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.     

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.     

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.     

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.     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

A comparative H2S corrosion study of 304L and 316L stainless steels in acidic media

H₂S corrosion of 304L and 316L in oxygen-free Na₂SO₄ + Na₂S solution at pH 3 and temperature of 60 °C were investigated by EIS, potentiodynamic polarisation, multi-component Pourbaix diagrams and microstructure characterization. At similar conditions, lower corrosion rate was observed on 316L, attributed to its denser (1.5 times) and smoother (6%) surface layer and confirmed by SEM micrograph. During polarisation, H₂S increases significantly the critical current density on 304L and passivation current density, i_p, on 316L. Higher i_p on 316L was associated to simultaneous FeS₂–MoS₂ preservation, confirmed by XRD examination. H₂S could have an inhibiting effect on 304L in passivity region.     

Improving the corrosion behaviour of powder metallurgical 316L alloy by prepassivation in 20% nitric acid

The electrochemical improvement of PM 316L stainless steels by pre-alloyed powder prepassivation in 20% nitric acid in comparison with as-received specimens has been studied in this work. For comparison purposes a simultaneous study was carried out on similar composition wrought AISI 316L steels. Corrosion resistance was studied using evolution of the corrosion potential vs. time, anodic polarisations curves and Zero Resistance Ammeter technique. Reductions of the corrosion rate (i_corr) were observed in prepassivated specimens in neutral chloride media. Crevice resistance was higher for prepassivated specimens and for higher densities and annealing as post-heat treatments.     

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.     

Electrochemical behaviour of Ni-base alloys exposed under oil/gas field environments

The electrochemical behaviour of Ni-base alloys (Inconel 625, Inconel 718, G3 and Incoloy 825) is carried out at 80 °C in CO₂/H₂S corrosion environments using cyclic potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. The passivity mechanisms are analysed and discussed. In addition, some significant characterisation parameters such as E_corr, I_pass, E_pit, E_pp, ΔE and I_pass in cyclic polarisation curves are analysed and compared to reveal the corrosion resistance of various Ni-base alloys. The equivalent circuit model and ZsimpWin software are utilised to discuss the Nyquist plots of various Ni-base alloys. The diffusion mechanism in EIS measurement is discussed. The result shows that the corrosion resistance of the Ni-base alloys to CO₂ corrosion or CO₂/H₂S corrosion follows the sequence: Inconel 625 > G3 > Inconel 718 > Incoloy 825. H₂S works as a cathodic depolariser with accelerating initiation of the corrosion process.     

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 die-cast AZ91D magnesium alloy in aqueous sulphate solutions

The corrosion behaviour of die-cast AZ91D magnesium alloys in sulphate solutions was investigated by SEM, FTIR and polarization measurements. For immersion times less than 48 h, no pitting corrosion occurred and only generalized corrosion was apparent. According to the polarization curves, the corrosion rate order of the die-cast AZ91D Mg alloy in three aqueous solutions was: NaCl > MgSO₄ > Na₂SO₄. The main corrosion products were Mg(OH)₂ and MgAl₂(SO₄)₄·22H₂O in the sulphate solutions and the product film was compact. Precipitation of MgAl₂(SO₄)₄·22H₂O required a threshold immersion time.     

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.     

A comparative study of the corrosion inhibition of mild steel in sulphuric acid by 4,4-dimethyloxazolidine-2-thione

The corrosion protection of mild steel in a 2.5 M H₂SO₄ solution by 4,4-dimethyloxazolidine-2-thione (DMT) was studied at different temperatures by measuring changes in open circuit potential (OCP), potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS). Corrosion current densities calculated from EIS data were comparable to those obtained from polarisation measurements. Results showed that DMT inhibited mild steel corrosion in a 2.5 M H₂SO₄ solution and indicated that the inhibition efficiencies increased with the concentration of inhibitor, but decreased proportionally with temperature. Polarisation curves showed that DMT is a mixed-type inhibitor. Changes in impedance parameters suggested the adsorption of DMT on the mild steel surface, leading to the formation of protective films. The DMT adsorption on the mild steel surface followed the Langmuir adsorption isotherm. The kinetic and thermodynamic parameters for dissolution and adsorption were investigated. Comprehensive adsorption (physisorption and chemisorption) of the inhibitor molecules on the mild steel surface was suggested based on the thermodynamic adsorption parameters.     

The effect of molybdenum on the corrosion behaviour of the high-entropy alloys Co1.5CrFeNi1.5Ti0.5Mox in aqueous environments

The purpose of this study is to investigate the electrochemical properties of the Co_1.5CrFeNi_1.5Ti_0.5Mo_x high-entropy alloys in three aqueous environments which simulate acidic, marine, and basic environments at ambient temperature (∼25 °C). The potentiodynamic polarisation curves of the Co_1.5CrFeNi_1.5Ti_0.5Mo_x alloys, obtained in aqueous solutions of H₂SO₄ and NaOH, clearly revealed that the corrosion resistance of the Mo-free alloy was superior to that of the Mo-containing alloys. On the other hand, the lack of hysteresis in cyclic polarisation tests and SEM micrographs confirmed that the Mo-containing alloys are not susceptible to pitting corrosion in NaCl solution.     

Modeling pipeline crevice corrosion under a disbonded coating with or without cathodic protection under transient and steady state conditions

Underground steel pipelines are protected by coatings and cathodic protection (CP). The pipeline corrosion occurs when the coating is disbonded away from a defect or holiday to form a crevice and the corrosion rate varies temporally and spatially in the crevice. In the presence of dissolved oxygen (O₂) in soil ground water, a differential O₂ concentration cell may develop in the crevice because O₂ diffuses more readily into the crevice through the holiday than through the disbonded coating. CP can decrease or eliminate the O₂ concentration cell depending on the potential applied at the holiday. Since the coatings are usually non-conductive, CP is unable to protect the steel surface deep inside the crevice. The transport of dissolved O₂, and that of dissolved carbon dioxide (CO₂) if present, into the crevice through holiday can be key to determining the crevice corrosion rate. In this work, the transient and steady state behavior of the corrosion process is investigated. The effect of the cathodic portion of iron vs. ferrous ion redox reaction on the crevice corrosion rate, which is often neglected traditionally, is further studied. At steady state, the effect of dissolved O₂ on the crevice corrosion rate and the added effect of dissolved CO₂ are mathematically modeled.     

Corrosion behaviour of bulk ultra-fine grained AZ91D magnesium alloy fabricated by equal-channel angular pressing

Effect of microstructure change on corrosion behaviour of equal-channel angular pressed (ECAPed) AZ91D Mg alloy was investigated. The ECAPed alloy with ultra-fine grained (UFG) α-phase matrix and refined β-phase particles displays a significantly lower corrosion resistance, resulting in more pits after in-situ corrosion, higher mass-loss rate immersed in NaCl solution, larger I_corr values in polarization curves and lower fitted R_t values in EIS plots. Two factors weaken the corrosion resistance: the first is the strains-induced crystalline defects providing the α-phase matrix more corrosion activation, the second is the refined β-phase particles losing barrier to the corrosion propagation in α-phase matrix.     

Corrosion resistance of HVOF-sprayed coatings for hard chrome replacement

HVOF-sprayed coatings (WC-17Co, WC-10Co-4Cr, Co-28Mo-17Cr-3Si) and electrolytic hard chrome (EHC) coatings corrosion resistances have been compared through electrochemical polarization tests (0.1 N HCl, 0.1 N HNO₃) and Corrodkote test. EHC coatings passivate in HNO₃, but undergo pitting corrosion in HCl and in Corrodkote test too. HVOF coatings do not passivate, but possess more noble corrosion potentials. Both in HNO₃ and HCl, they undergo more generalized corrosion, with similar i_corr; crevice corrosion along splat boundaries is sometimes detected after the HCl test. Their i_corr in 0.1 N HCl solution is lower than in several of EHC coatings. No visible damage in the HVOF coatings has occurred after the Corrodkote test.     

Corrosion behaviour of micro-plasma arc welded stainless steels in H3PO4 under flowing conditions at different temperatures

This paper studies the general corrosion behaviour of the micro-plasma arc welded AISI 316L stainless steel in phosphoric acid at different temperatures (25–60 °C) and at a Reynolds number of 1456. Galvanic corrosion has been studied using zero-resistance ammeter (ZRA) measurements and polarization curves (by the mixed potential theory). Results show that the microstructure of the stainless steel is modified due to the micro-plasma arc welding procedure. Coupled current density values obtained from polarization curves increase with temperature. ZRA tests present the highest i_G values at 60 °C; however, the values are very close to zero for all the temperatures studied. This is in agreement with the low value of the compatibility limit and of the parameter which evaluates the importance of the galvanic phenomenon. Both techniques present the most positive potentials at the highest temperature. This study reveals that micro-plasma arc welded AISI 316L stainless steels are appropriated working in the studied H₃PO₄ media from a corrosion point of view for all the temperatures analysed.     

In situ infrared reflection spectroscopy studies of the initial atmospheric corrosion of Zn–Al–Mg coated steel

NaCl induced atmospheric corrosion of ZnAl2Mg2 coated, electrogalvanised (EG) and hot dipped galvanised (HDG) steel was studied using in situ infrared reflection absorption spectroscopy, XRD and SEM. Initial corrosion leads to the formation of Mg/Al and Zn/Al layered double hydroxides (LDHs) on ZnAl2Mg2, due to the anodic dissolution of Zn–MgZn2 phases and cathodic oxygen reduction on Zn–Al–MgZn2, Al-phases and on zinc dendrites. In contrast to EG and HDG, were no ZnO and Zn₅(OH)₈Cl₂⋅H₂O detected. This is explained by the buffering effect of Mg and Al which inhibit the ZnO formation, reduce the cathodic reaction and corrosion rate on ZnAl2Mg2.     

Sodium molybdate as a corrosion inhibitor for aluminium in H3PO4 solution

The inhibition effect of sodium molybdate (Na₂MoO₄) on the corrosion of aluminium in 1.0 M H₃PO₄ solution was studied by weight loss, potentiodynamic polarisation curves and electrochemical impedance spectroscopy (EIS) methods. The results show that Na₂MoO₄ is a good inhibitor, and the inhibition efficiency obtained by three methods is higher than 84% at 20 mM. The adsorption of Na₂MoO₄ obeys Freundlich isotherm at lower concentrations (1–7 mM), while Langmuir isotherm at higher concentrations (7–20 mM). Polarisation curves indicate that Na₂MoO₄ acts as an anodic inhibitor. EIS spectra exhibit three loops (two capacitive loops and one inductive loop).