Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

The EIS technique was used to analyze the electrochemical reaction behavior of Alloy AZ91 in H₃PO₄/KOH buffered K₂SO₄ solution at pH 7. The corrosion resistance of Alloy AZ91 was directly related with the stability of Al₂O₃ · xH₂O rich part of the composite oxide/hydroxide layer on the alloy surface. The break down of the oxide layer was estimated to occur mainly on the matrix solid solution phase in Alloy AZ91. The mf capacitive loop arose from the relaxation of mass transport in the solid oxide phase in the presence of Al₂O₃ · xH₂O rich part and from Mg⁺ ion concentration within the broken area in the absence of Al₂O₃ · xH₂O rich part in the composite oxide structure on the alloy surface. The lf inductive loop had tendency of disappear when the dissolution rate of the alloy decreased as a result of the formation of the protective oxide layer.     

Corrosion prevention of passivated iron in 0.1 M NaCl by coverage with an ultrathin polymer coating and healing treatment in 0.1 M NaNO3

An ultrathin, ordered and two-dimensional polymer coating was prepared on a passivated iron electrode by modification of 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Subsequently, the electrode was healed in 0.1 M NaNO₃. Protection of passivated iron against passive film breakdown and corrosion of iron was examined by monitoring of the open-circuit potential and repeated polarization measurements of the polymer-coated and healed electrode in an aerated 0.1 M NaCl solution during immersion for many hours. Localized corrosion was markedly prevented by coverage with the polymer coating and the healing treatment in 0.1 M NaNO₃. Prominent protection of iron from corrosion in 0.1 M NaCl was observed before the breakdown occurred. The electrode surface covered with the healed passive film and polymer coating was analyzed by contact angle measurement, X-ray photoelectron spectroscopy and electron-probe microanalysis.     

Ceria/stannate multilayer coatings on AZ91D Mg alloy

In this work, CeO₂/stannate multilayer coatings on AZ91D magnesium alloy were successfully obtained by chemical conversion and sol–gel dip coating. The stannate conversion coatings were prepared from a stannate aqueous bath containing Na₂SnO₃, CH₃COONa, Na₃PO₄ and NaOH at different temperatures and immersion times. Ceria films were produced on stannate/AZ91D starting from Ce(III) nitrate solutions in H₂O. In some cases, the PVA was added as chelating agent. Ceria top coatings were fired at 200 °C for 1 h. Coating microstructure was examined by FE-SEM. Finally, the corrosion resistance features of the coatings were tested by the electrochemical impedance spectroscopy (EIS) in 3 wt.% NaCl solution. The effect of PVA addition was evaluated in terms of microstructure and corrosion resistance features. CeO₂/stannate multilayer films, 3 μm thick, uniform, well adherent and nearly crack free were obtained. The formation of CeO₂ phase was confirmed by XRD and XPS analyses. The XPS depth profiles showed a limited diffusion of Mg towards the ceramic film. The EIS tests showed a significant improvement of corrosion resistance of the multilayer coatings (~ 16.6 kΩ after 48 h in NaCl solution) with respect to the blank alloy (~ 2.4 kΩ after 48 h in NaCl solution).     

The influence of CO2, AlCl3 · 6H2O, MgCl2 · 6H2O, Na2SO4 and NaCl on the atmospheric corrosion of aluminum

The influence of salt deposits on the atmospheric corrosion of high purity Al (99.999%) was studied in the laboratory. Four chloride and sulfate-containing salts, NaCl, Na₂SO₄, AlCl₃ · 6H₂O and MgCl₂ · 6H₂O were investigated. The samples were exposed to purified humid air with careful control of the relative humidity (95%), temperature (22.0 °C), and air flow. The concentration of CO₂ was 350 ppm or <1 ppm and the exposure time was four weeks. Under the experimental conditions all four salts formed aqueous solutions on the metal surface. Mass gain and metal loss results are reported. The corroded surfaces were studied by ESEM, OM, AES and FEG/SEM equipped with EDX. The corrosion products were analyzed by gravimetry, IC and grazing incidence XRD. In the absence of CO₂, the corrosivity of the chloride salts studied increases in the order MgCl₂ · 6H₂O < AlCl₃ · 6H₂O < NaCl. Sodium chloride is very corrosive in this environment because the sodium ion supports the development of high pH in the cathodic areas, resulting in alkaline dissolution of the alumina passive film and rapid general corrosion. The low corrosivity of MgCl₂ · 6H₂O is explained by the inability of Mg²⁺ to support high pH values in the cathodic areas. In the presence of carbon dioxide, the corrosion induced by the salts studied exhibit similar rates. Carbon dioxide strongly inhibits aluminum corrosion in the presence of AlCl₃ · 6H₂O and especially, NaCl, while it is slightly corrosive in the presence of MgCl₂ · 6H₂O. The corrosion effects of CO₂ are explained in terms of its acidic properties and by the precipitation of carbonates. In the absence of CO₂, Na₂SO₄ is less corrosive than NaCl. This is explained by the lower solubility of aluminum hydroxy sulfates in comparison to the chlorides. The average corrosion rate in the presence of CO₂ is the same for both salts. The main difference is that sulfate is less efficient than chloride in causing pitting of aluminum in neutral or acidic media.     

Tribocorrosion of 316L stainless steel and TA6V4 alloy in H2SO4 media

Tribocorrosion of stainless steel 316L and titanium alloy TA6V4 has been conducted in a sulphuric acid solution using an apparatus designed and built for evaluating the joint action of corrosion and wear. The material electrochemical and wear behaviours have been investigated during friction tests under electrochemical potential control. The specimens have been submitted to friction against an alumina ball under cathodic, free and anodic potentials. The friction coefficient, the wear rate and the current density were measured and the obtained results were discussed in terms of passivating film stability and repassivation kinetics.     

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.     

Increasing the wear and corrosion resistance of magnesium alloy (AZ91D) with electrodeposition from eco-friendly copper- and trivalent chromium-plating baths

Mg alloy, AZ91D, which has a two-phase structure, was successfully electroplated in an alkaline Cu-plating bath. The Cu-coated Mg alloy specimen was further electroplated in eco-friendly acidic Cu and then trivalent Cr baths to obtain an anti-wear and anti-corrosion Cr/Cu coating. Experimental results show that the wear and corrosion resistance of the Mg alloy specimen was considerably improved by trivalent Cr electrodeposition. The hardness of the as-plated Cr deposit was drastically increased by using reduction-flame heating for 0.5 s. The above-mentioned results were measured via bonding strength, hardness, wear and corrosion tests. A superior wear and corrosion resistance was obtained when a Cu-coated Mg alloy specimen was electroplated with a trivalent Cr deposit, followed by heating with reduction-flame heating for 0.5 s.     

An ultrathin polymer coating of carboxylate self-assembled monolayer adsorbed on passivated iron to prevent iron corrosion in 0.1 M Na2SO4

For preparing an ultrathin two-dimensional polymer coating adsorbed on passivated iron, a 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer (SAM) was modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Protection of passivated iron against passive film breakdown and corrosion of iron was investigated by monitoring of the open-circuit potential and repeated polarization measurements in an aerated 0.1 M Na₂SO₄ solution during immersion for many hours. The time required for passive film breakdown of the polymer-coated electrode was markedly higher in this solution than that of the passivated one, indicating protection of the passive film from breakdown by coverage with the polymer coating. The protective efficiencies of the passive film covered with the coating were extremely high, more than 99.9% in 0.1 M Na₂SO₄ before the passive film was broken down, showing prominent cooperative suppression of iron corrosion in the solution by coverage with the passive film and polymer coating. The polymer-coated surface was characterized by contact angle measurement and electron-probe microanalysis (EPMA). Prevention of passive film breakdown and iron corrosion for the polymer-coated electrode healed in 0.1 M NaNO₃ was also examined in 0.1 M Na₂SO₄.     

Experimental and theoretical calculations on corrosion inhibition of steel in 1 M H2SO4 by crown type polyethers

The corrosion inhibitive efficiencies of two crown type polyethers, namely dibenzo-bis-imino crown ether (C-1) and dibenzo-diaza crown ether (C-2), which are macrocyclic Schiff base and its reduced form (macrocyclic amine), respectively, for the steel in 1 M H₂SO₄ have been investigated by Tafel extrapolation and linear polarization methods. Corrosion and adsorption isotherm parameters were determined from current-potential curves. The studies show that C-1 and C-2 inhibit the corrosion of the steel in H₂SO₄ solution. Semiempirical AM1 method was used for theoretical calculations. The obtained results of these calculations for the compounds were found to be consistent with the experimental findings.     

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.     

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.     

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.     

Corrosion product formation during NaCl induced atmospheric corrosion of magnesium alloy AZ91D

Magnesium alloy AZ91D was exposed in humid air at 95% relative humidity (RH) with a deposition of 70 μg/cm⁻² NaCl. The corrosion products formed and the surface electrolyte were analysed after different exposure times using ex situ and in situ FTIR spectroscopy, X-ray diffraction and Ion Chromatography. The results show that magnesium carbonates are the main solid corrosion products formed under these conditions. The corrosion products identified were the magnesium carbonates hydromagnesite (Mg₅ (CO₃)₄ (OH)₂4H₂O) and nesquehonite (MgCO₃ 3H₂O). The corrosion attack starts with the formation of magnesite at locations with higher NaCl contents. At 95% RH, a sequence of reactions was observed with the initial formation of magnesite, which transformed into nesquehonite after 2-3 days. Long exposures result in the formation of pits containing brucite (Mg(OH₂)) covered with hydromagnesite crusts. The hydromagnesite crusts restrict the transport of CO₂ and O₂ to the magnesium surface and thereby favour the formation of brucite. Analysis of the surface electrolyte showed that the NaCl applied on the surface at the beginning was essentially preserved during the initial corrosion process. Since the applied salt was not bound in sparingly soluble corrosion products a layer of NaCl electrolyte was present on the surface during the whole exposure. Thus, Na⁺ and Cl⁻ ions can participate in the corrosion process during the whole time and the availability of these species will not restrict the atmospheric corrosion of AZ91D under these conditions. It is suggested that the corrosion behaviour of AZ91D is rather controlled by factors related to the microstructure of the alloy and formation of solid carbonate containing corrosion products blocking active corrosion sites on the surface.     

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L⁻¹ H₂SO₄ solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA]_n polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases in solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L⁻¹ H₂SO₄ in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper.     

Corrosion behaviour of dc magnetron sputtered Fe1−xMgx alloy films in 3 wt% NaCl solution

Fe_1−xMg_x alloy films (with x ? 43.4 at.% Mg) were deposited by dc magnetron sputtering onto glass slide substrates. The objective of this study was to characterise the corrosion properties of these alloys in saline solution for application as new friendly environmentally sacrificial coatings in the protection of steel structures. The morphological and structural properties of the alloys were systematically studied prior to electrochemical experiments, and then the degraded surfaces were analysed to determine the composition and nature of corrosion products. Alloys with <25  at.% Mg were single-phase body-centred cubic (bcc) with enlarged lattice parameters, whereas for magnesium contents above 25 at.%, amorphisation occurred. The reactivity of the alloys in saline solution is strongly dependent on the Mg content and the alloy structure. The incorporation of magnesium leads to an open circuit potential shift of the alloy towards more negative values, that confers an attractive interest of these alloys as sacrificial coatings. A transition in corrosion activity is observed at 25 at.% Mg from which the reactivity decreases with the magnesium content increase. The evolution of the alloy corrosion behaviour is discussed in terms of structural and corrosion products evolution versus magnesium content.     

Corrosion behavior of iron-based alloys in the LiBr + ethylene glycol + H2O mixture

The corrosion resistance of 1018 carbon steel, 304 and 316 type stainless steels in the LiBr (55 wt.%) + ethylene glycol + H₂O mixture at 25, 50 and 80 °C has been studied using electrochemical techniques which included potentiodynamic polarization curves, electrochemical noise and electrochemical impedance spectroscopy techniques. Results showed that, at all tested temperature, the three steels exhibited an active-passive behavior. Carbon steel showed the highest corrosion rate, since both the passive and corrosion current density values were between two and four orders of magnitude higher than those found for both stainless steels. Similarly, the most active pitting potential values was for 1018 carbon steel. For 1018 carbon steel, the corrosion process was under a mixed diffusion and charge transfer at 25 °C, whereas at 50 and 80 °C a pure diffusion controlled process could be observed. For 316 type stainless steel, at 25 and 50 °C a species adsorption controlled process was observed, whereas at 80 °C a diffusion controlled mechanism was present. Additionally, at 25 °C, the three steels were more susceptible to uniform type of corrosion, whereas at 50 and 80 °C they were very susceptible to localized type of corrosion.     

The anodic dissolution of Mg in NaCl and Na2SO4 electrolytes by atomic emission spectroelectrochemistry

The dissolution of Mg has been investigated with atomic emission spectroelectrochemistry at open circuit and during potentiostatic control in chloride (NaCl) and sulfate (Na₂SO₄) electrolytes. A dissolution stoichiometry of approximately n = 2 is observed under all the conditions of these experiments with no evidence for the commonly invoked Mg⁺ intermediate. Nevertheless, in chloride electrolyte it is shown that anodic polarization results in a cathodic activation of the surface with increased hydrogen production during the polarization and an increased corrosion rate following the pulse. The formation of insoluble Mg oxides/hydroxides was also investigated in the sulfate electrolyte.     

AZ91D镁合金微弧氧化膜在不同浓度NaCl溶液中的腐蚀行为(英文)

采用微弧氧化技术(MAO)在镁合金 AZ91D 表面制备微弧氧化陶瓷膜。利用电化学技术和浸泡实验研究该镁合金试样在不同浓度(0.1%,0.5%,1.0%,3.5%和 5.0%,质量分数) NaCl 溶液中的腐蚀行为。结果表明,试样的腐蚀速率随着氯离子浓度的升高而增大。在较高浓度(1.0%,3.5%和 5.0%)的 NaCl 溶液中的主要腐蚀形式是点蚀,而在较低浓度(0.1%和 0.5%)中是全面腐蚀。腐蚀过程可以分为两个阶段:亚稳态蚀点的出现和蚀点的生长。根据腐蚀过程中阻抗谱的特点,对镁合金微弧氧化膜试样在不同浓度 NaCl 溶液中浸泡 120 h 提出了不同的等效电路来模拟其腐蚀行为。     

Baking treatment effect on materials characteristics and electrochemical behavior of anodic film formed on AZ91D magnesium alloy

The composition and microstructure of the anodic films formed on AZ91D Mg alloy, with or without baking, were investigated. The associated corrosion behavior of the anodized alloy in 3.5 wt% NaCl solution was also examined using electrochemical impedance spectroscopy (EIS). The results show that MgO was the main component in the anodic film which also contained some Mg(OH)₂, Al₂O₃, Al(OH)₃, and MgAl₂O₄. Both the amorphous and crystalline forms of anodic film were identified. The degree of crystallinity depended on baking temperature, which increased with increasing temperature in the range of 50-250 °C. The amounts of MgO and Al₂O₃ increased as a result of a dehydration reaction. The polarization resistance of anodized Mg alloy was improved significantly by increasing the oxide content in the anodic film. An optimum value of polarization resistance of anodic film was obtained for the alloy baked at 150 °C for 2 h followed by air cooling.