US20030172999A1 - Ferritic-austenitic stainless steel - Google Patents

Ferritic-austenitic stainless steel Download PDF

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Publication number
US20030172999A1
US20030172999A1 US10/381,673 US38167303A US2003172999A1 US 20030172999 A1 US20030172999 A1 US 20030172999A1 US 38167303 A US38167303 A US 38167303A US 2003172999 A1 US2003172999 A1 US 2003172999A1
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characteried
steel according
max
steel
ferrite
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Abandoned
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US10/381,673
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English (en)
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Elisabeth Alfonsson
Jun Wang
Mats Liljas
Per Johansson
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Outokumpu Stainless AB
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AvestaPolarit AB
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Application filed by AvestaPolarit AB filed Critical AvestaPolarit AB
Assigned to AVESTAPOLARIT AKTIEBOLAG (PUBL) reassignment AVESTAPOLARIT AKTIEBOLAG (PUBL) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WANG, JUN, ALFONSSON, ELISABETH, JOHANSSON, PER, LILJAS, MATS
Publication of US20030172999A1 publication Critical patent/US20030172999A1/en
Assigned to OUTOKUMPU STAINLESS AKTIEBOLAG reassignment OUTOKUMPU STAINLESS AKTIEBOLAG CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: AVESTAPOLARIT AKTIEBOLAG (PUBL)
Priority to US12/654,593 priority Critical patent/US20100172785A1/en
Priority to US14/725,713 priority patent/US9856551B2/en
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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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • 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
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • 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
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite

Definitions

  • the invention relates to a ferritic-austenitic stainless steel having a microstructure which essentially consists of 35-65 vol-% ferrite and 35-65 vol-% austenite.
  • the ferritic-austenitic stainless steels the duplex steels—combine a high mechanical strength and toughness with good corrosion resistance, particularly as far as stress corrosion is concerned.
  • the duplex steels to an increased extent compete with traditional austenitic stainless steels within offshore, paper and pulp industry, chemical industry, and other fields where high strength and corrosion resistance are required.
  • the duplex steels which so far are commercially available are, however, too expensive to find wider use, in spite of the fact that the duplex steels generally contain lower contents of the expensive alloy element nickel than comparable austenitic stainless steels.
  • a microstructure which contains 35-65% ferrite and 35-65% austenite, preferably 35-55% ferrite and 45-65% austenite,
  • the steel has a chemical composition which contains in weight-%:
  • Ni eq Ni+0.5 Mn+30 (C+N)+0.5 (Cu+Co)
  • carbon has a very small solubility in the ferrite, which means that the carbon content of the steel substantially is collected in the austenitic phase.
  • the carbon content therefore shall be restricted to max 0.07%, preferably to max 0.05%, and suitably to max 0.04%.
  • Silicon can be used as a reduction agent at the manufacturing of the steel and exists as a residue from the manufacturing of the steel in an amount of at least 0.1%. Silicon has favourable features in the steel to the effect that it strengthens the high temperature strength of the ferrite, which has a significant importance at the manufacturing. Silicon also is a strong ferrite former and participates as such in the stabilisation of the duplex structure and should from these reasons exist in an amount of at least 0.2%, preferably in an amount of at least 0.35%. Silicon, also have some unfavourable features because it pronouncedly reduces the solubility for nitrogen, which shall exist in high amounts, and if the content of silicon is high also the risk of precipitation of undesired intermetallic phases is increased. The silicon content therefore is limited to max 2.0%, preferably to max 1.5%, and suitably to max 1.0%. An optimal silicon content is 0.35-0.80%.
  • Manganese is an important austenite former and increases the solubility for nitrogen in the steel and shall therefore exist in an amount of at least 3%, preferably at least 4%, suitably at least 4.5%. Manganese, on the other hand, reduces the corrosion resistance of the steel. Moreover it is difficult to decarburise stainless steel melts having high contents of manganese, which means that manganese need to be added after finished decarburisation in the form of comparatively pure and consequently expensive manganese. The steel therefore should not contain more than 8% manganese, preferably max 6% manganese. An optimal content is 4.5-5.5% manganese.
  • Chromium is the most important element for the achievement of a desired corrosion resistance of the steel. Chromium also is the most important ferrite former of the steel and gives in combination with other ferrite formers and with a balanced content of the austenite formers of the steel a desired duplex character of the steel. If the chromium content is low, there is a risk that the steel will contain martensite and if the chromium content is high, there is a risk of impaired stability against precipitation of intermetallic phases and so called 475°-embrittlement, and an unbalanced phase composition of the steel.
  • the chromium content shall be at least 19%, preferably at least 20%, and suitably at least 20.5%, and max 24%, preferably max 23%, suitably max 22.5%.
  • a suitable chromium content is 21.0-22.0%, nominally 21.2-21.8%.
  • Nickel is a strong austenite former and has a favourable effect on the ductility of the steel and shall therefore exist in an amount of at least 0.5%.
  • nickel should exist in an amount of at least 0.8%, suitably at least 1.1%.
  • the raw material price of nickel often is high and fluctuates, wherefore nickel, according to an aspect of the invention, is substituted by other alloy elements as far as is possible.
  • An optimal nickel content therefore is 1.35-1.70% Ni.
  • Molybdenum is an element which can be omitted according to a wide aspect of the composition of the steel, i.e. molybdenum is an optional element in the steel of the invention. Molybdenum, however, together with nitrogen has a favourable synergy effect on the corrosion resistance. In view of the high nitrogen content of the steel, the steel therefore should contain at least 0.1% molybdenum, preferably at least 0.15%. Molybdenum, however, is a strong ferrite former, it can stabilize sigma-phase in the microstructure of the steel, and it also has a tendency to segregate. Further, molybdenum is an expensive alloy element.
  • molybdenum content is limited to max 1.0%, preferably to max 0.8%, suitably to max 0.65%.
  • An optimal molybdenum content is 0.15-0.54%.
  • Molybdenum can partly be replaced by the double amount of tungsten, which has properties similar to those of molybdenum. However, at least half of the total amount of Mo+W/2 should consist of molybdenum. In a preferred composition the steel, however, the steel does not contain more than max 0.3 tungsten.
  • Copper is also an optional element, which can be omitted according to the widest aspect on this element.
  • copper is a valuable austenite former and can have a favourable influence on the corrosion resistance in some environments, especially in some acid media, and should therefore exist in an amount of at least 0.1%.
  • the copper content should be maximized to 1.0%, preferably to max 0.7%.
  • the copper content should be at least 0.15, preferably at least 0.25 and max 0.54% in order to balance the favourable and possibly unfavourable effects of copper with reference to the features of the steel.
  • Nitrogen has a fundamental importance because it is the dominating austenite former of the steel. Nitrogen also contributes to the strength and corrosion resistance of the steel and shall therefore exist in a minimum amount of 0.15%, preferably at least 0.18%. The solubility of nitrogen in the steel, however, is limited. In case of a too high nitrogen content there is a risk of formation of flaws when the steel solidifies, and a risk of formation of pores in connection with welding of the steel. The steel therefore should not contain more than 0.30% nitrogen, preferably max 0.26% nitrogen. An optimal content is 0.20-0.24%.
  • Boron can optionally exist in the steel as a micro alloying addition up to max 0.005% (50 ppm) in order to improve the hot ductility of the steel. If boron exists as an intentionally added element, it should exist in an amount of at least 0.001% (10 ppm) in order to provide the desired effect with reference to improved hot ductility of the steel.
  • cerium and/or calcium optionally may exist in the steel in amounts of max 0.03% of each of said elements in order to improve the hot ductility of the steel.
  • the steel does not essentially contain any further intentionally added elements, but only impurities and iron.
  • Phosphorus is, as in most steels, a non-desired impurity and should preferably not exist in an amount higher than max 0.035%.
  • Sulphur also should be kept at as low as is possible from an economically manufacturing point of view, preferably in an amount of max 0.10%, suitably lower, e.g. max 0.002% in order not to impair the hot ductility of the steel and hence its rollability, which can be a general problem in connection with the duplex steels.
  • the contents of ferrite formers and austenite formers shall be balanced according to the conditions which have been mentioned in the foregoing, in order that the steel shall get a desired, stabile duplex character.
  • the nickel equivalent, Ni eq should be at least 10.5 and the chromium equivalent at least 21, most advantageously at least 22. Upwards, the nickel equivalent, Ni eq , should be limited to max 15, preferably to max 14. Further the chromium equivalent, Cr eq , should be at least 21, preferably at least 21.5 and most advantageously at least 22, but can be limited to max 23.5.
  • a steel with chromium- and nickel equivalents related to one another according to the said criteria has a balanced content of ferrite and austenite within above mentioned content rage.
  • the steel because of its alloy composition should contain less or even much less than 35 volume-% ferrite, but measurements carried out through image analyses of the microstructures instead have shown that the steel as a matter of fact contains a stabile content of at least 35 vol-% ferrite and, for several of the tested steels according to the invention, about 50% ferrite.
  • FIG. 1 shows microstructures and a Schaeffler diagram, illustrating the theoretical chromium- and nickel equivalents according to the invention
  • FIG. 2 is a bar chart which illustrates the real ferrite and austenite contents which have been measured in examined steels according to the invention
  • FIG. 3 is a bar chart illustrating the resistance to pitting corrosion of examined steels in the form of measured critical pitting temperatures, CPT,
  • FIG. 4 is a diagram illustrating the resistance to stress corrosion versus time to fracture at drop evaporation testing of a number of examined alloys
  • FIG. 5 is a bar charge illustrating the weldability of a number of examined alloys in terms of ferrite content in the heat effected zone (HAZ) and in the welding seam itself.
  • the critical pitting temperature, CPT was determined according to the standardized method which is known by the designation ASTM G 150. The results are represented by the chart diagram in FIG. 3. The test shows that the steels V251, V258, and V260 manufactured at a laboratory scale have a significantly better corrosion resistance than V254 and also essentially better than the reference steels Ref A, ASTM 304 and ASTM 201, but the steels of the invention manufactured at a laboratory scale do not reach the level of ASIM 316 L or UNS S 32304, which however, have a higher content of expensive alloy metals.
  • the corrosion resistance is essentially higher than for the austenitic steel ASTM 304, that no intercrystallin corrosion could be observed, and that also the stress corrosion resistance is essentially higher than for conventional austenitic steels.
  • the weldability of the test alloys was comparable to that of the reference material Ref. A and UNS S 31803. Non destructive testing with x-ray controls could not detect any high porosity levels.
  • the material of the invention had a high degree of austenite reformation in the heat affected zone, HAZ, and in the weld in comparison with the reference material Ref. A and UNS S 31803.
  • the ferrite content in the case of manual TIG welding a steel of type UNS S 31803, the reference steel Ref A, and the steel V258 of the invention with a filler metal of type AWS ER2209 is shown in the bar chart in FIG. 5. When subjected to tensile testing, all the welds were fractured in the parent material and not in the welds.
  • CPT critical pitting temperature

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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)
  • Heat Treatment Of Sheet Steel (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
US10/381,673 2000-09-27 2001-09-18 Ferritic-austenitic stainless steel Abandoned US20030172999A1 (en)

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US12/654,593 US20100172785A1 (en) 2000-09-27 2009-12-23 Ferritic-austenitic stainless steel
US14/725,713 US9856551B2 (en) 2000-09-27 2015-05-29 Ferritic-austenitic stainless steel

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SE0003448A SE517449C2 (sv) 2000-09-27 2000-09-27 Ferrit-austenitiskt rostfritt stål
SE0003448-8 2000-09-27

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US12/654,593 Abandoned US20100172785A1 (en) 2000-09-27 2009-12-23 Ferritic-austenitic stainless steel
US14/725,713 Expired - Lifetime US9856551B2 (en) 2000-09-27 2015-05-29 Ferritic-austenitic stainless steel

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US (3) US20030172999A1 (de)
EP (1) EP1327008B2 (de)
AT (1) ATE317919T1 (de)
AU (1) AU2001288179A1 (de)
DE (1) DE60117276T3 (de)
ES (1) ES2258546T5 (de)
SE (1) SE517449C2 (de)
WO (1) WO2002027056A1 (de)
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WO2006041344A1 (en) 2004-09-07 2006-04-20 Outokumpu Oyj A steel shell for a suction roll and a method of producing a steel product
US20070163679A1 (en) * 2004-01-29 2007-07-19 Jfe Steel Corporation Austenitic-ferritic stainless steel
WO2006097112A3 (en) * 2005-03-18 2008-05-02 Nkt Flexibles Is Use of a steel composition for the production of an armouring layer of a flexible pipe and the flexible pipe
US20110064601A1 (en) * 2008-05-16 2011-03-17 Outokumpu Oyj Stainless steel product, use of the product and method of its manufacture
WO2013048181A2 (ko) 2011-09-28 2013-04-04 주식회사 포스코 내식성 및 열간가공성이 우수한 저합금 듀플렉스 스테인리스강
CN104152818A (zh) * 2014-08-12 2014-11-19 昆明理工大学 一种双相不锈钢及其制备方法
JP2016003377A (ja) * 2014-06-18 2016-01-12 新日鐵住金株式会社 二相ステンレス鋼管
EP2258885A4 (de) * 2008-03-26 2017-04-26 Nippon Steel & Sumikin Stainless Steel Corporation Niedriglegierter rostfreier duplexstahl mit guter korrosionsbeständigkeit und festigkeit der von der schweisshitze betroffenen bereiche
US9816163B2 (en) 2012-04-02 2017-11-14 Ak Steel Properties, Inc. Cost-effective ferritic stainless steel
US10323308B2 (en) 2007-12-20 2019-06-18 Ati Properties Llc Corrosion resistant lean austenitic stainless steel
US10370748B2 (en) 2007-11-29 2019-08-06 Ati Properties Llc Lean austenitic stainless steel
US11566309B2 (en) * 2013-06-13 2023-01-31 Outokumpu Oyj Duplex ferritic austenitic stainless steel

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CA2462963C (en) 2001-10-30 2009-10-13 Ati Properties, Inc. Duplex stainless steels
DE10215598A1 (de) * 2002-04-10 2003-10-30 Thyssenkrupp Nirosta Gmbh Nichtrostender Stahl, Verfahren zum Herstellen von spannungsrißfreien Formteilen und Formteil
JP4760031B2 (ja) * 2004-01-29 2011-08-31 Ｊｆｅスチール株式会社 成形性に優れるオーステナイト・フェライト系ステンレス鋼
JP4760032B2 (ja) * 2004-01-29 2011-08-31 Ｊｆｅスチール株式会社 成形性に優れるオーステナイト・フェライト系ステンレス鋼
JP5109233B2 (ja) * 2004-03-16 2012-12-26 Ｊｆｅスチール株式会社 溶接部耐食性に優れたフェライト・オーステナイト系ステンレス鋼
KR20060074400A (ko) * 2004-12-27 2006-07-03 주식회사 포스코 니켈 절감형 고내식성 2상 스테인리스강
JP5021901B2 (ja) * 2005-02-28 2012-09-12 Ｊｆｅスチール株式会社 耐粒界腐食性に優れるオーステナイト・フェライト系ステンレス鋼
CN101765671B (zh) 2007-08-02 2012-01-11 新日铁住金不锈钢株式会社 耐蚀性和加工性优良的铁素体-奥氏体系不锈钢及其制造方法
AU2008341063C1 (en) 2007-12-20 2014-05-22 Ati Properties, Inc. Austenitic stainless steel low in nickel containing stabilizing elements
US8337749B2 (en) 2007-12-20 2012-12-25 Ati Properties, Inc. Lean austenitic stainless steel
JP5337473B2 (ja) 2008-02-05 2013-11-06 新日鐵住金ステンレス株式会社 耐リジング性と加工性に優れたフェライト・オーステナイト系ステンレス鋼板およびその製造方法
EP2295197B1 (de) 2008-05-27 2012-12-19 Nippon Steel & Sumikin Stainless Steel Corporation Fülldraht zur schweissung eines duplexedelstahls zur miniaturisierung gehärteter kristallpartikel
FR2934349B1 (fr) * 2008-07-28 2010-08-20 Technip France Conduite flexible pour le transport d'hydrocarbures a haute resistance a la corrosion et son procede de fabrication
EP2093303A1 (de) 2008-09-04 2009-08-26 Scanpump AB Duplexstahl
FI121340B (fi) 2008-12-19 2010-10-15 Outokumpu Oy Dupleksinen ruostumaton teräs
SE533635C2 (sv) 2009-01-30 2010-11-16 Sandvik Intellectual Property Austenitisk rostfri stållegering med låg nickelhalt, samt artikel därav
KR20120132691A (ko) * 2010-04-29 2012-12-07 오또꿈뿌 오와이제이 높은 성형성을 구비하는 페라이트-오스테나이트계 스테인리스 강의 제조 및 사용 방법
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US9816163B2 (en) 2012-04-02 2017-11-14 Ak Steel Properties, Inc. Cost-effective ferritic stainless steel
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DE60117276D1 (de) 2006-04-20
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