Einfluß von Passivierungs- und Kohlenstoffschichten auf austenitischen CrNiMo-Stählen auf die Beständigkeit gegen Lochfraß und Spannungsrißkorrosion

Effects of passivation and carbon films on austenitic CrNiMo steels on their piting and stress corrosion resistance The influence of passive film and combinations of a passivation and a carbon layer on the resistance to pitting and SCC of austenitic CrNiMo steels has been investigated in physiological sodium chloride solution (Tyrode solution) at pH 6.9 to 7.4 at 37 ± 1°C. The passive film was obtained after electrolytic polishing in H₃PO₄ + H₂SO₄ + C₆H₅NHCOCH₃ + oxalic acid + corrosion inhibitor CS by treatment with 40% nitric acid the carbon film was obtained by CVD. Impurities in the steel (non-metallic inclusions) and the different metallic phases were investigated and the chemical composition of the passive film was determined by quantitative analysis. The resistance to pitting of the steel with and without passive film was determined potentiodynamically in Tyrode's solution at 37 ± 1°C. The resistance to SCC was determined in Tyrode's solution at 37 ± 1°C, in neutral glycerole and in boiling magnesium chloride solution at 154 ± 1°C and evaluated in terms of K_σ and K_τ. The corrosion damage was investigated by optical and scanning electron microscopy. The investigations have revealed that the different surface conditions considerably improve the pitting and SCC resistance of the steels in the media used in this work, so that they make possible the use of these materials as surgical implants.     

Einfluß von Natriumchlorid auf die Oxidation von hochlegierten Chrom- und Chrom-Nickel-Stählen

Effects of sodium chloride on the oxidation of high alloy Cr- and Cr-Ni-steels The effects on the oxidation were investigated of solid NaCl deposits on the oxide scales of the technical steels X10 CrMoV 12 1, X15 CrNiSi 20 12 and X10 CrNiSi 25 20 at 700°C. Independent of the alloy composition the presence of NaCl(s) initiated a markedly accelerated Fe₂O₃ growth on the surface of preoxidized samples, under formation of voluminous, nonprotective layers. Below these scales on the metallic matrix in all cases chloride was detected. The oxides grow according to the mechanism of active oxidation in which chlorine plays a catalytic role. The presence of the chloride at the oxide/metal interface reduces the adhesion of the oxide scale and leads to spalling upon cooling to room temperature. The effects observed are independent of the alloy composition, however, the thickness of the oxide scale is decisive which means the diffusion distance for the gaseous iron chloride.     

Einflüsse von Werkstoff und Verarbeitung auf die Spannungsrißkorrosion von Spannstählen

Influence of material and processing on stress corrosion cracking of prestressing steel In prestressed concrete constructions the highstrength prestressing steels perform essential bearing effects. The alkaline layer of concrete or mortar protects the steels against corrosion and guarantees a permanent load capacity. If the corrosion protection as a result of poor workmanship is not guaranteed from the beginning, or is lost because of lacks of construction in the course of time, or the steels are predamaged during handling, stress corrosion cracking and failure of steel and construction may occur. Also an application of unsuitable materials (prestressing steel, injection mortar, concrete) can alone or in combination with the before mentioned influences favour stress corrosion cracking. In the contribution the correlations and typical failures are discussed.     

Einflüsse des Phosphors auf die Interkristalline Spannungsrißkorrosion von Kohlenstoffstählen

Influence of phosphorus on the intergranular stress corrosion cracking of carbon steels The effects of phosphorus on the intergranular stress corrosion cracking were studied for steels with 0.15% C and 0.4 or 2% Mn, the phosphorus contents were 0.003, 0.03 and 0.05% P. Constant strain rate tests were conducted at constant potentials in 55% Ca(NO₃)₂ at 75°C, in 5 N NH₄NO₃ at 75°C, and in 33% NaOH at 120°C. The strain rate was 10^?6/s. Different grain boundary concentrations of phosphorus were established by varying the annealing time at 500°C, they were determined by fracturing the samples in UHV and analyzing intergranular fracture faces by Auger-electron spectroscopy. In the nitrate solutions the toughness, i.e. resistance against stress corrosion cracking of the steels is somewhat decreased with increasing P-content within the range of the corrosion potential, that is ?300 mV_H to ?50 mV_H in NH₄NO₃ and ?80 mV_H to ?50 mV_H in Ca(NO₃)₂. It is shown that this effect is caused by phosphorus segregated at the grain boundaries. At potentials above ?50 mV_H the relative toughness is very low for all tested steels, also without stress intergranular attack is observed. In NaOH the steels are most sensitive against stress corrosion cracking at ?700 mV_H, here the phosphorus content or segregation shows no effect. At potentials varied in both directions the toughness increases and a somewhat negative effect of phosphorus becomes visible. In all tested electrolytes the effect of phosphorus is restricted to a small potential range. There is no effect of phosphorus in the range of the minimal toughness, thus the steels are sensitive anyway, with and without phosphorus segregation. Therefore low phosphorus contents in carbon steels cannot guarantee resistance against stress corrosion, most decisive are the potential and the electrolyte.     

Einfluß von Kohlenstoff,Stickstoff und Phosphor auf die interkristalline Korrosion und Spannungsrißkorrosion des Eisens

Effects of carbon, nitrogen and phosphorous on the intergranular corrosion and the stress-corrosion cracking of iron Experiments without stress, with constant load, or with constant strain rate were performed in boiling 55% Ca(NO₃)₂ solution (115°C) to elucidate the effects of carbon, nitrogen and phosphorous on the intergranular corrosion (IC) and stress-corrosion cracking (SCC) of iron. The original material contained 20 to 40 ppm C, 17 ppm N, and 20 ppm P. One batch of this material was normalized only, a second batch was also decarburized up to under 10 ppm C prior to normalizing, and a third batch was decarburized, and then nitrided up to 140 to 220 ppm N prior to normalizing. Some of the specimens were tempered at 550°C for one month. All normalized specimens showed no susceptibility to IC at applied potentials from 800 to 1000 mV (SHE). In contrast, specimens tempered at 550°C were very susceptible to IC, which was observed even at 200 mV after decarburization. Auger-spectra of intergranular fracture surfaces of a tempered specimen produced at liquid-nitrogen temperature revealed grain boundary segregation of P (about 10 atomic %). The as-normalized specimens fractured intergranularly within 1 to 2 h, when held at constant load of 0.8 and 0.9 of ultimate tensile strength (UTS), and 0 mV. By contrast, under identical conditions, the decarburized specimens and the nitrided specimens did not fracture in 30 d. The fracture energy tested with the constant strain-rate method at 0 mV, as compared with experiments in oil, was strongly lowered in the as-normalized specimens and significantly lowered in the nitrided specimens. The values of fracture energy obtained for the decarburized specimens were mostly similar to those in oil at 115°C. Only some of the decarburized specimens showed substantial decreases in fracture energy. However, the decarburized and tempered specimen showed an even larger decrease in fracture energy, with intergranular fracture mode.     

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.     

Erweiterte Diskussionsbemerkungen zum Einfluß von Silicium und Molybdän auf die Spannungsrißkorrosionsempfindlichkeit austenitischer und austeno-ferritischer Chrom-Nickel-Stähle

Amplified discussion of the influence of Silicon and Molybdenum on the stress corrosion cracking proneness of austenitic and austeno-ferritic chrome-nickel steels Tests have been carried out in boiling magnesium chloride, calcium chloride, NaCl, water (150–200°C) and hot steam (500°C); in the two last-named cases, the tests were carried out with and without the addition of chloride and oxygen. The following materials were tested: steels with (per cent.) 17 and 17.5 Cr, 12–15.5 Ni, 0 and 2.5 Mo, 0 and 4 Si, less than 0.03 C, as well as steels with 20 and 21 Cr, 8—10 Ni, 0 and 2.5 Mo, 0 and 3 Si, 0, 1.5 CU, less than 0.05 C. Silicon has a favourable effect on the stress corrosion cracking behaviour in magnesium chloride and also in calcium chloride, but a detrimental effect in NaCl and water. Its probable effect is to inhibit the extension of the crack by crystallographic obstacles and, later, by the formation of a surface film of poor conductivity (where Mo also plays a part). The attempt is made to interpret this behaviour on the strength of electro-chemical investigations; in this connection, renewed critical reservations are made in respect of the test in magnesium chloride.     

Einfluß der Oberflächenbeschaffenheit auf die Beständigkeit nichtrostender,austenitischer Chrom-Nickel-Stähle gegen transkristalline Spannungsrißkorrosion

Influence of surface conditions on the resistance of stainless austenitic bromium nickel steels to transcrystalline stress corrosion Grinding weld seams may result in an increased susceptibility to stress corrosion cracking of the areas treated in that way. This susceptibility may be eliminated by an ultimate pickling step; the thickness of the layer to be removed is 0.15 to 100 μm, depending on surface roughness. The susceptibility to stress corrosion cracking of the ground zones can be determined, however, only in the boiling 42% MgCl₂-solution; no stress corrosion cracking could be produced in solutions containing from 10 to 3O% MgCl₂ or 10 to 2O% and even 40% CaCl₂. Another possibility to eliminate stress corrosion cracking susceptibility is an ultimate sand blasting which produces compressive residual stresses in the ground surface.     

Spannungsrißkorrosion an austenitischen Chrom-Nickel-Stählen bei aktiver Korrosion in chloridhaltigen Elektrolyten

Stress corrosion cracking on austenitic chromium nickel steels during active corrosion in chloride containing electrolytes Austenitic stainless steels may suffer from stress corrosion cracking (SCC) in chloride containing environments not only in the passive state of the materials and at elevated temperatures, but also under the conditions of active corrosion at ambient temperatures. This type of active SCC was investigated for 18/8 CrNi-steel in sulphuric acid-sodium chloride solutions by potentiostatically controlled experiments with stressed specimens. Critical potential ranges of susceptibility to SCC were evaluated. Comparison with potentiodynamically measured current-potential-curves shows that these critical potential ranges of SCC are identical with the potential ranges of active dissolution of unstressed specimens. Also in boiling 42% MgCl₂, active SCC is observed in a narrow potential range more negative than the critical limiting potential of passive SCC. This range becomes more narrow by addition of Mo, but is extended by Ni. Incoloy 800 with about 32 wt.-% Ni shows exclusively active behaviour in the potential range interesting for testing the material in 42% MgCl₂. Active SCC is at last caused by the formation of an incomplete protecting layer of adsorbed chloride ions which allows local differences of anodic dissolution, hereby in the presence of mechanical stresses making SCC failures possible. At potentials sufficiently negative, the thickness of the adsorption layer can increase and a macroscopic salt-layer is formed. The chemical composition of such a layer, formed in magnesium chloride, was investigated. The layer consists nearly exclusively of nickel chloride.     

Einfluß des Kriechens auf die Spannungsrißkorrosion austenitischer Chrom-Nickel-Stähle in heißer 35%iger Magnesiumchloridlösung

Creep effect on stress corrosion cracking of austenitic CrNi steels in boiling 35% magnesium chloride solution Potentiostatic and potentiodynamic polarization curves of steel X 5 CrNi 18 9 in 35% MgCl₂-solution at 120° C do not show significant differences. Important for SCC tests is a narrow potential region before the onset of the potential of pit nucleation. SCC-experiments were carried out using two different techniques:

• (a) loading in the electrolyte
• (b) prestraining in air at 120° C; after transient creep the SCC test was initated.

Applying the technique described under (b) a decrease of SCC-susceptibility according to the crack nucleation expected in the slip dissolution model does not take place. Accordingly the dependence of time to failure on potential as well as on stress is found to be almost similar. Only in the absence of pitting a SCC threshold stress exists with its value in the range of yield strength. On the other hand SCC failure in the elastic region (< 0.1 σ_y) is observed when crack nucleation starts in corrosions pits.     

Über den Einfluß von Kohlenstoff und Stickstoff auf die Empfindlichkeit niedriglegierter Stähle gegen Spannungsrißkorrosion

The influecne of carbon and nitrogen on the sensitivity of low-alloyed steels to stress corrosion Application of stress to steels under the influence of certain media produces stress-corrosion cracking. This can be examined through experimental methods only, by which the specimens are kept under constant stress. The cracking time required for the specimen is then a measure of resistance of stress-corrosion failure. In this way it is possible to investigate the influence of alloying metals and the heat treatment on susceptibility of steels, by considering the respective strenght. Experiments were carried out to determine the effect of carbon content and the combined effect of carbon and nitrogen in a series of medium frequency and vacuum steels. It is found that increasing carbon content improves the resistance of specimens, taking also the higher strength into account. A higher nitrogen content shortens the cracking time. This shortening of resistance due to nitrogen content was much more note worthy in the case of high-carbon steels than in the case of low-carbon steels which were already sensitive in this respect. Comparing an open-hearth steel with the above steels, it seems as if there are other alloying metals which make the steels susceptible to stress-corrosion cracking. The effect of these alloying metals shall be investigated further.     

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.     

Spannungsrißkorrosion an Spannstählen

Stress corrosion cracking of prestressing steels During the investigation of a post-tensioned bridge structure incipient cracks of the prestressing steels of the transverse prestressed members were observed. Defects related to non-injected ducts or the presence of corrosion inducing substances could not be detected. The prestressing steel used is a quenched and tempered steel, strength class St 140/160, which was produced in the former GDR. The cause for the cracks is the susceptibility of this type of steel to hydrogen-induced stress corrosion cracking as could be shown in laboratory tests. Under unfavourable conditions cracks can be initiated before grouting. Additional magnetic particle tests at selected areas of the longitudinal prestressed members did not indicate any signs for incipient cracks.     

Einfluß von Oberflächenstruktur und chemischer Zusammensetzung auf die Lochfraßkorrosion von Ni-Einkristallen

Influence of surface structure and chemical composition on the pitting corrosion of nickel monocrystals With the aid of current density potential curves the pitting corrosion of nickel monocrystals (99.45–99.99 Ni) has been investigated in solutions containing 0.5 M each NiC1₂ and NiSO₄, using the pretreatment (chemical and electrochemical polishing) as a discriminating actor. As is shown by experimental results pitting is originated only at dislocations, not, however, at holidays in the passivating layer. This phenomenon is even more pronounced in the presence of impurities which may give rise to the formation of local elements. The low number of pits as compared to dislocation density can be explained in terms of special dislocation configurations required for starting pit formation.     

Wasserstoffinduzierte Spannungsrißkorrosion an unverzinkten und verzinkten Baustählen

Hydrogen induced stress corrosion cracking of non galvanized and galvanized construction steels The processes of atmospheric corrosion and corrosion in collected water which may lead to hydrogen induced stress corrosion cracking of high-strength reinforcing steels in casing tubes before injection with concrete are discussed. Hydrogen uptake during corrosion occurs in weakly acid solutions as well as in neutral or alkaline aqueous solutions. The hydrogen uptake by proton discharge in acid solutions decreases with increasing pH of the electrolyte. Hydrogen can also be absorbed in neutral to weakly alkaline solutions if steels are plastically deformed and water reacts with the fresh iron surface. In alkaline solutions, hydrogen uptake is possible if, at the generally passivated steel surface, localized corrosion (pitting or crevice corrosion), local galvanic cells and a sufficient decrease in the pH of the pit electrolyte occurs. In the case of galvanized steels with damaged zinc layers, hydrogen uptake may result from the cathodic polarization of the free steel surface by zinc dissolution. The absorbed hydrogen interacts with the microstructure of the steels and weakens the bonds between the iron atoms. The influence of the microstructure of high-strength steels on the fracture behaviour is discussed on the basic of the so-called decohesion theory.     

Spannungsrißkorrosion von Stählen in flüssigem Ammoniak

Stress corrosion cracking of steels in liquid ammonia The apparatus developped for the investigation of stress corrosion cracking of steel in liquid ammonia under controlled electrochemical conditions is described. The parameters of the experiments were set by a computer which also stored and correlated the experimental data. Cylindrical samples of the welding steel W. Nr. 1.0143 and of the steel STE 355 (W. Nr. 1.0562) in liquid ammonia containing ammonium chloride or lithium perchlorate as the electrolyte developped cracks only at negative electrode potentials in the regions of active dissolution and hydrogen deposition. Other parameters including contamination of the solution by air were unimportant. The results are explained by hydrogen induced stress corrosion cracking. No embrittlement was observed with passive samples. However, ultimate tensile strengths in liquid ammonia were clearly lower than at air also for samples breaking without formation of cracks. Experiments with notched sheets resulted in sharp, essentially transcrystalline cracks. Passivation of these samples was difficult in the region of the notch indicating the danger of anodic stress corrosion cracking.     

Dehnungsinduzierte Spannungsrißkorrosion an Stählen

Strain-induced stress corrosion cracking of steels Characterization of mechanical influencing factors and their effects on the corrosion of low alloy and high alloy steels. Stress- and strain-induced corrosion of steels. Influence of strain on the occurrence of stress corrosion cracking of low alloy steels in nitrate-, carbonate- and sodium hydroxide solutions and of high alloy steel in magnesium chloride solution. Significance of critical strain-rates.     

Spannungsrißkorrosion nichtrostender austenitischer Chrom-Nickel-Stähle bei Raumtemperatur

Stress corrosion cracking of austenitic chromium-nickel stainless steels at ambient temperature For the chloride-induced SCC with transgranular crack path in austenitic 18Cr10Ni stainless steel, a critical temperature between 45 and 50°C exists. This critical temperature, however, is valid only for the passive state of the steel in nearly neutral, chloride-containing aqueous environments. In the active state, SCC with transgranular crack mode can occur at temperatures down to ambient temperature. The active state is caused by highly acidic, high-chloride containing aqueous corrosive media. Adherent aqueous films with these properties can grow on the surface of structural components inside swimming-pools when the water is disinfected by addition of chlorine. Under these conditions, failure of austenitic CrNi and CrNiMo stainless steels by SCC with transgranular crack path at ambient temperature is possible and actually occurred. SCC with preferentially intergranular crack path can also occur at ambient temperature when austenitic stainless steels with a sensitized microstructure are used. Under these conditions, the corrosion attack is caused by non-specific aggressive environments, e.g., adherent aqueous films not containing chloride ions. The crack mode, intergranular or mixed, depends on the stress level.     

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.     

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.