EP1087029A2 - Verbesserte Stahlzusammensetzung - Google Patents

Verbesserte Stahlzusammensetzung Download PDF

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Publication number
EP1087029A2
EP1087029A2 EP00107561A EP00107561A EP1087029A2 EP 1087029 A2 EP1087029 A2 EP 1087029A2 EP 00107561 A EP00107561 A EP 00107561A EP 00107561 A EP00107561 A EP 00107561A EP 1087029 A2 EP1087029 A2 EP 1087029A2
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EP
European Patent Office
Prior art keywords
steel
nickel
nitrogen
chromium
manganese
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.)
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Application number
EP00107561A
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English (en)
French (fr)
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EP1087029A3 (de
Inventor
Stuart David c/o Heymark Metals Ltd. Wardall
John Edwin c/o Heymark Metals Limited Fryer
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Heymark Metals Ltd
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Heymark Metals Ltd
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Filing date
Publication date
Application filed by Heymark Metals Ltd filed Critical Heymark Metals Ltd
Publication of EP1087029A2 publication Critical patent/EP1087029A2/de
Publication of EP1087029A3 publication Critical patent/EP1087029A3/de
Withdrawn legal-status Critical Current

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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
    • C22C38/001—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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten

Definitions

  • This invention relates to an improved austenitic stainless steel composition which is comparatively ductile, has good corrosion resistance, has adequate biocompatibility, is readily cold worked to produce a product with excellent strength and ductility, machineability and is non magnetic under all conditions and more particularly to a steel which contains essentially no nickel.
  • the standard well known austenitic stainless steels containing generally 16-20% of chromium, 8-15% of nickel and 2-4% of molybdenum, are used in a wide variety of applications where their properties of good corrosion resistance, high strength, ductility and non-magnetic properties are well known.
  • nickel is an essential alloying element and it has become necessary to test patients for nickel allergy prior to an operation. Those patients found to give a positive response to the test must then have an implant made from nickel free materials which traditionally have inferior properties to the austenitic grades, limiting the choice to the significantly more expensive titanium and cobalt alloys.
  • Austenitic stainless steels represent the largest group of stainless steels in use.
  • the term "Austenitic” refers to the atomic structure of the alloy at room temperature which in this case is arranged in the form of a face centred cube (FCC).
  • FCC face centred cube
  • BCC body centred cube
  • Another object of the invention is to provide such an austenitic stainless steel which readily lends itself to hot working and cold working into a wide variety of products such as bars, rods, wires, plates and strip, which can be further fabricated to products of ultimate use by such processes as bending, coiling, cold drawing, machining, threading, cutting, polishing and the like.
  • a further object is to provide a stainless steel which is fully austenitic at room and cryogenic temperatures, is substantially free from ferrite, is paramagnetic, exhibits good corrosion resistance particularly in respect of chlorides, and can be provided in a wide variety of strength levels in excess of the standard austenitic stainless steels but retaining good ductility.
  • the present invention provides an austenitic stainless steel having as essential alloying elements: 0 to 0.15% of carbon, 0 to 0.3% of silicon, 12 to 25% of manganese, 12 to 20% of chromium, 0 to 2.4% of molybdenum, 0.3 to 0.55% of nitrogen, and from 0 to 10% of cobalt, 0 to 0.9% of copper, all percentages being percentages by weight, the remainder being iron together with incidental impurities and a concentration of nickel or less than 0.050%.
  • Particular preferred austenitic stainless steels in accordance with this invention are those in which the contents of alloying elements are: carbon 0 to 0.09%, silicon 0 to 0.3%, manganese 14 to 15%, chromium 16 to 18%, molybdenum 2.0 to 2.4%, nitrogen 0.45 to 0.55%, nickel 0.048% maximum.
  • the steel composition has amounts of Mn at 15% and Cr at 17%.
  • the most preferred composition is
  • austenite stabilisation may be aided by the addition of cobalt up to a maximum of 10% plus a small copper addition up to 0.9%.
  • the elements cobalt and copper will usually be present in incidental amounts which are not detrimental. Their concentration may be increased from the incidental level to a higher level to improve the properties of the steels of the invention.
  • molybdenum To further enhance corrosion resistance and provide a steel with a similar level of corrosion resisting elements to those currently in use for medical and cosmetic applications, a minimum level of the rust resisting element molybdenum was considered essential.
  • molybdenum One drawback of the addition of molybdenum is that, like chromium, this element also has ferrite forming properties. In combination chromium and molybdenum represent a chromium equivalent of 20% which requires a nickel equivalent of 14% to maintain a fully austenitic structure.
  • a high manganese content is desirable as it exhibits good austenite forming properties and is a relatively cheap and a readily available element. Too much manganese however can promote the formation of ferrite at hot working temperatures which may be retained after rapid cooling to room temperature. This would be undesirable as the alloy would exhibit some ferromagnetic tendencies. Carbon is a very strong austenite stabiliser but above approximately 0.15% it is very difficult to prevent the formation of undesirable chromium carbides which can render the steel brittle and can reduce corrosion resistance by precipitation at the steel grain boundaries.
  • Nitrogen like carbon is also a very potent austenite stabiliser; unfortunately, being a gas, the element has little solubility in steel especially during melting at temperatures of typically 1500 - 1600°C.
  • researchers have developed metal re-melting techniques which can be performed at pressures well above atmospheric pressure and under these conditions high concentrations of nitrogen can be introduced.
  • this equipment is expensive and unwieldy as it must produce significant positive pressure differentials above the furnace, and it was considered preferential to provide an alloy which could be manufactured using conventional and readily available furnaces. Consequently by careful adjustment of chromium manganese and molybdenum (all of which promote solubility of nitrogen) a composition was derived which would allow nitrogen solubility of typically 0.55% at normal atmospheric pressures. The careful adjustment has resulted in the claimed steel composition, and it is only within the ranges provided in the claim that Nitrogen can be forced to dissolve in the molten alloy to such a degree which prevents the formation of ferritic steel components at room temperature.
  • This level of nitrogen is also beneficial in terms of corrosion resistance as it has been shown that when present in combination with molybdenum a significant improvement in corrosion resistance can result.
  • the corrosion resistance of the steel according to the invention has been measured several ways with the aim of demonstrating an equivalence to the standard 316-type of chromium, nickel, molybdenum austenitic stainless steel.
  • Figure 2 shows the resistance to acid attack on the steel compared with the medical implant grade of 316-type stainless steel and the lower 302-type chromium, nickel austenitic stainless steel.
  • Short samples of wire were exposed to three mineral acids (hydrochloric, sulphuric, and nitric) at a concentration of 1% and a constant temperature of 80°C for periods of up to 42 days. The weight losses were measured and a corrosion rate in grammes/cm 2 /year calculated.
  • hydrochloric acid 316-type had a corrosion rate some 10 times higher whilst 302-type suffered up to almost 100 times more weight loss.
  • the test conducted was an Agar Overlay Assay cytotoxicity test using L929 cells according to British Standard EN30993-5:1994 and ISO 10993-5:1992. The alloy passed the test and was found to be non-cytotoxic.
  • austenite stabilisation may be aided by the addition of cobalt up to a maximum of 10% plus a small copper addition up to 0.9%.
  • a preferred composition contains carbon 0 to 0.09%, silicon 0 to 0.3%, manganese 14 to 15%, chromium 16 to 18%, molybdenum 2.0 to 2.4%, nitrogen 0.45 to 0.55%, nickel 0.048% maximum, with the remaining percentage being made up of iron.
  • other elements for example silicon for deoxidation, may be desirable in small quantities and traces of other elements present as impurities may be contained in the new steel without detriment.
  • the invention relates to a steel composition which is substantially free of nickel and which can be used for medical implants and/or jewellery manufacture.
  • Nickel is an important constituent of surgical grade steel because it is a good austenite promoter, and steel thus formed has good strength properties and has paramagnetic characteristics which are essential for such steels.
  • the absence of Nickel results in the formation of ferritic steel which is ferromagnetic, which cannot be used for medical implants.
  • the invention results from the realisation that Nitrogen is a good promoter of austenitic steel structures, and although Nitrogen is a gas and thus generally insoluble in molten steel, a careful balance of additional alloying elements such as Manganese, Chromium, and Molybdenum, with Iron can result in a molten alloy in which Nitrogen can be dissolved at atmospheric pressure to a degree at which its austenitic steel structure promotion effects are readily appreciable.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
EP00107561A 1999-09-27 2000-04-07 Verbesserte Stahlzusammensetzung Withdrawn EP1087029A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9922757.1A GB9922757D0 (en) 1999-09-27 1999-09-27 Improved steel composition
GB9922757 1999-09-27

Publications (2)

Publication Number Publication Date
EP1087029A2 true EP1087029A2 (de) 2001-03-28
EP1087029A3 EP1087029A3 (de) 2001-05-16

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EP00107561A Withdrawn EP1087029A3 (de) 1999-09-27 2000-04-07 Verbesserte Stahlzusammensetzung

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EP (1) EP1087029A3 (de)
GB (2) GB9922757D0 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010102601A1 (de) * 2009-03-10 2010-09-16 Max-Planck-Institut Für Eisenforschung GmbH Korrosionsbeständiger austenitischer stahl
US8356380B2 (en) 2003-04-22 2013-01-22 Curaden International Ag Interdental brush
EP2617839A1 (de) * 2012-01-18 2013-07-24 MeKo Laserstrahl-Materialbearbeitungen e.K. Nickelfreie Eisenlegierung für Stents
CN103233174A (zh) * 2013-04-26 2013-08-07 中国科学院金属研究所 一种血管支架用高氮奥氏体不锈钢及其应用
CN103374685A (zh) * 2012-04-23 2013-10-30 钢铁研究总院 一种不锈钢材料及其制造方法
CN104878316A (zh) * 2014-02-27 2015-09-02 南京理工大学 一种高强韧高氮奥氏体不锈钢
WO2021254143A1 (zh) * 2020-06-19 2021-12-23 香港大学 一种高强度超耐腐蚀无磁不锈钢及其制备方法
EP4316727A1 (de) 2022-08-05 2024-02-07 Outokumpu Oyj Füllmetall zum schweissen von ungleichartigen schweissungen

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200046831A (ko) * 2018-10-25 2020-05-07 주식회사 포스코 표면품질 및 응력부식균열 저항성이 우수한 극저온용 오스테나이트계 고 망간 강재 및 그 제조방법
WO2024056822A1 (en) 2022-09-14 2024-03-21 Danmarks Tekniske Universitet Methods for improving corrosion and wear resistance and strength of essentially nickel-free high-manganese austenitic stainless steel components

Family Cites Families (9)

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GB778597A (en) * 1955-02-15 1957-07-10 Ford Motor Co Improvements in or relating to the manufacture of nitrogen-rich wrought austenitic alloys
DE3143096A1 (de) * 1980-11-05 1982-05-19 General Electric Co., Schenectady, N.Y. "legierung auf eisenbasis, verfahren zu ihrer herstellung und damit hergestellte gegenstaende"
CA1205659A (en) * 1981-03-20 1986-06-10 Masao Yamamoto Corrosion-resistant non-magnetic steel and retaining ring for a generator made of it
JPS61238943A (ja) * 1985-04-15 1986-10-24 Kobe Steel Ltd 耐銹性の優れた高強度非磁性鋼
AT397968B (de) * 1992-07-07 1994-08-25 Boehler Ybbstalwerke Korrosionsbeständige legierung zur verwendung als werkstoff für in berührungskontakt mit lebewesen stehende teile
DE4242757C1 (de) * 1992-12-17 1994-03-24 Krupp Vdm Gmbh Verwendung einer korrosionsbeständigen Eisenbasislegierung für Gegenstände, die unter Hautkontakt am Körper getragen werden
DE19513407C1 (de) * 1995-04-08 1996-10-10 Vsg En & Schmiedetechnik Gmbh Verwendung einer austenitischen Stahllegierung für hautverträgliche Gegenstände
JP3845918B2 (ja) * 1996-10-09 2006-11-15 大同特殊鋼株式会社 生体用非磁性ステンレス鋼
ATE195767T1 (de) * 1997-04-29 2000-09-15 Boehler Edelstahl Gmbh & Co Kg Verwendung einer biokompatiblen hautverträglichen legierung

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8356380B2 (en) 2003-04-22 2013-01-22 Curaden International Ag Interdental brush
WO2010102601A1 (de) * 2009-03-10 2010-09-16 Max-Planck-Institut Für Eisenforschung GmbH Korrosionsbeständiger austenitischer stahl
CN104093862A (zh) * 2012-01-18 2014-10-08 Meko激光材料加工公司 用于支架的不含镍的铁合金
WO2013107730A1 (de) * 2012-01-18 2013-07-25 Meko Laserstrahl-Materialbearbeitungen E.K. Nickelfreie eisenlegierung für stents
EP2617839A1 (de) * 2012-01-18 2013-07-24 MeKo Laserstrahl-Materialbearbeitungen e.K. Nickelfreie Eisenlegierung für Stents
CN104093862B (zh) * 2012-01-18 2017-03-01 Meko激光材料加工公司 用于支架的不含镍的铁合金
CN103374685A (zh) * 2012-04-23 2013-10-30 钢铁研究总院 一种不锈钢材料及其制造方法
CN103374685B (zh) * 2012-04-23 2016-06-08 钢铁研究总院 一种不锈钢材料及其制造方法
CN103233174A (zh) * 2013-04-26 2013-08-07 中国科学院金属研究所 一种血管支架用高氮奥氏体不锈钢及其应用
CN103233174B (zh) * 2013-04-26 2015-06-10 中国科学院金属研究所 一种血管支架用高氮奥氏体不锈钢及其应用
CN104878316A (zh) * 2014-02-27 2015-09-02 南京理工大学 一种高强韧高氮奥氏体不锈钢
WO2021254143A1 (zh) * 2020-06-19 2021-12-23 香港大学 一种高强度超耐腐蚀无磁不锈钢及其制备方法
EP4316727A1 (de) 2022-08-05 2024-02-07 Outokumpu Oyj Füllmetall zum schweissen von ungleichartigen schweissungen
WO2024028438A1 (en) 2022-08-05 2024-02-08 Outokumpu Oyj Filler metal for welding of dissimilar welds

Also Published As

Publication number Publication date
GB9922757D0 (en) 1999-11-24
EP1087029A3 (de) 2001-05-16
GB2345491A (en) 2000-07-12
GB2345491B (en) 2000-12-06
GB0008103D0 (en) 2000-05-24

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