EP3899064B1 - Super austenitic material - Google Patents

Super austenitic material Download PDF

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EP3899064B1
EP3899064B1 EP19829564.4A EP19829564A EP3899064B1 EP 3899064 B1 EP3899064 B1 EP 3899064B1 EP 19829564 A EP19829564 A EP 19829564A EP 3899064 B1 EP3899064 B1 EP 3899064B1
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material according
threshold value
nitrogen
detection level
below detection
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German (de)
French (fr)
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EP3899064C0 (en
EP3899064A1 (en
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Andreas KEPLINGER
Rainer FLUCH
Clemens Vichytil
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Voestalpine Boehler Edelstahl GmbH and Co KG
Voestalpine Boehler Bleche GmbH and Co KG
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Voestalpine Boehler Edelstahl GmbH and Co KG
Voestalpine Boehler Bleche GmbH and Co KG
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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Definitions

  • the steel according to the invention should be free of precipitation, since precipitation has a negative impact on toughness and corrosion resistance.
  • the carbon content in particular is limited to 0.50%.
  • the copper content is deliberately added.
  • a special feature of the invention is that due to the high nitrogen content, the work hardening rate is higher than with other super austenites in order to be able to achieve tensile strengths (R m of 2000 MPa). This makes it possible as the last production step by cold rolling or other cold forming processes with high forming rates achieve strain hardening.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Heat Treatment Of Steel (AREA)
  • Conductive Materials (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Heat Treatment Of Articles (AREA)
  • Soft Magnetic Materials (AREA)

Description

Die Erfindung betrifft einen superaustenitischen Werkstoff und ein Verfahren zu seiner Herstellung.The invention relates to a super-austenitic material and a method for its production.

Derartige Werkstoffe werden z. B. im chemischen Anlagenbau, unter maritimen Bedingungen oder in der Ölfeld- oder Gasfeldtechnik eingesetzt.Such materials are z. B. in chemical plant construction, under maritime conditions or in oil field or gas field technology.

Eine Anforderung an derartige Materialien ist, dass diese einem korrosiven Angriff, insbesondere einem Angriff in Medien mit hohen Chloridkonzentrationen oder schwefelsauren Bedingungen widerstehen.A requirement for such materials is that they resist corrosive attack, especially attack in media with high chloride concentrations or sulfuric acid conditions.

Derartige Materialien sind z.B. aus der CN 107876562 A , der CN 104195446 A oder DE 43 42 188 bekannt. JP 2005 179733 offenbart einen superaustenitischen Werkstoff. bekannt.Such materials are, for example, from the CN 107876562A , the CN 104195446A or DE 43 42 188 known. JP2005 179733 discloses a super austenitic material. known.

Aus der EP 1 069 202 A1 ist ein paramagnetischer, korrosionsbeständiger, austenitischer Stahl mit hoher Dehngrenze, Festigkeit und Zähigkeit bekannt, der insbesondere in Medien mit hoher Chloridkonzentration korrosionsbeständig sein soll, wobei dieser Stahl 0,6 Gew.-% bis 1,4 Gew.-% Stickstoff enthalten soll, wobei 17 bis 24 Gew.-% Chrom, sowie Mangan und Stickstoff enthalten sind.From the EP 1 069 202 A1 a paramagnetic, corrosion-resistant, austenitic steel with a high yield point, strength and toughness is known, which is said to be corrosion-resistant in particular in media with a high chloride concentration, this steel being said to contain 0.6% by weight to 1.4% by weight of nitrogen, containing 17 to 24% by weight of chromium, as well as manganese and nitrogen.

Aus der WO 02/02837 A1 ist ein korrosionsbeständiger Werkstoff für die Anwendung in Medien mit hoher Chloridkonzentration in der Ölfeldtechnik bekannt. Hierbei handelt es sich um ein Chromnickelmolybdänsuperaustenit, der mit vergleichsweise niedrigen Stickstoffgehalten, jedoch sehr hohen Chrom- und sehr hohen Nickelgehalten ausgebildet ist.From the WO 02/02837 A1 is a corrosion-resistant material for use in media with a high chloride concentration in oil field technology. This is a chromium-nickel-molybdenum superaustenite that has a comparatively low nitrogen content but very high chromium and very high nickel contents.

Diese Chromnickelmolybdänstähle besitzen gegenüber den davor genannten Chrommanganstickstoffstählen üblicherweise noch ein verbessertes Korrosionsverhalten. Insgesamt sind Chrommanganstickstoffstähle eine eher kostengünstige Legierungszusammensetzung, die gleichwohl eine hervorragende Kombination aus Festigkeit, Zähigkeit und Korrosionsbeständigkeit bietet. Die genannten Chromnickelmolybdänstähle erreichen wesentlich höhere Korrosionsbeständigkeiten als Chrommanganstickstoffstähle, sind jedoch aufgrund des sehr hohen Nickelgehaltes mit wesentlich höheren Kosten verbunden.These chromium-nickel-molybdenum steels usually have improved corrosion behavior compared to the previously mentioned chromium-manganese-nitrogen steels. Overall, chromium manganese nitrogen steels are a more economical alloy composition that nonetheless offer an excellent combination of strength, toughness and corrosion resistance offers. The chromium-nickel-molybdenum steels mentioned achieve significantly higher corrosion resistance than chromium-manganese-nitrogen steels, but are associated with significantly higher costs due to the very high nickel content.

Kennwerte für die Korrosionsbeständigkeit sind unter anderem der sogenannte PREN16-Wert, wobei es auch üblich ist, die sogenannte pitting equivalent number mittels MARC zu definieren, wobei ein Superaustenit mit einer PREN16 zu o>42 gekennzeichnet ist, wobei PREN = % Cr + 3,3 x % Mo + 16 x % N ist.Key values for corrosion resistance include the so-called PREN 16 value, although it is also common to define the so-called pitting equivalent number using MARC, with a super austenite being marked with a PREN 16 of o>42, where PREN = % Cr + 3.3 x % Mo + 16 x % N.

Die bekannte MARC-Formel zur Beschreibung des Lochfraßwiderstands für derartige Stähle lautet wie folgt: MARC = % Cr + 3,3 x % Mo + 20 x % N + 20 x % C - 0,25 x % Ni - 0,5 x % Mn.The well-known MARC formula for describing the pitting resistance for such steels is as follows: MARC = % Cr + 3.3 x % Mo + 20 x % N + 20 x % C - 0.25 x % Ni - 0.5 x % Mn.

Vergleichbare Stahlgüten sind auch für die Verwendung als Schiffbaustähle für Unterseeboote bekannt, wobei es sich hierbei um Chromnickelmanganstickstoffstähle handelt, die zudem mit Niob legiert sind, um den Kohlenstoff zu stabilisieren, was jedoch die Kerbschlagzähigkeit verschlechtert. Diese Stähle besitzen grundsätzlich weniger Mangan und besitzen hierdurch eine relativ gute Korrosionsbeständigkeit, erreichen jedoch nicht die Festigkeit reinen hochstickstofflegierten CrMnN Stählen.Comparable steel grades are also known for use as shipbuilding steels for submarines, these being chromium-nickel manganese nitrogen steels which are also alloyed with niobium to stabilize the carbon, but this degrades the impact strength. These steels generally contain less manganese and therefore have relatively good corrosion resistance, but do not achieve the strength of pure high-nitrogen alloyed CrMnN steels.

Bekannte Superaustenite weisen für gewöhnlich Molybdängehalte > 4% auf, um die hohe Korrosionsbeständigkeit zu erreichen. Jedoch erhöht Molybdän die Neigung zu Seigerungen und somit eine erhöhte Anfälligkeit für Ausscheidungen (bevorzugt Sigma- oder Chi-Phasen), was zur Folge hat, dass diese Legierungen eine Homogenisierungsglühung benötigen bzw. bei Werten über 6% Molybdän ein Umschmelzen zur Reduzierung der Seigerungen notwendig ist.Known superaustenites usually have a molybdenum content > 4% in order to achieve high corrosion resistance. However, molybdenum increases the tendency to segregation and thus an increased susceptibility to precipitation (preferably sigma or chi phases), which means that these alloys require homogenization annealing or, for values above 6% molybdenum, remelting to reduce segregation is.

Aufgabe der Erfindung ist es, einen superaustenitischen, hochfesten und zähen Werkstoff zu schaffen, der in vergleichsweise einfacher und kostengünstiger Weise erzeugt werden kann und in besonderer Weise für eine schwefelsaure korrosive Umgebung geeignet ist.The object of the invention is to create a super-austenitic, high-strength and tough material that can be produced in a comparatively simple and cost-effective manner and is particularly suitable for a sulfuric acid corrosive environment.

Die Aufgabe wird mit einem Werkstoff mit den Merkmalen des Anspruchs 1 gelöst. Vorteilhafte Weiterbildungen sind in Unteransprüchen gekennzeichnet.The object is achieved with a material having the features of claim 1. Advantageous developments are identified in the dependent claims.

Es ist darüber hinaus eine Aufgabe der Erfindung, ein Verfahren zum Herstellen des Werkstoffs zu schaffen.It is also an object of the invention to provide a method for manufacturing the material.

Die Aufgabe wird mit den Merkmalen des Anspruch 16 gelöst. Vorteilhafte Weiterbildungen sind in den hiervon abhängigen Unteransprüchen gekennzeichnet.The object is achieved with the features of claim 16. Advantageous developments are characterized in the subclaims dependent thereon.

Wenn nachfolgend %-Angaben gemacht werden, sind diese in jedem Fall Gew.-% (Gewichtsprozent).If percentages are given below, these are in any case % by weight (percent by weight).

Erfindungsgemäß soll der Werkstoff, im Schiffbau und der Chemieanlagenbau bzw. die Kombination von beidem hier insbesondere Rauchgasentschwefelungsanlagen von seegehenden Schiffen verwendet werden. Auch alle anderen Bereiche in denen ein insbesondere schwefelsaurer oder Sauergas-Angriff zu erwarten sind. Dabei besitzt der Werkstoff ein vollkommen austenitisches Gefüge auch nach einer optionalen Kaltumformung. Nach der Kaltverfestigung soll die Dehngrenze bei Rp0,2>1000 MPa liegen.According to the invention, the material is to be used in shipbuilding and chemical plant construction or the combination of both here, in particular flue gas desulfurization systems of seagoing ships. Also all other areas in which a sulfuric acid or acid gas attack in particular is to be expected. The material has a completely austenitic structure even after optional cold forming. After strain hardening, the yield point should be R p0.2 >1000 MPa.

Die erfindungsgemäße Legierung besitzt insbesondere die nachfolgende Zusammensetzung (alle Angaben in Gew-%): Elemente bevorzugt weiter bevorzugt Kohlenstoff (C) 0,01 - 0,30 0,01 - 0,10 Silizium (Si) < 0,5 < 0,5 Mangan (Mn) 0,5 - 4,0 1,0 - 4,0 Phosphor (P) < 0,05 < 0,05 Schwefel (S) < 0,005 < 0,005 Eisen (Fe) Rest Rest Chrom (Cr) 24,0 - 30,0 26,0 - 29,0 Molybdän (Mo) 3,0 - 5,0 3,5 - 4,5 Nickel (Ni) 14,0 - 19,0 15,0 - 18,0 Vanadium (V) < 0,3 Unter Nachweisgrenze Wolfram (W) < 0,1 Unter Nachweisgrenze Kupfer (Cu) 0,75-3,5 1,0-2,0 Kobalt (Co) < 0,5 Unter Nachweisgrenze Titan (Ti) < 0,05 Unter Nachweisgrenze Aluminium (Al) < 0,1 < 0,1 Niob (Nb) < 0,025 Unter Nachweisgrenze Bor (B) < 0,005 < 0,005 Stickstoff (N) 0,40 - 0,70 0,45 - 0,60 In particular, the alloy according to the invention has the following composition (all data in % by weight): elements preferred more preferred carbon (C) 0.01 - 0.30 0.01 - 0.10 Silicon (Si) < 0.5 < 0.5 Manganese (Mn) 0.5 - 4.0 1.0 - 4.0 Phosphorus (P) < 0.05 < 0.05 Sulfur (S) < 0.005 < 0.005 iron (Fe) rest rest Chromium (Cr) 24.0 - 30.0 26.0 - 29.0 Molybdenum (Mo) 3.0 - 5.0 3.5 - 4.5 Nickel (Ni) 14.0 - 19.0 15.0 - 18.0 vanadium (V) < 0.3 Below detection limit Tungsten (W) < 0.1 Below detection limit copper (Cu) 0.75-3.5 1.0-2.0 cobalt (Co) < 0.5 Below detection limit Titanium (Ti) < 0.05 Below detection limit Aluminum (Al) < 0.1 < 0.1 niobium (Nb) < 0.025 Below detection limit boron (B) < 0.005 < 0.005 nitrogen (N) 0.40 - 0.70 0.45 - 0.60

Mit einer solchen Legierung werden die positiven Eigenschaften der unterschiedlichen bekannten Stahlgüten in synergistischer und überraschender Weise zusammengeführt.With such an alloy, the positive properties of the different known steel grades are brought together in a synergistic and surprising way.

Grundsätzlich soll der erfindungsgemäße Stahl ausscheidungsfrei vorliegen, da Ausscheidungen negativ sind für die Zähigkeit und die Korrosionsbeständigkeit. Bei der erfindungsgemäßen Legierung ist insbesondere der Kohlenstoffgehalt auf 0,50 % begrenzt. Gleichzeitig ist der Kupfergehalt bewusst zulegiert.In principle, the steel according to the invention should be free of precipitation, since precipitation has a negative impact on toughness and corrosion resistance. In the case of the alloy according to the invention, the carbon content in particular is limited to 0.50%. At the same time, the copper content is deliberately added.

Bei der erfindungsgemäßen Legierung ist völlig überraschend, dass sich sehr hohe Stickstoffwerte einstellen lassen, welches für die Festigkeit ausgesprochen gut ist, wobei diese Stickstoffwerte überraschenderweise über denen liegen, die in der Fachliteratur als möglich angegeben werden. Laut empirischen Methoden wären die hohen Stickstoffgehalte der erfindungsgemäßen Legierung überhaupt nicht ohne DESU zulegierbar siehe Fig. 4.In the case of the alloy according to the invention, it is completely surprising that very high nitrogen values can be set, which is extremely good for the strength, these nitrogen values surprisingly being above those that are indicated as possible in the technical literature. According to empirical methods, the high nitrogen contents of the alloy according to the invention could not be alloyed at all without DESU see 4 .

Im Folgenden werden die jeweiligen Elemente und gegebenenfalls im Zusammenwirken mit den übrigen Legierungsbestandteilen näher beschrieben. Alle Angaben bzgl. der Legierungszusammensetzung werden in Gewichtsprozent (Gew.-%) angeführt. Obere und untere Grenzen der einzelnen Legierungselemente können innerhalb der Grenzen der Ansprüche frei miteinander kombiniert werden.The respective elements and, if applicable, their interaction with the other alloy components are described in more detail below. All information regarding the alloy composition is given in percent by weight (% by weight). Upper and lower limits of the individual alloying elements can be freely combined with one another within the limits of the claims.

Kohlenstoff kann in einer erfindungsgemäßen Stahllegierung in Gehalten bis zu 0,50% enthalten sein. Kohlenstoff ist ein Austenitbildner und wirkt sich in Bezug auf hohe mechanische Kennwerte günstig aus. Im Hinblick auf eine Vermeidung von karbidischen Ausscheidungen sollte der Kohlenstoffgehalt zwischen 0,01 und 0,25 % bevorzugt zwischen 0,01 und 0,10 % eingestellt werden.A steel alloy according to the invention can contain carbon in contents of up to 0.50%. Carbon is an austenite former and has a favorable effect in terms of high mechanical parameters. With a view to avoiding carbidic precipitations, the carbon content should be set to between 0.01 and 0.25%, preferably between 0.01 and 0.10%.

Silizium ist in Gehalten < 0,5 % vorgesehen und dient in der Hauptsache der Desoxidation des Stahls. Die angegebene Obergrenze vermeidet sicher eine Ausbildung intermetallischer Phasen. Da Silizium überdies ein Ferritbildner ist, ist auch diesbezüglich die Obergrenze mit einem Sicherheitsbereich gewählt. Insbesondere kann Silizium in Gehalten von 0,1 - 0,4 % vorgesehen sein.Contents of <0.5% silicon are intended and are mainly used for deoxidizing the steel. The specified upper limit reliably avoids the formation of intermetallic phases. Since silicon is also a ferrite former, the upper limit is also selected with a safety range in this regard. In particular, silicon can be provided in contents of 0.1-0.4%.

Mangan ist in Gehalten von 0,1 - 5,0 % enthalten. Dies ist gegenüber Werkstoffen nach dem Stand der Technik ein ausgesprochen niedriger Wert. Bislang wurde angenommen, dass Mangangehalte von mehr als 19 %, möglichst mehr als 20 % für eine hohe Stickstofflöslichkeit notwendig sind. Überraschenderweise hat sich bei der vorliegenden Legierung ergeben, dass auch mit den erfindungsgemäß sehr niedrigen Mangangehalten eine Stickstofflöslichkeit erzielt wird, die über dem, was nach der herrschenden Fachmeinung möglich ist, liegt. Zudem wurde bislang angenommen, dass eine gute Korrosionsbeständigkeit mit sehr hohen Mangangehalten einhergeht, jedoch hat sich erfindungsgemäß ergeben, dass durch nicht aufgeklärte synergistische Effekte bei der vorliegenden Legierung dies offenbar nicht notwendig ist. Die untere Grenze für Mangan kann bei 0,5 oder 1,0 oder 2,0 oder 2,5 % gewählt werden. Die obere Grenze für Mangan kann bei 3,0 oder 3,5 oder 4,0 oder 4,5 % gewählt werden.Manganese is contained in levels of 0.1 - 5.0%. This is an extremely low value compared to materials according to the prior art. Up to now it has been assumed that manganese contents of more than 19%, if possible more than 20%, are necessary for high nitrogen solubility. Surprisingly, it has been found with the present alloy that even with the very low manganese contents according to the invention, a nitrogen solubility is achieved which is above what is possible according to prevailing expert opinion. In addition, it was previously assumed that good corrosion resistance goes hand in hand with very high manganese contents, but it has been found according to the invention that this is apparently not necessary due to unexplained synergistic effects in the present alloy. The lower limit for manganese can be chosen at 0.5 or 1.0 or 2.0 or 2.5%. The upper limit for manganese can be chosen at 3.0 or 3.5 or 4.0 or 4.5%.

Chrom erweist sich in Gehalten von 17 % oder mehr als für eine höhere Korrosionsbeständigkeit notwendig. Nach der Erfindung sind mindestens 23% und höchstens 33% Chrom enthalten. Bislang wurde angenommen, dass höhere Gehalte als 23 % sich nachteilig auf die magnetische Permeabilität auswirken, weil Chrom zu den ferritstabilisierenden Elementen zählt. Dem gegenüber konnte bei der erfindungsgemäßen Legierung festgestellt werden, dass selbst sehr hohe Chromgehalte oberhalb von 23% die magnetische Permeabilität in der vorliegenden Legierung nicht negativ beeinflussen, jedoch bekanntermaßen die Beständigkeit gegen Lochfraß und Spannungsrisskorrosion optimal beeinflusst werden. Die untere Grenze für Chrom kann bei 25 oder 26 % gewählt werden. Die obere Grenze für Chrom kann bei 28 oder 29 oder 30 oder 31 oder 32 % gewählt werden.Chromium levels of 17% or more are found to be necessary for higher corrosion resistance. According to the invention, at least 23% and at most 33% chromium are included. Up to now it was assumed that higher contents than 23% have an adverse effect on the magnetic permeability because chromium is one of the ferrite-stabilizing elements. In contrast, it was found in the alloy according to the invention that even very high chromium contents above 23% do not adversely affect the magnetic permeability in the present alloy, but the resistance to pitting and stress corrosion cracking is known to be optimally influenced. The lower limit for chromium can be selected at 25 or 26%. The upper limit for chromium can be chosen at 28 or 29 or 30 or 31 or 32%.

Molybdän ist ein Element, welches wesentlich zur Korrosionsbeständigkeit im Allgemeinen und zur Lochfraßkorrosionsbeständigkeit im Besonderen beiträgt, wobei die Wirkung von Molybdän durch Nickel verstärkt wird. Erfindungsgemäß werden 2,0 bis 5,0 % Molybdän zugesetzt. Es hat sich auch gezeigt, dass Mo Gehalte von > 5% und besonders > 6 % zu starken Seigerverhalten führen, was die Ausscheidungsneigung von Sigmaphase erhöht, was wiederum die Korrosionsbeständigkeit herabsetzen würde. Die untere Grenze für Molybdän kann bei 2,2 oder 2,3 oder 2,4 oder 2,5 oder 3,0 oder 3,2 oder 3,3 oder 3,4 oder 3,5 % gewählt werden. Die obere Grenze für Molybdän kann bei 4,4 oder 4,5 oder 4,6 oder 4,7 oder 4,8 oder 4,9 % gewählt werden.Molybdenum is an element which contributes significantly to corrosion resistance in general and pitting corrosion resistance in particular, the effect of molybdenum being enhanced by nickel. According to the invention, 2.0 to 5.0% molybdenum is added. It has also been shown that Mo contents of > 5% and especially > 6% lead to strong segregation behavior, which increases the tendency of sigma phase to precipitate, which in turn would reduce the corrosion resistance. The lower limit for molybdenum can be chosen at 2.2 or 2.3 or 2.4 or 2.5 or 3.0 or 3.2 or 3.3 or 3.4 or 3.5%. The upper limit for molybdenum can be chosen at 4.4 or 4.5 or 4.6 or 4.7 or 4.8 or 4.9%.

Wolfram ist erfindungsgemäß in Gehalten unter 0,5% anwesend und trägt zur Steigerung der Korrosionsbeständigkeit bei. Die obere Grenze für Wolfram kann bei 0,4 oder 0,3 oder 0,2 oder 0,1 % oder unter der Nachweisgrenze (d.h. ohne jegliche bewusste Zulegierung) gewählt werden.According to the invention, tungsten is present in amounts below 0.5% and contributes to the increase in corrosion resistance. The upper limit for tungsten can be chosen at 0.4 or 0.3 or 0.2 or 0.1% or below the detection limit (i.e. without any intentional addition).

Nickel ist erfindungsgemäß in Gehalten von 12 bis 20% anwesend, wodurch in chloridhaltigen Medien eine hohe Spannungsrisskorrosionsbeständigkeit erreicht wird. Die untere Grenze für Nickel kann bei 13 oder 14 oder 15 % gewählt werden. Die obere Grenze für Nickel kann bei 17 oder 18 oder 19 % gewählt werden.According to the invention, nickel is present in contents of 12 to 20%, as a result of which a high resistance to stress corrosion cracking is achieved in media containing chloride. The lower limit for nickel can be chosen at 13 or 14 or 15%. The upper limit for nickel can be chosen at 17 or 18 or 19%.

Es ist allgemein bekannt, dass das Zulegieren von Cu > 0,5% zu einer Erhöhung der Schwefelsäurebeständigkeit von austenitischen rostfreien Stahlgüten führt. Gleichzeitig wird in der Literatur auch erwähnt, dass Cu vor allem bei hochstickstofflegierten Stählen die Neigung zur Ausscheidung von unerwünschten CrzN-Ausscheidungen, welche Korrosionseigenschaften massiv verschlechtern, erhöht Erfindungsgemäß konnte ein Cr2N freies Gefüge erzielt werden, trotz Cu Gehalten > 0,5, bevorzugt >1,0 und hohen N Gehalten von > 0,40%. Dieser Effekt saturiert jedoch ab einer bestimmten Menge. Erfindungsgemäß wurde der obere Grenzwert für Kupfer auf 5,0% bevorzugt < 3 % oder < 2,5 % insbesondere < 2 % gewählt. Die untere Grenze für Kupfer kann bei 0,6 oder 0,7 oder 0,8 oder 0,9 oder 1 oder 1,1 % gewählt werden. Ein Anwendungsbereich ist speziell die Rauchgaswäsche, speziell z.B. bei seegehenden Schiffen. Mit diesen Gehalten kann einerseits eine gute Beständigkeit gegen schwefelsauren und auch Sauergas-Angriff erzielt werden, andererseits kann durch die Gesamtlegierung die Ausscheidung von Chromnitriden wie zuvor erwähnt weitestgehend unterbunden werden.It is well known that alloying Cu > 0.5% leads to an increase in the sulfuric acid resistance of austenitic stainless steel grades. At the same time, it is also mentioned in the literature that Cu increases the tendency to precipitate undesired CrzN precipitations, which massively impair corrosion properties, especially in high-nitrogen-alloyed steels. According to the invention, a Cr 2 N-free structure could be achieved, despite Cu contents > 0.5, preferably >1.0 and high N contents of >0.40%. However, this effect saturates above a certain amount. According to the invention, the upper limit value for copper was chosen to be 5.0%, preferably <3% or <2.5%, in particular <2%. The lower limit for copper can be chosen at 0.6 or 0.7 or 0.8 or 0.9 or 1 or 1.1%. One area of application is specifically flue gas scrubbing, especially for seagoing ships, for example. With these contents, on the one hand good resistance to sulfuric acid and acid gas attack can be achieved, on the other hand the precipitation of chromium nitrides can be largely prevented by the overall alloy, as mentioned above.

Kobalt kann in Gehalten < 5,0% insbesondere zur Substitution von Nickel vorgesehen sein.Cobalt can be provided in contents of <5.0%, in particular to replace nickel.

Die obere Grenze für Kobalt kann bei 3 oder 1 oder 0,5 oder 0,4 oder 0,3 oder 0,2 oder 0,1 % oder unter der Nachweisgrenze (d.h. ohne jegliche bewusste Zulegierung) gewählt werden.The upper limit for cobalt can be chosen at 3 or 1 or 0.5 or 0.4 or 0.3 or 0.2 or 0.1% or below the detection limit (i.e. without any intentional addition).

Stickstoff ist in Gehalten von 0,40 bis 0,90 % enthalten, um eine hohe Festigkeit sicherzustellen. Weiters trägt Stickstoff zur Korrosionsbeständigkeit bei und ist ein starker Austenitbildner, weshalb höhere Gehalte als 0,40 % günstig sind. Um stickstoffhaltige Ausscheidungen, insbesondere Chromnitrid, zu vermeiden, ist die Obergrenze des Stickstoffs auf 0,90 % begrenzt, wobei sich erwiesen hat, dass trotz des sehr geringen Mangangehaltes im Gegensatz zu bekannten Legierungen, diese hohen Stickstoffgehalte in der Legierung erzielbar sind. Aufgrund der guten Stickstofflöslichkeit einerseits und der Nachteile, die mit höheren Gehalten an Stickstoff, insbesondere über 0,90 % erhalten werden, verbietet sich jede Druckaufstickung im Rahmen einer DESU-Route sogar. Durch den erfindungsgemäß niedrigen und durch Chrom und Stickstoff kompensierten Molybdängehalt, ist dies auch nicht notwendig. Insbesondere vorteilhaft ist es, wenn das Verhältnis Stickstoff zu Kohlenstoff größer 15 ist. Die untere Grenze für Stickstoff kann bei 0,45 % gewählt werden. Die obere Grenze für Stickstoff kann bei 0,80 oder 0,70 oder 0,65 oder 0,60 % gewählt werden.Nitrogen is included at levels of 0.40 to 0.90% to ensure high strength. Furthermore, nitrogen contributes to corrosion resistance and is a strong austenite former, which is why higher contents than 0.40% are favorable. In order to avoid nitrogenous precipitates, in particular chromium nitride, the upper limit of nitrogen is limited to 0.90%, which has been shown to be the opposite despite the very low manganese content to known alloys, these high nitrogen contents can be achieved in the alloy. Due to the good nitrogen solubility on the one hand and the disadvantages that are obtained with higher nitrogen contents, in particular above 0.90%, any pressure increase is even out of the question as part of a DESU route. Due to the low molybdenum content according to the invention and compensated by chromium and nitrogen, this is also not necessary. It is particularly advantageous if the ratio of nitrogen to carbon is greater than 15. The lower limit for nitrogen can be chosen at 0.45%. The upper limit for nitrogen can be chosen at 0.80 or 0.70 or 0.65 or 0.60%.

Laut dem allgemeinen Stand der Technik ( V.G. Gavriljuk, H.Berns; "High Nitrogen Steels, S. 264, 1999 ) erreichen unter Atmosphärendruck erschmolzene CrNiMn(Mo) austenitische Stähle, wie der vorliegende, Stickstoffgehalte von 0,2 bis 0,5 %. Nur ChromManganMolybdänAustenite erreichen dabei Stickstoffgehalte von 0,5 bis 1 %.According to the general state of the art ( VG Gavrilyuk, H.Berns; "High Nitrogen Steels, p. 264, 1999 ) CrNiMn(Mo) austenitic steels melted under atmospheric pressure, such as the present one, achieve nitrogen contents of 0.2 to 0.5%. Only chromium-manganese-molybdenum austenite achieves a nitrogen content of 0.5 to 1%.

Erfindungsgemäß ist von Vorteil, dass gegen jede Erwartung hohe Stickstoffgehalte erreicht werden ohne dass ein Druckaufsticken notwendig wäre, was üblicherweise notwendig wäre, um diese Gehalte zu erzielen.According to the invention, it is advantageous that, contrary to all expectations, high nitrogen contents are achieved without the need for pressurization, which would usually be necessary in order to achieve these contents.

Hierdurch ist das erfindungsgemäße Verfahren auch kostengünstig, da das aufwendige Druckaufsticken nicht notwendig ist, wodurch wiederum auch das damit verbundene Umschmelzen entfallen kann.As a result, the method according to the invention is also cost-effective, since the expensive embroidering with pressure is not necessary, which in turn means that the associated remelting can also be omitted.

Zudem können als weitere Legierungsbestandteile Bor, Aluminium und Schwefel enthalten sein, jedoch lediglich optional. Die Legierungsbestandteile Vanadium und Titan sind in der vorliegenden Stahllegierung nicht notwendigerweise enthalten. Obwohl diese Elemente positiv zur Löslichkeit von Stickstoff beitragen, kann auch bei deren Abwesenheit die erfindungsgemäß hohe Stickstofflöslichkeit geboten werden.In addition, boron, aluminum and sulfur can be included as further alloy components, but only optionally. The alloy components vanadium and titanium are not necessarily contained in the present steel alloy. Although these elements contribute positively to the solubility of nitrogen, the high nitrogen solubility of the present invention can be provided even in their absence.

Niob soll in der erfindungsgemäßen Legierung nicht enthalten sein, da es die Zähigkeit herabsetzt und historisch nur zur Abbindung von Kohlenstoff verwendet wurde, was bei der erfindungsgemäßen Legierung nicht notwendig ist. Die Gehalte von Niob sind bis 0,1% noch tolerierbar, sollten aber den Gehalt unvermeidlicher Verunreinigungen nicht übersteigen.Niobium should not be contained in the alloy according to the invention since it reduces the toughness and was historically only used to bind carbon, which is not necessary in the alloy according to the invention. The niobium content is still tolerable up to 0.1%, but should not exceed the content of unavoidable impurities.

Die Erfindung wird anhand einer Zeichnung beispielhaft erläutert. Es zeigen dabei:

Figur 1:
eine Tabelle mit den Legierungselementen;
Figur 2:
stark schematisiert den Herstellungsweg und seine Alternativen;
Figur 3:
eine Tabelle mit drei unterschiedlichen Legierungen und den daraus resultierenden Ist-Werten des Stickstoffgehaltes gegen die rechnerische Stickstofflöslichkeit einer derartigen Legierung laut geltender Lehrmeinung;
Figur 4:
die Festigkeiten der in Figur 3 genannten Beispiele vor einer allfälligen Kaltverfestigung;
The invention is explained by way of example with reference to a drawing. They show:
Figure 1:
a table of alloying elements;
Figure 2:
strongly schematized the production route and its alternatives;
Figure 3:
a table with three different alloys and the resulting actual values of the nitrogen content against the calculated nitrogen solubility of such an alloy according to the prevailing doctrine;
Figure 4:
the strengths of the in figure 3 mentioned examples before any strain hardening;

Die Bestandteile werden unter atmosphärischen Bedingungen erschmolzen und anschließend sekundärmetallurgisch weiter behandelt. Anschließend werden Blöcke gegossen, die direkt anschließend warmumgeformt werden.The components are melted under atmospheric conditions and then further treated with secondary metallurgy. Blocks are then cast, which are immediately hot-formed.

Direkt anschließend im Sinne der Erfindung bedeutet, dass kein zusätzlicher Umschmelzprozess wie zb. Elektroschlacke-Umschmelzung (ESU) oder Druck-Elektroschlackeumschmelzung (DESU) erfolgt.Directly then within the meaning of the invention means that no additional remelting process such as. Electroslag remelting (ESR) or pressure electroslag remelting (DESU) takes place.

Erfindungsgemäß ist es vorteilhaft, wenn der folgende Zusammenhang gilt: MARC opt : 40 < % Cr + 3,3 × % Mo + 20 × % C + 20 × % N − 0,5 × % Mn

Figure imgb0001
According to the invention, it is advantageous if the following relationship applies: MARC opt : 40 < % Cr + 3.3 × % Mon + 20 × % C + 20 × % N − 0.5 × % Mn
Figure imgb0001

Die MARC-Formel ist dahingehende optimiert, dass herausgefunden wurde, dass der sonst übliche Abzug von Nickel für das erfindungsgemäße System nicht zutrifft sowie der Grenzwert von 40 notwendig ist.The MARC formula has been optimized in that it was found that the usual deduction of nickel does not apply to the system according to the invention and that the limit value of 40 is necessary.

Anschließend erfolgen bei Bedarf Kaltumformschritte, bei denen eine Kaltverfestigung stattfindet, und anschließend die mechanische Bearbeitung, die insbesondere ein Drehen, Fräsen oder Schälen sein kann.Subsequently, if necessary, cold forming steps take place, in which strain hardening takes place, and then mechanical processing, which can in particular be turning, milling or peeling.

In Figur 2 sind beispielhaft die möglichen Verfahrensrouten für die Fertigung der erfindungsgemäßen Legierungszusammensetzung dargestellt. Exemplarisch wird nun eine mögliche Route beschrieben. Im Vakuuminduktionsschmelzaggregat (VID) wird Schmelzgut gleichzeitig erschmolzen und sekundärmetallurgisch behandelt. Im Anschluss wird die Schmelze in Kokillen (Ingot) gegossen und erstarrt dort zu Blöcken. Diese werden danach in mehreren Schritten warmumgeformt, Z.B. auf der Langschmiedemaschine (Rotary Forging Machine) vorgeschmiedet und im Mehrlinienwalzwerk (Multiline Rolling Mill) auf End-maß gebracht oder auf Duo Walzgerüsten zu Blech ausgewalzt. Je nach Anforderungen kann noch ein Wärmebehandlungsschritt erfolgen.In figure 2 the possible process routes for the production of the alloy composition according to the invention are shown as examples. A possible one is now used as an example Route described. In the vacuum induction melting unit (VID), melted material is simultaneously melted and treated for secondary metallurgy. The melt is then poured into molds (ingot) and solidifies there into blocks. These are then hot-formed in several steps, eg pre-forged on the long forging machine (Rotary Forging Machine) and brought to final dimensions in the multi-line rolling mill or rolled out to sheet metal on duo rolling mills. Depending on the requirements, a heat treatment step can also be carried out.

Um die Festigkeit weiter zu erhöhen, kann noch ein Kaltumformungsschritt durchgeführt werden.In order to further increase the strength, a cold forming step can be carried out.

Ein erfindungsgemäßer superaustenitischer Werkstoff kann nicht nur über die beschriebenen (und insbesondere in Figur 2 dargestellten) Herstellungsrouten erzeugt werden, die vorteilhaften Eigenschaften der erfindungsgemäßen Legierung lassen sich auch durch einen pulvermetallurgischen Erzeugungsweg erzielen lassen.A super-austenitic material according to the invention can not only have the described (and in particular in figure 2 illustrated) production routes are produced, the advantageous properties of the alloy according to the invention can also be achieved by a powder-metallurgical production route.

In Figur 3 sind drei unterschiedliche Varianten innerhalb der erfindungsgemäßen Legierungszusammensetzungen gezeigt, mit den jeweils gemessenen Stickstoffwerten, die sich bei der erfindungsgemäßen Verfahrensweise in Verbindung mit den erfindungsgemäßen Legierungen ergeben haben. Diese sehr hohen Stickstoffanteile stehen im Widerspruch zu den in den rechten Spalten angegebenen Stickstofflöslichkeit nach Stein, Satir, Kowandar und Medovar aus "On restricting aspects in the production of non-magnetic Cr-Mn-N-alloy steels, Saller, 2005." Bei Medovar sind unterschiedliche Temperaturen angegeben. Es ist jedoch erkennbar, dass die hohen Stickstoffwerte die theoretisch zu erwartenden weit übersteigen.In figure 3 three different variants within the alloy compositions according to the invention are shown, with the nitrogen values measured in each case, which have resulted from the procedure according to the invention in connection with the alloys according to the invention. These very high nitrogen contents are in contradiction to the nitrogen solubility specified in the right columns according to Stein, Satir, Kowandar and Medovar from "On restricting aspects in the production of non-magnetic Cr-Mn-N-alloy steels, Saller, 2005." Different temperatures are given for Medovar. However, it can be seen that the high nitrogen values far exceed those that can be expected theoretically.

Dies ist umso erstaunlicher, als dass bei der erfindungsgemäßen Legierung ein Weg gegangen wurde, der eine hohe Stickstofflöslichkeit eben nicht zu erwarten lässt, insbesondere, weil der die Stickstofflöslichkeit stark positiv beeinflussende Mangangehalt gegenüber bekannten entsprechenden Legierungen stark herabgesetzt ist.This is all the more astonishing since the alloy according to the invention took a route that does not allow for the expectation of high nitrogen solubility, in particular because the manganese content, which has a strongly positive influence on nitrogen solubility, is greatly reduced compared to known corresponding alloys.

Somit ist bei der Erfindung von Vorteil, dass ein austenitischer, hochfester Werkstoff mit erhöhter Korrosionsbeständigkeit und niedrigem Nickelgehalt geschaffen wird, der gleichzeitig hohe Festigkeit und paramagnetisches Verhalten zeigt. Auch nach Kaltumformung liegt ein vollkommen austenitisches Gefüge vor, so dass es gelungen ist, die positiven Eigenschaften eines kostengünstigen CrMnN-Stahls mit den korrosionstechnischen herausragenden Eigenschaften eines CrNiMo-Stahls zu kombinieren.Thus, the advantage of the invention is that an austenitic, high-strength material with increased corrosion resistance and a low nickel content is created, which at the same time shows high strength and paramagnetic behavior. A completely austenitic structure is also present after cold forming, so that it has been possible to combine the positive properties of a cost-effective CrMnN steel with the excellent corrosion-related properties of a CrNiMo steel.

Eine Besonderheit der Erfindung ist, dass aufgrund des hohen Stickstoffgehalts die Kaltverfestigungsrate höher ist, als bei anderen Superausteniten um dadurch Zugfestigkeiten (Rm von 2000 MPa erreichen zu können. Dadurch ist es möglich als letzten Herstellungsschritt durch Kaltwalzen oder andere Kaltumformverfahren mit hohen Umformraten eine hohe Kaltverfestigung zu erreichen.A special feature of the invention is that due to the high nitrogen content, the work hardening rate is higher than with other super austenites in order to be able to achieve tensile strengths (R m of 2000 MPa). This makes it possible as the last production step by cold rolling or other cold forming processes with high forming rates achieve strain hardening.

Typische Anwendungsbereiche der erfindungsgemäßen Werkstoffe sind der Schiffbau und der Chemieanlagenbau bzw. die Kombination von beidem hier insbesondere Rauchgasentschwefelungsanlagen von seegehenden Schiffen, aber auch alle anderen Bereiche in denen ein insbesondere schwefelsaurer Angriff zu erwarten ist.Typical areas of application for the materials according to the invention are shipbuilding and chemical plant construction or the combination of both here, in particular flue gas desulfurization systems on seagoing ships, but also all other areas in which a particularly sulfuric acid attack is to be expected.

Speziell bei Anwendung bei denen sehr hohe Festigkeiten gefordert werden, kann mittels Kaltverformen die Festigkeit wie bereits beschrieben noch weiter gesteigert werden.Especially in applications where very high strength is required, the strength can be further increased by means of cold forming, as already described.

Claims (22)

  1. Superaustenitic material consisting of an alloy with the following alloy elements, with all details being in % by weight, as well as unavoidable impurities:
    Elements Carbon (C) 0.01 -0.50 Silicon (Si) < 0.5 Manganese (Mn) 0.1 - 5.0 Phosphorus (P) < 0.05 Sulphur (S) < 0.005 Iron (Fe) remainder Chromium (Cr) 24.0 - 33.0 Molybdenum (Mo) 2.0 - 5.0 Nickel (Ni) 12 - 20.0 Vanadium (V) < 0.5 Tungsten (W) < 0.5 Copper (Cu) 0.50 - 5.0 Cobalt (Co) < 5.0 Titanium (Ti) < 0.1 Aluminium (Al) < 0.2 Niobium (Nb) < 0.1 Boron (B) < 0.01 Nitrogen (N) 0.40 - 0.90
  2. Superaustenitic material according to claim 1,
    characterised in that the alloy consists of the following elements as well as unavoidable impurities, with all details being in % by weight:
    Elements Carbon (C) 0.01 - 0.30 Silicon (Si) < 0.5 Manganese (Mn) 0.5 - 4.0 Phosphorus (P) < 0.05 Sulphur (S) < 0.005 Iron (Fe) remainder Chromium (Cr) 24.0 - 30.0 Molybdenum (Mo) 3.0 - 5.0 Nickel (Ni) 14.0 - 19.0 Vanadium (V) < 0.3 Tungsten (W) < 0.1 Copper (Cu) 0.75 - 3.5 Cobalt (Co) < 0.5 Titanium (Ti) < 0.05 Aluminium (Al) < 0.1 Niobium (Nb) < 0.025 Boron (B) < 0.005 Nitrogen (N) 0.40 - 0.70
  3. Superaustenitic material according to claim 1 or 2,
    characterised in that the alloy consists of the following elements as well as unavoidable impurities, with all details being in % by weight:
    Elements Carbon (C) 0.01 - 0.10 Silicon (Si) < 0.5 Manganese (Mn) 1.0 - 4.0 Phosphorus (P) < 0.05 Sulphur (S) < 0.005 Iron (Fe) remainder Chromium (Cr) 26.0 - 29.0 Molybdenum (Mo) 3.5 - 4.5 Nickel (Ni) 15.0 - 18.0 Vanadium (V) below detection level Tungsten (W) below detection level Copper (Cu) 1.0 - 2.0 Cobalt (Co) below detection level Titanium (Ti) below detection level Aluminium (Al) < 0.1 Niobium (Nb) below detection level Boron (B) < 0.005 Nitrogen (N) 0.45 - 0.60
  4. Material according to one of the preceding claims,
    characterised in that
    the material is achieved by secondary metallurgical processing of the molten metal, casting into blocks, hot forming, optional cold forming, and optional further mechanical processing.
  5. Material according to one of the preceding claims,
    characterised in that
    the yield point Rp0.2>500 MPa.
  6. Material according to one of the preceding claims,
    characterised in that
    the notched bar impact work at room temperature in the longitudinal direction Av>300 J.
  7. Material according to one of the preceding claims,
    characterised in that
    after the cold deformation, the material is fully austenitic, thus free from deformation martensite.
  8. Material according to one of the preceding claims,
    characterised in that
    manganese has an upper threshold value of 3.0 % or 3.5 % or 4.0 % or 4.5 % or 5.0 % and
    a lower threshold value of 0.1 % or 0.5 % or 1.0 % or 2.0 % or 2.5 %.
  9. Material according to one of the preceding claims,
    characterised in that
    chromium has an upper threshold value of 28 % or 29 % or 29.8 or 31.5 % and
    a lower threshold value of 24.0 or 25 % or 26 %.
  10. Material according to one of the preceding claims,
    characterised in that
    molybdenum has an upper threshold value of 4.4 or 4.5 or 4.6 or 4.7 or 4.8 or 4.9 or 5.0 % and
    a lower threshold value of 2.05 % or 2.1 % or 2.2 % or 2.3 % or 2.4 % or 2.5 % or 3.0 % or 3.2 % or 3.3 % or 3.4 % or 3.5 %.
  11. Material according to one of the preceding claims,
    characterised in that
    nickel has an upper threshold value of 16.8 % or 17 or 18 or 19 % and
    a lower threshold value of 12 % or 13 % or 14 % or 15 %.
  12. Material according to one of the preceding claims,
    characterised in that
    nitrogen has an upper threshold value of 0.60 % or 0.65 % or 0.70 % or 0.75% or 0.80 % or 0.85 % or 0.88 % and
    a lower threshold value of 0.46 % or 0.50 % or 0.55 %.
  13. Material according to one of the preceding claims,
    characterised in that
    cobalt is at < 1 % or < 0.5 % or < 0.4 % or < 0.3 % or < 0.2 % or < 0.1 % or is below detection level.
  14. Material according to one of the preceding claims,
    characterised in that
    copper has an upper threshold value of 5.0 % or 4.5 % or 4.0 % or 3.5 % or 3.0 % or 2.5 % or 2 % and
    a lower threshold value of 0.60 % or 0.70 % or 0.80 % or 0.90 % or 1.0 % or 1.1 %.
  15. Material according to one of the preceding claims,
    characterised in that
    tungsten is at < 0.5 % or < 0.3 % or < 0.2 % or < 0.1 % or is below detection level.
  16. Method for producing a material according to one of the preceding claims,
    characterised in that
    the alloy consists of the following elements as well as unavoidable impurities, with all details being in % by weight:
    Elements Carbon (C) 0.01 - 0.50 Silicon (Si) < 0.5 Manganese (Mn) 0.1 - 5.0 Phosphorus (P) < 0.05 Sulphur (S) < 0.005 Iron (Fe) remainder Chromium (Cr) 24.0 - 33.0 Molybdenum (Mo) 2.0 - 5.0 Nickel (Ni) 12 - 20.0 Vanadium (V) < 0.5 Tungsten (W) < 0.5 Copper (Cu) 0.50 - 5.0 Cobalt (Co) < 5.0 Titanium (Ti) < 0.1 Aluminium (Al) < 0.2 Niobium (Nb) < 0.1 Boron (B) < 0.01 Nitrogen (N) 0.40 - 0.90
    is smelted and the material then produced by secondary metallurgical processing, then the thus-obtained alloy is cast into blocks and left to solidify, directly thereafter being heated and hot-formed, wherein the products are in particular subjected to a further cold forming and subsequent further mechanical processing.
  17. Method for producing a material according to claim 16,
    characterised in that
    the alloy consists of the following elements as well as unavoidable impurities, with all details being in % by weight:
    Elements Carbon (C) 0.01 - 0.30 Silicon (Si) < 0.5 Manganese (Mn) 0.5 - 4.0 Phosphorus (P) < 0.05 Sulphur (S) < 0.005 Iron (Fe) remainder Chromium (Cr) 24.0 - 30.0 Molybdenum (Mo) 3.0 - 5.0 Nickel (Ni) 14.0 - 19.0 Vanadium (V) < 0.3 Tungsten (W) < 0.1 Copper (Cu) 0.75 - 3.5 Cobalt (Co) < 0.5 Titanium (Ti) < 0.05 Aluminium (Al) < 0.1 Niobium (Nb) < 0.025 Boron (B) < 0.005 Nitrogen (N) 0.40 - 0.70
  18. Method for producing a material according to claim 16 or 17,
    characterised in that
    the alloy consists of the following elements as well as unavoidable impurities, with all details being in % by weight:
    Elements Carbon (C) 0.01 - 0.10 Silicon (Si) < 0.5 Manganese (Mn) 1.0 - 4.0 Phosphorus (P) < 0.05 Sulphur (S) < 0.005 Iron (Fe) remainder Chromium (Cr) 26.0 - 29.0 Molybdenum (Mo) 3.5 - 4.5 Nickel (Ni) 15.0 - 18.0 Vanadium (V) below detection level Tungsten (W) below detection level Copper (Cu) 1.0 - 2.0 Cobalt (Co) below detection level Titanium (Ti) below detection level Aluminium (Al) < 0.1 Niobium (Nb) below detection level Boron (B) < 0.005 Nitrogen (N) 0.45 - 0.60
  19. Method according to one of claims 16 to 18,
    characterised in that
    the hot forming takes place in a plurality of sub-steps.
  20. Method according to one of claims 16 to 19,
    characterised in that
    the product is reheated between the hot forming sub-steps and, if required, solution annealing takes place after the last hot forming sub-step.
  21. Method according to one of claims 16 to 20,
    characterised in that
    after the last hot forming sub-step as well as the optional solution annealing, a cold forming step takes place to achieve a tensile strength Rm > 1000 MPa, in particular Rm > 2000 MPa.
  22. Use of a material according to one of claims 1 to 15, in particular produced with a method according to one of claims 16 to 21, for systems and system components which are exposed to sulphuric acid corrosion, in particular flue gas desulphurisation systems.
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