EP0896072B1 - Acier inoxydable austénitique comportant une très faible teneur en nickel - Google Patents

Acier inoxydable austénitique comportant une très faible teneur en nickel Download PDF

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Publication number
EP0896072B1
EP0896072B1 EP98401734A EP98401734A EP0896072B1 EP 0896072 B1 EP0896072 B1 EP 0896072B1 EP 98401734 A EP98401734 A EP 98401734A EP 98401734 A EP98401734 A EP 98401734A EP 0896072 B1 EP0896072 B1 EP 0896072B1
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EP
European Patent Office
Prior art keywords
steel
composition
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content
steels
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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.)
Expired - Lifetime
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EP98401734A
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German (de)
English (en)
French (fr)
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EP0896072A1 (fr
Inventor
Laurent Chesseret
Jean-Michel Hauser
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.)
Ugine SA
Ugitech SA
Original Assignee
Ugine SA
Ugine Savoie Imphy SA
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Publication of EP0896072A1 publication Critical patent/EP0896072A1/fr
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Classifications

    • 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
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C22C38/06—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
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt

Definitions

  • the invention relates to an austenitic stainless steel with a very low nickel content.
  • Austenitic steels are steels generally comprising in their weight composition a nickel content greater than 3%.
  • a steel austenitic N ° 1.4301 of standard NF EN 10 088 (AISI 304) contains more than 8% nickel in its composition.
  • FR-A-2 074 865 discloses an austenitic stainless steel having a composition similar to that of the invention. We can add elements such as rare iron, Ti, up to 0.005% B or Nb. FR-A includes an Example which, apart from the lack such additions, only distinguished from a martensitic stability index higher than that of the invention.
  • the object of the invention is to produce an austenitic steel called "to very low nickel content ”with particular properties mechanical and welding equivalent, and even superior to those austenitic steels with a high nickel content.
  • the single figure shows necking characteristics in temperature function for different steels.
  • the austenitic steel according to the invention is produced by limiting the nickel content of the composition.
  • the austenitizing effect usually attributed to the nickel element, must necessarily be offset by gamagens such as manganese, copper, nitrogen and carbon and it is necessary to reduce, as far as possible, the contents of alphagenic elements such as chromium, molybdenum and silicon.
  • the steel according to the invention has a ferritic type solidification.
  • the solidifying ferrite regresses to austenite, when the steel cools, following the casting.
  • the ferrite content of the steels according to the invention is less than 5%.
  • the steel according to the invention contains less than 20% of ferrite after reheat for 30 min at 1240 ° C.
  • the steel according to the invention After hot rolling and hyper quenching treatment at 1100 ° C for 30 min, the steel according to the invention has a percentage of ferrite less than 5%. After hot working, annealing, cold working and annealing, a steel with only a few traces of residual ferrite.
  • the measurement of the austenite / ferrite proportion was evaluated by magnetization at saturation or by X-ray diffraction analysis.
  • the carbon is limited to a content of less than 0.1% for avoid sensitization of steel to intergranular corrosion after treatment at temperatures between 550 ° C and 800 ° C. Of preferably the carbon content is less than 0.08% for the same reason.
  • Nitrogen and carbon have a similar effect on the mode of solidification, the balance of the ferrite and austenite phases and the stability of austenite for martensite formation, although nitrogen has a slightly more austenitizing character than carbon.
  • Manganese increases the solubility of nitrogen.
  • a content minimum of 5% of this element is necessary to dissolve enough nitrogen and guarantee the steel an austenitic structure.
  • the effect of manganese on the proportion of ferrite is constant for contents between 5% and 9%.
  • the manganese content must also be limited to avoid deteriorate hot ductility.
  • Silicon is deliberately limited to less than 1%, and, from preferably less than 0.7% to avoid the formation of ferrite and to have satisfactory behavior of the steel during pickling.
  • Content minimum of 0.1% is necessary in the elaboration and a content 0.5% minimum is preferable to avoid the formation of oxide of olivine type.
  • olivine type oxides FeO / SiO2 / MnO
  • the hot rolling operation it is formed, if the content in silicon is less than 0.5%, a mixed zone with a metallic matrix containing these oxides in the liquid state, which leads to a bad state of surface on the steel strip, in particular after pickling.
  • the silicon is limited to a content of less than 2%, and, from preferably at 1% because taking into account the other elements of the composition, it does not contribute, when its content is higher, to obtaining an austenitic structure.
  • Nickel is an essential element of austenitic steels in general, and the problem posed of the invention is notably the obtaining of an austenitic steel containing little nickel, expensive element, price very variable, uncontrollable, which, due to price fluctuations, disrupts the proper functioning of the company responsible for developing steel. Nickel also has the disadvantage of increasing sensitivity to stress corrosion of austenitic steels. We have also found that the nickel limitation allowed the development of a new generation of steel with improved properties as will be described below.
  • chromium content is linked to the fact that the steel according to the invention must remain with a ferrite content less than 5% after the hyperhardening treatment. Chromium contents above 19% lead to chromium contents too large ferrite which does not guarantee an elongation in sufficient traction.
  • a content of at least 0.1% nitrogen is requested. Beyond a content of 0.4% nitrogen, it forms within steel, during solidification, bubbles of this so-called gas "Puffs".
  • the required nitrogen content can be high when introduced into the composition of steel, for the improvement of corrosion resistance, molybdenum with contents below 2%. Molybdenum contents greater than 2% require a more than 0.4% nitrogen to avoid the presence of ferrite, which which is not feasible during the production of pressure steel normal.
  • the composition of the steel according to the invention contains boron in a proportion of between 5.10 -4 % and 50.10 -4 %.
  • the addition of boron to the composition consequently improves the hot ductility, in particular between 900 ° C. and 1150 ° C., as materialized by the characteristics of necking in hot traction as a function of the temperature.
  • Above 50.10 -4 % of boron there is too great a reduction in the burn point, that is to say that there is a risk of formation of liquid metal areas upon reheating before rolling.
  • the sulfur is introduced into the steel in a proportion of less than 0.01% to ensure that the steel has satisfactory resistance to pitting corrosion.
  • the sulfur content is less than 20.10 -4 %, which notably improves the hot ductility at 1000 ° C. and beyond.
  • the low sulfur content can be obtained by the controlled use of calcium and aluminum generating final aluminum contents of less than 0.03%, preferably less than 50.10 -4 % or less than 30.10 -4 %% , and calcium contents of 10.10 -4 % and preferably less than 5.10 -4 %, the resulting oxygen content is then generally from 20.10 -4 to 60.10 -4 %.
  • the phosphorus content is limited to 0.05%, as in the most austenitic stainless steels to limit segregation during solidification of welds and phenomena hot tear that can result when cooling them.
  • the steel according to the invention is compared, in the description, to a AISl 304 type steel, called "reference" steel.
  • the composition of steel according to the invention is presented in Tables 1 and 2, pages 14 and 15.
  • compositions of the steel according to the invention are marked with an asterisk.
  • Table 4 presents the measured values of IF 2 , IF 1 , as well as the measured martensite IS rate formed after a deformation of 30% in tension.
  • Hot ductility was measured by tensile tests at hot. The measurements were carried out on a solidification raw steel and on a wrought and annealed steel.
  • Wrought steel is obtained by forging at a temperature of starting at 1250 ° C. The steel is then annealed at a temperature of 1100 ° C - for 30 min.
  • the thermal cycle of the tensile test includes a temperature rise to 1240 ° C with a speed of 20 ° C / s, maintaining at the temperature of 1240 ° C for one minute and a descent at a speed of 2 ° C / s to the temperature of deformation.
  • We measure the diametral constriction which corresponds to ratio, expressed in%, of the difference between the initial diameter and final diameter by the initial diameter.
  • the single figure shows necking characteristics in function of the deformation temperature for steels 769- (B) and 771- (C) according to the invention compared to low sulfur steels 774- (D), 768- (A) without boron and with 671 steel called “reference” (AISI 304).
  • the steel 771- (C) having a sulfur content of less than 20.10 -4 % has a better characteristic in hot ductility in the entire temperature range between 900 ° C and 1250 ° C and is close in ductility to reference steel 671.
  • the mechanical properties were evaluated on an annealed wrought steel. The working is carried out by forging from 1250 ° C. The steel is then annealed at a temperature of 1100 ° C. for 30 minutes in a salt bath.
  • the tensile test specimens used are barrel specimens of circular section having a diameter of 5 mm and a length of 50 mm. They are subjected to a traction speed of 20 mm / minute.
  • the steels according to the invention have an elongation of between 55% and 67%.
  • the following table 5 presents the measured characteristics of the steel according to the invention, of low-nickel steels outside the invention and of a reference steel of type AISI 304. Mechanical properties.
  • the rate of martensite after 30% of true deformation in tension was measured (table 4): For the steel according to the invention, it is less than 20%.
  • Steels outside the invention containing more than 0.1% carbon, like 594 and 596 steels, have no characteristics acceptable.
  • the steels according to the invention which contain in their composition less than 0.1% carbon, such as steels 567, 592, 584, are comparable in terms of intergranular corrosion, to steel AISI 304 for test b.
  • the pitting potential is significantly higher on steels whose composition has an aluminum content not exceeding 50.10 -4 % and which also contain less than 10.10 -4 % calcium, less than 60.10 -4 % d 'oxygen and less than 20.10 -4 % sulfur.

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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)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Catalysts (AREA)
EP98401734A 1997-07-29 1998-07-09 Acier inoxydable austénitique comportant une très faible teneur en nickel Expired - Lifetime EP0896072B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9709617 1997-07-29
FR9709617A FR2766843B1 (fr) 1997-07-29 1997-07-29 Acier inoxydable austenitique comportant une tres faible teneur en nickel

Publications (2)

Publication Number Publication Date
EP0896072A1 EP0896072A1 (fr) 1999-02-10
EP0896072B1 true EP0896072B1 (fr) 2002-12-04

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EP98401734A Expired - Lifetime EP0896072B1 (fr) 1997-07-29 1998-07-09 Acier inoxydable austénitique comportant une très faible teneur en nickel

Country Status (17)

Country Link
US (1) US6056917A (zh)
EP (1) EP0896072B1 (zh)
JP (1) JP4498481B2 (zh)
KR (1) KR100554935B1 (zh)
CN (1) CN1080774C (zh)
AT (1) ATE229094T1 (zh)
AU (1) AU742411B2 (zh)
BR (1) BR9802669A (zh)
CA (1) CA2243796C (zh)
DE (1) DE69809853T2 (zh)
DK (1) DK0896072T3 (zh)
ES (1) ES2187905T3 (zh)
FR (1) FR2766843B1 (zh)
ID (1) ID20642A (zh)
PT (1) PT896072E (zh)
TW (1) TW555870B (zh)
ZA (1) ZA986701B (zh)

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* Cited by examiner, † Cited by third party
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FR2780735B1 (fr) * 1998-07-02 2001-06-22 Usinor Acier inoxydable austenitique comportant une basse teneur en nickel et resistant a la corrosion
EP1194605A1 (de) 1999-06-24 2002-04-10 Basf Aktiengesellschaft Nickelarmer austenitischer stahl
FR2819526B1 (fr) * 2001-01-15 2003-09-26 Inst Francais Du Petrole Utilisation d'aciers inoxydables austenitiques dans des applications necessitant des proprietes anti-cokage
FR2827876B1 (fr) * 2001-07-27 2004-06-18 Usinor Acier inoxydable austenitique pour deformation a froid pouvant etre suivi d'un usinage
US20100119403A1 (en) * 2001-07-27 2010-05-13 Ugitech Austenitic Stainless Steel for Cold Working Suitable For Later Machining
PL197902B1 (pl) * 2001-10-30 2008-05-30 Ati Properties Stal nierdzewna wytwarzana w procesie dupleks oraz zastosowanie stali nierdzewnej wytwarzanej w procesie dupleks
US20050103404A1 (en) * 2003-01-28 2005-05-19 Yieh United Steel Corp. Low nickel containing chromim-nickel-mananese-copper austenitic stainless steel
TWI247813B (en) * 2002-10-23 2006-01-21 Yieh United Steel Corp Austenite stainless steel with low nickel content
KR20060025873A (ko) * 2004-09-17 2006-03-22 주식회사 포스코 열간 가공성 및 냉간 가공성이 우수한 고망간 고질소오스테나이트계 스테인리스강
EP1690957A1 (en) * 2005-02-14 2006-08-16 Rodacciai S.p.A. Austenitic stainless steel
KR101230201B1 (ko) * 2005-12-26 2013-02-05 주식회사 포스코 냉간가공성이 우수한 니켈저감형 고망간 오스테나이트스테인레스강
CN100386464C (zh) * 2006-07-21 2008-05-07 内蒙古华业特钢股份有限公司 稀土低镍铬锰氮不锈钢
CN101270455B (zh) * 2007-03-23 2010-08-11 宝山钢铁股份有限公司 1000MPa级节镍型亚稳奥氏体不锈钢
KR101587392B1 (ko) 2007-11-29 2016-01-21 에이티아이 프로퍼티즈, 인코퍼레이티드 린 오스테나이트계 스테인리스 강
US8337749B2 (en) 2007-12-20 2012-12-25 Ati Properties, Inc. Lean austenitic stainless steel
MX2010006038A (es) 2007-12-20 2010-08-11 Ati Properties Inc Acero inoxidable austenitico con bajo contenido de niquel que contiene elementos de estabilizacion.
NO2229463T3 (zh) 2007-12-20 2018-02-03
US8182963B2 (en) * 2009-07-10 2012-05-22 GM Global Technology Operations LLC Low-cost manganese-stabilized austenitic stainless steel alloys, bipolar plates comprising the alloys, and fuel cell systems comprising the bipolar plates
TWI450973B (zh) * 2011-05-19 2014-09-01 China Steel Corp 煉鋼製程
US9028745B2 (en) 2011-11-01 2015-05-12 Honeywell International Inc. Low nickel austenitic stainless steel
UA111115C2 (uk) 2012-04-02 2016-03-25 Ейкей Стіл Пропертіс, Інк. Рентабельна феритна нержавіюча сталь
EP2728028B1 (fr) * 2012-11-02 2018-04-04 The Swatch Group Research and Development Ltd. Alliage d'acier inoxydable sans nickel
US10975718B2 (en) 2013-02-12 2021-04-13 Garrett Transportation I Inc Stainless steel alloys, turbocharger turbine housings formed from the stainless steel alloys, and methods for manufacturing the same
CN104294176A (zh) * 2014-09-19 2015-01-21 东莞市迅盈精密五金有限公司 不锈钢无磁材料及由其制成的平衡块
JP6477181B2 (ja) * 2015-04-07 2019-03-06 新日鐵住金株式会社 オーステナイト系ステンレス鋼
CN105970115A (zh) * 2016-05-31 2016-09-28 上海大学兴化特种不锈钢研究院 一种经济型高性能含铜易切削奥氏体不锈钢合金材料
KR101903174B1 (ko) * 2016-12-13 2018-10-01 주식회사 포스코 강도 및 연성이 우수한 저합금 강판
CN107904489A (zh) * 2017-11-13 2018-04-13 广东广青金属科技有限公司 利用还原炉与aod炉联合冶炼的节镍奥氏体不锈钢及工艺
EP3739076A1 (fr) * 2019-05-16 2020-11-18 The Swatch Group Research and Development Ltd Composition de poudre d'acier inoxydable austenitique sans nickel et piece realisee par frittage au moyen de cette poudre
KR102268906B1 (ko) * 2019-07-17 2021-06-25 주식회사 포스코 강도가 향상된 오스테나이트계 스테인리스강 및 그 제조 방법
KR102403849B1 (ko) * 2020-06-23 2022-05-30 주식회사 포스코 생산성 및 원가 절감 효과가 우수한 고강도 오스테나이트계 스테인리스강 및 이의 제조방법
CN113462968B (zh) * 2021-06-20 2022-02-18 山东盛阳金属科技股份有限公司 一种节镍型奥氏体不锈钢制造工艺
CN113862573B (zh) * 2021-06-30 2022-04-26 青岛科技大学 一种用于纸浆磨盘的纳米晶不锈钢及其制备方法
CN115216709A (zh) * 2022-06-17 2022-10-21 攀钢集团攀枝花钢铁研究院有限公司 一种耐氢脆化的氢能工业管道合金及管道制备方法
CN115354131A (zh) * 2022-08-17 2022-11-18 东莞市灿煜金属制品有限公司 性价比高、低镍低磁不锈钢bf2的制造方法

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JP3486936B2 (ja) * 1993-12-08 2004-01-13 セイコーエプソン株式会社 時計外装部品用材料および時計用外装部品

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Publication number Publication date
CA2243796A1 (fr) 1999-01-29
FR2766843A1 (fr) 1999-02-05
CN1213013A (zh) 1999-04-07
US6056917A (en) 2000-05-02
DK0896072T3 (da) 2003-03-24
AU7733098A (en) 1999-02-11
DE69809853T2 (de) 2003-09-04
ID20642A (id) 1999-02-04
PT896072E (pt) 2003-04-30
KR100554935B1 (ko) 2006-04-21
AU742411B2 (en) 2002-01-03
EP0896072A1 (fr) 1999-02-10
ZA986701B (en) 1999-02-04
FR2766843B1 (fr) 1999-09-03
DE69809853D1 (de) 2003-01-16
ATE229094T1 (de) 2002-12-15
BR9802669A (pt) 1999-11-30
JP4498481B2 (ja) 2010-07-07
JPH1192885A (ja) 1999-04-06
KR19990014209A (ko) 1999-02-25
CA2243796C (fr) 2010-04-06
CN1080774C (zh) 2002-03-13
TW555870B (en) 2003-10-01
ES2187905T3 (es) 2003-06-16

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