EP0638658A1 - Stickstoff enthaltendes martensitisches Stahl mit niedrigem Kohlenstoffgehalt und Verfahren zur Herstellung - Google Patents

Stickstoff enthaltendes martensitisches Stahl mit niedrigem Kohlenstoffgehalt und Verfahren zur Herstellung Download PDF

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Publication number
EP0638658A1
EP0638658A1 EP94401751A EP94401751A EP0638658A1 EP 0638658 A1 EP0638658 A1 EP 0638658A1 EP 94401751 A EP94401751 A EP 94401751A EP 94401751 A EP94401751 A EP 94401751A EP 0638658 A1 EP0638658 A1 EP 0638658A1
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EP
European Patent Office
Prior art keywords
weight
steel
nitrogen
content
carbon
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
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EP94401751A
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English (en)
French (fr)
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EP0638658B1 (de
Inventor
André F. Grellier
Patrick De Vernon
Jean-Yves A. Moraux
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.)
Aubert and Duval SA
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Industrielle De Metallurgie Avancee Sima SA 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
    • C22C38/24—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
    • C22C38/001—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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten

Definitions

  • the present invention relates to a low-carbon nitrogen nitrogen martensitic stainless steel and its manufacturing process.
  • this steel after tempering at 500/525 ° C which are necessary to undergo several types of thermochemical and / or thermophysical deposits, no longer makes it possible to obtain sufficient hardness and sees its resistance to corrosion at temperature room further decreased.
  • a martensitic stainless steel of high purity nitrogen is obtained, having a high hardness (HRC ⁇ 58 after heat treatment) and having a fine structure (grade ES 2299 W).
  • This steel also guarantees good reproducibility of the results in response to heat treatments as well as great structural and, consequently, dimensional stability, which makes this steel more particularly suitable for the manufacture of bearings.
  • the nitrogen content is between 0.18 and 0.23% by weight.
  • the carbon content is between 0.30 and 0.60% by weight.
  • the carbon + nitrogen content is between 0.55 and 0.80% by weight.
  • the Rockwell C hardness of the steel of the invention is greater than or equal to 58 HRC after heat treatment.
  • Another object of the invention is a process for manufacturing a martensitic stainless steel with nitrogen and low carbon content, comprising in particular steps of preparing a metal bath, refining this steel bath to the liquid state, of casting the steel into ingots and of thermomechanical transformation of the solidified ingots, characterized in that the carbon content in the liquid steel is lowered to values between 0.30 and 0, 60% of the total weight of the steel and an amount of nitrogen is added to it so that the solubility limit of the latter is not exceeded in liquid steel.
  • the total carbon and nitrogen content is adjusted to a value between 0.50 and 0.85% of the weight of the steel.
  • nitrogen is introduced in gaseous form into the liquid steel by bubbling.
  • nitrogen is introduced in solid form by nitrided charges.
  • the partial pressure of nitrogen exerted above the liquid steel is maintained at a value less than or equal to 1 bar.
  • a heat treatment is carried out after thermomechanical transformation comprising a step of heating prior to an austenitization temperature of between 1020 ° C. and 1070 ° C. followed by quenching and then a tempering cycle between 130 ° C. and 180 ° C for 2 hours.
  • a heat treatment of the ingots is carried out comprising a preliminary heating step at an austenitization temperature of between 1070 ° C. and 1120 ° C. followed by quenching and then a double tempering cycle. between 500 ° C and 525 ° C for 2 hours.
  • a cryogenic treatment is carried out at -80 ° C. after quenching and before tempering.
  • Yet another object of the invention lies in the use of the above steel to produce mechanical parts, ball bearings, surgical tools, or intended for the chemical, food industries for the transformation of plastics.
  • the steel of the invention has a low concentration of coarse carbides and also offers the possibility of being treated with tempering temperatures up to 500 ° C. in order to have a hardness greater than or equal to 58 HRC in order to allow the performing thermochemical and / or thermophysical surface treatments and use in mechanical elements working up to around 450 ° C.
  • the chromium content was fixed between 14 and 17% by weight and the molybdenum at a value of 1-2.5% by weight. . Their action is reinforced by the presence of nitrogen.
  • the purpose of adding vanadium to less than 1% by weight is to limit softening during tempering and to promote the secondary hardening necessary for obtaining high hardness when this treatment is carried out at around 500 ° C.
  • the balance between all of the constituents has been determined so as to limit the residual austenite content, to a value of less than 10% by volume in order to respond to the concerns of manufacturers, in particular of bearings, to guarantee very good repeatability of response to heat treatments as well as great structural and therefore dimensional stability.
  • composition of the steel of the invention is thus adjusted within the following limits (the% being by weight): Carbon 0.30-0.60% Silicon ⁇ 0.50% Manganese ⁇ 0.70% Nickel ⁇ 0.50% Chromium 14-17% Molybdenum 1.00-2.50% Vandadium 0.10-0.70% or better 0.20-0.60% Nitrogen 0.15-0.24% or better 0.18-0.23% Carbon + nitrogen 0.50-0.85% or better 0.55-0.80%
  • the balance is made up of iron and conventional residues linked to the method of production.
  • FIG. 3 symbolizes an ingot transformed into a billet with the location of the five sampling zones used for the chemical analyzes, the results of which appear in Tables 1 and 2.
  • the addition of nitrogen is carried out directly in the bath constituted by the steel in the liquid state, by conventional means of the bubbling type for the introduction in gaseous form or of the nitrided charges type for the solid form.
  • the ingots were transformed into 150 x 135 mm billets then into bars of diameters 90 mm, 24 mm and 14 mm.
  • Annealing treatments are then carried out on all diameters, according to the ranges provided.
  • the manufacturing controls are then carried out as described below.
  • the chemical composition is checked on the billet from samples representative of various zones of the initial ingot (see Tables 1 and 2 and Figure 3).
  • the intermediate areas MT, M and MP are the intermediate areas MT, M and MP.
  • the hardness noted on the diameters of 90 mm, 24 mm and 14 mm is uniform.
  • HV50 192 - 212 for casting A HV50 207 - 229 for casting B.
  • Austenitization has always been followed by oil quenching and cryogenic treatment at -75 / -80 ° C before tempering, with the aim of eliminating the residual austenite as much as possible. Voluntarily studying tempering temperatures has been limited to two reduced temperature zones corresponding to two areas of steel use:
  • Double cycle tempering of 500-525 ° C / 2 h this tempering allows considering the use of steel up to service temperatures of 450 ° C and makes it possible to carry out thermochemical and / or thermophysical treatments requiring processing temperatures up to 500 ° C.
  • the size of the carbides observed on the two ends of the 90 mm diameter bars reaches 35 ⁇ m for the coarsest, in the case of casting A and 40 ⁇ m in the case of casting B.
  • FIGS. 1 and 2 represent the micrographic structures of the steel of casting B, respectively at x100 and x500 magnification. This structure was photographed at mid-ray after heat treatment first comprising a step at 1050 ° C for 30 min in oil, then at -80 ° C for 2 h and finally at 180 ° C for 2 h at 1 'air.
  • the toughness was determined on the steel of casting B, having the least favorable structure, after treatment with double tempering at 500-525 ° C.
  • the values of K1C (critical stress coefficient) obtained are as follows: 22 to 25 MPa.m 1/2 .
  • K1C critical stress coefficient
  • the hardness HRC ⁇ 58 was obtained by heat treatment with tempering at 130-180 ° C. The tests were carried out in parallel under the same conditions with the reference steel 1% carbon - 17% chromium - 0.5% molybdenum treated for HRC ⁇ 58 by quenching and tempering at 150 ° C.
  • Reference steel pitting with some "spots" of corrosion products around the pitting (level 8).
  • Casting B no trace of corrosion (level 10).
  • Potentiokinetic electrochemical test in a non-chlorinated medium This test takes place in an aqueous solution of sulfuric acid at 1% by weight, deaerated by bubbling argon.
  • the test piece of the steel to be tested is polarized for 15 min at 550 mV relative to the potential of the saturated calomel electrode (E.C.S.). Then there is a back and forth potentiokinetic scan between -550 and +500 mV / DHW with a scanning speed of 60 mV / min.
  • the criterion used to characterize the corrosion resistance is the value of the current density at the reactivation peak of the return curve.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Heat Treatment Of Articles (AREA)
  • Catalysts (AREA)
EP94401751A 1993-08-11 1994-07-29 Stickstoff enthaltendes martensitisches Stahl mit niedrigem Kohlenstoffgehalt und Verfahren zur Herstellung Expired - Lifetime EP0638658B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9309858A FR2708939B1 (fr) 1993-08-11 1993-08-11 Acier martensitique à l'azote à faible teneur en carbone et son procédé de fabrication.
FR9309858 1993-08-11

Publications (2)

Publication Number Publication Date
EP0638658A1 true EP0638658A1 (de) 1995-02-15
EP0638658B1 EP0638658B1 (de) 1998-09-30

Family

ID=9450117

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EP94401751A Expired - Lifetime EP0638658B1 (de) 1993-08-11 1994-07-29 Stickstoff enthaltendes martensitisches Stahl mit niedrigem Kohlenstoffgehalt und Verfahren zur Herstellung

Country Status (6)

Country Link
EP (1) EP0638658B1 (de)
AT (1) ATE171731T1 (de)
DE (1) DE69413632T2 (de)
DK (1) DK0638658T3 (de)
ES (1) ES2123735T3 (de)
FR (1) FR2708939B1 (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0694622A1 (de) * 1994-06-29 1996-01-31 BÖHLER YBBSTALWERKE Ges.m.b.H. Korrosionbeständige Legierung und Verfahren zur Herstellung korrosionsbeständiger Schneidwaren
EP0721995A2 (de) * 1995-01-16 1996-07-17 BÖHLER Edelstahl GmbH Verwendung einer Eisenbasislegierung für Kunststofformen
EP0710731A3 (de) * 1994-11-04 1996-11-27 Boehler Edelstahl Verwendung einer stickstoffhältigen Eisenbasislegierung für Maschinenteile, welche auf gleitende Flächenreibung beansprucht sind
DE19924515A1 (de) * 1999-05-28 2000-11-30 Edelstahl Witten Krefeld Gmbh Sprühkompaktierter Stahl, Verfahren zu seiner Herstellung und Verbundwerkstoff
EP1201775A1 (de) * 2000-10-24 2002-05-02 Böhler Edelstahl GmbH & Co KG Verfahren zur Herstellung zylindrischer Hohlkörper und Verwendung derselben
EP1238118A2 (de) * 1999-12-02 2002-09-11 ATI Properties, Inc. Martensitischer rostfreier stahl und stahlherstellungsprozess
EP1304393A1 (de) * 2000-07-17 2003-04-23 Kabushiki Kaisha Riken Kolbenring mit ausgezeichneter beständigkeit gegen reibung, rissbildung und ermüdung und herstellungsverfahren dafür und kombination von kolbenriing und zylinderblock
WO2005093112A1 (en) * 2004-03-26 2005-10-06 Sandvik Intellectual Property Ab Steel alloy for cutting details
DE102004051629A1 (de) * 2004-10-23 2006-04-27 Stahlwerk Ergste Westig Gmbh Rostfreier martensitischer Chromstahl
EP2159295A3 (de) * 2008-09-01 2011-04-20 MINEBEA Co., Ltd. Martensitischer Edelstahl und Wälzlager damit
WO2016146857A1 (fr) * 2015-04-30 2016-09-22 Aperam Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produit
JP2019196530A (ja) * 2018-05-11 2019-11-14 株式会社デンソー マルテンサイト系ステンレス鋼
CN115109891A (zh) * 2022-07-14 2022-09-27 中北大学 一种高碳高铬含氮马氏体不锈钢及其碳化物细化方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000337389A (ja) 1999-03-19 2000-12-05 Nsk Ltd 転がり軸受
JP4441947B2 (ja) 1999-05-20 2010-03-31 日本精工株式会社 転がり軸受

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB741935A (en) * 1952-08-22 1955-12-14 Hadfields Ltd Improvements in alloy steels
FR1140573A (fr) * 1956-01-25 1957-07-29 Birmingham Small Arms Co Ltd Aciers ferritiques au chrome
US3165400A (en) * 1961-06-27 1965-01-12 Chrysler Corp Castable heat resisting iron alloy
LU67301A1 (fr) * 1972-03-28 1973-07-27 Ugine Aciers Nouvelles applications d'aciers a haute frequence
DE3901470C1 (en) * 1989-01-19 1990-08-09 Vereinigte Schmiedewerke Gmbh, 4630 Bochum, De Cold-working steel and its use

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB741935A (en) * 1952-08-22 1955-12-14 Hadfields Ltd Improvements in alloy steels
FR1140573A (fr) * 1956-01-25 1957-07-29 Birmingham Small Arms Co Ltd Aciers ferritiques au chrome
US3165400A (en) * 1961-06-27 1965-01-12 Chrysler Corp Castable heat resisting iron alloy
LU67301A1 (fr) * 1972-03-28 1973-07-27 Ugine Aciers Nouvelles applications d'aciers a haute frequence
GB1417337A (en) * 1972-03-28 1975-12-10 Ugine Aciers Rolling mill roll or bearing members from high strength steels
DE3901470C1 (en) * 1989-01-19 1990-08-09 Vereinigte Schmiedewerke Gmbh, 4630 Bochum, De Cold-working steel and its use

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0694622A1 (de) * 1994-06-29 1996-01-31 BÖHLER YBBSTALWERKE Ges.m.b.H. Korrosionbeständige Legierung und Verfahren zur Herstellung korrosionsbeständiger Schneidwaren
EP0710731A3 (de) * 1994-11-04 1996-11-27 Boehler Edelstahl Verwendung einer stickstoffhältigen Eisenbasislegierung für Maschinenteile, welche auf gleitende Flächenreibung beansprucht sind
EP0721995A2 (de) * 1995-01-16 1996-07-17 BÖHLER Edelstahl GmbH Verwendung einer Eisenbasislegierung für Kunststofformen
EP0721995A3 (de) * 1995-01-16 1996-11-27 Boehler Edelstahl Verwendung einer Eisenbasislegierung für Kunststofformen
CN1068073C (zh) * 1995-01-16 2001-07-04 博哈里尔特种钢有限公司 铁基合金用于塑料模具的用途
DE19924515A1 (de) * 1999-05-28 2000-11-30 Edelstahl Witten Krefeld Gmbh Sprühkompaktierter Stahl, Verfahren zu seiner Herstellung und Verbundwerkstoff
EP1626097A1 (de) * 1999-12-02 2006-02-15 ATI Properties, Inc. Procédé de fabrication d'acier
EP1238118A2 (de) * 1999-12-02 2002-09-11 ATI Properties, Inc. Martensitischer rostfreier stahl und stahlherstellungsprozess
EP1238118A4 (de) * 1999-12-02 2003-06-25 Ati Properties Inc Martensitischer rostfreier stahl und stahlherstellungsprozess
EP1304393A1 (de) * 2000-07-17 2003-04-23 Kabushiki Kaisha Riken Kolbenring mit ausgezeichneter beständigkeit gegen reibung, rissbildung und ermüdung und herstellungsverfahren dafür und kombination von kolbenriing und zylinderblock
EP1304393A4 (de) * 2000-07-17 2005-08-03 Riken Kk Kolbenring mit ausgezeichneter beständigkeit gegen reibung, rissbildung und ermüdung und herstellungsverfahren dafür und kombination von kolbenriing und zylinderblock
EP1201775A1 (de) * 2000-10-24 2002-05-02 Böhler Edelstahl GmbH & Co KG Verfahren zur Herstellung zylindrischer Hohlkörper und Verwendung derselben
US7181847B2 (en) 2000-10-24 2007-02-27 Boehler Edelstahl Gmbh & Co. Kg Process for manufacturing a cylindrical hollow body and hollow body made thereby
WO2005093112A1 (en) * 2004-03-26 2005-10-06 Sandvik Intellectual Property Ab Steel alloy for cutting details
JP2007530784A (ja) * 2004-03-26 2007-11-01 サンドビック インテレクチュアル プロパティー アクティエボラーグ 細部切削用鋼
AU2005226606B2 (en) * 2004-03-26 2010-04-08 Sandvik Intellectual Property Ab Steel alloy for cutting details
CN100463996C (zh) * 2004-03-26 2009-02-25 山特维克知识产权股份有限公司 用于切割零件的合金钢
WO2006045383A1 (de) * 2004-10-23 2006-05-04 Stahlwerk Ergste Westig Gmbh Rostfreier martensitischer chromstahl
DE102004051629B4 (de) * 2004-10-23 2006-08-24 Stahlwerk Ergste Westig Gmbh Rostfreier martensitischer Chromstahl
DE102004051629A1 (de) * 2004-10-23 2006-04-27 Stahlwerk Ergste Westig Gmbh Rostfreier martensitischer Chromstahl
EP2159295A3 (de) * 2008-09-01 2011-04-20 MINEBEA Co., Ltd. Martensitischer Edelstahl und Wälzlager damit
US8591673B2 (en) 2008-09-01 2013-11-26 Minebea Co., Ltd. Martensitic stainless steel and antifriction bearing using the same
WO2016146857A1 (fr) * 2015-04-30 2016-09-22 Aperam Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produit
WO2016174500A1 (fr) * 2015-04-30 2016-11-03 Aperam Acier inoxydable martensitique, procédé de fabrication d'un demi-produit en cet acier et outil de coupe réalisé à partir de ce demi-produit
CN107567507A (zh) * 2015-04-30 2018-01-09 艾普伦 马氏体不锈钢、由该钢制造半成品的方法及由半成品制成的切削工具
JP2019196530A (ja) * 2018-05-11 2019-11-14 株式会社デンソー マルテンサイト系ステンレス鋼
WO2019216145A1 (ja) * 2018-05-11 2019-11-14 株式会社デンソー マルテンサイト系ステンレス鋼
US11560613B2 (en) 2018-05-11 2023-01-24 Denso Corporation Martensitic stainless steel
CN115109891A (zh) * 2022-07-14 2022-09-27 中北大学 一种高碳高铬含氮马氏体不锈钢及其碳化物细化方法

Also Published As

Publication number Publication date
DE69413632T2 (de) 1999-05-12
EP0638658B1 (de) 1998-09-30
FR2708939A1 (fr) 1995-02-17
DK0638658T3 (da) 1999-06-21
ATE171731T1 (de) 1998-10-15
DE69413632D1 (de) 1998-11-05
FR2708939B1 (fr) 1995-11-03
ES2123735T3 (es) 1999-01-16

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