Pitting and crevice corrosion behaviour of high alloy stainless steels in chloride‐fluoride solutions

The localised corrosion resistance (pitting and crevice corrosion) of two high alloy stainless steels, namely superduplex (SD) and superaustenitic (SA), has been studied in chloride‐fluoride solutions at pH values ranging from 2 to 6.5. The pitting potential (E_pit) and crevice potential (E_cre) have been calculated for these test media using electrochemical techniques (continuous current). The Critical Pitting Temperature (CPT) and Critical Crevice Temperature (CCT) are in both materials lower then the room temperature. In spite of this fact and due to the high repassivation rate, the resistance of these materials to localised corrosion is high in the tested media. At the highest tested concentration of aggressive anions and pH 6.5 both materials undergo a generalised attack.     

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.     

Pitting,Crevice and stress corrosion resistance of high chromium und molybdenum alloy stainless steels

This paper presents new data on the resistance of recently developed high-alloy stainless steels to localised corrosion in chloride solutions. Pitting potential was determined in artificial sea water, and critical pitting temperature CPT in very aggressive FeCl₃ solution. Critical crevice corrosion temperature CCT was tested in the same FeCl₃ solution. Stress corrosion measurements, made in a more familiar NaCl solution by the drop evaporation method, demonstrate that alloy stainless steels with high chromium and molybdenum have very long failure times, comparable with those of nickel alloys found to be SCC-resistant under practical conditions. Stainless steels of 20 Cr 25 Ni 6 Mo type showed the best resistance to localised corrosion.     

Zur Korrosionsprüfung von Schweißverbindungen hochlegierter CrNiMo-Stähle und NiCrMo-Legierungen

On the corrosion testing of weldments of high alloyed CrNiMo-stainless steels and NiCrMo-alloys Weluments of high-alloyed CrNiMo stainless steels and Nicro alloys can he more susceptible to localized corrosion than the solution annealed basic material owing to segregations and precipitations in the heat affected zone, the high temperature zone and/or in the weld. To investigate these differences the FeCl₃-test (10% FeCl₃ · 6aq), the test “green death” (11.5% H₂SO₄, 1.2% HCl, 1% CuCl₂, 1% FeCl₃) as well as chronopotentiostatic tests in artificial sea water or in 3% NaCl-solution are used. In particular for testing the highest alloyed materials a CaCl₂ test was developed (4.5M CaCl₂, chronopotentiostatic test in duration of 8 to 10 hours at + 200 mV (SCE)), which can be carried out to a temperature of 115°C at atmospheric pressure. The aggressivity increases in the range FeCl₃-test, “green death”-test, CaCl₂-test. Matching and graduated over-alloyed weldments (TIG, heat input of 7 and 15.5 kJ/cm) of materials 1.4529, 1.4562, 2.4856, 2.4819 (german materials No.) are comparingly examined in various tests, of materials 1.4406, 1.4539, 1.4439 and 1.4563 (german materials No.) only matching weldments in the FeCl₃-test. In strongly oxidizing media only a highly over-alloyed performed weldment (filler material 2.4607, german material No.) produces the best corrosion behaviour, measured as the critical temperatures of localized corrosion. Measurements of critical current densities of passivation can be used for investigations of corrosion behaviour of weldments, too. Critical current densities of passivation are showing a tendency to inverse proportion to the critical temperatures of localized corrosion. Suitable electrolytes are among others 0.2M H₂SO₄ + 1M NaCl + 10^?3% KSCN, N₂-bubbled, 25 to 60°C and xM H₂SO₄ + 4M NaCl + 10^?3% KSCN (x = 0.05 to 1), 25°C, in contact with air. An influence of heat input at the welding is indicated in the test of localized corrosion, but it is only small. It is sometimes more clearly shown at measurements of passivation.     

Die Oberflächenbehandlung von Schweißverbindungen hochkorrosionsbeständiger 6% Mo-Stähle und Nickel-Basis-Legierungen

Surface treatments of high alloy 6 Mo stainless steel and nickel alloy weldments High alloy stainless steels (6% Mo) and a high nickel alloy (alloy 625) weldment have been tested in order to answer the question whether post-treatment of the weldment has an effect on the corrosion resistance, especially on pitting corrosion. Therefore, the critical pitting temperature of weldments was tested in acidic chloride solution (standard tests). As a result grinding with rough emery paper as well as sand blasting lowers the localized corrosion resistance in the weldment area, while pickling has a positive effect, especially after blasting. Pickling can be done either by a solution of nitric + hydrofluoric acid or by a commercial pickling paste. In any event pickling is recommended as a final surface treatment for high alloy stainless steels and nickel alloys, especially in case of prevailing highly corrosive conditions such as pitting and crevice corrosion.     

Pitting and crevice corrosion of superaustenitic stainless steels

Superaustenites are mainly used in offshore applications, oil production and chemical industry. Most important types of localised corrosion of these steels are pitting and crevice corrosion. Investigated materials were N08028, S31254 and three modified alloys. Chromium content of investigated alloys varied between 20 and 27%, molybdenum between 3.2 and 6.0%, nitrogen between 0.1 and 0.36% and copper between 0 and 1.1%. For means of comparison stainless steel AISI 316L has been included in the study. Pitting and crevice corrosion of these highly corrosion resistant steels has been investigated by use of standardized tests. Critical pitting temperature and critical crevice temperatures were determined according to ASTM G 48, Methods C and D, respectively. Electrochemical measurements for determination of pitting potentials were done according to ASTM G 61 as well as for determination of critical pitting temperatures according to ASTM G 150. Results are presented as function of MARC (Measure of alloying for resistance to corrosion) defined by Speidel since linear correlation coefficients were higher when compared to conventional PREN. Results obtained by different testing methods must not be compared directly. Every test however is sensitive to microstructural defects like precipitations and segregations that decrease corrosion resistance. The higher alloyed a material is, the higher is its tendency to form microstructural defects, and the more difficult is it to reach its theoretical corrosion resistance at given chemical composition.     

Determination of the weaker phase in the pitting corrosion of non‐standard low‐Ni high‐Mn‐N duplex stainless steels

In this paper, the use of Energy Dispersive Spectrometry (EDS) is proposed to determine the partition coefficients of the elements of a new family of duplex stainless steels that are characterized by having low contents of nickel, together with high levels of manganese and nitrogen. From the values of the partition coefficients, the chemical compositions of the constituting phases have been determined, in order subsequently to calculate the value of the Pitting Resistance Equivalent Number (PREN) of each phase. The proposition put forward in this study is that the phase having the lower PREN determines the pitting corrosion behaviour of these types of steels. Results obtained by means of optical and scanning electron microscopy have provided confirmation that the pitting corrosion behaviour of these new materials gets determined by the resistance of the weaker phase and consequently by the phase having the lower PREN value. Lastly it has been proved possible to determine the existence of an exponential relationship between the alloys pitting potential (Ep) and the weaker phase PREN; this can be utilized for the low‐nickel duplex stainless steels design in which the pitting corrosion resistance is controlled.     

A double‐mode cell to measure pitting and crevice corrosion

Pitting corrosion and crevice corrosion of passivated steels were measured by using a double‐mode syringe electrolyte cell built on an environment chamber. The setup, when set in noncontact mode, could measure pitting potentials and critical temperatures, and crevice corrosion potentials if in contact mode. It could be employed to distinguish the pitting and crevice corrosion damage of reinforcing steel in concrete.     

Influence of the surface state on the Initiation of Crevice Corrosion on stainless steels

Results from sea-water and laboratory exposure tests with multiple crevice assemblies are presented. The results from tests on austenitic and ferritic-austenitic stainless steel samples subjected to various surface treatments demonstrate that an acid treatment greatly improves the crevice corrosion resistance of previously ground surfaces. Pickling in dilute sulphuric acid and passivation in nitric acid has thereby virtually the same beneficial effect as the common nitric + hydrofluoric pickling acid. The beneficial effect of pickling and passivation is related to the removal from the surface of sulphide inclusions, being potential nucleation sites for the initiation of discrete pitting attacks preceding the onset of crevice corrosion. Potentiodynamically determined pitting potentials and results from testing in 10% FeCl₃ · 6 H₂O according to ASTM G 48–76 show poor correlation with results from sea-water exposures.     

Korrosionsverhalten hochchromhaltiger,ferritischer, chemisch beständiger Stähle

Corrosion behaviour of high chromium ferritic stainless steels Ferritic steels developed for seawater desalination and containing 20 to 28% chromium, up to 5% Mo and additions of nickel and copper have been tested with respect to their corrosion behaviour, in particular in chloride containing media. The materials in the sensibilized state were tested for inter-crystalline corrosion susceptibility in the Strauß-, Streicher-, nitric acid hydrofluoric acid- and Huey-Tests. No intercrystalline corrosion was encountered in the case of the steels with 28% Cr and 2% Mo. The resistance to pitting was assessed on the basis of rupture potentials determined by potentiokinetic tests. The resistance of the steels with 20% Cr and 5% Mo or 28% Cr and 2% Mo is superior to that of the molybdenum containing austenitic types. Addition of nickel yields a significant increase in crevice corrosion resistance; the same applies to resistance in sulfuric acid. In boiling seawater all the materials tested are resistant to stress corrosion cracking. No sign of any type of corrosion was found on nickel containing steels after about 6000 hours exposure to boiling 50% seawater brine even under salt deposits.     

Der Einfluß von Schwefeldioxid,Schwefelwasserstoff und Kohlenmonoxid auf die Lochkorrosion von austenitischen Chrom-Nickel-Stählen mit bis zu 4 Massen-% Molybdän in 1 M Natriumchlorid-Lösung

The Influence of SO₂, H₂S and CO on Pitting Corrosion of Austenitic Chromium-Nickel Stainless Steels with up to 4 wt. % Molybdenum in 1 M NaCl Active corrosion of chromium-nickel stainless steel X 5 CrNi 189 (AISI 304) in H₂SO₄ is stimulated by H₂S as well as by SO₂ (extension of the potential range of active corrosion, increase of the maximum corrosion rate in the active state and of the passivation current density), but is inhibited by CO (decrease of both maximum active corrosion rate and passivation current density). It is investigated whether likewise stimulating and inhibiting effects are valid also in case of pitting corrosion of austenitic stainless steels with molybdenum contents ranging from about zero (material no. 1.4301) to 4 wt. % (material no. 1.4449), tested in 1 M NaCl (ambient temperature) saturated with the gases mentioned above. The pitting corrosion behaviour of the materials investigated is judged by their pitting potentials measured by potentiostatically controlled experiments (testing time 24 hrs). The pitting potentials are compared with those measured in 1 M NaCl, N₂-bubbled. Pitting corrosion is stimulated by SO₂, CO and H₂S, with the stimulating efficacy increasing in the sequence given before. No stimulation is found only in 1 M NaCl, SO₂-bubbled,-with the highest Mocontent. In all other cases, stimulation of pitting corrosion increases with increasing Mo-content of the stainless steels. In coarse approximation, the critical limiting potentials of stable pitting in 1 M NaCl, bubbled with H₂S, SO₂ CO, correspond to the critical potentials of repassivating pitting corrosion found in N₂-bubbled 1 M NaCl. The chemical reactions and reaction products of SO₂ in aqueous solution are discussed. The nature of the stimulating component of the corrosive medium is not quite clear. The stimulating effects of SO₂ or one of its reaction products and of H₂S on pitting are in keeping with their stimulating effect on active corrosion of the steels investigated. The stimulating effect of CO, however, is in contradiction to the results expected and cannot be explained.     

In vitro electrochemical investigations of advanced stainless steels for applications as orthopaedic implants

Potentiodynamic anodic polarization experiments on advanced stainless steels (SS), such as nitrogenbearing type 316L and 317L SS, were carried out in Hank’s solution (8 g NaCl, 0.14 g CaCl₂, 0.4 g KC1, 0.35 g NaHCO₃, 1 g glucose, 0.1 g NaH₂PO₄, 0.1 g MgCl₂, 0.06 g Na₂HPO₄ 2H₂O, 0.06 g MgSO₄ 7H₂O/1000 mL) in order to assess the pitting and crevice corrosion resistance. The results showed a significant improvement in the pitting and crevice corrosion resistance than the commonly used type 316L stainless steel implant material. The corrosion resistance was higher in austenitic stainless steels containing higher amounts of nitrogen. The pit-protection potential for nitrogen-bearing stainless steels was more noble than the corrosion potential indicating the higher repassivation tendency of actively growing pits in these alloys. The accelerated leaching study conducted for the above alloys showed very little tendency for leaching of metal ions, such as iron, chromium, and nickel, at different impressed potentials. This may be due to the enrichment of nitrogen and molybdenum at the passive film and metal interface, which could have impeded the releasing of metal ions through passive film.     

Die Bedeutung der metastabilen Lochkorrosion bei hochlegierten Stählen

The importance of metastable pitting corrosion in the case of high alloy steels A suitable computer-aided experimental method allows during potentiostatic tests to recognize and quantitatively treat current transients. The current transients result from metastable pitting phenomena below the pit propagation potential. It is possible under certain conditions to detect metastable pitting which in the SEM appears in the form of small (approximately 1 μm), in most cases hemispherical pits. A detailed study of metastable pitting has brought about fundamental knowledge about the mechanism of pit initiation, stable pit growth and repassivation in pitting and crevice corrosion processes.     

Temperature as a pitting and crevice corrosion criterion in the FeCl3 test

The FeCl₃ test is applied to an increasing extent for examining the resistance to pitting and crevice corrosion. Two methods having proved their value are described, the chemical properties of the FeCl₃ solution with regard to hydrolysis, pH and redox potential behaviour at various test temperatures are set forth and finally numerous results of the application of this test to high-alloy stainless steels and nickel alloys are presented. These results have been used to establish, be means of multiple regression, two empirical equations that allow to estimate rather accurately the critical pitting and crevice corrosion temperatures (CPT, CCT) from the contents of the decisive alloying constituents. These temperatures vary by about 2.5°C in the CPT test and by approx. 10°C in the CCT test, which can be reduced, however, by extending the test period beyond 24 hours. This is due to the fact that corrosion potentials in a 10% FeCl₃ · 6H₂O solution take a long time to stabilize. The variation of the critical crevice temperature can be further reduced by pressing the crevice blocks at a higher torque to the specimen. Another section particularly deals with the application of the CPT test for determining the influence of the matrix on the resistance to local corrosion. Consequently, the CPT test lends itself excellently to the examination of welds and as a quality control. Finally, CPT test results are compared with pitting data determined electro-chemically in artificial seawater. This shows that the ranking order with regard to corrosion resistance is identical, although media and processes differ considerably from each other.     

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.     

Zur Lochkorrosionsneigung von austenitischen CrNiMo-Stählen in konzentrierten Ammoniumrhodanidlösungen

Pitting corrosion of austenitic CrNiMo-steels in concentrated ammoniumrhodanide solutions Quasipotentiostatic and potentiokinetic polarisation measurements at various 18 Cr-10 Ni steels with molybdenum contents up to 4,3% were performed in 25 and 45% ammoniumrhodanide solutions. It was found that pitting corrosion is caused by incomplete passivation in the potential range of –300 to +250 m V _H. At these potentials the formation of stable passive layers is hindered by the formation and local oxidative dissolution of sulfidic layers. Above +250 m V _H rhodanide ions act in these weak acidic ammoniumrhodanide solutions as agents which destroy passive layers, comparable with chloride ions. The limiting potentials for stable pitting corrosion, obtained from potentiostatic experiments, are shifted from –300 to –150 m V _H with increasing molybdenum content of the steel. The least tendency of pitting corrosion was found for that steel with the highest molybdenum content.     

The stability of localized corrosion

Chloride pitting of iron group metals at noble potentials proceeds in the polishing state dissolution, provided that metal chloride in the pit solution is maintained above a critical concentration. It ceases to progress by pit repassivation if the pit is smaller than a critical size, or transforms into the active state pitting if the pit size is greater. The boundary potential between the polishing state and the active state pitting may be represented by the passivation-depassivation potential in the pit solution of the critical chloride concentration. Crevice corrosion is characterized by the crevice protection potential, at which the hydrogen ion concentration in the crevice solution is equivalent to pH_pd—the passivation-depassivation pH of the crevice metal. It continues to corrode at more noble potentials than the protection potential, where the crevice solution is more acidic than pH_pd, but is inhibited in the less acidic crevice solution at less noble potentials.     

Effects of shielding gases on the microstructure and localized corrosion of tube-to-tube sheet welds of super austenitic stainless steel for seawater cooled condenser

The effects of shielding gas on the microstructure and localized corrosion of tube-to-tube sheet welds of SR-50A super austenitic stainless steel for seawater cooled condense were investigated in highly concentrated chloride environments. The localized corrosion resistance of the weld metal after welding with an Ar shielding gas supplemented with N₂ increased due to a decrease in the pitting resistance equivalent number (PREN) difference between the PREN_IR of interdendritic region and the PREN_DC of dendrite core. The localized corrosion was selectively initiated at the dendrite core because the PREN of the dendrite core was smaller than that of the interdendritic region.     

Corrosion studies of austenitic and duplex stainless steels in aqueous lithium bromide solution at different temperatures

The corrosion behavior of three stainless steels EN 14311, EN 14429 (austenitic stainless steels) and EN 14462 (duplex stainless steel) was studied in a commercial LiBr solution (850 g/l LiBr solution containing chromate as inhibitor) at different temperatures (25, 50, 75 and 85 °C) by electrochemical methods.Open circuit potentials shifted towards more active values as temperature increased, while corrosion potentials presented the opposite tendency. The most resistant alloys to general corrosion were EN 14429 and EN 14462 because they had the lowest corrosion current for all temperatures. In all the cases corrosion current increases with temperature.Pitting corrosion resistance is improved by the EN 14462, which presented the highest pitting potential, and the lowest passivation current for the whole range of temperatures studied. The duplex alloy also presents the worst repassivation behavior (in terms of the narrowest difference between corrosion potential and pitting potential); it does not repassivate from 50 °C.     

Effect of chloride ions on electrochemical properties of anodized <Emphasis Type="Italic">AV</Emphasis> and <Emphasis Type="Italic">D</Emphasis>16 aluminum alloys in aqueous and glycerin-containing aqueous sodium sulfate solutions

The effect of chloride ions (0.01 N NaCl) on the electrochemical properties of anodized (in chromic anhydride or sulfuric acid) AV and D16 aluminum alloys in aqueous sulfate (0.5% Na₂SO₄) and glycerin-containing aqueous sulfate (0.5% Na₂SO₄, 33% glycerin) solutions is studied. Depending on the conditions of anodizing and the composition of the alloy and environment, currents on the anodized alloys in the passive range are shown to be smaller by one to four orders of magnitude compared to those on nonanodized alloys. Anodizing increases the resistance of alloys against pitting corrosion. Alloys anodized in sulfuric acid and then treated in dichromate are not susceptible to pitting corrosion. Alloys anodized in chromic anhydride are less resistant against pitting.