EP2245203B1 - Rostfreies austenitisches stahlblech und herstellungsverfahren eines solchen blechs - Google Patents

Rostfreies austenitisches stahlblech und herstellungsverfahren eines solchen blechs Download PDF

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EP2245203B1
EP2245203B1 EP08872296.2A EP08872296A EP2245203B1 EP 2245203 B1 EP2245203 B1 EP 2245203B1 EP 08872296 A EP08872296 A EP 08872296A EP 2245203 B1 EP2245203 B1 EP 2245203B1
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sheet
steel
temperature
rolled
hot
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EP2245203A1 (de
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Thomas Frohlich
Jean-Denis Mithieux
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Aperam Stainless France SA
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Aperam Stainless France SA
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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
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium 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
    • 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

Definitions

  • the invention relates to stainless steel sheets having high mechanical properties and good resistance to corrosion in order to be intended in particular for the manufacture of automotive parts, such as structural parts or engine head gaskets.
  • the stainless steels considered here are in the sense given to this expression by the ISO 6929 standard, ie steels containing at least 10.5% by weight of chromium and not more than 1 , 2% by weight of carbon.
  • austenitic steels are alloy steels containing chromium, nickel, manganese, nitrogen, carbon and optionally copper and molybdenum, in order to produce an austenitic microstructure, which has the advantage of presenting a large crystalline mesh for the iron (cubic face-centered), which increases the solubility of the various elements of alloys in iron, including carbon.
  • the usual process for producing austenitic stainless steels is as follows: after hot rolling of a strip followed by annealing, a cold rolling is carried out whose rate depends on the final characteristics concerned. The steel then has good mechanical strength, but its ductility is too low, especially for its subsequent shaping. To overcome this, it is subjected to a final recrystallization treatment in the form of an annealing furnace, that is to say a heating with temperature maintenance the time required for complete recrystallization before controlled cooling.
  • annealing The main purpose of annealing is to put the metal in a structural state close to the state of equilibrium. In short, the internal energy accumulated during the cold-working is evacuated. In fact, a recrystallization annealing will use this internal energy differential to promote the germination of new metal grains and their growth. It is understood that the greater the internal energy increase due to hardening is important, the more likely there will be new seeds during the annealing, and thus a small final grain size. Also, is it advantageous to perform a strong work hardening prior to annealing.
  • the recrystallization temperature is also an important parameter for controlling the final grain size since the grain boundary mobility increases with temperature. It is therefore recommended to lower the annealing temperature to obtain a fine grained structure.
  • the heating conventionally used during the recrystallization annealing is also a quenching, ie it must exceed the solvus of the chromium carbides to put in solution all the carbon in the austenite.
  • the objective of this step is to avoid any risk of localized corrosion caused by decrepit areas around chromium carbides.
  • the solution temperature of the chromium carbides thus constitutes a limit to the decrease of the annealing temperature in order to refine the microstructure. This limit depends on the chemical composition and mainly the carbon content.
  • the mechanical strength of the steel can be further improved by hardening after this heat treatment.
  • all tests of grain size refinement have failed, resulting in a high precipitation of chromium carbides caused by the lowering of the annealing temperature.
  • EP-A-1739200 discloses an austenitic stainless steel strip having an elastic limit Rp0.2 greater than or equal to 600 MPa, a tensile strength Rm greater than or equal to 800 MPa, an elongation A80 of greater than or equal to 40%, the composition of which comprises % by weight: 0.025 ⁇ C ⁇ 0.15%; 0.20 ⁇ If ⁇ 1.0%; 0.50 ⁇ Mn ⁇ 2.0%; 6.0 ⁇ Ni ⁇ 12.0%; 16.0 ⁇ Cr ⁇ 20.0%; Mo ⁇ 3.0%; 0.030 ⁇ N ⁇ 0.160%; Cu ⁇ 0.50%; P ⁇ 0.50%; S ⁇ 0.015%; possibly 0.10 ⁇ V ⁇ 0.50%, and 0.03 ⁇ Nb ⁇ 0.50% with 0.10% ⁇ Nb + V ⁇ 0.50%, the balance being iron and any impurities resulting from the preparation, the average size of the austenite grains is less than or equal to 4 m, and the surface has a gloss greater than 50.
  • GB-A-473,331 describes treatments carried out on austenitic stainless steels in order to limit their sensitivity to intergranular corrosion.
  • the precipitation of Cr carbides is carried out intragranularly, in particular by reheating at a temperature below the recrystallization temperature, and for a period of time sufficient to precipitate all excess C and redistribute the Cr homogeneously without causing significant recrystallization.
  • FR-A-2,864,108 discloses an austenitic stainless steel of composition 0.025% ⁇ C ⁇ 0.05%; 0.3% ⁇ If ⁇ 1%; 1% ⁇ Mn ⁇ 2%; 15% ⁇ Cr ⁇ 18.5%; 5% ⁇ Ni ⁇ 10%; Mo ⁇ 3%; 0.1% ⁇ N ⁇ 0.16%; Cu ⁇ 0.5%; P ⁇ 0.5%; S ⁇ 0.015%; optionally 0.1% ⁇ V ⁇ 0.5% and 0.1% ⁇ Nb ⁇ 0.5%, with 0.1% ⁇ Nb + Ti + V ⁇ 0.5%, the balance being iron and possible impurities resulting from the preparation, and whose microstructure is an essentially austenitic microstructure comprising from 0.1 to 0.2% by volume of martensitic islands distributed homogeneously.
  • the targeted mechanical properties are achieved thanks to only partial recrystallization. Cooling after recrystallization is carried out continuously
  • the object of the invention is to provide an answer to this problem which has not yet been solved by means of a steel with a very fine austenitic microstructure, whose carbon content significantly increased compared with the practice of the prior art, makes it possible to obtain increased mechanical strength together with very good corrosion resistance.
  • the invention relates to a stainless steel sheet whose composition comprises, the contents being expressed by weight: 0.05% ⁇ C ⁇ 0.30%, 0.3% ⁇ Si ⁇ 1%, 0 , 5% ⁇ Mn ⁇ 3%, 4% ⁇ Ni ⁇ 10%, 15% ⁇ Cr ⁇ 20%, N ⁇ 0.2%, P ⁇ 0.05%, S ⁇ 0.015%, optionally 0.1 ⁇ V ⁇ 0.5%, optionally Mo ⁇ 3%, optionally Cu ⁇ 0.5%, the rest of the composition being constituted of iron and unavoidable impurities resulting from the preparation, the microstructure of the steel being essentially austenitic completely recrystallized, the average size of the austenite grains being less than 2 micrometers, the sheet containing chromium carbides precipitated at the joints of austenitic grains for over 90% of them.
  • the composition preferably comprises, the contents being expressed by weight: 0.09% ⁇ C ⁇ 0.30%.
  • the composition comprises, the contents being expressed by weight: 16% ⁇ Cr ⁇ 18%.
  • the rapid heating is up to a temperature greater than 800 ° C and less than or equal to 900 ° C.
  • the cooled sheet is subjected to a cold deformation operation capable of generating the appearance of martensite within the steel structure.
  • the rapid heating is preferably carried out by electromagnetic induction.
  • the resistance may vary between about 1000 and 1600 MPa.
  • the invention also relates to a stainless steel sheet manufactured by the manufacturing method above.
  • the invention also relates to a mechanical stainless steel part obtained from a sheet made by the manufacturing process above.
  • the invention also relates to the use of a sheet obtained by the above manufacturing process for the manufacture of structural parts for automobiles.
  • the invention also relates to the use of a sheet obtained by the above manufacturing method for the manufacture of motor cylinder head gaskets.
  • the invention essentially consists of a new sheet of austenitic stainless steel with very fine grains, having a significant carbon content, greater than 0.05 or 0.09%, and in a new process for obtaining a sheet from this steel which offsets the undesired effects of this increase in the carbon content by a very rapid heating annealing to quickly reach the recrystallization temperature.
  • the main problem raised by the recrystallization annealing of austenitic stainless steel is that it can proceed to recrystallization without the precipitation of chromium carbides.
  • these carbides are detrimental to the corrosion resistance of the steel, but they also prevent the recrystallization from starting.
  • the nose of the precipitation zone of these carbides will shift to the left: the domain A 1 is relative to steels with steels less than 0.05% C, the domain A 2 to steels with higher carbon content. Carbides will form more easily and therefore faster.
  • One solution would be to heat the steel at temperatures beyond that zone and hold it there until the carbides recoat. Unfortunately, the temperatures to achieve to achieve this are such that the time elapsed and the mobility of the grain boundaries do not allow then to obtain a fine grain.
  • the present inventors have discovered that it is possible to obtain a homogeneous and complete recrystallization or quenching of the steel before the chromium carbides precipitate, and this for carbon contents of up to at 0.3%, or even a little beyond. This could be achieved by increasing the heating rate above 50 ° C / s, although the total recrystallization temperature Tc increases with heating, which increases the risk of reaching the carbide precipitation zone.
  • the balance of the composition consists of iron and other elements usually expected to be found as impurities resulting from the processing of stainless steel, in proportions that do not affect the properties sought.
  • the slab is hot rolled in a strip train to form a hot rolled sheet. This is annealed at a temperature above 1000 ° C in order to allow subsequent cold rolling. The sheet is then etched by a method known per se.
  • the hot rolled sheet is then cold rolled at room temperature at a reduction rate of greater than 40%.
  • This rolling will generate many dislocations within the steel. It will even form martensite (called martensite deformation) which is in the form of slats. These microstructural evolutions will increase the internal energy of steel. The increase in temperature during the heat treatment that will follow, will allow to bring the metal back to thermodynamic equilibrium.
  • the heat treatment according to the invention consists in subjecting the cold-rolled steel sheet to a total recrystallization annealing comprising, in a first step, a rapid heating phase at a speed of between 50 and 800 ° C./s. to reach a temperature between Tc and Tc + 50 ° C.
  • a rapid heating phase at a speed of between 50 and 800 ° C./s. to reach a temperature between Tc and Tc + 50 ° C.
  • This temperature must be reached before the onset of precipitation of chromium carbides. After cooling under the conditions according to the invention, an ultra-fine austenitic grain having an average size of less than 2 microns is obtained.
  • obtaining a fine grain does not only depend on the rate of preliminary hardening, but also the annealing conditions (temperature and hold time).
  • the higher the carbon content of the steel the higher the heating rate must be.
  • the heating rate should reach about 100 ° C / s.
  • such a heating rate is achieved by the use of an electromagnetic induction heating device.
  • an electromagnetic induction heating device Proper implementation of such a device, in particular by the choice of the frequency of the electric excitation current, makes it possible to obtain temperatures so high that it is no longer even necessary to provide a maintenance phase of homogenization as can be seen on the figure 2 .
  • an advantage of the process according to the invention is that there is less loss of internal energy during the heating phase. It therefore becomes possible to obtain the same fineness of grain for a lower work hardening rate than in the past.
  • a first cooling is carried out at a speed greater than 50 ° C./s so as to be placed in the vicinity of the precipitation nose under isothermal conditions.
  • This first cooling is carried out for example, up to a temperature Tm of about 750 ° C., that is to say between 700 and 800 ° C, which is maintained for a period of between 1 and 100 seconds.
  • the sheet is cooled to room temperature.
  • the chromium carbides will predominantly precipitate, that is to say for more than 90% of them, at the austenitic grain boundaries.
  • This precipitation after austenitization will destabilize the structure and increase the final mechanical characteristics of the steel. Indeed, chromium carbides predominantly precipitating at austenitic grain boundaries, and the latter being very thin (their average size is less than 2 micrometers), there is less risk at this level to deteriorate the resistance to intergranular corrosion.
  • the invention will be particularly useful for the manufacture of motor cylinder head gaskets, which require a high yield strength and good resistance to fatigue and corrosion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
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Claims (11)

  1. Rostfreies Stahlblech, dessen Zusammensetzung, deren Gehalte in Gewichtsprozent ausgedrückt sind, aufweist: 0,05 % ≤ C ≤ 0,30 %
    Figure imgb0011
     0,3 % ≤ Si ≤ 1 %
    Figure imgb0012
     0,5 % ≤ Mn ≤ 3 %
    Figure imgb0013
     4 % ≤ Ni ≤ 10 %
    Figure imgb0014
     15 % ≤ Cr ≤ 20 %
    Figure imgb0015
     N ≤ 0,2 %
    Figure imgb0016
     P ≤ 0,05 %
    Figure imgb0017
     S ≤ 0,015 %
    Figure imgb0018
    optional 0,1 % ≤ V ≤ 0,5 %
    optional Mo ≤ 3 %
    optional Cu ≤ 0,5 %
    wobei der Rest der Zusammensetzung aus Eisen und unvermeidbaren Verunreinigungen gebildet ist, die aus der Herstellung resultieren, die Mikrostruktur des besagten Stahls im Wesentlichen vollständig austenitisch rekristallisiert ist, die mittlere Größe der Austenitkörner kleiner als 2 Mikrometer ist, das besagte Blech Chromcarbide enthält, welche zu mehr als 90 % an Grenzen der besagten Austenitkörner zwischen diesen ausgeschieden sind.
  2. Stahlblech gemäß dem Anspruch 1, dadurch gekennzeichnet, dass dessen Zusammensetzung, deren Gehalte in Gewichtsprozent ausgedrückt sind, aufweist: 0,09 % ≤ C ≤ 0,30 %
    Figure imgb0019
  3. Stahlblech gemäß dem Anspruch 1 oder 2, dadurch gekennzeichnet, dass dessen Zusammensetzung, deren Gehalte in Gewichtsprozent ausgedrückt sind, aufweist: 16 % ≤ Cr ≤ 18 %
    Figure imgb0020
  4. Herstellungsverfahren eines rostfreien Stahlblechs mit:
    - Bereitstellen eines Stahls der Zusammensetzung gemäß irgendeinem der Ansprüche 1 bis 3, dann
    - Gießen des Stahls unter Ausformen einer Bramme, dann
    - Warmwalzen der besagten Bramme zum Erhalten eines warmgewalzten Blechs, dann
    - Glühen des besagten warmgewalzten Blechs bei einer Temperatur über 1000°C, dann
    - Beizen des besagten warmgewalzten Blechs, dann
    - Kaltwalzen des besagten warmgewalzten Blechs mit einer Reduktionsrate größer als 40 %, dann
    - Durchführen einer thermischen Behandlung des vollständigen Rekristallisierens am besagten kaltgewalzten Blech, wobei die besagte thermische Behandlung eine Phase des schnellen Heizens mit einer Geschwindigkeit Vc, welche zwischen 50 und 800°C/s liegt, bis zu einer Temperatur aufweist, welche zwischen Tc und Tc + 50°C liegt, wobei Tc die Temperatur der vollständigen Rekristallisation bezeichnet, damit ein erwärmtes und vollständig rekristallisiertes Blech erhalten wird, dann
    - Abkühlen des besagten erwärmten und vollständig rekristallisierten Blechs mit einer Geschwindigkeit über 50°C/s bis auf eine Temperatur Tm von in etwa 750°C, dann
    - Halten des besagten Blechs auf der besagten Temperatur Tm für eine Dauer, welche zwischen 1 bis 100s liegt, um ein Ausscheiden der Chromcarbide zu erzielen, dann
    - Abkühlen des besagten Blechs bis auf die Umgebungstemperatur.
  5. Verfahren gemäß dem Anspruch 4, dadurch gekennzeichnet, dass das besagte schnelle Heizen bis zu einer Temperatur über 800°C und unter oder gleich 900°C durchgeführt wird.
  6. Verfahren gemäß irgendeinem der Ansprüche 4 oder 5, dadurch gekennzeichnet, dass sobald die thermische Behandlung abgeschlossen ist, das besagte gekühlte Blech einem Vorgang des Kaltumformens unterzogen wird, welcher zum Hervorrufen eines Auftretens von Martensit innerhalb der Struktur des Stahls in der Lage ist.
  7. Verfahren gemäß irgendeinem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass das besagte schnelle Heizen durch elektromagnetische Induktion realisiert wird.
  8. Rostfreies Stahlblech, welches aus dem Herstellungsverfahren gemäß irgendeinem der Ansprüche 4 bis 7 hervorgeht.
  9. Mechanisches Bauteil aus rostfreiem Stahl, welches ausgehend von einem Blech gemäß dem Anspruch 8 erhalten wird.
  10. Verwendung eines Blechs gemäß dem Anspruch 8 zur Herstellung von Strukturbauteilen für Fahrzeuge.
  11. Verwendung eines Blechs gemäß dem Anspruch 8 zur Herstellung von Zylinderkopfdichtungen von Motoren.
EP08872296.2A 2007-12-20 2008-12-03 Rostfreies austenitisches stahlblech und herstellungsverfahren eines solchen blechs Active EP2245203B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
SI200832034T SI2245203T1 (sl) 2007-12-20 2008-12-03 Avstenitna nerjavna jeklena pločevina in postopek za izdelavo te pločevine
PL08872296T PL2245203T3 (pl) 2007-12-20 2008-12-03 Blacha z nierdzewnej stali austenitycznej i sposób otrzymywania tej blachy
EP08872296.2A EP2245203B1 (de) 2007-12-20 2008-12-03 Rostfreies austenitisches stahlblech und herstellungsverfahren eines solchen blechs

Applications Claiming Priority (3)

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EP07291575A EP2072631A1 (de) 2007-12-20 2007-12-20 Rostfreies austenitisches Stahlblech und Herstellungsverfahren eines solchen Blechs
PCT/FR2008/001687 WO2009101285A1 (fr) 2007-12-20 2008-12-03 Tôle en acier inoxydable austenitique et procede d'obtention de cette tôle
EP08872296.2A EP2245203B1 (de) 2007-12-20 2008-12-03 Rostfreies austenitisches stahlblech und herstellungsverfahren eines solchen blechs

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EP2245203A1 EP2245203A1 (de) 2010-11-03
EP2245203B1 true EP2245203B1 (de) 2018-10-31

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DK (1) DK2245203T3 (de)
ES (1) ES2708578T3 (de)
HU (1) HUE042000T2 (de)
PL (1) PL2245203T3 (de)
PT (1) PT2245203T (de)
SI (1) SI2245203T1 (de)
TR (1) TR201900950T4 (de)
WO (1) WO2009101285A1 (de)

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CN103484779A (zh) * 2013-09-05 2014-01-01 常熟市勤丰铸件厂 一种不锈钢铸件
CN106906428B (zh) * 2015-12-23 2020-07-14 宝钢德盛不锈钢有限公司 一种传送带用硬态奥氏体不锈钢及其制造方法和应用
CN106011681B (zh) * 2016-06-27 2018-04-20 武汉科技大学 一种提高316ln奥氏体不锈钢力学性能的方法
JP7049142B2 (ja) * 2018-03-15 2022-04-06 日鉄ステンレス株式会社 マルテンサイト系ステンレス鋼板およびその製造方法並びにばね部材
CN113637924A (zh) * 2020-04-27 2021-11-12 靖江市中信特种机械泵阀厂 一种醪液泵新型材料
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CN113957322A (zh) * 2021-10-29 2022-01-21 烟台汽车工程职业学院 一种提高301不锈钢变形过程中马氏体形核能力及含量的方法
CN114480977B (zh) * 2021-12-13 2023-04-07 四川大学 一种低温2500MPa级超高强高韧钢及其制备方法
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CN115948694B (zh) * 2022-11-07 2023-07-14 鞍钢股份有限公司 一种45mm以下高性能奥氏体不锈钢板及其制造方法
CN115595420B (zh) * 2022-12-13 2023-03-21 太原科技大学 一种高强韧含铜不锈钢及其生产工艺
CN115927965A (zh) * 2022-12-16 2023-04-07 广东甬金金属科技有限公司 一种铁镍合金及其应用以及一种焊接胀形强塑性铁镍不锈钢带及其制备方法

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Publication number Publication date
SI2245203T1 (sl) 2019-04-30
ES2708578T3 (es) 2019-04-10
PT2245203T (pt) 2019-02-06
EP2245203A1 (de) 2010-11-03
TR201900950T4 (tr) 2019-02-21
EP2072631A1 (de) 2009-06-24
WO2009101285A1 (fr) 2009-08-20
PL2245203T3 (pl) 2019-06-28
DK2245203T3 (en) 2019-02-18
HUE042000T2 (hu) 2019-06-28

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