Inter- und transkristalline Spannungsrißkorrosion austenitischer Mn- und CrNi-Stähle in Meerwasser

Intercrystalline and transcrystalline stress corrosion cracking of austenitic Mn and CrNi steels in seawater The MnCr steels which were originally used for the construction of special ships turned out to be susceptible to intercrystalline stress corrosion cracking in seawater; later on, transcrystalline corrosion susceptibility was found, too; this latter type of corrosion appears in cold seawater and is not due to a sensilizing annealing. This type of corrosion was also found with austenitic CrNi steels in chloride solutions of higher temperature, not, however, at room temperature. The author has made an effort at defining the susceptibility regions of the particular austenitic steels. According to the results obtained it is necessary always to take account of the possibility of stress corrosion cracking when Mn based austenitic steels are used, while austenitic CrNi steels can be considered to be resistant to this type of corrosion. Sensilizing annealing, too, has a bearing on the Mn containing steels only, while the influence of temperature, potential, specimen diameter and stress does not reveal any difference between the two types of steels.     

Passivierungsverhalten und Spannungsrißkorrosion von Eisen-Mangan-Chrom-Legierungen in Natriumchlorid-Lösung

Passivation behaviour and stress corrosion cracking of iron-maganese-chromium alloys in sodium chloride solution Electrochemical experiments with MnCr steels (20–28% Mn, up to 12% Cr) in 3% NaCl solution. High Mn contents reduce the passivation tendency, while increasing Cr contents broaden the range of passivity. The formation of surface layers is due primarily to a direct reaction with the solution (good adhesion, high protective value) and, secondarily, to precipitation from the solution (porosity, low protective value). The tendency to form secondary layers increases as the Cr content is reduced. In oxygen containing solution there is a pronounced corrosion in the pitting range. At low Cr contents, stress corrosion cracking is mostly transcrystalline, at higher Cr contents (8–12%) it is intercrystalline, in particular when Cr carbide precipitations are present at the grain boundaries. In the range of transcrystalline corrosion the susceptibility to selective corrosion extends beyond the pitting potential. At higher Cr contents there may be pitting without any indication of stress corrosion cracking.     

Gegen die Spannungsrißkorrosion beständige nichtrostende Manganchromstähle

Stress-corrosion resistant stainless manganese chromium steels The following conclusions may be drawn from the results of investigations into the stress corrosion cracking of austenitic and austeno-ferritic MnCr steels (19–22Mn, 13–18Cr, additions of Mo, V, Nb, Ti, N, B): Addition of nitrogen gives rise to a decrease of stress corrosion cracking resistance in magnesium chloride, sodium chloride with potassium dichromate and water at high temperatures. The same applies to the influence if nickel on corrosion in magnesium chloride and water, and for molybdenum in magnesium and sodium chlorides. From among laboratory melts the type 05 Mn 19Cr 13 had the highest resistance, followed by its modifications with additions of boron, vanadium, molybdenum, titanium, niobium and nitrogen. From among the semi-technical melts the nitrogen containing steels turned out to be least resistant, too. During further investigations the chromium level of 13% turned out to be insufficient to prevent pitting in sodium chloride solutions including seawater.     

Transkristalline Spannungsrißkorrosion an austenitischen Manganstählen in chlorionenhaltigen Angriffsmedien

Transcrystalline stress corrosion cracking of austenitic manganese steels in corrodent containing chloride ions Experimental investigation with steels (0,5% C, 20% Mn, 0.2—2.7% Cr) in the shape of U-bent specimens in seawater (RT and boiling) under loads between 30 and 45 kp/mm². The electrochemical behaviour of chromium-free types (i.e. below 0.5% Cr) at RT is identical to that of ferritic shipbuilding steels (equal break-through potential, then uniform attack). Addition of N, Ni, Co and Cu have little influence on the potential behavior. In boiling sea-water, however, transcrystalline corrosion takes place, accelerated by high tensional loads and anodic polarization, and slowed down by cathodic polarization. Additions, in particular of Co and Ni, reduce specimen life, perhaps by reducing yield strength. At higher Cr contents (1.7–2.8%) susceptibility to intercrystalline corrosion begins to supersede susceptibility to transcrystalline cracking. On the basis of ideas concerning the active-passive behavior under the influence of gliding phenomena the author shows analogies to the stress corrosion behaviour of austenitic stainless steels.     

Untersuchungen über den interkristallinen Kongrenzenangriff von austenitischen Mangan-Chrom-Stählen durch Wasser und wäßrige Lösungen

Research on intercrystalline grain boundary corrosion of austenitic manganesechrome steels caused by water and aqueous salt solutions Stressed bar specimens of welded and tempered austenitic manganesechrome steel such as as X 40 MnCr 18 and X 22 MnCrNi 885, exposed to sea water, tap water or destilled water, are liable to suffer intercrystalline stress corrosion cracking. The occurrence of intercrystalline corrosion is not necessarily dependent on mechanical tensil stress. In particular, even unstressed specimens exposed to tap or distilled water are liable to show marked intercrystalline corrosion. Additional tensile stress merely has the effect of speeding up the inter-crystalline corrosion. The cause for the intercrystalline corrosion must be seen in the segregation of chrome-rich carbids at the grain boundaries and the consequent reduction in the chrome content within the grain boundary zone. It is possible to prove the segregation of a chrome-rich carbide of the structure M₇C₃ at the grain boundaries of steel X 40 MnCr 18, and the aggregation of a chrome-rich carbide of the structure M₂₃C₆ at the grain boundaries of steel X 22 MnCrNi 885. Through contact with zinc, it is possible to obtain a complete corrosion protection with the manganese-chrome steels investigated. A short circuit with passive austenitic chrome-nickel steels increases the general or selective corrosion rate through anodic polarisation. By adding chromate to the sea water, the corrosion rate is retarded. In tap water, an addition of chromate result in complete corrosion protection.     

Austenitische gegen Spannungsrißkorrosion in konzentrierten Chloridlösungen beständige Manganchromstähle

Austenitic manganese chromium steels resistant to stress corrosion cracking in concentrated chloride solutions The testing of stress corrosion susceptibility in MgCl₂ and CaCl₂ shows that the classical Austenitic CrNi and CrMnNiN steels are not sufficiently resistant to this type of corrosion. On the other hand MnCr steels exhibit good resistance even in hot solutions. The resistance, however, is considerably deteriorated by addition of Ni even in small quantities; with Ni contents up to 0.5%, however, the time to failure is still considerable. This fact is important since such nickel contents must be counted with because of production conditions in metallurgy. On the basis of experiments including investigation into mechanical properties, microstructure, metallic phases present and stress corrosion resistance (under constant tensile load) in MgCl₂ solution (35%, 115–120 °C) the authors selected out of 62 types of steels tested four experimental austenitic MnCr steels meeting the following complex of requirements: high resistance in MgCl₂ solution, sufficiently high resistance to intercrystalline corrosion, certain resistance to pitting and practically monophasic (austenitic) structure.     

Zur Spannungsrißkorrosion austenitischer Chrom-Nickel-Stähle

Contribution to the stress corrosion cracking of austenitic chromium nickel steels The authors present a summarizing treatment of the transcrystalline stress corrosion cracking of chromium nickel steels in chloride solutions. The factors having a bearing on the susceptibility to this type of corrosion during operation, temperature and p_H of the medium. Residual stresses may be due to heat-input (during welding) or to grinding which, in addition, may give rise to notch effects. The medium generally used to test stress corrosion susceptibility (MgCl₂ solution) acts according to different mecanisms, depending on its concentration which, in term, has an influence on p_H and the boiling temperature. Quite generally it may be said that stress corrosion cracking always presupposes the existence of a lower of stresses, the amount of these stresses depending from the structural factors and from the surface condition.     

Der Einfluß der Strahlenschädigung durch schnelle Neutronen auf die Spannungsrißkorrosion (SKR) von Eisen-Chrom-Nickel-Stählen

Influence of radioactive deterioration by fast neutrons on stress corrosion cracking of chromium-nickel steels Neutron irradiation has a bearing on the mechanical properties of the pure and industrial steels investigated. The creep limit is increased while the range of uniform elongation is reduced. Under an integral fast neutron flux of about 2.5.10¹⁹ n/cm² there is a defined yield strength increasing the stress corrosion susceptibility and there are indications of intercrystalline cracking in some cases. The industrial alloy has exclusively transcrystalline cracks een after neutron irradiation; the crack density is higher than in the pure alloy.     

Bildung und Einfluß von α'-Martensit auf die Spannungsrißkorrosion von Chrom-Nickel-Stählen

Formation of martensite and influence of the latter on stress corrosion cracking of chromium nickel steels Martensite formation depends from alloy composition, deformation and undercooling. By contrast to an industrial alloy corresponding to (DIN) X 10 CrNiTi189 a pure Fe 19 Cr 10 Ni alloy becomes partially martensitic upon deformation and quenching to ?190 °C. Undercooling and subsequent deformation give rise to the addition of deformation and quenching martensite. The formation of α′-martensite is largely suppressed by addition of 2% Mo. Since corrosion resistance in aqueous MgCl₂ solutions increases with the α′-martensite contents, cracks grow predominantly along the martensite plates. Addition of molybdenum reduces stress corrosion resistance because of the suppression of martensite formation. In this type of alloy cracking is intercrystalline nature.     

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.     

The austenitic manganese-chromium steels resistant to stress corrosion cracking

The basic type of MnCr steels (composition 0.05Mn19Cr13) was found to be highly resistant to chlorides. Additions of titanium, niobium and vanadium did not impair resistance to stress corrosion cracking, but addition of nickel in excess of 0.5% appreciably impaired the resistance. The chemical composition of the stabilized steels was selected in such a way as to make the ferrite content as low as possible. The two stabilized steel grades ability to passivate was limited, also because of the presence of manganese; this makes these grades suitable only for less aggressive environments. The ferrite content can be controlled, or the chromium content increased for better corrosion resistance, only by adding another strong austenite-former. Considering the adverse effect of nickel on the resistance to stress corrosion cracking, attention was given to manganese-chromium grade modified with nitrogen and molybdenum.     

Die Abhängigkeit der Spannungskorrosionsanfälligkeit vom Werkstoffzustand bei homogenen Kupfer-Zink-Legierungen

Interdependence of stress corrosion susceptibility and structural state of homogeneous copper-zinc alloys Experimental investigations in ammoniacal solution of copper and ammonium sulfates have shown, that — with equal load ratio (σ/σ_0,2 = 0,9) — CuZn alloys are less sensitive to stress corrosion cracking after recrystallizing annealing than after cold working. The sensitivity increases with increasing Zn content and appears to depend primarily from the dislocation structure: parallel structures are highly sensitive while increasing transition to cellular dislocation structure reduces stress corrosion susceptibility. In the cold worked alloy the crack geometry is predominantly transcrystalline, in the recrystallized state intercrystalline. Similar relations between dislocation structure and susceptibility seem to exist in the case of austenitic stainless steels.     

Korrosion in der Wärmeeinflußzone geschweißter chemisch beständiger Stähle und Legierungen und ihre Verhütung

Corrosion in the heat-affected zone of welds in chemically resistant steels and alloys, and respective preventive measures As to weldability, chemically resistant steels and alloys can be classified as follows: (1) weldable without any restriction; (2) weldable only with reduced wall thickness; (3) weldable only with ultimate thermal treatment. These restrictions are due to the precipitation of chromium carbide and intermetallic phases at the grain boundaries; this effect gives rise to a Cr and Mo depletion and, finally, to intercrystalline corrosion susceptibility. In view of the fact that weldability requires the delay of the precipitation of chromium carbides at 650°C for at least 1 hour, and of intermetallic phases at 900°C for at least 10 min it is possible to reduce the carbon content and/or to add stabilizing elements (Ti, Nb). It should be taken into account, however, that the precipitation behaviour is not a function of carbon concentration, but rather of carbon activity which, again, depends from the overall composition of the respective alloy. This activity is increased by Ni and Si, while Mn and N function as decelerators and, consequently, contribute to weldability. In the case of the steel X 3 CrNiMoN 17 13 5 the addition of N inhibits not only the carbide precipitation but also the precipitation of the Chi-phase (at 950°C). In the case of the alloy NiMo 16 Cr the gradual reduction of the contents of secondary constituents has resulted in a practically pure ternary system characterized by high precipitation resistance: carbides are precipitated only after 5 hours at 800°C.     

Einfluß der Spannung auf die Empfindlichkeit eines austenitischen Chrom-Nickel-Stahles gegenüber Spannungsrißkorrosion

Influence of stress on the sensitivity of an austenitic chromium-nickel steel to stress corrosion cracking The transcrystalline stress corrosion cracking of a chromium-nickel steel (German designation X 5 CrNi I8 9) in 35 % magnesium chloride solution at 150°C exhibits a well defined limit at the 0.01 %yield stress. In the range of intermediate stresses the stress corrosion resistance increases as the load is increased. This behaviour may be interpreted in terms of the time required for the formation of stable cracks. This mechanism apparently follows the gliding step-repassivation model involving a reduction in height of the gliding steps and the influence of a cathodic protection due to the reduction of the mixed potential.     

Elektrochemische Methode zur Untersuchung der Anfälligkeit korrosionsbeständiger Stähle für interkristalline Korrosion

Electrochemical method to study the intercrystalline corrosion susceptibility of stainless steels In continuation of earlier work concerning a method suggested for the electrochemical evaluation of the intercrystalline corrosion susceptibility of corrosion resistant steels a potentiodynamic polarization method has been worked out which is based on the principle of the reactivation from the passive state. This method has been tested on austenitic chromium nickel and chromium nickel molybdenum steels with different carbon contents. In order to check and modify the sensitivity of the new method parallel tests of intercrystalline corrosion susceptibility have been carried out in a standard solution containing copper chips. The susceptibility to intercrystalline corrosion of the individual steels has been evaluated on the basis of the intercrystalline corrosion regions in function of temperature and duration of sensitization (so called Rollason curves). The ratio of the reactivation charge to the charge in the active range of the polarization curve (at increasing potential), expressed in per cent, appears to be an optimum quantitative criterion to asses corrosion susceptibility. On the basis of a comparison with the results obtained in the standard solution susceptibility to intercrystalline corrosion must be accounted for starting from a definite value of this ratio (in the case of chromium nickel steels e. g. at values above 18%). The sensitivity of the method may be modified for the individual types of steels either by modification of the test conditions, in particular temperature and potential change rates, or by the selection of the electrolyte or of its chemical composition.     

Oberflächenpotentialprofile von metallen

Surface potential profiles of metals Using a microcapillary method in connection with simultaneous metallographic observation surface potential profiles have been determined with the potential probe in alcoholic acid solutions on cast iron, CrNi aciers steels 188, Cr steel with 17% Cr (welded) and an AlCu alloy. It was possible to distinguish cementite from ledeburite, not however, from austenite. The potential of 188 steel under pitting conditions decreases as a linear function of pit depth. The appearance of potential minima in a weld of ferrite steels is evidence of a intercrystalline corrosion in that particular medium. The precipitation of CuAl₂ in AlCu alloys at 150 °C at the grain boundaries forms an element with the grain boundary as the anode giving rise to intercrystalline corrosion.     

Inkubationszeit und Rißverlauf bei der transkristallinen Spannungrißkorrosion austenitischer Chrom-Nickel-Stähle in Magnesiumchlorid-Lösungen

Incubation period and cracking progress during the transcrystalline stress corrosion cracking of austentitic chromium nickel steels in magnesium chloride solutions A very sensitive measuring method has enabled new details to be brought to light with respect to to the corrosion behavior of an austenitic steel. According to studies on a steel (German designation Werkstoff-Nr,1.4301) the stress corrosion cracking is a process in three stages, it is a creep stage proceeding apparently without perturbation, a period of discontinuous crack growth and finally a period of discontinuous crack growth. The duration of the incubation period which can be experimentally determined depends from the sensitivity of the measuring method; the ture incubation period, however, is always shorter than the experimentally determined value. The incubation period which is determined on the base of specimen elongation is followed by a discontinuous period characterized by crack-growth and subsequent repassivation and finally by a period with continuous crack growth. This behaviour can be interpreted in terms of the glide step-repassivation model.     

Elektrochemisches Verhalten und Deckschichtbildung hochlegierter Manganstähle

Electrochemical behaviour and scaling of high alloy manganese steels Passivating surface layers are considered to be one of the indispensable requirements for stress corrosion cracking of metallic materials. It is shown by potentiostatic and potentiokinetic current density-potential curves that the steel X 40 MnCrN 19 in neutral aqueous chloride solutions has a passive potential region. The passivation behaviour Of precipitation hardened samples is in agreement with the chromium depletion theory. The effect of alloying on the passivation behaviour of low carbon Mn steels is studied in 3 % NaCl solution at 20 and 100 °C Increasing proportions ε-martensite reduce the passivation of susceptibility. Increasing the Mn content has the same effect. The vital factor concerning passivation behaviour, however, is chromium content. Increasing the temperature of the corrodent results in an increased tendency to form scales of steels containing less than 8 % Cr. Long-term corrosion tests have shown, that increasing the Cr content produces a continuous transition from general localized and even pitting Corrosion. Tests made without applied current in aerated solutions have shown, that the variation in time of corrosion potentials depends from the tendency to be passivated of the materials and from the oxygen content of the solutions. In oxygen containing solutions passivable steels exhibit a pronounced corrosion in the pitting region, because with such alloys anodic dissolution current densities equal to those of the limiting diffusion current of oxygen reduction are obtained only at potentials above the pitting potential.     

Einfluß der Legierungselemente auf die Passivierung und die Korrosionsbeständigkeit der Legierungen auf Eisen-Chrom-Basis

Influence of alloying elements on the passivation and the corrosion resistance of iron chromium base alloys The authors investigated the influence of cathodic alloying (with 0.1–0.5% Pd) on the passivation and the corrosion resistance of alloys of the system FeCr(25–100% Cr) and 25% Cr steels containing Mn, Ni, Mo and N; the experiments have been carried out in hot concentrated sulfuric acid and diluted hydrochloric acid solutions. It has been found that the addition of Pd as a cathodically active component considerably increases the autopassivation tendency as well as the corrosion resistance of the alloys under the particular conditions. Mn gives rise to improved autopassivation of austenitic and austenitic ferritic CrNi and CrNiMo steels, since it is catodically active, too. Cr steels cathodically alloyed with Pd acquire resistance to hydrochloric acid, too.     

Untersuchung von Sonderfällen der Spannungskorrosion bei homogenen,nicht übersättigten Mischkristallen und der hierbei auftretenden elektrochemischen Prozesse

Research into special cases of stress corrosion with homogeneous non-over-saturated mixed crystals, and of the electro-chemical process associated with it Research has been carried out into the sensitivity to stress corrosion cracking of nickel-copper alloys with high nickel contents. It was found that these alloys are sensitive to stress corrosion in hydrofluoric acid containing CuF₂, but not in pure hydrofluoric acid. This was found to be due to the formation of cathodic areas consisting of Cu₂O or Cu, depending on the acidity of the agent. These are prequisite to the occurrence of a marked electro-chemical process in the gaps and the two mixed crystal effects, to the occurrence of stress corrosion. For the alloy showing the highest sensitivity — an alloy of the “Monel” type with some 70 weight per cnt. of nickel, the remainder copper — the correlation between lifetime and CuF₂ and HF concentration was determined, and plotted in a three-dimensional diagram. This alloy also shows, in diluted HF solutions containing CuF₂, a considerable intercrystalline corrosion whilst, in more highly concentrated solutions, a tensile stress causes transcrystalline cracks only. The investigations also comprised the chronological sequence and the stress and temperature dependence of the stress corrosion process as well as the activation energy.