EP0818552B1 - Ferritic-austenitic stainless steel casting alloy - Google Patents

Ferritic-austenitic stainless steel casting alloy Download PDF

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Publication number
EP0818552B1
EP0818552B1 EP97111887A EP97111887A EP0818552B1 EP 0818552 B1 EP0818552 B1 EP 0818552B1 EP 97111887 A EP97111887 A EP 97111887A EP 97111887 A EP97111887 A EP 97111887A EP 0818552 B1 EP0818552 B1 EP 0818552B1
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Prior art keywords
vanadium
niobium
ferritic
tantalum
tungsten
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EP97111887A
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German (de)
French (fr)
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EP0818552A2 (en
EP0818552A3 (en
Inventor
Willi Kleemann
Benno Hoffmann
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Schmidt and Clemens GmbH and Co KG
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Schmidt and Clemens GmbH and Co
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten

Definitions

  • the invention relates to the use of objects made of a stainless ferritic-austenitic Chromium-nickel steel alloy with small amounts of coordinated Contain further alloying agents, a structure that is 50 vol .-% Delta ferrite as the basic structure with finely divided austenite as the rest gives the duplex steel alloys have good corrosion resistance and high Strength.
  • Duplex alloys of this type are known per se. This is how the European describes Patent Specification 0 220 141 a stainless, high nitrogen-containing duplex wrought alloy with high corrosion resistance and structural stability, the maximum 0.05% carbon, 23 to 27% chromium, 5.5 to 9% nickel, 0.25 to 0.40% nitrogen, at most 0.8% silicon, at most 1.2% manganese, 3.5 to 4.9% Molybdenum, at most 0.5% copper, at most 0.5% tungsten, at most 0.010 % Sulfur, up to 0.5% vanadium and up to 0.18% cerium, balance including smelting contaminants contains iron; their levels Alloy elements within the specified salary limits in certain Are coordinated.
  • This alloy requires solution annealing at about 1075 ° C to adjust the structure to a ferrite content of 30 to 55%; it is suitable for solution-annealed, cold-formed and also welded Condition especially for use in a chloride environment.
  • European Patent 0 156 778 describes a corrosion-resistant, stainless ferritic-austenitic duplex steel alloy known.
  • the invention is based on the problem of corrosion resistance and To further improve the strength of this type of cast steel alloy.
  • the invention proposes use according to claim 1.
  • the steel to be used according to the invention preferably contains at least 0.1% better still at least 0.2% tungsten, vanadium, niobium and tantalum individually or side by side.
  • the tungsten content can also be above 0.5%, for example at 0.55% or also at 0.6%.
  • the total content can Tungsten and tantalum are 0.05 to 0.80%.
  • Table II below shows the critical pitting temperature limit of test alloys 1 and 2 in the test described above according to ASTM G 48-76.
  • the critical temperatures (T k ) determined in this case are considerably higher in comparison with commercially available cast steel alloys; they are compared to the respective PREN values of the individual alloys.
  • compositions of the heart mixtures cast or kneaded alloys A to E on which the diagram in FIG. 1 is based are shown in Table III below.
  • Alloy (%) A B C D e C 0.03 0.03 0.03 - - Si 0.35 0.31 0.20 - - Mn 0.75 0.54 0.80 - - P 0.019 0.031 0,012 - - S 0.005 0.011 0,002 - - Cr 25.5 27.2 27.4 25.0 27 Mo 4.1 3.1 3.1 3.0 3.1 Ni 7.0 8.3 8.0 5.5 8th Cu 0.24 2.71 2.51 1.7 1.0 V - - - - - W - - - - N 0.27 0.23 0.24 0.18 0.22 Nb - - - - - - - Fe rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest rest

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Description

Die Erfindung bezieht sich auf die Verwendung von Gegenstanden aus einer rostfreien ferritisch-austenitischen Chrom-Nickel-Stahllegierung mit geringen Mengen aufeinander abgestimmter Gehalte weiterer Legierungsmittel, Ein Gefüge, das zu 50 Vol.-% aus Deltaferrit als Grundgefüge mit feinverteiltem Austenit als Rest besteht, verleiht den Duplex-Stahllegierungen eine gute Korrosionsbeständigkeit und hohe Festigkeit.The invention relates to the use of objects made of a stainless ferritic-austenitic Chromium-nickel steel alloy with small amounts of coordinated Contain further alloying agents, a structure that is 50 vol .-% Delta ferrite as the basic structure with finely divided austenite as the rest gives the duplex steel alloys have good corrosion resistance and high Strength.

Duplex-Legierungen dieser Art sind an sich bekannt. So beschreibt die europäische Patentschrift 0 220 141 eine rostfreie, hoch-stickstoffhaltige Duplex-Knetlegierung mit hoher Korrosionsbeständigkeit und Gefügestabilität, die höchstens 0,05 % Kohlenstoff, 23 bis 27 % Chrom, 5,5 bis 9 % Nickel, 0,25 bis 0,40 % Stickstoff, höchstens 0,8 % Silizium, höchstens 1,2 % Mangan, 3,5 bis 4,9 % Molybdän, höchstens 0,5 % Kupfer, höchstens 0,5 % Wolfram, höchstens 0,010 % Schwefel, bis 0,5 % Vanadium und bis 0,18 % Cer, Rest einschließlich erschmelzungsbedingter Verunreinigungen Eisen enthält; deren Gehalte an Legierungselementen innerhalb der angegebenen Gehaltsgrenzen in bestimmter Weise aufeinander abgestimmt sind. Diese Legierung erfordert ein Lösungsglühen bei etwa 1075°C, um das Gefüge auf einen Ferritanteil von 30 bis 55% einzustellen; sie eignet sich im lösungsgeglühten, kaltverformten und auch geschweißten Zustand insbesondere für eine Verwendung in chloridischer Umgebung.Duplex alloys of this type are known per se. This is how the European describes Patent Specification 0 220 141 a stainless, high nitrogen-containing duplex wrought alloy with high corrosion resistance and structural stability, the maximum 0.05% carbon, 23 to 27% chromium, 5.5 to 9% nickel, 0.25 to 0.40% nitrogen, at most 0.8% silicon, at most 1.2% manganese, 3.5 to 4.9% Molybdenum, at most 0.5% copper, at most 0.5% tungsten, at most 0.010 % Sulfur, up to 0.5% vanadium and up to 0.18% cerium, balance including smelting contaminants contains iron; their levels Alloy elements within the specified salary limits in certain Are coordinated. This alloy requires solution annealing at about 1075 ° C to adjust the structure to a ferrite content of 30 to 55%; it is suitable for solution-annealed, cold-formed and also welded Condition especially for use in a chloride environment.

Des weiteren ist aus der europäischen Patentschrift 0 156 778 eine korrosionsbeständige, rostfreie ferritisch-austenitische Duplex-Stahliegierung bekannt. Furthermore, European Patent 0 156 778 describes a corrosion-resistant, stainless ferritic-austenitic duplex steel alloy known.

Diese Stahllegierungen haben sich wegen ihrer hohen Festigkeit und ihrer Beständigkeit gegen Lochfraß bzw. lokale Korrosion in Anwesenheit von Chloriden in der Praxis durchgesetzt; infolge ihrer Korrosionsbeständigkeit vermögen sie höherlegierte und demgemäß teurere Stahllegierungen zu ersetzen. Gleichwohl sind sie mit Nachteilen behaftet; denn ihre Korrosionsbeständigkeit ist im Vergleich zu gekneteten Stählen nur mäßig, weil es beim Erstarren zu einer Mikrosteigerung insbesondere von Molybdän und Chrom kommt, die von einer Verarmung an Molybdän und Chrom begleitet ist. Die molybdän- und chromverarmten Zonen des Gefüges sind naturgemäß von weniger Korrosionsbeständigkeit und erlauben daher den Beginn einer lokalen Korrosion und deren vergleichsweise leichte Ausbreitung.These steel alloys have become because of their high strength and their Resistance to pitting or local corrosion in the presence of chlorides enforced in practice; due to their corrosion resistance to replace them with higher alloyed and accordingly more expensive steel alloys. nevertheless they have disadvantages; because their corrosion resistance is in Compared to kneaded steels only moderately, because it solidifies into one Micro-enhancement in particular of molybdenum and chromium comes from one Depletion of molybdenum and chrome is accompanied. The molybdenum and chrome depleted Zones of the structure are naturally less resistant to corrosion and therefore allow the start of local corrosion and its comparative easy spread.

Der Erfindung liegt das Problem zugrunde, die Korrosionsbeständigkeit und Festigkeit dieser Art von Gußstahllegierungen weiter zu verbessern.The invention is based on the problem of corrosion resistance and To further improve the strength of this type of cast steel alloy.

Zur Lösung dieses Problems schlägt die Erfindung die Verwendung gemäß Anspruch 1 vor. To solve this problem, the invention proposes use according to claim 1.

Der erfindungsgemäß zu verwendende Stahl enthält vorzugsweise mindestens 0,1 % besser noch mindestens 0,2% Wolfram, Vanadium, Niob und Tantal einzeln oder nebeneinander. Der Wolframgehalt kann auch über 0,5% liegen, beispielsweise bei 0,55% oder auch bei 0,6%. Des weiteren kann der Gesamtgehalt an Wolfram und Tantal bei 0,05 bis 0.80% liegen.The steel to be used according to the invention preferably contains at least 0.1% better still at least 0.2% tungsten, vanadium, niobium and tantalum individually or side by side. The tungsten content can also be above 0.5%, for example at 0.55% or also at 0.6%. Furthermore, the total content can Tungsten and tantalum are 0.05 to 0.80%.

Die Erfindung wird nachfolgend anhand von Ausführungsbeispielen des näheren ertäutert. The invention is described in more detail below on the basis of exemplary embodiments ertäutert.

Um die Erfindung gemäß Anspruch 1 für eine kobaltfreie Basislegierung mit einer nominellen Zusammensetzung von bis 0,030% Kohlenstoff, bis 0,30% Silizium, bis 0,40% Mangan, 6,5 bis 8,5% Nickel, 0,25 bis 0,30% Stickstoff, 24,5 bis 26,5% Chrom, 4,0 bis 4,5% Molybdän, bis 1,0% Wolfram, bis 0,20% Vanadium, bis 0,3% Niob, 0,15 bis 0,3% Vanadium und Niob, bis 0,31% Tantal, bis 0,015% Phosphor, bis 0.005% Schwefel, Rest Eisen zu veranschaulichen, wurden im Rahmen einer weiteren Versuchsreihe zwei Schmelzen 1 und 2 mit der Zusammensetzung nach Tabelle 1 als Beispiel für eine Vanadium, Niob und Tantal enthaltende Gußstahllegierung (25,0 Cr- 4,25 Mo-7,4 Ni-0,28 N-Fe), jedoch mit niedrigem Chromgehalt hergestellt. Legierung (%) 1 2 C 0,026 0,016 Si 0,10 0,14 Mn 0,15 0,08 Ni 7,60 7,43 N 0,282 0,267 P 0,010 0,011 S 0,005 0,005 Cr 25,23 24,93 Mo 4,24 4,29 W 0,070 0,07 V 0,015 0,02 Nb 0,27 0,26 Ta 0,02 0,31 Fe Rest Rest In order to achieve the invention according to claim 1 for a cobalt-free base alloy with a nominal composition of up to 0.030% carbon, up to 0.30% silicon, up to 0.40% manganese, 6.5 to 8.5% nickel, 0.25 to 0, 30% nitrogen, 24.5 to 26.5% chromium, 4.0 to 4.5% molybdenum, to 1.0% tungsten, to 0.20% vanadium, to 0.3% niobium, 0.15 to 0 To illustrate 3% vanadium and niobium, up to 0.31% tantalum, up to 0.015% phosphorus, up to 0.005% sulfur, the rest iron, two melts 1 and 2 with the composition according to Table 1 were used as examples for a further test series Cast steel alloy containing vanadium, niobium and tantalum (25.0 Cr- 4.25 Mo-7.4 Ni-0.28 N-Fe) but made with a low chromium content. Alloy (%) 1 2 C 0.026 0.016 Si 0.10 0.14 Mn 0.15 0.08 Ni 7.60 7.43 N 0.282 0,267 P 0,010 0.011 S 0.005 0.005 Cr 25.23 24.93 Mo 4.24 4.29 W 0,070 0.07 V 0,015 0.02 Nb 0.27 0.26 Ta 0.02 0.31 Fe rest rest

Die nachfolgende Tabelle II gibt die kritische Lochfraß-Temperaturgrenze der Versuchstegierungen 1 und 2 bei dem oben geschilderten Versuch nach ASTM G 48-76 wieder. Die dabei ermittelten kritischen Temperaturen (Tk) liegen im Vergleich zu handelsüblichen Gußstahllegierungen wesentlich höher; sie sind den jeweiligen PREN-Werten der einzelnen Legierungen gegenübergestellt. Legierung 1 2 PREN 43,7 43,3 Tk (°C) 80 85 Table II below shows the critical pitting temperature limit of test alloys 1 and 2 in the test described above according to ASTM G 48-76. The critical temperatures (T k ) determined in this case are considerably higher in comparison with commercially available cast steel alloys; they are compared to the respective PREN values of the individual alloys. alloy 1 2 PREN 43.7 43.3 T k (° C) 80 85

Das Diagramm der Figur 1 zeigt die gemessenen kritischen Temperaturen in Abhängigkeit von den PREN-Werten herkömmlicher Gußstahllegierungen und der erfindungsgemäßen Gußstahllegierungen 1 und 2. Dabei zeigt sich, daß die kritischen Temperaturen der erfindungsgemäßen Versuchslegierungen nicht der üblichen Abhängigkeit Tk = f(PREN) herkömmlicher rostfreier ferritisch-austenitischer Gußstahllegierungen: Tk (°C) = 2,397 • PREN - 54,37 folgen.The diagram in FIG. 1 shows the measured critical temperatures as a function of the PREN values of conventional cast steel alloys and the cast steel alloys 1 and 2 according to the invention. It shows that the critical temperatures of the test alloys according to the invention are not more conventional than the usual dependency T k = f (PREN) rustproof ferritic-austenitic cast steel alloys: T k (° C) = 2.397 • PREN - 54.37 consequences.

Die in der Standardlösung nach einer Versuchszeit von 72 Stunden ermittelten Werte zeigen, daß die erfindungsgemäßen Legierungen mit ihren sorgfältig aufeinander abgestimmten Gehalten an Vanadium, Niob und Tantal einerseits sowie Kohlenstoff und Stickstoff andererseits für den Fall einer 25Cr-4,3Mo-0,28N-Legierung bei einem PREN-Wert von etwa 44% eine merklich bessere Korrosionsbeständigkeit besitzen; dies ergibt sich aus dem Diagramm der Fig. 2.Those determined in the standard solution after a test period of 72 hours Values show that the alloys of the invention with their care for each other coordinated levels of vanadium, niobium and tantalum on the one hand and Carbon and nitrogen, on the other hand, for the case of a 25Cr-4.3Mo-0.28N alloy with a PREN value of about 44%, a noticeably better corrosion resistance have; this results from the diagram in FIG. 2.

Die Zusammensetzungen der dem Diagramm der Figur 1 zugrundeliegenden herz kömmüchen gegossenen bzw. gekneteten Legierungen A bis E ergeben sich aus der nachfolgenden Tabelle III. Legierung (%) A B C D E C 0,03 0,03 0,03 -- -- Si 0,35 0,31 0,20 -- -- Mn 0,75 0,54 0,80 -- -- P 0,019 0,031 0,012 -- -- S 0,005 0,011 0,002 -- -- Cr 25,5 27,2 27,4 25,0 27 Mo 4,1 3,1 3,1 3,0 3,1 Ni 7,0 8,3 8,0 5,5 8 Cu 0,24 2,71 2,51 1,7 1,0 V -- -- -- -- -- W -- -- -- -- -- N 0,27 0,23 0,24 0,18 0,22 Nb -- -- -- -- -- Ta -- -- -- -- -- Fe Rest Rest Rest Rest Rest The compositions of the heart mixtures cast or kneaded alloys A to E on which the diagram in FIG. 1 is based are shown in Table III below. Alloy (%) A B C D e C 0.03 0.03 0.03 - - Si 0.35 0.31 0.20 - - Mn 0.75 0.54 0.80 - - P 0.019 0.031 0,012 - - S 0.005 0.011 0,002 - - Cr 25.5 27.2 27.4 25.0 27 Mo 4.1 3.1 3.1 3.0 3.1 Ni 7.0 8.3 8.0 5.5 8th Cu 0.24 2.71 2.51 1.7 1.0 V - - - - - W - - - - - N 0.27 0.23 0.24 0.18 0.22 Nb - - - - - Ta - - - - - Fe rest rest rest rest rest

Die Festigkeitseigenschaften der erfindungsgemäßen Legierungen 1 und 2 ergeben sich aus der nachfolgenden Tabelle IV.

Figure 00060001
The strength properties of alloys 1 and 2 according to the invention are shown in Table IV below.
Figure 00060001

Claims (5)

  1. Use of articles made of ferritic-austenitic stainless steel alloy of high strength and high resistance to corrosion, and particularly resistance to pitting corrosion, having up to 0.03% carbon up to 0.3% silicon up to 0.4% manganese 6.5 to 8.5% nickel 0.25 to 0.3% nitrogen 24.5 to 26.5% chromium 4 to 4.5% molybdenum up to 1% tungsten up to 0.2% vanadium up to 0.3% niobium 0.15 to 0.3% vanadium and niobium up to 0.31% tantalum up to 0.015% phosphorus up to 0.005% sulphur
    the remainder, including production-related impurities, being iron, the vanadium, niobium, tantalum, carbon and nitrogen contents of said alloy meeting the condition [(%V). + (%Nb) + (%Ta)] / [(%C) + (%N)] = 0.5 to 1, in the cast state.
  2. Use of articles according to claim 1 having at least 0.1% tungsten, vanadium, niobium and tantalum, singly or together, in the cast state.
  3. Use of articles according to claim 1 or 2 having a total tungsten and titanium content of 0.05 to 0.8%.
  4. Use of articles according to any of claims 1 to 3 having a total vanadium and niobium content of 0.15 to 30%.
  5. Use of articles according to one of claims 1 to 4 which, with good toughness, require high strength and high resistance to corrosion, and particularly resistance to pitting corrosion in chloridic media.
EP97111887A 1996-07-13 1997-07-12 Ferritic-austenitic stainless steel casting alloy Expired - Lifetime EP0818552B1 (en)

Applications Claiming Priority (2)

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DE19628350A DE19628350B4 (en) 1996-07-13 1996-07-13 Use of a stainless ferritic-austenitic steel alloy
DE19628350 1996-07-13

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EP0818552A3 EP0818552A3 (en) 1998-03-25
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WO2000073530A1 (en) 1999-05-27 2000-12-07 Sandvik Ab; (Publ) Surface modification of high temperature alloys
SE514816C2 (en) 2000-03-02 2001-04-30 Sandvik Ab Duplex stainless steel
CN104919072B (en) * 2013-01-15 2017-07-14 株式会社神户制钢所 Duplex stainless steel and duplex stainless steel pipe
WO2015029167A1 (en) * 2013-08-28 2015-03-05 株式会社日立製作所 Duplex stainless steel, and duplex stainless steel structure, marine structure, petroleum/gas environment structure, pump impeller, pump casing, and flow adjustment valve body using same
JP2017095794A (en) * 2015-11-17 2017-06-01 株式会社神戸製鋼所 Duplex stainless steel material and duplex stainless steel tube
CN113215478B (en) * 2021-05-14 2022-03-04 东北大学 Method for improving high-temperature oxidation resistance of super stainless steel
CN114921710A (en) * 2022-05-20 2022-08-19 青田保俐铸造有限公司 Casting process for improving corrosion resistance of stainless steel 304 casting

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DE3310693A1 (en) * 1983-03-24 1984-10-04 Fried. Krupp Gmbh, 4300 Essen CORROSION-RESISTANT CHROME STEEL AND METHOD FOR THE PRODUCTION THEREOF
SE451465B (en) * 1984-03-30 1987-10-12 Sandvik Steel Ab FERRIT-AUSTENITIC STAINLESS STEEL MICROLEGATED WITH MOLYBID AND COPPER AND APPLICATION OF THE STEEL
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JP3236713B2 (en) * 1993-10-20 2001-12-10 川崎製鉄株式会社 Fe-Cr-Ni alloy with excellent deep drawability

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ES2233986T3 (en) 2005-06-16
EP0818552A2 (en) 1998-01-14
DE19628350A1 (en) 1998-01-15
DE59712090D1 (en) 2004-12-30
EP0818552A3 (en) 1998-03-25

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