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EP3105358A1 - Titanium-free alloy - Google Patents

Titanium-free alloy

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Publication number
EP3105358A1
EP3105358A1 EP15716712.3A EP15716712A EP3105358A1 EP 3105358 A1 EP3105358 A1 EP 3105358A1 EP 15716712 A EP15716712 A EP 15716712A EP 3105358 A1 EP3105358 A1 EP 3105358A1
Authority
EP
European Patent Office
Prior art keywords
max
alloy
weight
titanium
alloy according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15716712.3A
Other languages
German (de)
French (fr)
Other versions
EP3105358B1 (en
Inventor
Julia Rosenberg
Jutta KLÖWER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VDM Metals International GmbH
Original Assignee
VDM Metals International GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102014002402.4A external-priority patent/DE102014002402A1/en
Priority claimed from DE102014002693.0A external-priority patent/DE102014002693A1/en
Application filed by VDM Metals International GmbH filed Critical VDM Metals International GmbH
Publication of EP3105358A1 publication Critical patent/EP3105358A1/en
Application granted granted Critical
Publication of EP3105358B1 publication Critical patent/EP3105358B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C22C1/02—Making non-ferrous alloys by melting
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    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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Definitions

  • the invention relates to a titanium-free alloy with high pitting and crevice corrosion resistance and high yield strength and strength in the work-hardened state.
  • the highly corrosion-resistant alloy Alloy 825 is used mainly in the chemical industry and in offshore technology. It is marketed under the material number 2.4858 and has the following chemical composition: C ⁇ 0.025%, S ⁇ 0.015%, Cr 19.5-23.5%, Ni 28-46%, Mn £ 1%, Si ⁇ 0.5% , Mo 2.5-3.5%, Ti 0.6-1.2%, Cu 1.5- 3%, Al ⁇ 0.2%, Co ⁇ 1%, Fe balance.
  • the alloy Alloy 825 is a titanium-stabilized material.
  • titanium can cause problems, especially in continuous casting, because it reacts with the casting powder S1O 2 (Problem 3). It would be desirable to avoid the element titanium, but this leads to a significant increase in the edge crack tendency.
  • JP 61288041 A1 relates to an alloy having the following composition: C ⁇ 0.045%, S ⁇ 0.03%, N 0.005-0.2%, Cr 14-26%, Mn ⁇ 1%, Si ⁇ 1%, Mo ⁇ 8% , Cu ⁇ 2%, Fe ⁇ 25%, Al ⁇ 2%, B 0.001 - 0.1%, Mg 0.005 - 0.5%, remainder Ni.
  • the content of Nb is generated by a formula.
  • at least one of the elements Ti, Al, Zr, W, Ta, V, Hf may be contained in contents 2.
  • the object of the invention is to provide an alloy which is alternative to Alloy 825, which meets the problems outlined above and
  • the hot forming and weldability is at least as good.
  • An expedient embodiment of the alloy according to the invention has the following composition (in% by weight)
  • the chromium content can be modified as follows:
  • the nickel content can be modified as follows:
  • molybdenum content can be modified as follows:
  • the alloy may still contain the element V in contents (in wt.)
  • V 0.2-0.7% may be added.
  • the iron content in the alloy according to the invention should be> 22%.
  • the PRE total in terms of corrosion resistance of Alloy 825 is PRE 33 and is very low compared to other alloys.
  • Table 2 shows the active quantities PRE according to the prior art.
  • Table 3 shows the results of various pitting corrosion studies.
  • the reduced titanium content has no negative influence on the pitting corrosion temperature.
  • the increased molybdenum content has positive effects.
  • Table 5 Tensile tests at RT Figures 1 and 2 below show results of tensile tests on the one hand of the reference alloy Alloy 825 and on the other hand of alternative alloys.
  • Molybdenum has a positive effect on yield strength and strength.
  • Figures 3 and 4 illustrate the positive influence of Molydbän.
  • Microcrack (stereomicroscope)
  • a homogenization annealing of the slabs / billets produced is carried out at 1 150-1250 ° C for 15 to 25 hours, wherein
  • the homogenization annealing is carried out in particular following a first hot working.
  • the alloy can also be produced by ESUA / AR remelting.
  • the alloy according to the invention should preferably be used as a component in the oil and gas industry.
  • Table 6 contrasts Alloy 825 (standard) with two alloys of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Steel (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Arc Welding In General (AREA)

Abstract

Titanium-free alloy which has great resistance to pitting and crevice corrosion and a high yield point in the strain-hardened state and comprises (in wt%) a maximum of 0.02% C, a maximum of 0.01% S, a maximum of 0.03% N, 20.0-23.0% Cr, 39.0-44.0% Ni, 0.4 - < 1.0 % Mn, 0.1 - < 0.5 % Si, > 4.0 - < 7.0 % Mo, a maximum of 0.15 % Nb, > 1.5 - < 2.5 % Cu, 0.05 - < 0.3 % Al, a maximum of 0.5 % Co, 0.001 - < 0.005 % B, 0.005 - < 0.015 % Mg, the remainder consisting of Fe and smelting-related impurities.

Description

Titanfreie Legierung  Titanium-free alloy

Die Erfindung betrifft eine titanfreie Legierung mit hoher Lochfraß- und Spaltkorrosionsbeständigkeit sowie hoher Streckgrenze und Festigkeit im kaltverfestigten Zustand. The invention relates to a titanium-free alloy with high pitting and crevice corrosion resistance and high yield strength and strength in the work-hardened state.

Der hochkorrosionsbeständige Werkstoff Alloy 825 wird schwerpunktmäßig in der chemischen Industrie und in der Offshore-Technik eingesetzt. Er wird unter der Werkstoffnummer 2.4858 vertrieben und hat folgende chemische Zusammensetzung: C < 0,025 %, S < 0,015 %, Cr 19,5 - 23,5 %, Ni 28 - 46 %, Mn £ 1 %, Si < 0,5 %, Mo 2,5 - 3,5 %, Ti 0,6 - 1 ,2 %, Cu 1 ,5 - 3 %, AI < 0,2 %, Co < 1 %, Fe Rest. The highly corrosion-resistant alloy Alloy 825 is used mainly in the chemical industry and in offshore technology. It is marketed under the material number 2.4858 and has the following chemical composition: C <0.025%, S <0.015%, Cr 19.5-23.5%, Ni 28-46%, Mn £ 1%, Si <0.5% , Mo 2.5-3.5%, Ti 0.6-1.2%, Cu 1.5- 3%, Al <0.2%, Co <1%, Fe balance.

Für neue Anwendungen in der Öl- und Gas-Industrie sind die Lochfraß- und Spaltkorrosionsbeständigkeit (Problem 1) sowie die Streckgrenze und Festigkeit (Problem 2) zu gering. For new applications in the oil and gas industry, Pitting and Crevice Corrosion Resistance (Problem 1) and Yield Strength and Strength (Problem 2) are too low.

Im Hinblick auf den geringen Chrom- und Molybdängehalt weist Alloy 825 nur eine vergleichsweise geringe Wirksumme auf (PRE = 1 x % Cr + 3,3 x % Mo). Unter der Wirksumme PRE versteht der Fachmann Pitting Resistance Equivalent. In view of the low chromium and molybdenum content, Alloy 825 has only a comparatively small amount of effect (PRE = 1 ×% Cr + 3.3 ×% Mo). Under the sum of the PRE, the specialist understands Pitting Resistance Equivalent.

Bei der Legierung Alloy 825 handelt es sich um einen titanstabilisierten Werkstoff. Titan kann jedoch zu Problemen, insbesondere beim Strangguss führen, da es mit dem S1O2 des Gießpulvers reagiert (Problem 3). Wünschenswert wäre ein Vermeiden des Elements Titan, was allerdings zu einer signifikanten Erhöhung der Kantenrissneigung führt. The alloy Alloy 825 is a titanium-stabilized material. However, titanium can cause problems, especially in continuous casting, because it reacts with the casting powder S1O 2 (Problem 3). It would be desirable to avoid the element titanium, but this leads to a significant increase in the edge crack tendency.

Die JP 61288041 A1 betrifft eine Legierung folgender Zusammensetzung: C < 0,045 %, S < 0,03 %, N 0,005 - 0,2 %, Cr 14 - 26 %, Mn < 1 %, Si < 1 %, Mo < 8 %, Cu < 2 %, Fe < 25 %, AI < 2 %, B 0,001 - 0,1 %, Mg 0,005 - 0,5 %, Rest Ni. Der Gehalt an Nb wird durch eine Formel generiert. Darüber hinaus kann mindestens eines der Elemente Ti, AI, Zr, W, Ta, V, Hf in Gehalten 2 enthalten sein. JP 61288041 A1 relates to an alloy having the following composition: C <0.045%, S <0.03%, N 0.005-0.2%, Cr 14-26%, Mn <1%, Si <1%, Mo <8% , Cu <2%, Fe <25%, Al <2%, B 0.001 - 0.1%, Mg 0.005 - 0.5%, remainder Ni. The content of Nb is generated by a formula. In addition, at least one of the elements Ti, Al, Zr, W, Ta, V, Hf may be contained in contents 2.

Bestätigungskopiel Die US 2,777,766 offenbart eine Legierung folgender Zusammensetzung: C < 0,25 %, Cr 18 - 25 %, Ni 35 - 50 %, Mo 2 - 12 %, Nb 0,1 - 5 %, Cu bis 2,5 %, W bis 5 %, Fe Rest (min. 15 %). Bestätigungskopiel US 2,777,766 discloses an alloy of the following composition: C <0.25%, Cr 18-25%, Ni 35-50%, Mo 2-12%, Nb 0.1-5%, Cu up to 2.5%, W up to 5%, Fe remainder (at least 15%).

Der Erfindung liegt die Aufgabe zugrunde, eine zu Alloy 825 alternative Legierung bereitzustellen, die den vorab aufgezeigten Problemen gerecht wird und The object of the invention is to provide an alloy which is alternative to Alloy 825, which meets the problems outlined above and

- titanfrei ist,  - is titanium free,

- eine erhöhte Lochfraß- und Spaltkorrosionsbeständigkeit aufweist,  has increased pitting and crevice corrosion resistance,

- eine höhere Streckgrenze im kaltverfestigten Zustand hat,  - has a higher yield strength in the work-hardened state,

- deren Warmumform- und Schweißbarkeit zumindest gleich gut ist.  - The hot forming and weldability is at least as good.

Darüber hinaus soll ein Verfahren zur Herstellung der Legierung vorgestellt werden. In addition, a method for producing the alloy will be presented.

Diese Aufgabe wird gelöst durch eine titanfreie Legierung mit hoherThis object is achieved by a titanium-free alloy with high

Lochfraßkorrosionsbeständigkeit mit (in Gew.-%) Pitting corrosion resistance with (in% by weight)

C max. 0,02 %  C max. 0.02%

S max. 0,01 %  S max. 0.01%

N max. 0,03 %  N max. 0.03%

Cr 20,0 - 23,0 %  Cr 20.0 - 23.0%

Ni 39,0 - 44,0 %  Ni 39.0 - 44.0%

Mn 0,4 - < 1 ,0 %  Mn 0.4 - <1, 0%

Si 0,1 - < 0,5 %  Si 0.1 - <0.5%

Mo > 4,0 - < 7,0 %  Mo> 4.0 - <7.0%

Nb max. 0,15 %  Nb max. 0.15%

Cu > 1 ,5 - < 2,5 %  Cu> 1, 5 - <2.5%

AI 0,05 - < 0,3 %  AI 0.05 - <0.3%

Co max. 0,5 %  Co max. 0.5%

B 0,001 - < 0,005 %  B 0.001 - <0.005%

Mg 0,005 - < 0,015 %  Mg 0.005 - <0.015%

Fe Rest sowie erschmelzungsbedingte Verunreinigungen. Vorteilhafte Weiterbildungen der erfindungsgemäßen Legierung sind den zugehörigen gegenständlichen Unteransprüchen zu entnehmen. Fe remainder as well as smelting-related impurities. Advantageous developments of the alloy according to the invention can be found in the associated subject subclaims.

Eine zweckmäßige Ausgestaltung der erfindungsgemäßen Legierung weist folgende Zusammensetzung (in Gew.-%) An expedient embodiment of the alloy according to the invention has the following composition (in% by weight)

C max. 0,015 %  C max. 0.015%

S max. 0,005 %  S max. 0.005%

N max. 0,02 %  N max. 0.02%

Cr 21 ,0 - < 23 %  Cr 21, 0 - <23%

Ni > 39,0 - < 43,0 %  Ni> 39.0 - <43.0%

Mn 0,5 - 0,9 %  Mn 0.5 - 0.9%

Si 0,2 - < 0,5 %  Si 0.2 - <0.5%

Mo > 4,5 - 6,5 %  Mo> 4.5 - 6.5%

Nb max. 0,15 %  Nb max. 0.15%

Cu > 1 ,6 - < 2,3 %  Cu> 1, 6 - <2.3%

AI 0,06 - < 0,25 %  AI 0.06 - <0.25%

Co max. 0,5 %  Co max. 0.5%

B 0,002 - 0,004 %  B 0,002 - 0,004%

Mg 0,006 - 0,015 %  Mg 0.006 - 0.015%

Fe Rest sowie erschmelzungsbedingte Verunreinigungen.  Fe remainder as well as smelting-related impurities.

Der Gehalt an Chrom kann bedarfsweise noch wie folgt modifiziert werden: If necessary, the chromium content can be modified as follows:

Cr > 21 ,5 - < 23 % Cr> 21, 5 - <23%

Cr 22,0 - < 23 % Cr 22.0 - <23%

Der Nickelgehalt kann bedarfsweise noch wie folgt modifiziert werden: If necessary, the nickel content can be modified as follows:

Ni > 39,0 - < 42 % Ni> 39.0 - <42%

Ni > 39,0 - < 41 % Ni> 39.0 - <41%

Der Molybdängehalt kann bedarfsweise noch wie folgt modifiziert werden: If necessary, the molybdenum content can be modified as follows:

Mo > 5 - < 6,5 % Mo> 5 - <6.5%

Mo > 5 - < 6,2 % Der Gehalt an Kupfer kann bedarfsweise noch wie folgt eingestellt werden: Mo> 5 - <6.2% The content of copper can, if necessary, still be set as follows:

Cu > 1 ,6 - < 2,0 % Cu> 1, 6 - <2.0%

Bedarfsweise kann der Legierung noch das Element V in Gehalten (in Gew.-)If necessary, the alloy may still contain the element V in contents (in wt.)

V > 0 - 1 ,0 % V> 0 - 1, 0%

V 0,2 - 0,7 % zugesetzt werden.  V 0.2-0.7% may be added.

Der Eisengehalt soll in der erfindungsgemäßen Legierung > 22 % sein. The iron content in the alloy according to the invention should be> 22%.

Durch das Weglassen des Elements Titan entstehen - wie vorab dargelegt - beim Walzen Kantenrisse. Die Rissneigung kann durch Magnesium in der Größenordnung 50-150 ppm positiv beeinflusst werden. In der Tabelle 1 sind die dazugehörigen/untersuchten Laborschmelzen aufgeführt. By omitting the element titanium arise - as stated above - when rolling edge cracks. The tendency to crack can be positively influenced by magnesium in the order of 50-150 ppm. Table 1 lists the associated / investigated laboratory melts.

Tabelle 1: Einfluss von Desoxidationselementen auf die Kantenrissneigung beim Warmwalzen Table 1: Influence of deoxidizing elements on the edge crack tendency during hot rolling

Die Wirksumme PRE im Hinblick auf die Korrosionsbeständigkeit des Alloy 825 liegt bei PRE 33 und ist im Vergleich zu anderen Legierungen sehr gering. In Tabelle 2 sind die Wirksummen PRE gemäß dem Stand der Technik abgebildet. The PRE total in terms of corrosion resistance of Alloy 825 is PRE 33 and is very low compared to other alloys. Table 2 shows the active quantities PRE according to the prior art.

Tabelle 2: Wirksumme PRE für verschiedene dem Stand der Technik entsprechende Legierungen  Table 2: Sum of PRE for various prior art alloys

Durch Erhöhung des Molybdängehalts lässt sich diese Wirksumme und somit die Korrosionsbeständigkeit steigern. PRE = 1 x % Cr + 3,3 x % Mo (Pitting Resistance Equivalent). By increasing the molybdenum content, this amount of activity and thus the corrosion resistance can be increased. PRE = 1 x% Cr + 3.3 x% Mo (Pitting Resistance Equivalent).

Tabelle 3 zeigt die Ergebnisse diverser Lochfraßkorrosionsuntersuchungen. Der reduzierte Titangehalt hat keinen negativen Einfluss auf die Lochfraßkorrosionstemperatur. Der erhöhte Molybdängehalt hat positive Auswirkungen. Table 3 shows the results of various pitting corrosion studies. The reduced titanium content has no negative influence on the pitting corrosion temperature. The increased molybdenum content has positive effects.

Tabelle 3: Kritische Lochfraßkorrosionstemperatur in 6 % FeC + 1 % HCL, über 72 h (ASTM G-48 Methode C).  Table 3: Critical pitting corrosion temperature in 6% FeC + 1% HCL over 72 hours (ASTM G-48 Method C).

Weitere Korrosionsuntersuchungen zeigten ebenfalls eine Verbesserung der kritischen Spaltkorrosionstemperaturen im Vergleich zum Alloy 825. Diese sind in Tabelle 4 dargestellte. Alloy CPT in °C CCT in °C Ni Cr Mo V Ti PRE Further corrosion testing also showed an improvement in critical crevice corrosion temperatures compared to Alloy 825. These are shown in Table 4. Alloy CPT in ° C CCT in ° C Ni Cr Mo V Ti PRE

825* 30 < 5 33  825 * 30 <5 33

PV661 40 15 40 23 3,3 < 0,002 0,8 34  PV661 40 15 40 23 3.3 <0.002 0.8 34

PV662 50 20 40 23 5,9 < 0,002 < 0,002 42  PV662 50 20 40 23 5.9 <0.002 <0.002 42

PV663 50 20 39 23 5,8 0,4 < 0,002 42  PV663 50 20 39 23 5.8 0.4 <0.002 42

Tabelle 4: Kritische Lochfraß- (CPT) und Spaltkorrosionstemperatur (CCT)  Table 4: Critical Pitting (CPT) and Crevice Corrosion Temperature (CCT)

Durch 15 und 30-% Kaltverformung kann die Streckgrenze und die Festigkeit erhöht werden. In der folgenden Tabelle sind die dazugehörigen Untersuchungsergebnisse diverser Laborlegierungen aufgeführt. By 15 and 30% cold working, the yield strength and the strength can be increased. The following table lists the corresponding test results of various laboratory alloys.

Tabelle 5: Zugversuche bei RT In den nachstehenden Abbildungen 1 und 2 sind Ergebnisse von Zugversuchen, einerseits der Referenzlegierung Alloy 825 und andererseits alternativer Legierungen dargestellt. Table 5: Tensile tests at RT Figures 1 and 2 below show results of tensile tests on the one hand of the reference alloy Alloy 825 and on the other hand of alternative alloys.

Graphische Darstellung der Ergebnisse der Zugversuche bei Raumtemperatur (Mittelwerte) in Abhängigkeit vom Zustand.  Graphical representation of the results of the tensile tests at room temperature (mean values) as a function of the state.

Molybdän wirkt sich positiv auf die Streckgrenze und die Festigkeit aus. In den Abb. 3 und 4 wird der positive Einfluss von Molydbän verdeutlicht. Molybdenum has a positive effect on yield strength and strength. Figures 3 and 4 illustrate the positive influence of Molydbän.

Abbildung 3 Abbildung 4  Figure 3 Figure 4

Graphische Darstellung der Ergebnisse der Zugversuche bei Raumtemperatur (Mittelwerte) in Abhängigkeit vom Molybdängehalt.  Graphical representation of the results of the tensile tests at room temperature (mean values) as a function of the molybdenum content.

Mithilfe des PVR-Tests (Programmierten-Verformungs-Riss-Test) wurde die Heißrisssensibilität der Ni-Basislegierung Alloy 825 untersucht. Durch Anlegen einer linear ansteigenden Zuggeschwindigkeit während des WIG-Schweißens, wurde die kritische Zuggeschwindigkeit VKr bestimmt. In der folgenden Graphik sind die Untersuchungsergebnisse dargestellt. Je höher die Zuggeschwindigkeit und je geringer die Heißrissneigung, umso besser ist die Schweißbarkeit des Werkstoffs. Die titanfreien, hochmolybdänhaltigen Varianten (PV 506 und PV 507) zeigten weniger Risse als die Standard legierung (PV 942). Using the PVR test (Programmed Deformation Crack Test), the hot crack sensitivity of Alloy 825 Ni base alloy was investigated. By applying a linearly increasing train speed during TIG welding, the critical train speed V Kr was determined. The following graph shows the examination results. The higher the pulling speed and the lower the hot cracking tendency, the better the weldability of the material. The titanium-free, high molybdenum-containing variants (PV 506 and PV 507) showed fewer cracks than the standard alloy (PV 942).

45,0 45.0

Makroriss (PT)  Macroriss (PT)

40,0  40.0

Mikroriss (Stereomikroskop)  Microcrack (stereomicroscope)

35,0  35.0

30,0  30.0

25,0  25.0

20,0  20.0

15,0  15.0

10,0  10.0

5.0  5.0

0,0  0.0

LG = losungsgeglüht  LG = solution annealed

WG - weichgeglüht  WG - annealed

Abbildung 5 Kritische Verformungsgeschwindigkeiten für den 1. Heißriss (PT- und Stereomikroskopprüfung) an Alloy 825, unabhängig von der Rissart  Figure 5 Critical deformation rates for the 1st hot crack (PT and stereomicroscope test) on Alloy 825, regardless of the crack type

Tabelle 6 (chemische Zusammensetzung in Gew.-%) Die Aufgabe wird auch gelöst durch ein Verfahren zur Herstellung einer Legierung, die eine Zusammensetzung gemäß einem der gegenständlichen Ansprüche aufweist, indem Table 6 (chemical composition in% by weight) The object is also achieved by a method for producing an alloy having a composition according to one of the subject claims, by

a) die Legierung offen im Strang- oder Blockguss erschmolzen wird,  a) the alloy is melted open in strand or block casting,

b) zur Aufhebung der durch den erhöhten Molybdängehalt verursachten Seigerungen eine Homogenisierungsglühung der erzeugten Brammen/Knüppel bei 1 150-1250 °C über 15 bis 25 h durchgeführt wird, wobei  b) to cancel the segregations caused by the increased molybdenum content, a homogenization annealing of the slabs / billets produced is carried out at 1 150-1250 ° C for 15 to 25 hours, wherein

c) die Homogenisierungsglühung insbesondere im Anschluss an eine erste Warmumformung durchgeführt wird.  c) the homogenization annealing is carried out in particular following a first hot working.

Optional kann die Legierung auch durch ESUA/AR-Umschmelzen erzeugt werden. Optionally, the alloy can also be produced by ESUA / AR remelting.

Die erfindungsgemäße Legierung soll bevorzugt als Bauteil in der Öl- und Gasindustrie eingesetzt werden. The alloy according to the invention should preferably be used as a component in the oil and gas industry.

Als Produktformen bieten sich hierbei Bleche, Bänder, Rohre (längsnahtgeschweißt und nahtlos), Stangen oder Schmiedeteile an. As product forms here are offered sheets, strips, tubes (longitudinally welded and seamless), rods or forgings.

Tabelle 6 stellt Alloy 825 (Standard) zwei erfindungsgemäßen Legierungen gegenüber. Table 6 contrasts Alloy 825 (standard) with two alloys of the present invention.

Tabelle 6 (chemische Zusammensetzung in Gew.-%)  Table 6 (chemical composition in% by weight)

Claims

Patentansprüche claims 1. Titanfreie Legierung mit hoher Lochfraß- und Spaltkorrosionsbeständigkeit sowie hoher Streckgrenze im kaltverfestigten Zustand, mit (in Gew.-%)1. Titanium-free alloy with high pitting and crevice corrosion resistance and high yield strength in the work-hardened state, with (in% by weight) C max.0,02 % C max.0.02% S max.0,01 %  S max.0.01% N max.0,03 %  N max.0.03% Cr 20,0 - 23,0 %  Cr 20.0 - 23.0% Ni 39,0 - 44,0 %  Ni 39.0 - 44.0% Mn 0,4 -< 1,0%  Mn 0.4 - <1.0% Si 0,1 -<0,5%  Si 0.1 - <0.5% Mo > 4,0 - < 7,0 %  Mo> 4.0 - <7.0% Nb max.0,15 %  Nb max.0,15% Cu > 1,5 -< 2,5%  Cu> 1.5 - <2.5% AI 0,05 - < 0,3 %  AI 0.05 - <0.3% Co max.0,5 %  Co max.0.5% B 0,001 - < 0,005 %  B 0.001 - <0.005% Mg 0,005 -< 0,015%  Mg 0.005 - <0.015% Fe Rest sowie erschmelzungsbedingte Verunreinigungen.  Fe remainder as well as smelting-related impurities. 2. Legierung nach Anspruch 1 mit (in Gew.-%) 2. Alloy according to claim 1 with (in% by weight) C max.0,015 %  C max.0.015% s max.0,005 %  s max.0,005% N max.0,02 %  N max.0,02% Cr 21,0 -< 23%  Cr 21.0 - <23% Ni > 39,0 - < 43,0 %  Ni> 39.0 - <43.0% Mn 0,5 - 0,9 %  Mn 0.5 - 0.9% Si 0,2 - < 0,5 %  Si 0.2 - <0.5% Mo > 4,5- 6,5 %  Mo> 4.5-6.5% Nb max.0,15 %  Nb max.0,15% Cu > 1,6 -< 2,3%  Cu> 1.6 - <2.3% AI 0,06 - < 0,25 % Co max. 0,5 % AI 0.06 - <0.25% Co max. 0.5% B 0,002 - 0,004 %  B 0,002 - 0,004% Mg 0,006 - 0,015 %  Mg 0.006 - 0.015% Fe Rest sowie erschmelzungsbedingte Verunreinigungen.  Fe remainder as well as smelting-related impurities. Legierung nach Anspruch 1 oder 2 mit (in Gew.-%) Alloy according to claim 1 or 2 with (in% by weight) Cr > 21 ,5 - < 23 % Cr> 21, 5 - <23% Ni > 39,0 - < 42 % Ni> 39.0 - <42% Mo > 5 - < 6,5 % Mo> 5 - <6.5% Cu > 1 ,— < 2,2 % Cu> 1, - <2.2% Legierung nach einem der Ansprüche 1 bis 3, die bedarfsweise (in Gew.-%) V > 0 - 1 ,0 %, insbesondere 0,2 - 0,7 % aufweist. Alloy according to one of claims 1 to 3, which, if necessary (in% by weight), has V> 0-1.0%, in particular 0.2-0.7%. Verfahren zur Herstellung einer Legierung, die eine Zusammensetzung gemäß einem der Ansprüche 1 bis 4 aufweist, indem A process for producing an alloy comprising a composition according to any one of claims 1 to 4, characterized a) die Legierung offen im Strang- oder Blockguss erschmolzen wird, b) zur Aufhebung der durch den erhöhten Molybdängehalt verursachten Seigerungen eine Homogenisierungsglühung der erzeugten Brammen/Knüppel bei 1150-1250 °C über 15 bis 25 h durchgeführt wird, wobei a) the alloy is melted open in continuous casting or block casting, b) to annul the segregations caused by the increased molybdenum content, a homogenization annealing of the produced slabs / billets is carried out at 1150-1250 ° C for 15 to 25 hours, c) die Homogenisierungsglühung insbesondere im Anschluss an eine erste Warmumformung durchgeführt wird. c) the homogenization annealing is carried out in particular following a first hot working. Verwendung der Legierung nach einem der Ansprüche 1 bis 4 als Bauteil in der Öl- und Gasindustrie. Use of the alloy according to one of claims 1 to 4 as a component in the oil and gas industry. Verwendung nach Anspruch 6, wobei die Bauteile in den Produktionsformen Blech, Band, Rohr (längsnahtgeschweißt und nahtlos), Stangen oder als Schmiedeteil vorliegen. Use according to claim 6, wherein the components in the production forms sheet metal, strip, tube (longitudinally welded and seamless), rods or be present as a forged part.
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