Untersuchungen über den Einfluß der Wärmebehandlung auf die Korrosion titanstabilisierter ferritischer Chromstähle in siedender konzentrierter Salpetersäure

Investigations into the influence of the thermal treatment on the corrosion of titanium-stabilized ferritic chromium steels in boiling concentrated nitric acid Titanium-stabilized ferritic chromium steels with about 17% Cr are, after quenching from high temperature, susceptible to grain boundary corrosion in boiling nitric acid; this corrosion is attributable to the chemical dissolution of the titanium carbonitrides coherently segregated at the grain boundaries. This carbide corrosion can be reduced by heat treatment within the temperature range around 850°C. In this process, the segregated carbo-nitrides are formed-in (in-formation annealing). The influence of quenching (0.5–5 hours, 900–1200°C/W[L]) and subsequent in-formation annealing (1–30 hours, 850°C/W) on the corrosion rate in boiling 65% nitric acid has been investigated in detailed on two steels of types X 8 Cr Ti 17 and X 8 Cr Mo Ti 17. In addition, the corrosion behaviour of titanium-stabilized and unstabilized ferritic chromium steels with about 17 pC chromium have been compared with each other.     

Korrosionsschäden am Förderband eines Ofens zur Reinigung von mit organischen Chlorverbindungen kontaminiertem Erdboden

Corrosion damage to the conveyor belt of a furnace for the removal of soil from organic chlorine compounds This paper reports the corrosion behaviour of metallic materials which were used in components of a conveyor belt of a decontamination furnace or of which specimens were attached to the belt for testing purposes. The furnace was used for decontaminating soil containing organic chlorine compounds. A total of 1 ferritic and 8 austenitic steels, 9 nickel base alloys, 2 east steels with 15 % Si and 15 % Si + 5 % Cr respectively, and 3 aluminised steels were tested and afterwards investigated by metallographic and micro-analytical methods. Most of the materials failed due to external and/or internal corrosion, preferentially along grain boundaries. The 2 cast steels revealed fairly good corrosion resistance. The material 2.4061 (LC-Ni 99.6) displayed surprisingly good behaviour, however it remains to be seen whether the inward migration of O and C along grain boundaries causes embrittlement. The materials 2.4610 and 2.4831, containing 14-17 % Mo and 8.5-9,5 % Mo respectively, showed good resistance. The reason for this good corrosion resistance could not be clarified. One reason may be the relatively high Mo content but other materials with a comparable Mo content, like materials 2.4856 and 2.4663, were significantly attacked. It appears necessary to check the long-term behaviour of these two materials.     

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.     

Der Einfluß von Stickstoff auf die korrosionschemischen Eigenschaften lösungsgeglühter und angelassener austenitischer 18/10 Chrom-Nickel- und 18/12 Chrom-Nickel-Molybdän-Stähle - II. Interkristalline Korrosion in Kupfersulfat-Schwefelsäure-Lösungen und in siedender 65% iger Salpetersäure

Influence of nitrogen on the corrosion behaviour of solution treated and annealed austenitic 18/10 chromium-nickel and 18/12 chromium-nickel-molybdenum steels. - II. Intercrystalline corrosion in copper sulfate sulfuric acid solution and in boiling 65% nitric acid Heat-treated steels containing 18.5 Cr, 11 Ni or 17.2 Cr, 13 Ni 2.6 Mo were investigated in the Strauß-Test (also in more rigid version) and the Huey-Test. The parameter studied is the precipitation behaviour and its influence on susceptibility to intercrystalline corrosion. The two methods of investigation differ with respect to the information obtainable; the influence of nitrogen e. g. can be recognized in the Huey-Test only. Nitrogen shifts the lower borderline of the grain disintegration field toward higher annealing temperatures and longer annealing times; the Z-phase appearing in the nitrogen and molybdenum containing steels influences the upper borderline and produces a significant increase of corrosion rate in nitric acid. The results are interpreted in terms of the chromium depletion theory.     

Corrosion resistance and mechanical properties of nickel-bearing ferritic stainless steels

Additions of nickel to ferritic steels containing 25–28% Cr and 2–4% Mo increased the impact toguhness especially when more than 2% Ni was present. The effect of nickel content increased up to 4% Ni, the largest addition studied. Steels stabilized with niobium had lower transition temperatures then did corresponding steels stablizied with titanium. Steels containing 4% Ni required annealing at 1050 C to avoid intermetalic compounds. It was also noted that nickel reduced the upper shelf energy in the Charpy impact test and eliminated a sharp transition from ductile to brittle behaviour. No definite effect of nickel on pitting potential was pound but steels in the series 25Cr-3.5 Mo-Ni-Ti consistenly had more noble pitting potentials and greater resistance to crevice corrosion than the 28 Cr-2Mo-Ni-Ti steels. Nickel contents of 1 or 2% tended to improve crevice corrosion resistance while larger nickel contents were somewhat ditrimental. Nickel strongly reduced critical current densities for passivity both in l N H₂SO₄ and in l N HCL and yielded corresponding increases in resistance to corrosion by these acids. Although 1% Ni or more caused the annealed steels to be susceptible to stress corrosion cracking in MgCl₂ boiling at 140 C, while the as-Welded steels containing 4% Ni did not crack in boiling 25% Nacl at pH 1.     

Besonderheiten im Korrosionsverhalten hochchrom- und molybdänhaltiger Legierungen in heißer 92, 5%iger Schwefelsäure

Peculiarities in the corrosion behaviour of high chromium and molybdenum containing alloys in hot 92.5% sulfuric acid In laboratory tests at temperatures above 50°C unusual high corrosion rates of passivating stainless steels and nickel alloys containing more than 26% Cr were observed in 92.5% sulphuric acid. In order to investigate the cause of this phenomenon further corrosion tests and additional chemical analyses were performed. The H₂SO₄ concentration tested displays a relative maximum of the electrical conductivity, the reason being a stronger dissociation of the sulfuric acid. Electrochemical investigations revealed an enhanced activity of the cathodic reactions which lead to higher corrosion rates. The cathodic reactions are strongly dependend on alloy constitution with special emphasis on the contents of Cr, Ni and Mo. Mo containing stainless steel show potential oscillations (of the open circuit potential) between ?50 and +550 mV_H. These alloys corrode under development of SO₂ (reduction of H₂SO₄ molecules) and formation of several sulfur compounds with different oxidation numbers (6+ and 2?). Alloys with chromium contents above 26% develop additionally hydrogen gas due to a lower hydrogen overvoltage of these alloys. With increasing nickel content the overvoltage for the reduction reaction of H₂SO₄ molecules will be lowered. This fact results in an elevation of the exchange current density for the Alloy NiCr45 and therefore to the highest corrosion rate observed. Alloy B-2 shows the best resistance, i.e. very low corrosion rates. Obviously high levels of molybdenum can compensate the influence of nickel on the overvoltage of the reduction reaction or even hinder the cathodic reaction.     

Korrosionsuntersuchungen an ausgewählten metallischen Werkstoffen im System Essigsäure/Esigsäureanhydrid

Corrosion tests of selected metallic materials in the system acetic acid/acetic anhydride The corrosion behaviour of the ferritic austenitic stainless steels X2 CrNiMoN 22 5 (UNS S31803) and X2 CrNiMoN 25 7 4 (UNS S32750), the nickel base alloy NiMo16Cr16Ti (alloy C-4) and the titanium grades Ti2 (Grade 2) and Ti2Pd (Grade 7) was investigated by immersion tests in boiling mixtures of acetic acid and acetic anhydride in the presence of air. All materials tested were corrosion resistant in acetic acid and acetic anhydride but were corroded rapidly by the mixtures with a corrosion loss up to 1 mm/a, except the nickel base alloy (alloy C-4). It was corrosion resistant in all solutions with a corrosion loss not exceeding 0.01 mm/a. Electrochemical tests show that all materials tested exhibit stable passivity in glacial acetic acid and active corrosion in the presence of 10% acetic anhydride.     

Cr对钢耐海水腐蚀性的影响

获得了５种含铬低合金钢在海水中暴露１、２、４、８（７）年的腐蚀数据,讨论Ｃｒ对钢耐海水腐蚀的影响,铬钢的耐海水腐蚀性不仅与Ｃｒ的含量有关,还与其他复合合金元素有关。短期浸泡时,钢的耐海水腐蚀性随铬含量（无其他合金元素复合）增加而提高。长期浸泡,Ｃｒ对钢的耐海水腐蚀性有害,约１％Ｃｒ与Ｍｏ（－Ａｌ）复合对钢的耐海水腐蚀性的影响与Ｃｒ的影响没有左别大于２％Ｃｒ与Ｍｏ（－Ａｌ）复合大幅度提高钢在海水中短期浸泡的耐蚀性,并使耐蚀性逆转时间明显推迟.小于1%Cr与Mn-Cu、Cu-Si-V、Ni-Cu-Si、Ni-Mn等复合对钢的耐海水腐蚀性有害。     

Widerstand der Schweißverbindungen kohlenstoffarmer und mit Molybdän legierter korrosionsbeständiger Stähle gegen interkristalline und Messerlinienkorrosion

Resistance to intercrystalline and knifeline corrosion of welds in low carbon stainless steels containing molybdenum Welds in steels containing (%) 0,019–0,080 C, 1,00–1,56 Mn, 0,03–0,92 Si, 0–0,026 P, 0–0,018 S, 10–13,60 Ni, 16–20,50 Cr, 0–3 Mo, 0–0,057 Ti, 0–0,87 Nb, prepared by electroslag and automatic submerged arc welding are as a general rule not susceptible to intercrystalline and knifeline corrosion; a certain susceptibility encountered with the Mo containing types can be largely eliminated by sensibilizing at 650 °C. Differences in the corrosion behaviour between base metal and weld seam could not be encountered; in some cases the weld metal turned out to be even more resistant. The test solutions used were: sulfuric acid + Cu sulfate + Cu, boiling, 48 hrs, and 65% nitric acid, boiling, 3 · 48 hrs.     

Langzeit-Korrosionsuntersuchungen an austenitischen Stählen im Hochdruckteil einer Harnstoffanlage

Longterm corrosion field tests with austenitic steels in the high pressure parts of a urea plant In view of the conditions encountered in urea manufacture, in particular in the high pressure section the corrosion resistance is investigated using various austenitic steels immersed in reaction mixtures typical of urea manufacture. The specimens were placed in an operating plant; different test durations (total 13 000 hours) enable the time dependence of the attack to be assessed. The steels tested were CrNi steels with nitrogen and 17.45?19.8% Cr and 10.3-12% Ni, CrNiMo steels, some of them with Ti and Cu addition and 17% Cr and 20 and 13.8% Ni, respectively. According to the results the corrosion resistance increases with the chromium level while ferrite in particular with longer test durations has a pronounced negative effect. A suitable screening test for corrosion resistance under the conditions of urea manufacture is testing in boiling nitric acid.     

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.     

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.     

Das Verhalten von Großbaustählen in Meerwasser

Behaviour of construction steels in seawater The chemical composition of steel has a considerable bearing on their corrosion in seawater. Systematic laboratory studies have shown that addition of Si, Cr and Cu, but also Al and P yields considerable improvements of the sea water resistance of construction steels. Long term tests in natural seawater (in harbours, bays and straits) close to the surface and at depth up to 90 m have revealed that the seawater resistance of steels containing about 1% Si, 3% Cr and 1% Cu may be 3 to 6 times (depending on exposure conditions) the resistance of unalloyed construction steel. This behaviour may be attributed to the fact that by forming sulfates Si and Cr inhibit the growth of bacteria which would enhance corrosion, and to the fact that Si, Cr and Cu give rise to the formation of a dense rust layer which slows down the exchange phenomena between seawater and corrosion products. The use of such steels may constitute an alternative to the use of unalloyed steels with an appropriate corrosion protection system.     

Neue Erkenntnisse auf dem Gebiet der ferritischen rostfreien Stähle

Recent developments in ferritic stainless steels The pitting resistance of ferritic stainless steels in HCl is visibly improved by Mo, in particular in the case of vacuum-melted material. In this context the ratio Cr:Mo = 25:2 is superior ta Cr:Mo = 17:3; addition of Mo prevents, beyond that, crevice corrosion. Ti increases resistance in the Strauß test but not in the Huey test, while Nb turns out to have a positive effect in either test. Steels containing Cr: Mo = 17:l are certainly still susceptible to pitting, but no longer to stress corrosion cracking in boiling MgCl₂, solution; stress corrosion cracking is not observed in 55% boiling Ca(NO₃)₂, and 25% boiling NaOH, but after annealing at 980 °C intercrystalline corrosion takes place. The test duration required for establishing cracking susceptibility is considerably shorter with ferritic than with austenitic steels (100 and 1000 to 2000 hours respectively).     

Herstellung und Eigenschaften stickstofflegierter,korrosionsbeständiger Stähle und Sonderstähle mit niedrigen Kohlenstoffgehalten

Production and properties of nitrogen alloyed, corrosion resistant steels and special steels with low carbon contents Alloying with nitrogen has favourable influence in particular on the mechanical properties of CrNiMo steels (X 2 CrNiMoN 17 12, materials No. 1.4406, X 2 CrNiMoN 17 13 5, materials No. 1.4439 und X 2 CrNiMoN 22 5, materials No. W.-Nr. 1.4462). This comes to bear when ambient temperature and low temperature strength and toughness are concerned. With respect to the corrosion behaviour the data concerning the effect of nitrogen are contradictory. It has become clear that nitrogen improves pitting corrosion resistance; this applies, however, only to pit initiation but not to pit growth. Stress corrosion cracking is not delayed by nitrogen but different results have been obtained with different media: while the duplex steel X 2 CrNiMoN 22 5 is attacked considerably faster than the corresponding nitrogen-free steel in 42% boiling magnesium chloride solution the time-to-failure of both steels are comparable in 30% boiling MgCl₂-solution. The nitrogen alloyed steels can be welded by all known welding procedures, provided fully austenitic welding rods are used.     

Die Ermittlung der Beständigkeit gegen Spannungsrißkorrosion (SpRK) von hochlegierten Sonderstählen in chloridhaltigen wäßrigen Medien

Determination of resistance to stress corrosion cracking (SCC) of high-alloy special steels in chloride-containing aqueous media The 18 Cr 10 Ni(Mo) based stainless steels have been continually improved by raising the Cr, Ni and Mo contents. The behavior of these high-alloy steels towards SCC was determined in test media generally used in practice since the question of the resistance to stress corrosion cracking (SCC) had still remained unanswered to a large extent. SCC tests on U-bend samples in boiling 62% CaCl₂ solution showed a good differentiation depending on the Ni and Mo contents. With increasing Ni content, the susceptibility of special high-alloy steels to SCC is shifted towards longer service lives, alloys containing ≧ 42% by weight of Ni being resistant. High-Mo special alloy steels are more resistant to SCC than low-Mo special alloy steels. These results could be confirmed by tests carried out on circular cross section samples in boiling 62% CaCl₂ solution under constant load and potentiostatic control. The free corrosion potentials recorded for 25% Ni special alloy steel and Ni-based alloys are within the potentiostatically determined range of insusceptibility to SCC. The high-Mo special alloy steel X 2 NiCrMoCu 25 20 6 (1.4529) shows the same critical SCC potential on the anodic side as the Ni alloy NiCr21 Mo (2.4858). Superferrit X 1 CrNiMoNb 28 4 2 (1.4575) and austenitic ferritic steel X 2 CrNiMoN 22 5 (1.4462) showed that the SCC behavior was unsatisfactory in both tests as in the case of steel X 10 CrNiMoTi 18 10 (1.4571). Tests in boiling 4 m NaCl showed no SCC, not even under the aggrevated test conditions in the test set-up. The great influence of the oxygen content was demonstrated in tests carried out in the autoclave with defined oxygen and chloride concentrations. The resistance of the steels to SCC decreases under air-saturated conditions (8 … 10 ppm O₂) whereas the chloride concentration (200 and 2000 ppm Cl^?) does not exercise an important influence. U-bend samples should be given preference to Erichsen samples for SCC tests. SCC break characteristics could be determined metallographically and by scanning electron microscope.     

Das Ausscheidungsverhalten von hochlegierten austenitischen Stählen mit 6% Molybdän und sein Einfluß auf die Korrosionsbeständigkeit

Precipitation behaviour of high-alloyed austenitic steels with 6% molybdenum and its influence on the corrosion resistance The high-alloy austenitic steels with 6 to 7% Mo, 20 to 21% Cr and 18 to 25% Ni are increasingly used in seawater and chemical applications. This is due to the excellent resistance to pitting and crevice corrosion in chloride-containing neutral and acidic environments. It is the high chromium and molybdenum content which provides the excellent corrosion behaviour but, at the same time favors the tendency to precipitation of intermetallic phases. Therefore, time-temperature-precipitation diagrams have been established for two steels with 6% Mo, 21% Cr, 25% Ni, 0.14 and 0.19% N and for one steel with 6% Mo, 20% Cr, 18% Ni and 0.21% N. The corresponding time-temperature-sensitization diagrams (in accordance to SEP 1877/II) and time-temperature-pitting diagrams (testing in 6% FeCl₃ solution) have been evaluated as well. Precipitation of intermetallics occurs rapidly especially in the range between 700 and 1000°C. In case of the 18% Ni steel and the 25% Ni/0.14% N steel grain boundaries are covered to a large extent with precipitates after only 15 min at 850 or 950°C. In case of the 25% Ni/0.19% N steel precipitation is considerably slower. The precipitates are interpreted to be chi-phase. After very long annealing times additionally small amounts of Laves phase appear. Neither carbides nor nitrides were observed. In spite of the rapid precipitation, sensitization in terms of the 50 m?m grain boundary penetration criterion is observed not before 0.7 h at 850 °C and not before about 2 h at 800°C in case of the 25% Ni/0.19% N steel. After about the same times of annealing also the critical pitting temperature as observed in the FeCl₃-test is dropping below 50°C. Therefore, when welding according to established rules and recommendations, no deterioration of the corrosion resistance in the heat-affected zone is to be expected. If high heat inputs will occur during manufacturing because of hot forming operations or welding of heavy sections, or if more severe test conditions are a requirement, a steel with 25% Ni and about 0.2% N (UNS N 08925, Cronifer hMo) is recommended due to its retarded precipitation and sensitization behaviour when compared to steels with only 18% Ni (UNS S 31 254). Additionally, the steel with 25% Ni has an increased resistance to general corrosion in acids. Notch impact strength of the materials under consideration is increased by the initial precipitation of the intermetallic phases and decreases only after longer times of annealing below the ductility of the solution annealed material.     

Corrosion characteristics of the wrought Ni‐Cr‐Mo alloys

This paper concerns the wrought, nickel‐chromium‐molybdenum (Ni‐Cr‐Mo) alloys, a family of materials with a long history of use in the chemical process industries. Their attributes include resistance to the halogen acids and resistance to pitting, crevice attack, and stress corrosion cracking in hot, halide salt solutions. The purpose of this paper is to characterize the performance of the Ni‐Cr‐Mo alloys in several key chemicals, using iso‐corrosion diagrams. These indicate the expected corrosion rates over wide ranges of concentration and temperature. Furthermore, the differences between individual Ni‐Cr‐Mo alloys, and their behavior relative to the stainless steels are defined. The data indicate benefits of both a high chromium content and a copper addition, as used in Hastelloy® C‐2000® alloy.     

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.     

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.