Iron dissolution in acid water-methanol mixtures

Dissolution rates of Armco iron in de-aereated and aereated acid (10⁻³ M H₂SO₄) water-methanol mixtures have been evaluated by accurate weight loss measurements, by extrapolation of Tafel lines to the corrosion potential and by using the linear polarization method. The corrosion rate was found to decrease and then to increase at increasing molar fraction of methanol both in aereated and aereated solutions, showing a minimum at an intermediate solvent composition which is significantly different from the values observed in pure solvents. Furthermore the corrosion rate in de-aereated acid pure methanol is greater than that in pure water by a factor of nearly two. The experimental results have been plotted in terms of ratio versus methanol mole fraction, where r_s is the corrosion rate in the mixture and r_w that in pure water. A behaviour was found quite similar to that exhibited by the ratio of exchange current density for the hydrogen evolution reaction. This similarity leads to a theoretical expression for the ratio as well as to a physical explanation for the greatest iron dissolution rate in de-aereated acid methanol solution compared to that in pure water which is in satisfactory agreement with experimental results.     

Plug-In Specimens for Measurement of the Corrosion Rate of Mg Alloys

Magnesium alloy corrosion is often nonlinear. The corrosion rate accelerates to steady state after an initial period of low corrosion. Plug-in specimens permit simultaneous measurement of the corrosion rate using hydrogen evolution, P _H, and Tafel extrapolation of cathodic polarization curves, P _i. Moreover, weight loss allows independent verification. P _H is consistently greater than P _i. The data, for short exposure periods up to 10?days, are consistent with the unipositive Mg⁺ ion being a short-lived intermediate. Tafel extrapolation needs to be used with caution for estimation of Mg corrosion, as the measured corrosion rate can have a significant contribution from crevice corrosion. Furthermore, measurements made at short immersion times may not reflect the steady-state corrosion rate, and the corrosion reaction at the Mg surface may be decoupled from the electrochemical measurement.     

The effect of ion implantation on the corrosion behaviour of pure iron-III. Tantalum ion implantation

Pure iron specimens were implanted with doses of 5 × 10¹⁴ and 2 × 10¹⁵ tantalum ions/mm². Using a three sweep potentiokinetic polarization technique the corrosion behaviour of these surface alloy layers was compared with that of pure iron and of a conventional Fe-4.9 wt% Cr alloy. It was found that tantalum implantation improved the corrosion resistance of pure iron and in particular reduced both the critical current density for passivation and the passive current density. The corrosion resistance of tantalum implanted iron was similar to that of the conventional Fe-4.9 wt% Cr alloy. The beneficial effects of tantalum implantation were unexpectedly persistent.     

Corrosion of Mg alloys EV31A,WE43B,and ZE41A in chloride- and sulfate-containing solutions saturated with magnesium hydroxide

This study studied corrosion in 0.1 M Na₂SO₄, 0.1 M NaCl, and 0.6 M NaCl, all saturated with Mg(OH)₂, using weight loss, hydrogen evolution, and electrochemical measurements. Corrosion was similar in all cases. Nevertheless, the corrosion rates were alloy-dependent, were somewhat lower in 0.1 M Na₂SO₄ than in 0.1 M NaCl, and increased with NaCl concentration. The corrosion damage morphology was similar for all solutions; the extent correlated with the corrosion rate. The corrosion rates evaluated by the electrochemical methods were lower than those evaluated from hydrogen evolution, consistent with the Mg corrosion mechanism involving the unipositive Mg⁺ ion.     

Corrosion of a cast iron boiler in a model central heating system

The rate of corrosion of a grey, cast iron boiler in a model central heating system was measured by chromatographic analysis of evolved gases (H₂ + N₂). The rate of H₂ evolution rose to a maximum and then declined parabolically as a protective Fe₃O₄ scale formed. Comparison with published results on corrosion of steel at ～ 300°C suggests that the rate-controlling process is the diffusion of FeOH⁺ ions through pores in the scale. A reaction mechanism is proposed which is similar to the established mechanism for conversion of Fe to Fe₃O₄ in aerated waters except that H⁺ ion reduction is the cathodic process. The relevance of these findings to the corrosion of central heating systems in service is discussed.     

Inhibitory effects of manganeous,cadmium and zinc ions on hydrogen evolution reaction and corrosion of iron in sulphuric acid solutions

The presence of metal ions (Cd²⁺, Mn²⁺, Zn²⁺), more electronegative than the cathodic potential for the hydrogen evolution reaction on iron in a 0.25M H₂SO₄ solution, inhibits the hydrogen evolution reaction and corrosion of iron. This effect has been explained as the under-potential deposition of the adatoms of these metals on iron.     

Corrosion behavior of iron thin film in deaerated phosphate solutions by an electrochemical quartz crystal microbalance

The corrosion rates of iron thin film in deaerated phosphate solutions were measured by an electrochemical quartz crystal microbalance as a function of solution pH or phosphorus concentration in solutions. The dependences of corrosion rate and corrosion potential on solution pH and phosphorus concentration have suggested that the corrosion mechanism changes in the vicinity of pH 5 and H₂PO₄⁻ contributes to both anodic dissolution of iron and hydrogen evolution. The corrosion mechanism which contains iron-phosphate-hydroxide complex ion as an adsorbed intermediate was proposed to explain the experimental results.     

Über den Einfluß von Schwefelwasserstoff auf die Korrosion des Eisens in sauren Lösungen

The influence of hydrogen sulphide on the corrosion of iron in acid solutions A considerable change of the polarisation behaviour of iron electrodes in acidic perchlorate and sulphate solutions was observed if they where saturated with hydrogen sulfide gas. H₂S markedly increased the anodic current densities and increases the corrosion rates by a factor of ten. The anodic Tafel slopes d log i_A/dE are only about half as steep as those in the absence of hydrogen sulphide. It is probable that the SH^?-ions behave as catalysts of the iron dissolution reaction in a similar manner as the OH^?-ions, but are adsorbed almost to saturation.     

The effect of ion implantation on the corrosion behaviour of pure iron—II. Chromium ion implantation

As part of a programme to investigate the effect of ion implantation on the corrosion behaviour of iron, pure iron specimens have been implanted with doses of 5 × 10¹⁴ and 2 × 10¹⁵ chromium ions/mm². Using a three-sweep potentiokinetic polarization technique the corrosion behaviour of these surface alloy layers has been compared with that of conventional binary FeCr alloys containing from 0.8 to 12.5 wt%Cr. It was found that apart from a slight thickening of the air-formed oxide film induced by the ion implantation process, the polarization behaviour of conventional alloys and of alloys produced by ion implantation was qualitatively very similar. Quantitatively the low dose chromium implanted specimens corresponded to a conventional Fe-4.9%Cr alloy while the high dose chromium implanted specimens resembled conventional alloys containing x12.5%Cr. These data provide a sound basis for the interpretation of the potentiokinetic polarization and corrosion behaviour of the novel surface alloy layers which can be produced by ion implantation.     

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.     

High frequency and low voltage plasma immersion ion implantation of nitrogen on industrial pure iron at different Rf power

Traditional plasma ion immersion implantation (PIII) can effectively improve material mechanical property and corrosion resistance. But the modified layer by PIII is too thin for many industrial applications. High frequency and low voltage plasma immersion ion implantation (HLPIII) has advantages of PIII and nitriding. Comparing with traditional ion nitriding, HLPIII can obtain higher implantation energy and create a thick modified surface layer. In the present paper nitriding layers were synthesized on industrial pure iron using high frequency and low voltage plasma immersion ion implantation with different RF power (400 W, 600 W, and 800 W). The microstructure of the nitriding layers was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The mechanical properties such as microhardness and wear resistance were analyzed using HXD1000 microhardness and CSEM pin-on-disk wear testing machine. The anodic polarization characteristics were measured in a 0.9% NaCl solution at room temperature to examine the corrosion resistance of the nitriding layer. The results reveal that Fe₂N, Fe₃N and Fe₄N coexist in the nitriding layer. The nitriding layer is a corrosion protective coating on industrial pure iron in 0.9% NaCl solution. The hardness, wear resistance and corrosion resistance of the nitrided layers on industrial pure iron increase with RF power.     

Effect of phosphine on acid corrosion of iron

The effect of the phosphine-concentration (10^?8–10^?3 M) in strong acid solutions (pH = 0) on the corrosion rate of pure iron and Fe- 0.12% P alloy has been investigated. It was shown that at low concentrations (10^?7–10^?6M), phosphine accelerates the corrosion of iron, whereas at adequately high concentrations (10^?5–10^?3 M) it has inhibitory properties. In the presence of PH₃ the cathodic reduction of hydrogen ions is strongly accelerated. At the same time, the increase in PH₃ concentration causes an increase of surface coverage by PH₃ molecules, which results in the inhibition of both partial electrode processes.     

The kinetics of hydrogen evolution and oxygen reduction on Alloy 22

The kinetics of hydrogen evolution and oxygen reduction on Alloy 22 in 5 M NaCl + xHCl + yNaOH solutions as a function of pH at temperatures ranging from 20 to 95 °C have been investigated. The hydrogen evolution reaction proceeds via two basic mechanisms; the reduction of H⁺ at pH < 4 and the reduction of H₂O at higher pH values. Analytical expressions for the exchange current density for the hydrogen evolution reaction on Alloy 22 are also developed for the two mechanisms, in a form that they can be used in corrosion models for assessing the performance of this alloy in high level nuclear waste (HLNW) repositories. The kinetics of oxygen reduction have also been explored over wide ranges of pH and temperature. However, this reaction is complicated by the formation of H₂O₂ as an intermediate in a two-electron transfer reaction. Nevertheless, kinetic parameters have been obtained for this reaction and an expression has been developed that allows calculation of the exchange current density over a wide range of conditions. Finally, the kinetic data are used to identify probable mechanisms for hydrogen evolution and the reduction of oxygen on Alloy 22.     

Surface nanostructure modification of Al substrates by N+ ion implantation and their corrosion inhibition

The influence of implantation of N⁺ ions of different energies on the nanostructure of 7049 Al substrates and the corrosion inhibition of produced Al samples in a 3.5% NaCl solution was studied. The X-ray diffraction (XRD) results confirmed the formation of AlN as a result of N⁺ ion implantation. The atomic force microscope (AFM) results showed that grains of larger scale are formed by increasing N⁺ energy which can be due to heat accumulation in the sample during implantation causing higher rate of diffusion in the sample, hence decreasing the number of defects. Corrosion resistance of the samples was studied by the electrochemical impedance spectroscopy (EIS) measurements. Results showed that corrosion resistance of implanted Al increases with increasing N⁺ ion energy. The equivalent circuits for the N⁺ implanted Al samples with different energies were obtained, using the EIS data which showed strong dependence of the equivalent circuit elements on the surface morphology of the samples. Finally, the relationship between corrosion inhibition and equivalent circuit elements was investigated.     

Elektrochemische Untersuchungen über die Korrosion des Eisens in sulfidhaltigen Lösungen

Electro-chemical investigations into the corrosion of iron in solutions containing sulphides In order to investigate the corrosion behaviour of steel reinforcements in concrete containing sulphides, measurements have been carried out of electro-chemical current potentials. The electrode material consisted of carbonyl iron; the air-less electrolyte solutions had varying contents of H₂S, HS^. and S^?, with a PH value ranging from 4 to 12.6. The tests showed that, with PH= 12.6, iron remains protected by a passive oxide film even in a solution containing sulphur. However, from about PH = 10-11 downwards, the passive film is replaced by a non-protective iron sulphide layer. But at least down to PH = 9, the corrosion rate is still very low due to the strong inhibition of the cathodic part-reaction of the hydrogen segregation. The kinetics of the hydrogen segregation due to H₂S reduction are discussed.     

Identification of oxidizing agents in aqueous amine-CO2 systems using a mechanistic corrosion model

The purpose of this paper was to perform studies in order to obtain a better understanding of corrosion in an aqueous amine-CO₂ environment. A mechanistic corrosion model, built as a fortran-90 program, is established to identify the oxidizing agents responsible for corrosion reactions. The model incorporates the rigorous electrolyte nonrandom two-liquid (NRTL) equilibrium model and mixed potential theory in order to simulate the concentrations of chemical species and polarization behavior taking place at a metal-solution interface. The simulation results, based on monoethanolamine (MEA) system, indicates that bicarbonate ion (HCO₃⁻) and water (H₂O) are the primary oxidizing agents and hydrogen ion (H⁺) or hydronium ion (H₃O⁺) plays an insignificant role in the reduction reaction.     

Hydrogen entry into steel during atmospheric corrosion process

Hydrogen entry and permeation into iron were measured by an electrochemical method during atmospheric corrosion reaction. The hydrogen permeation was enhanced on passive films because the hydrogen adsorption increased by the hydrogen evolution mechanism which is different from that on a bear iron surface. The permeation rate during a wet and dry corrosion cycle showed a maximum in the drying process depending upon the surface pH and the corrosion potential. The pollutant such as Na₂SO₃ which decreases the pH and the corrosion potential causes an increase in the permeation rate. The mechanism of the change in the permeation rate during the wet and dry cycles is explained by the polarization diagram of the electrode covered by thin water layer.     

X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanised steel implanted with rare earths

The present paper studies the effect of ion implantation of 2 × 10¹⁶ ions/cm² of Ce⁺ and 2 × 10¹⁶ ions/cm² of La⁺ at 150 keV on the corrosion behaviour of hot-dip galvanised steel. After implantation, galvanised steel was characterised by means of XPS previous to and following immersion in the medium. The results revealed incorporation of cerium and lanthanum on the surface as Ce₂O₃ and La₂O₃, respectively. Electrochemical impedance spectroscopy was carried out in order to evaluate its corrosion behaviour in 0.6 M NaCl during 1 month of immersion. The corrosion resistance was improved by an increase in the charge transfer resistance of the implanted specimens in the medium. This effect could be associated with changes in the morphology/microstructure of the corrosion products layer rather than in its composition variations.     

Nano-wear, nano-hardness and corrosion-resistance of electroplated nickel surfaces after co-implantation of Cr and N2 ions

In this work, a successful sequential co-implantation treatment of Cr⁺ and N₂⁺ ions into electrodeposited nickel plates is presented. The goal of this treatment is the simultaneous enhancement of the wear resistance, mechanical stability and corrosion-protection properties of the Ni surfaces. The ion-implanted surfaces have been characterized by glow-discharge optical-emission spectroscopy, X-ray diffraction, nano-hardness, roughness, nano-wear and potentio-dynamic corrosion tests. It has been observed that the implantation of Cr⁺ or N₂⁺ alone is not sufficient to achieve simultaneously the enhancement of both the wear-resistance and the corrosion-protection properties. Conversely, the sequential implantation of Cr⁺ and N₂⁺ at 140 keV and fluencies of 3 × 10¹⁷ and 1.5 × 10¹⁷ ions/cm² respectively, permits the formation of a functional surface capable of reducing both the corrosion rate and the wear rates, with respect to those exhibited by the un-implanted Ni surfaces.This treatment can be used to protect the surfaces of micro-embossing/stamping dies based on electroformed Nickel, as an alternative to other coating strategies. Furthermore, the ion implantation assures the non-modification of the net-shape and surface finish of these types of dies, which is of crucial importance when they are used for high-precision micro-texturing/imprinting applications.     

Corrosion behaviour of nitrogen ion implanted AISI type 304L stainless steel in nitric acid medium

The effects of nitrogen ion implantation on corrosion behaviour of 304L stainless steel in 1 N HNO₃ medium were investigated using surface analytical and electrochemical techniques. Nitrogen ion was implanted at 70 keV in the dose range of 1 × 10¹⁵, 1 × 10¹⁶, 1 × 10¹⁷ and 2.5 × 10¹⁷ N⁺/cm², respectively. Grazing incidence X-ray diffraction results for unimplanted and up to dose of 1 × 10¹⁶ N⁺/cm² showed co-existence of γ-Fe and α′-Fe and, at higher doses (1 × 10¹⁷ and 2.5 × 10¹⁷) preferential formation of chromium nitride was observed. X-ray photoelectron spectroscopy investigation confirmed the formation of chromium nitride at higher doses. Electrochemical corrosion investigation revealed nobler open circuit potential, decrease in corrosion current densities, passive current densities and increase in polarization resistance with increase in dose rate. Surface morphology analysis after polarization study using atomic force microscope showed grain boundary dissolution for unimplanted specimens and resistance to surface dissolution with increase in dose rate for implanted specimens.