Behaviour of copper during alkaline corrosion of Al–Cu alloys

Enrichment of copper beneath amorphous anodic films on relatively dilute, solid-solution Al–Cu alloys is necessary before copper can be oxidized and incorporated into the oxide layer. A similar enrichment arises during electropolishing, which also develops an amorphous oxide. In these cases, external polarization is applied, usually generating a relatively high oxidation rate. In contrast, enrichment behaviour at the corrosion potential has received less attention. The present study examines the corrosion of Al–Cu alloys, containing up to 6.7 at.% Cu, in 0.1 M sodium hydroxide solution at 293 K. Copper is again found to enrich in the alloy, similarly to behaviour with anodic polarization. However, following enrichment, discrete copper-rich particles appear to be generated in the corrosion product. These are suggested to be nanoparticles of copper, since the corrosion potentials of the alloys are low relative to that required for oxidation of copper. The corrosion rate increases with increase of both time and copper content of the alloy, probably associated with a greater cathodic activity due to an increasing number of nanoparticles. The corrosion proceeds with loss of aluminium species to the sodium hydroxide solution, but with retention of copper in the layer of hydrated alumina corrosion product.     

An electrochemical framework to explain the intergranular stress corrosion behavior in two Al-Cu-Mg-Ag alloys as a function of aging

A modified version of the Cu-depletion electrochemical framework was used to explain the metallurgical factor causal to intergranular stress corrosion cracking (IGSCC) susceptibility in two Al-Cu-Mg-Ag alloys (i.e., Al-5.0%Cu-0.8%Mg-0.5%Ag and Al-5.4%Cu-0.5%Mg-0.5%Ag). This framework was also used to explain the specific cases of IGSCC susceptibility in the under-aged condition and increased IGSCC resistance with over-aging. Susceptibility in the under-aged and T8 (peak-aged) conditions is consistent with the grain boundary Cu-depletion mechanism and high concentrations of Cu in solid solution in grain interiors. Improvement in resistance to IGSCC of the over-aged T8+ condition (i.e., T8 temper followed by an additional thermal exposure of 5000 h at 107.2 °C) can be explained by elimination of the differential Cu concentration adjacent to the grain boundary compared to that of the grain interior. The resultant leveling of Cu concentration leads to the suppression of a preferential dissolution path at the grain boundaries associated with IGSCC.     

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.     

Copper corrosion inhibition in O2-saturated H2SO4 solutions

Corrosion inhibition of copper in O₂-saturated 0.50 M H₂SO₄ solutions by four selected amino acids, namely glycine (Gly), alanine (Ala), valine (Val), or tyrosine (Tyr), was studied using Tafel polarization, linear polarization, impedance, and electrochemical frequency modulation (EFM) at 30 °C. Protection efficiencies of almost 98% and 91% were obtained with 50 mM Tyr and Gly, respectively. On the other hand, Ala and Val reached only about 75%. Corrosion rates determined by the Tafel extrapolation method were in good agreement with those obtained by EFM and an independent chemical (i.e., non-electrochemical) method. The chemical method of confirmation of the corrosion rates involved determination of the dissolved Cu²⁺, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of chemical analysis. Nyquist plots exhibited a high frequency depressed semicircle followed by a straight line portion (Warburg diffusion tail) in the low-frequency region. The impedance data were interpreted according to two suitable equivalent circuits. The kinetics of dissolved O₂ reduction and hydrogen evolution reactions on copper surface were also studied in O₂-saturated 0.50 M H₂SO₄ solutions using polarization measurements combined with the rotating disc electrode (RDE). The Koutecky-Levich plot indicated that the dissolved O₂ reduction at the copper electrode was an apparent 4-electron process.     

N-Aminorhodanine as an effective corrosion inhibitor for mild steel in 0.5 M H2SO4

The corrosion inhibition effect of N-aminorhodanine (N-AR) on mild steel (MS) in 0.5 M H₂SO₄ was studied in both short and long immersion duration using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), chronoamperometry and hydrogen gas evolution. The surface morphology of MS was examined with scanning electron microscopy (SEM) in absence and presence inhibitor. The inhibitor adsorption process on MS surfaces obeys the Langmuir adsorption isotherm. The results show that NAR is a good inhibitor for MS in the acidic medium. The inhibition efficiency obtained from potentiodynamic polarization, EIS and LPR up to 98% is determined.     

Investigation of the inhibition effect of indole-3-carboxylic acid on the copper corrosion in 0.5 M H2SO4

Inhibition of the copper corrosion by means of indole-3-carboxylic acid (ICA), was studied in 0.5 M H₂SO₄ solutions in the temperature range from 25 °C to 55 °C using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results obtained from the both measurement techniques revealed good inhibitor efficiency in the studied concentration range. Nyquist plots showed depressed semicircles with their centre below real axis. Moreover, the impedance spectra in the case of both non inhibited solutions and inhibited ones by means of lower inhibitor concentrations exhibited Warburg impedance. The adsorption behaviour of ICA followed Langmuir’s isotherm.     

Tuning DOS measuring parameters based on double-loop EPR in H2SO4 containing KSCN by Taguchi method

In the present work, a higher resolution than that of standard DL-EPR technique was obtained by tuning the degree of sensitisation (DOS) measuring parameters. SS304 with different sensitisation conditions was chosen. Acid and depassivator concentration, temperature, scan rate and reverse potential were defined as key factors and Taguchi was applied. The optimal condition was found to be 1 M H₂SO₄, 0.02 M KSCN, 40 °C, 30 mV/min scan rate and 200 mV reverse potential. Main factors were acid concentration, scan rate, depassivator concentration. An increase in DOS from 18 to 42.2 in the 60 min sensitised sample was observed.     

Three pyrazine derivatives as corrosion inhibitors for steel in 1.0 M H2SO4 solution

The inhibition effect of three pyrazine derivatives of 2-methylpyrazine (MP), 2-aminopyrazine (AP) and 2-amino-5-bromopyrazine (ABP) on the corrosion of cold rolled steel (CRS) in 1.0 M H₂SO₄ solution was studied by weight loss, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) methods. The results show that all pyrazine compounds are good inhibitors, and inhibition efficiency follows the order: ABP > AP > MP. The adsorption of each inhibitor on CRS surface obeys Langmuir adsorption isotherm. For all these pyrazine derivatives, they act as mixed-type inhibitors. The probable inhibitive mechanism is proposed from the viewpoint of adsorption theory.     

Acoustic emission during the electrochemical corrosion of 304 stainless steel in H2SO4 solutions

Acoustic emission (AE) behaviour during the electrochemical corrosion of 304 stainless steel (304SS) in H₂SO₄ solutions was studied. AE signals which related to transpassive dissolution are detected in solutions with low pH, and are very slightly influenced by current density and pre-strain. During hydrogen bubble evolution, a weak correlation exists between the AE signal amplitude and the hydrogen bubble diameter. The concept of potential – pH – AE diagram is proposed and such a diagram is drawn based on AE activity and b-values. The main mechanisms of AE sources which are transpassive dissolution and hydrogen bubble evolution, are also discussed.     

The study of intergranular corrosion in aircraft aluminium alloys using X-ray tomography

Atmospheric corrosion is one of the leading causes of structural damage to aircraft. Of particular importance is pitting and intergranular corrosion, which can develop into fatigue cracks, stress corrosion cracks, or exfoliation. Therefore it is of interest to the Australian Defence Force (ADF) to understand how corrosion ensues in susceptible aircraft aluminium alloys, such as AA2024-T351 and 7050-T7451. However, there are many difficulties in measuring the extent of intergranular corrosion, since it is predominantly hidden below the surface. Traditionally, cross-sectioning has been used to view and measure the depth of attack. In the present work, 2 mm diameter pin specimens were contaminated with a droplet of 3.5% NaCl and exposed to constant humidity that resulted in intergranular corrosion. X-ray computed tomography was then used to non-destructively assess the depth and volume of corrosion both as a function of time in 97% relative humidity, and as a function of relative humidity after 168 h exposure. Both corrosion depth and volume increased with time, but there was evidence for a limiting depth in AA2024. Depth and volume also increased with relative humidity of the environment, for which the time-of-wetness and oxygen concentration of the droplets were considered the important factors in driving the corrosion process.     

Passivation of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys in 1 M H2SO4 and 1 M NaOH solutions

The corrosion mechanisms of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys have been investigated by potentiodynamic and potentiostatic polarization. Very good passivation of the Al–Cr–Fe surface is exhibited from 1 M H₂SO₄ to 1 M NaOH solutions, which was confirmed by ICP-OES analysis over a period of 273 days. Potentiostatically formed passive films analysed by XPS revealed chromium enrichment in the outermost layer of the aluminium oxy-hydroxide film. Although Al–Cu–Fe–Cr showed passivation during potentiodynamic polarization, heavy active corrosion at OCP was revealed by ICP-OES. For the Al–Cu–Fe–Cr alloy, the 10% content of Cr is insufficient to maintain a protective “chemically stable” Cr oxide/hydroxide.     

Numerical simulation of corrosion process with two-step charge transfer mechanism in the Cu/CuSO4 + H2SO4 system

The corrosion process in the Cu/CuSO₄ + H₂SO₄ system is considered as the sum of two coupled single-electron electrochemical reactions that occur simultaneously and independently on the surface of the copper electrode. Our numerical model incorporates diffusion and migration of solution species including cuprous ions, as well as the chemical equilibria for copper sulphate and sulphuric acid dissociation. Numerical simulations are compared with the trends discovered during experimental investigation of copper corrosion in similar systems.     

Effect of Mo and Mn additions on the corrosion behaviour of AISI 304 and 316 stainless steels in H2SO4

The work addresses the influence of Mn and Mo additions on corrosion resistance of AISI 304 and 316 stainless steels in 30 wt.% H₂SO₄ at 25 and 50 °C. Corrosion mechanism was determined by gravimetric tests, DC polarization measurements and electrochemical impedance spectroscopy (EIS). The morphology and nature of the reaction products formed on the material surface were analysed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Reduction of temperature from 50 to 25 °C drastically decreased the corrosion rate of AISI 304 and 316 stainless steels in sulphuric acid solution. Mn additions did not affect significantly the general corrosion resistance due to its low ability to form insoluble compounds in acid medium. Meanwhile, the formation of molybdenum insoluble oxides enhanced the corrosion performance.     

Corrosion behaviour of cermet-based coatings with a bond coat in 0.5 M H2SO4

The corrosion behaviour of an HVOF Ni–5Al/WC–17Co coating on Al-7075 is investigated in 0.5 M H₂SO₄. In the temperature range of 25–45 °C, the coating exhibits pseudopassivity that effectively protects from localized corrosion. At 25 °C, pseudopassivity proceeds via three stages: during the first stage, oxidation of W in the binder phase occurs. The second stage is characterized by oxidation of W in both the binder and the carbide particles. The third stage is characterized by intensive hydration of WO₃ and formation of Co₃O₄. During the second and third pseudopassive stages, the formation of a bi-layer surface film is postulated. The inner layer, consisting of anhydrous oxides, has a barrier character. The outer layer, composed of WO₃ · xH₂O, is unstable. In case of surface film disruption, the bond coat successfully hinders corrosion propagation into the Al-alloy. Higher electrolyte temperatures lead to faster corrosion kinetics and higher tendency for pitting.     

Synergistic effect of iodide ion and polyacrylic acid on corrosion inhibition of iron in H2SO4 investigated by electrochemical techniques

Corrosion inhibition of iron in H₂SO₄ by polyacrylic acid (PAA) was investigated using electrochemical techniques at 30 °C. Results obtained indicate that PAA inhibited the corrosion of iron in the acid medium. Inhibition efficiency increases with increase in PAA concentration and synergistically enhanced on addition of iodide ions. Potentiodynamic polarization results suggest that PAA functions as a modest cathodic inhibitor. The adsorption of PAA onto the iron surface followed Temkin adsorption isotherm. FTIR analysis revealed that the synergistic effect due to co-adsorption of iodide ions and PAA is co-operative in nature.     

Corrosion and corrosion control of mild steel in concentrated H2SO4 solutions by a newly synthesized glycine derivative

A newly synthesized glycine derivative (GlyD1), 2-(4-(dimethylamino)benzylamino)acetic acid hydrochloride, was used to control mild steel corrosion in 4.0 M H₂SO₄ solutions at different temperatures (278–338 K). Tafel extrapolation, linear polarization resistance (LPR) and impedance methods were used to test corrosion inhibitor efficiency. 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. Results obtained were compared with an available glycine derivative (GlyD2) and glycine (Gly). Tafel polarization measurements revealed that the three tested inhibitors function as mixed-type compounds. The inhibition efficiency increased with increase in inhibitor concentration and decreased with temperature, suggesting the occurrence of physical adsorption. The adsorptive behaviour of the three inhibitors followed Temkin-type isotherm and the standard free energy changes of adsorption () were evaluated for the three tested inhibitors as a function of temperature. The inhibition performance of GlyD1 was much better than those of GlyD2 and Gly itself. Results obtained from the different corrosion evaluation techniques were in good agreement.     

Corrosion behavior of alumina ceramics in aqueous HCl and H2SO4 solutions

The corrosion behavior of cold isostatically pressed (CIP) high purity alumina ceramics in aqueous HCl and H₂SO₄ solutions with various concentrations has been studied simultaneously at room temperature (25 °C). Corrosion tests were also performed with 0.65 mol/l HCl and 0.37 mol/l H₂SO₄ solutions at 40, 55 and 70 °C for 48 h. Chemical stability was monitored by determining the amount of Al³⁺, Mg²⁺, Ca²⁺, Na⁺ Si⁴⁺ and Fe³⁺ ions eluted in different concentrations of HCl and H₂SO₄ solutions by means of atomic absorption spectrometry (AAS). By increasing the concentration from 0.37 to 6.5 mol/l, it was notified that the corrosion susceptibility in HCl and H₂SO₄ solutions for the CIP alumina specimens at room temperature decreases.     

Creep corrosion cracking of Sn–3.0Ag and Sn–0.5Cu solder alloys in NaCl solution

The surface crack nucleation of Sn–3.0Ag and Sn–0.5Cu solder alloys has been examined by performing sustained tensile-loading tests in 0.9 mass% NaCl solution at room temperature. For Sn–3.0Ag alloy, many cracks nucleate and propagate on the side surface of the specimen, similarly to Sn–3.0Ag–0.5Cu alloy reported previously. For Sn–0.5Cu alloy, such cracks are not observed, and ordinary creep deformation occurs in the solution. The effect of sustained applied stress, i.e., creep, on the dissolution of ions is smaller for Sn–0.5Cu alloy than for Sn–3.0Ag alloy. The present results suggest that there are differences in the susceptibility to cracking under applied stress in a solution, i.e., creep corrosion cracking, among lead-free solder alloys.     

Inhibition effect of 6-benzylaminopurine on the corrosion of cold rolled steel in H2SO4 solution

The inhibition effect of 6-benzylaminopurine (BAP) on the corrosion of cold rolled steel (CRS) in 1.0-7.0 M H₂SO₄ at 25-50 °C was studied by weight loss and potentiodynamic polarization methods. Fourier transform infrared spectroscopy (FTIR) and atomic force microscope (AFM) were used to characterize the CRS surface. The results showed that BAP was a good inhibitor in 1.0 M H₂SO₄, and the adsorption of BAP obeyed the Temkin adsorption isotherm. Polarization curves showed that BAP acted as a mixed-type inhibitor in sulfuric acid. Depending on the results, the inhibitive mechanism was proposed.