EP3147380A1 - Nickelfreier austenitischer edelstahl - Google Patents

Nickelfreier austenitischer edelstahl Download PDF

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EP3147380A1
EP3147380A1 EP16174780.3A EP16174780A EP3147380A1 EP 3147380 A1 EP3147380 A1 EP 3147380A1 EP 16174780 A EP16174780 A EP 16174780A EP 3147380 A1 EP3147380 A1 EP 3147380A1
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nickel
stainless steel
nitrogen
austenitic stainless
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EP3147380B1 (de
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Joël Porret
Guido Plankert
Tommy Carozzani
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Swatch Group Research and Development SA
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    • 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
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
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    • C21D6/00—Heat treatment of ferrous alloys
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    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn

Definitions

  • the present invention relates to nickel-free austenitic stainless steel compositions. More specifically, the present invention relates to nickel-free austenitic stainless steels particularly well suited for use in the fields of watchmaking and jewelery.
  • the nickel-free austenitic stainless steel compositions are of interest for applications in the field of watchmaking and jewelery because they are non-magnetic and hypoallergenic.
  • These nickel-free austenitic stainless steels are mainly based on Fe-Cr-Mn-Mo-CN elements. Indeed, to replace the nickel which guarantees the austenitic structure, it has been proposed to use elements such as manganese, nitrogen and carbon. These elements, however, have the effect of increasing certain mechanical properties such as the hardness, yield strength and strength of the resulting alloys, which makes it very difficult to shape the parts by machining and forging which are usual operations in the field of manufacturing components for watchmaking and jewelery.
  • compositions proposed by Berns and Gavriljuk can be obtained by performing the melting and solidification of the atmospheric pressure alloy elements but have high concentrations of manganese, carbon and nitrogen, in order to maximize the properties. mechanical. This results in shaping by machining and forging very difficult. In addition, the high concentration of manganese is unfavorable from the point of view of corrosion resistance.
  • compositions are particularly intended for use in the production of parts that can be in contact with the human body (wristwatches, jewelry, medical prostheses).
  • Examples of nickel-free austenitic stainless steels that can be used to produce parts coming into contact with the human body are disclosed by the European patent EP 875 591 B1 in the name of Böhler Brass GmbH.
  • the compositions disclosed in this document exhibit in particular high concentrations of molybdenum, in order to obtain a corrosion resistance allowing the use of these alloys in the medical field.
  • compositions are disclosed in particular in the European patent application. EP 2 455 508 A1 . Nevertheless, despite their low concentration in these compositions have high concentrations of carbon and nitrogen, resulting again in shaping by difficult machining and forging. By removing molybdenum, it is possible to reduce the carbon and nitrogen concentration while producing the alloy at atmospheric pressure, as disclosed in US Patent Application US 2013/0149188 A1 , but the corrosion resistance is then no longer sufficient for applications in the field of watchmaking and jewelery.
  • Nitrogen and carbon are the only elements capable of completely offsetting the absence of nickel.
  • these gammagenic elements have the effect of considerably increasing the hardness of the resulting austenitic steels by solid insertion solution, making very difficult the shaping operations such as machining and stamping such steels, particularly in the fields of watchmaking and jewelery.
  • the effect of nitrogen is even more marked than that of carbon with regard to the hardness of the resulting austenitic steel. Its concentration must therefore be as low as possible. Nevertheless, a minimum nitrogen level is necessary to obtain a totally austenitic structure because, unlike nitrogen, carbon alone does not make it possible to obtain a austenitic structure without precipitates. However, these precipitates are detrimental in terms of polishing ability and corrosion resistance of austenitic steels.
  • Manganese favors only the austenitic structure. Its presence is nevertheless essential in order to increase the solubility of the nitrogen and thus to guarantee the obtaining of a completely austenitic nickel-free structure. In fact, the more manganese is added, the higher the solubility of the nitrogen. However, manganese adversely affects the corrosion resistance of austenitic steels and is also responsible for increasing the hardness of austenitic steels. Manganese is therefore detrimental in terms of machinability and forgeability properties of the resulting steels.
  • the presence of a small quantity of molybdenum is essential because it makes it possible to achieve a sufficient corrosion resistance as defined by the salt spray test from the ISO 9227 standard. Indeed, as shown with alloys 1.3816 and 1.3815, chromium alone does not make it possible to obtain sufficient corrosion resistance of the cladding parts in watchmaking. It is therefore necessary to also have some molybdenum which many studies have proven to improve the corrosion resistance of the resulting austenitic steels. In addition, the corrosion resistance increases with the nitrogen content as long as it is in solid solution. However, it is necessary to limit the concentration of molybdenum and chromium alloys because these elements favor the ferritic structure to the detriment of the austenitic structure. Therefore, to compensate for the effects of molybdenum and chromium, it would be necessary to increase the concentration of the alloy in elements such as nitrogen or carbon, which would go against the properties of machinability and forgeability of the alloys. .
  • the first possibility consists in imposing a nitrogen overpressure during casting or remelting, for example using techniques known under the English names Pressurized Induction Melting or Pressure ElectroSlag Remelting. This makes it possible to increase the amount of nitrogen in the liquid alloy beyond the solubility at ambient atmospheric pressure, thus being able to limit or even prevent the formation of ferrite during solidification.
  • the formation of pores is made more difficult because of the overpressure applied to the alloy which solidifies.
  • the use of these techniques greatly increases the price of the alloys obtained, especially because the production facilities are expensive.
  • the second possibility to avoid or limit the formation of porosity during the solidification of the alloy is to judiciously select the elements involved in the composition of the alloy, for example by increasing the concentrations of gammagens (C, Mn, Cu) and / or by reducing the concentrations of alphagenes (Cr, Mo) and / or by increasing the concentrations of elements that increase the solubility of nitrogen (Mn, Cr, Mo).
  • Some elements have opposite effects, but not necessarily in the same proportions. Thus, completely austenitic solidification avoiding the release of nitrogen by ferrite formation is possible at ambient atmospheric pressure, or even lower.
  • the other technique that can be used to manufacture nickel-free austenitic steel components uses powder metallurgy, for example by injection molding, a technique also known by the Anglo-Saxon name Metal Injection Molding or MIM. In this case, it is not necessary to use a 100% austenitic powder, since nitrogen can be added during sintering, thus transforming the ferrite residue into austenite.
  • compositions of a nickel-free austenitic stainless steel whose forming operations are facilitated, which exhibit sufficient corrosion resistance, and which can be obtained by conventional metallurgy (foundry) in particular at ambient atmospheric pressure or by metallurgy of powders.
  • sufficient resistance to corrosion is meant sufficient strength for the fields of watchmaking and jewelery as defined in particular by the salt spray test (ISO 9227).
  • the nickel-free stainless steel contains at least one of S, Pb, B, Bi, P, Te, Se, Nb, V, Ti, Zr, Hf, Ce, Ca , Co, Mg which can each be present with a mass concentration of up to 1%.
  • a nickel-free austenitic stainless steel is understood to mean an alloy containing not more than 0.5% by mass percentage of nickel.
  • Potential impurities means elements that are not intended to modify one (or more) properties of the alloy, but whose presence is unavoidable because of the melting process. In particular in the field of watchmaking and jewelery, it is necessary to limit the presence of these impurities to the maximum, since these impurities can in particular form in the alloy non-metallic inclusions such as oxides, sulfides and silicones. silicates which may have adverse consequences on the corrosion resistance and the polishing ability of the resulting alloys.
  • the mass concentration of the molybdenum must be less than 2.5%. Indeed, the presence of molybdenum is necessary because it promotes the resistance of the resulting steels to corrosion, in particular the resistance to pitting corrosion. It is, however, necessary to limit the concentration of molybdenum to small quantities because molybdenum has the disadvantage of favoring the ferritic structure. Consequently, the higher the molybdenum concentration, the more elements such as nitrogen, carbon and manganese which favor the austenitic structure must be added, but which have the disadvantage of making the resulting alloy harder and therefore less easy machinable and forgeable.
  • the mass concentration of the copper must be greater than 0.5% and less than 4%.
  • the copper which, in the prior art, is considered as an impurity is added voluntarily in the compositions according to the invention, in particular because the copper favors the austenitic structure and thus makes it possible to limit the concentration of nitrogen and carbon.
  • the presence of copper improves the resistance of alloys to generalized corrosion and intrinsically promotes the machinability and forging ability of the alloys according to the invention.
  • the copper concentration must however be limited to 4% because the copper tends to weaken the steel at high temperature, which can make thermomechanical treatments difficult.
  • the manganese concentration of the alloys according to the invention must be greater than 10% and less than 20%. It is known that manganese promotes the solubility of nitrogen in nickel-free austenitic stainless steel compositions. However, the higher the concentration of manganese, the harder the alloys and the poorer their ability to be machined and forged. In addition, their resistance to corrosion decreases. Therefore, by teaching to limit the manganese concentration of nickel-free stainless steel alloys, the present invention makes it possible to promote the resistance of these alloys to corrosion as well as their ability to be machined and forged. However, a minimum concentration of manganese is necessary to be able to guarantee a sufficient solubility of the nitrogen, in particular to be able to solidify the alloy at ambient atmospheric pressure.
  • nickel-free austenitic stainless steel comprises in percentages by weight of carbon in proportions of 0.2 ⁇ C ⁇ 1%.
  • nickel-free austenitic stainless steel comprises, in mass percentages of molybdenum, in proportions of 1 ⁇ Mo ⁇ 2%.
  • the first two compositions are especially interesting when the corresponding nickel-free austenitic steel is obtained by conventional metallurgy (casting, recasting and thermomechanical treatments). Indeed, at ambient atmospheric pressure, without overpressure, the solidification is completely austenitic, thus avoiding the formation of unwanted pores in the alloy.
  • these compositions are optimized so that the temperature at which precipitates such as carbides or nitrides appear as low as possible. The temperature range of the austenitic domain is therefore maximal, thus facilitating all the thermomechanical treatments.
  • the advantage of the first composition, containing 1% copper, lies in the fact that the temperature range of the austenitic phase is higher than that of the second composition, which contains 2% copper.
  • the second composition containing 2% copper will be easier to shape by machining and stamping. Indeed, copper naturally promotes the machinability and forgeability properties of alloys.
  • the nitrogen and carbon content can be reduced while ensuring an austenitic structure.
  • the first two compositions can also be interesting in the case of metallurgical shaping of the powders. Indeed, these compositions make it possible to obtain particularly dense components after sintering, in particular by carrying out a sintering in the liquid phase, a technique better known by its English name "supersolidus liquid-phase sintering".
  • the third and fourth compositions are especially suitable for metallurgical shaping of powders.
  • they offer the possibility of performing solid-phase sintering in an atmosphere containing a reduced nitrogen partial pressure. This thus makes it possible to complete the atmosphere with, for example, hydrogen, known to improve the densification of stainless steels during sintering. Since these alloys also have a low interstitial content after sintering, any subsequent sintering operations such as machining or forging are further facilitated.
  • these two compositions are optimized so that the onset temperature of the precipitates, such as carbides or nitrides, is as low as possible. It should be noted, however, that although these third and fourth compositions are particularly well suited to metallurgical shaping of the powders, these compositions can also be obtained by the traditional route using, for example, a nitrogen overpressure during melting and solidification.
  • the aim was to maximize the corrosion resistance and hardness of austenitic steels by favoring high levels of nitrogen and molybdenum in alloys.
  • the specification for wearing parts usable in the field of watchmaking and jewelery is different.
  • the alloys proposed have optimized properties that make them particularly well suited for use in the fields of watchmaking and jewelery.
  • the machinability of the alloys according to the invention is improved, mainly because the quantity of nitrogen present in these alloys is low. Indeed, by limiting the molybdenum content to less than 2.5% by weight and by adding other gamma elements such as carbon and copper, the amount of nitrogen can be reduced while ensuring an austenitic structure. The addition of a little sulfur (up to 0.015% by weight) also improves the machinability, by manganese sulfide formation, but you have to be careful because it can have an impact on the resistance to corrosion of the alloy obtained. It is specified that machinability means any type of machining operation such as drilling, milling, boring or other.
  • Nitrogen being the main element that increases the mechanical properties in this type of alloy, a limited concentration of nitrogen makes it possible to obtain a shaping by deformation easier.
  • the copper reduces the rate of hardening of the alloy, which therefore facilitates its shaping by deformation. Finally, thanks to copper, there is a better resistance to generalized corrosion.
  • the invention also relates to the use of a nickel-free austenitic stainless steel as described above for producing trim elements for timepieces and jewelery articles.
  • the present invention proceeds from the general inventive idea which consists in proposing alloys of austenitic stainless steels without nickel representing a very good compromise between their ability to be machined and forged and their resistance to corrosion, taking into account the specific problems. in the field of watchmaking.
  • the compositions proposed can be obtained by means of conventional metallurgy (foundry), in particular under pressure ambient atmospheric which is very advantageous from the point of view of production costs, or by metallurgy of powders with very high densities after sintering.
  • concentrations of alphagenic elements such as chromium and molybdenum are defined to obtain sufficient corrosion resistance.
  • the concentrations of manganese, carbon and nitrogen are sufficiently low to promote the ability of the resulting alloys in machining and forging but high enough to be able to obtain the alloy by melting and solidification at atmospheric pressure or to obtain very good parts. dense by metallurgy of powders.
  • the concentrations are optimized to obtain a maximum temperature range of the austenitic domain.
  • the copper makes it possible to reduce the concentration of the above-mentioned gamma-elements, to facilitate shaping by machining or deformation, and to improve the resistance to generalized corrosion.
  • the copper concentration must however be limited because the copper decreases the temperature range of the austenitic domain and tends to weaken the austenitic steel at high temperature, making it more difficult the possible thermomechanical treatments (forging / rolling, annealing, etc.). .
  • composition whose phase diagram is illustrated at figure 1 (Fe-17Cr-17Mn-2Mo-1Cu-0.3C-0.5N)
  • the temperature the appearance of the precipitates is as low as possible (intersection between line 1 and line 3).
  • the temperature range of the austenitic domain is therefore the widest possible.
  • This composition is also interesting for obtaining very dense parts by powder metallurgy. Indeed, the existence of a wide "austenite-liquid" domain (between lines 4, 5 and 6) at 900 mbar of nitrogen makes it possible to perform sintering in the liquid phase without loss of nitrogen.
  • the sintering temperature is then defined to have about 30% of liquid during sintering.
  • the increase in copper concentration makes it possible to shift the boundary of the austenitic domain (line 6) to lower nitrogen concentrations.
  • the concentration of manganese can be reduced and the alloy obtained after solidification contains less nitrogen. Due to this higher concentration of copper and reduced concentrations of nitrogen and manganese, machinability and deformability of the alloy are facilitated compared to the first composition.
  • the higher copper concentration reduces the temperature range of the austenitic domain, the latter is maximum for the target nitrogen concentration (between 1300 ° C and 1050 ° C).
  • composition illustrated in figure 3 Fe-17Cr-11Mn-2Mo-1Cu-0.25C-0.4N
  • this composition is optimized for metallurgical shaping of the powders.
  • the sintering can be carried out at high temperature (1300 ° C.) with a reduced nitrogen partial pressure (about 600mbars).
  • the sintering atmosphere can therefore be supplemented with hydrogen, which thanks to its high reducing power improves the densification of the parts obtained after sintering.
  • composition illustrated in figure 4 (Fe-17Cr-14.5Mn-2Mo-2Cu-0.22C-0.35N) is also of interest for metallurgical shaping of the powders. Compared to the previous example, sintering can be carried out at high temperature (1300 ° C) with an even lower nitrogen partial pressure (about 400 mbar). Finally, this alloy has a very low concentration of interstitial elements, thus facilitating any machining or forging operations after sintering.
  • the table shown at figure 5 allows to compare the MARC (Measure of Alloying for Resistance to Corrosion) indices of the examples of the above compositions with the standard austenitic stainless steels with nickel and the nickel-free austenitic stainless steels available on the market.
  • the MARC index is a great way to compare the corrosion resistance of austenitic steels, especially those without nickel. The higher the MARC index, the more resistant the alloy is to corrosion.
  • This table comprises two standard austenitic stainless steels with nickel commonly used in watchmaking and jewelery, six commercial nickel-free austenitic stainless steels, as well as the four examples of preferred compositions mentioned above.
  • MARC Cr (%) + 3.3Mo (%) + 20C (%) + 20N (%) - 0.5Mn (%) - 0.25Ni (%).
  • compositions according to the invention have in particular a higher MARC index than that of austenitic stainless steel 1.4435 which is the steel most commonly used in watchmaking and jewelery.
  • Three of the four examples of compositions according to the invention even have a MARC index higher than that of steel 1.4539 which is known for its excellent resistance to corrosion.
  • the present invention seeks to improve the machinability and deformability of nickel-free austenitic stainless steels by teaching to reduce the contents of these alloys in carbon and nitrogen and to add copper.
  • the alloys proposed have, however, indices superior to those of alloys 1.3816 and 1.3815, which is sufficient to allow them to pass with success salt spray corrosion tests.
  • the first, second and fourth examples of compositions according to the invention exhibit pressure austenitic solidification. atmospheric, thus avoiding the use of special installations. This therefore reduces the cost of the alloys obtained.
  • the present invention is not limited to the embodiments which have just been described and that various simple modifications and variants can be envisaged by those skilled in the art without departing from the scope of the invention as defined. by the appended claims.
  • the alloys proposed have an excellent compromise between corrosion resistance, ease of shaping (machinability and forgeability) and density of the parts after sintering. It is indeed possible to sinter the parts at low nitrogen pressure and to compensate with hydrogen.
  • the metal matrix can be produced using the steel compositions according to the invention. It is also possible to treat the sintered parts under high isostatic pressure, also known by its English name High Isostatic Pressure. It is It is also possible to sinter under high pressure isostatic parts shaped by pressing or injection molding. It is also possible to make semi-finished products under high isostatic pressure. Finally, it is possible to forge the pieces after sintering.

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KR102020507B1 (ko) * 2017-12-20 2019-09-10 주식회사 포스코 강도, 표면전도성이 향상된 비자성 오스테나이트계 스테인리스강
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CH715726B1 (fr) * 2019-01-11 2022-10-14 Richemont Int Sa Procédé d'obtention d'un composant fonctionnel pour mouvement horloger.
CN110117746B (zh) * 2019-02-01 2021-07-27 上海加宁新材料科技有限公司 一种高性能无磁不锈钢的制造方法
EP3739076A1 (de) * 2019-05-16 2020-11-18 The Swatch Group Research and Development Ltd Pulverzusammensetuzng aus nickelfreiem austenitischem edelstahl, und werkstück, das aus diesem pulver durch sintern hergestellt wird
EP3835438A1 (de) * 2019-12-13 2021-06-16 The Swatch Group Research and Development Ltd Paramagnetischer harter edelstahl und sein herstellungsverfahren
CN111519006B (zh) * 2020-04-24 2021-04-20 深圳市泛海统联精密制造股份有限公司 一种高锰氮无镍不锈钢的真空固溶方法
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CN112553533A (zh) * 2020-12-25 2021-03-26 宝钢德盛不锈钢有限公司 一种经济性高强度奥氏体不锈钢
CN112553533B (zh) * 2020-12-25 2022-05-10 宝钢德盛不锈钢有限公司 一种经济性高强度奥氏体不锈钢

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