EP2728028B1 - Nickel-free stainless-steel alloy - Google Patents

Nickel-free stainless-steel alloy Download PDF

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Publication number
EP2728028B1
EP2728028B1 EP12191101.0A EP12191101A EP2728028B1 EP 2728028 B1 EP2728028 B1 EP 2728028B1 EP 12191101 A EP12191101 A EP 12191101A EP 2728028 B1 EP2728028 B1 EP 2728028B1
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Prior art keywords
maximum value
valeur
minimum value
value
nickel
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EP12191101.0A
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English (en)
French (fr)
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EP2728028A1 (de
Inventor
Jean-François DIONNE
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Swatch Group Research and Development SA
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Swatch Group Research and Development SA
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Priority to EP12191101.0A priority Critical patent/EP2728028B1/de
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to US14/425,455 priority patent/US20150225820A1/en
Priority to JP2015533640A priority patent/JP5976945B2/ja
Priority to PCT/EP2013/071770 priority patent/WO2014067795A1/fr
Priority to RU2015120760A priority patent/RU2625363C2/ru
Priority to CN201380057112.4A priority patent/CN104769145B/zh
Priority to EP13785379.2A priority patent/EP2914759B1/de
Priority to TW102138458A priority patent/TWI586816B/zh
Publication of EP2728028A1 publication Critical patent/EP2728028A1/de
Priority to HK15112788.4A priority patent/HK1211992A1/xx
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Publication of EP2728028B1 publication Critical patent/EP2728028B1/de
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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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
    • 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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G—PHYSICS
    • G04—HOROLOGY
    • G04G—ELECTRONIC TIME-PIECES
    • G04G17/00—Structural details; Housings
    • G04G17/02—Component assemblies
    • G—PHYSICS
    • G04—HOROLOGY
    • G04G—ELECTRONIC TIME-PIECES
    • G04G17/00—Structural details; Housings
    • G04G17/08—Housings

Definitions

  • the invention relates to a stainless steel alloy having a base of iron and chromium.
  • the invention also relates to a watch component made of such an alloy.
  • the invention relates to the fields of watchmaking, jewelery, and jewelery, in particular for structures: watch cases, squares, turntables, bracelets, rings, earrings and others.
  • Stainless steels are commonly used in the fields of watchmaking, jewelery, and jewelery, especially for structures: watch cases, casebacks, turntables, bracelets, and others.
  • Nickel is, however, a basic component of most common stainless steels because it improves mechanical properties and ductility, malleability and resilience. By cons nickel is harmful in the field of friction surfaces. Nickel improves the properties of the passive layer, and integrates with the surface layer of oxide.
  • alloy X2CrNiMo17-12 EN (or 316L AISI) comprises between 10.5 and 13% of nickel. Nickel is a metal whose cost is growing continuously, and which, in 2012, is close to 20'000 USD per ton, which increases the cost of alloys containing it.
  • Nickel-free stainless steel alloys are known which are ferritic steels with a cubic centered structure. However, these ferritic steels are not hardenable by heat treatment, but only by hardening. Their structure is not very fine, and this family of alloys is not very suitable for polishing.
  • Austenitic steels of face-centered cubic structure, generally have very good forming properties, which is particularly advantageous for watchmaker or jeweler-type components. They have a very high chemical resistance. They are also non-magnetic because of their face-centered cubic structure. They are also the most suitable for welding. But conventional austenitic stainless steels still contain from 3.5 to 32% of nickel, and more commonly from 8.0 to 15.0% of nickel. Indeed, nickel is a gammagene element which makes it possible to obtain the austenitic structure, and in particular to obtain sheets capable of forming deformations. Some documents, such as FR 2,534,931 on behalf of CABOT CORPORATION go so far as to say that nickel must be present to favor an austenitic structure in the alloy.
  • the gamma loop of the iron-chromium system specific to stainless steels defines an austenitic domain, even with a low or zero nickel content, but the loop is of very limited magnitude compared to that of alloys containing nickel. in higher proportion. In addition, this austenitic domain exists at temperatures much higher than ambient. The effect of the gammagenic alloy elements is twofold since it also makes it possible to widen the austenitic loop in chemical composition (relative to chromium) and to widen the temperature range on which this structure is stable.
  • Austeno-ferritic steels also called duplex, are weak magnetic, and generally comprise between 3.5% and 8% nickel.
  • the nickel-free stainless steels are mainly ferritic steels
  • the advantages of the austenitic steels, which are generally cataloged as nickel steels, should be available.
  • gammagens such as nickel, manganese or nitrogen are generally used (these are called super-austenitic steels for the last two mentioned), which increase the range of stability of austenite. Theoretically it would therefore be possible to use a super-austenitic steel with manganese or nitrogen in place of nickel.
  • the patent EP 1 025 273 B1 on behalf of SIMA describes such a nickel-free austenitic stainless steel, comprising 15 to 24% manganese, 15 to 20% chromium, 2.5 to 4% molybdenum, 0.6 to 0.85% d nitrogen, 0.1 to 0.5% vanadium, less than 0.5% copper, less than 0.5% cobalt, less than 0.5% for total niobium and tantalum, less than 0.06% of carbon, other elements each limited to 0.020% by weight, the balance being iron, and the compositions of certain metals being limited to each other by means of a system of equations and inequalities, which regulate the contents of chromium, molybdenum, nitrogen, vanadium, niobium, and manganese.
  • the invention also relates to a watch or jewelery component made of such an alloy.
  • the invention proposes to produce stainless steels without nickel, which have properties similar to those of austenitic stainless steels with nickel.
  • nickel-free alloy will be referred to below as an alloy comprising less than 0.5% by weight of nickel.
  • the alloy comprises, in addition to a base consisting of iron and chromium, at least one filler metal selected from a first group consisting of copper, ruthenium, rhodium, palladium and rhenium. , osmium, iridium, platinum, and gold.
  • the alloy comprises, in addition to a base consisting of iron, carbon and chromium, at least one filler metal chosen from a subset of the first set consisting of ruthenium, rhodium, palladium, rhenium, osmium, iridium, and platinum.
  • these metals are part of PGM (platinum group metals) or platinoids, that is to say that they are characterized by common and unusual properties for metals.
  • PGM platinum group metals
  • platinoids that is to say that they are characterized by common and unusual properties for metals.
  • These PGM group metals are also more soluble in iron than copper and gold.
  • a suitable (mass) composition is 18% chromium, 35% palladium, and 46 to 47% iron. Like all stainless steel, this alloy can contain up to 0.03% carbon.
  • its mass composition is 18% chromium, 35% palladium, 0% to 0.03% carbon, and the iron supplement. More particularly, its mass composition is 18% chromium, 35% palladium, and 46.97 to 47% iron, and 0 to 0.03% carbon.
  • the figure 2 is a Schaeffler diagram, which has on the abscissa an equivalent chromium, and on the ordinate a nickel equivalent, both in percentage by mass.
  • This Schaeffler diagram delimits the ferritic, martensitic and austenitic domains, the latter limited by the curve corresponding to the zero ferrite content.
  • So-called stainless steels are, according to current standards, those containing more than 10.5% of chromium.
  • the curves C1 and C2 delimit the possible presence of austenite A: above C1 and C2 we have austenite A, underneath there is none.
  • the curve C3 delimits the possible presence of ferrite F: below C3 there is ferrite F, above there is none.
  • the curve C4 delimits the possible presence of martensite M: below C4 there is martensite M, above there is none.
  • the composition must be such that one is both above the C3 and C4 curves, so as to have only austenite A.
  • a first variant of the invention consists in incorporating into the alloy, in the limit of 0.5% by weight of the total, at least one carburigenic element taken from a second group consisting of tungsten, vanadium, niobium and zirconium. , and titanium, replacing an equivalent mass of iron in the alloy.
  • This incorporation of one or more carburigenic elements has the effect of forcing the precipitation of specific carbides less harmful to the corrosion resistance than chromium carbides.
  • the invention also relates to a watch or jewelery component made of such an alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Adornments (AREA)
  • Heat Treatment Of Steel (AREA)
  • Soft Magnetic Materials (AREA)

Claims (5)

  1. Rostfreie Stahllegierung auf der Basis von Eisen und Chrom, dadurch gekennzeichnet, dass sie weniger als 0,5 Massen-% Nickel enthält und in einer flächenzentrierten kubischen austenitischen Struktur angeordnet ist und dass sie in Massenwerten besteht aus:
    - Chrom: Minimalwert 16 %, Maximalwert 20 %,
    - mindestens einem Zusatzmetall, wobei der Gesamtwert des mindestens einen Zusatzmetalls oder der Zusatzmetalle im folgenden Bereich liegt: Minimalwert 30 %, Maximalwert 40 %, wobei das mindestens eine Zusatzmetall aus einer ersten Menge gewählt ist, die aus Kupfer, Ruthenium, Rhodium, Palladium, Rhenium, Osmium, Iridium, Platin und Gold besteht:
    - wobei der Wert von Kupfer im folgenden Bereich liegt: Minimalwert 0 %, Maximalwert 2 %;
    - wobei der Wert von Gold im folgenden Bereich liegt: Minimalwert 0 %, Maximalwert 2 %;
    - Kohlenstoff: Minimalwert 0 %, Maximalwert 0,03 %;
    - Molybdän: Minimalwert 0 %, Maximalwert 2 %;
    - Mangan: Minimalwert 0 %, Maximalwert 2 %;
    - Silicium: Minimalwert 0 %, Maximalwert 1 %;
    - Stickstoff: Minimalwert 0 %, Maximalwert 0,1 %;
    - wobei innerhalb des Grenzwerts von 0,5 % der Gesamtmasse mindestens ein karbidbildendes Element, das einer zweiten Menge entnommen ist, die aus Wolfram, Vanadium, Niob, Zirkonium und Titan besteht, eine entsprechende Masse an Eisen in der Legierung ersetzt;
    - Eisen und unvermeidbare Verunreinigungen: die Vervollständigung auf 100 %.
  2. Legierung nach Anspruch 1, dadurch gekennzeichnet, dass mindestens ein Zusatzmetall aus einer Teilmenge der ersten Menge, den sogenannten Platinoiden, gewählt ist, wobei die Teilmenge der Platinoiden aus Ruthenium, Rhodium, Palladium, Rhenium, Osmium, Iridium und Platin besteht.
  3. Legierung nach Anspruch 2, dadurch gekennzeichnet, dass das mindestens eine Zusatzmetall ausschließlich aus der Teilmenge der Platinoiden gewählt ist.
  4. Legierung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es in Massenwerten besteht aus:
    - Chrom: 18 %;
    - Palladium: 35 %;
    - Kohlenstoff: 0 % bis 0,03 %;
    - Eisen und unvermeidbaren Verunreinigungen: die Vervollständigung auf 100 %.
  5. Uhren- oder Schmuckkomponente, die aus einer Legierung nach einem der vorhergehenden Ansprüche gebildet ist.
EP12191101.0A 2012-11-02 2012-11-02 Nickel-free stainless-steel alloy Active EP2728028B1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP12191101.0A EP2728028B1 (de) 2012-11-02 2012-11-02 Nickel-free stainless-steel alloy
JP2015533640A JP5976945B2 (ja) 2012-11-02 2013-10-17 ニッケルフリーステンレス鋼合金
PCT/EP2013/071770 WO2014067795A1 (fr) 2012-11-02 2013-10-17 Alliage d'acier inoxydable sans nickel
RU2015120760A RU2625363C2 (ru) 2012-11-02 2013-10-17 Нержавеющая сталь, не содержащая никеля
US14/425,455 US20150225820A1 (en) 2012-11-02 2013-10-17 Nickel free stainless steel alloy
CN201380057112.4A CN104769145B (zh) 2012-11-02 2013-10-17 无镍的不锈钢合金
EP13785379.2A EP2914759B1 (de) 2012-11-02 2013-10-17 Nickel-free stainless-steel alloy
TW102138458A TWI586816B (zh) 2012-11-02 2013-10-24 不含鎳之不鏽鋼合金
HK15112788.4A HK1211992A1 (en) 2012-11-02 2015-12-29 Nickel-free stainless steel alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP12191101.0A EP2728028B1 (de) 2012-11-02 2012-11-02 Nickel-free stainless-steel alloy

Publications (2)

Publication Number Publication Date
EP2728028A1 EP2728028A1 (de) 2014-05-07
EP2728028B1 true EP2728028B1 (de) 2018-04-04

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EP12191101.0A Active EP2728028B1 (de) 2012-11-02 2012-11-02 Nickel-free stainless-steel alloy
EP13785379.2A Active EP2914759B1 (de) 2012-11-02 2013-10-17 Nickel-free stainless-steel alloy

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Application Number Title Priority Date Filing Date
EP13785379.2A Active EP2914759B1 (de) 2012-11-02 2013-10-17 Nickel-free stainless-steel alloy

Country Status (8)

Country Link
US (1) US20150225820A1 (de)
EP (2) EP2728028B1 (de)
JP (1) JP5976945B2 (de)
CN (1) CN104769145B (de)
HK (1) HK1211992A1 (de)
RU (1) RU2625363C2 (de)
TW (1) TWI586816B (de)
WO (1) WO2014067795A1 (de)

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EP3147378A1 (de) * 2015-09-25 2017-03-29 The Swatch Group Research and Development Ltd. Nickelfreier austenitischer edelstahl
CN106636947A (zh) * 2016-12-16 2017-05-10 安徽宝恒新材料科技有限公司 一种耐海水腐蚀不锈钢及其制作方法
EP3486009B1 (de) * 2017-11-17 2024-01-17 The Swatch Group Research and Development Ltd Sinterverfahren für einen austenitischen edelstahl
RU2650949C1 (ru) * 2017-11-27 2018-04-18 Юлия Алексеевна Щепочкина Сталь для изготовления ювелирных изделий
RU2650947C1 (ru) * 2017-11-27 2018-04-18 Юлия Алексеевна Щепочкина Сталь для изготовления ювелирных изделий
RU2663501C1 (ru) * 2018-01-09 2018-08-07 Юлия Алексеевна Щепочкина Сплав на основе железа

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Also Published As

Publication number Publication date
TW201432064A (zh) 2014-08-16
HK1211992A1 (en) 2016-06-03
US20150225820A1 (en) 2015-08-13
EP2914759B1 (de) 2016-10-05
JP2015535888A (ja) 2015-12-17
JP5976945B2 (ja) 2016-08-24
RU2015120760A (ru) 2016-12-27
CN104769145A (zh) 2015-07-08
RU2625363C2 (ru) 2017-07-13
WO2014067795A1 (fr) 2014-05-08
EP2728028A1 (de) 2014-05-07
CN104769145B (zh) 2016-10-19
TWI586816B (zh) 2017-06-11
EP2914759A1 (de) 2015-09-09

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