EP3249060B1 - Wärmebehandlungsverfahren von austenitischen stählen - Google Patents

Wärmebehandlungsverfahren von austenitischen stählen Download PDF

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EP3249060B1
EP3249060B1 EP17167986.3A EP17167986A EP3249060B1 EP 3249060 B1 EP3249060 B1 EP 3249060B1 EP 17167986 A EP17167986 A EP 17167986A EP 3249060 B1 EP3249060 B1 EP 3249060B1
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Prior art keywords
austenitic
hns
precipitates
steel
temperature
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French (fr)
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EP3249060A1 (de
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Joël Porret
Christian Charbon
Vincent Fays
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Swatch Group Research and Development SA
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Swatch Group Research and Development SA
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    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/02—Hardening by precipitation
    • 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
    • C22C38/04—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
    • C22C38/22—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
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • 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
    • 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
    • C21D2211/004—Dispersions; Precipitations
    • 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
    • C21D2261/00—Machining or cutting being involved

Definitions

  • the present invention relates to a process for the heat treatment of austenitic steels. More specifically, the present invention relates to austenitic steels alloyed with nitrogen well known under their Anglo-Saxon name Austenitic High Nitrogen Steel or austenitic steels HNS. The invention is also interested in austenitic steels with high concentrations of interstitial atoms, better known by their Anglo-Saxon name Austenitic High Interstitial Steel or austenitic steels HIS.
  • Austenitic steels alloyed with nitrogen which, for convenience, we will call hereafter austenitic steels HNS
  • austenitic steels with high concentrations of interstitial atoms which will be called hereafter austenitic steels HIS have properties of hardness, corrosion resistance and hypoallergenic which make them very interesting in particular for applications in the field of watchmaking and jewelry, both for the manufacture of trim elements intended to come into contact with the skin due to their very low nickel concentration, and for the manufacture of watch movement components because they are very hard, in particular after hardening.
  • HNS austenitic steels contain interstitial nitrogen atoms in high concentrations which can extend up to 1.5% in weight depending on the composition and use of the alloy.
  • HIS austenitic steels directly derived from HNS austenitic steels, contain significant amounts of interstitial carbon atoms in addition to interstitial nitrogen atoms.
  • HNS and HIS austenitic steels exhibit in particular interesting hypoallergenic properties due to their very low nickel content and their resistance to corrosion.
  • HNS and HIS austenitic steels are very difficult to machine, especially because they have a very high elastic limit, strain hardening rate and ductility. Tests show, for example, that the machining operations are two to three times longer than for steel 1.4435 and the wear of the machining tools is very important.
  • the machining of these austenitic HNS and HIS steels which, in many respects, is similar to machining titanium, is therefore long, difficult and expensive and constitutes the main obstacle to the use of these steels, particularly in the field of watchmaking and jewelry.
  • the document US 5,714,115 describes an austenitic steel alloy having the chemical composition 17.5% Cr, 4% Mo, 11% Mn, 0.02% C, 0.88% N and 0.01% Ni, the residue consisting of Fe The alloy is remelted in an electrically conductive slag, then forged. After annealing in solution at 1150 ° C., a homogeneous austenitic alloy is obtained, free from precipitation and delta ferrite, that is to say completely non-magnetic.
  • CN103233174B discloses a process for preparing high nitrogen austenitic stainless steel for vascular stents.
  • the subject of the present invention is a process for the heat treatment of austenitic steels of the HNS and HIS type, the aim of which is to make such austenitic steels more easily machinable.
  • an austenitic steel alloy HNS is provided. or HIS that is brought to its austenitization temperature or that is sintered at the austenitization temperature, then, immediately from the austenitization temperature, the temperature of the austenitic steel alloy HNS is lowered or HIS sufficiently slowly for precipitates of the nitride, carbide or even carbonitride type of chromium and / or molybdenum to appear in the structure of the resulting austenitic steel HNS or HIS, then finally the austenitic steel HNS or HIS is brought back at room temperature.
  • step which consists in causing precipitates to appear in an HNS or HIS austenitic steel precedes the step which, after machining this austenitic HNS or HIS steel, consists in putting the precipitates back into solution.
  • the heat treatment process applies equally well to parts obtained by casting and subsequent thermomechanical treatment, as to parts obtained by powder metallurgy such as metal injection molding also known by its English name. -saxonne Metal Injection Molding or MIM.
  • powder metallurgy such as metal injection molding also known by its English name.
  • MIM powder metallurgy
  • immediately after sintering the alloy at its austenitization temperature in order to obtain an austenitic steel of the HNS or HIS type it is possible, according to a method which is not part of the claimed invention, to cool slowly. the alloy in order to promote the formation of precipitates.
  • Slow cooling is understood to mean cooling which, after austenitization or sintering, promotes the appearance of precipitates in the microstructure of the austenitic HNS and HIS steels thus treated, as opposed to the classic heat treatment of quenching which consists in rapidly cooling the HNS and HIS steels. HIS after austenitization or sintering in order to avoid the formation of precipitates.
  • the austenitic steels HNS and HIS be subjected to a slow cooling heat treatment which is not part of the of the invention claimed to promote the appearance of precipitates, it goes against the usual practice of cooling the alloys as quickly as possible in order to avoid as much as possible the formation of precipitates in austenitic HNS steels and Resulting HIS.
  • the austenitic steel HNS or HIS after the austenitic steel HNS or HIS has undergone a heat treatment of austenitization or sintering at the austenitization temperature, then quenching, it is heats the austenitic steel HNS or HIS again to a temperature and for a period of time such that precipitates of the nitride, carbide or else carbonitride type of chromium and / or molybdenum appear.
  • This second variant is the most practical because it makes it possible to be able to perfectly control the parameters of the various heat treatments.
  • the first and second implementation variants of the heat treatment process of an austenitic HNS or HIS steel are therefore more particularly intended for obtaining trim elements for timepieces or jewelry, because they promote the corrosion resistance of these steels.
  • These two variants have in common that after application of a heat treatment of austenitization to an austenitic steel HNS or HIS and subsequent machining, one can indeed bring the resulting part to the annealing temperature, then quench the latter in order to return precipitates in solution.
  • an HNS or HIS austenitic steel is brought to its annealing temperature, in other words to its austenitization temperature, then it is rapidly cooled (quenching) so that no precipitate does not form, it is cold deformed and then this austenitic HNS or HIS steel is brought to a temperature and for a period of time such that precipitates of the nitride, carbide or else carbonitride type of chromium and / or molybdenum appear.
  • the hardness of the austenitic steel HNS or HIS obtained after austenitization and cold deformation is very little affected by the precipitation treatment carried out subsequently.
  • the machinability of such steels is appreciably improved.
  • the present invention proceeds from the general inventive idea which consists in subjecting the austenitic steels HNS and HIS to a heat treatment aiming to make the precipitates which have been made to appear in such austenitic steels HNS or HIS, for example during ironing back into solution. a pre-treatment of precipitation.
  • heat treatment of precipitation means a treatment which aims to place these austenitic steels HNS and HIS for a certain period of time under temperature conditions which allow the appearance of precipitates such as nitrides, carbides or carbonitrides, in particular of molybdenum and / or of chromium.
  • this annealing treatment will preferably but not be limited to trim elements for watches or for jewelry for which corrosion resistance and ability to polish are more important properties than hardness.
  • each HNS or HIS austenitic steel composition has a time-temperature-transformation diagram which is specific to it and which is also a function of the nature of the precipitate considered.
  • the figure 1 is a time (t) - temperature (T) - transformation diagram which illustrates the heat treatment of an austenitic HNS or HIS steel according to the implementation variant of the process which is not part of the claimed invention.
  • Tr1 be the austenitization or annealing temperature of an austenitic steel of the HNS or HIS type and let a be the curve which, on the time-temperature-transformation diagram of the figure 1 , delimits an area which corresponds to the time and temperature conditions which allow the formation of rushed.
  • the figure 2 is a time (t) - temperature (T) - transformation diagram which illustrates the heat treatment of an austenitic HNS or HIS steel according to the first implementation variant of the process.
  • Tr2 be the austenitization or annealing temperature of an austenitic steel of the HNS or HIS type and let b be the curve which, on the time-temperature-transformation diagram of the figure 2 , delimits an area which corresponds to time and temperature conditions which allow the formation of precipitates.
  • Tr2 the austenitization or annealing temperature of an austenitic steel of the HNS or HIS type
  • b the curve which, on the time-temperature-transformation diagram of the figure 2 , delimits an area which corresponds to time and temperature conditions which allow the formation of precipitates.
  • the figure 3 is a time (t) - temperature (T) - transformation diagram which illustrates the heat treatment of an austenitic steel HNS or HIS according to the second implementation variant of the process.
  • Tr3 be the austenitization or annealing temperature of an austenitic steel of the HNS or HIS type and let c be the curve which, on the time-temperature-transformation diagram of the figure 3 , delimits an area which corresponds to time and temperature conditions which allow the formation of precipitates.
  • the steel in question here is an austenitic HNS or HIS steel which has been cooled sufficiently rapidly from its temperature of annealing Tr3 to room temperature in order to avoid any formation of precipitates.
  • such an austenitic HNS or HIS steel is heated according to curve 10 and maintained at a temperature and for a period of time such that precipitates appear (curve 12), then is cooled (curve 12). 14).
  • the third implementation variant of the process differs from the second variant of the same process only in that, after receiving treatment followed by quenching and before the precipitation treatment, the austenitic steel HNS or HIS is work hardened, that is, cold-deformed.
  • the heat treatment which consists in bringing an austenitic steel to a temperature and for a period of time such that precipitates are formed is therefore applied, in this fourth variant, to a material hardened beforehand by work hardening.
  • the fourth and last implementation variant of the process consists in subjecting the austenitic steel to a cold deformation treatment after heat treatment according to one of the first three implementation variants.
  • the figure 4 is a view of a metallographic section of a sample of HIS X20CrMnMoN17-11-3 steel which has been annealed at its austenitization temperature and then quenched. It is noted on examination of this figure that the grain boundaries are not very marked, which denotes the absence of precipitates.
  • the figure 5 is a view of a metallographic section of a sample of austenitic steel HIS X20CrMnMoN17-11-3 having undergone a heat treatment in accordance with the second variant implementation of the method.
  • the grain boundaries are marked, which denotes the presence of significant amounts of precipitates along these grain boundaries.
  • Some larger precipitates have grown inside the grains from the grain boundaries.
  • concentration of precipitates could be obtained by bringing, after rapid cooling from the annealing temperature, the austenitic steel HIS X20CrMnMoN17-11-3 at a temperature of 800 ° C for two hours.
  • the figure 6 is a view of a metallographic section of a sample of austenitic steel HIS X20CrMnMoN17-11-3 which is in the form of a bar whose outer diameter is reduced from 3 mm to 2.5 mm by cold deformation by wire drawing, ie a reduction in diameter of 16.6%.
  • this sample was then brought to a temperature of 800 ° C. for two hours according to the temperature curve shown in figure 3 .
  • the steel has many precipitates, both at the grain boundaries and inside the grains.
  • the figure 7 is a graph which shows the evolution of the hardness of the austenitic steel HIS X20CrMnMoN17-11-3 of the figure 6 depending on the temperature to which this steel is brought to form the precipitates. It is observed that the hardness of austenitic steel without precipitation treatment and after cold working is 450 HV10 (symbol in the form of a square on the graph). The same austenitic steel is, after cold work hardening, heat treated in accordance with the third implementation variant of the process.
  • Samples of this steel are brought respectively to temperatures of 750 ° C, 800 ° C, 850 ° C, 900 ° C and 950 ° C for a period of two hours, then cooled (diamond-shaped symbols on the graph) . It is observed that, for samples heated between 700 ° C and 900 ° C, the hardness is between approximately 425 HV10 and 375 HV10. In other words, the hardness of these samples of austenitic steel heat-treated in accordance with the third variant of the process varies little with respect to the hardness of austenitic steel which has been cold-worked but which has not been subjected to a precipitation treatment.
  • the machinability of the austenitic steel samples which have undergone a precipitation heat treatment according to this third variant of the process is markedly improved. Only the austenitic steel sample heated to 950 ° C for two hours has a hardness significantly lower than that of austenitic steel without precipitation treatment (less than 350 HV10). Finally, a sample of austenitic steel HIS X20CrMnMoN17-11-3 having only undergone an annealing treatment followed by quenching (symbol in the form of a triangle on the graph) has a hardness less than 250 HV10.
  • the figure 8 is a view of a metallographic section of a sample of austenitic steel HIS X20CrMnMoN17-11-3 which is in the form of a bar whose outer diameter is reduced from 3 mm to 2 mm by cold deformation by drawing , or an even greater reduction in diameter of 33.3%.
  • This steel sample undergoes the same heat treatment as at the figure 6 by being brought to a temperature of 800 ° C. for two hours in accordance with the third variant of the implementation of the method.
  • the phenomenon of precipitation is even more pronounced since, in addition to the precipitates which form along the grain boundaries and from the grain boundaries towards the interior of the grains, there is a high concentration of precipitates within themselves. grains.
  • the figure 9 is a graph which shows the evolution of the hardness of the steel of the figure 8 depending on the time and the temperature to which this steel is heated after work hardening to form the precipitates. It is observed that the hardness of austenitic steel without precipitation treatment and after cold work hardening is between 550 HV10 and 560 HV10 (symbol in the form of a square on the graph). This hardness is greater than that at the figure 7 because the work hardening rate is higher.
  • the diamond-shaped symbols on the figure 9 correspond to samples of austenitic steel brought to respective temperatures of 700 ° C, 750 ° C, 800 ° C and 850 ° C for 45 minutes.
  • HNS and HIS steels to which the precipitation process can be applied are: X5CrMnN18-18, X8CrMnN19-19, X8CrMnMoN18-18-2, X13CrMnMoN18-14-3, X20CrMnMoN17-11-3 or even X5MnCrMoN23-21.
  • precipitates that can form during the precipitation process are: M23C, MC, M6C or even M2N, where M denotes one or more of the metallic elements of the alloy which can be combined with carbon or nitrogen. to form carbides or nitrides or carbonitrides.
  • the invention applies in particular to jewelry and to the trim elements of timepieces.
  • the present invention teaches a process for the heat treatment of a HNS or HIS austenitic steel containing precipitates, this process comprising the step which consists, after machining of parts, in particular of jewelry or watchmaking, carried out in using an HNS or HIS austenitic steel containing precipitates, to put the precipitates back into solution by bringing these HNS or HIS austenitic steel parts to their austenitization temperature, then cooling these parts sufficiently quickly, typically by quenching, to prevent the precipitates to form again.
  • machining operations is understood to mean in particular but not exclusively the operations of boring, milling, drilling, threading, tapping and cutting.

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Claims (3)

  1. Wärmebehandlungsverfahren eines austenitischen Stahls vom Typ High Nitrogen Steel oder austenitischer Stahl HNS oder eines austenitischen Stahls vom Typ High Interstitial Steel oder austenitischer Stahl HIS, wobei dieser austenitische Stahl HNS oder HIS Absetzungen vom Typ Nitride, Carbide oder Carbonitride von Chrom und/oder Molybdän enthält, wobei das Verfahren den folgenden Schritt umfasst:
    • vor der Bearbeitung Sichtbarmachen der Absetzungen von Nitriden, Carbiden oder Carbonitriden von Chrom und/oder Molybdän in dem austenitischen Stahl HNS oder HIS, wobei dies dadurch erreicht wird, dass eine Legierung aus austenitischem Stahl HNS oder HIS bereitgestellt wird, die auf ihre Austenitisierungstemperatur gebracht wird oder die bei der Austenitisierungstemperatur gesintert wird, und dann unmittelbar ausgehend von der Austenitisierungstemperatur einer thermischen Abkühlungsbehandlung unterzogen wird, wobei die Abkühlung des resultierenden austenitischen Stahls HNS oder HIS unterbrochen wird, wenn die Temperatur einen Wert erreicht hat, bei dem die Absetzungen erscheinen, wobei der austenitische Stahl HNS oder HIS über einen solchen Zeitraum auf dieser Temperatur gehalten wird, dass die Absetzungen sichtbar werden, wobei der austenitische Stahl HNS oder HIS schließlich wieder auf Raumtemperatur zurückgebracht wird;
    wobei das Verfahren weiterhin einen Schritt umfasst, der darin besteht,
    • nach der Bearbeitung des austenitischen Stahls HNS oder HIS, der die Absetzungen enthält, die Absetzungen wieder in Lösung zu bringen, indem der austenitische Stahl HNS oder HIS auf seine Austenitisierungstemperatur gebracht wird, anschließend den austenitischen Stahl HNS oder HIS ausreichend schnell abzukühlen, um neu sich bildende Absetzungen zu vermeiden.
  2. Wärmebehandlungsverfahren eines austenitischen Stahls vom Typ High Nitrogen Steel oder austenitischer Stahl HNS oder eines austenitsichen Stahls vom Typs High Interstitial Steel oder austenitischer Stahl HIS, wobei dieser austenitische Stahl HNS oder austenitischer Stahl HIS Absetzungen vom Typ Nitride, Carbide oder Carbonitride von Chrom und/oder Molybdän enthält, wobei das Verfahren den folgenden Schritt umfasst:
    • vor der Bearbeitung Sichtbarmachen der Absetzungen von Nitriden, Carbiden oder Carbonitriden von Chrom und/oder Molybdän in dem austenitischen Stahl HNS oder HIS, wobei dies dadurch erreicht wird, dass die Legierung aus austenitischem Stahl HNS oder HIS einer Austenitisierungs- oder Sinter-Wärmebehandlung bei der Austenitisierungstemperatur unterzogen wird, und dann diese Legierung aus austenitischem Stahl HNS oder HIS abgeschreckt wird und erneut über einen solchen Zeitraum bis auf eine Temperatur erwärmt wird, dass die Absetzungen vom Typ Nitride, Carbide oder aber Carbonitride von Chrom und/oder Molybdän sichtbar werden,
    wobei dieses Verfahren weiterhin einen Schritt umfasst, der darin besteht,
    • nach der Bearbeitung des austenitischen Stahls HNS oder HIS, der die Absetzungen enthält, die Absetzungen wieder in Lösung zu bringen, indem der austenitische Stahl HNS oder HIS auf seine Austenitisierungstemperatur gebracht wird, anschließend den austenitischen Stahl HNS oder HIS ausreichend schnell abzukühlen, um neu sich bildende Absetzungen zu vermeiden.
  3. Verfahren nach Anspruch 2, wobei nach dem Härten und bevor der austenitische Stahl HNS oder HIS für einen solchen Zeitraum auf eine Temperatur gebracht wird, dass die Absetzungen vom Typ Nitride, Carbide oder aber Carbonitride von Chrom und/oder Molybdän sichtbar werden, der austenitische Stahl HNS oder HIS kaltverformt wird.
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US5158745A (en) * 1990-02-19 1992-10-27 Nippon Steel Corporation High-nitrogen ferritic heat-resisting steel

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US11136638B2 (en) 2021-10-05
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