Hochlegierte nichtrostende Stähle und Nickelbasislegierungen im Chemie-Apparatebau

High alloy stainless steels and nickel-base alloys in chemical equipment construction The new ferritic chromium steels and ferritic-austenitic steels, high alloy special austenitic steels and nickel-base alloys presented in recent years have by now yielded some years' positive industrial experience in several applications. The group of austenitic steels containing 6 wt.-% molybdenum are at the threshold for large size application in chemical equipment construction. The results of the first comparative investigations with other high alloy steels are rather promising. The spectrum of nickel-base alloys will certainly be complemented by Hastelloy alloy C-22, so that this alloy will be used in addition to titanium alloys in contact with strongly oxidizing media.     

Korrosionsbeständige metallische Werkstoffe für Rauchgas-Entschwefelungsanlagen

Corrosion resistant metallic materials for flue gas desulfurization plants Forced by environmental legislation installations for flue gas desulfurization (FGD) are presently being built to a large extent in the Federal Republic of Germany as in some other countries. Absorption by lime/limestone slurries is used in most cases for desulfurization. The components of the flue gas as well as the kind of process applied are of primary importance for the corrosive behaviour of the materials of construction. In view of pH values going down below 1 in some cases, chloride contents of occasionally more than 10% Cl^?, temperatures between 40 and 160°C and local deposits of solids it is the resistance to pitting and crevice corrosion which has to be considered in the first place while stress corrosion cracking and erosion corrosion are of minor importance. Therefore, only austenitic materials with molybdenum contents of more than 2 wt.-% have to be considered. According to the severity of the corrosive media these are predominantly alloys as e.g. Cronifer 1925 LCN (Alloy 904 LN), 1925 hMo (Alloy 904 LM) going up to the high alloyed nickel base materials Nicrofer 6020 hMo (Alloy 625) and 5716 hMo W (Alloy C-276), which exhibit molybdenum contents of 9 and 16 wt.-% and are to be used at places where corrosion is extremely severe as e.g. at the raw gas inlet. The use of such high alloyed materials plated on carbon steel has been tried successfully. Special attention has to be paid to all aspects of welding in order to avoid welds to become locations being vulnerable by corrosive attack. Therefore, welding of corrosion resistant materials in FGD units has been investigated extensively. The results of application oriented laboratory tests as well as practical experience with existing FGD units are to be considered. Correct use of corrosion resistant metallic materials will be an important contribution to minimizing repair and shut downs of FGD units and to extend their life.     

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.     

Corrosion behaviour of carbon S-phase created on Ni-free biomedical stainless steel

Following the success of forming a carbon S-phase (expanded austenite) surface layer on medical grade Ni-free austenitic stainless steel by DC plasma carburising, the established commercial carburising process Kolsterising® was performed on both Ni-containing (AISI 304) and Ni-free austenitic stainless steels. While the Ni-containing stainless steel responded very well to Kolsterising®, the Ni-free alloy did not. The carbon absorption and the hardness of the Kolsterised® Ni-free alloy are inferior to Kolsterised® AISI 304 Ni-containing stainless steel, however, the hardness of the untreated Ni-free alloy was doubled by Kolsterising®. The response of both Kolsterised® Ni-free and Ni-containing alloys to pitting, crevice corrosion and intergranular corrosion resistance was similar. From this work it can be concluded that the Kolsterised® austenitic stainless steels do not suffer from intergranular corrosion but are susceptible to intragranular pitting when tested in boiling sulphuric acid and copper sulphate solution. It was also observed that Kolsterising® improves significantly the pitting and crevice corrosion resistance of the alloys used in this study.     

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.     

Untersuchungen zum Einfluss des Stickstoffs auf das Lochkorrosionsverhalten hochlegierter austenitischer Cr‐Ni‐Mo‐Stähle

Investigation of the influence of nitrogen on the pitting corrosion of high alloyed austenitic Cr‐Ni‐Mo‐steels Austenitic stainless steels (18% Cr, 12% Ni, Mo gradation between 0.5 to 3.6%) had been gas‐nitrided. By stepwise removal, samples could be prepared with various surface content of nitrogen up to 0.45%. The susceptibility against pitting corrosion of these samples had been tested by two methods: – determination of the stable pitting potential in 0.5 M NaCl at 25°C – determination of the critical pitting temperature in artificial sea water (DIN 81249‐4) The influence of nitrogen to both determined parameter can be described well by PRE = Cr + 3,3 · Mo + 25 · N That means for the investigated steel composition and the used corrosion system there is no influence of molybdenum on the effectiveness of nitrogen.     

Corrosion behaviour of Lotus-type porous high nitrogen nickel-free stainless steels

Corrosion behaviour of three austenitic Lotus-type porous high nitrogen Ni-free stainless steels exposed to an acidic chloride solution has been investigated by electrochemical tests and weight loss measurements. Polarization resistance indicates that the corrosion rate of Lotus-type porous high nitrogen Ni-free stainless steels is an order of magnitude lower than that of Lotus-type porous 316L stainless steel in acidic environment. The localised corrosion resistance of the investigated high nitrogen Ni-free stainless steels, measured as pitting potential, E_b, also resulted to be higher than that of type 316L stainless steel. The influences of porous structure, surface finish and nitrogen addition on the corrosion behaviour were discussed.     

Die Bedeutung des Oxalsäure-Tests für die Prüfung der Korrosionsbeständigkeit nichtrostender Stähle

The meaning of the oxalic acid etch test for testing the corrosion resistance of stainless steels In the oxalic acid etch test according to ASTM A 262 practice A, precipitations of phases rich in chromium and molybdenum which can occur in stainless steels, are preferentially dissoved. The behaviour of such phases in the oxalic acid etch test was investigated taking precipitations of carbide M₂₃C₆, s?-phase, χ-phase and Laves-phase in stainless steels AISI 304 L and 316 L as examples. The chemical composition of these was evaluated with a scanning transmission electron microscope (STEM) by EDS. With coarser precipitations, it was possible to support this analytical method by EDS of metallographic cross sections in a scanning electron microscope (SEM). In oxalic acid, critical threshold potentials exist above which the above mentioned phases are preferably attacked, furthermore critical pH values, below which no selective attack of the precipitated carbides and intermetallic phases occurs. The numerical values of the threshold potentials as well as the critical pH values were evaluated. When testing stainless steels in the oxalic acid etch test, the steel specimens are polarized to a highly positive potential in the very trans passive range. In this potential range the corrosion rate of stainless steels increases with increasing chromium content, while in the active and passive range the corrosion rate decreases with increasing chromium content. Other than the nitric-hydrofluoric acid test, the copper-copper sulfate-sulfuric acid test, and the ferric sulfate-sulfuric acid test, the oxalic acid etch test does therefore not indicate any chromium depletion. Hence, an intergranular attack also occurs when precipitations of carbides rich in chromium are present at the grain boundaries of austenitic stainless steels with the carbides being precipitated without any chromium depletion of the areas adjacent to the grain boundaries. Sensitized austenitic stainless steels which are susceptible to intergranular corrosion due to the precipitation of chromium rich carbides and chromium depletion of the areas adjacent to the grain boundaries, can suffer intergranular SCC in high temperature aqueous environments when additionally critical conditions with respect to the mechanical stress level and the oxygen concentration in the environment are given. For the detection of sensitized microstructures, the oxalic acid etch test must be valued critically due to the dependence of the corrosion rate on the chromium content mentioned above, and is obviously by far less suited than the conventional tests for establishing resistance to intergranular corrosion in sulfuric acid-copper sulfate solutions with additions of metallic copper (Strauß test, severe Strauß test).     

Hochlegierte korrosionsbeständige Stähle für Chemie‐, Energie‐ und Meerestechnik – Rückblick und Ausblick

High‐alloyed corrosion resistant steels for the chemical process industry, power engineering and marine technology – past and future Today's most common high‐alloyed corrosion resistant steels are in their majority characterised by very low contents of carbon and sulphur and, in many cases, by substantial amounts of nitrogen as an alloying constituent. Their broad use in the chemical process industry, power generation and marine technology has become possible when new metallurgical processes for steel making had been introduced in the 1960s. The time before had seen mainly stabilised grades, being highly alloyed with copper in many cases, which have disappeared to a large extent in our days. The superferritic grades (ferritic steels with ≥ 25% chromium) had been the materials of great expectations in the 1970s, but have found a very limited application only in the chemical industry since then, e.g. for the handling of hot concentrated sulphuric acid, due to the high risks of low ductility cracking of these materials at greater wall thickness. These risks can be managed better if the highly alloyed ferritic phase is present in a finely dispersed compound with an austenitic phase where the ferritic part is adding its advantages, higher strength and resistance to stress corrosion cracking, to the duplex compound. This can result in low weight and corresponding cost saving. The application of the corrosion resistant duplex grades will expand further as much as users will better learn the special requirements of manufacturing of these materials and to take advantage of their unique properties. However, the most important alloy developments since the 1960s have been seen in the field of the austenitic stainless steels being highly alloyed with chromium, molybdenum and nitrogen. Especially the austenitic 6% Mo grades as e.g. X1NiCrMoCuN25‐20‐7 – alloy 926 (1.4529) have found many applications in chemical process industry, power generation and marine technology. Higher alloyed grades as e.g. X1NiCrMoCu32‐28‐7 – alloy 31 (1.4562) are excelling in extraordinary resistance to corrosion by acids and pitting attack. In addition today's upper limits of alloying austenitic corrosion resistant grades have been explored with grade X1CrNiMoCu33‐32‐1 – alloy 33 (1.4591) for chromium additions up to about 33% and with grade X1NiCrSi24‐9‐7 – alloy 700 Si (1.4390) for additions of silicon up to about 7%, providing a high corrosion resistance mainly in oxidising acids. When considering the prospects of further development of the corrosion resistant duplex grades the ferritic phase within these materials is both offering chances and setting limits. The high‐alloyed austenitic corrosion resistant steels have a potential being unexplored so far in the alloy range where molybdenum and nitrogen are becoming more prominent compared to the chromium content.     

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.     

Forthcoming corrosion events

Abstract

Pitting potentials have been measured and some gravimetric testing has been carried out on a series of experimental austenitic stainless steels with varying chromium, molybdenum and nitrogen contents. All three of these elements were found to contribute to the resistance to the initiation of pitting corrosion, and synergistic effects have been noted. The effect of nitrogen is especially potent in a steel with 22% chromium and 3% molybdenum.     

Pitting,Crevice and stress corrosion resistance of high chromium und molybdenum alloy stainless steels

This paper presents new data on the resistance of recently developed high-alloy stainless steels to localised corrosion in chloride solutions. Pitting potential was determined in artificial sea water, and critical pitting temperature CPT in very aggressive FeCl₃ solution. Critical crevice corrosion temperature CCT was tested in the same FeCl₃ solution. Stress corrosion measurements, made in a more familiar NaCl solution by the drop evaporation method, demonstrate that alloy stainless steels with high chromium and molybdenum have very long failure times, comparable with those of nickel alloys found to be SCC-resistant under practical conditions. Stainless steels of 20 Cr 25 Ni 6 Mo type showed the best resistance to localised corrosion.     

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.     

Localized Corrosion Characteristics of Nickel Alloys:A Review

There are a great variety of commercial nickel alloys mainly because nickel is able to dissolve a large amount of alloying elements while maintaining a single ductile austenitic phase.Nickel alloys are generally designed for and used in highly aggressive environments,for example,those where stainless steels may experience pitting corrosion or environmentally assisted cracking.While nickel alloys are generally resistant to pitting corrosion in chloride-containing environments,they may be prone to crevice corrosion attack.Addition of chromium,molybdenum and tungsten increases the localized corrosion resistance of nickel alloys.This review on the resistance to localized corrosion of nickel alloys includes specific environments such as those present in oil and gas upstream operations,in the chemical process industry and in seawater service.     

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.     

HASTELLOY® Alloy C-22 –ein neuer und vielseitig anwendbarer Werkstoff für die chemische Industrie

HASTELLOY® alloy C-22–a new and versatile material for the chemical process industries HASTELLOY® alloy C-22 is designed based on a critical balance of chromium, molybdenum, and tungsten contents. Such a balance provides unique corrosion resistance in the Ni-Cr-Mo system to oxidizing acids, localized corrosion, and non-oxidizing acids. Alloy C-22 also possesses thermal stability equivalent to HASTELLOY alloy C-4 in high heat input welding procedures. Applications of HASTELLOY alloy C-22 demonstrate its ability to solve difficult plant corrosion problems in services where other high performance alloys have failed.     

Einfluß von Verformung und spannungsinduzierten Ausscheidungen auf die Korrosionsbeständigkeit von siliciumlegiertem,nichtrostendem Stahl X2CrNiSi 18 15 in Salpetersäure

Effect of deformation and stress-induced precipitations on the corrosion resistance of silicon alloyed stainless steel X2CrNiSi 18 15 in nitric acid The corrosion resistance of silicon alloyed X2 CrNiSi 18 15 stainless steel with about 4 wt.-% Si in nitric acid depends on both deformation degree of the material and number and distribution of precipitations in the microstructure. After cold deformation and subsequent heat-treatment at 700°C (1292°F), the corrosion rate in 5 M HNO₃ is higher than that of non-deformed material. This result was established with specimens isolated from each other but was particularly pronounced with specimens being in galvanic contact. By deformation and subsequent annealing at 700°C, precipitations are formed at the grain boundaries the number of which increases with increasing degree of deformation. With higher degree of deformation, the precipitations are preferably arranged at slip-lines. They were identified as chromium carbide, M₂₃C₆, and silicide of the Cr₅Ni₃FeSi₂ type. It is shown by electrochemical measurements that these precipitations stimulate the cathodic partial reaction, i.e., the reduction of nitric acid. Hence, the corrosion resistance of the silicon alloyed stainless steel is impaired by deformation and stress-induced precipitations formed during annealing at 700°C.     

Corrosion behaviour of alloy 31 – UNS N08031 – under conditions of oil & gas production

The corrosion behaviour of alloy 31 (UNS N08031‐31Ni – 27Cr – 6.5Mo – 1.2Cu – 0.2N – bal. Fe) was tested in laboratory and field tests in seawater with and without additions of CO₂ and/or H₂S in slow strain rate tests, and in SSC (Sulphide Stress Corrosion) tests according to NACE MR0175. The results demonstrate a high resistance of alloy 31 to localised corrosion. Due to the high chromium and molybdenum concentration, its resistance to pitting and crevice corrosion in chloride‐contaminated seawater is significantly higher than that of alloy 28 and alloy 825 and it equals that of typical nickel base alloys like alloy 625. Alloy 31 is not sensitive to chloride‐induced stress corrosion cracking, either with or without H₂S, or sulphide stress cracking. Alloy 31 is approved for sour gas applications up to LEVEL VI in NACE MR 0175. The combination of properties makes alloy 31 an attractive choice for components in oil and gas production including wirelines, umbilicals, tubing, piping and topside application.     

Surface property enhancement of Ni-free medical grade austenitic stainless steel by low-temperature plasma carburising

Based on the success of the feasibility study reported, the surface properties of low-temperature plasma carburised P558 Ni-free medical grade (ASTM F2581) austenitic stainless steel have been fully evaluated in terms of electrochemical corrosion, dry- and corrosion-wear and fretting-wear in Ringer's solution. Anodic polarization tests demonstrated that the precipitate-free S-phase generated by low-temperature plasma carburising at 500 °C for 15 h can retain the good corrosion resistance of the untreated ASTM F2581 Ni-Free material in Ringer's solution. The wear resistance of the Ni-free austenitic stainless steel can be improved by 700% and 140% when reciprocating against a WC ball in air (dry-wear) and in Ringer's solution (corrosion-wear) respectively. In addition, the low-temperature plasma carburising treatment can considerably reduce the friction coefficient and improve the fretting-wear resistance of the Ni-free austenitic stainless steel in Ringer's solution.     

Corrosion fatigue of a manganese–nitrogen stabilized austenitic stainless steel

Austenitic chromium–manganese–nitrogen stabilized stainless steels have been developed to replace chromium–nickel–nitrogen stainless steels in certain applications. In comparison, chromium–manganese–nitrogen steels have improved mechanical properties and acceptable corrosion resistance in hot, high chloride containing media. In this paper, corrosion fatigue investigations of a solution annealed and for practice more relevant 14% cold worked high alloyed chromium–manganese–nitrogen steel have been done. Inert glycerine was used as reference media and 62% calcium chloride solution as corrosive media, both aerated at a temperature of 120 °C. The stress ratio between upper and lower stress levels was 0.05 (tension–tension loading) to avoid the destruction of the fracture surfaces. As testing frequency for the dynamic experiments, 20 Hz was chosen considering possible application areas. Maximum stress versus number of cycles curves were recorded and representative specimens were investigated in a scanning electron microscope. In addition, electrochemical tests, exposure tests and constant load tests were done. This paper shows results on the corrosion fatigue of a manganese–nitrogen stabilized austenitic steel in a hot high chloride containing salt solution and helps to get a better understanding of occurring failure mechanisms.