Behaviour of crevice corrosion in iron

Crevice corrosion was investigated in iron exposed to a strong-buffered acetate solution (0.5 M CH₃COOH + 0.5 M NaC₂H₃O₂), pH = 4.66. The current and the potential gradient within the crevice were measured at crevice depth (L) = 7.35, 8, 10, and 15 mm, for a crevice that was positioned facing the electrolyte in a downward position. A remarkable shift in potential (>1.2 V) in the active direction was measured inside the crevice cavity, when the potential at the outer surface was held at 800 mV(SCE). Experimentation showed that there is a critical depth value, above which little changes occur on the transition boundary between passive and active regions on the crevice wall, x_pass, and below which x_pass location shifts sharply towards the crevice bottom. Steeping of the potential gradient occurred with time indicating enhancement of crevice corrosion, which was seen by the gradual increase in the current. These findings were in close agreement with the IR voltage theory and related mathematical model predictions. Morphological examination showed an intergranular attack around the active/passive boundary (x_pass) on the crevice wall.     

Effect of the applied potential on the potential and current distributions within crevices in pure nickel

The electrode potential profile within a crevice was measured in situ during crevice corrosion of nickel in 1N H₂SO₄ under conditions of effective convective mixing of the crevice and bulk electrolytes. Oxidizing power was investigated by applying potentials in the passive region. A steep potential gradient and constant pH were always measured during crevice corrosion. The magnitude of the potential drop and the distance into the crevice of the passive-to-active transition, X_pass,both increased linearly with increasing applied potential, in accordance with the IR>ΔΦ1 criterion. The in situ measured potential E_passatX_pass was, at all times, constant and in the range of the passive-to-active transition for the polarization curve of the bulk solution.     

The nature of crevice corrosion of aluminum in chloride solutions

To study crevice corrosion of pure aluminum, polished specimens partly covered with a glass foil were polarized potentiostatically in 1 N NaCl-solution at potentials negative to the critical potential for stable pitting (pitting potential). For comparison, non-crevice experiments were performed on polycrystalline and singlecrystalline material in neutral as well as acidified 1 N NaCl-solution and in AlCl₃-solutions. Corrosion morphology was examined by scanning electron microscopy. In current-time plots recorded during experiments on crevice corrosion, both an incubation and a propagation stage are discernible. If experiments were interrupted during the induction period, micropits were found inside the crevice. This unstable micropitting is detectable down to 0.30 V below the pitting potential. In contrast, during crevice corrosion propagation, the aluminum surface undergoes general attack. In a range of 0.2 V below the pitting potential, dimpled surfaces are produced. At more negative potentials, metal dissolution occurs crystallographically oriented. An identical behaviour was detected on unshielded samples polarized in the same potential range in both 1 N AlCl₃- and acidified 1 N NaCl-solution. Hence, the build-up of an acidic electrolyte is considered the sufficient requirement for crevice corrosion initiation.     

Hydrothermal synthesis of titanium-supported nanoporous palladium–copper electrocatalysts for formic acid oxidation and oxygen reduction reaction

Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction (ORR) in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPd₈₁Cu₁₉/Ti catalyst presents the highest current density of 39.8 mA/cm² at ?0.5 V or 66.4 mA/cm² at ?0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPd₈₁Cu₁₉/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at ?0.3 V is 2.12 mA/cm², which is 3.7 times larger than that on the nanoPd/Ti.     

An Ellipsometric,XPS and Electrochemical Study of the Passivity of Zircaloy-2

The electrochemical behaviour of zircaloy-2 in the annealed and quenched conditions was determined in 0.5 M H₂SO₄ by the potentiodynamic polarization method Passive films on zircaloy-2 obtained in air as well as in sulphuric acid under open circuit conditions, were characterised and their refractive index and thickness determined. It was seen that the beta quenched alloy showed a nobler potential (-270 mV against standard Calomel electrode) compared with the annealed alloy (-320 mV). It also showed a passive current density about one order less than the annealed material. Ellipsometry showed that the films formed on the quenched alloy were thinner than those on the annealed alloy. After exposure to 0.5 M H₂SO₄ zircaloy developed films which were thicker with power refractive index than both the heat treated conditions. XPS analysis of the films has confirmed incorporation of sulphate into the film which probably leads to a defective and hence a thicker film in acid.     

Das elektrochemische Verhalten von Titan

The electrochemical behaviour of titanium Current-potential curves established in 6 N sulfuric acid show at ?0,45 V the formation of a passive layer of titanium hydride and Ti-O (oxygen content 0 to 1.0). In the subsequent range of 200 mV this layer is converted into a passive layer of the n-conductor and which consists of TiO₂ with a little Ti₃O₅. In NaOH (1.0 and 6.0 N) a layer consisting exclusively of TiO₂ is formed above ?0.614 V, and above 1.8 V there is evolution of oxygen. The results are interpreted in terms of thermodynamics. The rest potential requires considerable time for reaching its stationary value, depending on the state of the surface and the moisture content of the electrode.     

Crevice corrosion monitoring of titanium and its alloys using microelectrodes

Crevice corrosion of titanium and its alloys in 10% sodium chloride was investigated at 100°C with the aid of microelectrodes. Potential, pH and chloride ion concentration inside the crevice were monitored using an Ag/AgCl electrode, a tungsten microelectrode and a Ag/AgCl chloride ion selective microelectrode, respectively. The pH and Cl^? concentrations within the crevice were calculated from the standard potential‐pH and potential‐log[Cl^?] calibration curves. The effect of Mo on the crevice corrosion of titanium was also studied. The passivation behavior on the titanium and Ti‐15%Mo alloy was studied using electrochemical impedance studies. There was no apparent change in pH and Cl^? ion activity inside the crevice for the alloy at 100°C, whereas a marginal decrease in pH and increase in Cl^? ion concentration were observed for pure titanium. Thus pure titanium is susceptible to crevice corrosion in hot 10% NaCl solutions at 100°C. The chloride ion activity was found to be reduced for the alloy so that the pH inside the crevice increased. The corrosion reaction resistance (R_t) was found to increase with the addition of Mo as an alloying element. It also increases with externally applied anodic potential. Hence, Mo is an effective alloying element, which enhances the crevice corrosion resistance of titanium.     

The characteristics of the pitting corrosion of stainless steel above breakdown potential

The pitting corrosion of AISI 304 stainless steel is studied in 1 N H₂SO₄|;0.5 N NaCl at 25°C. With the potentiokinetic method, a linear relationship is obtained between the breakdown potential and the cubic root of the scanning rate. Extrapolating to zero scanning rate gives the steady state breakdown potential E_b = 596 mV(SHE). At constant potential above E_b, the pits density first increases with time and tends to a steady state value (S.S.D.P.) which is reached above 10 mA cm⁻². The average deepening rate of pits V_dp increases with E − E_b according to log V_dp = −7.5 + 2.89 log (E − E_b). The time dependance of current density J at constant potential above E_b follows the equation log J = a + b log t. The values of b are different below and above 10 mA cm⁻², confirming the change in mechanism of pit corrosion: no new pit is initiated above that value. It is suggested that it is possible to characterize the quality of passivating layers not only on the basis of E_b, but also in terms of S.S.D.P., V_dp and b at given values of E − E_b.     

Pitting and pitting inhibition of iron in sodium sulphate solutions

The anodic behaviour of high purity iron in 0.5 M sodium sulphate solutions was studied. Experiments were made in both acid and alkaline solutions (pH 2.7, pH 9.0, pH 10.0 without buffers; and pH 9.2 with borate buffer). Anodic polarization curves, and surface scratching experiments, showed pitting potentials in 0.5 M Na₂SO₄ pH 9.0 and pH 10.0 solutions. Their values were very close to the corrosion potential obtained in a 0.5 M Na₂SO₄, pH 2.7, pit-like solution. The pitting potential in a borate buffered 0.5 M Na₂SO₄ solution was 50 mV higher than that in the unbuffered solutions. The pitting inhibition potential measured in a 0.5 M Na₂SO₄ solution, pH 10.0, was very close to the passivation potential found in the pit-like solution. All these facts can be explained by the localized acidification mechanism for pitting. The pitting potential is the minimum potential at which an acidified solution can be produced and maintained in contact with the dissolving metal. Similarly the pitting inhibition potential is the electrode potential at which the metal becomes passive in the pit-like solution.     

Der Einfluß von Kupfer auf das Korrosions und Passivierungsverhalten von Eisen-Chrom-Legierungen Teil I: Elektrochemisches Verhalten in schwefelsauren Elektrolyten

The influence of copper on corrosion and passiviation of iron-chromium-alloys Part I: Electrochemical behavior in sulfuric acid solutions The kinetic of dissolution and passivation of alloys type FeCrXCuY (X = 5; 7; 9; 11%; Y = 0; 0.5; 1%) was investigated in 1N H₂SO₄ (pH 0.3) and 0.5 M Na₂SO₄ (pH 3), using rotating disc electrodes (RDE) and hydrodynamically modulated rotating ring disc electrodes (HMRRDE). Instationary current density-potential curves (10 mV/s) were measured. For both types of electrodes the transients of current density after pulse polarisation into the passive range were investigated. The selfactivation of one hour prepassivated electrodes (open circuit breakdown) was investigated by potential scans. The dissolution of Cu bearing samples led to the formation of a visible film of copper lowering the current densities in the active and prepassive range as well as the critical current and charge densities of passiviation. Copper accelerates similar to chromium the decline of current transients after pulse passivation, whereas the partial current for film formation was increased as deduced from studies with the HMRRDE, leading to the conclusion of a larger film thickness. However, according to the accelerated open circuit breakdown of copper bearing samples, films on these alloys are less stable than expected, which is related to a faster removal of the oxide film. The results demonstrate an ambivalent effect of copper in the passive state of these alloys.     

Influence of activated carbon on crevice corrosion in adsorption tower of advanced liquid processing system

ABSTRACT

The adsorption tower made of type 316L stainless steel (SS) in Multi-nuclide Removal Equipment (Advanced Liquid Processing System) which uses Ag-impregnated activated carbon (Ag AC) as an adsorbent experienced crevice corrosion. The influence of Ag AC on the crevice corrosion susceptibility and E_sp of 316L SS was investigated by performing electrochemical experiments. Crevice corrosion was observed in the specimen in contact with the Ag AC. On the other hand, there was no crevice corrosion without the Ag AC in both pH 7.4 and pH 12 solutions. Clear ennoblement of spontaneous potential (E_sp) by in contact with activated carbon was observed and that was clearly higher than the repassivation potential for crevice corrosion (E_R,CREV). Thus, the presence of the AC notably increased E_sp of 316L SS and this resulted in increased crevice corrosion susceptibility by the galvanic effect.

This paper is part of a supplementary issue from the 17th Asia-Pacific Corrosion Control Conference (APCCC-17).     

Die passivierende Wirkung von SiO2 auf Zink

Passivating effect of SiO₂ on zinc In this work the influence of SiO₂ in alkaline solution of 0.01 N KOH on the process of anodic passivation of zinc has been investigated. The steady-state current-potential method (the potential range from -1100 mV to 2000 mV vs. s.c.e.) and the determination of the impedance of the passive zinc/electrolyte system (at + 500 mV vs. s.c.e., with frequency of 1000 c/s) have been applied. It has been established that the presence of SiO₂ promotes the passivity of zinc and in-fluences essentially the passive state. This influence already begins in the first phases of the passivation.     

Loch- und Spaltkorrosion von Chrom- und Chromnickelstählen in chloridhaltigen Lösungen

Pitting and crevice corrosion of stainless steels in chloride solutions In practice stainless steels in chloride containing waters are found to be susceptible to crevice corrosion and pitting. Corrosion tests were carried out on AISI 304 L stainless using a simulated crevice and the compositions of the electrolyte in the crevice determined. Long term potentiostatic tests were used to determine the critical potentials for crevice corrosion (U_S), for various steels in sodium chloride solutions at different concentrations and temperatures. The steels studied were 22 CrMo V 121, X 22 CrNi 17 and AISI 304 L. Like the critical pitting potential (U_L), U_S was found to have a strong dependence on the chloride content of the external solution. At higher concentrations the two potentials were similar. At lower concentrations the U_S was lower than U_L. The knowledge of these critical potentials together with well known rest potentials for a steel in an electrolyte of known concentration, allows conclusions to be drawn about its susceptibility to pitting and crevice corrosion. The method is suitable also for other passive metals.     

Observation of corrosion behavior of stainless steels in a salt manufacturing plant environment using the multichannel electrode method

Crevice corrosion of four kinds of stainless steel, SUS316L, NAS64, NAS185N and NAS254N, in saturated NaCl solution at temperatures up to 100 °C was investigated using the multichannel electrode method. In this method, a pile of five individual working electrodes (WEs) of stainless steel sheet were embedded in epoxy resin and a small hole penetrating through the five WEs was treated as an artificial crevice. Time transition and distribution of the coupling current between the five WEs were measured as a function of crevice depth, kind of stainless steel, temperature and concentration of dissolved oxygen (DO). Anodic or cathodic coupling current on the five WEs of SUS316L changed depending on their corroding state. On the other hand, NAS64, NAS185N and NAS254N showed that the WE outside the crevice contributed as a cathode and that WEs inside the crevice contributed as an anode. The coupling current on SUS316L was strongly affected by concentration of DO, while the coupling current on NAS64, NAS185N and NAS254N was not affected by DO, probably due to the establishment of a passive state inside the crevice.     

In vitro electrochemical investigations of advanced stainless steels for applications as orthopaedic implants

Potentiodynamic anodic polarization experiments on advanced stainless steels (SS), such as nitrogenbearing type 316L and 317L SS, were carried out in Hank’s solution (8 g NaCl, 0.14 g CaCl₂, 0.4 g KC1, 0.35 g NaHCO₃, 1 g glucose, 0.1 g NaH₂PO₄, 0.1 g MgCl₂, 0.06 g Na₂HPO₄ 2H₂O, 0.06 g MgSO₄ 7H₂O/1000 mL) in order to assess the pitting and crevice corrosion resistance. The results showed a significant improvement in the pitting and crevice corrosion resistance than the commonly used type 316L stainless steel implant material. The corrosion resistance was higher in austenitic stainless steels containing higher amounts of nitrogen. The pit-protection potential for nitrogen-bearing stainless steels was more noble than the corrosion potential indicating the higher repassivation tendency of actively growing pits in these alloys. The accelerated leaching study conducted for the above alloys showed very little tendency for leaching of metal ions, such as iron, chromium, and nickel, at different impressed potentials. This may be due to the enrichment of nitrogen and molybdenum at the passive film and metal interface, which could have impeded the releasing of metal ions through passive film.     

Galvanic reactions during localized corrosion on stainless steel

During localized (crevice and pitting) corrosion, a local cell is established between an anode within a crevice or pit and a cathode on the surrounding passive surface. Data are presented to show that concentrated acidic chloride solutions, simulating corrosion product hydrolysis within a crevice or pit, produce potentials which are active (negative) to the normal surface passive potential. This behaviour explains the previously observed active drift of corrosion potential after initiation of crevice or pitting attack in dilute chloride solutions. The active state in concentrated chloride solutions was quite noble (positive) compared to the active state in more dilute solutions. Thus, there is no need to invoke ohmic resistance effects to account for the active state within a crevice or pit.Experiments were devised in which the local anode within a crevice was physically separated from the nearby passive-surface cathode. When the two were coupled together electrically, the cathode surfaces were polarized nearly to the unpolarized local anode potential, with only a few millivolts anodic polarization at the anode within the crevice. The rate of localized corrosion appears from the data to be limited by the rate of dissolved-oxygen reduction on the cathode surfaces. Thus, localized corrosion in dilute chloride solutions will be increased by (a) raising the temperature, (b) adding an oxidizer such as Fe³⁺ ions, or (c) substituting external anodic polarization for dissolved oxidizers.The overall potential, E_corr acquired by a specimen undergoing pitting or crevice corrosion is demonstrated to be near the protection potential, E_p below which pitting corrosion cannot propagate. Any potential active to E_corr and E_p results in cathodic polarization and suppression of the anode reaction in a crevice or pit. Since both E_corr and E_p vary with the extent of previous localized attack, E_p is not a unique property of the alloy as has been sometimes suggested and is of limited value in classifying alloy resistance to localized corrosion.     

The corrosion behavior of carbon steel in CO2‐saturated NaCl crevice solution containing acetic acid

The corrosion behavior of X52 carbon steel electrodes in CO₂‐saturated NaCl crevice solution containing HAc was investigated by electrochemical measurements. Chemical environment measurements by Cl^? and pH microprobes show an enrichment of Cl^? ions and an increase of pH values inside the crevice. Moreover, both increments could accelerate with the decreasing dimension of the crevice mouth due to the high diffusive resistance. When the electrode in the crevice solution is coupled with the electrode in bulk solution, the alkalization and the enrichment of Cl^? ions in the crevice solution can result in a negative shift of potential of the electrode in crevice solution, while the potential of the electrode in bulk solution shifts positively during the corrosion process. Thus, a galvanic corrosion is established with the electrode in the crevice solution acting as anode while another in the bulk solution as cathode, i.e., the corrosion in the crevice solution was enhanced while the corrosion in the bulk solution was retarded. The anodic dissolution and the cathodic reduction processes dominate in the crevice solution and in the bulk solution, respectively.     

The corrosion behavior and microstructure of high-velocity oxy-fuel sprayed nickel-base amorphous/nanocrystalline coatings

The corrosion characteristics of two Ni-Cr-Mo-B alloy powders sprayed by the high-velocity oxy-fuel (HVOF) process have been studied using potentiodynamic and potentiostatic corrosion analysis in 0.5 M H₂SO₄. The deposits were also microstructurally characterized using x-ray diffraction (XRD), scanning electron microscopy (SEM) (utilizing both secondary electron and backscattered electron modes), and transmission electron microscopy (TEM). Results from the microstructural examination of the two alloys have revealed a predominantly amorphous/nanocrystalline face centered cubic (fcc) matrix containing submicron boride precipitates as well as regions of martensitically transformed laths. Apparent recrystallization of the amorphous matrix has also been observed in the form of cellular crystals with a fcc structure. The oxide stringers observed at splat boundaries were found to be columnar grained α-Cr₂O₃, though regions of the spinel oxide NiCr₂O₄ with a globular morphology were also observed. The coatings of the two alloys exhibited comparable resistance to corrosion in 0.5 M H₂SO₄, as revealed by potentiodynamic tests. They both had rest potentials approximately equal to −300 mV saturated calomel electrode (SCE) and passive region current densities of ∼1 mA/cm². Microstructural examination of samples tested potentiostatically revealed the prevalence of degradation at splat boundaries, especially those where significant oxidation of the deposit occurred. This paper originally appeared in Thermal Spray: Meeting the Challenges of the 21st Century; Proceedings of the 15th International Thermal Spray Conference, C. Coddet, Ed., ASM International, Materials Park, OH, 1998. This proceedings paper has been extensively reviewed according to the editorial policy of the Journal of Thermal Spray Technology.     

Effect of chloride ions on electrochemical properties of anodized <Emphasis Type="Italic">AV</Emphasis> and <Emphasis Type="Italic">D</Emphasis>16 aluminum alloys in aqueous and glycerin-containing aqueous sodium sulfate solutions

The effect of chloride ions (0.01 N NaCl) on the electrochemical properties of anodized (in chromic anhydride or sulfuric acid) AV and D16 aluminum alloys in aqueous sulfate (0.5% Na₂SO₄) and glycerin-containing aqueous sulfate (0.5% Na₂SO₄, 33% glycerin) solutions is studied. Depending on the conditions of anodizing and the composition of the alloy and environment, currents on the anodized alloys in the passive range are shown to be smaller by one to four orders of magnitude compared to those on nonanodized alloys. Anodizing increases the resistance of alloys against pitting corrosion. Alloys anodized in sulfuric acid and then treated in dichromate are not susceptible to pitting corrosion. Alloys anodized in chromic anhydride are less resistant against pitting.     

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.