Pitting corrosion of intermetallic compound Ni3(Si,Ti) with 2 at% Mo in sodium chloride solutions

The pitting corrosion of Ni₃(Si,Ti) with 2 at% Mo consisting of a single intermetallic compound Ni₃(Si,Ti) phase of L1₂ structure and a two phase mixture of L1₂ and fcc nickel solid solution was investigated as functions of test temperature and chloride concentration in sodium chloride solutions by using a potential step method and compared with that of intermetallic compound, Ni₃(Si,Ti). The pitting potential obtained for the Ni₃(Si,Ti) with 2 at% Mo decreased with increasing chloride concentration and test temperature. A critical chloride concentration below which no pitting corrosion took place was found to exist and to decrease with increasing test temperature. The specific pitting potential at the critical chloride concentration also decreased with increasing test temperature. The pitting potential of Ni₃(Si,Ti) with 2 at% Mo was higher than pure nickel, but lower than that of Ni₃(Si,Ti). A critical chloride concentration was found to be lower than that of Ni₃(Si,Ti), whereas the specific pitting potentials at the critical chloride concentration was found to be higher than that of Ni₃(Si,Ti). Pitting corrosion occurred in the two phase mixture region.     

Corrosion of 304 stainless steel exposed to nitric acid-chloride environments

In an effort to examine the combined effect of HNO₃, NaCl, and temperature on the general corrosion behavior of 304 stainless steel (SS), electrochemical studies were performed. The corrosion response of 304 SS was bifurcated: materials were either continuously passive following immersion or spontaneously passivated following a period of active dissolution. Active dissolution was autocatalytic, with the corrosion rate increasing exponentially with time and potential. The period of active corrosion terminated following spontaneous passivation, resulting in a corrosion rate decrease of up to five orders of magnitude. The length of the active corrosion period was strongly dependent on the solution volume-to-surface area ratio. This finding, coupled with other results, suggested that spontaneous passivation arises solely from solution chemistry as opposed to changes in surface oxide composition. Increasing NaCl concentrations promoted pitting, active dissolution upon initial immersion, a smaller potential range for passivity, longer active corrosion periods, larger active anodic charge densities preceding spontaneous passivation, and larger corrosion current and peak current densities. In contrast, intermediate HNO₃ concentrations promoted active dissolution, with continuous passivity noted at HNO₃ concentration extremes. During active corrosion, increased HNO₃ concentrations increased the anodic charge density, corrosion current density, and peak current density. The time required for spontaneous passivation was greatest at intermediate HNO₃ concentrations. Susceptibility to pitting was also greatest at intermediate HNO₃ concentrations: the pit initiation and repassivation potentials decreased with increasing HNO₃ concentration until the HNO₃ concentration exceeded a critical concentration beyond which susceptibility to pitting was entirely eliminated. Increasing solution temperature increased the susceptibility to both pitting and active dissolution.     

Pitting corrosion of Type 430 stainless steel under chloride solution droplet

To clarify the critical relative humidity (RH) to initiate pitting corrosion and the rusting mechanism in a marine atmospheric environment, pitting corrosion of Type 430 stainless steels under drops of MgCl₂ solutions were investigated. A pitting corrosion test was performed at different relative humidities under droplets with various diameters and thicknesses. The probability of pitting decreased as the diameter and thickness decreased. Pitting progressed only when the chloride concentration exceeded 4 M, which is the equilibrium concentration at 80% RH. Accordingly, pitting of Type 430 could be initiated when the RH was less than 80%. Additionally, a pitting corrosion mechanism of Type 430 stainless steel under droplets containing chloride ions is proposed.     

On the corrosion mechanism of AISI 204Cu stainless steel in chlorinated alkaline media

Electrochemical techniques (CV, SECM, CPT) and surface analysis techniques (EDX, SEM) have been employed to assess the corrosion behaviour of the AISI 204Cu stainless steel. The behaviour of this steel has been compared with that of AISI 304 and AISI 434 stainless steels in chlorinated alkaline media. All samples performed well at room temperature under potentiodynamic polarisation up to a chloride to hydroxyl ratio of 10. At this ratio the AISI 204Cu and the AISI 434 steels presented pitting potential at +0.47 V vs. SCE and +0.31 V vs. SCE, respectively. Moreover, the critical pitting temperature was higher for the AISI 204Cu steel than for the AISI 434 steel, respectively 58 °C and 28 °C.In terms of corrosion performance of the AISI 204Cu stainless steel can be classified better than the AISI 434 steel and worse than the AISI 304 steel.Local electrochemical and chemical examinations allowed evidencing the local activity of some pits over long period, and to conclude that the improved corrosion performance of the low nickel alloy AISI 204Cu stainless steel should be ascribed to copper cementation at active corrosion sites.     

Untersuchung über das Korrosionsverhalten von Zirkoniumlegierungen. IV. Das Lochfraßverhalten Zirkoniumlegierungen

Investigation into corrosion behaviour of zirconium alloys. IV-Pitting behaviour of zirconium alloys Electrochemical investigations into the resistance of a number of Zr-alloys in different solutions against pitting corrosion have shown that additions of Va- and VIa-group metals and in particular Ti improve the resistance of pure Zr. Metals forming local elements decrease pitting corrosion resistance. Minor amounts of Fe, Ni and Cr have practically no influence. The pitting corrosion resistance of Zr and its alloys decreases with increasing concentration of chloride ions in the solutions. Additions of SO₄-ions retard the beginning of the pitting but do not shift the pitting corrosion potential. NO₃-ions on the other hand produce a real inhibition. Newly developed methods for the quick determination of the pitting corrosion potential were very useful for the described investigations.     

Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions

Pitting corrosion of Type 304 stainless steel under drops of MgCl₂ solution has been investigated to clarify the rusting mechanism in marine atmospheres. A pitting corrosion test was performed under the droplets with various combinations of the diameter and thickness (height) by exposure to a constant relative humidity. Probability of occurrence of pitting corrosion decreased with decreasing the diameter and thickness. Pitting corrosion progressed only when the [Cl⁻] exceeded 6 M (RH < 65%). In almost cases, there was a small hole (∼10 μm diameter) in the center of a single pit, which may be the trace of an inclusion particle like MnS dissolved out. The pitting corrosion mechanism of Type 304 under droplets containing chloride ions has been proposed.     

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.     

Corrosion behaviour of stainless steel exposed to highly concentrated chloride solutions

The characteristics of pitting corrosion of Type 304L stainless steel (SS) exposed to highly concentrated chloride solutions were studied through the evaluation of the corrosion potential, the pitting potential, the structure of the passive layer and the statistics of pitting depth and density. Both as-received and weld metal samples were studied. The weld metal sample was machined from the welding zone of a butt weld of Type 304L SS. The results showed an accelerated anodic dissolution and depressed film resistance at the welding zone, but no dramatic change on pitting corrosion was observed from the statistics of pitting during the test duration up to 720?h. The pitting corrosion resistance was significantly affected by the chloride concentration and slightly affected by the temperature under the investigated conditions.     

Hot corrosion behaviour of Ni3Al in sulphate-chloride mixtures in the atmosphere

Hot corrosion of Ni₃Al intermetallic compound in the presence of sulphate-chloride mixtures was studied. A comminuted Ni₃Al mixed with NaCl-Na₂SO₄, NaCl-Li₂SO₄, LiCl-Na₂SO₄, LiCl-Li₂SO₄ additions was oxidized in the air up to 1000 °C with linearly increasing temperature and isothermally within the temperature range of 500-700 °C. The corrosion process was observed by thermogravimetric method using Mettler thermoanalyzer.The experiments indicated that LiCl (∼10 wt.%)-Li₂SO₄ mixture was the most corrosive agent. It was also found that by addition of MgO the corrosion of Ni₃Al was reduced. Phase composition of the corrosion products was established by X-ray diffraction analysis; there were detected Al₂O₃, Al₂S₃, NaAlO₂ (or LiAlO₂) as intermediate products, nickel sulphides, NiO and NiAl₂O₄. NiAl₂O₄ spinel was formed only at the highest temperatures, while at lower temperatures alumina was present instead of spinel.Hot corrosion behaviour of Ni₃Al in sulphate-chloride mixtures in air atmosphere.     

Microsegregation-related pitting corrosion characteristics of AL-6XN superaustenitic stainless steel laser welds

Pitting corrosion resistance of laser welds of AL-6XN superaustenitic stainless steel (SASS) was investigated in acidic chloride ion medium. It was found that the critical pitting temperature (CPT) of the laser welds increased with increasing welding speed or decreasing laser power. Pitting attack preferentially occurred at selective dendrite cores of the laser welds. Analytical electron microscope (AEM) microanalysis revealed that depletion of Mo at dendrite cores due to microsegregation is the basic cause for the pitting corrosion susceptibility. The higher partition coefficient k_Mo and Mo concentration at dendrite cores of laser welds were attributed to the lower heat input welding parameters.     

Corrosion of an Al–Mg–Si alloy under MgCl2 solution droplets

The corrosion behavior of an Al–0.63Mg–0.28Si alloy under droplets of MgCl₂ solution in environments of 75% and 33% RH was studied using a Kelvin Probe. The equilibrium chloride concentrations in these two environments are 5.8 and 9.8 M chloride, respectively. In the 33% RH environment, metastable pitting was the main form of corrosion. In some cases at 75% RH, the potential baseline decreased slowly by hundreds of millivolts and remained at the lower value. These samples exhibited filiform-like corrosion inside micro-droplets that formed outside of the main MgCl₂ drop. A model for the filiform-like attack in a micro-droplet is presented.     

Critical pitting temperature for Type 254 SMO stainless steel in chloride solutions

The variation with time of the open circuit potential of high molybdenum containing stainless steel (Type 254 SMO) was measured in 4% sodium chloride solution in the temperatures range 30-100 °C. The plot of steady state potentials as function of temperature showed an inflection at 50 °C, attributed to the decrease of oxygen solubility in test solution above 50 °C. Potentiodynamic cycling anodic polarization technique was used to determine the critical pitting potential (E_pit) and the critical protection potential (E_prot) of the steel in 4-30% NaCl solutions at temperatures between 30 and 100 °C. By plotting the two values versus solution temperature, the corresponding critical pitting (CPT) and the critical protection (CPrT) temperatures were determined. Both parameters decreased with increasing chloride content. Above the CPT, E_pit and E_prot decreased linearly with log[Cl⁻]. The addition of bromide ions to the solution shifted both E_pit and E_prot towards positive values. In 4% NaCl, E_pit increased linearly with pH in the range 1-10. The combined effect of chloride ion concentration and pH on the morphology of the pits was examined by scanning electron microscopy (SEM) following potentiodynamic cycling anodic polarization.     

Corrosion behaviour of vacuum induction-melted Ni-based alloy in sulphuric acid

A vacuum induction-melted (VIM) Ni-based alloy was immersed in 60% H₂SO₄ solution to investigate its corrosion behaviour and resistance. The results indicate that the microstructure contains a γ-Ni solid solution + Ni₃Si particles, dendrite Ni₃Si, Ni₃B, Cr₇C₃, and CrB. The corrosion started at the zones of the γ-Ni solid solution + Ni₃Si particles and dendrite Ni₃Si. These zones transformed to oxide films and protected the alloy from significant attack. However, the pitting corrosion created paths for acid solution and/or to further attack. Therefore, the corrosion rate decreased and then stabilised at a high value as the immersion time increased.     

Interpretation of electrochemically and chemically investigated corrosion behaviors of 316L SS in acid chloride environments

The electrochemical behavior of 316L stainless steel was investigated in acid chloride environments, and pitting potentials were determined electrochemically and chemically. An increase in the anodic maximum current density was observed upon decreasing the cathodic potential from which the scan was initiated to determine the polarization curve. To determine the critical pitting potential through the chemical method, the potential was increased by increasing the concentration of ferric ions in ferric chloride while holding the chloride ion concentration constant with sodium chloride. When 316L stainless steel was immersed in 15 g/1 of FeCl₃6H₂O containing the same chloride ion concentration as 5% NaCl with pH=2 at 57°C, the corrosion potential increased to 0.47 V (SHE) within two minutes due to initial passivation. Immediately after reaching 0.47 V (SHE), which was just above the pitting potential of 0.45 V (SHE) determined electrochemically in 5% NaCl (pH=2, 57°C), the corrosion potential continuously decreased, indicating the onset and propagation of pitting corrosion. A correlation between the electrochemical and chemical methods can be verified if the proper measurements are made and the observations are properly interpreted.     

In-situ investigation on the pitting corrosion behavior of friction stir welded joint of AA2024-T3 aluminium alloy

The surface corrosion behavior of an AA2024-T3 aluminium alloy sheet after friction stir welding was investigated by using an “in-situ observation” method. SEM observations showed that the density and degree of the pitting corrosion in the shoulder active zone were slightly larger compared to the other regions on the top surface. The origins of the pitting corrosion were in the regions between the S phase particles and the adjacent aluminium base. The effect of Al-Cu-Fe-Mn-(Si) intermetallic compounds on the pitting corrosion was attributed to their high self-corrosion potential which induced the anodic dissolution of the surrounding aluminium matrix.     

Corrosion behaviour of an Fe3Al-type intermetallic in a chloride containing solution

The corrosion behaviour of an Fe₃Al-base intermetallic compound with different crystal structures in a chloride containing solution has been investigated. The corrosion current densities of this intermetallic were independent of the material crystal structure showing a passive state stable with time. These corrosion rates were of the same order of magnitude as for 316L stainless steel. The pitting corrosion resistance evaluated by means of cyclic anodic polarization curves was high for all different states. Amongst the different crystal structures of this intermetallic alloy, the two ordered states present the lowest pitting probability. This Fe₃Al intermetallic shows higher pitting corrosion resistance than the 316L stainless steel but its capacity for repassivation is lower. A damaging factor of influence on the pitting corrosion behaviour is the presence of non-metallic inclusions on the surface which reduce the pitting corrosion resistance by almost a half.     

Corrosion characteristics of nickel, copper, and stainless steel in a Lewis neutral chloroaluminate ionic liquid

Corrosion of nickel, copper, and 316 stainless steel in aluminum chloride/1-ethyl-3-methylimidazolium chloride ionic liquid (IL) is investigated by means of electrochemical techniques. SEM analyses are performed to examine the reaction mechanisms. While Ni shows good stability, Cu has high corrosion susceptibility in this IL. For 316 steel, pitting corrosion occurs at a lower potential than that of passivation. In the non-aqueous, low-oxygen, and high-ion-containing IL, the material corrosion properties are totally different from those found in conventional environments. Since ILs have found increasing potential in diverse applications, new corrosion prevention strategies are needed to overcome the IL-derived material corrosion problems.     

Microstructure and electrochemical properties of high entropy alloys—a comparison with type-304 stainless steel

High entropy alloys (HEAs) are a newly developed family of multi-component glassy alloys composed of several major alloying elements, such as copper, nickel, aluminum, cobalt, chromium, iron, silicon, titanium, etc. The HEA studied had a nearly amorphous structure as proven by X-ray diffraction (XRD), selected area diffraction (SAD), and differential scanning calorimetry (DSC) analysis. The dendritic phase was composed mainly of a non-crystalline phase with a little body centered cubic (BCC) structure whereas the interdendritic phase had an amorphous structure containing small amounts of nano-scale precipitates. The HEA had a high degree of atomic disorder with mechanical properties comparable to that of glass and it was therefore hard but brittle. Its hardness (Hv860) was much higher than that of type-304 stainless steel (Hv265). The anodic polarization curves of the HEA, obtained in aqueous solutions of NaCl and H₂SO₄, clearly indicated that the general corrosion resistance of the HEA at ambient temperature (∼25 °C) is superior to that of 304S, irrespective of the concentration of electrolyte in the range 0.1-1 M. On the other hand, the HEA’s resistance to pitting corrosion in a Cl⁻ environment is inferior to that of 304S, as indicated by a lower pitting potential and a narrower passive region for the HEA. Tests in 1 N sulfuric acid containing different concentrations of chloride ions showed that the HEA has least resistance to general corrosion at a chloride ion concentration of 0.5 M (close to the concentration in seawater). The lack of hysteresis in cyclic polarization tests confirmed that the HEA—like 304S—is not susceptible to pitting corrosion in chloride-free 1 N H₂SO₄.     

Influences of Cr/Ni equivalent ratios of filler wires on pitting corrosion and ductility-dip cracking of AISI 316L weld metals

To study the pitting corrosion of AISI 316L weld metals according to the chromium/nickel equivalent ratio (Cr_eq/Ni_eq ratio), three filler wires were newly designed for the flux-cored arc welding process. The weld metal with delta-ferrite at less than 3 vol.%, was observed for ductility-dip cracking (DDC) in the reheated region after multi-pass welding. The tensile strength and yield strength increased with increasing Cr_eq/Ni_eq ratio. The result of anodic polarization tests in a 0.1 M NaCl solution at the room temperature (25) for 45 min, revealed that the base metal and weld metals have a similar corrosion potential of −0.34 V_SCE. The weld metal with the highest content of Cr had the highest pitting potential (0.39 V_SCE) and the passivation range (0.64 V_SCE) was higher than the base metal (0.21 V_SCE and 0.46 V_SCE, respectively). Adding 0.001 M Na₂S to the 0.1M NaCl solution, the corrosion occurred more severely by H2S. The corrosion potentials of the base metal and three weld metals decreased to −1.0 V_SCE. DDC caused the decrease of the pitting potential by inducing a locally intense corrosion attack around the crack openings.     

Effect of Al‐Fe‐Si intermetallic compound phases on initiation and propagation of pitting attacks for aluminum 1100

It is well known that iron and silicon are major elements in industrial pure aluminum alloy 1100. These elements form Al‐Fe‐Si ternary intermetallic compounds such as FeAl₃, Fe₃SiAl₁₂, Fe₃Si₂Al₉, Fe₂Si₂Al₉ etc. The corrosion characteristics of the 1100 specimen and the Al‐Fe‐Si intermetallic compound specimens are experimentally investigated in NaCl and AlCl₃ solutions. The electrochemical measurements, SEM surface observation and EPMA analysis reveal that (1) the iron content of the compounds influences the initiation of pitting attacks: the higher content of iron in the compound is, the more easily occurs the initiation of pitting attack, and (2) an existence of the compound in the bottom of the active pitting cavity, whether the iron content of the compound is higher or not, contributes to the further propagation of pitting attack as a cathodic site.