EP0446188B1 - Rostfreier Stahl - Google Patents

Rostfreier Stahl Download PDF

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Publication number
EP0446188B1
EP0446188B1 EP91850036A EP91850036A EP0446188B1 EP 0446188 B1 EP0446188 B1 EP 0446188B1 EP 91850036 A EP91850036 A EP 91850036A EP 91850036 A EP91850036 A EP 91850036A EP 0446188 B1 EP0446188 B1 EP 0446188B1
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EP
European Patent Office
Prior art keywords
steel alloy
weight
amount
alloy
strength
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
Application number
EP91850036A
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English (en)
French (fr)
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EP0446188A1 (de
Inventor
Hakan Holmberg
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Sandvik AB
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Sandvik AB
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Publication date
Application filed by Sandvik AB filed Critical Sandvik AB
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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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of 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

Definitions

  • the invention relates to a non-magnetic high strength stainless steel in which the austenite phase is sufficiently stable so as to resist transformation into the ferromagnetic phase martensite even at extended reduction for instance by cold rolling of strips or drawing of wire.
  • the very high strength achievable with this type of steel depends from the (para-magnetic) austenitic structure which during deformation transforms into the (ferromagnetic) martensite, a phase of exceptional hardness.
  • the amount of alloy elements is increased primarily of Ni and Mo such as in type SS 2343/2353 the tendency for the formation of deformation martensite is reduced but thereby has also the possibility of achieving high strength become limited.
  • US-A-4 689 190 discloses steel alloys which have some of the components within the same order of magnitude as the present invention. However, also these alloys are prohibitively magnetic for the purposes of the present invention.
  • the strictly controlled optimized composition (in weight-%) of the alloy of this invention comprises following analysis: C 0,04-0,25 Si 0,1-2 Mn 2-15 Cr 16-20, 37 Ni 8-14 N 0,10-1,5 V 0,1-2,5 the remainder being iron and normal impurities.
  • the amounts of alloy elements which are very critical, are governed by structural requirements which structure shall consist of an austenitic matrix with inclusions of vanadium nitrides.
  • the structure should not comprise any amounts of ferrite.
  • the austenite phase shall be sufficiently stable such that no significant portion thereof is transformed into ferromagnetic martensite at cooling from high temperature annealing or at substantial cold working, typically > 70 % thickness/reduction at cold rolling or corresponding degree of reduction at wire drawing.
  • the austenite phase shall during deformation exhibit a substantial cold hardening which results in that high mechanical strength is achieved without presence of ferromagnetic phase.
  • Of importance is also the possibility of additionally increasing the strength in the cold rolled condition by a simple heat treatment.
  • Carbon is an element which strongly contributes to austenite formation. Carbon also contributes to a stabilization of austenite against martensite transformation and it has consequently a double positive effect in this alloy. Carbon also positively contributes to the work hardenability at cold working. The carbon content should therefore exceed 0,04 %. High carbon amounts however leads to negative effects. The high chromium affinity results in an increased tendency for carbide precipitation with increased carbon content. This also leads to impaired corrosion properties embrittlement problems and a destabilization of the matrix which might lead to local martensite transformation which renders the material being partially ferromagnetic. The maximum content of C is therefore limited to 0,25 %, preferably below 0,20 %.
  • Si is an important element for the purpose of facilitating the manufacturing process.
  • the amount of Si should therefore be at least 0,1 %.
  • Si is however a ferrite stabilizer which rather drastically tends to increase the tendency for the formation of the ferromagnetic phase of ferrite.
  • High Si amounts additionally promote the tendency of precipitating easily melting intermetallic phases and thereby impairs the hot working.
  • the Si-content should therefore be limited to max 2 % preferably max 1,0 %.
  • Manganese has been found to contribute positively to several properties of the alloy of this invention. Mn stabilizes austenite without simultaneously negatively affecting the work hardening. Mn has the additional important ability of providing increased solubility of nitrogen, properties described more specifically hereunder, in melted and solid phase. The Mn content should therefore exceed 2 % and preferably exceed 4 %. Mn increases the coefficient of linear expansion and reduces electrical conductivity which could be of disadvantage for applications within electronics and computer areas. High amounts of Mn also reduce corrosion resistance in chloride containing environments. Mn is also much less efficient than nickel as a corrosion reducing element under oxidizing corrosion conditions. The Mn content should therefore not exceed 15 % and should preferably amount to 4-10 %, and more preferably 4,0-7,5 %.
  • Cr is an important alloy element from several aspect. Cr content should be high in order to achieve good corrosion resistance. Cr also increases nitrogen solubility in the melt and in the solid phase and thereby enables increased alloyed presence of nitrogen. Increased Cr content also contributes to stabilized austenite phase towards martensite transformation.
  • the alloy of the present invention can, to advantage, as described below be subject of precipitation hardening and precipitate high chromium containing nitrides. In order to reduce the tendency for too strong local reduction of Cr-content with non-stabilization and reduction in corrosion resistance the Cr content should exceed 16 %.
  • Cr is a ferrite stabilizing element presence of very high Cr contents will lead to the presence of ferromagnetic ferrite.
  • the Cr content should therefore be equal to or less than 20,37 %.
  • Ni is, next after carbon and nitrogen, the most efficient austenite stabilizing element Ni also increases austenite stability towards deformation into martensite.
  • Ni is also, in contrast of Mn, known for efficiently contributing to corrosion resistance under oxidizing conditions.
  • Ni is, however, an expensive alloy element at the same time as it has a negative impact on work hardening during cold working.
  • the Ni-content should exceed 8 %.
  • the Ni-content should not exceed 14 %, preferably not exceed 12 % but preferably exceed 9 %.
  • N is a central alloy element in the present alloy.
  • N is a strong austenite former, it promotes solution hardening and stabilizes the austenite phase strongly towards deformation into martensite.
  • N is also of advantage for the purpose of achieving increased work hardening at cold working and it acts as a precipitation hardening element at heat treatment. Nitrogen can therefore contribute to a further increase of the cold rolled strength.
  • Chromium nitrides precipitated during heat treatment also appear to be less sensibilizing than corresponding chromium carbides.
  • the N content should not be less than 0,10 %, preferably not less than 0,15 %.
  • the N content should therefore be equal to or less than 1,5 %, and preferably amount to max 0,6 %, more preferably 0,2-0,5 %.
  • Vanadium is an element having several positive effects. Vanadium increases the solubility of nitrogen and contributes to the formation of vanadium nitrides which promotes fine grain formation during heat treatment. By optimizing the heat treatment the mechanical properties can also be improved by precipitation hardening.
  • the content of V should be at least 0,1 %, preferably higher than 0,25 %. is also a ferrite stabilizing element and its content should therefore not exceed 2,5 %, preferably max 2,0 %.
  • Production of the testing materials included melting in a high-frequency induction furnace and casting to ingots at about 1600°C. These ingots were heated to about 1200°C and hot worked by forging the material into bars. The materials were then subject of hot rolling into strips which hereafter were quench annealed and clean pickled. The quench annual was carried out at 1080°-1120°C and quenching occurred in water.
  • the strips obtained after quench annealing were then cold rolled to various reduction degrees after which test samples were taken out for various tests. In order to avoid variations in temperature and its possible impact on magnetic properties the samles were cooled to room temperature after each cold rolling step.
  • Table 1 The chemical analysis of the testing materials in weight-% appears from Table 1 below: Table 1. Chemical analysis, in weight-%, of testing materials. Steel No. C Si Mn Cr Ni N V 875* .20 .56 4.20 18.03 8.97 0.29 0.94 876* .058 .54 5.06 20.37 10.00 0.40 1.57 877* .018 .60 13.1 19.20 9.00 0.42 1.64 879* .057 .51 2.15 20.03 12.03 0.30 0.51 900* .014 .64 14.0 19.1 9.10 0.51 1.01 880** .052 .89 3.82 20.25 10.01 0.29 - 866** .11 .83 1.49 18.79 9.47 0.20 - AISI** 304 .034 .59 1.35 18.56 9.50 0.17 - AISI** 305 .042 .42 1.72 18.44 11.54 0.036 - * alloys of the invention ** comparison samples P,S ⁇ 0.030 weight-% is valid
  • test alloys fulfill the requirement of being free from ferrite and martensite in quench annealed condition.
  • the annealed hardness is somewhat higher than that of the reference materials AISI 304/305.
  • Alloy AISI 305 appears to have a substantially slower work hardening due to its low amounts of interstitially dissolved alloy elements, i.e. nitrogen and carbon, combined with rather high nickel content.
  • Spring steel of the type SS 2331 are often annealed for the purpose of achieving an additional increase of the mechanical properties. This contributes favorably to several important spring properties such as fatigue strength and relaxation resistance and the ability of forming this material in a rather soft condition. The higher ductility at lower strength can hereby be used favorably to a more specific formation of the material.
  • Table 5 shows the effects of such annealing upon the mechanical properties after 75 % cold reduction.
  • the annealing tests gave as result an optimal effect at a temperature of 450/500°C and 2 hours maintenance.
  • Table 5 Yield point, ultimate strength and elongation after annealing 450/500°C/ 2h at 75 % cold reduction.
  • the figures in parenthesis indicate the change in percentage of strength values as a result of such anneal. Steel No.
  • the alloys of this invention appear to have obtained a very good effect as a result of the anneal. It is of specific importance to notice the extremely high increase in R p 0,05 value of 45-55 %. This is the value that is best correlated with the elastic limit which is an indication of how much a spring can be loaded without being subject of plastification. By having reached such an increase in the R p 0,05 value a larger work area can be used for a spring made of such material. It is of specific interest to notice the rather minor increase in ultimate strength in AISI 304 and AISI 305. This is an essential disadvantage since the ultimate strength by experience is the value that is best correlated with the fatigue strength.
  • a material according to this invention it is the objective to achieve the objective of a high strength material at the same time as the material exhibits para-magnetic behaviour, i.e. a magnetic permeability very close to 1.
  • Table 6 discloses the magnetic permeability depending upon field strength the various alloys after 75 % cold reduction and annealing at 450/500 % / 2 hours.
  • Table 6 discloses that by cold working and precipitation hardening of an alloy of the invention it is possible, by strictly controlling the composition in cold rolled and precipitation hardened condition, to obtain a strength exceeding 1800 or even 1900 MPa combined with a very low value of the magnetic permeability 1,002-1,025.
  • the inventive alloy thus enables using the property advantages given by a high strength for spring applications at the same time as the material is able to preserve its para-magnetic structure and thereby be useful in applications where a magnetic inert material is desired.
  • the reference materials outside the composition ranges of this invention have lower values for both its mechanical properties and the effect of precipitation treatment while the magnetic permeability is higher. This is relevant for commercial alloys AISI 304/305.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Glass Compositions (AREA)
  • Catalysts (AREA)
  • Hard Magnetic Materials (AREA)

Claims (9)

  1. Ausscheidungshärtbare, nichtmagnetische kaltbearbeitete Stahllegierung mit hoher Festigkeit, dadurch gekennzeichnet, daß sie aus den folgenden Elementen in Gewichtsprozenten besteht: C 0,04 - 0,25 % Si 0,1 - 2 % Mn 2 - 15 % Cr 16 bis 20,37 % Ni 8 bis 14 % N 0,10 bis 1,5 % V 0,1 bis 2,5 %,
    wobei der Rest aus Eisen und normalen Verunreinigungen besteht und die Stahllegierung eine magnetische Permeabilität von 1,025 oder weniger bei einer Feldstärke zwischen 50 unmd 700 Oersted hat, selbst wenn sie einer Kaltbearbeitung bis zu 75 %iger Dickenreduktion unterzogen wird.
  2. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Hartbearbeitung bis zu einer >70 %igen Dickenreduktion erfolgt.
  3. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Stickstoffmenge 0,15 bis 0,6 Gew.% beträgt.
  4. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Kohlenstoffmenge 0,04 bis 0,20 Gew.% beträgt.
  5. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Siliciummenge 0,1 bis 1 Gew.% beträgt.
  6. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Manganmenge 4 bis 10, vorzugsweise 4 bis 7,5 Gew.% beträgt.
  7. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Nickelmenge 9 bis 12 Gew.% beträgt.
  8. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Vanadinmenge 0,25 bis 2 Gew.% beträgt.
  9. Stahllegierung nach Anspruch 1, dadurch gekennzeichnet, daß die Stickstoffmenge 0,2 bis 0,5 Gew.% beträgt.
EP91850036A 1990-02-26 1991-02-13 Rostfreier Stahl Expired - Lifetime EP0446188B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9000673A SE506886C2 (sv) 1990-02-26 1990-02-26 Vanadinlegerat utskiljningshärdbart omagnetiskt austenitiskt stål
SE9000673 1990-02-26

Publications (2)

Publication Number Publication Date
EP0446188A1 EP0446188A1 (de) 1991-09-11
EP0446188B1 true EP0446188B1 (de) 1997-12-03

Family

ID=20378678

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91850036A Expired - Lifetime EP0446188B1 (de) 1990-02-26 1991-02-13 Rostfreier Stahl

Country Status (6)

Country Link
EP (1) EP0446188B1 (de)
JP (1) JP3169978B2 (de)
KR (1) KR100190442B1 (de)
AT (1) ATE160827T1 (de)
DE (1) DE69128293T2 (de)
SE (1) SE506886C2 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5217111A (en) * 1992-05-15 1993-06-08 General Electric Company Screw retainer for a molded case circuit breaker movable contact arm arrangement
FR2698104B1 (fr) * 1992-11-19 1995-02-03 Creusot Loire Acier inoxydable contenant du vanadium.
JPH0817733B2 (ja) * 1993-12-16 1996-02-28 株式会社丸エム製作所 被服用ハンガーの金属部品
SE506550C2 (sv) * 1994-11-02 1998-01-12 Sandvik Ab Användning av ett omagnetiskt, rostfritt stål vid supraledande lågtemperaturapplikationer
JP4337268B2 (ja) * 2001-02-27 2009-09-30 大同特殊鋼株式会社 耐食性に優れた高硬度マルテンサイト系ステンレス鋼
EP1605072B1 (de) 2003-03-20 2012-09-12 Sumitomo Metal Industries, Ltd. Nichtrostender stahl für hochdruckwasserstoffgas, behülter und einrichtungen, die den stahl enthalten
EP1605073B1 (de) * 2003-03-20 2011-09-14 Sumitomo Metal Industries, Ltd. Verwendung einer austenitischer nichtrostender stahl
WO2004111285A1 (ja) 2003-06-10 2004-12-23 Sumitomo Metal Industries, Ltd. 水素ガス用オーステナイトステンレス鋼とその製造方法
US20090129967A1 (en) * 2007-11-09 2009-05-21 General Electric Company Forged austenitic stainless steel alloy components and method therefor
JP5667504B2 (ja) * 2011-04-14 2015-02-12 日本高周波鋼業株式会社 非磁性ステンレス鋼
KR101304657B1 (ko) 2011-06-30 2013-09-05 주식회사 포스코 극저온 인성이 우수한 용접이음부
WO2014133058A1 (ja) 2013-02-28 2014-09-04 日新製鋼株式会社 オーステナイト系ステンレス鋼板およびそれを用いた高弾性限非磁性鋼材の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3592634A (en) * 1968-04-30 1971-07-13 Armco Steel Corp High-strength corrosion-resistant stainless steel

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE865604C (de) * 1940-11-03 1953-02-02 Eisen & Stahlind Ag Stahllegierung fuer Gegenstaende, die eine grosse Dauerstandfestigkeit haben muessen
DE934836C (de) * 1942-07-19 1955-11-03 Eisen & Stahlind Ag Verwendung von Stahllegierungen als Werkstoff fuer Maschinenteile, die bei hohen Temperaturen beansprucht werden, insbesondere Ventilteile fuer Verbrennungsmotoren
GB936872A (en) * 1959-09-18 1963-09-18 Allegheny Ludlum Steel Improvements in or relating to a process of heat treating austenitic stainless steel and austenitic stainless steels whenever prepared by the aforesaid process
SE364996B (de) * 1971-07-21 1974-03-11 Uddeholms Ab
US4689198A (en) * 1984-02-09 1987-08-25 Kabushiki Kaisha Kobe Seiko Sho Austenitic stainless steel with high corrosion resistance and high strength when heat treated

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3592634A (en) * 1968-04-30 1971-07-13 Armco Steel Corp High-strength corrosion-resistant stainless steel

Also Published As

Publication number Publication date
EP0446188A1 (de) 1991-09-11
SE506886C2 (sv) 1998-02-23
SE9000673L (sv) 1991-08-27
SE9000673D0 (sv) 1990-02-26
DE69128293T2 (de) 1998-03-26
KR910021491A (ko) 1991-12-20
ATE160827T1 (de) 1997-12-15
DE69128293D1 (de) 1998-01-15
JP3169978B2 (ja) 2001-05-28
KR100190442B1 (ko) 1999-06-01
JPH0598391A (ja) 1993-04-20

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