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.     

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.     

Pitting corrosion of intermetallic compound Ni3(Si,Ti) in sodium chloride solutions

The pitting corrosion of intermetallic compound Ni₃(Si,Ti) was investigated as functions of test temperature and chloride concentration in sodium chloride solutions by using a potential step method. In addition, the pitting corrosion of solution-annealed austenitic stainless steel type 304 and pure nickel was also studied under the same experimental condition for comparison. The pitting potential obtained for the intermetallic compound 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. In addition, the pitting potential at various constant chloride concentrations above the critical chloride concentration decreased with increasing test temperature. The pitting potential of Ni₃(Si,Ti) was higher than pure nickel, but lower than that of type 304.     

Corrosion dependence of an Al?Mg?Si alloy under MgCl2 solution drop on initial concentration and humidity

The corrosion behavior of an Al–0.63Mg–0.28Si alloy under MgCl₂ solution droplets with different initial concentration in environments of 33, 75, and 88% relative humidity (RH) was studied using a Kelvin probe. The available cathodic limiting current associated with oxygen reduction was highly dependent on the environment RH and initial concentration. In the 33% RH environment, metastable pitting was the main form of corrosion. In some cases at 75 and 88% RH, the potential baseline decreased slowly by hundreds of mV and remained at the lower value, indicating stable filiform‐like corrosion grew. The initiation time of the stable corrosion was determined by the environment RH and initial concentration. With increasing initial concentration or decreasing environment RH, the available cathodic limiting current decreased, stable corrosion was difficult to occur. The stable corrosion could occur outside the drop and/or inside the drop, which was dependent on not only the cathodic limiting current but also the environment RH.     

Environmental factors affecting pitting corrosion of type 304 stainless steel investigated by electrochemical noise measurements under potentiostatic control

Electrochemical noise measurements on anodically polarised type 304 stainless steel surfaces in contact with buffer solutions of neutral pH were performed to study the effect of chloride ions in the nucleation of pitting corrosion. Passive layer stability and susceptibility to pitting corrosion after pickling and passivation at different environmental conditions were also investigated by means of electrochemical current noise measurements under cathodic and anodic polarisation. According to the obtained experimental results pits nucleate independently on the presence of chloride ions. It has been also shown that protectiveness of stainless steel surfaces after pickling strongly depends on the relative humidity of the environment in which the surface is subsequently passivated.     

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 mechanism of Mo/Nd16Fe71B13/Mo film in a simulated marine atmosphere

This study describes the corrosion mechanism of Mo/Nd₁₆Fe₇₁B₁₃/Mo film induced by sodium chloride particles in 80% relative humidity (RH) environment. The deliquescence of sodium chloride particles on the Mo/Nd₁₆Fe₇₁B₁₃/Mo film caused the step by step attacks. Initial loosening of the Mo layer allows permeation of electrolyte into Nd–Fe–B layer, resulting in cavitations of electrolyte and subsequent film failure. The second failure step involves corrosion of Nd element in the Nd–Fe–B layer, with Fe element remaining beneath the corrosion product. Corrosion of Fe constitutes the third-step failure, forming a mixture of Nd and Fe corrosion product.     

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.     

Corrosion behavior of iron-based alloys in the LiBr + ethylene glycol + H2O mixture

The corrosion resistance of 1018 carbon steel, 304 and 316 type stainless steels in the LiBr (55 wt.%) + ethylene glycol + H₂O mixture at 25, 50 and 80 °C has been studied using electrochemical techniques which included potentiodynamic polarization curves, electrochemical noise and electrochemical impedance spectroscopy techniques. Results showed that, at all tested temperature, the three steels exhibited an active-passive behavior. Carbon steel showed the highest corrosion rate, since both the passive and corrosion current density values were between two and four orders of magnitude higher than those found for both stainless steels. Similarly, the most active pitting potential values was for 1018 carbon steel. For 1018 carbon steel, the corrosion process was under a mixed diffusion and charge transfer at 25 °C, whereas at 50 and 80 °C a pure diffusion controlled process could be observed. For 316 type stainless steel, at 25 and 50 °C a species adsorption controlled process was observed, whereas at 80 °C a diffusion controlled mechanism was present. Additionally, at 25 °C, the three steels were more susceptible to uniform type of corrosion, whereas at 50 and 80 °C they were very susceptible to localized type of corrosion.     

Corrosion studies of stainless steel protected by a TiO2 thin film deposited on a sulfonate-functionalized self-assembled monolayer

Thioacetate hexadecyltrimethoxysilane was deposited on SiO₂-coated stainless steel to form a thioacetate-functionalized monolayer. In situ oxidation of the thioacetate yielded a sulfonate-functionalized monolayer. Solution deposition of TiO₂ on this monolayer covered the stainless steel with a thin layer of the metal oxide (5-10 nm). Cyclic voltammetry (CV) and potentiostatic current transient demonstrated the efficiency of the corrosion protection in sodium chloride media, including protection against pitting corrosion.     

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.     

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.     

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.     

Effects of solution heat-treatment and nitrogen in shielding gas on the resistance to pitting corrosion of hyper duplex stainless steel welds

The effects of solution heat-treatment and shielding gas on the pitting corrosion of hyper duplex stainless steel (HDSS) welds were investigated in highly concentrated chloride environments. The pitting resistance of a solution heat-treated HDSS after welding with an Ar shielding gas supplemented with N₂ was greatly increased due to the dissolution of Cr₂N in α-phase, which followed the diffusion of N atoms from the α-phase to the γ-phase and an increase of the γ-phase in the weld metal and heat affected zone. It was also attributed to a decrease of the pitting resistance equivalent number difference between the two phases.     

Importance of initial surface film in the degradation of stainless steels by atmospheric exposure

The surface compositions of stainless steels types 304, 316, 430, and 444 combined with four types of surface finishes, 2B finish, hairline polishing, mirror polishing, and bright annealing, were measured by ICP-AES, EPMA, and XPS before exposure. The surface finish that most enriched the chromic species in the surface film was mirror polishing, followed by bright annealing, 2B finish, and hairline polishing. The order of corrosion-resistance was type 444, type 316, type 304, and type 430. The surface compositions were correlated with the rating number and pitting depth after exposure to atmospheric environments. The rating number had a high positive correlation with the concentration of Cr in the surface film, and had a slight correlation with the near-surface composition measured by EPMA at 12 kV, but did not show any correlation with bulk composition within the composition range covered in the present work. This same trend was observed for pitting depth. It was concluded that the cationic concentration of Cr in the surface film before atmospheric exposure is the prime factor in controlling the resistance of stainless steels to atmospheric 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 behaviour of duplex stainless steels sintered in nitrogen

Duplex stainless steels obtained through powder metallurgy (PM) technology from austenitic AISI 316L and ferritic AISI 430L powders were mixed on different amounts to obtain biphasic structures with austenite/ferrite ratio of 50/50, 65/35 and 85/15. Prepared mixes of powders have been compacted at 750 MPa and sintered in N₂-H₂ (95% and 5%) at 1250 °C for 1 h. Corrosion behaviour, using electrochemical techniques such as anodic polarization measurement, cyclic anodic polarization scan and electrochemical potentio-kinetic reactivation test and double loop electrochemical potentio-kinetic reactivation double loop test were evaluated. For duplex stainless steels, when austenite/ferrite ratio increases the corrosion potential shifts to more noble potential and passive current density decreases. The beneficial effect of annealing solution heat treatment on corrosion behaviour was established and was compared with corrosion behaviour of vacuum sintered duplex stainless steels. The results were correlated with the microstructural features.     

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.     

Corrosion behaviour of Lotus-type porous high nitrogen nickel-free stainless steels

Corrosion behaviour of three austenitic Lotus-type porous high nitrogen Ni-free stainless steels exposed to an acidic chloride solution has been investigated by electrochemical tests and weight loss measurements. Polarization resistance indicates that the corrosion rate of Lotus-type porous high nitrogen Ni-free stainless steels is an order of magnitude lower than that of Lotus-type porous 316L stainless steel in acidic environment. The localised corrosion resistance of the investigated high nitrogen Ni-free stainless steels, measured as pitting potential, E_b, also resulted to be higher than that of type 316L stainless steel. The influences of porous structure, surface finish and nitrogen addition on the corrosion behaviour were discussed.     

The effect of annealing on the corrosion behaviour of 444 stainless steel for drinking water applications

In this study, the corrosion behaviour of annealed and not annealed AISI 444 ferritic stainless steel in tap water with and without addition of selected concentrations of chloride ions was investigated. Cyclic potentiodynamic macro (large area) and micro (small area) polarization measurements (CPP), salt spray test, SEM and EDS analysis were employed to evaluate the pitting and crevice corrosion susceptibility of annealed and not annealed AISI 444. The results obtained indicate that annealing does not improve the resistance to pitting and crevice corrosion. Moreover, micro CPP indicates local susceptibility to pitting on both annealed and not annealed materials; such susceptibility was not evident from macropolarization tests.