Influence of the electrolyte composition and temperature on the transpassive dissolution of austenitic stainless steels in simulated bleaching solutions

The transpassive corrosion of highly alloyed austenitic stainless steels—UNS N08904, UNS S31254 and UNS S32654—was investigated at 20 and 70 °C in a range of simulated bleaching solutions with conventional and rotating ring-disc electrode voltammetry, as well as electrochemical impedance spectroscopy. The overall transpassive oxidation rate of UNS S32654 was found to be much higher than that of the other two alloys. The general features of the impedance spectra demonstrate that transpassive dissolution is favoured for UNS S32654 and secondary passivation predominates for the two other steels. The addition of oxalic acid resulted in a significant increase of the transpassive oxidation rate at both temperatures. At room temperature, the addition of diethylenetriaminopentaacetic acid (DTPA) led to a decrease of the transpassive oxidation rate, especially at pH 3. Conversely, the addition of DTPA to the pH 3 solution at 70 °C has been found to increase the transpassive oxidation rate. A kinetic model of the process is proposed, featuring a two-step transpassive dissolution of Cr via a Cr(VI) intermediate species and taking into account the dissolution of Fe(III) through the anodic film. The model has been found to be in quantitative agreement with the steady-state current versus potential curves and the impedance spectra. The kinetic parameters of transpassive dissolution have been determined and the relevance of their values is discussed.     

Transpassive dissolution of Ni-Cr alloys in sulphate solutions—comparison between a model alloy and two industrial alloys

The application of a general model for the transpassive dissolution mechanism of binary Ni-based alloys to industrial alloys, Alloy 600 and Alloy C276, containing Ni, Cr, Fe and Mo, in 1 M sulphate solutions at pH 0 and 5 is described. A comparison of the electrochemical behaviour of these two alloys to a binary Ni-15%Cr alloy is also included. The techniques used were ring-disc voltammetry, impedance spectroscopy and resistance measurements. Soluble high-valency products were found to be released in a considerable amount from all the materials. The presence of Mo in Alloy C276 was found to increase the transpassive oxidation rate in comparison to alloys 600 and Ni-15%Cr at pH 0, but the same effect of Mo is not so well pronounced at pH 5. The mechanism of transpassive dissolution was found to be similar on every material at pH 0. At pH 5 the mechanism of the transpassive dissolution on Alloy C276 at high overpotentials is different from that at low overpotentials or from that at pH 0. This change is concluded to be due to the increased effect of adsorbed intermediates at the film/solution interface. The model was found to reproduce the steady state current and the impedance spectra satisfactorily.     

Oxidative dissolution and anion-assisted solubilisation in the transpassive state of nickel-chromium alloys

The transpassive state of pure Ni, Cr and two Ni-Cr alloys (10 and 20 wt.% Cr) in 14.8 M H₃PO₄ is studied by voltammetric, rotating ring-disc electrode and impedance spectroscopic measurements. The results indicate that the rate of transpassive dissolution of the alloys in a major part of the transpassive range is higher than the rate of this process for both pure metals. A kinetic model retaining the essential features of the corresponding models for the pure metals proposed in the literature has been found to reproduce both the steady-state current versus potential curves and the ac impedance spectra in the transpassive range. The parameters of the model are determined by a fitting procedure and the relevance of their values for the relative importance of two possible pathways in the transpassive state—oxidative dissolution and anion-assisted solubilisation—are discussed.     

Passive and transpassive behaviour of CoCrMo in simulated biological solutions

In this work, the behaviour of a CoCrMo alloy under simulated body conditions was investigated. More specifically, the electrochemical properties of the alloy and the relevant mechanisms in the passive and transpassive states were studied in detail. Electrochemical techniques such as potentiodynamic and potentiostatic polarisation, cyclic voltammetry, rotating disc electrode and electrochemical impedance spectroscopy were employed. Further, ex situ X-ray photoelectron spectroscopy analysis of the passive films was carried out. A good correlation between the results obtained from all the experimental techniques was achieved. Overall, it was found that the passive film on CoCrMo changed in composition and thickness with both potential and time. The passive behaviour of the CrCrMo alloy is due to a formation an oxide film highly enriched with Cr (≈90% Cr oxides) on the alloy surface. The passive and transpassive behaviour of the alloy is hence dominated by the alloying element Cr. In the transpassive region, strong thickening of the oxide film takes place, combined with a change in the composition of the film, and strongly increased dissolution rate. In the transpassive region, all alloying elements dissolve according to the composition of the alloy. The metal ion release is also very strongly enhanced by cyclic variation of the potential between reducing and oxidizing conditions. In this case, during activation/repassivation cycles, cobalt dissolution is greater than expected from the composition of the alloy. Therefore, active dissolution behaviour is mainly dominated by the alloying element Co.     

The improvement of the corrosion resistance of 309 stainless steel in the transpassive region by nano-crystallization

The effect of nano-crystallization on the corrosion behavior of 309 stainless steel in the transpassive region was investigated in 0.5 M Na₂SO₄ (pH 2) solution. Three parts defined as transpassive dissolution, secondary passivity and oxygen evolution can be observed in the transpassive potential region of the anodic polarization curves. In the whole transpassive region the nano-crystalline coating has a smaller corrosion current density than the bulk steel, which indicates the transpassive dissolution rate is decreased by nano-crystallization. In addition, there is an obvious difference in the surface micrographs of the two materials at transpassive potentials, as scanning electron microscopy (SEM) shows. The electron probe microanalysis (EPMA) reveals that nano-crystallization improves the homogeneity of Cr on the surface. Mott-Schottky plots displays that the carrier density of the oxide film in the transpassive region is decreased by nano-crystallization. Thus, the interfacial reactions are decelerated and the corrosion resistance of the stainless steel in the transpassive region has been greatly improved by nano-crystallization.     

Photoelectrochemical analysis on the passive film formed on Fe-20Cr in pH 8.5 buffer solution

The electronic properties of passive film formed on Fe-20Cr stainless steel in pH 8.5 buffer solution were examined by the photocurrent measurements of the film. The passive film on Fe-20Cr exhibited an n-type semiconductor, which was confirmed by anodic photocurrent. The photocurrent spectrum for the passive films formed on Fe-20Cr was almost same in shape to that for the passive film on Fe except for the large difference in photocurrent intensity, which demonstrated that the passive film on Fe-20Cr is composed of Cr-substituted γ-Fe₂O₃ involving the d-d and p-d electron transitions. However, the large difference in photocurrent intensity for passive film between Fe and Fe-20Cr was due presumably to the fact that Cr³⁺ ions in passive film act as effective recombination sites of electron-hole pairs. The abrupt increase in the photocurrent intensity for the passive film formed on Fe-20Cr at a transpassive potential is due presumably to the decrease in the recombination site resulting from the reduction of Cr³⁺ content accompanying the oxidation of Cr³⁺ to Cr⁶⁺ in transpassive region.     

Anodic film studies on nickel under high rate transpassive dissolution conditions

Coulometry and Auger Electron Spectroscopy (AES) were employed to study thickness and composition of anodic films formed on nickel under high rate transpassive dissolution conditions. Nickel anodes were polarized at constant current densities up to 30 A/cm² in alkaline nitrate electrolytes of different nitrate and hydroxyl ion concentration using a flow channel cell with a constant electrolyte flow velocity of 10m/sec. Results show that with increasing current density film thickness goes through a maximum. Nitrogen is detected at the apparent film metal interface in the current region where metal dissolution occurs. No correlation between anodic film thickness and dissolution efficiency is found. The data, together with previous observations, suggest that high rate transpassive dissolution takes place from film free sites.     

Atomic emission spectroelectrochemistry applied to dealloying phenomena II. Selective dissolution of iron and chromium during active-passive cycles of an austenitic stainless steel

Atomic emission spectroelectrochemistry was used to investigate selective dissolution of a 304 austenitic stainless steel sample in 2 M H₂SO₄. The partial dissolution rates of Fe, Cr, Ni, Mn, Mo, and Cu were measured as function of time during a series of potentiostatic triggered activation/passivation cycles. When first exposed to sulfuric acid solution, the steel sample was in a passive state with a total steady state ionic dissolution rate expressed as an equivalent current density of 10 μA cm⁻². A transition into the active and passive state could be triggered by cathodic (−700 mV vs. Ag/AgCl) and anodic (+400 to +700 mV vs. Ag/AgCl) potentiostatic pulses respectively of variable time. Excess Cr dissolution was observed during the activation cycle as compared to Fe and a depletion of Cr dissolution was observed during the passivation cycle. These results are interpreted in terms of the dissolution of a Cr rich passive layer during activation and selective dissolution of Fe, Mn, Ni and other elements to form a Cr rich passive layer during passivation. Quantitative analysis of the excess Cr showed that the residual film contained approximately 0.38 μg Cr/cm². Fe does not appear to be incorporated into the film at this early stage of passive film growth. Residual films of metallic nickel and copper were formed on the surface during the active period that subsequently dissolved during passivation.     

A kinetical model for the electrochemical grooving of grain boundaries

In the case of FeNiCr alloys (without precipitation), we propose an electrochemical method which allows us to obtain a reproducible selective corrosion of grain boundaries (H₂SO₄-2N-25°C in the transpassive domain). We establish a model of dissolution to explain the morphology of etched grooves. From this model we deduce a parameter α₀ which characterizes the intergranular corrosion susceptibility of a given alloy.Electrochemical kinetic allows us to calculate the ratio of the density of active sites at the emergence of the grain boundary and on the surface of the grain. This electrochemical method permits us to study the effects of the segregation phenomena, of composition alloy and of grain boundary structure on intergranular corrosion.     

Transpassive dissolution of mild steel in NaNO3 electrolytes

A study has been made of the transpassive dissolution of mild steel in sodium nitrate solution over a range of current densities from 2 to 100 A cm^–2. The dissolution current efficiency and the anode potential free from the electrolyte IR component were measured in a flow cell; optical and scanning electron microscopy were then used to examine the sample surfaces after the dissolution tests. The results show that during the early stage of transpassive dissolution, the mild steel is covered with a compact, electronically conductive Fe₃O₄ film, and the current is consumed mainly in oxygen generation on the film/electrolyte interface. With increasing anode potential and current density, this film is gradually broken and the underlying metal surface becomes exposed to the electrolyte. At this stage, iron dissolution begins at a high rate. The film rupturing process is strongly dependent on nitrate concentration; the higher this is, the lower is the current density required to rupture the film.     

Mechanism of anodic dissolution of iron-chromium alloys investigated by electrode impedances—II. Elaboration of the reaction model

On the basis of experimental results exhibited in Part I, a reaction model of the dissolution—passivation process of FeCr alloy in acidified sulfate media is proposed. This reaction mechanism of alloy is considered as that of Fe perturbed by the Cr addition. However, the change in the dissolution—passivation process of Fe alone is not sufficient to interpret the whole results. Hence, firstly an interaction between adsorbed species was introduced: a chromium passivating species hinders drastically the rate of the Fe(II)_ads→ Fe(II)_sol dissolution path. Finally, it was also considered that the uniform dissolution of alloy is accounted for by the change of the surface concentration of alloy elements. The proposed model interprets satisfactorily the experimental results.     

Atomic emission spectroelectrochemistry applied to dealloying phenomena: I. The formation and dissolution of residual copper films on stainless steel

The rates of elemental dissolution were measured for a 304 stainless steel containing 0.19% Cu in real time during linear sweep voltammetry experiments using the atomic emission spectroelectrochemistry (AESEC) method. The results demonstrate that Fe, Cr, Ni, Mn, and Mo dissolve simultaneously leaving a residual copper film that inhibits the steel dissolution. The formation and dissolution of the copper film leads to the appearance of two peaks in the anodic dissolution transient, one due to inhibition of steel by residual copper and the other due to the formation of the passive film. The addition of NaCl to the electrolyte results in a marked increase in the intensity of the second dissolution peak, while hardly affecting the first peak. This is interpreted in terms of the lowering of copper dissolution potential by chloride ions due to the stabilization of CuCl₂⁻. A simple phenomenological kinetic model is used to simulate the variation of dissolution rate with potential.     

Surface modification of Inconel-600 by growth of a hydrous oxide film

In this study, Inconel-600 (Ni–Cr–Fe alloy) was modified by repetitive potential cycling in 1M NaOH solution. This procedure induced the growth of a hydrous oxide film, following the same mechanism as previously reported for pure nickel in alkaline solution under similar experimental conditions. The electrode, modified by 30 repetitive potential cycles, exhibited about one order of magnitude lower current density in both the active and passive ranges of the anodic polarization curve. Selective dissolution of nickel and iron in acid solution was determined by rotating ring–disc electrode measurements. This process resulted in chromium enrichment as shown by use of X-ray electron spectroscopy. The proposed model for the enhanced stability of the modified electrode agrees with the percolation model of passivity of stainless steels and Fe–Cr alloys.     

Electropolishing of metals in alcoholic solution of sulphuric acid

The potentiodynamic polarization curves of iron, nickel, cobalt, molybdenum, copper and iron-nickel and cobalt-nickel alloys were measured in the polishing solution of 1M H₂SO₄ in CH₃OH. The above mentioned metals and alloys may be divided into three groups: metals and alloys with high dissolution rate in the active state in which the polishing follows immediately behind the active dissolution region (Fe, Co and Ni-Fe and NiCo alloys with a low nickel content), metals and alloys with low passivating current density that become passive at first and the polishing takes place behind the region of localized corrosion (nickel and NiFe and NiCo alloys with a high nickel content) are metals that are polished in the transpassive region (molybdenum).     

Transpassive dissolution of iron in sulphuric acid solution

Anodic oxidation characteristics of iron in 3, 10 and 12 mol dm^–3 sulphuric acid solutions have been studied in the transpassive region. Dissolution current efficiency measurements have been carried out using potentiostatic current-voltage curves and solution analysis techniques. The current-voltage curves were split into metal dissolution and oxygen evolution curves assuming that the iron goes into solution as Fe³⁺. The current density value in the passive region increased whereas the current density in the transpassive region decreased with the increase of sulphuric acid solution concentration. In order to obtain information about the nature of the films present on the surface, potential decay curves from different anodic potentials in the transpassive region have been recorded. It seems that there is no passive film present on the specimen surface in 12 mol dm^–3 sulphuric acid solution and a better surface finish is obtained after the dissolution. Depth profile analysis of oxide films by the AES technique in 3 mol dm^–3 sulphuric solution reveals that the sulphur concentration is maximum at the metal/oxide interface rather than at the oxide/electrolyte solution interface as required by an ion exchange mechanism for film dissolution.     

Nucleation and growth of anodic films on stainless steel alloys I. Influence of minor alloying elements and applied potential on passive film growth

The influence of minor alloying elements (Mo, V, W) when added to a Fe18Cr alloy on the ability of a passive film to nucleate and grow on a freshly generated metal surface, and on the subsequent stability of the film was investigated as a function of electrolyte composition and applied potential using a scratch chronoamperometric technique. Mo and V decreased the rate of active dissolution prior to passivation, allowing the onset of passivation to occur more rapidly, and also improved the stability of the passive film, especially to attack by Cl^– in acidic (H₂SO₄, HClO₄) solutions. W additions had a detrimental effect on the repassivation behaviour of Fe18Cr. Repassivation of the scratch scars was evaluated, from the current transients, in terms of the number of layers of surface film formed.     

Electrochemical and XPS studies of sputter-deposited ternary Mn-Ta-Cr alloys in chloride-free and chloride-containing sulphuric acid solutions

Amorphous manganese-rich (67-80 at.%) Mn-Ta-Cr alloy films were prepared by DC magnetron sputtering method. The corrosion behavior and stability of the Mn-Ta-Cr alloy films were examined in chloride-free and -containing 1 M H₂SO₄. AC and DC electrochemical techniques in combination with XPS analysis were used. Mn-Ta-Cr alloys exhibited very high corrosion resistance and stability up to transpassive dissolution region of chromium. The high corrosion resistance of Mn-Ta-Cr sputtered films is based on the formation of double oxyhydroxide passive film composed mainly of chromium and tantalum. The partial substitution of tantalum with chromium improves the corrosion resistance of the sputter-deposited alloys via accelerating the preferential dissolution of manganese and stabilizing alloy/passive film interface. A change in the passive film structure was observed when the alloys were anodically polarized at potentials higher than 0.6 V (SCE).     

Steel corrosion in alkaline batteries

During extended shelf storage and accelerated aging, low carbon steel may corrode producing soluble iron species that cause internal cell shorting and/or gassing (leakage), thus undermining battery reliability. Soluble iron may be generated from the active/passive and/or transpassive dissolution of the battery can steel. To minimize corrosion effects in commercial battery applications, NiCo plated steel is typically used. This report focuses on corrosion behavior of pure metals (iron, nickel, and cobalt) in 40% KOH at temperatures between 20 °C and 80 °C. A marked difference is found for the elements regarding the actual passivating behavior with time and temperature. As expected, nickel spontaneously passivates at all temperatures under study (20-80 °C). Cobalt on the other hand, is active at all temperatures but shows an active/passive-transition. Iron spontaneously passivates only at temperatures below 60 °C and activates at temperatures >60 °C. At sufficiently anodic potentials, passivity of Fe is lost by transpassive Fe dissolution to form ferrates [FeO₄]²⁻. The latter is considered the most likely cause for corrosion-induced failure in alkaline batteries.     

海绵钛中Fe,Ni和Cr杂质引入过程分析

采用Kroll法,以TiCl4和液态金属镁制备海绵钛,对海绵钛分部位取样,对高Fe, Ni和Cr含量样品进行MLA检测,计算Ti?Mg?Fe, Ti?Mg?Ni和Ti?Mg?Cr三元系的混合焓,研究海绵钛中Fe, Ni和Cr杂质的来源及引入过程。结果表明,海绵钛中Fe, Ni和Cr杂质主要来自钢制(1Cr18Ni9Ti)反应容器,其引入经历了在液态金属镁中溶解和与海绵钛合金化两步。当海绵钛于反应器壁处生成后,其与以单质形式溶于液态金属镁中的Fe, Ni和Cr原子结合将杂质富集。采取反应容器镀膜处理、控制反应区温度、使用低杂质含量的液态金属镁、将海绵钛坨底部与边部分离等措施可有效降低海绵钛中杂质含量。     

Surface enhanced Raman spectroelectrochemical studies of the corrosion films on iron and chromium in aqueous solution environments

“In situ” laser Raman spectra of the corrosion films on iron have been observed in aerated 5 M KOH and 0.15 M NaCl solutions via surface enhancement by the electrodeposition of a silver overlayer. Essentially the same spectra are observed in the two solutions as a function of applied potential in spite of a breakdown of passivity on iron in the chloride solution. Fe(OH)₂ and Fe₃O₄ are found in the prepassive potential region while FeOOH is present in the passive region. A film which is very difficult to reduce appears to be always present on the electrode surface even at hydrogen evolution potentials; this film is believed to be -FeOOH. Surface enhanced Raman spectra of the corrosion films on chromium have also been obtained in NaCl solution for the first time. The passive film has a composition that corresponds most closely to an amorphous form of Cr₂O₃, with some Cr(OH)₃ also present. The film is converted in the transpassive region to a higher oxide form, presumably CrO²⁻₄. Reversible reduction of this species to Cr₂O₃ is indicated.