WO2017150738A1 - Élément en acier inoxydable et son procédé de fabrication, et composant en acier inoxydable et son procédé de fabrication - Google Patents

Élément en acier inoxydable et son procédé de fabrication, et composant en acier inoxydable et son procédé de fabrication Download PDF

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WO2017150738A1
WO2017150738A1 PCT/JP2017/008675 JP2017008675W WO2017150738A1 WO 2017150738 A1 WO2017150738 A1 WO 2017150738A1 JP 2017008675 W JP2017008675 W JP 2017008675W WO 2017150738 A1 WO2017150738 A1 WO 2017150738A1
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stainless steel
nitrogen
less
mass
steel member
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PCT/JP2017/008675
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Japanese (ja)
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西田　純一
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日立金属株式会社
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Priority to JP2018503440A priority Critical patent/JP6631860B2/ja
Priority to US16/074,434 priority patent/US20190040506A1/en
Publication of WO2017150738A1 publication Critical patent/WO2017150738A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • 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
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • 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
    • C21D6/004—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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D6/04—Hardening by cooling below 0 degrees Celsius
    • 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
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—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
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C23C8/80—After-treatment
    • 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
    • C21D2211/008—Martensite

Definitions

  • the present invention relates to a stainless steel member that can be used for stainless steel parts such as sliding parts such as piston rings and cams of internal combustion engines, and tool parts such as molds and blades, and a method for manufacturing the same. And this invention relates to said stainless steel components and its manufacturing method.
  • the corrosion resistance of stainless steel can be evaluated by a Pitting Resistance Equivalent (PRE) defined by the component composition of the stainless steel, and the larger this value, the better the corrosion resistance.
  • PRE Pitting Resistance Equivalent
  • Cr + 3.3Mo + 30N—Mn which is proposed as an example of a definition formula of the pitting corrosion index
  • an ingot with a high nitrogen content is produced by adding nitride to the molten steel or dissolving it in a pressurized nitrogen atmosphere. There is a way to do it. However, if the amount of nitrogen added at the time of molten steel is large, nitrogen gas is generated during solidification and blowholes are generated in the ingot. In addition, when electroslag remelting is used for melting in the above nitrogen atmosphere, a special modification for maintaining a pressurized nitrogen atmosphere is required for a normal electroslag remelting apparatus.
  • nitride precipitation method in which stainless steel is treated in an environment around 500 ° C. using ammonia or nitrogen plasma is known. Widely used.
  • nitride precipitation method a nitrogen-enriched layer on which fine nitrides are deposited is formed on the surface of the stainless steel, and the surface of the stainless steel after the nitrogen-enriched layer is formed is hardened.
  • a brittle nitrogen compound such as ⁇ -nitride is easily generated in the nitrogen-enriched layer.
  • nitrogen absorption treatment in which stainless steel is heated and held at a temperature of, for example, about 1000 ° C. in a nitrogen atmosphere.
  • nitrogen absorption treatment nitrogen is added to the surface of stainless steel exclusively in the form of a solid solution, so that a lot of brittle nitrogen compounds are not generated unlike the above-described nitride precipitation method.
  • it processes at high temperature compared with the nitride precipitation method it is advantageous to forming a nitrogen-rich layer thickly.
  • a nitrogen absorption treatment is carried out by contacting the product to austenite the entire product or a part thereof to austenite to produce a product that does not contain Ni (Patent Document 1).
  • Patent Document 2 A method of forming an austenite surface layer containing dissolved nitrogen of 30 wt% or more on stainless steel has been proposed (Patent Document 2).
  • the stainless steel which has a martensitic structure.
  • We have a chemical composition containing Cr: 13.0 to 20.0% by weight, C: 0.1% or less, N: 0.1% or less and the balance being Fe and inevitable impurities.
  • a chromium-based stainless steel plate having a nitrided layer a stainless steel plate having a structure in which the inner layer portion is a single phase of a ferrite phase and a martensite phase appears in the nitrided surface layer portion has been proposed.
  • Patent Document 3 The martensite phase structure has a thickness of about 10 to 30 ⁇ m and a hardness of about 250 HV.
  • the component is wt%, C is in the range of 0.26 to 0.40%, Si is in the range of 1% or less, Mn is in the range of 1% or less, P is in the range of 0.04% or less, S In the range of 0.03% or less, Cr in the range of 12 to 14%, N in the range of 0.02% or less, B in the range of 0.0005 to 0.002%, the balance being Fe and inevitable
  • a martensitic stainless steel is proposed in which a steel material composed of mechanical impurities is heated in a nitrogen atmosphere so that the nitrogen concentration in the surface layer is 0.25 to 0.3%, and is then water quenched. Patent Document 4).
  • the heating in the nitrogen atmosphere is a solid-phase nitrogen absorption method in which the heating is performed in a high-temperature nitrogen atmosphere at 1200 ° C. and 0.1 MPa for 1 to 3 hours, whereby the nitrogen concentration in the steel surface layer is 0.25 to 0.3.
  • the surface hardness of 700 HV or higher is obtained by absorbing nitrogen until it reaches%.
  • a stainless steel containing 0.4 mass% or less of carbon is heated to Ac1 point or more, 0.2 to 0.8 mass% of nitrogen is diffused on the surface, and directly quenched and tempered as it is.
  • Has proposed a method of curing the surface (Patent Document 5).
  • JP 2006-316338 A Japanese Patent Laid-Open No. 7-188733 Japanese Patent Laid-Open No. 5-31336 JP 2010-138425 A German Patent Application Publication No. 4033706
  • An object of the present invention is a stainless steel member having a nitrogen-enriched layer formed on the surface by nitrogen absorption treatment, and the surface of the stainless steel part after quenching and tempering can achieve excellent corrosion resistance and wear resistance. And a method of manufacturing the same. And it is providing the stainless steel components excellent in said corrosion resistance and abrasion resistance, and its manufacturing method.
  • C 0.10 to 0.40%, Si: 1.00% or less, Mn: 0.10 to 1.50%, Cr: 10.0 to 18.0% , N: 2.00% or less, the composition of the remaining Fe and impurities, a stainless steel member having a thickness of 0.3 mm or less, A stainless steel member in which the N content in the range from the surface of the stainless steel member to a depth of at least 0.05 mm is 0.80 to 2.00% by mass.
  • the present invention in mass%, C: 0.10 to 0.40%, Si: 1.00% or less, Mn: 0.10 to 1.50%, Cr: 10.0 to 18.0% N: 2.00% or less, the composition of the remaining Fe and impurities, a martensitic structure having an average crystal grain size of 20 ⁇ m or less, and a stainless steel part having a thickness of 0.3 mm or less, A stainless steel part in which the N content in the range from the surface of the stainless steel part to a depth of at least 0.05 mm is 0.80 to 2.00% by mass, and the hardness in this range is 650 HV or more.
  • the present invention in mass%, C: 0.10 to 0.40%, Si: 1.00% or less, Mn: 0.10 to 1.50%, Cr: 10.0 to 18.0% , N: Less than 2.00%, balance Fe and impurity component composition, stainless steel having a thickness of 0.3 mm or less, heated to 860 ° C. or higher in a nitrogen atmosphere, and then cooled It is a manufacturing method of a member. And this invention is a manufacturing method of the stainless steel component which quenches and tempers the stainless steel member manufactured by the manufacturing method of an above-described stainless steel member.
  • the component composition of the stainless steel, the stainless steel member, or the stainless steel part is further in terms of mass%, Mo: 4.00% or less, W: 8.00%
  • Mo molybdenum
  • W molybdenum
  • at least one of Ni: 1.00% or less and Nb: 0.10% or less may be included.
  • the corrosion resistance and wear resistance of the surface of the stainless steel part can be improved.
  • the characteristics of various sliding parts, molds, blades and the like used in a corrosive environment can be improved.
  • Fig. 6 is a drawing-substituting photograph showing the state of rust generation after a salt spray test of No. 6 (invention example). Sample No. evaluated in the examples. It is a drawing substitute photograph which shows the generation
  • Sample No. evaluated in the examples. 5 is a microphotograph showing an example of a cross-sectional structure in the thickness direction of No. 5 (Example of the present invention).
  • Sample No. evaluated in the examples. 5 is a calibration curve diagram showing the relationship between the N content and the hardness when the N content of this component composition is changed for stainless steel having the component composition of the base material of 5 (Example of the present invention).
  • Sample No. evaluated in the examples. 21 and 22 (examples of the present invention) and sample nos. It is a figure which shows an example of the hardness distribution of the thickness direction of 23 and 24 (comparative example).
  • a feature of the present invention is that a "stainless steel member" having a nitrogen-enriched layer formed on the surface by nitrogen absorption treatment is formed on a “stainless steel part” produced by quenching and tempering.
  • the corrosion resistance and wear resistance of the surface are improved. That is, with respect to wear resistance, first, stainless steel itself as a base material is adjusted to a component composition that “expresses a martensite structure” by quenching and tempering. Then, a nitrogen-enriched layer to which a large amount of nitrogen of “0.80 to 2.00% by mass” is added to the above component composition is formed on the surface of the base material.
  • the surface of the stainless steel part after quenching and tempering (that is, the nitrogen-enriched layer) has achieved a high hardness of “650 HV or higher”.
  • the component composition of the stainless steel that expresses the martensite structure further adjusts the carbon content to a lower level.
  • the formation of coarse carbides in the martensitic structure is suppressed, and the occurrence of corrosion starting from these carbides is suppressed.
  • the average grain size confirmed in the martensite structure is set to “20 ⁇ m or less”, so that the grain boundaries that are the starting points of fracture and corrosion are dispersed, and fatigue characteristics and corrosion resistance are improved.
  • the stainless steel member of the present invention will be described together with a stainless steel part using the member and a preferable manufacturing method for achieving these.
  • the stainless steel member of the present invention is, in mass%, C: 0.10 to 0.40%, Si: 1.00% or less, Mn: 0.10 to 1.50%, Cr: 10.0 ⁇ 18.0%, N: 2.00% or less, balance Fe and impurity component composition.
  • the stainless steel member of the present invention has a component composition in which a quenching and tempering structure “expresses a martensite structure” in a stainless steel part produced by quenching and tempering the member. And about this component composition, it is as follows.
  • C 0.10 to 0.40 mass% (hereinafter simply expressed as “%”)
  • C is an element that suppresses stabilization of ferrite and increases the hardness of the martensite structure. And in said martensitic structure, it is an element which suppresses the coarsening of a crystal grain.
  • coarse Cr-based carbides crystallize in the solidified structure during solidification in the melting process.
  • carbonized_material does not lose
  • cold workability falls and the yield until it finishes to the stainless steel member and stainless steel component of a predetermined shape falls.
  • the hardness of the surface of the stainless steel part is largely achieved by the formation of a nitrogen-enriched layer, which will be described later, so that the composition of the stainless steel itself is designed to be “low carbon”. Is possible. Therefore, the C content is 0.10 to 0.40%. In addition, about a minimum, Preferably it is 0.11%, More preferably, it is 0.12%, More preferably, it is 0.13%. Further, the upper limit is preferably 0.38%, more preferably 0.36%, and still more preferably 0.34%.
  • Si is an element that is used as a deoxidizing agent or the like during steelmaking and can be inevitably included. And when there is too much Si, hardenability will fall. Therefore, the Si content is set to 1.00% or less. Preferably it is 0.80% or less, More preferably, it is 0.65% or less, More preferably, it is 0.50% or less. The lower limit is not particularly limited. And the content of 0.01% or more is realistic.
  • Mn is an element that is used as a deoxidizing agent or the like during steelmaking and can be inevitably included. And in this invention, it is an element which has the effect which accelerates
  • ⁇ Cr: 10.0-18.0% Cr is an element that forms an amorphous passive film on the surface of the stainless steel and imparts corrosion resistance to the stainless steel. It also has an effect of increasing the amount of nitrogen that can be dissolved in stainless steel, and is an element that works effectively in the formation of a nitrogen-enriched layer described later.
  • the Cr content is set to 10.0 to 18.0%. Preferably, it is less than 15.0%. More preferably, it is 14.0% or less. Moreover, Preferably it is 12.0% or more.
  • nitrogen that can be contained in "stainless steel" before nitrogen absorption treatment is performed is an "impurity".
  • the nitrogen amount is 0.02% or less.
  • the shape of the stainless steel is small (thin), such as a plate, strip, or foil, the purpose that nitrogen wants to absorb when nitrogen absorption treatment is performed In some cases, it can be absorbed beyond the surface of the stainless steel, which is a part of the stainless steel, to the central part of the stainless steel (that is, over the entire stainless steel). Therefore, the content of nitrogen in the state of the stainless steel member is 2.00%, assuming the level of impurities before the nitrogen absorption treatment is performed, and eventually the amount that can be added by the nitrogen absorption treatment. The following.
  • the component composition including the above-described element species and the balance being Fe and impurities can be a basic component composition. And it is also possible to contain the following element seed
  • Mo 4.00% or less as required Mo is an effective element for enhancing the corrosion resistance of stainless steel. And it has the effect which strengthens the function of the passive film by Cr in a solid solution state.
  • the passive film made of Cr itself has a self-healing function.
  • Mo has the function of increasing the repair amount of the passive film by increasing the amount of Cr at the spot where the passive film is deposited when Cr is deposited.
  • Mo has a great effect of promoting nitrogen absorption of stainless steel.
  • ferrite will be stabilized like Cr, and the strength of the entire stainless steel part will be reduced. Further, when forming a nitrogen-enriched layer, which will be described later, it takes time for the nitrogen absorption treatment, and the production efficiency is lowered.
  • Mo can contain 4.00% or less as needed. Preferably it is 3.00% or less, More preferably, it is 2.50% or less, More preferably, it is 2.00% or less. In addition, when it contains Mo, Preferably it is 0.10% or more, More preferably, it is 0.50% or more, More preferably, it is 1.00% or more.
  • W 8.00% or less, if necessary W has the same effect as Mo. And since the atomic weight of W is about twice that of Mo, the W content for obtaining an effect amount equivalent to that of Mo can be regarded as twice the amount of Mo. Therefore, W can contain 8.00% or less as needed. Preferably it is 6.00% or less, More preferably, it is 5.00% or less, More preferably, it is 4.00% or less. And when cost etc. are considered, 2.00% or less is especially preferable. In the case where W is contained, it is preferably 0.10% or more, more preferably 0.30% or more, and further preferably 0.50% or more in consideration of cost and the like.
  • Ni 1.00% or less as required Ni has an effect of suppressing further progress of corrosion at the initial stage of corrosion. It also has the effect of increasing the toughness of the base in the organization. On the other hand, when there is too much Ni, austenite becomes stable and it becomes difficult to obtain a martensite structure. Therefore, Ni can contain 1.00% or less as needed. In the present invention in which the stainless steel part has a martensite structure, it is important to suppress the Ni content to 1.00% or less. Preferably it is 0.90% or less, More preferably, it is 0.80% or less. In addition, when it contains Ni, Preferably it is 0.10% or more, More preferably, it is 0.20% or more, More preferably, it is 0.40% or more.
  • Nb 0.10% or less as required Nb has an effect of suppressing the coarsening of the martensite crystal grains in the stainless steel part after quenching and tempering.
  • Nb can contain 0.10% or less as needed.
  • it is 0.09% or less, More preferably, it is 0.08% or less.
  • it is 0.01% or more, More preferably, it is 0.03% or more.
  • the component composition described above can be applied not only to the “stainless steel member” of the present invention but also to the “stainless steel part” of the present invention obtained by quenching and tempering the stainless steel member. And it is applicable also to "stainless steel” which is a base material of these stainless steel members and stainless steel parts, before the nitrogen absorption process mentioned later is performed (before a nitrogen enriched layer is formed in the surface).
  • stainless steel which is a base material of these stainless steel members and stainless steel parts, before the nitrogen absorption process mentioned later is performed (before a nitrogen enriched layer is formed in the surface).
  • the component composition of the stainless steel member (or steel part) and the stainless steel that is the base material thereof is less than 2.00% (that is, N contained in the stainless steel member or stainless steel part). It can be considered substantially the same in its entirety, except that it is less than the upper limit of the quantity.
  • the stainless steel member of the present invention has a nitrogen-enriched layer on the surface of the stainless steel described in (1) above, and the nitrogen content of the nitrogen-enriched layer is nitrogen in the central portion of the stainless steel. It is equal to or greater than the amount and is 0.80 to 2.00% by mass.
  • the stainless steel member of the present invention is obtained by adding nitrogen to the surface of this member in order to achieve excellent corrosion resistance and wear resistance in the state of a stainless steel part produced by quenching and tempering. It has an “enriched layer”.
  • the nitrogen-enriched layer is formed by adding “directly” nitrogen to the above-described stainless steel component composition by a nitrogen absorption treatment described later.
  • the component composition of the nitrogen-enriched layer according to the present invention is the addition of a predetermined amount of nitrogen to the component composition of the stainless steel (base material) before the nitrogen-enriched layer is formed.
  • the component composition of the stainless steel after the analysis is “re-analyzed”.
  • the nitrogen-enriched layer according to the present invention has a reanalyzed component composition in which the amount of nitrogen contained in the stainless steel base material (that is, the central portion of the stainless steel after the nitrogen-enriched layer is formed) And an effective N (nitrogen) amount of “0.80 to 2.00% by mass”.
  • the surface of the stainless steel part (that is, the nitrogen-enriched layer) can be increased in hardness.
  • carbon has the same effect as nitrogen.
  • the effect of improving the hardness is saturated when the amount of addition reaches 0.80% by mass.
  • the hardness is improved even after the addition amount reaches 0.80 mass%.
  • the amount of nitrogen added exceeds about 2.00% by mass, the toughness decreases.
  • the nitrogen amount of the nitrogen-enriched layer according to the present invention is set to 0.80 to 2.00% by mass in the definition of the above component composition.
  • it is 0.85 mass% or more, More preferably, it is 0.90 mass% or more. More preferably, it is 1.00 mass% or more.
  • the surface of the stainless steel part can achieve a high hardness of 650 HV or higher by the nitrogen content.
  • it is 670HV or more, More preferably, it is 700HV or more. More preferably, it is 720HV or more. Although it is not necessary to specify the upper limit of the hardness, 800 HV or less is realistic.
  • the nitrogen added to the surface of the stainless steel is adjusted to the above-mentioned “component that expresses the martensite structure” by adjusting the component composition of the stainless steel.
  • carbon has the same effect as nitrogen.
  • nitrogen has a higher solid solution ability in the austenite structure than carbon.
  • the solid solution amount of nitrogen in the nitrogen-enriched layer can be increased.
  • the formation amount of brittle ⁇ -nitride in the nitrogen-enriched layer is reduced, and the formation amount of coarse carbide due to the low carbonization of the stainless steel is also reduced. Due to these comprehensive effects, the surface of the stainless steel part of the present invention achieves the improvement in corrosion resistance that was effective in the austenitic stainless steel in addition to the above-described increase in hardness.
  • such a nitrogen-enriched layer having an effective N-component composition is formed on the surface of the stainless steel member (or stainless steel part) with an effective thickness of at least about 0.05 mm.
  • This is effective in improving the corrosion resistance and wear resistance of stainless steel parts.
  • the thickness is preferably 0.1 mm or more, more preferably 0.15 mm or more.
  • the stainless steel member has an “effective nitrogen-enriched layer” having the above effective N amount and effective thickness on the surface, thereby improving the corrosion resistance and wear resistance of the stainless steel part. it can.
  • the surface of the stainless steel member is at least 0.05 mm deep.
  • Nitrogen-enriched layer with a sufficient thickness (depth) relative to the thickness of the stainless steel member is ensured by setting the range of N to 0.80 to 2.00% by mass of nitrogen. It is possible to improve the corrosion resistance and wear resistance of the stainless steel part.
  • the component composition of the nitrogen-enriched layer is as follows: “In mass%, C: 0.10 to 0.40%, Si: 1.00% or less, Mn: 0.10 to 1.50%, Cr: 10.0 to 18.0%, N: 0.80 to 2.00%, balance Fe and impurity component composition ”.
  • the lower limit of the thickness of the stainless steel member of the present invention is not particularly required. However, in terms of manufacturing efficiency and handling properties, for example, 0.02 mm or more is realistic.
  • the center of the thickness of the stainless steel member (that is, the position at a depth of T / 2 from the surface of the stainless steel member) or the center
  • the amount of N in the part is the amount of N in the nitrogen-enriched layer (that is, the amount of N of 0.80% by mass or more). It does not have to be included.
  • the amount of N at the center and the center of the stainless steel member is maintained, for example, when the stainless steel base material is used.
  • the amount of nitrogen is within a range of less than 2.00%.
  • the N amount is lower than the N amount of the enriched layer, or the N amount is less than 0.80%.
  • the hardness of the center of a stainless steel part obtained by performing quenching and tempering on such a stainless steel member and the hardness of the central part is less than 650 HV. For example, the hardness when a stainless steel base material is quenched and tempered “as is”.
  • the N amount of the center or central portion of the stainless steel member of the present invention may, of course, be equivalent to (the same value as) the N amount (0.80 to 2.00% by mass) of the nitrogen-enriched layer. If the shape of the stainless steel base material is thin (small), nitrogen may be absorbed up to the center of the stainless steel base material when nitrogen absorption treatment is performed. In other words, this is the case when the “entire” of the stainless steel member is a nitrogen-enriched layer.
  • the thickness T of the stainless steel member of the present invention is 0.1 mm or less, when the surface has the above effective nitrogen-enriched layer (thickness ⁇ 0.05 mm), the stainless steel member The amount of N at the center of (that is, the position at a depth of T / 2 from the surface of the stainless steel member) is also (necessarily) equivalent to (same as) that of the nitrogen-enriched layer.
  • the component composition of this stainless steel member is In the whole, “in mass%, C: 0.10 to 0.40%, Si: 1.00% or less, Mn: 0.10 to 1.50%, Cr: 10.0 to 18.0% , N: 0.80 to 2.00%, remaining Fe and impurity component composition ”. Even such a stainless steel member can achieve excellent corrosion resistance and wear resistance when finished into a stainless steel part.
  • the nitrogen-enriched layer having the above-mentioned component composition is formed by heating and holding the stainless steel as the base material at 860 ° C. or higher in a nitrogen atmosphere. Is preferred. And it is preferable to cool the stainless steel (member) after forming this nitrogen rich layer.
  • the effect of the amount of nitrogen that contributes to the improvement of the hardness of martensitic stainless steel is slightly lower than that of carbon. Therefore, when the low-carbon stainless steel according to the present invention is used as a base material, a large amount of nitrogen can be added to the nitrogen-enriched layer in increasing the hardness to form the nitrogen-enriched layer on the surface. A technique is needed.
  • nitrogen absorption treatment in which stainless steel is heated and held in a nitrogen atmosphere is effective as a method for adding nitrogen to the surface of stainless steel.
  • nitrogen atmosphere for example, nitrogen gas can be used.
  • the atmosphere contains 90% by volume or more of this nitrogen gas.
  • nitrogen of “0.80 mass% or more” is added to the surface of stainless steel by this nitrogen absorption treatment, the stainless steel is heated to a high temperature exceeding 1000 ° C. and held for a long time. There was a need. And if this high temperature and long time heating and holding, a large amount of nitrogen can be added, but at the same time, there is a problem that the crystal grains of the entire stainless steel become coarse. When the crystal grains become coarse, strength characteristics deteriorate and fatigue strength deteriorates.
  • the component composition is adjusted so as to increase the amount of nitrogen dissolved in the austenite structure, so that the nitrogen enrichment can be achieved at a holding temperature of 860 ° C. or higher. It is possible to add 0.80% by weight or more of nitrogen to the layer.
  • the amount of nitrogen added to the nitrogen-enriched layer at the same holding temperature is limited to around 0.5% by mass. Further, when the holding time is a short time of about several minutes assuming a continuous heating furnace or the like, the limit is around 0.3% by mass.
  • the thickness of the proposed stainless steel of the present invention is 0.3 mm or less, it is assumed that N absorbed from the surface of the stainless steel by the above nitrogen absorption treatment diffuses to the center of the stainless steel. However, a sufficient amount of N can be secured even on the surface of the stainless steel, and a nitrogen-enriched layer having an effective thickness (depth) can be formed.
  • the fatigue resistance and corrosion resistance of the stainless steel part can be improved.
  • it is 18 micrometers or less, More preferably, it is 16 micrometers or less, More preferably, it is 14 micrometers or less. It is not necessary to specify the lower limit of the average crystal grain size. However, 8 ⁇ m or more is realistic.
  • the upper limit of the holding temperature is preferably 1000 ° C. or less in consideration of the coarsening of crystal grains. And it is preferable to set the optimal combination of holding temperature and holding time within this temperature range.
  • the holding time is 1 hour or more or 2 hours or more.
  • the holding temperature is 6 hours or less or 5 hours or less.
  • a preferable holding temperature is 870 ° C. or higher.
  • a more preferable holding temperature is 980 ° C. or lower, more preferably 970 ° C. or lower.
  • the stainless steel (member) after the nitrogen absorption treatment is once cooled as described above, and the structure of the formed nitrogen-enriched layer is a ferrite structure or a martensite structure.
  • the structure of the nitrogen-enriched layer is austenite transformed again in the heating step, new austenite grains are generated, and the refinement of crystal grains is achieved.
  • the quenching temperature is, for example, 950 to 1200 ° C.
  • the heating atmosphere to said quenching temperature shall be "non-oxidizing atmosphere" which can suppress the chemical influence (change of N amount) to a nitrogen rich layer.
  • the non-oxidizing atmosphere for example, a vacuum environment (including a reduced pressure atmosphere) or a non-oxidizing gas such as hydrogen gas can be used. And as a specific example, it is a non-oxidizing atmosphere of purity containing 90 volume% or more of non-oxidizing gas. Moreover, after quenching, it is preferable to perform a sub-zero treatment in order to promote transformation into a martensite structure and stabilize the refined crystal grains. Then, by tempering the quenched stainless steel member, a stainless steel part having an average crystal grain size of 20 ⁇ m or less in the structure and a hardness of the surface nitrogen-enriched layer of 650 HV or more is obtained. Can do.
  • the tempering temperature is, for example, 150 to 650 ° C.
  • tempering is preferably “low temperature tempering”. For example, 200 to 400 ° C. By lowering the tempering temperature, it is possible to suppress the precipitation of Cr-based carbides and nitrides in the nitrogen-enriched layer, and the deficiency of Cr in the portion adjacent to this precipitation location can be suppressed. Corrosion resistance can be maintained high.
  • the stainless steel before performing the nitrogen absorption treatment may be subjected to a soaking treatment that is held for a long time at a high temperature of around 1200 ° C. at the time of ingot, for example.
  • a component design is performed so that coarse Cr carbides do not crystallize during solidification.
  • coarse Cr carbide may crystallize due to segregation.
  • the coarse Cr-based carbide can be dissolved in the structure by the soaking process described above.
  • the stainless steel before performing the nitrogen absorption treatment is arranged in a substantially part (product) shape by machining or the like. If it is the state of the low carbon steel which does not contain nitrogen, it will be easy to process and a manufacturing yield will also be large. Therefore, it is desirable to process the shape as close to the final shape as possible before curing by adding nitrogen.
  • a 10 kg molten metal melted in a high-frequency induction melting furnace was cast to produce a stainless steel ingot having chemical components shown in Table 1. Note that the N content of these ingots was 0.02% or less.
  • hot forging with a forging ratio of about 10 was performed on these ingots, and after cooling, annealing was performed at 780 ° C. to obtain annealed materials.
  • plate material was cut out from these annealing materials, the cold rolling was performed to this board
  • the furnace After performing the “nitrogen absorption treatment” in which the stainless steel base material made of the above-mentioned strip is heated in a nitrogen atmosphere made of atmospheric nitrogen gas (purity 99%), the furnace is cooled to 600 ° C. or lower, and the furnace The outside was taken out (room temperature), and the stainless steel member was produced.
  • Table 1 shows the heating temperature and holding time in the nitrogen absorption treatment.
  • Table 1 also shows the nitrogen content of the nitrogen-enriched layer formed by the nitrogen absorption treatment.
  • the shape of the stainless steel subjected to the nitrogen absorption treatment was a thin strip with a thickness of 0.15 mm, the entire surface in the thickness direction was more than both surfaces (front and back surfaces).
  • the amount of nitrogen contained in the nitrogen-enriched layer could be replaced with the amount of nitrogen obtained for the entire sample including the surface to the center of the sample.
  • the amount of nitrogen generated by melting the entire sample was obtained from the thermal conductivity, and this was used as the amount of nitrogen contained in the nitrogen-enriched layer.
  • this stainless steel member was quenched and tempered to produce a stainless steel part.
  • the above stainless steel member was put in a furnace having an atmosphere of hydrogen gas (atmospheric pressure, purity 99%) heated to 1100 ° C. for 2 minutes, and then rapidly cooled. After quenching, sub-zero treatment at ⁇ 75 ° C. was performed. The tempering temperature was 350 ° C. Then, the average crystal grain size of the martensite structure of the stainless steel part and the hardness of the nitrogen-enriched layer were measured. The average crystal grain size was measured by a line segment method. First, the structure of the cross section (so-called TD cross section) in the thickness direction of the stainless steel part was observed with an optical microscope ( ⁇ 1000) (FIG.
  • Sample No. 1 aims at increasing the hardness of the surface of stainless steel parts by “the effect of carbon addition” by increasing the carbon content of stainless steel used as a base material and not performing nitrogen absorption treatment. .
  • the average crystal grain size in the martensite structure was 20 ⁇ m or less.
  • the result of the salt spray test is the generation
  • FIG. 3 shows the sample No. when the tempering temperature is 550 ° C. 1 is a microphotograph of a cross-sectional structure in the thickness direction observed with an optical microscope ( ⁇ 1000 magnification) (upper and lower limits in the figure correspond to both surfaces of a strip). It is easy to confirm the shape of the carbide by observing at a tempering temperature of 550 ° C. From FIG. In 1, a slightly coarse carbide was confirmed.
  • Sample No. Nos. 2 to 4 are obtained by subjecting stainless steel having the same composition to a base material to nitrogen absorption treatment under various conditions.
  • Sample No. No. 2 exhibited excellent corrosion resistance due to the appropriate component composition of stainless steel as a base material.
  • the average crystal grain size of the martensitic structure was 20 ⁇ m or less.
  • the amount of nitrogen contained in the nitrogen-enriched layer was low and the hardness was less than 650 HV due to the low heating and holding temperature during the nitrogen absorption treatment.
  • Sample No. No. 3 also showed sufficient corrosion resistance due to the appropriate component composition of stainless steel as a base material, although there was some nitride formation in the nitrogen-enriched layer.
  • the average crystal grain size of the martensite structure was also 20 ⁇ m or less.
  • FIG. 5 shows sample No. 1 when the tempering temperature is 550 ° C. 4 shows a microstructure photograph.
  • Sample No. 5 is a case where stainless steel as a base material contains about 2% of Mo. By containing Mo, the base material easily absorbs nitrogen, and the amount of nitrogen contained in the nitrogen-enriched layer is increased. And sample no. 5 is coupled with the fact that the structure of the entire sample was almost completely martensitic (FIG. 6 is a microphotograph of the cross-sectional structure of sample No. 5 when the tempering temperature is 550 ° C.). The hardness of the nitrogen-enriched layer achieved a high hardness exceeding 700 HV. Sample No. No. 5 was also excellent in corrosion resistance. And the average crystal grain size was 20 ⁇ m or less.
  • Sample No. 6 is obtained by adding a small amount of Nb to stainless steel as a base material.
  • the amount of nitrogen contained in the nitrogen-enriched layer was high, and the average crystal grain size of the martensite structure was 20 ⁇ m or less, which was excellent in both hardness and corrosion resistance characteristics.
  • Sample No. Nos. 7 and 8 are obtained by subjecting stainless steel having the same component composition adjusted to a higher carbon content to a base material and nitrogen absorption treatment under various conditions. In both samples, there was no formation of coarse carbides in the structure, and excellent corrosion resistance was achieved. However, sample No. No. 7 had a low nitrogen content and a hardness of less than 650 HV due to the low heating and holding temperature during the nitrogen absorption treatment. In both samples, the average crystal grain size of the martensite structure was 20 ⁇ m or less.
  • Sample No. 9 is prepared by adjusting the Cr contained in the stainless steel as the base material to about 8%. And by reducing this amount of Cr, it became difficult for the base material to absorb nitrogen, and the amount of nitrogen contained in the nitrogen-enriched layer was low. And sufficient corrosion resistance was not obtained.
  • the average crystal grain size of the structure exceeded 20 ⁇ m.
  • Sample No. 10 and 11 are obtained by adding W to stainless steel as a base material.
  • the amount of nitrogen contained in the nitrogen-enriched layer increased to achieve high hardness exceeding 700 HV and sufficient corrosion resistance.
  • the average crystal grain size of the martensite structure was 20 ⁇ m or less.
  • Sample No. No. 12 is obtained by increasing Cr contained in stainless steel as a base material to 17% and adding about 2% Mo. This makes it easier for the base material to absorb nitrogen, and a large amount of nitrogen can be added to the nitrogen-enriched layer even with nitrogen absorption treatment under almost the same conditions as other samples. And the structure
  • Sample No. No. 13 is obtained by adding Ni to stainless steel as a base material. And the nitrogen content which a nitrogen enrichment layer contains was high, and the average crystal grain diameter of the martensite structure
  • tissue is also 20 micrometers or less, and achieved the outstanding hardness and sufficient corrosion resistance.
  • the above stainless steel member was quenched and tempered to produce a stainless steel part. Quenching is performed by putting the above stainless steel member in a furnace made of hydrogen gas (atmospheric pressure, purity 99%) heated to 1100 ° C. for 2 minutes in common for all thicknesses. It was supposed to be cooled rapidly. After quenching, sub-zero treatment at ⁇ 75 ° C. was performed. The tempering temperature was 350 ° C. And the average crystal grain diameter of the martensitic structure of these stainless steel parts and the N amount, depth, and hardness of the nitrogen-enriched layer formed on the stainless steel parts were measured.
  • hydrogen gas atmospheric pressure, purity 99%
  • the procedure for measuring the average crystal grain size was in accordance with Example 1.
  • sample No For a stainless steel having a component composition of 5 base material, a “calibration curve” showing the relationship between the N content and the hardness when the N content of this component composition changed was prepared (FIG. 7).
  • TD cross section the structure of the cross section in the thickness direction of the stainless steel part
  • the hardness distribution in the thickness direction is measured, and the N amount corresponding to the hardness obtained by this measurement is calculated by the above calibration.
  • FIG. 8 shows the hardness distribution in the thickness direction of the above four types of stainless steel parts. Then, the amount of N from the surface of the above four types of stainless steel parts is evaluated, and the portion whose value is “0.80 to 2.00% by mass” is defined as a nitrogen-enriched layer. Was able to identify the depth of. As a result of the measurement using the calibration curve, the above four types of stainless steel parts had a converted N amount of “2.00% by mass or less” in the entire range in the thickness direction.
  • FIG. 9 shows the N amount distribution in the thickness direction of the above four types of stainless steel parts.
  • Sample No. 21 and 22 are stainless steel parts (members) having a thickness of 0.3 mm or less, and N absorbed from both surfaces (front and back surfaces) by the nitrogen absorption treatment reached the center.
  • the N amount is “0.80 to 2.00% by mass” over the entire thickness range (that is, the entire stainless steel part (member) can be regarded as a nitride-enriched layer).
  • a surface hardness of 650 HV or higher was achieved.
  • the average crystal grain size was also 20 micrometers or less, and it was excellent also in corrosion resistance.
  • sample No. 23 and 24 are stainless steel parts (members) having a thickness exceeding 0.3 mm. Sample No.
  • the N content at the center is higher than the nitrogen content (0.02% or less) of the stainless steel base material, and the N absorbed from the surface by the nitrogen absorption treatment reaches the center. It was. However, the thickness (depth from the surface) of the nitrogen-enriched layer where the N amount is “0.80 mass% or more” is as small as less than 0.05 mm, and the depth of 0.05 mm from the surface after quenching and tempering. The hardness at this position was less than 650 HV. Note that the average crystal grain size exceeded 20 ⁇ m. Corrosion resistance was measured according to Sample No. Compared to 21 and 22.

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Abstract

L'invention concerne un composant en acier inoxydable présentant une excellente résistance à la corrosion et une excellente résistance à l'abrasion et son procédé de fabrication, un élément en acier inoxydable approprié pour fabriquer le composant, et un procédé de fabrication de l'élément en acier inoxydable. La présente invention est un élément en acier inoxydable présentant une épaisseur de 0,3 mm ou moins et contenant une composition de composant comprenant, en termes de % en masse, 0,10 à 0,40 % de C, 1,00 % ou moins de Si, 0,10 à 1,50 % de Mn, 10,0 à 18,0 % de Cr, et 2,00 % ou moins de N, le reste étant Fe et des impuretés, la quantité de N dans une plage de profondeurs d'au moins 0,05 mm depuis la surface de l'élément en acier inoxydable étant comprise entre 0,80 et 2,00 % en masse. La présente invention concerne également un procédé de fabrication de l'élément en acier inoxydable, un composant en acier inoxydable qui utilise l'élément en acier inoxydable, et un procédé de fabrication du composant en acier inoxydable.
PCT/JP2017/008675 2016-03-04 2017-03-06 Élément en acier inoxydable et son procédé de fabrication, et composant en acier inoxydable et son procédé de fabrication WO2017150738A1 (fr)

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JP2019173171A (ja) * 2018-03-27 2019-10-10 大阪冶金興業株式会社 ステンレス鋼の熱処理方法
JP2020094275A (ja) * 2018-12-04 2020-06-18 日立金属株式会社 マルテンサイト系ステンレス鋼部品およびその製造方法

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ES2805067T3 (es) * 2016-04-22 2021-02-10 Aperam Procedimiento de fabricación de una pieza de acero inoxidable martensítico a partir de una chapa
KR102326693B1 (ko) * 2020-03-20 2021-11-17 주식회사 포스코 고내식 마르텐사이트계 스테인리스강 및 그 제조방법
JP2024008729A (ja) 2022-07-08 2024-01-19 大同特殊鋼株式会社 窒素富化処理用マルテンサイト系ステンレス鋼及びマルテンサイト系ステンレス鋼部材

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