EP1228253B1 - Stahlzusammensetzung, herstellungsverfahren und hergestellte formteile aus diesen zusammensetzungen insbesondere ventilen - Google Patents

Stahlzusammensetzung, herstellungsverfahren und hergestellte formteile aus diesen zusammensetzungen insbesondere ventilen Download PDF

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Publication number
EP1228253B1
EP1228253B1 EP01931816A EP01931816A EP1228253B1 EP 1228253 B1 EP1228253 B1 EP 1228253B1 EP 01931816 A EP01931816 A EP 01931816A EP 01931816 A EP01931816 A EP 01931816A EP 1228253 B1 EP1228253 B1 EP 1228253B1
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EP
European Patent Office
Prior art keywords
steel
steel composition
weight
compositions
composition
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Expired - Lifetime
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EP01931816A
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English (en)
French (fr)
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EP1228253B8 (de
EP1228253A1 (de
Inventor
Jacques Montagnon
Frédéric PERDRISET
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Aubert and Duval SA
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Industrielle De Metallurgie Avancee (sima) Ste
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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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • 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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to more steel compositions particularly intended for the manufacture of intake valves and Exhaust systems for vehicles with internal combustion engines.
  • this type of parts is subject to important mechanical stresses at temperatures that continue to grow with the increase in power and engine efficiency.
  • this temperature is generally between 200 and 400 ° C, but can reach 800 ° C at the exhaust when the fuel used is essence.
  • the exhaust valves can thus be submitted at temperatures up to 900 ° C at each explosion followed by a exhaust.
  • the materials used for these valves must also withstand sudden and significant changes in temperature.
  • the steel or alloy used for their manufacture must also fulfill certain additional criteria. Indeed, the manufacture of valves has usually takes place in two stages. The metallurgist will first develop a grade of steel or alloy that it will then deliver to the manufacturer of valves in the form of rectified bars, but also peeled or according to any other surface condition specified by the customer. This manufacturer will then shear these bars, an operation also called cutting in plots. In a first manufacturing process, the slice cut is performed at high temperature, and is followed by transformation by extrusion of slugs into valves at temperatures ranging from 1150 to 1200 ° C, which supposes that the granular structure of the delivered bar remains stable up to forging temperatures.
  • the slugs are obtained by shearing at room temperature, which requires a weakly brittle metal to avoid non-uniform shearing and cracking of these slugs.
  • problems with the segregation of carbides in the plots which in particular, excessive wear of the tools.
  • the materials traditionally used for the manufacture of such valves are, in particular, stainless austenitic steels, which have iron-nickel-chromium base and are divided between high-grade steels manganese content (up to 10% by weight) and high grade steels nickel (up to 21% by weight).
  • Their resistance to high oxidation temperature is not always satisfactory, especially when, for example, for example, the engine operates in a marine atmosphere and ingests chlorine, or even when an increase in engine efficiency implies warmer combustion gases.
  • These shortcomings bring the developers to increase the chromium content ever more, which has disadvantage of favoring the formation of ferrite at high temperature and of embrittling intermetallic phases at the temperatures of use.
  • Austenitic steel having improved resistance to high temperature containing Cr, Ni, Mn and one or more Carburigenic elements such as Nb have been proposed in EP-A1-0467756.
  • the present invention is therefore essentially intended to remedy the aforementioned drawbacks of known steel compositions, providing steel compositions having in particular a resistance to oxidation, mechanical characteristics as well as improved processing properties, which are particularly suitable for allow the manufacture of exhaust valves having a uniform mechanical and oxidation resistance excellent in the range of 800 to 900 ° C.
  • a first object of the invention is constituted by a steel composition comprising, expressed in percentages by weight: VS 0.25 - 0.35% Cr 24 - 28% Or 10 - 15% mn 3 - 6% Nb 1.75 - 2.50% NOT 0.50 - 0.70% Yes 0 - 0.30% it being understood that C + N ⁇ 0.8%, the balance being iron and unavoidable impurities.
  • the steel composition comprises, expressed in percentages by weight: VS 0.25 - 0.32% Cr 25 - 26% Or 11.50 - 12.50% mn 4.80 - 5.20% Nb 1.90 - 2.30% NOT 0.61 - 0.70% Yes 0 - 0.30% with the understanding that C + N ⁇ 0.9%, the balance being iron and unavoidable impurities.
  • Figures 4, 6 and 7 show steel structures according to the invention at different stages of implementation.
  • Figure 5 shows a steel structure of the prior art.
  • heterogeneity of the structure may have other disadvantages when making parts. So, during manufacturing of valves for vehicles with crush-fueled engines, the car manufacturer shears round steel wires with a diameter of 6 to 13 mm in automated production lines. The structure of the steel being not homogeneous, the shearing will not be uniform which leads to the appearance of cracks and requires frequent adjustments of production lines.
  • the nitrogen contents, in niobium and carbon, which are the three elements forming the carbonitride of niobium Nb (C, N) are chosen so that the compositions resultants are hyper-eutectic in phase diagrams theoretical.
  • the phase diagram of Figure 3 represents an example of such a composition for which eutectic E corresponds to a content carbon of about 0.15% by weight.
  • compositions can be described as hyper-eutectic in the theoretical phase diagrams, that in practice industrialists the inventors still observe the primary precipitation of the austenite phase: this disagreement between theory and experimental reality can be justified by supercooling, germination and phase growth.
  • compositions according to the invention are conserved even with low carbon levels, because nitrogen is substituted for carbon in the compound Nb (C, N).
  • Nb Nb
  • the present inventors have also sought to limit the carbon content of the compositions according to the invention in order to reduce the potential rate of intergranular precipitation of the harmful carbide M 23 C 6 , during the final heat treatment of stabilization of the parts or during use. of these pieces.
  • This potential precipitation rate remains high in the compositions according to the invention, nitrogen being substituted for carbon to form nitrides and carbonitrides.
  • the ductility at room temperature measured by the elongation at the tensile test A 5d , remains very good. The characteristics of resistance to oxidation are also excellent.
  • the present inventors have also found that the structure obtained after the solidification of ingots undergoes a modification important after conventional transformation operations thermomechanical (rolling, etc ).
  • Chromium is mainly used to obtain good performance in oxidation thanks to the passivated layer of oxide that it forms on the surface of the metal. It also has a beneficial influence on the mechanical strength at high temperature. Its content in the compositions according to the invention is 24 to 28%, preferably 25 to 26% by weight.
  • Nickel has a desired gamma-gen effect. It is limited because of its price, at a content just sufficient for the solidification of the matrix in austenitic mode. Its content in the compositions according to the invention is 10 to 15%, preferably 11.5 to 12.5% by weight.
  • Carbon has a desired hardening effect, but too much high temperature leads to the precipitation of weakening and harmful carbides for the resistance to oxidation.
  • Its content in the compositions according to the invention is 0.25 to 0.35% by weight, preferably 0.25 to 0.32%.
  • Nitrogen is a highly gamma-generating element that allows compositions according to the invention to remain in the austenitic field by delaying the precipitation of the intermetallic phases. Its content is however limited because of difficulties in introducing it in steel compositions because of its low solubility limit in liquid steel. Its content is 0.5 to 0.7%, preferably 0.61 to 0.7% in weight. These levels also correspond to the near-saturation at the equilibrium of the liquid metal at conventional temperatures of elaboration, which is an advantage, because this addition is then easy with the means usual known to those skilled in the art.
  • Manganese makes it easier to introduce nitrogen into the composition by increasing the value of its phase solubility limit liquid and solid, but its quantity is limited because of its harmfulness for the resistance to oxidation. Its content in the compositions according to the invention is 3 to 6%, preferably 4.8 to 5.2% by weight.
  • Niobium besides its favorable carburizing properties for the mechanical resistance to heat, allows to obtain the eutectic previously described. Its content in the compositions according to the invention is from 1.75 to 2.50%, preferably 1.90 to 2.30% by weight.
  • Silicon is limited to a content of not more than 0.30% by weight, although it improves the resistance to oxidation because it is strongly sigmagene and further lowers the solubility of nitrogen.
  • the steel compositions according to the invention can be manufactured according to the methods applicable to the standard materials referred to, in taking into account these particularities.
  • the remelting can be done, for example, under slag with electrode consumable if you are looking for a great inclusiveness.
  • thermomechanical transformation such as forging or rolling then a softening treatment, which will preferably maintained at 1,050-1,100 ° C for 1 to 16 hours in air or in another fluid, which guarantees a complete recrystallization fine grain, and satisfactory ductility characteristics.
  • Thermal treatments for dissolution and recrystallization as well as the preheating of products for valve manufacture may be carried out between 1100 and 1200 ° C; the most brought a grain magnification which remains limited.
  • the stabilizing heat treatment is intended to guarantee a certain structural and dimensional stability at operating temperatures. It may be achieved, for example, in the form of 700-1000 ° C for 1 to 16 hours in air or other fluid. On the one Generally speaking, it is preferable to carry out this treatment at a temperature greater than or equal to the operating temperature of the part in service.
  • R m , R p0,2 and A 5d are measured using a tensile test.
  • AT B * VS D E F VS 0.30% 0.30% 0.286% 0.52% 0.35% 0.35% Cr 25.46% 25.35% 25.21% 20.70% 22.75% 25.50% Or 12.00% 12.10% 11.92% 3.60% 7.50% 9.00% mn 4.90% 4.84% 4.93% 8.60% 3.25% 5.00% Nb 2.00% 1.98% 1.55% 2.10% - 0.45% NOT 0.644% 0.55% 0.50% 0.47% 0.275% 0.515% Yes 0.22% 0.25% 0.292% 0.35% 0.70% 0.18% W - - - 0.99% - 0.725% MB - - - - 0.725% V - - - - - 0.45% Fe complement complement complement complement complement complement complement complement C + N 0.944 0,850 0.786 0,990 0.625 0.865
  • compositions tested were put in solution to 1 160 ° C for 1 hour then cooled in water, then aged for 4 hours at 850 ° C, with the exception of the grade F which was dissolved in 1 120 ° C for 1 hour then cooled in water and then aged at 820 ° C for 4 hours.
  • Aging at 850 ° C corresponds to an estimated temperature greater than or equal to the temperature of use of the valves in modern engines where very high temperatures prevail.
  • Materials Test temperature (° C) R m (MPa) R p0.2 (MPa) A 5d (%) ambient 1001 605 26 AT 800 ° C 419 263 27 850 ° C 348 226 29 ambient 964 563 26.5 B 800 ° C 394 249 35.5 850 ° C 342 226 40 ambient 957 558 28.5 VS 800 ° C 375 234 36 850 ° C 298 203 30 ambient 968 555 23.8 D 800 ° C 350 209 41 850 ° C 281 187 41 ambient 916 491 32 E 800 ° C 352 209 51.5 850 ° C 286 175 68.5 ambient 1033 606 24 F 800 ° C 373 244 34 850 ° C 307 191 49
  • the alloys according to the invention levels of mechanical strength higher than the steels of reference, especially since the nitrogen content is between 0.64% and 0.70% by weight, at least.
  • This behavior is determined from the value of the constraint causing 1% elongation by creep in 100 hours.
  • the three shades A, B and C were previously processed by placing in solution and aging at 850 ° C for 4 hours, while the reference steel grades have been treated conventionally for each steel, which is favorable to them in the comparison.
  • the steel specimen is a cylinder 12 mm in diameter by 12 mm long cut in the axis of the products.
  • the specimen is then removed from the crucible and allowed to cool the air. It is then scoured by immersion for about 15 minutes in an aqueous solution, previously heated to 100 ° C, and containing 12% of ferric sulphate and 2.6% of a 40% HF solution, then the lost mass.
  • the steel test piece is a 6 mm diameter cylinder on 20 mm long cut in the axis of the products, and having a hole of diameter 3 to 4 mm.
  • the first stripping is carried out for 10 minutes, then their duration is gradually brought to 20, 40 and 60 minutes. We stop stripping when the sound metal is attacked.
  • the steel according to the invention can provide a very high good resistance to oxidation despite concentrations in C + N also higher than 1%.
  • the present inventors have found a very marked improvement in the corrosion resistance in the Na 2 SO 4 + NaCl medium with the increase in the nitrogen content of the steel according to the invention.
  • this resistance to corrosion in the molten salts is equivalent to that of the best reference steel, despite a rate of intergranular precipitation nitrides and carbides much stronger.
  • the steels according to the invention present both excellent mechanical properties at room temperature and at very high temperatures as well as excellent resistance to oxidation and corrosion by molten salts.
  • compositions according to the invention described here are the manufacture of valves for motor vehicles to internal combustion
  • the invention is not limited to such application and that it can be used to make all the pieces withstand similar or similar constraints, as may be be the case for tools for hot deformation, elements of fixing (screws, nuts) or control devices, for example.

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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 Articles (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
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Claims (12)

  1. Stahlzusammensetzung, umfassend, ausgedrückt in Gewichtsprozent: C 0,25 - 0,35 % Cr 24 - 28 % Ni 10 - 15 % Mn 3 - 6 % Nb 1,75 - 2,50 % N 0,50 - 0,70 % Si 0 - 0,30 %
    vorausgesetzt, daß:   C + N ≥ 0,8 %,
    wobei der Rest aus Eisen und unvermeidlichen Verunreinigungen besteht.
  2. Stahlzusammensetzung entsprechend Anspruch 1, dadurch gekennzeichnet, daß sie 25 bis 26 Gew.-% Chrom umfaßt.
  3. Stahlzusammensetzung entsprechend Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie 1,90 bis 2,30 Gew.-% Niob umfaßt.
  4. Stahlzusammensetzung entsprechend irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie 0,61 bis 0,70 Gew.-% Stickstoff umfaßt.
  5. Stahlzusammensetzung entsprechend irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß
       C + N ≥ 0,9 % ist.
  6. Stahlzusammensetzung, umfassend, ausgedrückt in Gewichtsprozent: C 0,25 - 0,32 % Cr 25 - 26 % Ni 11,50 - 12,50 % Mn 4,80 - 5,20 % Nb 1,90 - 2,30 % N 0,61 - 0,70 % Si 0 - 0,30 %
    vorausgesetzt, daß:   C + N ≥ 0,9 %,
    wobei der Rest aus Eisen und unvermeidlichen Verunreinigungen besteht.
  7. Stahlzusammensetzung entsprechend irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Gehalte an Kohlenstoff, Stickstoff und Niob außerdem derart ausgewählt sind, daß die Zusammensetzungen hypereutektisch in den theoretischen Phasendiagrammen sind.
  8. Verfahren zur Herstellung eines Stahlteiles, welches eine Zusammensetzung entsprechend irgendeinem der Ansprüche 1 bis 7 hat, umfassend:
    Ausarbeitung einer Elektrode, welche die Zusammensetzung dieses Stahles hat,
    Wiederaufschmelzen dieser Verbrauchselektrode unter elektrisch leitender Schlacke,
    und gegebenenfalls Informbringen dieses Stahles mittels eines thermomechanischen Verfahrens in der Wärme wie Schmieden oder Walzen.
  9. Verfahrten entsprechend Anspruch 8, dadurch gekennzeichnet, daß es außerdem eine thermische Weißglühbehandlung des Stahle zwischen 1050 und 1100°C nach den gegebenenfalls durchgeführten thermomechanischen Umformungsbehandlungen umfaßt.
  10. Verfahren entsprechend irgendeinem der Ansprüche 8 oder 9, dadurch gekennzeichnet, daß es außerdem die folgenden späteren Stufen umfaßt:
    Überführen des Stahles in Lösung bei 1100 - 1200°C, und
    eine thermische Stabilisierungsbehandlung bei einer Temperatur größer oder gleich der Gebrauchstemperatur dieses Teiles.
  11. Teile, insbesondere Ventile, geformt aus einem Stahl mit einer Zusammensetzung entsprechend irgendeinem der Ansprüche 1 bis 7, oder erhalten durch ein Verfahren entsprechend irgendeinem der Ansprüche 8 bis 10.
  12. Verwendung einer Zusammensetzung entsprechend irgendeinem der Ansprüche 1 bis 7 zur Herstellung von Ventilen für Motore, die in mariner Atmosphäre arbeiten.
EP01931816A 2000-05-10 2001-05-07 Stahlzusammensetzung, herstellungsverfahren und hergestellte formteile aus diesen zusammensetzungen insbesondere ventilen Expired - Lifetime EP1228253B8 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0005967 2000-05-10
FR0005967A FR2808807B1 (fr) 2000-05-10 2000-05-10 Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapes
PCT/FR2001/001388 WO2001086009A1 (fr) 2000-05-10 2001-05-07 Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapes

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EP1228253A1 EP1228253A1 (de) 2002-08-07
EP1228253B1 true EP1228253B1 (de) 2005-07-20
EP1228253B8 EP1228253B8 (de) 2005-09-21

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US (1) US6656418B2 (de)
EP (1) EP1228253B8 (de)
JP (1) JP5288674B2 (de)
AT (1) ATE299953T1 (de)
AU (1) AU5850901A (de)
BR (1) BR0106337B1 (de)
DE (1) DE60112032T2 (de)
ES (1) ES2248325T3 (de)
FR (1) FR2808807B1 (de)
MX (1) MXPA02000345A (de)
WO (1) WO2001086009A1 (de)

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JP5223046B2 (ja) * 2005-11-02 2013-06-26 国立大学法人九州大学 生体用高窒素ニッケルフリーオーステナイト系ステンレス鋼の結晶粒微細化熱処理方法
FR2896514B1 (fr) * 2006-01-26 2008-05-30 Aubert & Duval Soc Par Actions Acier martensitique inoxydable et procede de fabrication d'une piece en cet acier, telle qu'une soupape.
JP6020957B2 (ja) * 2012-02-02 2016-11-02 住友電気工業株式会社 内燃機関用材料の評価試験方法
WO2017021565A1 (es) 2015-08-05 2017-02-09 Gerdau Investigacion Y Desarrollo Europa, S.A. Acero débilmente aleado de alta resistencia y alta resistencia a la oxidación en caliente
US10927439B2 (en) 2018-05-30 2021-02-23 Garrett Transportation I Inc Stainless steel alloys, turbocharger components formed from the stainless steel alloys, and methods for manufacturing the same
US11725266B2 (en) * 2019-10-30 2023-08-15 Garrett Transportation I Inc. Stainless steel alloys, turbocharger components formed from the stainless steel alloys, and methods for manufacturing the same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5040099B1 (de) * 1971-03-09 1975-12-22
DE3310693A1 (de) * 1983-03-24 1984-10-04 Fried. Krupp Gmbh, 4300 Essen Korrosionsbestaendiger chromstahl und verfahren zu seiner herstellung
JP2543417B2 (ja) * 1989-12-05 1996-10-16 トヨタ自動車株式会社 弁用鋼
FR2664909B1 (fr) * 1990-07-18 1994-03-18 Aubert Duval Acieries Acier austenitique ayant une resistance amelioree a haute temperature et procede pour son obtention et la realisation de pieces mecaniques, en particulier de soupapes.
JP2945112B2 (ja) * 1990-10-09 1999-09-06 株式会社東芝 吸振ばね合金およびこれを用いたばね部材と、このばね部材を用いた電子機器
US5257453A (en) * 1991-07-31 1993-11-02 Trw Inc. Process for making exhaust valves
JPH0849512A (ja) * 1994-08-03 1996-02-20 Hitachi Metals Ltd エンジンバルブ
JP3486713B2 (ja) * 1998-02-25 2004-01-13 株式会社クボタ 可逆式熱間圧延機のファーネスコイラードラム鋳造用高温強度・耐熱疲労特性にすぐれた耐熱鋳鋼
JP3486714B2 (ja) * 1998-09-25 2004-01-13 株式会社クボタ 可逆式熱間圧延機の保熱炉内コイラードラム鋳造用耐肌荒れ性等にすぐれた耐熱鋳鋼

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BR0106337A (pt) 2002-04-02
US6656418B2 (en) 2003-12-02
FR2808807B1 (fr) 2002-07-19
JP2003532795A (ja) 2003-11-05
MXPA02000345A (es) 2004-05-21
US20030044304A1 (en) 2003-03-06
DE60112032T2 (de) 2006-07-20
EP1228253B8 (de) 2005-09-21
ES2248325T3 (es) 2006-03-16
EP1228253A1 (de) 2002-08-07
WO2001086009A1 (fr) 2001-11-15
DE60112032D1 (de) 2005-08-25
BR0106337B1 (pt) 2014-09-30
ATE299953T1 (de) 2005-08-15
FR2808807A1 (fr) 2001-11-16
JP5288674B2 (ja) 2013-09-11
AU5850901A (en) 2001-11-20

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