The electrochemical behaviour of the bright chromium deposits plated with direct- and pulse-current in 1 M H2SO4

The electrochemical behaviour of bright Cr-deposits was studied in 1 M H₂SO₄ at 27 °C. The bright Cr-deposits were electroplated by using direct- or pulse-current (DC or PC) at 50 °C in a sulfate-catalyzed chromic acid bath with plating current densities of 30, 40, 50 and 60 A/dm² respectively. The results show that the surface-crack density of bright Cr-deposits plated with either DC or PC decreased with increasing the plating current density, whereas the passive current densities in their anodic polarization curves increased when plating current densities increased. From the results of electrochemical tests, it was found that passive and active dissolution rates of the Cr-deposits were not affected by the amount of the surface cracks developed on the Cr-deposit. Corrosion resistance of the Cr-deposit plated with PC was better than that with DC. The critical current density in the anodic polarization curve of the former is approximately one order less than that of the latter. The Cr-deposit plated with PC can be passivated more easily than that with DC. The rate of active dissolution of Cr deposits is much higher than that of passive dissolution. The aforementioned results can be recognized with AC impedance test polarized in passive and open-circuit potentials.     

Effect of Different Degrees of Sensitization on the EIS Response of 316L and 316 SS in Transpassive Region

Different heat treatments were conducted on 316L and 316 stainless steels, and the sensitized specimens were characterized using anodic polarization and EIS tests in 0.5 M H₂SO₄ containing 0.01 molar KSCN. The potential ranges related to the transpassive region related to each specimen were determined. The EIS experiments were conducted at different potentials in that region, and the results showed the presence of three different regions, namely the anodic dissolution of the passive layer, dissolution of the grain boundaries, and the occurrence of pitting corrosion owing to the variations in the anodic potential. The higher the applied sensitization temperature, the lower the obtained charge-transfer resistance (R _ct) values, but healing effect was observed at the temperatures above 600 °C for these alloys.     

The transpassive dissolution mechanism of highly alloyed stainless steels: I. Experimental results and modelling procedure

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring-disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

Temperature effect in the corrosion resistance of Ni-Fe-Cr alloy in chloride medium

The corrosion susceptibility of alloy 33 in 0.5 mol/L sodium sulphate solutions containing or not 0.1 mol/L sodium chloride was tested at three different temperatures: 22 °C, 40 °C and 60 °C. Electrochemical studies were performed using corrosion potential measurements (E_corr) as well as potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. Corrosion potential measurements showed that alloy 33 was passivated by a previously air formed film which was not destroyed during immersion in both solutions. No corrosion was observed during these tests although the temperature affected the film. Potentiodynamic polarization experiments showed that at high anodic potentials the previous film was broken up, and localized corrosion occurred in both solutions and at the three temperatures tested. Electrochemical impedance spectroscopy tests confirmed the presence of a stable passive film on the alloy surface at open circuit potential. Mott-Schottky analysis indicated that the passive film is an n-type semiconductor due to the presence of point defects of donor species, such as oxygen vacancies and interstitial metallic cations. As the potential increases the Cr(III) present in the barrier layer oxidizes producing Cr(VI) soluble species. The dissolution creates metallic cation vacancies that are acceptor species and the film changes from n-type to p-type semiconductor. The passive film rupture and the following localized attack are related to the drastic oxidative dissolution of the film at high anodic potentials, independent of its p-nature, chloride presence or increased temperature.     

The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring–disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

Electrochemical study on hot corrosion of Si-modified aluminide coated In-738LC in Na2SO4-20 wt.% NaCl melt at 750 °C

The corrosion performance of the slurry Si-modified aluminide coating on the nickel base superalloy In-738LC exposed to low temperature hot corrosion condition has been investigated in Na₂SO₄-20 wt.% NaCl melt at 750 °C by combined use of the anodic polarization and characterization techniques.The coated specimen showed a passive behavior up to −0.460 V vs. Ag/AgCl (0.1 mol fraction) reference electrode, followed by a rapid increase in anodic current due to localized attack in the higher potential region. In the passive region, the anodic dissolution of constituents of the coating occurred through the passive film, probably SiO₂, at slow rate of 20-30 μA/cm². The passive current for the Si-modified coating was two orders of magnitude smaller than that for bare In-738LC, which is known as Cr₂O₃ former in this melt. This indicates that the SiO₂ film is chemically more stable than Cr₂O₃ film under this condition. However, pitting-like corrosion commenced around −0.460 V and proceeded at the high rate of 100 mA/cm² in the higher potential region than +0.400 V. The corrosion products formed on the coating polarized in different anodic potentials were characterized by SEM, EDS and XRD. It was found from the characterization that oxidation was dominant attack mode and no considerable sulfidation occurred at 750 °C. The SiO₂ oxide was not characterized in the passive region because the thickness of the passive film was extremely thin, but was detected as the primary oxide in the localized corrosion region, where the selective oxidation of Al was observed by further progress of the corrosion attack front into the inner layer of coating.     

Impedance investigation of the anodic iron dissolution in perchloric acid solution

The anodic iron dissolution in 0.5 mol dm⁻³ perchloric acid (HClO₄) was investigated by the electrochemical impedance spectroscopy, the potentiodynamic sweep and the scanning electron microscopy measurements. The anodic polarization behavior of iron in HClO₄ solution showed that the strong current oscillations occurred in a narrow potential region, particularly the pitting corrosion was observed in the active dissolution region. These characteristics were quite different from those of iron in the sulfuric acid (H₂SO₄). At the potentials 82 and 132 mV more positive than the corrosion potential (−482 mV vs. SCE), the impedance spectra for the iron in HClO₄ displayed two inductive arcs; however, by gradually increasing potential the lower frequency inductive arc disappeared at −300 mV at first, and then the higher frequency inductive arc changed into a capacitive arc at −250 mV. Based on the impedance display of iron at various potentials, a reaction model involving two adsorbed intermediate species was proposed, in terms of which the impedance behavior at different potentials were described. Occurrence of the pitting corrosion in active dissolution region was explained.     

硫酸溶液中铁在过钝化区电极行为

本文应用电位衰减和交流阻抗等电化学方法对H_2SO_4溶液中处于过钝化区的铁的钝化膜的性质进行了研究。发现在钝化-过钝化过渡区域,钝化膜的厚度随着电位的升高而下降。当电位升到1800mV(VS·SCE)以后,钝化膜的厚度不再随电位的变化而变化。对不同电位下的交流阻抗频谱图进行了拟合分析,得到了一些与钝化膜的性质有关的参数。     

The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

The effect of pH and solution anion on the kinetics of transpassive dissolution of highly alloyed austenitic stainless steels (AISI 904L, 254SMO and 654SMO) was studied by a combination of electrochemical techniques. The experiments were performed in 0.5 M sulphate and 0.5 M chloride solutions, and in an equimolar mixture of the two. The transpassive dissolution was found to start at higher potentials in solutions with higher pH. The rate of transpassive dissolution was shown to decrease with increasing pH and to be the lowest in chloride solutions and the highest in sulphate electrolytes. The steady-state current vs. potential curves and the impedance spectra of the studied materials in the transpassive potential region were found to be consistent with a proposed kinetic model. The model describes the process as dissolution of Cr as Cr(VI) and Fe as Fe(III) through the anodic oxide film via parallel reaction paths. The kinetic parameters of the model in solutions with different pH values and different anions were determined. The role of pH and solution anion in the transpassive dissolution process is discussed in relation to changes induced by these parameters in the composition of the anodic passive film. The factors determining the efficiency of Fe as a secondary passivating agent are also considered.     

Effect of electrolyte composition on the active-to-passive transition behavior of 2205 duplex stainless steel in H2SO4/HCl solutions

Selective dissolution could occur in duplex stainless steels (DSSs) due to the difference in chemical composition between the two constituent phases. In this study, the effect of H₂SO₄/HCl composition on the selective dissolution behavior was investigated. The results indicated that there were two distinct peaks appeared in the active-to-passive transition region in the polarization curve. The peak appeared at a lower potential region was associated with the preferential dissolution of ferrite phase while that for austenite at a higher potential. In the concentration ranges of 0.25-2 M of H₂SO₄ and 0.25-2 M of HCl, the magnitude of the peak anodic current density and the resolution between these two peaks greatly depended on the composition of H₂SO₄/HCl. However, the anodic peaks corresponding to the respective dissolutions of ferrite and austenite became less distinguishable when the concentrations of HCl exceeded 1.2 M. Image analysis using scanning electron microscopy (SEM) was performed to confirm the selective dissolution of each constituent phase after potentiostatic polarization at the respective anodic peak potential.     

The corrosion behavior of Cu–Al and Cu–Al–Be shape-memory alloys in 0.5 M H2SO4 solution

The corrosion behavior of Cu–Al and Cu–Al–Be (0.55–1.0 wt%) shape-memory alloys in 0.5 M H₂SO₄ solution at 25 °C was studied by means of anodic polarization, cyclic voltammetry, and alternative current impedance measurements. The results of anodic polarization test show that anodic dissolution rates of alloys decreased slightly with increasing the concentrations of aluminum or beryllium. Severe intergranular corrosion of Cu–Al alloy was observed after alternative current impedance measurement performed at the anodic potential of 0.6 V. However, the addition of a small amount of beryllium was effective to prevent the intergranular corrosion. The effect of beryllium addition on the prevention of intergranular corrosion is possibly attributed to the diffusion of beryllium atoms into grain boundaries, which in turn deactivates the grain boundaries.     

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 effect of cysteine on the corrosion of 304L stainless steel in sulphuric acid

The effect of cysteine on the corrosion of 304L stainless steel in 1 mol l⁻¹ H₂SO₄ was studied using open-circuit potential measurements, anodic polarization curves, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). All the electrochemical measurements obtained in the presence of low cysteine concentration (10⁻⁶-10⁻⁵ mol l⁻¹) presented the same behaviour as those obtained in the absence of cysteine, a passivated steel surface. However, for higher cysteine concentrations (10⁻⁴-10⁻² mol l⁻¹), a different behaviour was observed: the corrosion potential stabilized at a more negative value; an active region was observed in the anodic polarization curves and the electrochemical impedance diagrams showed an inductive loop at lower frequencies and a much lower polarization resistance. These results show that the presence of cysteine at high concentration turns the surface of 304L stainless steel electrochemically active, probably dissolving the passivation layer and promoting the stainless steel anodic dissolution. SEM experiments performed after immersion experiments at corrosion potential were in good agreement with the electrochemical results.     

An investigation on the effect of bleaching environment on pitting corrosion and transpassive dissolution of 316 stainless steel

Pitting corrosion and transpassive dissolution of 316 stainless steel in a solution containing five percent of commercial bleaching liquid was investigated by employing potentiodynamic polarization method and recording corrosion potential during immersion. Today commercial bleaching liquids are widely used as a cleaner additive. Therefore those house appliances made from stainless steels are in contact with aqueous solution containing bleaching liquid. This may cause severe localized corrosion and transpassive dissolution. In order to investigate the possibility of tranpassive dissolution of stainless steel by bleaching liquid, potentiodynamic polarization and recording the variation of corrosion potential of specimens were carried out in 0.2 M Na₂SO₄ solution containing 5%wt. commercial bleaching liquid. A 500 mV drop in transpassive potential and also instantaneously ennobled corrosion potential revealed the possibility of transpassive dissolution due to the oxidizing effect of the species such as free chlorine and its derivatives in bleaching liquid. Evaluation of the occurrence of localized corrosion at the presence of Cl^? and bleaching liquid was investigated by similar electrochemical experiments in 0.2 M Na₂SO₄ + 0.4 M NaCl containing 5%wt. bleaching solution. Initiation of stable pitting at potentials lower than the transpassive potential as well as a sharp increase of the corrosion potential in this environment demonstrates the possibility of pitting corrosion.     

Detection of deleterious phases in duplex stainless steel by weak galvanostatic polarization in alkaline solution

A novel electrochemical procedure has been developed to quantify the presence of secondary phases (nitride, χ, σ) in duplex stainless steel. This is based on anodic galvanostatic polarization in a weakly alkaline solution to detect the transpassive dissolution of Cr- and Mo-rich phases. By adjusting the current density, an almost linear relation can be obtained between the “time to reach a given potential” and impact toughness. The material used was UNS S32760 (Zeron 100), isothermally aged at 650, 750, 825 and 850 °C. Distinctive features on the potential-time curves were correlated with the microstructure by examining reacted surfaces with backscattered imaging in the SEM.     

The effect of 180 °C-annealing on the electrochemical behavior of nano-thick zinc-electroplated copper in aqueous solutions with different pH

The anodic polarization and a.c. impedance measurements of 4 nm- and 25 nm-zinc-electroplated copper specimens were conducted in aqueous solutions with four different pH-values. The nano-thick zinc-electroplated copper was tested after electroplating and annealing at 180 °C for 1, 2 and 3 h, respectively. The results showed that the open-circuit potential (OCP) of 25 nm-zinc electroplated copper shifted toward noble potential after annealing. A more noble OCP of 25 nm zinc-electroplated copper could be achieved when zinc plated copper was annealed at 180 °C up to 1 h. Similar change was found for 4 nm-zinc electroplated copper only in neutral and alkaline solutions. The a.c. impedance response of all nano-thick zinc-electroplated copper corresponded to two Randle’s circuits in series, in which the circuit measured in a high frequency region of their Nyquist diagrams revealed the electrochemical behavior of nano-thick zinc deposits. The charge transfer resistance of the nano-thick zinc electroplated copper was significantly raised after annealing at 180 °C when tested in pH 9.5 solution. Microstructures of the aforementioned nano-thick zinc electroplated copper were examined with cross-sectional TEM specimens. A distinct phase interface between zinc and copper was observed for as plated specimens, while alloying of zinc and copper at the interface was detected after annealing at 180 °C for 1 h. Electroplated zinc diffused into the copper foil during the 180 °C-annealing and the corrosion potential of the anodic polarization curve indicated the condition of the alloy surface. The annealing effect of 4 nm- and 25 nm-zinc electroplated copper specimens could be related to the results of electrochemical measurement.     

Effect of Nitrogen and Sensitization on the Microstructure and Pitting Corrosion Behavior of AISI Type 316LN Stainless Steels

High-nitrogen stainless steels (SS) are receiving increased attention because of the advantages of their strength over the SS with nominal composition. However, they are susceptible to dichromium nitride (Cr₂N) precipitation during thermal exposure between 873 and 1323 K resulting in sensitization and subsequent intergranular corrosion. Round tensile specimens of AISI type 316LN SS, with three different nitrogen content 0.07, 0.14, and 0.22 wt.% in mill-annealed and sensitized (973 K for 24 h) condition were studied for their pitting corrosion behavior. The results of the potentiodynamic anodic polarization studies were correlated with the results obtained using electrochemical impedance spectroscopy (EIS) technique. Critical pitting potential (E _pp) increased with increasing nitrogen content but the same was found to decrease on aging. The parameters indicating passive film stability measured by EIS revealed faster passive film dissolution as indicated by low polarization resistance, in sensitized condition and vice-versa in mill-annealed condition. The EIS results correlated well with the variation in the respective E _pp obtained from the potentiodynamic polarization diagrams.     

电弧喷涂Al-Zn-Si-RE合金涂层在3.5%NaCl溶液中的电化学腐蚀行为(英文)

采用电弧喷涂方法在低碳钢表面获得高铝含量的Al-Zn-Si-RE涂层。通过测量Al-Zn-Si-RE涂层在3.5%NaCl溶液中的动电位极化曲线,腐蚀电位-时间曲线和电化学阻抗谱,系统地研究涂层的电化学腐蚀行为。通过将测量电化学阻抗谱拟合成等效电路图,研究涂层在3.5%NaCl溶液中浸泡不同时间的阻抗行为。结果表明:Al-Zn-Si-RE涂层与Zn-15Al涂层具有相似的极化行为,阳极极化曲线均无钝化特征,仅呈现出活性溶解,但其腐蚀性能优于Zn-15Al涂层。Al-Zn-Si-RE涂层可以给钢基体提供有效的牺牲阳极保护作用,且牺牲阳极保护作用在涂层腐蚀过程中占主导地位。此外,腐蚀电位-时间曲线和电化学阻抗谱结果表明:在浸泡过程中存在点蚀-溶解-再沉积、活化溶解、阴极保护、腐蚀产物引起的物理屏蔽和涂层失效五个腐蚀阶段。     

Corrosion resistance of nickel in artificial sweat and synthetic seawater

The corrosion resistance of nickel 200 has been determined in artificial sweats (perspiration) and in synthetic seawater by several electrochemical methods. Nickel 200 is not stable in the two electrolytes investigated and the attack occurs with the formation of pits. The electrochemical behaviour is characterized by a short passive region with a current density of about 0.1 mA/cm² then by a transpassive region. The corrosion rate has been measured in N₂-and O₂-saturated electroytes by the potentiostatic (10 mV potential step per min), polarization resistance in the vicinity of the corrosion potential and ac impedance methods. The three techniques gave comparable results. Corrosion rates were roughly 10 times larger in artificial sweat than in seawater. Nickel 200 cannot be used for application where it may be in direct contact with the skin because of its high corrosion rate in oxygenated sweat. The released nickel ion is responsible for contact dermatitis observed in some individuals.     

Corrosion of stainless steel grades in H2O/KOH 50% at 120 °C: AISI304 austenitic and 2205 duplex

We report on the corrosion of austenitic (AISI304) and duplex (2205) stainless steels in H₂O/KOH 50% at 120 °C. The research is based on a combination of electrochemical, structural and compositional analyses, aimed at assessing the surface modifications resulting from anodic attack and their impact on corrosion resistance. Linear sweep voltammetry and electrochemical impedance spectrometry measurements were carried out in an air‐tight high‐temperature cell. In‐plane and cross‐sectional SEM micrography, X‐ray diffractometry and EDX profiling were used to characterise samples attacked under electrochemically controlled conditions. Electrochemical results have shown that AISI304 exhibits a complex passivating behaviour, while the anodic electrokinetics of the duplex is characterised by mixed kinetic control. AISI304 was found to fail by intergranular corrosion and to be covered: in passive conditions by acicular compounds and in transpassive conditions by a compact layer of corrosion products. Duplex samples, instead, exhibit an uniform form of corrosion morphology and bear a compact layer of corrosion products both in passive and in transpassive conditions.