EP3105358B1 - Process of producing a titanium-free alloy - Google Patents

Process of producing a titanium-free alloy Download PDF

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Publication number
EP3105358B1
EP3105358B1 EP15716712.3A EP15716712A EP3105358B1 EP 3105358 B1 EP3105358 B1 EP 3105358B1 EP 15716712 A EP15716712 A EP 15716712A EP 3105358 B1 EP3105358 B1 EP 3105358B1
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max
alloy
titanium
weight
producing
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German (de)
French (fr)
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EP3105358A1 (en
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Julia Rosenberg
Jutta KLÖWER
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VDM Metals International GmbH
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VDM Metals International GmbH
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Priority claimed from DE102014002693.0A external-priority patent/DE102014002693A1/en
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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    • 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
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Definitions

  • the invention relates to a method for producing 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 mainly used in the chemical industry and 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, since it reacts with the SiO 2 of the casting powder (Problem 3). It would be desirable to avoid the element titanium, but this leads to a significant increase in the edge crack tendency.
  • the JP 61288041 A1 refers to an alloy of 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 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%).
  • GB 2123031 A is an austenitic high nickel-containing alloy of the following composition: ⁇ 0.05% C, ⁇ 0.04 N, ⁇ 1.0% Si, ⁇ 1.0% Mn, 35-45% Ni, 20-30% Cr, 4 - 7% Mo, balance iron and unavoidable impurities, where Cr + 3 Mo is at least 40%.
  • an austenitic stainless steel which has the following composition (in% by weight):> 0.05-0.15% C, ⁇ 2% Si, 0.1-3% Mn, ⁇ 0.04% P, ⁇ 0.01% S,> 20 - ⁇ 28% Cr,> 15 - 55% Ni,> 2 to 6% Cu, 0.1 - 0.8% Nb, 0.02 - 1.5% V, 0.001 - 0.1% Al,> 0.05 - 0.3% N, ⁇ 0.006% O, balance iron and impurities.
  • the EP 2163655 A1 describes a method for producing a high alloy steel pipe.
  • the following alloy is to be formed into a tube by multi-stage hot and cold forming processes: ⁇ 0.03% C, ⁇ 1.0% Si, 0.05 - 1.5% Mn, ⁇ 0.03% P, ⁇ 0.03 % S,> 22 - ⁇ 40% Ni, 20 - 30% Cr,> 0.01 - ⁇ 4.0% Mo, 0 - 4% Cu, 0.001 - 0.3% Al,> 0.05 - ⁇ 0 , 3% N, ⁇ 0.01% O, balance iron and impurities.
  • a suitable embodiment of the alloy has the following composition (in% by weight) C Max. 0.015% S Max. 0.005% N Max. 0.02% Cr 21.0 - ⁇ 23% Ni > 39.0 - ⁇ 43.0% Mn 0,5 - 0,9% Si 0.2 - ⁇ 0.5% Not a word > 4.5-6.5% Nb Max. 0.15% Cu > 1.6 - ⁇ 2.3% al 0.06 - ⁇ 0.25% Co Max. 0.5% B 0.002 - 0.004% mg 0.006 - 0.015% Fe Remainder as well as smelting-related impurities
  • the chromium content can be modified as follows: Cr > 21.5 - ⁇ 23% Cr 22.0 - ⁇ 23%
  • the molybdenum content can be modified as follows: Not a word > 5 - ⁇ 6.5% Not a word > 5 - ⁇ 6.2%
  • the content of copper can, if necessary, still be set as follows: Cu > 1.6 - ⁇ 2.0%
  • the alloy may still contain the element V in contents (in wt.) V > 0 - 1.0% V 0.2 - 0.7% 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 2: Sum of PRE for various prior art alloys Alloy Ni Fe Cr Not a word Other PRE Duplex 2205 5.5 rest 22 3 0.15 N 37 825 40 31 23 3.2 33 28 31 35 27 3.5 1.3 Cu 38 926 25 rest 19 6 0.16 N 47
  • 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 3 Critical pitting corrosion temperature in 6% FeCl 3 3 /% + 1% HCL, over 72 hours (ASTM G-48 Method C).
  • 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.
  • the alloy can also be produced by ESR / VAR remelting.
  • the inventive method is intended to be used for the production of a component in the oil and gas industry.
  • Table 6 contrasts Alloy 825 (standard) with two alloys of the present invention.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer titanfreien Legierung mit hoher Lochfraß- und Spaltkorrosionsbeständigkeit sowie hoher Streckgrenze und Festigkeit im kaltverfestigten Zustand.The invention relates to a method for producing 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 %, Al ≤ 0,2 %, Co ≤ 1 %, Fe Rest.The highly corrosion-resistant alloy Alloy 825 is mainly used in the chemical industry and 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 SiO2 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, since it reacts with the SiO 2 of the casting powder (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 %, Al < 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, Al, Zr, W, Ta, V, Hf in Gehalten ≤ 2 enthalten sein.The JP 61288041 A1 refers to an alloy of 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.

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 %).The 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 GB 2123031 A ist eine austenitische hochnickelhaltige Legierung folgender Zusammensetzung zu entnehmen: ≤ 0,05 % C, ≤ 0,04 N, ≤ 1,0 % Si, ≤ 1,0 % Mn, 35 - 45 % Ni, 20 - 30 % Cr, 4 - 7 % Mo, Rest Eisen und unvermeidbare Verunreinigungen, wobei Cr + 3 Mo mindestens 40 % beträgt.Of the GB 2123031 A is an austenitic high nickel-containing alloy of the following composition: ≤ 0.05% C, ≤ 0.04 N, ≤ 1.0% Si, ≤ 1.0% Mn, 35-45% Ni, 20-30% Cr, 4 - 7% Mo, balance iron and unavoidable impurities, where Cr + 3 Mo is at least 40%.

In der EP 1471158 A1 wird ein austenitischer rostfreier Stahl beschrieben, der folgende Zusammensetzung (in Gew.-%) aufweist: > 0,05 - 0,15 % C, ≤ 2 % Si, 0,1 - 3 % Mn, ≤ 0,04 % P, ≤ 0,01 % S, > 20 - < 28 % Cr, > 15 - 55 % Ni, > 2 bis 6 % Cu, 0,1 - 0,8 % Nb, 0,02 - 1,5 % V, 0,001 - 0,1 % Al, > 0,05 - 0,3 % N, ≤ 0,006 % O, Rest Eisen und Verunreinigungen.In the EP 1471158 A1 an austenitic stainless steel is described which has the following composition (in% by weight):> 0.05-0.15% C, ≦ 2% Si, 0.1-3% Mn, ≦ 0.04% P, ≤ 0.01% S,> 20 - <28% Cr,> 15 - 55% Ni,> 2 to 6% Cu, 0.1 - 0.8% Nb, 0.02 - 1.5% V, 0.001 - 0.1% Al,> 0.05 - 0.3% N, ≤ 0.006% O, balance iron and impurities.

Die EP 2163655 A1 beschreibt ein Verfahren zur Herstellung eines hochlegierten Stahlrohres. Nachstehende Legierung soll durch mehrstufige Warm- und Kaltverformungsprozesse zu einem Rohr umgeformt werden: ≤ 0,03 % C, ≤ 1,0% Si, 0,05 - 1,5 % Mn, ≤ 0,03 % P, ≤ 0,03 % S, > 22 - < 40 % Ni, 20 - 30 % Cr, > 0,01 - < 4,0 % Mo, 0 - 4 % Cu, 0,001 - 0,3 % Al, > 0,05 - < 0,3 % N, ≤ 0,01 % O, Rest Eisen und Verunreinigungen.The EP 2163655 A1 describes a method for producing a high alloy steel pipe. The following alloy is to be formed into a tube by multi-stage hot and cold forming processes: ≤ 0.03% C, ≤ 1.0% Si, 0.05 - 1.5% Mn, ≤ 0.03% P, ≤ 0.03 % S,> 22 - <40% Ni, 20 - 30% Cr,> 0.01 - <4.0% Mo, 0 - 4% Cu, 0.001 - 0.3% Al,> 0.05 - <0 , 3% N, ≤ 0.01% O, balance iron and impurities.

Durch die DE 10 2007 005 605 A1 ist eine Eisen-Nickel-Chrom-Silizium-Legierung folgender Zusammensetzung bekannt geworden: 34 - 42 % Ni, 18 - 26 % Cr, 1,0 - 2,5 % Si und Zugaben von 0,05 - 1,0 % Al, 0,01 - 1 % Mn, 0,01 - 0,26 % La, 0,0005 - 0,05 % Mg, 0,01 - 0,14 % C, 0,01 - 0,14 % N, max. 0,01 % S, max. 0,0005 % P, Rest Eisen und den üblichen verfahrensbedingten Verunreinigungen. Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung einer zu Alloy 825 alternativen Legierung bereitzustellen, das den vorab aufgezeigten Problemen gerecht wird, wobei die Legierung

  • titanfrei ist,
  • eine erhöhte Lochfraß- und Spaltkorrosionsbeständigkeit aufweist,
  • eine höhere Streckgrenze im kaltverfestigten Zustand hat,
  • eine zumindest gleich gute Warmumform- und Schweißbarkeit aufweist.
By the DE 10 2007 005 605 A1 an iron-nickel-chromium-silicon alloy of the following composition has become known: 34-42% Ni, 18-26% Cr, 1.0-2.5% Si and additions of 0.05-1.0% Al, 0.01 - 1% Mn, 0.01 - 0.26% La, 0.0005 - 0.05% Mg, 0.01 - 0.14% C, 0.01 - 0.14% N, max. 0.01% S, max. 0.0005% P, balance iron and the usual process-related impurities. The object of the invention is to provide a method for producing an alloy which is alternative to Alloy 825, which meets the problems indicated above, wherein the alloy
  • is titanium free,
  • has increased pitting and crevice corrosion resistance,
  • has a higher yield strength in the work-hardened state,
  • has at least the same good hot forming and weldability.

Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung einer titanfreien Legierung mit (in Gew.-%) C max. 0,02 % S max. 0,01 % N max. 0,03 % Cr 20,0 - 23,0 % Ni 39,0 - 44,0 % Mn 0,4 - < 1,0 % Si 0,1 - < 0,5 % Mo > 4,0 - < 7,0 % Nb max. 0,15 % Cu > 1,5 - < 2,5 % Al 0,05 - < 0,3 % Co max. 0,5 % B 0,001 - < 0,005 % Mg 0,005 - < 0,015 % V bedarfsweise 0 - 1,0 %, insbesondere 0,2 - 0,7% Fe Rest sowie erschmelzungsbedingte Verunreinigungen, indem

  1. a) die Legierung offen im Strang- oder Blockguss erschmolzen wird,
  2. 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
  3. c) die Homogenisierungsglühung im Anschluss an eine erste Warmumformung durchgeführt wird.
This object is achieved by a method for producing a titanium-free alloy with (in% by weight) C Max. 0.02% S Max. 0.01% N Max. 0.03% Cr 20.0 - 23.0% Ni 39.0 - 44.0% Mn 0.4 - <1.0% Si 0.1 - <0.5% Not a word > 4.0 - <7.0% Nb Max. 0.15% Cu > 1.5 - <2.5% al 0.05 - <0.3% Co Max. 0.5% B 0.001 - <0.005% mg 0.005 - <0.015% V if necessary 0-1.0%, in particular 0.2-0.7% Fe Remainder as well as impurities caused by melting, by doing
  1. a) the alloy is melted open in strand or block casting,
  2. b) to cancel the segregation caused by the increased molybdenum content, a homogenization annealing of the produced slab / billet at 1150-1250 ° C for 15 to 25 h is carried out, wherein
  3. c) the homogenization annealing is performed following a first hot working.

Eine zweckmäßige Ausgestaltung der Legierung weist folgende Zusammensetzung (in Gew.-%) C max. 0,015 % S max. 0,005 % N max. 0,02 % Cr 21,0 - < 23 % Ni > 39,0 - < 43,0 % Mn 0,5 - 0,9 % Si 0,2 - < 0,5 % Mo >4,5-6,5% Nb max. 0,15 % Cu > 1,6 - < 2,3 % Al 0,06 - < 0,25 % Co max. 0,5 % B 0,002 - 0,004 % Mg 0,006 - 0,015 % Fe Rest sowie erschmelzungsbedingte Verunreinigungen A suitable embodiment of the alloy has the following composition (in% by weight) C Max. 0.015% S Max. 0.005% N Max. 0.02% Cr 21.0 - <23% Ni > 39.0 - <43.0% Mn 0,5 - 0,9% Si 0.2 - <0.5% Not a word > 4.5-6.5% Nb Max. 0.15% Cu > 1.6 - <2.3% al 0.06 - <0.25% Co Max. 0.5% B 0.002 - 0.004% mg 0.006 - 0.015% Fe Remainder as well as smelting-related impurities

Der Gehalt an Chrom kann bedarfsweise noch wie folgt modifiziert werden: Cr > 21,5 - < 23 % Cr 22,0 - < 23 % If necessary, the chromium content can be modified as follows: Cr > 21.5 - <23% Cr 22.0 - <23%

Der Nickelgehalt kann bedarfsweise noch wie folgt modifiziert werden: Ni > 39, 0 - < 42 % Ni > 39,0 - < 41 % If necessary, the nickel content can be modified as follows: Ni > 39, 0 - <42% Ni > 39.0 - <41%

Der Molybdängehalt kann bedarfsweise noch wie folgt modifiziert werden: Mo > 5 - < 6,5 % Mo > 5 - < 6,2 % If necessary, the molybdenum content can be modified as follows: Not a word > 5 - <6.5% Not a word > 5 - <6.2%

Der Gehalt an Kupfer kann bedarfsweise noch wie folgt eingestellt werden: Cu > 1,6 - < 2,0 % The content of copper can, if necessary, still be set as follows: Cu > 1.6 - <2.0%

Bedarfsweise kann der Legierung noch das Element V in Gehalten (in Gew.-) V > 0 - 1,0 % V 0,2 - 0,7 % zugesetzt werden.If necessary, the alloy may still contain the element V in contents (in wt.) V > 0 - 1.0% V 0.2 - 0.7% 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. Element in Gew-% C S N Cr Ni Mn Si Mo Ti Nb Cu Fe Al B Mg in ppm Ca in ppm Kantenrisse Ref825 0,002 0.0048 0,006 22,25 39,41 0,8 0,3 3,27 0,8 0,01 2 R 0,14 0 - - nein LB2181 0,002 0,004 0,006 22,57 39,76 0,8 0,3 3,27 0,4 0,01 2,1 R 0,12 0 - - gering LB2182 0,006 0,003 0,052> 22,46 39,71 0,8 0,3 3,27 - 0,01 2 R 0,11 0 - - ja LB2183 0,002 0,004 0,094> 22,65 39,61 0,8 0,3 3,28 - 0,01 1,9 R 0,1 0 - - ja LB2218 0,005 0,0031 0,048> 22.50 39,59 0,8 0,3 3,27 - 0,01 2 R 0,12 0,01 100 - nein LB2219 0,005 0,0021 0,043> 22,71 39,99 0,8 0,3 4,00> - 0,01 2 R 0.10 0,01 100 - nein LB2220 0,004 0.00202 0,042> 22,56 39,84 0,8 0.33 4,93> - 0,01 2 R 0,11 0 100 - nein LB2221 0,004 0,0022 0,038> 22,43 39,66 0,8 0,3 3,74> - 0,01 1,9 R 0,11 0 10 - ja LB2222 0,003 0,0033 0,042> 22,5 39,62 0,8 0,3 3,66> - 0,01 2 R 0,18 0 20 - ja LB2223 0,002 0,0036 0,041> 22.4 39,78 0,7 0,3 3,65> - 0,01 2.00 R 0,27> 0 20 - ja LB2234 0,003 0,005 0,007 22,57 39,77 0,8 0,3 3,26 - 0,01 2,1 R 0,15 0 80 10 nein LB2235 0,003 0,0034 0,006 22,56 39,67 0,8 0,3 3,28 - 0,01 2,1 R 0,12 0 150 12 nein LB2236 0,002 0,004 0,006 22,34 39,46 0,8 0,3 3,27 - 0,01 2 R 0,11 0 30 42 gering LB2317 0,001 0,0025 0.030 22.48 40,09 0,8 0,3 4,21 - 0,01( 2 R 0,16 0 100 5 nein LB2318 0,002 0,0036 0,038> 22,76 39,77 0,8 0,3 5,20> - 0,01 2,1 R 0,15 0 100 4 nein LB2319 0,002( 0,0039 0,043> 22,93> 39,79 0,8 0,3 6,06 - 0,01 2,2 R 0,12 0 100 3 nein LB2321 0,002 0.0051 0,040> 22,56 40,23> 0,7 0,3 6,23 - 0,01 2,1 R 0.10 0 100 4 nein Tabelle 1: Einfluss von Desoxidationselementen auf die Kantenrissneigung beim Warmwalzen 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. Element in% by weight C S N Cr Ni Mn Si Not a word Ti Nb Cu Fe al B Mg in ppm Ca in ppm edge cracks Ref825 0,002 0.0048 0,006 22.25 39.41 0.8 0.3 3.27 0.8 0.01 2 R 0.14 0 - - No LB2181 0,002 0,004 0,006 22.57 39.76 0.8 0.3 3.27 0.4 0.01 2.1 R 0.12 0 - - low LB2182 0,006 0,003 0,052> 22.46 39.71 0.8 0.3 3.27 - 0.01 2 R 0.11 0 - - Yes LB2183 0,002 0,004 0.094> 22.65 39.61 0.8 0.3 3.28 - 0.01 1.9 R 0.1 0 - - Yes LB2218 0.005 0.0031 0.048> 22:50 39.59 0.8 0.3 3.27 - 0.01 2 R 0.12 0.01 100 - No LB2219 0.005 0.0021 0.043> 22.71 39.99 0.8 0.3 4.00> - 0.01 2 R 12:10 0.01 100 - No LB2220 0,004 0.00202 0.042> 22.56 39.84 0.8 12:33 4.93> - 0.01 2 R 0.11 0 100 - No LB2221 0,004 0.0022 0.038> 22.43 39.66 0.8 0.3 3.74> - 0.01 1.9 R 0.11 0 10 - Yes LB2222 0,003 0.0033 0.042> 22.5 39.62 0.8 0.3 3.66> - 0.01 2 R 0.18 0 20 - Yes LB2223 0,002 0.0036 0.041> 22.4 39,78 0.7 0.3 3.65> - 0.01 2:00 R 0.27> 0 20 - Yes LB2234 0,003 0.005 0,007 22.57 39.77 0.8 0.3 3.26 - 0.01 2.1 R 0.15 0 80 10 No LB2235 0,003 0.0034 0,006 22.56 39.67 0.8 0.3 3.28 - 0.01 2.1 R 0.12 0 150 12 No LB2236 0,002 0,004 0,006 22.34 39.46 0.8 0.3 3.27 - 0.01 2 R 0.11 0 30 42 low LB2317 0.001 0.0025 0030 22:48 40.09 0.8 0.3 4.21 - (0.01 2 R 0.16 0 100 5 No LB2318 0,002 0.0036 0.038> 22.76 39.77 0.8 0.3 5.20> - 0.01 2.1 R 0.15 0 100 4 No LB2319 (0,002 0.0039 0.043> 22.93> 39.79 0.8 0.3 6.06 - 0.01 2.2 R 0.12 0 100 3 No LB2321 0,002 0.0051 0.040> 22.56 40.23> 0.7 0.3 6.23 - 0.01 2.1 R 12:10 0 100 4 No 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. Tabelle 2: Wirksumme PRE für verschiedene dem Stand der Technik entsprechende Legierungen Alloy Ni Fe Cr Mo Andere PRE Duplex 2205 5,5 Rest 22 3 0,15 N 37 825 40 31 23 3,2 33 28 31 35 27 3,5 1,3 Cu 38 926 25 Rest 19 6 0,16 N 47 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 2: Sum of PRE for various prior art alloys Alloy Ni Fe Cr Not a word Other PRE Duplex 2205 5.5 rest 22 3 0.15 N 37 825 40 31 23 3.2 33 28 31 35 27 3.5 1.3 Cu 38 926 25 rest 19 6 0.16 N 47

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. Tabelle 3: Kritische Lochfraßkorrosionstemperatur in 6 % FeCl3 + 1 % HCL, über 72 h (ASTM G-48 Methode C). T in °C Ni Cr Mo N Ti PRE LB 2316 35 39,2 22,4 3,1 0,04 < 0,04 33 LB 2317 40 40,1 22,5 4,2 0,03 < 0,04 36 LB 2318 50 39,8 22,8 5,2 0,04 < 0,04 40 LB 2319 55 38,8 22,9 6,1 0,04 < 0,04 43 LB 2320 50 39 22,1 6,2 0,1 < 0,03 43 LB 2321 50 40,2 22,6 6,2 0,04 0,4 43 LB 2322 40 40 23,1 6,3 0,1 0,4 44 Alloy 825 Referenz 30 40 23 3,2 < 0,02 0,8 33 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 3: Critical pitting corrosion temperature in 6% FeCl 3 3 /% + 1% HCL, over 72 hours (ASTM G-48 Method C). T in ° C Ni Cr Not a word N Ti PRE LB 2316 35 39.2 22.4 3.1 0.04 <0.04 33 LB 2317 40 40.1 22.5 4.2 0.03 <0.04 36 LB 2318 50 39.8 22.8 5.2 0.04 <0.04 40 LB 2319 55 38.8 22.9 6.1 0.04 <0.04 43 LB 2320 50 39 22.1 6.2 0.1 <0.03 43 LB 2321 50 40.2 22.6 6.2 0.04 0.4 43 LB 2322 40 40 23.1 6.3 0.1 0.4 44 Alloy 825 reference 30 40 23 3.2 <0.02 0.8 33

Weitere Korrosionsuntersuchungen zeigten ebenfalls eine Verbesserung der kritischen Spaltkorrosionstemperaturen im Vergleich zum Alloy 825. Diese sind in Tabelle 4 dargestellte. Tabelle 4: Kritische Lochfraß- (CPT) und Spaltkorrosionstemperatur (CCT) Alloy CPT in °C CCT in °C Ni Cr Mo V Ti PRE 825* 30 <5 33 PV661 40 15 40 23 3,3 < 0,002 0,8 34 PV662 50 20 40 23 5,9 < 0,002 < 0,002 42 PV663 50 20 39 23 5,8 0,4 < 0,002 42 Further corrosion testing also showed an improvement in critical crevice corrosion temperatures compared to Alloy 825. These are shown in Table 4. Table 4: Critical Pitting (CPT) and Crevice Corrosion Temperature (CCT) Alloy CPT in ° C CCT in ° C Ni Cr Not a word V Ti PRE 825 * 30 <5 33 PV661 40 15 40 23 3.3 <0.002 0.8 34 PV662 50 20 40 23 5.9 <0.002 <0.002 42 PV663 50 20 39 23 5.8 0.4 <0.002 42

Durch 15 und 30-% Kaltverformung kann die Streckgrenze und die Festigkeit erhöht werden. In der folgenden Tabelle sind die dazugehörigen Untersuchungsergebnisse diverser Laborlegierungen aufgeführt. Tabelle 5: Zugversuche bei RT Zustand Alloy Rp0,2 Rm A (%) Z (%) Lösungsgeglüht 825 Referenz 304 646 - 51 825 Plus (A) 389 754 39 59 369 772 39,5 61 825 Plus (B) 390 765 42,5 62 383 755 40 63 15 % KV 825 670 775 22 71 697 793 19,5 65 685 779 23,5 69 825 Plus (A) 903 973 14,5 51 893 964 13,5 50 943 987 13,5 54 825 Plus (B) 929 974 12,5 56 877 964 12,5 51 887 962 9,5 49 30 % KV 825 852 923 14 63 832 922 13,5 66 842 920 17,5 64 825 Plus (A) 979,0 1071,0 11,5 51,0 970,0 1079,0 8,5 35,0 996,0 1078,0 11,0 46,0 825 Plus (B) 980,0 1078,0 11,5 47,0 980,0 1071,0 11,0 48,0 996,0 1083,0 10,5 48,0 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. Table 5: Tensile tests at RT Status Alloy Rp0.2 rm A (%) Z (%) Solution heat 825 reference 304 646 - 51 825 Plus (A) 389 754 39 59 369 772 39.5 61 825 Plus (B) 390 765 42.5 62 383 755 40 63 15% KV 825 670 775 22 71 697 793 19.5 65 685 779 23.5 69 825 Plus (A) 903 973 14.5 51 893 964 13.5 50 943 987 13.5 54 825 Plus (B) 929 974 12.5 56 877 964 12.5 51 887 962 9.5 49 30% KV 825 852 923 14 63 832 922 13.5 66 842 920 17.5 64 825 Plus (A) 979.0 1,071.0 11.5 51.0 970.0 1,079.0 8.5 35.0 996.0 1078.0 11.0 46.0 825 Plus (B) 980.0 1078.0 11.5 47.0 980.0 1,071.0 11.0 48.0 996.0 1,083.0 10.5 48.0

In den nachstehenden Abbildungen 1 und 2 sind Ergebnisse von Zugversuchen, einerseits der Referenzlegierung Alloy 825 und andererseits alternativer Legierungen dargestellt.

Figure imgb0001
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.
Figure imgb0001

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.

Figure imgb0002
Molybdenum has a positive effect on yield strength and strength. Figures 3 and 4 illustrate the positive influence of Molydbän.
Figure imgb0002

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 Standardlegierung (PV 942).

Figure imgb0003
Figure imgb0004
 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).
Figure imgb0003
Figure imgb0004

Die Aufgabe wird gelöst durch ein Verfahren zur Herstellung einer Legierung, die eine Zusammensetzung gemäß einem der gegenständlichen Ansprüche aufweist, indem

  1. a) die Legierung offen im Strang- oder Blockguss erschmolzen wird,
  2. 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
  3. c) die Homogenisierungsglühung insbesondere im Anschluss an eine erste Warmumformung durchgeführt wird.
The object is achieved by a method for producing an alloy, which has a composition according to one of the subject-matter claims, by
  1. a) the alloy is melted open in strand or block casting,
  2. b) to cancel the segregation caused by the increased molybdenum content, a homogenization annealing of the produced slab / billet at 1150-1250 ° C for 15 to 25 h is carried out, wherein
  3. c) the homogenization annealing is carried out in particular following a first hot working.

Optional kann die Legierung auch durch ESU/VAR-Umschmelzen erzeugt werden. Das erfindungsgemäße Verfahren soll zur Herstellung eines Bauteils in der Öl- und Gasindustrie eingesetzt werden.Optionally, the alloy can also be produced by ESR / VAR remelting. The inventive method is intended to be used for the production of 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.

Figure imgb0005
Figure imgb0006
 Table 6 contrasts Alloy 825 (standard) with two alloys of the present invention.
Figure imgb0005
Figure imgb0006

Claims (5)

  1. A method for producing a titanium-free alloy comprising (in % by weight) C max. 0.02 % S max. 0.01 % N 0.03% Cr 20.0 - 23.0% Ni 39.0 - 44.0% Mn 0.4 - < 1.0% Si 0.1 - < 0.5% Mo > 4.0 - < 7.0 % Nb max. 0.15% Cu > 1.5 - < 0.3% Al 0.05 - < 0.3% Co max. 0.5% B 0.001 - < 0.005% Mg 0.005 - < 0.015% V if needed, 0 - 1.0 %, especially 0.2 - 0.7% Fe rest as well as elaboration-related impurities,
    in that
    a) the alloy will be openly molten in strand or ingot casting,
    b) a homogenizing annealing of the produced slabs/billets will be carried out at 1150-1250°C for 15 through 25 h for removing the segregations caused by the higher molybdenum content, wherein
    c) the homogenizing annealing will be carried out after a first hot working operation.
  2. A method according to claim 1, comprising (in % by weight) C max. 0.015 % S max. 0.005% N 0.02% Cr 21.0 - < 23% Ni > 39.0 - < 43.0% Mn 0.5 - 0.9% Si 0.2 - < 0.5% Mo >4.5-6.5% Nb max. 0.15% Cu > 1.6 - < 2.3% Al 0.06 - < 0.25% Co max. 0.5% B 0.002 - 0.004% Mg 0.006 - 0.015% Fe rest as well as elaboration-related impurities.
  3. A method according to claim 1 or 2 comprising (in % by weight) Cr > 21.5 - < 23% Ni > 39.0 - < 42% Mo > 5 - < 6.5% Cu > 1 - 2.2%.
  4. A use of the method according to one of the claims 1 through 3 for manufacturing a structural element in the oil and gas industry.
  5. A use according to claim 4, wherein the structural elements are present in the production forms of sheet metals, bands, tubes (longitudinally welded and seamless), rods or as forged parts.
EP15716712.3A 2014-02-13 2015-02-10 Process of producing a titanium-free alloy Active EP3105358B1 (en)

Applications Claiming Priority (3)

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DE102014002402.4A DE102014002402A1 (en) 2014-02-13 2014-02-13 Titanium-free alloy
DE102014002693.0A DE102014002693A1 (en) 2014-02-28 2014-02-28 Titanium-free alloy
PCT/DE2015/000053 WO2015120832A1 (en) 2014-02-13 2015-02-10 Titanium-free alloy

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KR20230024248A (en) 2020-03-09 2023-02-20 에이티아이 인코포레이티드 Corrosion-resistant nickel-base alloy
CN114058903B (en) * 2020-07-30 2022-06-14 宝武特种冶金有限公司 Nickel-iron-based alloy large-caliber thick-wall pipe and manufacturing method thereof
JP2024505366A (en) * 2021-02-04 2024-02-06 ファオデーエム メタルズ インターナショナル ゲゼルシャフト ミット ベシュレンクテル ハフツング Use of titanium-free nickel-chromium-iron-molybdenum alloy
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CN115747576B (en) * 2022-10-26 2024-03-22 中国科学院金属研究所 Preparation method of hydrogen embrittlement-resistant fatigue-resistant plate for hydrogen-contacting membrane of high-pressure hydrogen compressor

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CN114000032A (en) 2022-02-01
JP6300941B2 (en) 2018-03-28
US20170002437A1 (en) 2017-01-05
KR101865406B1 (en) 2018-06-07
US10174397B2 (en) 2019-01-08
EP3105358A1 (en) 2016-12-21
BR112016012184A2 (en) 2017-09-26
CN105745345A (en) 2016-07-06

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