EP1228253A1 - Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapes - Google Patents
Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapesInfo
- Publication number
- EP1228253A1 EP1228253A1 EP01931816A EP01931816A EP1228253A1 EP 1228253 A1 EP1228253 A1 EP 1228253A1 EP 01931816 A EP01931816 A EP 01931816A EP 01931816 A EP01931816 A EP 01931816A EP 1228253 A1 EP1228253 A1 EP 1228253A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- steel
- composition according
- weight
- compositions
- nitrogen
- Prior art date
- 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.)
- Granted
Links
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
- C22C38/48—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 steel compositions more particularly intended for the manufacture of intake and exhaust valves for vehicles with internal combustion engines.
- this type of parts is subjected to significant mechanical stresses at temperatures which do not cease increasing with the increase in the power and the yields of the engines.
- the engine intake includes a turbo
- this temperature is generally between 200 and 400 ° C, but can reach 800 ° C at the exhaust when the fuel used is gasoline.
- the exhaust valves can thus be subjected to temperatures of up to 900 ° C on each explosion followed by an exhaust.
- the materials used for these valves must also resist sudden and significant variations in temperature. This increase in valve operating temperatures makes them even more sensitive to oxidation and corrosion by certain components contained in the fuels used, such as lead, sulfur or vanadium pentoxide, thereby reducing their duration of life.
- the steel or alloy used for their manufacture must also fulfill certain additional criteria.
- the manufacture of the valves generally takes place in two stages. The metallurgist will first develop a grade of steel or alloy which he will then deliver to the valve manufacturer in the form of rectified bars, but also peeled or according to any other surface condition specified by the customer. This manufacturer will then proceed to shear these bars, an operation also called cutting in plots.
- the cut into pieces is carried out at high temperature, and is followed by the transformation by extrusion of the pieces into valves at temperatures ranging from 1150 to 1200 ° C., which supposes that the granular structure of the bar delivered remains stable up to forging temperatures.
- the pieces are obtained by shearing at room temperature, which requires a slightly brittle metal to avoid non-uniform shearing and cracking of these pieces.
- a slightly brittle metal to avoid non-uniform shearing and cracking of these pieces.
- problems linked to the segregation of carbides in the pieces which leads, in particular, to excessive wear of the tools.
- the steels of the prior art are particularly problematic during shearing because the appearance of cracks in the parts requires frequent adjustments of the production lines.
- the materials traditionally used for the manufacture of such valves are, in particular, austenitic stainless steels, which have an iron-nickel-chromium base and are distributed between steels with high manganese content (up to 10% by weight) and steels with high nickel content (up to 21% by weight).
- Their resistance to oxidation at high temperature is not always satisfactory, in particular when, for example, the engine operates in a marine atmosphere and ingests chlorine, or even when an increase in the efficiency of the engine involves combustion gases. warmer.
- the present invention therefore essentially aims to remedy the aforementioned drawbacks of known steel compositions, by providing steel compositions having in particular an oxidation resistance, mechanical characteristics as well as improved processing properties. , which are in particular able to allow the manufacture of exhaust valves having a holding excellent mechanical and oxidation resistance in the range of 800 to 900 ° C.
- a first object of the invention consists of a steel composition comprising, expressed in percentages by weight: C 0.25 - 0.35%
- the steel composition comprises, expressed in percentages by weight:
- FIG. 5 represents a steel structure of the prior art.
- the heterogeneity of the structure can have other drawbacks during the manufacture of the parts.
- the automobile manufacturer shears round steel wires having a diameter of
- the nitrogen, niobium and carbon contents which are the three elements forming the niobium carbonitride Nb (C, N), are chosen such that the compositions results are hyper-eutectic in theoretical phase diagrams.
- the phase diagram of FIG. 3 represents an example of such a composition for which the eutectic E corresponds to a carbon content of approximately 0.15% by weight.
- compositions can be described as hyper-eutectic in theoretical phase diagrams, that in industrial practice 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 phenomena.
- the recrystallized structures are therefore homogeneous, a property which is very appreciable and very difficult to obtain in a reproducible manner by using the steel compositions of the prior art.
- 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 M23C6, during the final heat treatment for stabilizing the parts or when using these parts. .
- This potential rate of precipitation remains high, however, in the compositions according to the invention, nitrogen replacing carbon to form nitrides and carbonitrides.
- the ductility at room temperature measured by the elongation in the tensile test As d , remains very good.
- the oxidation resistance characteristics are also excellent.
- the present inventors have also found that the structure obtained at the end of the solidification of the ingots undergoes a significant modification after the conventional thermomechanical transformation operations (rolling, etc.). Indeed, we see that the network of rods of eutectic carbonitrides Nb (C, N) disappears, leaving room for a relatively homogeneous distribution of globular carbonitrides Nb (C, N) in processed products, such as rolled bars, by example, as can be seen in FIG. 6. When the nitrogen, niobium and carbon contents are such that the resulting compositions are hypo-eutectic in the theoretical phase diagrams, the niobium carbonitrides do not precipitate until the end of solidification, leading to an a priori less advantageous distribution.
- Chromium is essentially used to obtain good resistance to oxidation thanks to the passivated oxide layer which it forms on the surface of the metal. It also has a beneficial influence on the mechanical behavior 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 sought-after gamma effect. Due to its price, it is limited to 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 high a content leads to the precipitation of embrittling carbides which are harmful to oxidation resistance. Its content in the compositions according to the invention is from 0.25 to 0.35% by weight, preferably from 0.25 to 0.32%.
- Nitrogen is a highly gammagenic element which in particular allows the compositions according to the invention to remain in the austenitic range by delaying the precipitation of the intermetallic phases. Its content is however limited due to the difficulties encountered in introducing it into steel compositions due to its low solubility limit in liquid steel. Its content is from 0.5 to 0.7%, preferably from 0.61 to 0.7% by weight. These contents also correspond to the quasi-saturation at equilibrium of the liquid metal at conventional processing temperatures, which is an advantage, because this addition is then easy with the usual means known to those skilled in the art.
- Niobium in addition to its carburogenic properties which are favorable for mechanical resistance to heat, makes it possible to obtain the eutectic previously described.
- Its content in the compositions according to the invention is 1.75 to 2.50%, preferably 1.90 to 2.30% by weight.
- the silicon is limited to a content of 0.30% by weight at most, although it improves the resistance to oxidation, because it is strongly sigmagenic and also lowers the solubility of nitrogen.
- the steel compositions according to the invention can be manufactured according to the methods applicable to the usual materials cited in reference, taking these characteristics into account.
- an electric furnace or an AOD reactor or any other means suitable for the production of steels containing high contents of the nitrogen alloy element, including secondary refining processes by slag remelting, may be used. electrically.
- the reflow can be done, for example, under slag with consumable electrode if one is looking for great inclusiveness.
- thermomechanical hot transformation process such as forging or rolling then by a softening treatment, which will preferably be carried out by maintaining at 1050-1 100 ° C for 1 to 16 hours. in air or in another fluid, which guarantees complete fine grain recrystallization and satisfactory ductility characteristics.
- the heat treatment for dissolving and recrystallization as well as the preheating of the products for manufacturing the valves may be carried out between 1100 and 1200 ° C; the higher temperatures bringing a grain magnification which remains limited.
- the stabilization heat treatment is intended to guarantee a certain structural and dimensional stability at the temperatures of use. It can be carried out, for example, in the form of a maintenance at 700-1000 ° C for 1 to 16 hours in air or in another fluid. In general, it is preferable to carry out this treatment at a temperature greater than or equal to the temperature of use of the part in service.
- valve steels being very strongly dependent on their thermal state
- the values which will be compared hereinafter are average values obtained for different thermal states of use all comprising a solution treatment at high temperature followed by '' aging at a lower temperature.
- the three grades A, B and C were previously treated by dissolving and aging at 850 ° C for 4 hours, while the reference steel grades were treated conventionally for each steel, which is favorable to them. in the comparison.
- the steel specimen is a 6 mm diameter cylinder on
Landscapes
- 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)
- Contacts (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
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 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1228253A1 true EP1228253A1 (fr) | 2002-08-07 |
EP1228253B1 EP1228253B1 (fr) | 2005-07-20 |
EP1228253B8 EP1228253B8 (fr) | 2005-09-21 |
Family
ID=8850073
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01931816A Expired - Lifetime EP1228253B8 (fr) | 2000-05-10 | 2001-05-07 | Composition d'acier, procede de fabrication et pieces formees dans ces compositions, en particulier soupapes |
Country Status (11)
Country | Link |
---|---|
US (1) | US6656418B2 (fr) |
EP (1) | EP1228253B8 (fr) |
JP (1) | JP5288674B2 (fr) |
AT (1) | ATE299953T1 (fr) |
AU (1) | AU5850901A (fr) |
BR (1) | BR0106337B1 (fr) |
DE (1) | DE60112032T2 (fr) |
ES (1) | ES2248325T3 (fr) |
FR (1) | FR2808807B1 (fr) |
MX (1) | MXPA02000345A (fr) |
WO (1) | WO2001086009A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3575430A1 (fr) * | 2018-05-30 | 2019-12-04 | Garrett Transportation I Inc. | Alliages d'acier inoxydable, composants de turbocompresseur formés à partir d'alliages d'acier inoxydable et procédés de fabrication associés |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 (fr) | 2015-08-05 | 2017-02-09 | Gerdau Investigacion Y Desarrollo Europa, S.A. | Acier faiblement allié à résistance élevée et à résistance élevée à l'oxydation à chaud |
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5040099B1 (fr) * | 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 |
-
2000
- 2000-05-10 FR FR0005967A patent/FR2808807B1/fr not_active Expired - Lifetime
-
2001
- 2001-05-07 ES ES01931816T patent/ES2248325T3/es not_active Expired - Lifetime
- 2001-05-07 BR BRPI0106337-5A patent/BR0106337B1/pt not_active IP Right Cessation
- 2001-05-07 US US10/030,860 patent/US6656418B2/en not_active Expired - Lifetime
- 2001-05-07 EP EP01931816A patent/EP1228253B8/fr not_active Expired - Lifetime
- 2001-05-07 AU AU58509/01A patent/AU5850901A/en not_active Abandoned
- 2001-05-07 DE DE60112032T patent/DE60112032T2/de not_active Expired - Lifetime
- 2001-05-07 JP JP2001582596A patent/JP5288674B2/ja not_active Expired - Lifetime
- 2001-05-07 AT AT01931816T patent/ATE299953T1/de active
- 2001-05-07 WO PCT/FR2001/001388 patent/WO2001086009A1/fr active IP Right Grant
- 2001-05-07 MX MXPA02000345A patent/MXPA02000345A/es active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO0186009A1 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3575430A1 (fr) * | 2018-05-30 | 2019-12-04 | Garrett Transportation I Inc. | Alliages d'acier inoxydable, composants de turbocompresseur formés à partir d'alliages d'acier inoxydable et procédés de fabrication associés |
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 |
Also Published As
Publication number | Publication date |
---|---|
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 (fr) | 2005-09-21 |
ES2248325T3 (es) | 2006-03-16 |
WO2001086009A1 (fr) | 2001-11-15 |
DE60112032D1 (de) | 2005-08-25 |
BR0106337B1 (pt) | 2014-09-30 |
ATE299953T1 (de) | 2005-08-15 |
EP1228253B1 (fr) | 2005-07-20 |
FR2808807A1 (fr) | 2001-11-16 |
JP5288674B2 (ja) | 2013-09-11 |
AU5850901A (en) | 2001-11-20 |
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