Uniformity of passive films formed on ferrite and martensite by different inorganic inhibitors

A comparison of uniformity of passive films formed on ferrite and martensite by three kinds of inorganic inhibitors, chromate, bicarbonate and nitrite, has been made by anodic polarization curve and AC impedance measurements. It was found, by anodic polarization curve analyses, that there was different pitting susceptibility of passive films formed on ferrite and martensite by chromate or bicarbonate. In the solution containing chloride ions, the broken potential of the passive film formed on ferrite by chromate or bicarbonate was more negative than that on martensite. However, the passive films formed on both ferrite and martensite by nitrite had similar pitting susceptibility. Their broken potentials were almost the same. The difference in pitting susceptibility of the passive films was explained by Mott-Schottky analyses. It was found that the passive film formed on ferrite by chromate or bicarbonate had a higher donor concentration than the passive film on martensite. The passive films with higher donor concentrations were more sensitive to chloride ions. However, the passive films formed on both ferrite and martensite by nitrite had the same donor concentration. A uniform passive film can be formed on a martensite mild steel with ferrite bands by nitrite.     

Electrolyte and temperature effects on pitting corrosion of type 316LN stainless steels

Abstract

The influence of electrolyte composition and temperature on the pitting corrosion resistance of nitrogen bearing (0·015, 0·198, and 0·56%N) type 316L stainless steels has been investi gated. Anodic polarisation curves were determined in neutral chloride solution at room temperature and at elevated temperatures of 308, 318, and 333 K. Similar polarisation studies were also conducted at room temperature in 1N H₂ SO₄ and in an acidic chloride solution containing 1N H₂ SO₄ and 0·5M NaCl. The results show that the critical pitting potential E_pp in neutral chloride and acidic chloride media increases as the nitrogen content of the alloy increases, indicating that resistance to pitting increases with the addition of nitrogen. However, in 1N H₂ SO₄ solution, the transpassive potential was almost independent of the nitrogen content. As the temperature of the neutral chloride medium was increased, the E_pp values decreased, irrespective of nitrogen content. The decrease in E_pp is attributed not only to the temperature induced modification of the passive oxide film but also to chloride induced activity at the passive film/solution interface. Nevertheless, the alloy con taining 0·56% nitrogen showed better resistance to pitting at 333 K than did the alloy with 0·015% nitrogen at room temperature. SEM examination of the pitted specimens showed clear evidence of pitting for the alloy with 0·015% nitrogen, but insignificant pitting attack for the alloy with 0·56%N. However, the alloy with 0·56%N displayed some pitting attack when the experiments were conducted at 333 K.     

Synergistic effect of Ni and N on improvement of pitting corrosion resistance of high nitrogen stainless steels

Abstract

The pitting corrosion resistance of Fe18Cr10Mn(0·33–0·69)N, Fe18Cr10Mn1Ni(0·33–0·84)N, and Fe18Cr10Mn0·35N(0–3)Ni alloys were investigated. The pitting potential increased as the N content increased in both Fe18Cr10Mn(0·33–0·69)N and Fe18Cr10Mn1Ni(0·33–0·84)N alloys. The rise in the pitting potential was more pronounced in Fe18Cr10Mn1Ni(0·33–0·84)N alloys than in Fe18Cr10Mn(0·33–0·69)N alloys. However, it was found that Ni alone had no effect on the pitting corrosion resistance of Fe18Cr10Mn0·35N based alloys. Thus, it was concluded that the alloyed N worked synergistically with Ni to promote the pitting corrosion resistance in Fe18Cr10Mn based alloys. Analyses of passive films of Fe18Cr10Mn(0·33–0·69)N and Fe18Cr10Mn1Ni(0·33–0·84)N alloys revealed that N was incorporated into the passive film, with N enriched at the film/metal interface. However, the alloyed N increased the Cr cation fraction in passive films of Fe18Cr10Mn1Ni(0·33–0·84)N alloys, whereas N decreased in that of Fe18Cr10Mn(0·33–0·69)N alloys. This difference was considered as the reason for the synergistic effect between N and Ni in Fe18Cr10Mn based alloys.     

Formation and Breakdown of Surface Films on Copper in Sodium Hydrogen Carbonate and Sodium Chloride Solutions: I. Effects of anion concentrations

Abstract

The formation, breakdown and composition of surface films on copper in air-saturated solutions at 25°c has been studied by potentiokinetic polarisation. In 0·01 M NaHCO₃, the protective oxide layer breaks down at a critical potential togive pitting corrosion. Increasing the concentration of hydrogen carbonate ions decreases the protectiveness of the oxide film towards general corrosion, but makes the filmmore resistant to breakdown. In 0·01 M NaCl, the oxide film formed is initiallyfairly protective and exhibits a breakdown potential on rapid polarisation. As the chloride concentration is increased, the oxide film becomes less protective and the breakdown potential becomes displaced to more negative potentials and is more poorly defined.     

Inhibition effect of chromate on the passivation and pitting corrosion of a duplex stainless steel in LiBr solutions using electrochemical techniques

The electrochemical behavior of duplex stainless steel (DSS) in LiBr media was investigated by anodic cyclic polarization curves and AC impedance measurements. The effect of bromide concentration and the presence of chromate in the solutions on the corrosion behavior of AISI 2205 was studied. Cyclic polarization curve analyses showed that there was different pitting susceptibility of passive films depending on the LiBr concentration. Pitting potential decreases with LiBr concentration in a semilogarithmic scale following two different slopes. Chromate presence displaces pitting potentials towards more positive values at low LiBr concentrations but it has no effect when LiBr concentration increases.The comparative analysis carried out in LiBr and LiBr chromate-containing solutions at two different concentrations, 0.016 M and 0.032 M, verifies the assumption that halogen ions facilitate inhibitor adsorption. The addition of halides strongly increased the inhibition efficiency of chromate. The passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

The effect of chromate in the corrosion behavior of duplex stainless steel in LiBr solutions

The electrochemical behavior of duplex stainless steel (DSS) in LiBr media was investigated by anodic cyclic polarization curves and AC impedance measurements. The effect of bromide concentration and chromate presence in the solutions on the corrosion behavior of DSS was studied. It was found, by cyclic polarization curves analyses, that there was different pitting susceptibility of passive films formed on DSS depending on the chromate/bromide ratio: pitting corrosion susceptibility highly decreased from a chromate/bromide ratio lower than 0.01.The comparative investigations carried out in LiBr and LiBr + 0.032Li₂CrO₄ verify the assumption that the halide ions facilitate inhibitor adsorption. The addition of halides increased inhibition efficiency to a considerable extent. Passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

The Anodic Passivation of Iron in Solutions Of Inhibitive Anions*

Abstract

The anodic passivation of iron in air-saturated and de-aerated solutions of a number of inhibitive anions has been studied by the determination of potentiostatic polarisation curves. The critical passivation potential, critical passivation current density and leakage currents through the passive films have been found to depend on pH and on the nature of the anion present in the solution. The critical passivation potential (N.H.E. scale) in solutions of anions, where passivation occurs relatively easily, varies with pH in the range 6–12 according to E_p = + 0.09 – 0.06 pH volt For the anions studied, the critical passivation current densities in de-aerated 0·1 M-solution increase (and the difficulty of passivation increases) in the order: nitrite < hydroxide < chromate < borate < phosphate < carbonate < benzoate < bicarbonate < nitrate.     

Chromate passivation of hot dipped Zn25Al alloy coatings

Abstract

A low concentration chromate passivation treatment has been successfully applied to a new type of hot dipped Zn2 5Al alloy coating, and the corrosion resistance of the chromate passive film has been assessed using the copper accelerated acetic salt spray (CASS) test, electrochemical measurements, and sea water immersion testing. The results showed that the corrosion resistance of the Zn2 5Al alloy coating was significantly better after the chromate passivation treatment. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) analyses showed that the composition (at.-%) of the low concentration chromate passive film was: 5·5S–3·4Na–11·8C–7·9Ti–41·6O–1 3·7Cr–16·0Zn. Aluminium was not found in the film, which is attributed to the dissolution behaviour of the Zn2 5Al alloy coating in acidic chromate solution.     

Electrochemical Behavior of 2205 Duplex Stainless Steel in NaCl Solution with Different Chromate Contents

The electrochemical behavior of 2205 duplex stainless steel in NaCl solution with different chromate contents were investigated by potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), Mott-Schottky analysis, and scanning electron microscope (SEM). The effect of chromate on passivity and pitting behavior of stainless steel was also studied. The results showed that pitting susceptibility as well as semiconducting properties of passive film is heavily dependent on the chromate concentration. There exists a critical chromate value (about 0.03?M in 1?M NaCl solutions) below which the pitting corrosion on the stainless steel would be inhibited and above which it would be accelerated.     

Nature of the Oxide Film Present on Iron after Inhibition in 0·05 M Chromate Solutions

Abstract

Chemical and microprobe analyses have been used to study the composition of the oxide films formed on iron by 0·05 M potassium chromate, pH 4–8.

Chemical analyses have shown that the air-formed oxide film was thinned and evenly reinforced with a normal iron chromium spinel having a composition in the range Fe²⁺ (Fe³⁺_0·5 Cr³⁺_1·5)O₄ — Fe³⁺ Cr³⁺ O₃

Microprobe analyses indicated enrichment of chromium at scratch lines, but the effect was small compared with the overall thickening of the films.     

Chloride induced pitting initiation on 304L stainless steel in acidic sodium sulphate solutions

Abstract

The kinetics of pit initiation on 304L austenitic stainless steel in aqueous sodium sulphate solutions containing various concentrations of sodium chloride have been investigated by induction time measurements using the potentiostatic test method. Oxide films were grown on the surface of the steel by potentiostatic oxidation in the passive region. Pitting induction time has been found to be dependent on the oxide film thickness: the thicker the oxide film, the longer the induction time. Measurements at temperatures rangingfrom 20 to 80°C gave an apparent activation energy for pitting initiation of ~ 48·1 kJ mol^?1, which suggests that the mechanism of single ion transport through the film is the rate determining step.     

Electrochemical behaviour of 254SMO stainless steel in comparison with 316L stainless steel and Hastelloy C276 in HCl media

Abstract

The electrochemical behaviour of 254SMO stainless steel in HCl solutions has been studied and compared with that observed for other alloys using open circuit potential measurements, potentiodynamic polarisation curves, and SEM analysis techniques. 254SMO does not display pitting corrosion at room temperature in HCl solutions having concentrations ≤5·0M. Its performance is comparable with that of Hastelloy C276 in HCl media in solutions of strength ≤1·0M. The critical pitting temperature for 254SMO exceeds 76°C in 3M HCl solutions.     

Decreasing pitting susceptibility of passive films on X70 pipeline steel in NaCl solutions by illumination

The influence of UV illumination on passivity and pitting susceptibility on X70 pipoeline steel in a borate buffer （pH=8.4 ） solution containing NaCl is described. It is observed that illumination of the sample leads to a decrease in its pitting susceptibility as indicated by pitting potential and incubation time measurements in chloride containing electrolytes. This effect is strongly dependent on the applied potential during passivation. The electronic properties of the passive films on X70 steel were studied by Mott-Schottky analysis and photocurrent transient measurements. The results indicated that illumination during passivation led to modifications in the electronic properties of the passive films, mainly to a decrease of the bulk doping and an increase in the surface state density. The cause for the decrease in the pitting susceptibility is preliminary explained in terms of such modifications of the passive flm.     

A two step anodizing process of aluminium as a means for improving the chemical and physical properties of oxide films

An anodizing process was developed to form corrosion resistant and hard oxide films on aluminium. The process consists of two steps: first the formation of chromate/phosphate treated layer on the surface of aluminium and secondly anodizing in a sulphuric acid solution. The anodic oxide films formed by the present process contain Cr(III) and phosphate species mostly in the outer part of the porous layer. The films formed by the present process provided a better corrosion resistance to the substrate aluminium from pitting in a chloride medium than the films formed by conventional anodizing and sealed in a boiling chromate solution. Further, Vickers hardness on the cross section of film increased compared with the films formed by conventional anodizing. This two step process can be developed to form other composite oxide films by using different treatments for the first step.     

Effect of surface polishing on SCC susceptibility of sensitised type 304 stainless steel

Abstract

The effect of surface polishing on the stress corrosion cracking (SCC) susceptibility of sensitised SUS 304 stainless steel was studied by using the well controlled surface polishing method which has been developed for the surface preparation of the semiconductor material. The SCC susceptibility of the polished specimen was examined by using the slow strain rate testing method, at which the specimen was kept at a constant potential in 0·1M Na₂SO₄ solution kept at 368 K. The most effective suppression effect on the SCC susceptibility was found in the case of surface polishing using alumina slurry, followed by water soluble fullerene and diamond slurry, compared with the mechanical polishing with #0/6 paper. Surface roughness and pitting potential of polished surface were compared with the SCC susceptibility of polished sensitised SUS 304 stainless steel. It was found that the SCC susceptibility was decided mainly by the roughness factor rather than pitting resistance. Experimental evidences suggest that the SCC susceptibility was decided by the crack initiation being controlled by surface roughness.     

Effectiveness of pretreatment method to hinder rebar corrosion in concrete

Abstract

This paper aims to evaluate the ability of phosphate pretreatments applied on steel rebars to hinder the corrosion reinforcements using synthetic pore electrolyte and mortar contaminated by chloride ions. The electrochemical behaviour of the pretreated substrate was assessed by corrosion potential, polarisation resistance and electrochemical impedance spectroscopy measurements. The results have demonstrated that the treatment of the rebar by immersion in the Na₃PO₄ (0·5M) solution favours the formation of a passive layer on the steel rebar surface, which increases the resistance to corrosion initiation up to 0·3M Cl^– instead of 0·1M Cl^– without treatment. The pretreatment also provides enhancement of corrosion protection of the steel rebar in mortar. The evolution of the impedance spectra in function of chloride concentration is in a fairly good agreement with the results obtained from R_P measurements.     

Formation and Breakdown of Surface Films on Copper in Sodium Hydrogen Carbonate and Sodium Chloride Solutions: II. Effects of temperature and pH

Abstract

The anodic behaviour of copper in air-saturated solutions at 25°, 60° and 90°c has been determined by stepwise potentiortatic polarisation. In 0·01 M NaHCO₃, the critical breakdown potential of the protective oxide layer is displaced to considerably more positive potentials as the temperature increases. In 0·01 M NaHCO₃ containing 0·01 M NaCl, the critical breakdown potential is displiiced tornore negative values with increasing temperature, but the corrosion potential–breakdown potential difference undergoes little change. In 0·01 M NaCl, the surface film on copper is essentially non-protective, and linear Tafelplots are observed. A change in the pH of 0·01 M NaHCO₃, with or without 0·01 M NaCl, from 8·6 to 7·3 has little effect on the valuesof the breakdown potentials. The significance of the results in relation to the initiation of pitting corrosion of copper in natural waters is discussed.     

Electrochemical methods for evaluating inhibitors of steel corrosion in concrete

Abstract

Electrochemical methods were used to evaluate sodium phosphate and sodium nitrite as inhibitors for the corrosion of steel in saturated calcium hydroxide solution containing chloride ions. The studies included immersion, potentiodynamic, potentiostatic, and galvanostatic tests. The results obtained from these methods were in good agreement. They show that sodium nitrite is an anodic inhibitor which is not effective if its concentration is lower than that of the chloride ions. Sodium phosphate acts as an anodic inhibitor if its concentration is higher than 0·6 times the chloride concentration. It is totally effective when its concentration equals the chloride concentration.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

Photoelectrochemical investigation of ac modulated passive films on 304 stainless steel in weak alkaline and neutral solutions

Abstract

A photoelectrochemical investigation has been carried out on an ac modulated passive film on AISI 304 stainless steel in 0·1M Na₂ B₄O₇ and 0·5M Na₂ SO₄ solutions. The results of the photocurrent measurements indicate that the photoresponse is determined by defects in the electronic structure of the films when the defects lead to localised states in the band gap region and that the photoresponse is sensitive to the passive condition and testing solutions. It is concluded that the passive film on 304 stainless steel is in a highly disordered amorphous state.