EP3299487B2 - Verfahren zur oberflächenhärtung eines kaltverformten artikels - Google Patents

Verfahren zur oberflächenhärtung eines kaltverformten artikels Download PDF

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EP3299487B2
EP3299487B2 EP16190934.6A EP16190934A EP3299487B2 EP 3299487 B2 EP3299487 B2 EP 3299487B2 EP 16190934 A EP16190934 A EP 16190934A EP 3299487 B2 EP3299487 B2 EP 3299487B2
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French (fr)
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EP3299487B1 (de
EP3299487A1 (de
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Andreas Karl
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Bodycote PLC
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Bodycote PLC
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C21D1/06—Surface hardening
    • 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
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • 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
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • 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
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
    • C21D7/10—Modifying the physical properties of iron or steel by deformation by cold working of the whole cross-section, e.g. of concrete reinforcing bars
    • 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
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20—Carburising
    • C23C8/22—Carburising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
    • C23C8/30—Carbo-nitriding
    • C23C8/32—Carbo-nitriding of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C23C8/38—Treatment of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
    • C23C8/44—Carburising
    • C23C8/46—Carburising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
    • C23C8/48—Nitriding
    • C23C8/50—Nitriding of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/52—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions more than one element being applied in one step
    • C23C8/54—Carbo-nitriding
    • C23C8/56—Carbo-nitriding of ferrous surfaces
    • 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

Definitions

  • the present invention relates to a method for surface hardening a cold deformed article at least partially consisting of stainless steel or a nickel base alloy with a chromium content of at least 10 % by weight. Moreover, the present invention relates to a surface hardened cold deformed article obtainable with this method.
  • Articles such as metal articles made of steel or a nickel base alloy, are often shaped by means of cold deformation, such as extrusion or cold forging.
  • Cold deformation is a method for strengthening a metal by plastic deformation, which is usually performed in the course of shaping an article at a temperature below the recrystallization temperature of the material, from which the article is made.
  • Stainless steels such as austenitic stainless steel, usually have an excellent corrosion resistance, toughness and weldability, but have a comparable low yield strength as well as a comparable low wear resistance.
  • Cold forming improves the yield strength of such articles on account of structural changes, i.e. in particular changes of the microstructure, such as the formation of martensite and the like, in the steel occurring as consequence of the plastic deformation occurring during the cold working.
  • such articles are often also diffusion hardened in addition to the cold working, by subjecting the articles to a heat treatment at a temperature of typically 350 to 510°C in an atmosphere comprising a chemical compound forming during the heat treatment a species, which diffuses into the surface of the articles and thus improves the characteristics of the articles.
  • Most prominent diffusion hardening methods are carburizing, nitriding and nitrocarburizing. While carbon diffuses during carburization into the surface area of the article, nitrogen diffuses during nitriding, carbon and nitrogen diffuse during nitrocarburizing and boron diffuses during boriding into the surface area of the article.
  • Carburization for example, is performed by heat treating the article in an atmosphere containing for instance an alkane, such as propane, and optionally further including hydrogen at 500°C for 10 hours.
  • the article has to be activated during or better before the carburization, in order to remove the oxide layer of the article, which would act during the carburization as barrier.
  • Such an activation is usually performed in a fluorine compound containing atmosphere, such as in a gaseous atmosphere comprising NF 3 at a temperature of 250 to 500°C, such as for instance described in EP 0 678 589 A1 .
  • a major disadvantage of diffusion hardening cold worked articles made of stainless steel or comparable alloys is that as consequence of the microstructural changes of the stainless steel or alloy, respectively, occurred during the cold working, compounds consisting of the diffusion element and of chromium from the stainless steel or alloy, respectively, precipitate during the diffusion hardening.
  • compounds consisting of the diffusion element and of chromium from the stainless steel or alloy, respectively precipitate during the diffusion hardening.
  • chromium carbide precipitates in the surface area of a cold worked stainless steel article during the carburization
  • chromium nitride precipitates in the surface area of a cold worked stainless steel article during the nitridation
  • chromium carbide as well as chromium nitride precipitate in the surface area of a cold worked stainless steel article during the nitrocarburization.
  • the free chromium content is reduced in the surface area of the cold worked and diffusion hardened stainless steel article, which significantly reduces its corrosion resistance.
  • WO 2012/146254 A1 relates to a method for formation of expanded austenite and/or expanded martensite by solution hardening of a cold deformed workpiece of a passive alloy, which comprises a first step of dissolving at least nitrogen in the workpiece at a first temperature, which is higher than the solubility temperature for carbide and/or nitride and lower than the melting point of the passive alloy, and a subsequent second step of dissolving nitrogen and/or carbon in the workpiece at a second temperature, which is lower than the temperature at which carbides and/or nitrides form in the passive alloy.
  • WO 2011/009463 A1 describes a method of activating an article of passive ferrous or non-ferrous metal, wherein the activation comprises the steps of i) heating the article to a first temperature, ii) heating at least one compound containing nitrogen and carbon to a second temperature for providing one or more gaseous species, and iii) contacting the article with the gaseous species, wherein the at least one compound containing nitrogen and carbon comprises at least four atoms.
  • WO 2015/173380 A1 discloses a method of case hardening a workpiece made from a stainless steel comprising at least 9% chromium and up to 5% nickel, wherein the method comprises the steps of i) providing a workpiece punched from a sheet of the stainless steel, ii) optionally embossing the workpiece, iii) dissolving in an atmosphere of a nitrogen containing gas at least nitrogen in the workpiece at a first temperature, which is higher than the solubility temperature for nitride and lower than the melting point of the stainless steel, wherein dissolution of nitrogen at the first temperature is performed to obtain a diffusion depth of 10 ⁇ m to 50 ⁇ m with a content of nitrogen in the range of 0.05% to 0.5%, and iv) cooling the workpiece after the dissolution step to a second temperature which is lower than the temperature at which nitrides form in the stainless steel.
  • US 2006/0070685 A1 refers to a process for producing a bearing component with an edge zone the process comprising the steps of i) providing an austenitic cold-rolled strip with a carbon content of 0.15-0.25% and a chromium alloying content of at least 12%; ii) initially deep-drawing the component from the strip; then enriching the strip at the edge zone with nitrogen as part of a heat treatment in a nitrogen-rich atmosphere; and iii) thereafter cooling the component to form a martensitic microstructure in which nitrogen is present in dissolved form.
  • the object underlying the present invention is to provide a method for surface hardening a cold deformed article at least partially consisting of stainless steel or a nickel base alloy with a chromium content of at least 10 % by weight, which leads to an article with an excellent surface hardness, a high hardness beneath the surface area of the article, an excellent yield strength, a high wear resistance as well as an excellent corrosion resistance.
  • this object is satisfied by providing a method for surface hardening a cold deformed article at least partially consisting of stainless steel or a nickel base alloy with a chromium content of at least 10 % by weight, comprising the steps of:
  • the process in accordance with the present invention does not only lead to a high hardness of the article over its whole thickness as a consequence of the cold working as well as to an extremely high surface hardness as a consequence of the diffusion hardening, but in addition to an excellent wear resistance and corrosion resistance of the article on account of the annealing step.
  • the articles obtained with the method in accordance with the present invention have a significantly increased surface hardness and an improved wear resistance.
  • the articles obtained with the method in accordance with the present invention have an increased surface hardness, an improved hardness beneath the surface area of the article as well as an improved wear resistance.
  • the articles obtained with the method in accordance with the present invention have an increased hardness beneath the surface area of the article as well as an improved wear resistance.
  • the articles obtained with the method in accordance with the present invention have an increased corrosion resistance.
  • Cold forming in the sense of the present patent application which is typically also called work hardening or strain hardening, is a method of strengthening a metal-article by plastic deformation. The strengthening occurs on account of dislocation movements and dislocation generation within the crystal structure of the material. Usually, cold forming is also used for shaping or forming the article, respectively, and is in general performed at a temperature below the full recrystallization temperature of the material, from which the article consists.
  • the annealing step b) of the method in accordance with the present invention may be performed at any temperature between 450°C and 750°C and for any time between 5 minutes and 50 hours, as long as it is performed in a non-carburizing atmosphere, a non-nitriding atmosphere and a non-nitrocarburizing atmosphere, i.e. in an atmosphere which is non-carburizing atmosphere, non-nitriding and non-nitrocarburizing.
  • the non-carburizing, non-nitriding and non-nitrocarburizing atmosphere contains no compound selected from the group consisting of nitrogen containing compounds, carbon containing compounds and mixtures of two or more of the aforementioned compounds.
  • Nitrogen and/or carbon may be included in the atmosphere of step b), as long as step b) is performed at a temperature, at which the nitrogen and/or carbon is not diffused into the surface of the substrate. So the annealing step b) may be performed in a pure nitrogen atmosphere at a temperature below 850°C, since then no nitriding occurs.
  • the temperature and duration of the annealing step b) slightly depends on the precise composition of the alloy, from which the article to be treated is made. Typically, the more severe the conditions during the annealing step, the more the hardness of the article decreases, but on the other hand the better the chromium containing precipitate generation is suppressed during the later diffusion hardening process.
  • the annealing step b) is conducted for a duration and at a temperature selected from the aforementioned numeric value ranges so that the hardness of the cold worked article is not reduced in average by more than 15% during the annealing step b).
  • the annealing step b) is preferably performed so that the hardness of the cold worked and annealed article is in average at least 85% of the hardness of the cold worked article before annealing.
  • Hardness means in this connection the Vickers hardness.
  • the annealing step b) is performed for a time of 5 minutes to 50 hours, preferably for 10 minutes to 20 hours and most preferably for 20 minutes to 10 hours.
  • the annealing step b) of the method in accordance with the present invention is performed at a temperature between 550 and 700°C.
  • the present invention is not particularly limited concerning the pressure, at which the annealing step b) is conducted.
  • the annealing step b) may be performed at atmospheric pressure or under reduced pressure.
  • the annealing step is performed in a non-carburizing atmosphere, a non-nitriding atmosphere and a non-nitrocarburizing atmosphere, i.e. in an atmosphere containing no compound selected from the group consisting of nitrogen containing compounds, carbon containing compounds and mixtures of two or more of the aforementioned compounds that would form diffusible compounds during the annealing step.
  • a diffusion of carbon and/or nitrogen would occur during the annealing step b) at least to a small degree and this would initiate the formation of chromium containing precipitates, which would oppose the effects achieved with the method in accordance with the present invention.
  • the effects of the annealing step b namely the reduction of chromium containing precipitates during the later diffusion hardening, are in a particular excellent extent obtained, when the annealing step b) is performed in an atmosphere which does not lead to a structural change of the surface, in particular to a change of the surface roughness and surface morphology of the article.
  • the oxide layer of the article is maintained during the annealing step b).
  • the annealing step b) is performed under vacuum, namely preferably at a pressure of at most 10.000 Pa and more preferably of at most 5.000 Pa.
  • the annealing step b) is performed in an atmosphere, which also- i.e. in addition to diffusible compounds selected from the group consisting of nitrogen containing compounds, carbon containing compounds and mixtures thereof - does not include any compound, which would remove or even partially remove the oxide layer on the alloy, from which the article is made, during the annealing step b).
  • the annealing step b) is performed in an atmosphere, which does not contain more than 5 % by volume of fluorine, of a fluorine containing compound and/or of a fluoride containing compound, preferably not more than 1 % by volume of fluorine, of a fluorine containing compound and/or of a fluoride containing compound, preferably not more than 0.1 % by volume of fluorine, of a fluorine containing compound and/or of a fluoride containing compound and most preferably no fluorine, no fluorine containing compound and no fluoride containing compound at all.
  • the annealing step b) is performed in an atmosphere, which does not contain more than 5 % by volume of chlorine, of a chlorine containing compound and/or of a chloride containing compound, preferably not more than 1 % by volume of chlorine, of a chlorine containing compound and/or of a chloride containing compound, preferably not more than 0.1 % by volume of chlorine, of a chlorine containing compound and/or of a chloride containing compound and most preferably no chlorine, no chlorine containing compound and no chloride containing compound at all.
  • the annealing step b) is performed in a reducing atmosphere, which assures that the oxide layer of the article is maintained during the annealing step b). Good results are in particular obtained, when the annealing step b) is performed in an atmosphere containing hydrogen.
  • At least the surface region of the article is made of an alloy selected from the group consisting of stainless steel and nickel base alloys with a chromium content of at least 10 % by weight. However, it is preferred that the whole article consists completely of the alloy.
  • step a) consists of austenitic stainless steel and/or duplex stainless steel.
  • the thickness of the article there is no limitation concerning the thickness of the article and surprisingly good results are even obtained with comparable thick articles, which may be not processed for example with a method of the prior art comprising a solution nitriding treatment of the cold worked article before subjecting it to the diffusion hardening process.
  • the method in accordance with the present invention is suitable for articles having a thickness of at least 100 ⁇ m and even for articles having a thickness of at least 5 mm.
  • the cold forming for obtaining the article provided in step a) may be any cold forming step known to a person skilled in the art.
  • the step a) may comprise plastically deforming the article at a temperature of at most 300°C, preferably by a technique selected from the group consisting of forging, extrusion, shaping, drawing, pressing, roll burnishing, rolling and combinations of two or more of the aforementioned techniques.
  • step a) may comprise the machining of the article at a temperature of at most 200°C, preferably by a technique selected from the group consisting of turning, milling, punching, grinding, polishing and combinations of two or more of the aforementioned techniques.
  • step a) comprises plastically deforming the article at a temperature of at most 300°C and machining the article at a temperature of at most 200°C, wherein the plastically deforming is preferably performed by a technique selected from the group consisting of forging, extrusion, shaping, drawing, pressing, roll burnishing, rolling and combinations of two or more of the aforementioned techniques and wherein the machining preferably performed by a technique selected from the group consisting of turning, milling, punching, grinding, polishing and combinations of two or more of the aforementioned techniques.
  • the heat treatment in step d) is performed as carburizing step in a gaseous atmosphere comprising a carbon containing compound.
  • the carbon containing compound is selected form the group consisting carbon monoxide, carbon dioxide, mixtures of carbon monoxide and carbon dioxide, hydrocarbon compounds and mixtures of two or more of the aforementioned compounds, wherein the hydrocarbon compound is preferably selected from the group consisting of C 1-6 -alkanes, fluorinated C 1-6 -alkanes, C 1-6 -alkenes, fluorinated C 1-6 -alkenes, C 1-6 -alkynes, fluorinated C 1-6 -alkynes and mixtures of two or more of the aforementioned compounds, wherein C 1-6 -alkynes and/or fluorinated C 1-6 -alkynes are particularly preferred.
  • the aforementioned carburization gas may further comprise hydrogen, which promotes the decomposition of the carbon containing compound and thus the formation of diffusible carbon.
  • the carburization gas may contain an inert gas, such as argon, as diluent.
  • the heat treatment in step d) is performed as nitriding step in a gaseous atmosphere comprising a nitrogen containing compound.
  • a nitrogen containing compound is ammonia and/or urea.
  • the aforementioned nitriding gas may further comprise hydrogen, in order to promote the decomposition of the nitrogen containing compound and thus the formation of diffusible nitrogen, and/or an inert gas, such as argon, as diluent.
  • the heat treatment in step d) is performed as nitrocarburization step in a gaseous atmosphere comprising a carbon containing compound as well as a nitrogen containing compound.
  • a gaseous atmosphere comprising i) carbon monoxide, carbon dioxide, a mixture of carbon monoxide and carbon dioxide and/or a hydrocarbon compound, wherein the hydrocarbon compound is preferably selected from the group consisting of C 1-6 -alkanes, fluorinated C 1-6 -alkanes, C 1-6 -alkenes, fluorinated C 1-6 -alkenes, C 1-6 -alkynes, fluorinated C 1-6 -alkynes and mixtures of two or more of the aforementioned compounds, and ii) a nitrogen containing compound, wherein the nitrogen containing compound is ammonia and/or urea.
  • the aforementioned nitrocarburization gas may further comprise hydrogen, in order to promote the decomposition of the carbon containing compound and of the nitrogen containing compound and thus the formation of diffusible nitrogen and carbon, and/or an inert gas, such as argon, as diluent.
  • an inert gas such as argon
  • the diffusion hardening performed during the heat treatment in step d) is performed as so called low temperature diffusion hardening at a temperature between 350 and less than 550°C in plasma, in a salt bath or in a gaseous atmosphere to obtain a nitride, carburized and/or nitrocarburized diffusion zone in the surface area of the article.
  • a temperature between 350 and 510°C is particularly good.
  • the diffusion hardening is performed for 2 to 50 hours.
  • the heat treatment in step d) is preferably performed at atmospheric or subatmospheric pressure between 500 and 10,000 MPa.
  • the heat treatment of the article in step d) is performed in plasma.
  • the plasma heat treatment step d) is performed in plasma at a pressure of 100 to 1.000 Pa for 10 minutes to 100 hours in a carburizing atmosphere, in a nitriding atmosphere or in a nitrocarburizing atmosphere at a temperature of 100 to 550°C.
  • the atmosphere preferably comprises carbon monoxide, carbon dioxide, a hydrocarbon compound, such as in particular methane, or a mixture thereof.
  • the preferably oxygen free atmosphere preferably comprises ammonia and/or urea.
  • the preferably oxygen free atmosphere preferably comprises i) carbon monoxide, carbon dioxide, a hydrocarbon compound, such as in particular methane, or a mixture thereof and ii) ammonia and/or urea.
  • the atmosphere may further contain an inert gas, such as argon, as diluent and/or hydrogen, in order to promote the decomposition of the carbon and/or nitrogen containing compound and thus the formation of diffusible carbon and/or nitrogen.
  • an inert gas such as argon, as diluent and/or hydrogen
  • the plasma heat treatment step d) is performed in plasma at a pressure of 100 to 1.000 Pa in a carburizing atmosphere, in a nitriding atmosphere or in a nitrocarburizing atmosphere at a temperature of 400 to 500°C.
  • the plasma treatment not only a diffusion hardening is performed, but also an activation of the surface of the article, i.e. the removal of the oxide layer of the article, is achieved.
  • the plasma treatment simultaneously fulfils the activation step c) and the diffusion hardening step d).
  • the activation in step c) is preferably performed before the heat treatment step d) and by sputtering the annealed article obtained in step b) preferably in an atmosphere comprising argon, hydrogen, a rare gas, such as helium, or a mixture thereof.
  • the sputter activation step may be performed at a temperature between 100 and 550°C and preferably at a temperature of 300 to 500°C for 10 minutes to 10 hours and preferably for 1 to 10 hours.
  • the heat treatment of the article in step d) is performed in a salt bath.
  • the heat treatment is performed for 1 to 100 hours in a molten salt bath including as carbon donor and nitrogen donor a cyanide salt, such as sodium cyanide and/or potassium cyanide.
  • a cyanide salt such as sodium cyanide and/or potassium cyanide.
  • potassium chloride and lithium chloride are included in the salt bath and more preferably also an activator compound selected from the group consisting of barium chloride, strontium chloride, magnesium chloride, calcium chloride and mixtures of two or more of the aforementioned salts.
  • the salt bath treatment simultaneously fulfils the activation step c) and the diffusion hardening step d).
  • the heat treatment of the article in step d) is performed in a gaseous atmosphere.
  • the preferred temperature conditions, pressure conditions and gas compositions for carburization, nitridation and nitrocarburization have been described above.
  • the activation in step c) is preferably performed before the heat treatment step d) in a gaseous atmosphere comprising a fluorine compound at a temperature of 250 to 500°C.
  • the fluorine compound is selected from the group consisting of fluorine, NF 3 , BF 3 , CF 4 , HF, SF 6 , C 2 F 6 , WF 6 , CHF 3 , SiF 4 , C 1-6 -fluorinated alkanes, C 1-6 -fluorinated alkenes, C 1-6 -fluorinated alkynes and mixtures of two or more of the aforementioned compounds.
  • Good results are in particular achieved in this embodiment, when the activation is performed at a temperature of 250 to 550°C and preferably of 350 to 500°C for of 0.5 to 50 hours and preferably 1 to 15 hours in a gaseous atmosphere including NF 3 and/or N 2 at atmospheric pressure.
  • step c) it is also possible to perform the activation according to step c) simultaneously with the heat treatment of the article in a gaseous atmosphere according to step d) for instance by using specific carbon containing compounds which also function as carbon donor.
  • Suitable carbon containing compounds therefor are unsaturated C 1-6 -hydrocarbon compounds, such as C 1-6 -alkenes and C 1-6 -alkynes, such as acetylene.
  • Particularly suitable for this purpose are halogenates hydrocarbon compounds and in particular unsaturated halogenates hydrocarbon compounds, such as fluorinated C 1-6 -alkenes and fluorinated C 1-6 -alkynes.
  • the method in accordance with the present invention does not comprise any heating to a temperature above 900°C, preferably does not comprise any heating to a temperature above 800°C, more preferably does not comprise any heating to a temperature above 750°C and most preferably does not comprise any heating to a temperature above 700°C.
  • the method in accordance with the present invention consists of steps a) to d) and optionally a cooling step between steps b) and c) to a temperature between 0°C and 100°C and preferably to a temperature between 23°C and 60°C and/or a cooling step between steps c) and d) to a temperature between 0°C and 100°C and preferably to a temperature between 23°C and 60°C.
  • the present invention refers to a surface hardened article obtainable by a method in accordance with claim 13.
  • the surface hardened article obtainable by a method in accordance with the present invention is characterized in that it does not only have a high hardness over its whole thickness as a consequence of the cold working as well as an extremely high surface hardness as a consequence of the diffusion hardening, but in addition an excellent wear resistance and corrosion resistance of the article on account of the annealing step.
  • the surface hardened article in accordance with the present invention has in average a Vickers hardness HV1 measured in accordance with ASTM E92-16 of at least 150 and/or a surface hardness HV0.05 measured in accordance with ASTM E92-16 of at least 500.
  • the surface hardened article has in average a Vickers hardness HV1 of at least 200, more preferably of at least 210 and most preferably of at least 220.
  • the surface hardened article in accordance with the present invention preferably has a surface hardness HV0.05 measured in accordance with ASTM E92-16 of at least 600, more preferably of at least 650 and most preferably of at least 675.
  • the surface hardened article in accordance with the present invention has a corrosion resistance measured in accordance with DIN EN ISO 8442-1 of December 1997 of less than 15 pitting corrosion points per 20 cm 2 surface area, preferably of less than 5 pitting corrosion points per 20 cm 2 surface area and more preferably of less than 1 pitting corrosion points per 20 cm 2 surface area.
  • a set of key lock washers was prepared from austenitic stainless steel AISI 316 by cold working. More specifically, key lock washers 2, each of which comprising a first side 3 with radial teeth 4 and an opposite cam-side 5 with cams 6, were prepared by fine blanking of the inner and outer diameter of each key lock washer and subsequently embossing the first side with radial teeth and the camside with a cold working tool.
  • key lock washers were subjected to an annealing step, in which the key lock washers were heated for 1 hour at 700°C in a vacuum furnace in a vacuum of about 500 Pa. The heating-up was performed in the furnace with a rate of 50°C per minute.
  • the furnace was purged with 100 liter argon gas, before the annealed key lock washers were activated and simultaneously carburized at 420°C for 20 hours in an atmosphere comprising 5%by volume of acetylene, 50%by volume of hydrogen and 45%by volume of nitrogen.
  • the so obtained surface hardened key lock washers showed the following propertied: Surface hardened washers of the example Base material hardness 1) 222 ⁇ 11 HV1 Surface hardness 2) 690 to 890 HV0.05 Diffusion zone depth 3) 11 to 14 ⁇ m Evaluation of corrosion resistance 4) No Corrosion products are visible on the surface in an optical microscope at 100x magnification. Evaluation of corrosion resistance 5) Surface free form corrosion products (cf. fig. 2 ).
  • a set of key lock washers was prepared and surface hardened as described in the example except that no annealing step was performed between the cold working and the carburization.
  • the so obtained surface hardened key lock washers showed the following propertied: Surface hardened washers of the comparative example Base material hardness 1) 235 ⁇ 13 HV1 Surface hardness 2) 680 to 840 HV0.05 Diffusion zone depth 3) 12 to 14 ⁇ m Evaluation of corrosion resistance 4) Corrosion products are visible on the surface and pitting corrosion spots can be seen in an optical microscope at 100x magnification. Evaluation of corrosion resistance 5) Corrosion products are visible on the surface on the camside and the cutting edge on the inner diameter and the outer diamete (cf. fig. 3 ). 1) to 5) As described for the example

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Claims (14)

  1. Verfahren zum Oberflächenhärten eines kaltverformten Gegenstands, der zumindest teilweise aus Edelstahl oder einer Legierung auf Nickelbasis mit einem Chromgehalt von mindestens 10 Gew.-% besteht, die folgenden Schritte umfassend:
    a) Vorsehen eines kaltverformten Gegenstands, wobei mindestens der Oberflächenbereich des Gegenstands aus einer Legierung gefertigt ist, die aus der Gruppe bestehend aus Edelstahl und Legierungen auf Nickelbasis mit einem Chromgehalt von mindestens 10 Gew.-% ausgewählt ist,
    b) Tempern des kaltgeformten Gegenstands über 5 Minuten bis 50 Stunden bei einer Temperatur zwischen 450 °C und 750 °C in einer nicht carburierenden Atmosphäre, einer nicht nitrierenden Atmosphäre und einer nicht nitrocarburierenden Atmosphäre,
    c) Aktivieren des getemperten Gegenstands, der in Schritt b) erhalten wird, und
    d) gleichzeitig mit Schritt c) oder nach Schritt c) Hitzebehandlung des getemperten Gegenstands bei einer Temperatur 350 bis weniger 550 °C über 2 bis 50 Stunden in Plasma, in einem Salzbad oder in einer gasförmigen Atmosphäre, um eine Nitrid-, aufgekohlte und/oder nitrocarburierte Diffusionszone im Oberflächenbereich des Gegenstands zu erzielen, wobei das Plasma, das Salzbad oder die gasförmige Atmosphäre eine Verbindung umfasst, die aus der Gruppe bestehend aus Kohlenstoff, stickstoffhaltigen Verbindungen, kohlenstoffhaltigen Verbindungen und Gemischen aus zwei oder mehr der vorstehen erwähnten Verbindungen ausgewählt sind,
    wobei das Tempern in Schritt b) bei einer höheren Temperatur als die Hitzebehandlung in Schritt d) durchgeführt wird.
  2. Verfahren nach Anspruch 1,
    dadurch gekennzeichnet, dass
    das Tempern in Schritt b) in einer Atmosphäre durchgeführt wird, die keine Verbindung enthält, die aus der Gruppe bestehend aus stickstoffhaltigen Verbindungen, kohlenstoffhaltigen Verbindungen und Gemischen aus zwei oder mehr der vorstehend erwähnten Verbindungen ausgewählt ist, und vorzugsweise auch keinen Stickstoff und Kohlenstoff.
  3. Verfahren nach Anspruch 1 oder 2,
    dadurch gekennzeichnet, dass
    das Tempern in Schritt b) bei einer Temperatur zwischen 550 und 700 °C durchgeführt wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    das Tempern in Schritt b) unter Vakuum mit einem Druck von höchstens 10,000Pa und vorzugsweise höchstens 5,000 Pa durchgeführt wird oder das Tempern in Schritt b) in einer reduzierenden Atmosphäre, bevorzugt einer wasserstoffhaltigen Atmosphäre, besonders bevorzugt einer Atmosphäre, die aus Wasserstoff besteht, bei Atmosphärendruck durchgeführt wird.
  5. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    der Gegenstand aus der Legierung besteht, wobei bevorzugt der in Schritt a) vorgesehene kaltverformte Gegenstand aus austenitischem Edelstahl und/oder Duplexstahl besteht und bevorzugt eine Dicke von mindestens 100 µm und bevorzugt von mindestens 5 mm aufweist.
  6. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    Schritt a) das plastische Verformen des Gegenstands bei einer Temperatur von höchstens 300 °C umfasst, bevorzugt anhand einer Methode, die aus der Gruppe bestehend aus Schmieden, Extrusion, Formen, Ziehen, Pressen, Glättwalzen, Walzen und Kombinationen aus zwei oder mehr der vorstehend erwähnten Methoden ausgewählt ist,
    und/oder
    Schritt a) das maschinelle Bearbeiten des Gegenstands bei einer Temperatur von höchstens 200 °C umfasst, bevorzugt anhand einer Methode, die aus der Gruppe bestehend aus Drehen, Fräsen, Stanzen, Schleifen, Polieren und Kombinationen aus zwei oder mehr der vorstehend erwähnten Methoden ausgewählt ist,
    und/oder
    Schritt a) das plastische Verformen des Gegenstands bei einer Temperatur von höchstens 300 °C und maschinelle Bearbeiten des Gegenstands bei einer Temperatur von höchstens 200 °C umfasst, wobei das plastische Verformen vorzugsweise anhand einer Methode durchgeführt wird, die aus der Gruppe bestehend aus Schmieden, Extrusion, Formen, Ziehen, Pressen, Glättwalzen, Walzen und Kombinationen aus zwei oder mehr der vorstehend erwähnten Methoden ausgewählt ist und wobei das maschinelle Bearbeiten bevorzugt anhand einer Methode durchgeführt wird, die aus der Gruppe bestehend aus Drehen, Fräsen, Stanzen, Schleifen, Polieren und Kombinationen aus zwei oder mehr der vorstehend erwähnten Methoden ausgewählt ist.
  7. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    die Hitzebehandlung in Schritt d) als Carburieren in einer gasförmigen Atmosphäre durchgeführt wird, die eine Verbindung umfasst, die aus der Gruppe bestehend aus Kohlenmonoxid, Kohlendioxid, Gemischen aus Kohlenmonoxid und Kohlendioxid, Kohlenwasserstoffverbindungen und Gemischen aus zwei oder mehr der vorstehend erwähnten Verbindungen ausgewählt ist, wobei die Kohlenwasserstoffverbindung bevorzugt aus der Gruppe bestehend aus C1-6-Alkanen, fluorierten C1-6-Alkanen, C1-6-Alkenen, fluorierten C1-6-Alkenen, C1-6-Alkinen, fluorierten C1-6-Alkinen und Gemischen aus zwei oder mehr der vorstehend erwähnten Verbindungen ausgewählt ist, wobei die gasförmig Atmosphäre bevorzugt ferner Wasserstoff umfasst.
  8. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    die Hitzebehandlung in Schritt d) als Nitrieren in einer gasförmigen Atmosphäre durchgeführt wird, die eine stickstoffhaltige Verbindung umfasst und optional ferner Wasserstoff umfasst, wobei die stickstoffhaltige Verbindung bevorzugt Ammoniak und/oder Harnstoff ist.
  9. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    die Hitzebehandlung in Schritt d) als Nitrocarburieren in einer gasförmigen Atmosphäre durchgeführt wird, die i) eine Verbindung umfasst, die aus der Gruppe bestehend aus Kohlenmonoxid, Kohlendioxid, einem Gemisch aus Kohlenmonoxid und Kohlendioxid, Kohlenwasserstoffverbindungen und Gemischen aus zwei oder mehr der vorstehend erwähnten Verbindungen ausgewählt ist, und ii) eine stickstoffhaltige Verbindung umfasst, wobei die Kohlenwasserstoffverbindung bevorzugt aus der Gruppe bestehend aus C1-6-Alkanen, fluorierten C1-6-Alkanen, C1-6-Alkenen, fluorierten C1-6-Alkenen, C1-6-Alkinen, fluorierten C1-6-Alkinen und Gemischen aus zwei oder mehr der vorstehend erwähnten Verbindungen ausgewählt ist, and wobei die stickstoffhaltige Verbindung bevorzugt Ammoniak und/oder Harnstoff ist, wobei die gasförmige Atmosphäre bevorzugt ferner Wasserstoff umfasst.
  10. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    die Hitzebehandlung in Schritt d) bei einer Temperatur zwischen 350 und 510 °C durchgeführt wird, wobei die Hitzebehandlung in Schritt d) bevorzugt über 5 bis 20 Stunden durchgeführt wird.
  11. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    die Hitzebehandlung des Gegenstands in Schritt d) in einer gasförmigen Atmosphäre durchgeführt wird und die Aktivierung in Schritt c) durch Hitzebehandeln des Gegenstands in einer gasförmigen Atmosphäre, die eine Fluorverbindung umfasst, bei einer Temperatur von 250 bis 500 °C durchgeführt wird, wobei die Fluorverbindung bevorzugt aus der Gruppe bestehend aus Fluor, NF3, BF3, CF4, HF, SF6, C2F6, WF6, CHF3, SiF4, fluorierten C1-6-Alkanen, fluorierten C1-6-Alkenen, fluorierten C1-6-Alkinen und Gemischen aus zwei oder mehr der vorstehend erwähnten Verbindungen ausgewählt ist.
  12. Verfahren nach einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass
    das Verfahren kein Erhitzen auf eine Temperatur über 900 °C umfasst, bevorzugt kein Erhitzen auf eine Temperatur über 800 °C umfasst, besonders bevorzugt kein Erhitzen auf eine Temperatur über 750 °C umfasst und ganz besonders bevorzugt kein Erhitzen auf eine Temperatur über 700 °C umfasst.
  13. Oberflächengehärteter Gegenstand, der anhand eines Verfahrens gemäß einem der vorhergehenden Ansprüche erzielt werden kann,
    dadurch gekennzeichnet, dass
    er eine vickers-Härte HV1 aufweist, die nach ASTM E92-16 bei mindestens 150, bevorzugt mindestens 200, besonders bevorzugt mindestens 210 und ganz besonders bevorzugt mindestens 220 gemessen wird,
    und/oder
    eine Oberflächenhärte HV0.05 aufweist, die gemäß ASTM E92-16 bei mindestens 500, bevorzugt mindestens 600, besonders bevorzugt mindestens 650 und ganz besonders bevorzugt mindestens 675 gemessen wird,
    und dadurch gekennzeichnet, dass
    er eine gemäß der DIN EN ISO 8442-1 vom Dezember 1997 gemessene Korrosionsbeständigkeit von weniger als 15 Lochfraßkorrosionspunkten pro 20 cm2 Oberfläche aufweist.
  14. Oberflächengehärteter Gegenstand nach Anspruch 13, wobei dieser eine gemäß der DIN EN ISO 8442-1 vom Dezember 1997 gemessene Korrosionsbeständigkeit von weniger als 5 Lochfraßkorrosionspunkten pro 20 cm2 Oberfläche und bevorzugt von weniger als 1 Lochfraßkorrosionspunkt pro 20 cm2 Oberfläche aufweist.
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