Avoiding crevice corrosion by laser surface treatment

The present work shows that laser surface alloying of the creviced area on Al 7175-T7351 with chromium can avoid crevice corrosion. Corrosion takes places outside the crevice in conditions where the ratio of anodic area to cathodic area is favourable to minimize corrosion. As laser surface processing is adequate for treating small areas there is an enormous potential in this technology.     

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.     

Corrosion product analysis on crevice corroded Alloy-22 specimens

Surface analytical techniques were applied to characterize corrosion products formed during the crevice corrosion of the Ni–Cr–Mo(W) Alloy-22 in 5 mol/L NaCl at 120 °C. Micro-Raman spectroscopy demonstrated the formation of polymeric molybdates within the crevice corroded region where intergranular corrosion dominated. The location and chemical speciation of the Mo and W species formed was investigated by Raman mapping. Crevice corrosion was found to propagate preferentially across the alloy surface rather than to penetrate deeply at localized sites, a feature which appears to be linked to the formation and build-up of polymeric molybdates.     

An experimental study of crevice corrosion behaviour of 316L stainless steel in artificial seawater

The effects of applied torque on corrosion behaviour of 316L stainless steel with crevices were investigated using the cyclic potentiodynamic polarization method. Three kinds of crevices (316L-to-polytetrafluoroethylene, 316L-to-fluoroelastomeric and 316L-to-316L) were tested in artificial seawater at 50 °C. Corroded surface morphology was also investigated using scanning electron microscopy. Results indicate similar trends in crevice corrosion susceptibility with increasing applied torque. Among the three crevices, the 316L stainless steel specimen, coupled to the 316L stainless steel crevice former, is the most susceptible to crevice corrosion.     

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.     

Susceptibility of stainless steel alloys to crevice corrosion in ClO2 bleach plants

Stainless steels, including duplex stainless steels, are extensively used for equipment in pulp bleaching plants. One serious corrosion problem in chlorine dioxide bleach plants is crevice corrosion of stainless steels, which is frequently the factor that limits their use in bleach plants. Crevice corrosion susceptibility of alloys depends on various environmental factors including temperature, chemical composition of environment and resulting oxidation potential of system. Upsets in the bleaching process can dramatically change the corrosivity of the bleaching solutions leading to temperatures and chemical concentrations higher than those normally observed in the bleach process. When the environmental limits are exceeded the process equipment made of stainless steel can be severely affected. Environmental limits for crevice corrosion susceptibility of eight stainless steel alloys with PRE numbers ranging from 27 to 55 were determined in chlorine dioxide environments. Alloys used in this study included austenitic, ferritic-austenitic (duplex), and superaustenitic stainless steels. The performance of the different stainless steel alloys mostly followed the PRE numbers for the respective alloys. The 654SMO alloy with the highest PRE number of 55 showed the highest resistance to crevice corrosion in this environment. Under the most aggressive chlorine dioxide bleach plant conditions tested, even alloys Nicr3127 and 654SMO with PRE numbers 51 and 55 respectively were susceptible to crevice corrosion attack. The two factors that seem to contribute the most to crevice corrosion and pitting in the investigated environments are temperature and potential.     

In situ investigation of crevice corrosion on UNS S32101 duplex stainless steel in sodium chloride solution

The crevice corrosion of UNS S32101 in neutral 0.1 M NaCl solutions at room temperature was investigated directly by a facile method. Experimental results showed that both delayed and immediate crevice corrosion can be initiated. Morphology study indicated that the heaviest corrosion attack happened just below the passive/active boundary on the crevice wall. The relocation of the active dissolution regions during crevice corrosion was observed and explained by established theory. The mechanisms of the delayed and immediate types of crevice corrosion on UNS S32101 duplex stainless steel were discussed.     

Influence of ultrasound on pitting corrosion and crevice corrosion of SUS304 stainless steel in chloride sodium aqueous solution

The change of polarization curves and surface morphologies of SUS304 stainless steel was investigated in 3.5 mass% NaCl solution with or without the application of ultrasound (US). As the result, both the pitting corrosion and the crevice corrosion were largely suppressed by the application of US. The reason is attributed to the decrease in the concentration of hydrogen and chloride ions in pits or in the crevice by removing the corrosion product and stirring the liquid there.     

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.     

A study on the modeling of parameters affecting the Ir drop mechanism in the initiation stage of crevice corrosion

The sizable potential difference between the crevice mouth and the crevice tip is difficult to explain from theories mainly based on the chemical changes in crevice solution. In this study, the IR drop theory was adopted to explain the initiation of crevice corrosion in the framework of IR drop in the crevice electrolyte. Furthermore, the parameters linking the two components of potential drop — one due to accumulated charges from chemical changes of ionic species by mass transfer and the physical one caused by the current path through the crevice electrolyte — are examined. The mathematical model is constructed and the IR drop in the crevice is calculated using the FVM method. The chemical composition change in the crevice solution can affect the IR drop behavior through the intermediate parameter form of ion conductivity and viscosity, etc., together with the potential difference generated by the electric charge of locally charged ions. Viewed in this light, it can be concluded that the initiation mechanism only by IR drop is insufficient to explain the initiation of crevice corrosion in stainless steels that have very strong passivity.     

Influence of the microstructure and alloying element on the polarization behaviour within the crevice of UNS S32304 duplex stainless steel

The influence of microstructure evolution and alloying element redistribution of UNS S32304 duplex stainless steel induced by annealing treatment on the crevice corrosion behaviour was studied. As the annealing temperature was increased from 1030 to 1150 °C, the crevice corrosion resistance was decreased and the active peaks were not only increased in magnitude but also shifted towards the more noble direction. Austenite and ferrite have greatly different polarization behaviour within the crevice. This study provides guidance to the material design and usage in industry field in consideration of different polarization behaviour induced by the evolution of microstructure and alloying elements.     

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.     

Stainless steel crevice corrosion testing in natural and synthetic seawater

Susceptibility of stainless steel to crevice corrosion in natural and synthetic seawater was investigated by a new test method, developed by a research group, CrevCorr, of the Marine Working Party of the European Federation of Corrosion. The method was defined on the basis of a Round Robin test performed by twenty laboratories over the world [1, 2]. Among them was our Institute at the Adriatic coast. Geometry of the crevice model, gasket materials, finishing of metal surface and the electrochemical potential increase rate were strictly defined. The monitoring of the free corrosion potential of two austenitic steels and a duplex steel, in the constant flowing conditions, as well as the redox potential, temperature, chloride and oxygen content, have been carried out during six months in the natural seawater from the Adriatic Sea at the location in Dubrovnik, Croatia. Sharp drop of the corrosion potential was used as an indication of the crevice corrosion initiation. After exposure to the seawater eventual crevice damage on a steel specimen was detected by visual and microscopic inspections. In the synthetic seawater the organic component was simulated by glucose and glucose oxidase [3, 4]. The monitoring of the free corrosion potential and the redox potential was performed at 20, 30 and 40°C during five days, and results compared with those obtained in the natural seawater at same temperatures.     

Application of the multichannel electrode method to monitoring of corrosion of steel in an artificial crevice

Crevice corrosion of iron was evaluated using the multichannel electrode method in which 10 individual working electrodes (WEs) of pure iron were embedded in resin, placed in an artificial crevice in the range from 0.5 mm to 2.0 mm, and immersed in 0.51 mol dm⁻³ NaCl solution. The WEs were connected to an electronic circuit which allowed galvanic coupling between them and measurement of their individual coupling current or open circuit potential. Time-transient of the spatial distribution of coupling current and open circuit potential showed sequential transition of the coupling current on WEs at the middle position of the crevice from cathode to anode. The WE near the opening of the crevice initially showed a large anodic current, then a decreasing the anodic current corresponding to the current transition of other WEs, and finally a large cathodic current coupled with the other anodic WEs in the crevice. The transition of coupling current was explained by the change in pH and concentration of dissolved oxygen in the crevice. Thickness of the gap of the artificial crevice affected the transition behavior of coupling current distribution. For example, slower current transition with smaller coupling current was found in the case of a narrower gap. Such properties were related to the introduction and consumption of dissolved oxygen in the crevice solution and the circulation of gap solution from/to the outside of the crevice.     

Selective oxidation of a ferritic stainless steel and its influence on resistance to crevice corrosion initiation

The correspondence between alloy surface composition of a thermally oxidized ferritic stainless steel and resistance to crevice corrosion initiation has been elucidated by means of Auger electron spectroscopy, ion-sputtering and standard electrochemical analyses. When no chromium-alloy depletion is detected, the resistance to crevice corrosion initiation increases with the chromium content of the protective film. When chromium depletion is detected, its detrimental effect on resistance to crevice corrosion initiation increases with the polarizing potential of the sample. Those protective films which possess the highest resistance are shown to have thicknesses < 5 nm.     

Theoretical description of the practical possibility of stress corrosion cracking from crevice corrosion sites

Stress corrosion cracking (SCC) from crevice corrosion sites had been found in an experimental work at polarization potential of + 200 mV_SCE. In that work, an occluded U‐bend specimen of Type 316L (UNS S31603) stainless steel was used. The testing was done in sodium chloride (NaCl) solution. Based on that work, the practical possibility of SCC from the occluded U‐bend specimen was described theoretically. It was shown that it would also be possible for SCC to occur in practice (i.e. at practical corrosion potential), but the crevice needs to be tighter. Meanwhile, it would take a longer time for obvious SCC to emerge. For a practical crevice usually formed by placing a crevice former on a large uniform metal surface, the crevice geometry may have little effect on SCC although the crevice can sustain an acidified solution more easily than pitting. The possibility of SCC should mainly depend on the corrosion system itself, i.e. material and environment.     

Ability of acoustic emission technique for detection and monitoring of crevice corrosion on 304L austenitic stainless steel

This experimental work was aimed at investigating the ability of acoustic emission (AE) technique for detection and monitoring of crevice corrosion on 304L austenitic stainless steel. Crevice initiation, propagation and repassivation was controlled by additions of hydrogen peroxide and hydrochloric acid and by the extent of the applied torque of crevice assembly, in the presence of chloride ions. The simultaneous measurements of corrosion potential of the specimen and AE global activity during the test, as well as the characterization of acoustic parameters of AE signals, evidences a good correlation between potential and AE activity fluctuations, AE rate and amplitude of crevice damage in terms of weight loss and metallic surface affected, in each tested experimental condition. Moreover, the evolution of cumulative% of AE signals number versus selected acoustic parameters shows that rise time, counts number, duration and cumulative energy of AE signals are affected by crevice development. Finally, visualization of crevice initiation and propagation during the test allows to propose that bubbles formation from cathodic reactions within the crevice is the emissive mechanism.     

Implications of internal cathodic reactions for crevice attack of stainless steels in chloride environments

Abstract

Modelling of the crevice chemistry in stainless steels in chloride environments at ambient temperatures has been conducted in order to evaluate the impact of internal cathodic reactions on the potential and pH within the crevice. Consideration of the internal cathodic reactions is of particular importance in predicting the behaviour of crevices formed between dissimilar metals. The model is based on mass conservation of species and incorporates a range of chemical and electrochemical reaction processes. Hydrogen ion reduction within the crevice has a marked effect on the time evolution of the pH in the crevice and consequently on predictions of the time to passivity breakdown based on the critical pH concept. The impact on the steady state pH depends on the corrosion potential and on crevice dimensions. In the latter context, decreasing the gap or increasing the length does not invariably create more severe conditions for passivity breakdown. There is an optimum magnitude of the dimensions for inducing crevice attack. Coupling the stainless steel to a more noble material within the crevice, when the main cathodic reaction is reduction of hydrogen ions, may be more likely to retard crevice attack by virtue of the higher crevice pH, provided that effective coupling of the materials in the external environment is constrained. A specific bulk conductivity exists below which the critical crevice chemistry does not develop, but this is associated with potential drop in the bulk solution rather than in the crevice.     

A clearer view of how crevice corrosion occurs

Crevice corrosion is a poorly understood and very damaging form of corrosion. This paper presents the essential characteristics of crevice corrosion established during the last four decades as well as some recent results that provide a fresh approach to understanding the process. A simple criterion has been developed that involves two factors. First is the current and resistance between the anodic reaction in the crevice and the cathodic reaction at the outer surface; second is the polarization curve. Practices for preventing crevice corrosion are also discussed. The size of the active peak in the polarization curve and, in particular, whether it increases or decreases can be used to determine whether or not a change in a system parameter (e.g., a solute addition to the alloy) will promote or inhibit crevice corrosion. A second indicator is whether the solution resistivity increases or decreases.