Corrosion of high purity Mg, Mg2Zn0.2Mn, ZE41 and AZ91 in Hank’s solution at 37 °C

The CO₂ partial pressure required to maintain a synthetic body fluid (SBF) at a constant pH, based on the initial bicarbonate concentration, was evaluated to be 0.013 atm for Hank’s solution and 0.083 atm for SBF27. Corrosion of high purity Mg and three Mg alloys in Hank’s solution was studied using hydrogen evolution, weight loss and Tafel extrapolation. The solution pH was maintained constant by CO₂. There was initially an incubation period with a low corrosion rate, a period of increasing corrosion rate, and subsequently steady state corrosion. Some hydrogen dissolved in the Mg metal.     

An exploratory study of the corrosion of Mg alloys during interrupted salt spray testing

A first systematic investigation was carried out to understand the corrosion of common Mg alloys (Pure Mg, AZ31, AZ91, AM30, AM60, ZE41) exposed to interrupted salt spray. The corrosion rates were also evaluated for these alloys immersed in 3 wt.% NaCl by measuring hydrogen evolution and an attempt was made to estimate the corrosion rate using Tafel extrapolation of the cathodic branch of the polarisation curve. The corrosion of these alloys immersed in the 3 wt.% NaCl solution was controlled by the following factors: (i) the composition of the alpha-Mg matrix, (ii) the volume fraction of second phase and (iii) the electrochemical properties of the second phase. The Mg(OH)₂ surface film on Mg alloys is probably formed by a precipitation reaction when the Mg²⁺ ion concentration at the corroding surface exceeds the solubility limit. Improvements are suggested to the interrupted salt spray testing; the ideal test cycle would be a salt spray of duration X min followed by a drying period of (120-X) min. Appropriate apparatus changes are suggested to achieve 20% RH rapidly within several minutes after the end of the salt spray and to maintain the RH at this level during the non-spray part of the cycle. The electrochemical measurements of the corrosion rate, based on the “corrosion current” at the free corrosion potential, did not agree with direct measurements evaluated from the evolved hydrogen, in agreement with other observations for Mg.     

Corrosion behaviour of Terfenol-D

The corrosion behaviour of pseudo-binary compound Tb_0.3Dy_0.7Fe_1.92 (Terfenol-D) was studied in 3.5% NaCl and 0.01 N Na₂SO₄ solutions using Tafel polarisation, linear polarisation, electrochemical impedance spectroscopy and weight loss techniques. Electrochemical testing revealed the adverse effect of chloride ions, as corrosion rates were higher in 3.5% NaCl solutions than in 0.01 N Na₂SO₄ solutions. The effect of aeration was studied by conducting experiments in freely-aerated, deaerated and fully-aerated conditions. Absence of oxygen accelerated corrosion in chloride environment, due to increased hydrogen interaction in presence of destabilised surface films. The improved corrosion resistance in chloride-free environment was correlated with morphological features of the corroded surfaces. Micro-compositional analysis of the corrosion products revealed that the corrosion products were primarily rich in rare earth elements. A comparison of all experimental techniques showed that Tafel extrapolation and EIS techniques provided reliable estimates of corrosion rate.     

An innovative specimen configuration for the study of Mg corrosion

Based on an analysis of galvanic corrosion research, the research reported herein was formulated to examine the measurement of polarisation curves for Mg to develop a methodology whereby reliable polarisation curves can be measured for Mg. Cathodic polarisation curves were measured for high purity Mg in 3.5% NaCl saturated with Mg(OH)₂ using three specimen types: (i) mounted specimens, (ii) specimens hung by fishing line and (iii) plug-in specimens. Cathodic polarisation curves were evaluated to yield the corrosion current density i_corr and the corresponding corrosion rate P_i, which was compared with the corrosion rate evaluated from hydrogen evolution measurements, P_H, and the corrosion rate evaluated by weight loss measurements, P_W. Mounted specimens produced values of corrosion rate, P_i, three times larger than values of corrosion rate, P_i, for plug-in specimens, attributed to crevice corrosion in the mounted specimens. Crevice corrosion in Mg is totally unexpected from prior research. The plug-in specimen configuration was designed to have no crevice and to allow simultaneous measurement of P_H and P_i; P_i was consistently less than P_H and indicated an apparent valence for Mg of 1.45 in support of the Mg corrosion mechanism involving the uni-positive Mg⁺ ion. The plug-in specimen has advantages for the study of Mg corrosion.     

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.     

Investigating accuracy of the Tafel extrapolation method in HCl solutions

This paper discusses the validity and accuracy of the Tafel extrapolation method for determining corrosion rates of carbon steel in 1, 2 and 3 M HCl solutions open to air. Corrosion rates obtained from polarization experiments were compared with that of weight loss method. For analysing data obtained from polarization experiments electrochemical impedance spectroscopy (EIS) measurements were performed before polarization experiments. The results showed that formation of a corrosion product film and increasing the polarization resistance (R_p) of this film with time cause the corrosion rates obtained from Tafel extrapolation tend to be higher than corrosion rates obtained from weight loss test.     

Limitations in the use of the potentiodynamic polarisation curves to investigate the effect of Zn on the corrosion behaviour of as-extruded Mg–Zn binary alloy

The effects of Zn on corrosion behaviour of as-extruded Mg-(1-4)Zn alloys were investigated using an immersion test, a zero resistance ammeter technique, and a potentiodynamic polarisation test. As a result, it was revealed that the solutionised Zn enhanced protectiveness of the passive film, and accelerated the H₂ evolution rate of the Mg–Zn binary alloys. The acceleration of the H₂ evolution rate by addition of Zn leads to an increase in the net corrosion rate of the Mg–Zn alloy. In this research, the polarisation test was found to have some limitations for evaluating the true corrosion behaviour of passive Mg–Zn alloy.     

Polarisation behaviour of steel bar samples in concrete in seawater. Part 1: Experimental measurement of polarisation curves of steel in concrete

The most widely used technique for the investigation of corrosion of reinforcing steel in concrete is the linear polarisation resistance (LPR) method, which however needs to assume the Tafel slopes or the B constant for calculation of the corrosion rate. This paper aims to explore the use of a polarisation curve technique to study the polarisation behaviour and to evaluate simultaneously the corrosion rate and Tafel slopes of steel samples in concrete. As the first part of the study, this paper reviews the relevant literature, and examines the effect of the experimental technique on the measured polarisation curves of steel in concrete in seawater. In particular, differences in the results obtained by two different test procedures are examined. A comparison of the experimental polarisation curves with the theoretical curves based on charge transfer reactions is made.     

Corrosion of ultra-high-purity Mg in 3.5% NaCl solution saturated with Mg(OH)2

Corrosion was evaluated for ultra-high-purity magnesium (Mg) immersed in 3.5% NaCl solution saturated with Mg(OH)₂. The intrinsic corrosion rate measured with weight loss, P_W = 0.25 ± 0.07 mm y⁻¹, was slightly smaller than that for high-purity Mg. Some specimens had somewhat higher corrosion rates attributed to localised corrosion. The average corrosion rate measured from hydrogen evolution, P_AH, was lower than that measured with weight loss, P_W, attributed to dissolution of some hydrogen in the Mg specimen. The amount of dissolution under electrochemical control was a small amount of the total dissolution. A new hydride dissolution mechanism is suggested.     

Effect of grain size and twins on corrosion behaviour of AZ31B magnesium alloy

Grain refining is a promising approach to improve mechanical properties of magnesium alloys, but how grain size and twins affect corrosion behaviour is not well understood. In this work, corrosion resistance of AZ31B alloy with different grain sizes is studied in 3.5% NaCl solution using immersion testing, evolved hydrogen gas measurement and potentiodynamic polarisation measurement. Intra-granular corrosion was predominant and the existence of twins further accelerated the corrosion. The effect of grain size was more pronounced in the corrosion of the untwinned microstructure. The corrosion rate significantly increased as the average grain size increased from 65 to 250 μm.     

Galvanic corrosion behavior of Ni?C filled conductive silicone rubber coupled to AZ31 magnesium alloys

The galvanic corrosion behaviors of Ni? C filled conductive silicon rubber (CSR) with different resistivity coupled to magnesium alloys were investigated in 3.5% sodium chloride solution at different temperatures. Such investigations were carried out by means of electrochemical measurement, weight‐loss determination, and surface characterization. The results indicated that the changes of CSRs' resistivity and the temperature of the electrolyte would affect the Tafel slope, cathodic corrosion current, and linear polarization resistance of the cathodic branch of the polarization curve. The lower the resistivity, the larger the average galvanic corrosion current density and the average galvanic corrosion rate of Mg alloys at the same temperature. The corrosion morphology revealed that the greater the corrosion current density, the more serious the corrosion on the surface of Mg alloys.     

Application of harmonic analysis in measuring the corrosion rate of rebar in concrete

The corrosion rate (CR) of rebar embedded in cement mortar, concrete and cement extract is determined using harmonic analysis technique (HA). Simultaneously using other electrochemical techniques such as impedance spectroscopy (EIS) and Tafel extrapolation (TET), the CR was determined and compared with the weight loss method. CR obtained from HA is comparable to that of EIS provided that the Stern–Geary constant (B value) obtained from HA is used in the calculation. In concrete, comparable corrosion rates are obtained between TET and HA only under active condition of the rebar whereas under passive state, the corrosion current (i_corr) by TET is 10 times lower than that of HA. A good agreement is obtained between the HA and weight loss method. The outcome of the result suggests that HA is capable of providing a higher degree of accuracy than that of EIS and TET in the determination of i_corr in the medium like rebar in concrete having very low rate of corrosion.     

Corrosion behaviour in salt spray and in 3.5% NaCl solution saturated with Mg(OH)2 of as-cast and solution heat-treated binary Mg–X alloys: X = Mn,Sn, Ca,Zn, Al,Zr, Si,Sr

Corrosion of binary Mg–X alloys (as-cast and solution heat-treated) was characterised by immersion tests in 3.5% NaCl solution saturated with Mg(OH)₂, and by salt spray. Alloys with high corrosion rates in immersion tests also had high corrosion rates in salt spray. Corrosion rates of the solution heat-treated alloys did not meet the expectation that they should be equal to or lower than those of high-purity Mg. There was circumstantial evidence that the higher corrosion rates were caused by the particles in the microstructure; the second phases had been dissolved. The corrosion rate of all alloys was faster than that of high-purity Mg.     

A study of the inhibition of iron corrosion in HCl solutions by some amino acids

The performance of three selected amino acids, namely alanine (Ala), cysteine (Cys) and S-methyl cysteine (S-MCys) as safe corrosion inhibitors for iron in aerated stagnant 1.0 M HCl solutions was evaluated by Tafel polarization and impedance measurements. Results indicate that Ala acts mainly as a cathodic inhibitor, while Cys and S-MCys function as mixed-type inhibitors. Cys, which contains a mercapto group in its molecular structure, was the most effective among the inhibitors tested, while Ala was less effective than S-MCys. The low inhibition efficiency recorded for S-MCys compared with that of Cys was attributed to steric effects caused by the substituent methyl on the mercapto group. Electrochemical frequency modulation (EFM) technique and inductively coupled plasma atomic emission spectrometry (ICP-AES), were also applied to make accurate determination of corrosion rates. Validation of the Tafel extrapolation method for measuring corrosion rates was tested. Rates of corrosion rates (in μm y⁻¹) obtained from Tafel extrapolation method are in good agreement with those measured using EFM and ICP methods. Some theoretical studies, including molecular dynamics (MD) and density functional theory (DFT), were also employed to establish the correlation between the structure (molecular and electronic) of the three tested inhibitors and the inhibition efficiency. Adsorption via hydrogen bonding was discussed here based on some theoretical studies. Experimental and theoretical results were in good agreement.     

Corrosion monitoring of mild steel in sulphuric acid solutions in presence of some thiazole derivatives – Molecular dynamics, chemical and electrochemical studies

The physical behavior of three selected thiazole derivatives, namely 2-Amino-4-(p-tolyl)thiazole (APT), 2-Methoxy-1,3-thiazole (MTT) and Thiazole-4-carboxaldehyde (TCA) at iron (1 1 0) surface dissolved in aqueous solution were studied via molecular dynamics (MD) simulations. From the calculated binding energies, APT showed preferred adsorption on the steel surface among the three tested thiazole derivatives. The inhibition performance of the three thiazoles on the corrosion of mild steel in 0.5 M H₂SO₄ solutions was investigated at 25 °C. Measurements were conducted under various experimental conditions using weight loss, Tafel polarization and electrochemical impedance spectroscopy. Electrochemical frequency modulation (EFM) technique was also employed here to make accurate determination of the corrosion rates and test validation of the Tafel extrapolation method for measuring corrosion rates. Polarization curves showed that the three thiazole derivatives were of mixed-type inhibitors for mild steel corrosion in 0.5 M H₂SO₄ solution. EFM results were in agreement with other traditional chemical and electrochemical techniques used in corrosion rate measurements. Chemical and electrochemical measurements are consistent with computational study that APT is the most effective inhibitor among the tested thiazoles.     

Corrosion behaviour in salt spray and in 3.5% NaCl solution saturated with Mg(OH)2 of as-cast and solution heat-treated binary Mg–RE alloys: RE = Ce,La, Nd,Y, Gd

Corrosion behaviour was characterised in salt spray and in 3.5% NaCl solution saturated with Mg(OH)₂ of as-cast and solution heat-treated binary Mg–RE alloys. The corrosion rate in the immersion test for the solution heat-treated Mg–RE alloys was substantial, and was greater than that of high-purity Mg. These corrosion rates were probably caused by the particles in the microstructure and/or by Fe rich particles precipitated during the solution heat-treatment. The corrosion rate in the immersion tests for each as-cast Mg–RE alloy was greater than that of high-purity Mg, attributed to micro-galvanic acceleration caused by the second phase. Corrosion rates in salt spray had a general correlation with corrosion rates in the immersion tests, but there were differences. The values of apparent valence were always less than 2 consistent with Mg corrosion being only partly under electrochemical control.     

Fast visualization of corrosion processes using digital speckle photography

This work shows the feasibility of using non-intrusive optical techniques to determine surface changes associated with corrosion processes even when they are very small and to obtain complementary information to the conventional electrochemical measurements. These techniques have been applied to the study of iron samples in H₂SO₄ corrosive solutions with different concentrations. Corrosion rate values have been estimated from the polarisation and Tafel curves obtained by linear sweep voltammetry. These measurements have been correlated with the surface changes determined from Digital Speckle Photography. This technique also provides a local 2D information about the evolution of the corrosion process at each surface position.     

The influence of yttrium (Y) on the corrosion of Mg-Y binary alloys

Corrosion of Mg-Y alloys was studied using electrochemical evaluations, immersion tests and direct observations. There were two important effects. In 0.1 M NaCl, the corrosion rate increased with increasing Y content due to increasing amounts of the Y-containing intermetallic. In 0.1 M Na₂SO₄, the corrosion rate decreased with increasing Y content above 3%, attributed to a more protective surface film, despite the intermetallic. The corrosion rate evaluated by electrochemical impedance spectroscopy was somewhat smaller than that evaluated from H evolution as expected from the Mg corrosion mechanism. A mechanism is proposed for filiform corrosion. Direct in situ corrosion observations revealed that a predominant feature was hydrogen evolution from particular parts of the alloy surface.     

Monitoring corrosion and corrosion control of iron in HCl by non-ionic surfactants of the TRITON-X series – Part II. Temperature effect, activation energies and thermodynamics of adsorption

The inhibition characteristics of non-ionic surfactants of the TRITON-X series, namely TRITON-X-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on the corrosion of iron was studied in 1.0 M HCl solutions as a function of inhibitor concentration (0.005–0.075 g L⁻¹) and solution temperature (278–338 K). Measurements were conducted based on Tafel extrapolation method. Electrochemical frequency modulation (EFM), a non-destructive corrosion measurement technique that can directly give values of corrosion current without prior knowledge of Tafel constants, is also presented. Experimental corrosion rates determined by the Tafel extrapolation method were compared with corrosion rates obtained by the EFM technique and an independent method of chemical analysis. The chemical method of confirmation of the corrosion rates involved determination of the dissolved cation, using ICP-AES (inductively coupled plasma atomic emission spectrometry). The aim was to confirm validation of corrosion rates measured by the Tafel extrapolation method. Results obtained showed that, in all cases, the inhibition efficiency increased with increase in temperature, suggesting that chemical adsorption occurs. The adsorptive behaviour of the three surfactants followed Temkin-type isotherm. The standard free energies of adsorption decreased with temperature, reflecting better inhibition performance. These findings confirm chemisorption of the tested inhibitors. Thermodynamic activation functions of the dissolution process were also calculated as a function of each inhibitor concentration. All the results obtained from the methods employed are in reasonable agreement.     

Microstructure and biocorrosion behaviors of solution treated and as-extruded Mg–2.2Nd–xSr–0.3Zr alloys

Mg–2.2Nd–xSr–0.3Zr alloys (x=0, 0.4 and 0.7, mass fraction, %) were prepared by gravity casting. Solution treatment was conducted on the as-cast alloys to homogenize microstructure, and hot extrusion was subsequently conducted. Microstructure was observed using an optical microscope and a scanning electron microscope. Biocorrosion behaviors of the alloy in simulated body fluid were analyzed by mass loss, hydrogen evolution and Tafel polarization experiments. The results show that the amount of residual eutectic phase of the solution treated alloys increases with increasing Sr addition, and the grains are significantly refined after hot extrusion. The corrosion resistance of the solution treated alloys deteriorates apparently with increasing Sr addition, while the corrosion resistance of the as-extruded alloys is improved with Sr addition. Nevertheless, the biocorrosion behavior of the as-extruded alloys obtained by Tafel polarization shows different trends from those obtained by the other two methods.