Beobachtungen über die Aufstickung hochhitzebeständiger austenitischer Werkstoffe in Luft und Verbrennungsgasen

Observations concerning nitridation of refractory austenitic materials in air and combustion gases Damage due to nitridation has frequently encountered on radiation tubes of refractory materials used in industrial furnace construction. Nitridation occurs although the material surface is covered with an oxide layer. Investigations on specimens annealed in air for extended periods have shown that nitridation of materials numbers 1.4848 and 1.4840 starts after an annealing duration dependent on temperature and specimen geometry. At 900° C it begins after approx. 25000 hours, at 1000° C after approx. 1000 hours and at 1100° C after approx. only 100 hours, convex surface zones being preferentially affected. Nitrogen adsorption first results in a transformation from M₂₃C₆ to M₂(C, N). The latter subsequently grows by chromium extraction from the matrix. The M₆C-carbide found in these materials, too, and corresponding to the approximate formula (Cr₃Ni₂Si)C does not undergo structural changes by nitridation although carbon is partially substituted by nitrogen. Nitridation can probably be attributed to repeated cracking and healing of the oxide layer after a critical oxide layer thickness has been exceeded; this critical thickness is estimated to be approximately 20–30 microns.     

Über den Zusammenhang zwischen Lochkorrosion und Festigkeitsverhalten austenitischer Chrom-Nickel-Stähle

Relations between pitting corrosion and mechanical strength of austenitic chromium nickel steels The shape, depth and size as well as the frequency of pits formed under potentiostatic conditions on the surfaces of chromium-nickel steels (German designations X 5 CrNi 18 9 and X 5 CrNiMo 18 10) in 3% NaCl are studied with reference to stress mechanical effects of pitting corrosion. Comparative studies of pitting corrosion and strength behaviour of specimens at- tacked under pitting enable the residual tensile strength to be represented as a function of potential, and the tensile strength as such to be plotted as a function of a corrosion index containing pit depth and number. External effects like thermal treatment, alloy composition and cold deformation can be interpreted uniformly on the basis of all these graphical representations.     

Die Lochkorrosion austenitischer Chrom-Nickel- und Chrom-Nickel-Molybdän-Stähle in schwefelsaurer Bromidlösung und ihre Inhibition durch Nitrationen

Pitting corrosion of austenitic chromium nickel and chromium nickel molybdenum steels in sulfuric acid containing bromides, and its inhibition nitrate ions In acidified bromide solution CrNi steels are attacked under pitting when a certain critical potential has been exceeded; this potential is higher than in the case of chloride containing solutions. Bromides are, consequently, less active than chlorides, but the pit density is considerably higher under idential corrosion conditions. While the pitting corrosion in chloride solutions can be considerably reduced by molybdenum addition to the steel, this effect is but little pronounced in the case of bromide solutions (with Mo additions up to 4% the potential is displaced by 0.2 V toward positive values). Mo additions around 2% are even dangerous since the pitting density is considerably increased in that range. Similar to the conditions in chloride solutions corrosion in bromide solutions is inhibited by nitrate additions; the potential limit is considerably higher in the bromide solution; this phenomenon points to stronger adsorption of bromide ions at the metal surface.     

Korrosion nichtrostender austenitischer Stähle in (kondensierender) chloridhaltiger Salpetersäure

Corrosion of austenitic stainless steels in (condensing) nitric acid containing chlorides The corrosion parameters involved in the behaviour of austenitic stainless steels and nickelbase alloys in chloride containing nitric acid are being stated. Investigation of the corrosion resistance of the austenitic stainless steel 1.4306, ESR grade for application in nitric acid, in nitric acid condensates containing small amounts of chlorides. The condensates were formed from boiling nitric acids of molarities 6 to 10 containing 15 to 45 mg chlorides/1. The calculated corrosion rates of < 1 μm/y can be considered rather small. Especially in cases of insufficient wetting of the heat exchanger surfaces, however, local roughening and pitting corrosion is to be expected, mostly under rust-colored, chloride-containing deposits. The intensity of pitting corrosion increases with increasing chloride contents of the nitric acid solutions that evaporate. The sealing surfaces consisting of steel 1.4306 and PTFE did not exhibit any crevice corrosion. Nitric acid grade ESR-1.4306 definitely does not suffice requirements as described in this paper. It is suggested to use stainless steels which exhibit an improved resistance against chlorides and, at the same time, a high resistance against nitric acid attack. The following steel grades may be considered: X 1 CrNi 25 21 (Mat. No. 1.4335), X 2 CrNiMoN 25 22 2 (Mat. No. 1.4466) and/or X 1 NiCrMoCuN 31 27 4 (Mat. No. 1.4563).     

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.     

Über die Korrosion feuerfester keramischer Werkstoffe im Plasma von Verbrennungsgasen

The corrosion of refractory ceramic materials in the plasma of combustion gases The paper describes the testing of the corrosion resistance of refractory ceramics based on Al₂O₂, MgO and ZrO₂, as well as of phosphate cements, in flowing ionized gases as are present in the cornbustion products of conventional combustibles. A qualitative interpretation of the corrosion phenomena has been obtained experimentally using known test conditions and available thermodynamic and chechemical data.     

Der Einfluß des Molybdängehaltes auf die Korrosion austenitischer Cr-Ni-Stähle im Aktivzustand

The influence of the molybdenum content on the corrosion rate of austenitic Cr-Ni steels in the active condition The corrosion rate of steels X 5 CrNi 189, X 5 CrNoMo 18 10, X 5 CrNiMo 18 12 and X 5 CrNiMo 17 13 has been investigated under potentiostatic conditions in the active zone in 2 n H₂SO₄ flushed with nitrogen and sulphur dioxide. The active rest potential of the steels is in the vicinity of the active-passive transition, and the corrosion rate increase at cathodic polarisation. With increasing Mo content, the corrosion rate is reduced in the active condition, but the passivation potential and the corrosion rate in the passive condition are not influenced. In the acid flushed with SO₂, the corrosion rate is increased in the active range, and the latter is extended in the direction of the electronegative potentials. With these steels, even a pre-activation of the specimens has an influence on the test results. In the active-passive transition zone, the steels in the test solution containing SO₂ are partially passive and subject to local corrosion attacks.     

Über die Werkstoffzerstörung durch Kavitation und Korrosion in Äthylenglykol-Wasser-Gemischen

The destruction of material through cavitation and corrosion in ethylene glycol-water mixes Destruction of structural parts in contact with liquids through cavitation and corrosion is the consequence of complex mechanical and corrosive stresses. In recent years, extensive research at model test beds has yielded information on the stress conditions encountered in waters. It was now intended to ascertain to what extent the destruction of material through cavitation and corrosion in ethylene glycol-water mixes differs from that in waters. For this purpose, tests have been carried out with magnetostrictive oscillators on grey cast iron and copper in water, in ethylene glycol, and in mixes of both liquids; the tests on grey cast iron were extended to solutions with inhibitor additives. It was found that the mechanical stress through cavitation is about the same in the liquids investigated. Certain differences in the destruction rate are mainly due to the high boiling point of ethylene glycol and the corrosion resistance of the material concerned. In aqueous ethylene glycol solutions as well as in water, the damage can be reduced by the addition of corrosion inhibitors.     

Über die Auswirkung von Seigerungen auf das Korrosionsverhalten austenitischer Cr-Ni-Mo-Stähle

Contribution to the Effect of Segregation on the Corrosion Resistance of Austenitic Cr-Ni-Mo-Steels Investigations of segregated austenitic Cr-Ni-Mo-steels by means of the Huey-test showed that even a short annealing at 800°C can reduce the corrosion resistance. Especially for steels having a pronounced segregation this reduction of corrosion resistance can be such that it hinders the practical application of the material. This sensitivity to corrosion can be explained by the formation of intermetallic phases from ferrite which appears in small quantities within the segregated areas. It can be reduced by slightly altering the chemical composition towards a better austenite-stability and by remelting the steels to lower their segregated.     

Der Einfluß des Titangehaltes auf die Aktivkorrosion ferritischer Cr-Stähle und austenitischer Cr-Ni-Stähle in Schwefelsäure

The influence of the Titanium content on the active corrosion of ferritic Cr steels and austenitic Cr-Ni steels in sulphuric acids Non-stabilized and Ti-stabilized steels of types X8Cr17, X8Crti17, X5CrNi189, X10CrNiTi189 and X5CrNiMoTi25 25 are compared with each other in respect of their behaviour in the potential range of active corrosion in sulphuric acid. With ferritic 17 per cent. chromium steels, no Ti influence was detected. With more highly alloyed austenitic Cr-Ni or Cr-Ni-Mo steels, the titanium had the effect of narrowing down the potential range of active corrosion and reducing the corrosion rate which facilitates the passivation capacity of the steels. These phenomena are particularly marked with the steel known as X5CrNiMoTi25 25. With this steel, the corrosion rate in the active-passive transition range with titanium contents from 0.41 to 0.66 per cent. and about 0.66 per cent. C ist increased in the sensitivized state. Within a narrow potential range of about 200 mV, intercrystalline corrosion is encountered which decreases with increasing Ti content and is completely prevented if the C content is reduced below 0.03 per cent. The potential range of the inter-crystalline corrosion is more negative than the test potential of the Strauss test normally used for testing the grain disintegration resistance.     

Interkristalline Korrosion nichtrostender austenitischer Stähle,gemessen auf Grund der inneren Reibung bei Schallfrequenzen

Intercrystalline corrosion of stainless austenitic steels measured by internal friction at accoustic frequences The internal friction of stainless austenitic steels after isochronal-isothermal treatment and corrsion in Strauß reagent has been measured with an electro-acoustic apparatus. By measuring the variation of the logarithmic decay of free oscillations and of the variation of the Young modulus vs corrosion time the cientics of intercristalline corrosion have been determined for the steels AISI 301, 302 and 304. The variation of Young's modulus can be determined more readily and is also better reproducible. The first stage of corrosion shows a linear dependence from time and is probably related to the penetration of the Strauß reagent along grain boundaries. The peneration depends from the morphology of carbide precipitates. A continuous thin precipitate film enhances corrosion while precipitates in the form of separated globules have no accelerating effect on corrosion. The progress of intercrystalline corrosion shows a very sensitive reaction shows a very sensitive reaction to variations of carbon content, i particular between 0.08 and 0,10%C.     

Überblick über die Entwicklung und Eigenschaften stickstofflegierter austenitischer Stähle für den chemischen Apparatebau

A review of the devolopment and the properties of nitrogen containing austenitic steels for chemical apparatus construction Addition of nitrogen results in increased strength austenitic steels and in increased austenite stability, so that the formation of undesirable phases is suppressed or at least delayed. This feature eliminates in particular the Structural stability problems encountered during welding. The increase of mechanical strength involves qualitatively all the properties related to strength, including fatigue strength and corrosion fatigue strength; it should be noted that this improvement has not been achieved at the expense of ductility, so that the steels are suitable for low temperature application as well. For these reasons it is recommended to include nitrogen alloyed steels in standardization projects.     

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.     

Die Bedeutung der Ionen starker Säuren und Basen bei der Korrosion unlegierter Stähle mit und ohne Beschichtungen

Importance of ions of strong acids and bases for the corrosion of coated and uncoated unalloyed steels Neutral salts can deteriorate the formation of protective layers in water. Furthermore, formation of corrosion cells due to different pH-values is possible. Low pH-values and anodes resp. high pH-values and cathodes are related to reactions of the ions of strong acids resp. strong bases. Similar reactions are responsible for blistering of coated steel being anodically or cathodically polarized.     

Korrosion nichtrostender Stähle und Nickelbasislegierungen in Salpetersäure-Flußsäure-Gemischen

Corrosion of stainless steels and nickel-base alloys in solutions of nitric acid and hydrofluoric acid Reactions involving nitric acid may always result in the contamination of this acid with fluorides. In highly concentrated nitric acid, the presence of small amounts of HF will substantially reduce the corrosion of metallic materials. Mixtures consisting of hydrofluoric acid and hypo-azeotropic nitric acid on the other hand will strongly attack: the metal loss will markedly increase with increasing HNO₃ and HF concentrations as well as with rising temperatures. The investigation covered 12 stainless steel grades and nickel-base alloys. With constant HNO₃ content, corrosion rates will rise linearly when increasing the HF concentration. With constant HF concentration (0.25 M), corrosion rates will increase rapidly with increasing nitric acid concentration (from 0.3 M to 14.8 M). This can best be described by superimposing a linear function and a hyperbolic function that is reflecting the change in the HNO₃ content. Alloys containing as much chromium as possible (up to 46 wt.%) will exhibit the best corrosion resistance. Alloy NiCr30FeMo (Hastelloy alloy G-30) proved to be well suitable in this investigation.     

Beitrag zur Spannungsrißkorrosion austenitischer Stähle

Contribution to the problem of stress corrosion cracking of austenitic steels It is shown on the basis of a stress corrosion cracking theories that the incubation phase is the factor determining the useful life of an element because in this phase protective layers are destroyed and crack nuclei are formed. Testing corrosion susceptibility in boiling magnesium chloride solution has the shortcoming that the solution is highly aggressive so that minor changes of the surface condition which may yield a considerable improvement of material behaviour in less aggressive conditions do not come to bear. Another shortcoming of MgC1₂ testing are divergent literature data concerning concentration so that there is also a scatter of boiling temperatures which has a pronounced influence on test results. Likewise an important role can be attributed to foreign ions and silicates from glas in the solution. It is more advantageous to use less concentrated solutions (up to 35%) because they enable clear current density potential curve to be obtained. An important factor concerning the test method is the previous investigation of specimens with a view to a residual stresses due to cold reduction. Under certain conditions the time to failure may be longer under cycling loads.     

Untersuchungen der Spannungsrißkorrosion austenitischer Stähle durch saure Chloridlösungen bei Niedrigen Temperaturen

Investigation of stress corrosion cracking of austenitic steels in acid chloride solutions at low temperatures Tests were carried out on materials 1.4301, 1.4571, 1.4439 and 1.4558 in cold hydrocloric acid (c(Cl^?) = 1.5 mol/L and c(H⁺) = 1 mol/L, a few tests also at 0.1 and 0.01 mol/L). Chronopotentiostatic tests yielded data on active corrosion, passivity and pitting corrosion. CERT tests (10^?6s^?1, a few tests also at 2 · 10^?7s^?1) showed superposition of general corrosion on stress corrosion under free corrosion condition, while the rest potential was relatively negative in the active range. Oxygen purging has only a minor effect. The extent of cracking decreases with decreasing c(H⁺). In the case of cathodic polarisation straining induced surface notches occur which can be attributed to hydrogen induced effects. In the case of anodic polarisation pittings are generated without any crack initiation. Characteristic features of stress corrosion increase with decreasing strain rate. It follows from the results that high acid concentrations are necessary for stress corrosion cracking in the active state to occur. CERT tests cannot be used as an accelerated test for this kind of stress corrosion cracking. Few CERT tests carried out in warm NaCl solution did not show any stress corrosion cracking though these solutions are known to cause stress corrosion cracking after long periods. Furthermore, predamage in the form of pitting does not alter the situation.     

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.     

Potentialabhängigkeit der Korrosion Mo-freier und Mo-haltiger Stähle in Calciumnitrat-Lösung und Natronlauge

Effect of potential on corrosion of Mo-free and Mo-bearing steels in solutions of calcium nitrate and sodium hydroxide The effect of potential on the corrosion behaviour of three low alloy steels with different carbon and molybdenum contents (0.08 C, 0.01 Mo; 0.08 C, 0.98 Mo; 0.18 C, 1.10 Mo) was investigated in boiling 60 wt.% Ca(NO₃)₂ solution (DIN 50 915) and in boiling concentrated NaOH solutions (20 and 35 wt.% NaOH) by potentiodynamic and chronopotentiostatic polarization measurements (i/E curves) and chronopotentiostatic mass loss measurements (corrosion rate v vs. potential E curves). In Ca(NO₃)₂ solution, i/E measurements give no information about the effect of potential on the anodic dissolution. For the materials investigated, v/E measurements indicate the existence of potential ranges with pronounced differences of the corrosion response. It can be differentiated between active, passive, and transpassive ranges, and also a potential range of secondary passivity was established. Transpassivity and secondary passivity are markedly pronounced with the molybdenum bearing steels but not with the steel free from molybdenum. There are no hints to the occurrence of intergranular attack in the specimens which are free from of internal and external mechanical stresses, whereas such hints could be derived from the shape of the i/E curves. Nevertheless, under mechanical stresses (constant load, CERT conditions) the materials are susceptible to intergranular SCC. The conception that intergranular SCC of low alloy steels in Ca(NO₃)₂ solution is connected with a break-through potential of grain boundary corrosion and hence is to be interpreted as an intergranular attack which, under mechanical stresses, runs in a modified form as SCC with intergranular crack path, cannot be maintained in such general terms. A pronounced active/passive behaviour is observed in NaOH. The effect of potential on anodic metal dissolution which is derived from v/E curve is also established by i/E measurements. For molybdenum bearing steels, the active potential range is somewhat extended to more positive potentials. Manifestations of localized attack, e.g., intergranular corrosion, do not occur. From the investigations, no hints to the cause of the deterioration of the resistance to intergranular SCC in caustic solutions by molybdenum can be derived.     

Temperatur- und Konzentrationsabhängigkeit der Korrosion nichtrostender austenitischer und ferritischer Werkstoffe in 20- bis 75%iger Salpetersäure

Corrosion resistance of austenitic and ferritic stainless alloys in 20 to 75% nitric acid as a function of temperature and concentration A series of stainless austenitic and ferritic materials was exposed for 100 days to boiling nitric acid which contained no corrosion products; the corrosion rates and depths of the grain boundary attack were observed. Provided the structure is precipitation-free, the following are suitable for long-term exposure; the austenitic steels X 2 CrNi 1912, X1 CrNi 25 21, X1 CrNiMoN 25 222 and X1 NiCrMoCu31274, the practically Mo-free and Cu-free development steel X1 NiCr31 27, and the highly Mo-alloyed variant X1 NiCrMoCu 31275. In the case of alloy NiCr21 Mo it is advisable to limit the concentration and/or the temperature of the nitric acid. The “superferrite” X1CrNiMoNb2842, the Japanese steel X1 CrNiNb 30 2 and the austenitic steels X2 CrNiMoN 1713 3 and X1 CrNiMoN 25 22 2 in the version with high nickel content are unsuitable. Thus, as an alloying element, molybdenum does not always impair the resistance of stainless steels to nitric acid. The decisive factor affecting the corrosion rates is the chromium content of the material. The temperature-dependent function of the corrosion in azeotropic nitric acid conforms to Arrhenius relations. The concentration-dependent function of the corrosion in 20 to 75 (80)% nitric acid can be described by a hyperbolic equation. An exception is formed by X1 CrNiSi 1815; here the corrosion rate increases with the concentration of the acid until the azeotropic point is reached; then, owing to the formation of a surface film, it falls until the acid becomes highly concentrated.