Crevice corrosion damage function for grade-2 titanium of iron content 0.078 wt% at 95 °C

A crevice corrosion damage function has been developed for grade-2 titanium in 0.27 mol/dm³ NaCl at 95 °C. Crevice corrosion experiments were conducted for various durations using a galvanic coupling technique, and corrosion depth profiles subsequently measured using a combination of metallographic and image analysis techniques. The damage function was then determined by plotting the maximum penetration depth (d_max) in μm as a function of time (days). This function possessed two clear stages; an initial stage in which d_max = 89.4t^0.87, and a second stage in which corrosion spread laterally without an increase in d_max, before the crevice finally passivated. The initial high penetration rate was associated with an intergranular attack down Fe-containing grain boundaries. In the second stage, further increases in d_max were limited by the IR drop between the propagation sites deep within the grain boundaries and the external cathode.     

The crevice corrosion behaviour of stainless steel in sodium chloride solution

The crevice corrosion behaviour of 13Cr stainless steel in NaCl solution was investigated mainly by electrochemical noise measurements, considering the influences of the crevice opening dimension (a) and the area ratio of the electrode outside the crevice to the one inside the crevice (r). Results show that the increase of r value prolongs the incubation period of crevice corrosion, but crevice corrosion develops rapidly once the crevice corrosion occurs. The crevice corrosion develops preferentially at the crevice bottom and then spreads to the whole electrode surface. Proton could reduce on the uncorroded area and hydrogen bubbles form inside the crevice.     

Initiation and repassivation of crevice corrosion of type 444 stainless steel in chloride solution

Effects of chloride ion concentrations, solution temperature, and crevice-forming materials on the crevice corrosion of type 444 stainless steel were investigated using a potentiostatic method. Critical crevice potential (E_crev) and repassivation potential (E_r) of the creviced alloy decreased with an increase in chloride concentration [Cl⁻], satisfying the logarithmic relationship between E and [Cl⁻]. In addition, E_crev and E_r of the alloy with silicone crevice former were measured to be higher than those of the alloy with an EPDM (Ethylene Propylene Diene Monomer) crevice former, suggesting that silicone was more effective in preventing water from penetrating crevices between a stainless steel sheet and the crevice former. In electrochemical current transient measurements with an applied potential, the intensity of current transients corresponding to the initiation of metastable pits increased abruptly near the E_r of the alloy, indicating that the stability of crevice corrosion is associated with the initiation of metastable pits.     

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.     

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.     

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.     

Electrochemical and SEM study on Type 254 SMO stainless steel in chloride solutions

An investigation was conducted to examine the critical crevice potential (E_crev) and the critical protection potential (E_prot) for Type 254 SMO stainless steel in 4% NaCl solution by using potentiodynamic cyclic anodic polarization (PCAP) technique at temperature ranging from 30 to 90 °C. The critical crevice temperature (CCT) and the critical crevice protection temperature (T_prot) were determined by plotting the values of breakdown potential and E_prot versus solution temperature, respectively. The values of CCT and T_prot were recorded at the abrupt transition with increasing the temperature from transpassive corrosion to crevice corrosion and were found to be at 55 and 52 °C, respectively. Above CCT (70 °C) the following points were recorded. The E_crev and E_prot decreased linearly with log [Cl⁻]. The addition of bromide ions to chloride ions at a fixed halide content of 4% increased both E_crev and E_prot. The E_crev value in 4% NaCl increased linearly with increasing pH in the range 1-10. The addition of 0.5 M bicarbonate ions to 4% NaCl completely removed the crevices effect while increasing the addition of sulphate ions to 4% NaCl increased both of E_crev and E_prot. The morphology of the crevice corrosion produced on the steel surface was examined by scanning electron microscope (SEM) after PCAP treatment under different test conditions.     

Electrochemical Behavior and Stress Corrosion Sensitivity of X70 Steel Under Disbonded Coatings in Korla Soil Solution

The corrosion of X70 pipeline steel under a model disbonded coating was studied in a simulated solution of Korla soil by combining in situ electrochemical measurements at different locations in the crevice and stress corrosion cracking (SCC) sensitivity analyses in the corresponding simulated environments. The results from electrochemical impedance spectroscopy showed that the corrosion product resistance R _t and charge transfer resistance R _ct of X70 steel first increased and then decreased with increasing distance from the opening of the crevice in the disbonded coating. Scanning electron micrographs showed that pitting in the crevice became more severe at deeper locations in the crevice. Slow strain rate tests showed that the lowest SCC sensitivity of X70 steel was found at 15 cm away from the opening, and the highest SCC sensitivity was at the end of the crevice.     

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.     

Crevice corrosion initiation and propagation on Alloy-22 under galvanically-coupled and galvanostatic conditions

The initiation and propagation of crevice corrosion on the Ni–Cr–Mo Alloy-22 has been studied in concentrated chloride solutions under galvanically-coupled and galvanostatic conditions. Under galvanically-coupled natural corrosion conditions crevice corrosion initiated but propagation was limited by repassivation. This was attributed to the slow kinetics of oxygen reduction on passive surfaces external to the crevice. Under galvanostatic conditions a potential more positive than 200 mV_Ag/AgCl and an applied current greater than 5 μA were required to stabilize propagation. A minimum critical current density to establish active sites within the crevice was estimated to be around 250 μA cm⁻².     

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).     

An innovative specimen configuration for the study of Mg corrosion

Based on an analysis of galvanic corrosion research, the research reported herein was formulated to examine the measurement of polarisation curves for Mg to develop a methodology whereby reliable polarisation curves can be measured for Mg. Cathodic polarisation curves were measured for high purity Mg in 3.5% NaCl saturated with Mg(OH)₂ using three specimen types: (i) mounted specimens, (ii) specimens hung by fishing line and (iii) plug-in specimens. Cathodic polarisation curves were evaluated to yield the corrosion current density i_corr and the corresponding corrosion rate P_i, which was compared with the corrosion rate evaluated from hydrogen evolution measurements, P_H, and the corrosion rate evaluated by weight loss measurements, P_W. Mounted specimens produced values of corrosion rate, P_i, three times larger than values of corrosion rate, P_i, for plug-in specimens, attributed to crevice corrosion in the mounted specimens. Crevice corrosion in Mg is totally unexpected from prior research. The plug-in specimen configuration was designed to have no crevice and to allow simultaneous measurement of P_H and P_i; P_i was consistently less than P_H and indicated an apparent valence for Mg of 1.45 in support of the Mg corrosion mechanism involving the uni-positive Mg⁺ ion. The plug-in specimen has advantages for the study of Mg corrosion.     

EIS monitoring study of atmospheric corrosion under variable relative humidity

Electrochemical impedance spectroscopy (EIS) technique was used to investigate atmospheric corrosion in laboratory simulated environments with variable relative humidity (RH) and fixed Cl⁻ content. The results show the suitability of EIS for analyzing electrochemical corrosion behaviour at 5-100% RH. At 5-30% RH, EIS spectra reflected the character of the electrode, whereas at 40-100% RH, the model of EIS spectra was established with the help of surface analysis. From 70% RH, the film resistance (R_r) reflects the degree of corrosion and the charge transfer resistance (R_t) provides quantitative representation of the corrosion rate, which were verified by weight loss tests.     

Corrosion resistance of HVOF-sprayed coatings for hard chrome replacement

HVOF-sprayed coatings (WC-17Co, WC-10Co-4Cr, Co-28Mo-17Cr-3Si) and electrolytic hard chrome (EHC) coatings corrosion resistances have been compared through electrochemical polarization tests (0.1 N HCl, 0.1 N HNO₃) and Corrodkote test. EHC coatings passivate in HNO₃, but undergo pitting corrosion in HCl and in Corrodkote test too. HVOF coatings do not passivate, but possess more noble corrosion potentials. Both in HNO₃ and HCl, they undergo more generalized corrosion, with similar i_corr; crevice corrosion along splat boundaries is sometimes detected after the HCl test. Their i_corr in 0.1 N HCl solution is lower than in several of EHC coatings. No visible damage in the HVOF coatings has occurred after the Corrodkote test.     

Rainbow fringes around crevice corrosion formed on stainless steel AISI 316 after ennoblement in seawater

The crevice corrosion occurrence probability of stainless steel (SS) AISI 316 was increased under ennoblement condition due to chemically added H₂O₂ into seawater. The H₂O₂ was used to simulate the important factor causing ennoblement in natural marine biofilm. Morphology of the crevice corrosion was observed using an incident‐light source microscopy. Some interesting “rainbow” fringes were observed around micro‐crevices. The mechanism was discussed from the ions diffusion and potential distribution during the crevice formation. This result shows that under ennoblement condition the colored fringe is a distinct characteristic of the morphology of localized corrosion for stainless steel.     

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.     

A crevice corrosion study by Electrochemical Noise Analysis

The use of the Electrochemical Noise Analysis (ENA) for the evaluation of crevice corrosion is illustrated in the case of AISI 430 stainless steel in 3% sodium chloride. A crevice former was used in order to induce a crevice corrosion attack. Current and potential noise signals were simultaneously recorded allowing the determination of the noise resistance (R_n). ENA was able to detect the four stages mechanism of crevice corrosion. The comparison of R_n with the Polarization Resistance (R_p) determined by Electrochemical Impedance Spectroscopy (EIS) gave good agreement in particular during the initiation and propagation of the attack. The evaluation of the noise data in the frequency domain gave interesting results in particular in the evaluation of the roll‐off slopes in the Power Spectrum Density (PSD) plot that are correlated to the corrosive status. Finally a new analysis for noise data is shown. The application of spectral ratio discriminant function to noise data in the frequency domain, permits to deduce the best sampling frequency and sampling duration for ENA acquisition, able to discriminate between two different situations.     

Plug-In Specimens for Measurement of the Corrosion Rate of Mg Alloys

Magnesium alloy corrosion is often nonlinear. The corrosion rate accelerates to steady state after an initial period of low corrosion. Plug-in specimens permit simultaneous measurement of the corrosion rate using hydrogen evolution, P _H, and Tafel extrapolation of cathodic polarization curves, P _i. Moreover, weight loss allows independent verification. P _H is consistently greater than P _i. The data, for short exposure periods up to 10?days, are consistent with the unipositive Mg⁺ ion being a short-lived intermediate. Tafel extrapolation needs to be used with caution for estimation of Mg corrosion, as the measured corrosion rate can have a significant contribution from crevice corrosion. Furthermore, measurements made at short immersion times may not reflect the steady-state corrosion rate, and the corrosion reaction at the Mg surface may be decoupled from the electrochemical measurement.     

Studies on the initial stages of zinc atmospheric corrosion in the presence of chloride

A four-year exposure program was carried out in Taiwan in which 23 test sites with different climatic and pollution conditions were chosen and evaluated according to ISO standards 9223-9226. Examination of the results indicated that most of the tests sites were very corrosive to zinc specimens and there was a severe white rust problem for freshly galvanized items stored in high humidity outdoors environments. In addition, the initial stages of zinc atmospheric corrosion in the presence of chloride were studied quantitatively in a non-aqueous electrolyte (methanol) using ex situ electrochemical impedance spectroscopy (EIS) to determine polarization resistance (R_p). The samples were exposed to the synthetic atmospheres with careful controlled relative humidity, temperature, and contaminating salts. It was observed that a change of R_p was accompanied by a change in the corrosion product on the zinc surface, and that the R_p increased with relative humidity (RH) during pre-exposure. Furthermore, the corrosion products of zinc were analyzed qualitatively by grazing-angle X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Zinc hydroxycarbonate (Zn₅(CO₃)₂(OH)₆) and zinc oxide (ZnO) in this surface layer were found to provide protection against chloride contaminants.