EP0638658B1 - Acier martensitique à l'azote à faible teneur en carbone et son procédé de fabrication - Google Patents

Acier martensitique à l'azote à faible teneur en carbone et son procédé de fabrication Download PDF

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Publication number
EP0638658B1
EP0638658B1 EP94401751A EP94401751A EP0638658B1 EP 0638658 B1 EP0638658 B1 EP 0638658B1 EP 94401751 A EP94401751 A EP 94401751A EP 94401751 A EP94401751 A EP 94401751A EP 0638658 B1 EP0638658 B1 EP 0638658B1
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EP
European Patent Office
Prior art keywords
weight
steel
nitrogen
fact
content
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.)
Expired - Lifetime
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EP94401751A
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German (de)
English (en)
French (fr)
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EP0638658A1 (fr
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
Original Assignee
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 martensitic stainless steel with nitrogen and low carbon as well as its manufacturing process.
  • the vanadium content is between 0.20 and 0.70%.
  • a martensitic stainless steel is obtained with high purity nitrogen with high hardness (HRC ⁇ 58 after treatment thermal) and having a fine structure (grade ES 2299 W).
  • HRC ⁇ 58 after treatment thermal high hardness
  • grade ES 2299 W fine structure
  • the nitrogen content is understood 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 size of the carbides is less than or equal to 40 ⁇ m.
  • Another object of the invention is a method of manufacturing a steel stainless martensitic with nitrogen and low carbon content, comprising in particular steps for preparing a metal bath, for refining this bath by steel in the liquid state, casting of steel into ingots and processing thermomechanics of solidified ingots, characterized in that the content of carbon in liquid steel up to values between 0.30 and 0.60% of the total weight of the steel and add a quantity of nitrogen such that it does not exceed not the solubility limit of the latter in liquid steel.
  • the total content of carbon and nitrogen at a value between 0.50 and 0 85% of the weight of the steel.
  • the nitrogen is introduced under gas form in liquid steel by bubbling.
  • nitrogen is introduced in the form solid by nitrided charges.
  • the partial pressure of nitrogen exerted above the liquid steel at a value less than or equal to 1 bar.
  • thermomechanical heat treatment including a step of pre-heating to an austenitization temperature between 1020 ° C and 1070 ° C followed by quenching and then a tempering cycle between 130 ° C and 180 ° C for 2 hours.
  • thermomechanical after transformation thermomechanical, we carry out a heat treatment of the ingots comprising a step of heating prior to a temperature austenitization between 1070 ° C and 1120 ° C followed by quenching then a double tempering cycle between 500 ° C and 525 ° C for 2 hours.
  • cryogenic treatment it is carried out after quenching and before tempering, cryogenic treatment at -80 ° C.
  • Yet another object of the invention lies in the use of the previous steel to make mechanical parts, bearings ball, surgical tools, or intended for the chemical industries, food 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 of up to 500 ° C to present a hardness greater than or equal to 58 HRC to allow the realization thermochemical and / or thermophysical surface treatments and employment in mechanical elements working up to approximately 450 ° C.
  • the chromium content has been fixed between 14 and 17% by weight and molybdenum at a value of 1-2.5% by weight. Their action is enhanced by the presence of nitrogen.
  • the purpose of adding vanadium to less than 1% by weight is to limit softening during income and promote secondary hardening necessary to obtain a high hardness when this treatment is carried out towards 500 ° C.
  • the balance between all of the constituents was determined by so as to limit the residual austenite content to a value of less than 10% by volume to meet the concerns of manufacturers, especially bearings, guarantee a very good repeatability of response to heat treatments as well that a great structural stability and, consequently, dimensional.
  • composition of the steel of the invention is thus adjusted within the following limits (the% being by weight): Silicon ⁇ 0.50% Manganese ⁇ 0.70% Nickel ⁇ 0.50% Chromium 14-17% Molybdenum 1.00-2.50% Vanadium 0.20-less than 1% or better 0.20-0.70% and preferably 0.2 to 0.6% Nitrogen 0.15-0.24% or better 0.18-0.23% Carbon + nitrogen 0.50-0.85% or better 0.55-0.80% and preferably carbon 0.30 - 0.60
  • the balance is made up of iron and conventional residues linked to the mode of elaboration.
  • Figure 3 symbolizes an ingot transformed into a billet with location of the five sampling zones used for chemical analyzes, the results are shown in Tables 1 and 2.
  • ESR Electro Slag Remelting reflow Preparation in an electric oven and remelting under slag by consumable electrode (ESR Electro Slag Remelting reflow) are conducted under controlled conditions.
  • the ingots obtained are healthy, without shrinkage or puffiness.
  • Hot processing operations were carried out according to processes identical to those usually carried out with steels from the same family.
  • the ingots were transformed into 150 x 135 mm billets then into diameter bars 90 mm, 24 mm and 14 mm.
  • Annealing treatments are then performed on all diameters, according to the ranges provided.
  • the manufacturing controls are then carried out from the as described below.
  • the chemical composition is checked on the billet from representative samples from various areas of the initial ingot (see Tables 1 and 2 and Figure 3).
  • the hardness noted on the diameters of 90 mm, of 24 mm and 14 mm is homogeneous.
  • Austenitization has always been followed by oil quenching and a cryogenic treatment at -75 / -80 ° C before tempering, in order to to eliminate as much as possible the residual austenite. Voluntarily studying tempering temperatures was limited to two temperature zones reduced 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 both ends of bars with a diameter of 90 mm reaches 35 ⁇ m for the coarsest, in the case of casting A and 40 ⁇ m in the case of casting B.
  • Figures 1 and 2 show the micrographic structures of steel from casting B, respectively at x100 and x500 magnification. This structure was photographed at mid-radius after treatment thermal first comprising a step at 1050 ° C for 30 min at oil, then at -80 ° C for 2 h and finally at 180 ° C for 2 h in 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
  • HRC hardness ⁇ 58 was obtained by heat treatment with tempering at 130-180 ° C. The trials were conducted in parallel in the same conditions with the reference steel 1% carbon - 17% chromium - 0.5% molybdenum treated for HRC ⁇ 58 by quenching and tempering 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 non-medium chloride This test takes place in an aqueous solution of sulfuric acid at 1% by weight, deaerated by bubbling argon.
  • the test tube 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 it is done a round trip potentiokinetic scan between -550 and +500 mV / DHW with a scanning speed of 60 mV / min.
  • Casting B I ⁇ 20 ⁇ A / cm 2 (i.e. at the measurement threshold).

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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 Acier martensitique à l'azote à faible teneur en carbone et son procédé de fabrication Expired - Lifetime EP0638658B1 (fr)

Applications Claiming Priority (2)

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

Publications (2)

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

Family

ID=9450117

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94401751A Expired - Lifetime EP0638658B1 (fr) 1993-08-11 1994-07-29 Acier martensitique à l'azote à faible teneur en carbone et son procédé de fabrication

Country Status (6)

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

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT401387B (de) * 1994-06-29 1996-08-26 Boehler Ybbstalwerke Korrosionsbeständige legierung und verfahren zur herstellung korrosionsbeständiger schneidwaren
AT402224B (de) * 1994-11-04 1997-03-25 Boehler Edelstahl Verwendung einer eisenbasislegierung sowie plungerkolben und kolbenring
AT405193B (de) * 1995-01-16 1999-06-25 Boehler Edelstahl Verwendung einer chromhältigen, martensitischen eisenbasislegierung für kunststofformen
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
DE19924515A1 (de) * 1999-05-28 2000-11-30 Edelstahl Witten Krefeld Gmbh Sprühkompaktierter Stahl, Verfahren zu seiner Herstellung und Verbundwerkstoff
US6273973B1 (en) * 1999-12-02 2001-08-14 Ati Properties, Inc. Steelmaking process
JP4724275B2 (ja) * 2000-07-17 2011-07-13 株式会社リケン 耐スカッフィング性、耐クラッキング性及び耐疲労性に優れたピストンリング及びその製造方法
AT413195B (de) * 2000-10-24 2005-12-15 Boehler Edelstahl Verfahren zur herstellung zylindrischer hohlkörper und verwendung derselben
SE526805C8 (sv) * 2004-03-26 2006-09-12 Sandvik Intellectual Property Stållegering
DE102004051629B4 (de) * 2004-10-23 2006-08-24 Stahlwerk Ergste Westig Gmbh Rostfreier martensitischer Chromstahl
JP5368887B2 (ja) 2008-09-01 2013-12-18 ミネベア株式会社 マルテンサイト系ステンレス鋼および転がり軸受
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
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
CN115109891B (zh) * 2022-07-14 2022-12-20 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

Family Cites Families (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
FR2178319A5 (fr) * 1972-03-28 1973-11-09 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

Also Published As

Publication number Publication date
DE69413632T2 (de) 1999-05-12
FR2708939B1 (fr) 1995-11-03
FR2708939A1 (fr) 1995-02-17
EP0638658A1 (fr) 1995-02-15
ES2123735T3 (es) 1999-01-16
DE69413632D1 (de) 1998-11-05
DK0638658T3 (da) 1999-06-21
ATE171731T1 (de) 1998-10-15

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