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.     

Effect of nickel alloying on crevice corrosion resistance of stainless steels

The crevice corrosion behaviour of stainless steels containing 25 mass% Cr, 3 mass% Mo and various amounts of Ni was investigated in natural seawater. The results showed that ferritic steels containing nickel were more resistant to corrosion than both ferritic steels without nickel and austenitic steels. The superiority of the Ni bearing ferritic steel over the other steels was in close agreement with the depassivation pH of those steels in acidic chloride solutions. The results showed that the addition of Ni to ferritic steel was effective in decreasing the depassivation pH and the dissolution rate in acidic chloride solutions at crevices.     

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.     

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.     

The enrichment of hydrogen and chloride ions in the crevice corrosion of steels

The changes in concentration of hydrogen and chloride ions during corrosion in an artificial crevice on steel were observed from potential changes of Pd-H and Ag/AgCl micro-electrodes inserted in the crevice. Increasing the bulk chloride ion concentration accelerated the rate of pH change and resulted in more acidic conditions in the crevice. Such pH changes were delayed by the addition of inhibitor such as dialkylamines. Though the free chloride ion concentration did not change appreciably, the total concentration of free and complex ions in the crevice increased with continuous dissolution of the steel. Increasing the hydrogen and total chloride ion concentration in the crevice accelerated the anodic dissolution of steels within the crevice.     

Effects of chloride and crevice on corrosion resistance of stainless steels buried in soil within Seoul Metropolitan

Field and laboratory tests were conducted to find the factors affecting corrosion of stainless steels in soil. During one-year exposure, corrosion occurred within a joint and on the surface of type 304 pipe with the joint, which was buried at the site with a high chloride concentration of about 3680 ppm; however, corrosion was not observed at any of the other sites independent of the stainless steel grade and the presence of joints. At some sites, a seasonal fluctuation of corrosion potential was observed in the soil though corrosion did not occur. This observation may be due to the activity of sulfate reducing bacteria because a decrease of corrosion potential with the inoculated bacteria did not cause corrosion of stainless steels. These results indicate that both the level of chloride and the presence of crevices are the main factors affecting corrosion of stainless steels in soil but that the activity of bacteria is not. From measurements of pitting potential, a guideline for stainless steel use in soil is drawn as follows: Corrosion of stainless steels in soil occurs when the pitting potential of stainless steel under crevices in synthetic ground water that contains the same chloride concentration as the soil is less than the saddle potential. Finally, the guideline for stainless steels applications was provided in this paper according to this criterion.     

An X-ray photo-electron spectroscopic study on the role of molybdenum in increasing the corrosion resistance of ferritic stainless steels in HC1

X-ray photo-electron spectroscopy has been used to investigate the correlation between composition of surface films and the beneficial effects of molybdenum addition to high purity, 30Cr ferritic stainless steels in improving the corrosion resistance properties in HCI. It has been found that the passive films formed consist mainly of hydrated chromium oxy-hydroxide and the composition of the films on 30Cr and 30Cr-2Mo stainless steels is essentially the same, except for the existence of a small amount of hexavalent molybdenum on the latter steel. The surface film formed in the active region contains a large amount of hexavalent molybdenum. The beneficial effects of molybdenum have been interpreted as follows: molybdenum eliminates the active surface sites through the formation of molybdenum oxy-hydroxide or molybdate on these site, on which it is difficult to form the stable passive film. This leads to the appearance of a homogeneous steel surface and to the formation of a homogeneous passive film.     

Effect of nitrogen on crevice corrosion in austenitic stainless steel

Corrosion properties of high nitrogen austenitic steels in chloride solutions have been investigated. Nitrogen behavior was evaluated at various electrode potentials, and analysis of the surface film was carried out with XPS. The alloy used for the experiments had a composition of 23%Cr-4%Ni-0-1%Mo-0.7-1%N and was obtained through electro-slag remelting (ESR) under high nitrogen pressure. High nitrogen austenitic steel produced in the solution by crevice corrosion under a constant potential of 0.2 V (SCE). In the transpassive region and at 0.7 V (SCE), the products in the solution were , and . The amount of dissolved and increased with the electrode potential. in the solution suppressed decreases of pH, having a re-passivation effect. For crevice corrosion under a higher electrode potential than 0.4 V (SCE), the number of crevice corrosion points and the corrosion loss decreased as the electrode potential increased. This behavior can be attributed to the corrosion suppressing effect of dissolved in the solution as a product of crevice corrosion. The presence of chromium and iron oxides in the passivation film and crevice corrosion surface film were identified from XPS analysis. N 1s spectra indicated the presence of a nitride (CrN) or NH₃.     

A role of manganese in the corrosion and electrochemical behavior of stainless steels

Sections of phase diagrams for the Fe-Mn-O system and potential-pH diagrams for the systems Fe-Mn-H₂O, -phase (austenite of 12X18H10T or 10X1414H4T steels)-H₂O, and MnS-H₂O at 25°C are plotted. Thermodynamic aspects of the effect of manganese on the corrosion and electrochemical behavior of stainless steels are discussed.Translated from Zashchita Metallov, Vol. 41, No. 1, 2005, pp. 74–81.Original Russian Text Copyright © 2005 by Tyurin.     

The role of inclusions in crevice corrosion of high- alloy austenitic stainless steel tube used in seawater- cooled condensers

In view of the reported superiority of high chromiuni-nickel-molybdenuni austenitic stainless steel tube over copper alloy tube in seawater-cooled condensers, two such compositions were tested for crevice cor-rosion performance in seawater using a Campbell test rig. Tube of one particular alloy composition was free of crevice attack in seawater testing, whereas tube of the other alloy composition experienced exten-sive crevice attack. Anodic cyclic polarization test results carried out in the laboratory were in agreement with the field test results for these alloys. It was thus concluded that inclusion morphology, together with alloy composition, should be considered in the selection of tube materials for condenser applications.     

The role of molybdenum additions to austenitic stainless steels in the inhibition of pitting in acid chloride solutions

In order to clarify the mechanism for increased resistance to pitting in acid chloride solutions by addition of Me to CrNi stainless steels, the anodic polarization curves, a.c. electrode impedances, ellipsometric parameters and X-ray photo-electron spectra have been measured on the Mo-containing steels passivated in 1N HCl. The results showed that the presence of an adequate amount of Cr is indispensable for the improvement of pitting resistance by the Mo addition. The passive films of the Mo-containing steels were found to be composed of a complex oxyhydroxide containing Cr³⁺ Fe²⁺, Ni²⁺, Mo⁶⁺ and Cl^? and showed a rather higher d.c. resistance in HCl solution than in H₂SO₄ solution. The thickness of the passive film increases with increase in Mo content.     

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.     

Influences of alloyed molybdenum and molybdate addition on the corrosion properties and passive film composition of stainless steels

The influences of alloyed molybdenum and molybdate addition on the corrosive properties and passive film composition of stainless steels were evaluated. Anodic polarization measurement, solution analysis, and surface analysis were conducted to investigate the influences. The roles of alloyed molybdenum and molybdate addition were observed to vary with the environment. In addition, the role of molybdate addition depended on the presence of nitrogen in the alloy. The composition of the passive film formed by alloyed molybdenum was found to be different from that of the film formed by molybdate addition. These observations suggest that when the thermodynamical condition in the film is suitable for the formation of molybdate, it first forms in the film and then later partially dissolves into a solution and partially evaporates.     

The role of electrolyte concentration on crevice corrosion of pure nickel

In this work an artificial crevice electrode was used in conjunction with a fine microprobe assembly to measure the potential inside the crevice. Using this setup crevice corrosion of commercially pure nickel was investigated in sulfuric acid with concentrations: 0.5, 1 and 2N. The outer surface of the Ni was held at a passive potential of 530 mV(SCE) while the experiment was running. The results showed a steep potential decay observed in all concentrations. For 0.5, 1 and 2N H₂SO₄, the total potential drop inside the crevice was: 681, 619 and 593 mV, respectively. This indicates the higher the acid concentration is the lower the potential drop will be. On the other hand, the measured current was highest (4.09 mA) for 2N and lowest (1 mA) for 0.5N. On the crevice wall a boundary was found to exist between the passive and the active regions. These findings point toward the IR voltage drop mechanism operating for this system.     

Crevice corrosion of stainless steels in sodium chloride solution

Nucleation of crevice corrosion of five stainless steels in NaCl solution has been studied using potentiokinetic and galvanostatic methods. It is inferred that a well reproducible critical potential for crevice corrosion nucleation exists. This potential depends on the type of steel and is more negative than the critical potential for pit nucleation. The difference between the potential for crevice corrosion and that for pitting is higher for more resistant steels than for less resistant ones. A mechanism explaining the crevice corrosion in chloride solutions is proposed.