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.     

Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation

The hypothesis that the corrosion of Mg alloys can be adequately estimated using Tafel extrapolation of the polarisation curve is termed herein the electrochemical measurement hypothesis for Mg. In principle, such a hypothesis can be disproved by a single valid counter example. The critical review of Mg corrosion by Song and Atrens in 2003 indicated that, for Mg alloys, Tafel extrapolation had not estimated the corrosion rate reliably. This paper examines the recent literature to further examine the electrochemical measurement hypothesis for Mg. The literature shows that, for Mg alloys, corrosion rates evaluated by Tafel extrapolation from polarisation curves have not agreed with corrosion rates evaluated from weight loss and hydrogen evolution. Typical deviations have been ∼50-90%. These were much larger than the precision of the measurement methods and indicate a need for careful examination of the use of Tafel extrapolation for Mg. For research that nevertheless does intend to use Tafel extrapolation to elucidate corrosion of Mg associated with service, it is strongly recommended that these measurements be complemented by the use of at least two of the three other simple measurement methods: (i) weight loss rate, (ii) hydrogen evolution rate, and (iii) rate of Mg²⁺ leaving the metal surface. There is much better insight for little additional effort.     

Evaluation of corrosion rate from polarisation curves not exhibiting a Tafel region

Evaluation of corrosion rate by Tafel extrapolation is often impossible, simply because an experimental polarisation curve does not exhibit linear Tafel regions. This paper shows how such curves for the Fe/H₂O/H⁺/O₂ corrosion system can be accurately deconstructed to furnish both kinetic and thermodynamic parameters for the anodic and cathodic reactions. The curved anodic branch (due to film formation) is then amenable to correction for IR voltage drop and the resulting Tafel slope and other parameters are then substituted in the Tafel equation to accurately determine i_corr. An alternative method to obtain the anodic Tafel slope has been used to validate the above approach. Polarisation curves describing the inhibition of mild steel in industrial cooling water were scanned/digitised from the literature.     

A newly synthesized glycine derivative to control uniform and pitting corrosion processes of Al induced by SCN anions - Chemical, electrochemical and morphological studies

A newly synthesized glycine derivative (termed GlyD), 2-(4-(dimethylamino)benzylamino)acetic acid hydrochloride, was used to inhibit uniform and pitting corrosion processes of Al in 0.50 M KSCN solutions (pH 6.8) at 25 °C. For uniform corrosion inhibition study, Tafel extrapolation, linear polarization resistance and impedance methods were used, complemented with SEM examinations. An independent method of chemical analysis, namely ICP-AES (inductively coupled plasma atomic emission spectrometry) was also used to test validity of corrosion rate measured by Tafel extrapolation method. GlyD inhibited uniform corrosion, even at low concentrations, reaching a value of inhibition efficiency up to 97% at a concentration of 5 × 10⁻³ M. Results obtained from the different corrosion evaluation techniques were in good agreement. This new synthesized glycine derivative was also used to control pit nucleation and growth on the pitted Al surface based on cyclic polarization, potentiostatic and galvanostatic measurements. The pitting potential (E_pit) and the repassivation potential (E_rp) increased by the addition of GlyD. Thus GlyD suppressed pit nucleation and propagation. Nucleation of pit was found to take place after an incubation time (t_i). The rate of pit nucleation and growth decreased with increase in inhibitor concentration. Morphology of pitting was also studied as a function of the applied anodic potential and solution temperature. Cross-sectional view of pitted surface revealed the formation of large distorted hemispherical and narrow deep pits. GlyD was much better than Gly in controlling uniform and pitting corrosion processes of Al in these solutions.     

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.     

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 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.     

Calculation of Uniform Corrosion Current Density of Iron in Hydrochloric Acid Solutions based on the Principle of Maximum Entropy Production Rate Applied to Literature Data

In this paper a new procedure for the calculation of uniform corrosion current density is presented. The procedure is based on the following criterion: corrosion current and extent of anodic and cathodic areas are such that the entropy production rate is maximum. Experimental data for the reaction Fe(s) + HCl(aq) = FeCl₂(aq) + H₂(g), taken from literature, are used to test the new model. A comparison between corrosion current density calculated from weight loss measurements and current density calculated from polarization curves by means of the proposed model is carried out. The proposed model provides a better agreement, between Tafel line extrapolation and gravimetric measurement, in comparison to the mixed potential theory usually adopted.     

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.     

Determination of Tafel slopes from coulostatically induced transients using an integral algorithm

The analysis of coulostatically induced transients (CITs) has been used as a tool to evaluate the corrosion rate of metallic materials, and a new algorithm has been developed to calculate the Tafel slopes (b_a and b_c). This new algorithm is based on the coulostatic strong polarization integration (CSPI) method. Experimental results for carbon steels exposed to 0.5 M H₂SO and 1 M HCl show excellent agreement between the proposed method and the Tafel line extrapolation method with IR drop correction. Furthermore, the calculated average corrosion currents over 8 h tests are in good agreement with solution analysis data from atomic absorption spectroscopy. The improved CSPI algorithm shows superior performance over the differential algorithm and the conventional algorithm due to its simplicity and higher signal/noise ratio.     

Electrochemical characterisation of the porosity and corrosion resistance of electrochemically deposited metal coatings

Electrochemical techniques for the assessment of porosity in electrodeposited metal coatings are reviewed. The determination of porosity and corrosion, resistance is illustrated by electrochemical data from three coating/substrate systems namely: electroless nickel on aluminium and steel and immersed gold coatings on an electroless copper-plated ABS polymer. Nickel coatings were up to 24 μm thick while gold deposits had thickness between 75 and 190 nm. Tafel extrapolation and linear polarisation resistance methods were used to determine the corrosion rate of the coated substrates. The aluminium samples were tested in 5% w/v (0.85 mol dm^− 3) NaCl, while coated steel and ABS samples were immersed in 0.125 mol dm^− 3 H₂SO₄ and 0.1 mol dm^− 3 NaBH₄, respectively, at 295 K. Current vs. time curves and anodic polarisation behaviour have also been considered.     

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.     

Evaluation of corrosion rates by the faradaic rectification method

Accurate evaluation of corrosion currents from polarization data has been the aim of many workers in the recent past. This, however, requires both polarization resistance and Tafel slope measurements. Although many accurate methods have been developed for polarization resistance measurements a certain amount of ambiguity still exists regarding the measurement and the validity of Tafel slopes at corrosion potential. A method for evaluation of corrosion currents is presented in this paper based on the faradaic rectification technique. According to this method the corrosion current (ICorr is given by

where R_p is the polarization resistance and (δE/V²)_ω→O and (δE/V²)_ω→∞ are the rectification ratios at low and high frequency a.c. signals. The method does not require Tafel slope measurements, hence the controversy generated as to the validity of Tafel slopes at E_Corr is completely eliminated.     

The Stern-Geary method. Basic difficulties and limitations and a simple extension providing improved reliability

Application of the Stern-Geary relation to corroding metals or redox electrodes to determine i_o (the corrosion current or exchange current, respectively) requires the value of the sum of the component current reciprocal Tafel slopes appropriate to i = 0. The shape of the polarization curve close to i = 0 contains all the information for determination of the reciprocal slopes but this will only provide improved reliability when i_o is very large indeed. It is proposed that the readily estimated difference between the reciprocal Tafel slopes close to i = 0 be applied in various ways described.     

Inhibition of copper corrosion by isatin in aerated 0.5 M H2SO4

The corrosion inhibition of commercial copper by means of isatin was studied in aerated 0.5 M H₂SO₄ in the temperature range 25-55 °C using weight-loss, potentiodynamic and spectrophotometric tests, and determination of double layer capacitance. Inhibition efficiencies up to 94% in the concentration range of 1×10⁻⁴-7.5×10⁻³ M of isatin were obtained. The corrosion rates estimated with weight-loss measurements were higher than those correspondingly determined with the potentiodynamic test, especially at higher concentrations of inhibitor. This is in accord with other researches that have pointed out the limitation of the Tafel line extrapolation method in the determination of corrosion rates. The kinetics of cuprous and cupric ion formation and UV-visible spectra support the formation hypothesis of a complex between copper and isatin. The adsorptive behaviour of isatin on copper 0.5 M H₂SO₄ was also investigated.     

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.     

Effect of the cerium (III) chloride heptahydrate on the corrosion inhibition of aluminum alloy

In the present work, the corrosion protection of aluminum alloy AA2024-T3 has been studied in NaCl solution, with and without the addition of cerium (III) chloride heptahydrate. The corrosion inhibitor efficiency after immersion into 10 mM NaCl, with or without 3 mM of CeCl₃·7H₂O at 20°C, 40°C, and 60°C was investigated. The performed quantitative tests include electrochemical techniques, such as the method of quasipotentiostatic polarization (Tafel extrapolation), cyclic polarization, and electrochemical impedance s pectroscopy to determine corrosion rate (v_corr), inhibition efficiency (η %), protective ability (γ), degree of coverage (ϑ), and pitting nucleation resistance. The samples were analyzed with scanning electron microscopy and energy dispersive X-ray analysis to evaluate and characterize the precipitates formed on the surface of aluminum samples and to determine dominant type of corrosion. The formation of Ce³⁺ precipitates occurred on cathodic intermetallic sites and the surface, in general, resulting in improved corrosion resistance. Tested cerium (III) chloride heptahydrate proved to be an effective inorganic corrosion inhibitor for AA2024-T3 in chloride solution, which, by the action of cerium ions, reduced corrosion on the surface of the studied aluminum alloy.     

The protective effect of polypyrrole coating on the corrosion of steel electrode in acidic media

In this study, the corrosion parameters of stainless steel containing 12% Cr, have been determined by Tafel extrapolation method in 1 M HCl, H₂SO₄ and H₃PO₄ media. Later, steel was coated with polypyrrole in 0.1 M Pyrrole + 0.3 M Oxalic acid solution by cyclic voltametric method. The corrosion parameters and percentage inhibition efficiencies of coated electrodes were investigated according to immersion times in the same media. In all acidic media studied, increases in immersion time, produced increased corrosion densities and a decrease in percentage inhibition efficiencies were determined.     

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.     

Die instationäre Korrosion des passiven Eisens in saurer Lösung

The instationary corrosion of passive iron in acid solution The corrosion rate of the passive iron, i.e. the dissolution rate of the passivating layer, in 1 n H₂SO₄ is investigated, with the layer thickness being increased and decreased, respectively (non-stationary conditions). The corrosion rate is determined chemical-analytically as well as coulometrically on the basis of galvanostatic measurements. Both methods yield the same result. The corrosion current density, i_K, increases as the formation current density, i_S, of the layer increases, and decreases the more below the stationary corrosion value, i_K, the higher the layer reduction current density (i_S <0) is. i_K and i_S, are independent of the electrode Potential of the passive iron electrode, similar to the behaviour of the stationary value, i_K,0. This independence is explained by the semiconductor properties of the passivating oxide (γ-Fe₂O₃). There is an unique correlation between i_K and i_Ss which can be explained also theoretically by a variable overvoltage at the phase boundary oxidelectrolyte. The kinetics of the corrosion and of the layer formation is evaluated from the values of the apparent charge transfer coefficients by referring to the p_H dependence of the stationary corrosion.