in water bath at 90°C for 6 h and filtered the second day. The mild steel with a known weight was immersed inside the respective concentration of the blank and inhibitors (2–10% vol/vol) solutions at room temperature, after which it was retrieved and weighed at 1-day interval progressively for 12 days. A collection of compositional data was from AAS, FTIR. Polarization resistant, current density (I _corr), and corrosion potentials (E _corr) obtained from Methro Ohms Potentiostat. Phytochemical screening of the corrosion product was carried out using Spectrophotometer. Polarization calculation shows that the root acid extracts on mild steel have corrosion resistance potentials even after preserving it for 60 days.     

Corrosion behavior of boro-tempered ductile iron

In this study, the effect of boro-tempering heat treatment on the microstructure and corrosion behavior of unalloyed ductile iron was investigated. The corrosion characteristics of ductile iron have been determined by current-potential curves. To determine the corrosion rates, the anodic and cathodic Tafel regions extrapolating to corrosion potentials were used. The inhibitor efficiency was calculated from i _corr values. Optical microscope and X-ray diffraction (XRD) were used to examine the microstructure of polished and etched specimens. Thicknesses of the boride layers formed on samples were measured by an optical micrometer attached to the optical microscope. Results show that boro-tempering heat treatment can be successfully applied to ductile iron. The corrosion potential has shifted to more positive values in the boronized samples. The boride layer has behaved like an anodic inhibitor. The boronizing time has affected the corrosion rate. The increase in boronizing time has made the coating thicker, which has increased the corrosion resistance of the material. The best inhibition and the lowest corrosion rate have been performed on the sample which was boronized for 5 hours after cooling in furnace. The tempering at higher temperatures leads to an increase in the corrosion resistance of the materials tested here.     

Galvanic currents and corrosion rates of reinforcements measured in cells simulating different pitting areas caused by chloride attack in sodium hydroxide

Chlorides induce localized corrosion in the reinforcement. The pits formed a substantial reduction in the cross-sectional area. The smaller is the ratio between the size of the corrosion spot and the surrounding passive metal area acting as cathode, the higher is the corrosion rate or the progression in the pit depth. This, however, is not always the case. To understand well the macro or microcell behavior of the corrosion of reinforcements, this paper reports a study on the effect of decreasing sizes of anodic zones until relatively small, maintaining the size of the cathode constant. In addition, to enhance the pure anodic behavior of the corroding zone, an acidic solution was used as an anolyte. Measuring the galvanic current (I_g) and the corrosion rate (I_corr) by using zero resistance ammeter (ZRA) and polarization resistance (R_p) techniques, respectively, was crucial to differentiate the microcell contribution from that of the macrocell. The results indicate that while I_g increased as the anodic area decreased, I_corr presented a maximum for the area ratios, S_A/S_C = 1/3.     

Corrosion of titanium in phosphoric acid at 250 °C

Corrosion studies of a commercially pure titanium in phosphoric acid solutions at 250 °C were carried out by immersion test in an autoclave. At lower phosphoric acid concentration (0.1 mol/L), the corrosion was mild. At higher phosphoric concentration (1.0 mol/L) corrosion, a 25 μm-thick white corrosion products layer was formed on the samples after 24 h immersion. XRD analysis shows that the white layer consists mainly of titanium oxide phosphate hydrate (π-Ti₂O(PO₄)₂·2H₂O). The corrosion product shows the morphology of fiber bundles. A thermodynamic analysis of the formation of the corrosion product is presented.     

Galvanic reactions during localized corrosion on stainless steel

During localized (crevice and pitting) corrosion, a local cell is established between an anode within a crevice or pit and a cathode on the surrounding passive surface. Data are presented to show that concentrated acidic chloride solutions, simulating corrosion product hydrolysis within a crevice or pit, produce potentials which are active (negative) to the normal surface passive potential. This behaviour explains the previously observed active drift of corrosion potential after initiation of crevice or pitting attack in dilute chloride solutions. The active state in concentrated chloride solutions was quite noble (positive) compared to the active state in more dilute solutions. Thus, there is no need to invoke ohmic resistance effects to account for the active state within a crevice or pit.Experiments were devised in which the local anode within a crevice was physically separated from the nearby passive-surface cathode. When the two were coupled together electrically, the cathode surfaces were polarized nearly to the unpolarized local anode potential, with only a few millivolts anodic polarization at the anode within the crevice. The rate of localized corrosion appears from the data to be limited by the rate of dissolved-oxygen reduction on the cathode surfaces. Thus, localized corrosion in dilute chloride solutions will be increased by (a) raising the temperature, (b) adding an oxidizer such as Fe³⁺ ions, or (c) substituting external anodic polarization for dissolved oxidizers.The overall potential, E_corr acquired by a specimen undergoing pitting or crevice corrosion is demonstrated to be near the protection potential, E_p below which pitting corrosion cannot propagate. Any potential active to E_corr and E_p results in cathodic polarization and suppression of the anode reaction in a crevice or pit. Since both E_corr and E_p vary with the extent of previous localized attack, E_p is not a unique property of the alloy as has been sometimes suggested and is of limited value in classifying alloy resistance to localized corrosion.     

Characteristics and wear behavior of cenosphere dispersed titanium matrix composite developed by powder metallurgy route

The cenosphere dispersed Ti matrix composite was fabricated by powder metallurgy route, and its wear and corrosion behaviors were investigated. The results show that the microstructure of the fabricated composite consists of dispersion of hollow cenosphere particles in α-Ti matrix. The average pore diameter varies from 50 to 150 μm. The presence of porosities is attributed to the damage of cenosphere particles due to the application of load during compaction as well as to the hollow nature of cenospheres. A detailed X-ray diffraction profile of the composites shows the presence of Al₂O₃, SiO₂, TiO₂ and α-Ti. The average microhardness of the composite (matrix) varies from HV 1100 to HV 1800 as compared with HV 240 of the as-received substrate. Wear studies show a significant enhancement in wear resistance against hardened steel ball and WC ball compared with that of commercially available Ti–6Al–4V alloy. The wear mechanism was established and presented in detail. The corrosion behavior of the composites in 3.56% NaCl (mass fraction) solution shows that corrosion potential (φ_corr) shifts towards nobler direction with improvement in pitting corrosion resistance. However, corrosion rate of the cenosphere dispersed Ti matrix composite increases compared with that of the commercially available Ti–6Al–4V alloy.     

Aqueous corrosion behaviour of sintered stainless steels manufactured from mixes of gas atomized and water atomized powders

The electrochemical corrosion improvement of a powder metallurgical (PM) stainless steel is studied in this work. Water atomized (WA) ferritic AISI 434L powders have been mixed with gas atomized (GA) austenitic (AISI 316L type) and ferritic (AISI 430L type) powders and processed through the traditional PM route. The addition of GA powder to the usual WA powder decreases the mean size of the pores of the sintered stainless steels. As the bigger pores are the ones that are able to act as crevices, unlike the smaller ones - that act as closed porosity, reduction in the number of big pores tends to improve the corrosion behaviour of PM stainless steels. Reductions of the corrosion rate (i_corr) and increases of the corrosion potential (E_corr) have been measured in neutral media, with and without chlorides. Moreover, the additional beneficial effect of achieving a duplex microstructure through the addition of GA austenitic powders to the WA ferritic powders has also been verified.     

Corrosion performance of high pressure die-cast Al-6Si-3Ni and Al-6Si-3Ni-2Cu alloys in aqueous NaCl solution

The corrosion performance of high pressure die-cast Al-6Si-3Ni (SN63) and Al-6Si-3Ni-2Cu (SNC632) alloys in 3.5% (mass fraction) NaCl solution was investigated. X-ray diffraction (XRD) and microstructural studies revealed the presence of single phase Si and binary Al₃Ni/Al₃Ni₂ phases along the grain boundary. Besides, the single Cu phase was also identified at the grain boundaries of the SNC632 alloy. Electrochemical corrosion results revealed that, the SNC632 alloy exhibited nobler shift in corrosion potential (?_corr), lower corrosion current density (J_corr) and higher corrosion resistance compared to the SN63 alloy. Equivalent circuit curve fitting analysis of electrochemical impedance spectroscopy (EIS) results revealed the existence of two interfaces between the electrolyte and substrate. The surface layer and charge transfer resistance (R_ct) of the SNC632 alloy was higher than that of the SN63 alloy. Immersion corrosion test results also confirmed the lower corrosion rate of the SNC632 alloy and substantiated the electrochemical corrosion results. Cu addition improved the corrosion resistance, which was mainly attributed to the absence of secondary Cu containing intermetallic phases in the SNC632 alloy and Cu presented as single phase.     

Determination of corrosion potential of coated hollow spheres

Copper hollow spheres were created on porous iron particles by electro-less deposition. The consequent Ni plating was applied to improve the mechanical properties of copper hollow micro-particles. Corrosion properties of coated hollow spheres were investigated using potentiodynamic polarisation method in 1 mol dm⁻³ NaCl solution. Surface morphology and composition were studied by scanning electron microscopy (SEM), light microscopy (LM) and energy-dispersive X-ray spectroscopy (EDX). Original iron particles, uncoated copper spheres and iron particles coated with nickel were studied as the reference materials. The effect of particle composition, particularly Ni content on the corrosion potential value was investigated. The results indicated that an increase in the amount of Ni coating layer deteriorated corrosion resistivity of coated copper spheres. Amount of Ni coating layer depended on conditions of Ni electrolysis, mainly on electrolysis time and current intensity. Corrosion behaviour of sintered particles was also explored by potentiodynamic polarisation experiments for the sake of comparison. Formation of iron rich micro-volumes on the particle surface during sintering caused the corrosion potential shift towards more negative values. A detailed study of the morphological changes between non-sintered and sintered micro-particles provided explanation of differences in corrosion potential (E_corr).