EP2832876B1 - High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same - Google Patents

High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same Download PDF

Info

Publication number
EP2832876B1
EP2832876B1 EP13767507.0A EP13767507A EP2832876B1 EP 2832876 B1 EP2832876 B1 EP 2832876B1 EP 13767507 A EP13767507 A EP 13767507A EP 2832876 B1 EP2832876 B1 EP 2832876B1
Authority
EP
European Patent Office
Prior art keywords
steel wire
spring
stainless steel
strength
wire
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13767507.0A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2832876A1 (en
EP2832876A4 (en
Inventor
Masayuki Tohjoh
Kohji Takano
Haruhiko Kajimura
Tsuneo Akiura
Gou TOYODA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Seisen Co Ltd
Nippon Steel Stainless Steel Corp
Original Assignee
Nippon Seisen Co Ltd
Nippon Steel and Sumikin Stainless Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Seisen Co Ltd, Nippon Steel and Sumikin Stainless Steel Corp filed Critical Nippon Seisen Co Ltd
Publication of EP2832876A1 publication Critical patent/EP2832876A1/en
Publication of EP2832876A4 publication Critical patent/EP2832876A4/en
Application granted granted Critical
Publication of EP2832876B1 publication Critical patent/EP2832876B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • 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
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—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
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—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
    • 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
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • 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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • 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
    • 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
    • C21D9/02—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs

Definitions

  • the present invetion relates to a high-strength stainless steel wire used as parts which require heat resistance and high-strength properties, such as automobile engine exhaust system parts and electrical components, and mainly used as a heat resistant steel wire rod for such as a heat setting resistant spring, and a heat resistant rope.
  • the present invetion relates to a precipitation hardening metastable austenitic stainless steel wire with high-strength having a metallographic structure of austenite ( ⁇ ) phase + deformation induced martensite ( ⁇ ') phase, and fine precipitates are controlled by cold working and aging treatment with addition of Mo, Al, and the like.
  • the present invetion relates to a high-strength heat resistant stainless steel wire, a high-strength spring using the same, and particularly to, a high-strength heat resistant spring, and a method for manufacturing the same.
  • Patent Documents 1 and 2 an austenitic stainless steel wire to which Mo, Al, Ti, and the like are added has been proposed (Patent Documents 1 and 2).
  • the heat setting resistance is improved by such component adjustment.
  • the amount of deformation induced martensite is small and the tensile strength is less than 1800 MPa.
  • the strength is insufficient and is not sufficient as a high-strength spring product.
  • Patent Document 3 martensite stainless steel obtained by using precipitation hardening of Mo, Al, and the like has been also proposed.
  • Patent Document 3 since the content of C is high, and martensite is already formed in the stainless steel after heat treatment, workability is deteriorated. Further, a large amount of work hardening cannot be expected and the strength is not sufficient as a high-strength spring product.
  • Patent Document 4 precipitation hardening austenitic steel with high-strength obtained by using precipitation hardening of Mo, Al, Cu, and the like also has been proposed.
  • Patent Document 4 since a large amounts of Ni and Cu are contained in the stainless steel, high material costs are required.
  • deformation induced martensite is suppressed in the stainless steel, heat setting resistance is not satisfactory.
  • Patent Document 5 discloses precipitation hardenable martensitic stainless steels for the production of stainless springs with a composition consising of (in wt.%) up to 0.08 C, 0.5-4 Si, up to 4.0 Mn, 5-9 Ni, 10-17 Cr, more than 0.3-2.5 Mo, 0.15-1 Ti, up to 1 Al, up to 0.03 N, balance Fe and unavoidable impurities.
  • Patent Document 6 discloses precipitation hardenable stainless steel of such composition balance as to be martensitic in the solution-treated condition and precipitation-hardenable both by single heat-treatment and by double heat-treatment.
  • An object of the present invention is to provide a high-strength stainless steel wire having both of sufficient high-strength properties and heat setting resistance (heat deformation resistance) even under a temperature environment on the assumption that the stainless steel wire is used as a heat resistant material for particularly a heat setting resistant spring which is frequently used in the warm temperature region, and to provide a high-strength spring made of the steel wire, and a method for manufacturing the same.
  • the precipitation hardening high-strength stainless steel wire having excellent heat setting resistance has a large amount of deformation induced martensite ( ⁇ ') and a predetermined tensile strength in a wire drawing stage.
  • the high-strength stainless steel wire according to the aspect of the present invention is formed into a spring shape and then subjected to aging treatment to facilitate formation of fine compounds, particularly, precipitation of fine compounds uniformly dispersed in the surface layer of the steel wire. Accordingly, it is possible to impart higher strength and heat setting resistance, particularly in a warm temperature region. Therefore, it is possible to provide a high-strength spring product having both of high strength and excellent heat setting resistance, which are hardly achieved in a conventional steel wire. Accordingly, the high-strength stainless steel wire according to the aspect of the present invention is suitable for a high-strength spring which particularly requires severe quality properties.
  • the method for manufacturing a spring according to the aspect of the present invention can be performed in a normal low-temperature heat treatment range and can be performed stably without particular cost increase by continuously performing treatments.
  • a high-strength stainless steel wire having excellent heat setting resistance contains, by mass%, C 0.04% to 0.12%, N: 0.005% to 0.03%, 0.05% ⁇ (C + N) ⁇ 0.13%, Si: 0.1% to 2.0%, Mn: 0.1% to 2.0%, Ni: 6.8% to 9.0%, Cr: 12.0% to 14.4%, Mo: 1.0% to 3.0%, and Al: 0.5% to 2.0%, further optionally comprising one or more selected from V: 0.01% to 1.0%, Nb: 0.01% to 1.0%, Ti: 0.01% to 1.0%, W: 0.05% to 2.0%, Ta: 0.05% to 2.0%, Cu: 0.8% or less, Co: 0.1% to 2.0%, B: 0.0005% to 0.015%, Ca: 0.0005% to 0.01%, Mg: 0.0005% to 0.01% and REM: 0.0005% to 0.1% and/or P:0.015 to 0.045%, and/or S: 0.0001% to 0.01%, and with a balance being Fe and una balance being Fe
  • the amount of deformation induced martensite ( ⁇ ') in the matrix is in a range of 80 vol% to 99 vol%, and the tensile strength is in a range of 1800 MPa to 2200 MPa.
  • the high-strength stainless steel wire according to the embodiment is a heat resistant stainless steel wire having high-strength, and is suitable for, for example, a spring wire rod, particularly, a wire rod that is used in a warm temperature region in which an environment temperature is in a range of 100°C to 300°C.
  • MdS 551 ⁇ 462 C + N ⁇ 9.2 ⁇ Si ⁇ 8.1 ⁇ Mn ⁇ 29 Ni + Cu ⁇ 13.7 ⁇ Cr ⁇ 18.5 ⁇ Mo
  • the chemical symbols in the expression represent the contents (mass%) of the respective elements.
  • 0 is substituted for the content of the element.
  • the shape of the stainless steel wire is not particularly limited and the stainless steel wire of the embodiment is frequently used as a normal wire rod, for example, as a fine wire for secondary working having a wire diameter of 6 mm or less, more specifically, having a wire diameter of about 0.05 mm to 3 mm.
  • the shape thereof is not particularly limited, and for example, the stainless steel wire of the embodiment is used as a non-circular wire rod such as a flat wire or a square wire, in addition to a round wire.
  • the wire can be applied to various shapes.
  • the shape of the stainless steel wire of the embodiment also includes a wire rod whose cross section shape is not circular, and thus, regarding the wire diameter indication, for example, an equivalent wire diameter (d) calculated from an area of an arbitrary transverse cross section of the wire is used.
  • the stainless steel wire has a precipitation hardening function, and fine compound particles are precipitated and distributed in the matrix by aging treatment which is performed in the final stage.
  • a precipitation element such as Al or Mo
  • an appropriate amounts of N and C are added to the composition so as to exhibit the precipitation hardening function.
  • NiAl or Mo based compound particles are uniformly dispersed and precipitated in the deformation induced martensite phase near the surface layer of the steel wire which is subjected to hard working according to conditions in drawing such as cold wire drawing, cold rolling, and the like.
  • austenitic stainless steel is work-hardened by cold working, and one of the factors is an influence of a deformation induced martensite phase induced by the working.
  • the amount of deformation induced martensite (the amount of formed deformation induced martensite) varies greatly depending on the balance of component composition of each element constituting the steel and the working conditions.
  • the amount of formed deformation induced martensite is only about several percents.
  • formation of deformation induced martensite due to cold working is actively facilitated and the composition is adjusted such that the amount of the formed deformation induced martensite is increased to 80 vol% to 99 vol%.
  • the tensile strength of the steel wire itself is increased to 1800 MPa to 2200 MPa in a state of being subjected to cold working such as wire drawing, to achieve high strength, which is one of the features of the embodiment.
  • the composition is adjusted so that a deformation induced martensite formation index MdS value is in a range of 15 to 60, and the stainless steel is subjected to wire drawing under predetermined working conditions.
  • a deformation induced martensite formation index MdS value is an index indicating the balance of each component composition.
  • the MdS value refers to a temperature at which 50% of the structure is transformed into a martensite phase when 30% of tensile deformation is applied to the stainless steel, and a level of the amount of deformation induced martensite formed during working is grasped from a relationship with the component elements.
  • the reason why MdS value is set in the above range is as follows. In the case where the MdS value is less than 15, stabilization of the austenite phase is increased and the amount of deformation induced martensite is decreased to less than 80 vol% after wire drawing, and thus, high-strengthening is hardly achieved. In addition, the amount of precipitation hardening by aging treatment at a temperature of 300°C to 600°C is reduced and heat setting resistance is also deteriorated. On the other hand, in the case where the MdS value is more than 60, surplus deformation induced martensite of more than 99 vol% is formed in predetermined wire drawing, and ductility and toughness is decreased after the wire drawing, and thus, manufacturability is deteriorated.
  • the range of the MdS value is more preferably in a range of 20 to 50.
  • the amount of deformation induced martensite can be set to be in a range of 80 vol% to 99 vol% and improvement of each property is facilitated in the stainless steel wire of the embodiment. That is, in the case where the amount of deformation induced ⁇ ' (martensite) is less than 80 vol% in the matrix, even when aging treatment is performed, required high-strength properties cannot be obtained in the spring product. Contrarily, in the case where the amount of deformation induced ⁇ ' (martensite) is more than 99 vol%, structure stability is poor, and corrosion resistance and toughness are hardly satisfied. In addition, deterioration in spring fatigue resistance is expected.
  • the amount of deformation induced martensite is preferably in a range of 83 vol% or more and more preferably in a range of 85 vol% or more. Further, the amount of deformation induced martensite is preferably in a range of 95 vol% or less, and more preferably in a range of 90 vol% or less.
  • a method for measuring an amount of martensite for example, various methods such as a method using a ferrite scope, a magnetic method, and a method using an X-ray can be employed and a test sample which is arbitrarily collected from the stainless steel wire is used in the measurement.
  • a magnetic method there are many descriptions in "Iron and Steel” (81-S1163) of The Iron and Steel Institute of Japan, and the like.
  • a saturation magnetization value of the wire rod was measured at 1.0 ⁇ 10 4 Oe using a DC flux meter, and the amount of deformation induced martensite ( ⁇ ') was calculated by using the following Expressions (4) to (6).
  • the stainless steel wire has high-strength properties in which tensile strength ( ⁇ B ) is in a range of 1800 MPa to 2200 MPa in a state in which the steel wire is subjected to cold wire drawing.
  • the tensile strength can be measured according to, for example, JIS-Z2241. In the case where the tensile strength is less than 1800 MPa, significant improvement in strength properties cannot be expected even by the following aging treatment. In addition, in the case where the tensile strength is more than 2200 MPa, problems occur in terms of product quality in a spring forming stage, for example, variations in the shape of the spring increases, brittle fracture is easily induced, or the like arises.
  • the tensile strength is more preferably in a range of 1900 MPa to 2100 MPa.
  • the stainless steel wire of the embodiment which is subjected to cold wire drawing, is subjected to aging treatment, strength properties are further rapidly improved.
  • a preferable value of a tensile strength of 2100 MPa to 2600 MPa can be obtained. Accordingly, for example, in the case where the spring product is used in a linear state such as a microshaft part, the wire is subjected to the wire drawing and then subjected to shape correction, and the shape-corrected wire is subjected to continuous aging treatment to form a long spring material. In this manner, it is possible to further increase mechanical properties in the wire state. These treatments can be continuously performed.
  • the embodiment includes the stainless steel wire subjected to aging treatment after the cold wire drawing as another configuration.
  • the tensile strength in the case where the stainless steel wire is subjected to aging treatment is in a range of 2100 MPa to 2600 MPa.
  • the lower limit of the tensile strength is more preferably 2200 MPa, and the upper limit thereof is more preferably 2500 MPa.
  • the aging treatment condition of the steel wire can be appropriately set so that the tensile strength is within the above range after the aging treatment is performed. Examples of the condition include the aging treatment condition after spring forming which will be described later.
  • a proof stress ratio ⁇ ( ⁇ 0.2 / ⁇ B ) ⁇ 100 ⁇ of the tensile strength ( ⁇ B ) to 0.2% proof stress ( ⁇ 0.2 ) can be obtained with the tensile strength ( ⁇ B ).
  • the proof stress ratio is preferably in a range of 80% to 95%.
  • Such stainless steel wire is effective as a heat resistant spring material in which the strength is high and the fatigue fracture is improved. In the case where the proof stress ratio is less than 80%, predetermined elastic properties cannot be obtained. In the case where the proof stress ratio is more than 95%, there is a concern of adverse influence on a yield during severe spring working.
  • the lower limit of the proof stress ratio is more preferably 83%, and the upper limit thereof is more preferably 91%.
  • twisting properties measured by the following torsion test can be mentioned.
  • the twisting properties are measured as follows. While a test sample collected from the stainless steel wire is held in a gage length which is 100 times longer than the equivalent wire diameter, one end of the test sample is twisted and rotated. Then, a torsion number is measured until the stainless steel wire is fractured.
  • the torsion number indicates torsional performance. For example, when the cold-worked stainless steel wire has high torsional performance in which the torsion number is 5 times or more, for example, about 5 times to 10 times or more without vertical cracks, the steel wire can be widely used in various spring products.
  • the torsional performance is about 2 times or 3 times, or vertical cracks easily occur. Therefore, for example, when the steel wire is worked into a spring under severe conditions as in the case where the steel wire is worked into a coil spring in which a ratio D/d of a wire diameter (d) to an average coil diameter (D) is 4 times or less, there is a concern of adverse influence on a yield. That is, a spring can be formed irrespective of the torsion value, but a stainless steel wire exhibiting a torsion value of 5 times or more without vertical cracks is preferable for spring forming and the torsion value is more preferably 6 times or more.
  • torsion test 2 for example, as described in JIS-G4314, the stainless steel wire is twisted and rotated until the steel wire is fractured. Then, the toughness state of the stainless steel wire is evaluated by observing the fracture surface.
  • FIG. 1 shows an example of a fracture surface.
  • FIG. 1(a) shows an almost uniform fracture surface and the fracture surface is good.
  • FIG. 1(b) torsional cracks and brittle fracture are observed in a part of the transverse cross section.
  • the above torsion number can be satisfied.
  • the unit of the content of each element is mass%.
  • the amount of C is preferably less than 0.10%, and more preferably in a range of 0.04% to 0.09%.
  • N is an element which contributes to increasing strength and is effective in refining grains of the material before cold working during solution treatment by forming carbonitrides. Therefore, 0.005% or more of N is added. However, in the case where the added amount of N is more than 0.03%, coarse nitrides such as AlN and the like are formed, and ductility and toughness are deteriorated. Thus, manufacturability is greatly deteriorated. Accordingly, the upper limit of the amount of N is set to 0.03%.
  • the lower limit of the N content is preferably 0.01%, and the upper limit thereof is preferably 0.025%.
  • Both of C and N are interstitial elements and cause strain to contribute to solute strengthening acting on strengthening.
  • C and N are effective in forming a Cottrell atmosphere or fine carbonitrides and fixing dislocations in the metallographic structure.
  • a total amount (C + N) of added C and N is 0.05% or more.
  • the upper limit of C + N is set to 0.13%.
  • the amount of C + N is preferably in a range of 0.08% to 0.11%.
  • Si causes deoxidation, 0.1% or more of Si is added. However, in the case where the added amount of Si is more than 2.0%, the effect is saturated and also manufacturability is deteriorated. Thus, the upper limit of the amount of Si is set to 2.0%.
  • the amount of Si is preferably in a range of 0.3% to 1.0%.
  • Mn causes deoxidation, 0.1% or more of Mn is added. However, in the case where the added amount of Mn is more than 2.0%, corrosion resistance is deteriorated. In addition, the amount of deformation induced martensite ( ⁇ ') is reduced and thus, strength is decreased. Also, heat setting resistance is deteriorated. Thus, the upper limit of the amount of Mn is set to 2.0%. The amount of Mn is preferably in a range of 0.5% to 1.5%.
  • Ni 6.8% or more of Ni is added to secure the ductility and toughness of the material and to obtain an appropriate amount of deformation induced martensite in wire drawing.
  • the added amount of Ni is more than 9.0%, the MdS value is decreased and the amount of deformation induced martensite is reduced, and thus, strength is decreased. Further, heat setting resistance is also deteriorated. Therefore, the upper limit of the amount of Ni is set to 9.0%.
  • the amount of Ni is preferably in a range of more than 7.0% and 8.5% or less, and more preferably in a range of 7.5% to 8.2%.
  • the amount of Cr is preferably in a range of 13.0% to 14.0%.
  • Mo is solid-solubilized in an austenite matrix to increase the hardness of the matrix and further Mo alleviates heat setting caused by temperature rising when the steel wire is used. Moreover, Mo allows fine Mo-based metal clusters to be finely precipitated in the deformation induced martensite by aging treatment at a temperature of 300°C to 600°C when a spring is manufactured. Accordingly, strength is increased and heat setting resistance is improved. Therefore, Mo is an effective element in increasing strength and improving heat setting resistance, and 1.0% or more of Mo is added. However, in the case where the added amount of Mo is more than 3.0%, the effect is saturated and the MdS value is decreased. Thus, the amount of deformation induced martensite is reduced and strength is decreased. Also, heat setting resistance is deteriorated. Therefore, the upper limit of the amount of Mo is set to 3.0%. The amount of Mo is preferably in a range of 1.5% to 2.6%, and more preferably in a range of 1.7% to 2.3%.
  • A1 allows fine NiAl-based metal compounds to be finely precipitated in the deformation induced martensite by, for example, aging treatment at a temperature of 300°C to 600°C when a spring is manufactured. Accordingly, strength is increased and heat setting resistance is improved. Therefore, A1 is an effective element in increasing strength and improving heat setting resistance, and 0.5% or more of A1 is added. However, in the case where the added amount of A1 is more than 2.0%, the effect is saturated and manufacturability is deteriorated. Therefore, the upper limit of the amount of A1 is set to 2.0%.
  • the amount of A1 is preferably in a range of 0.7% to 1.5%, and more preferably in a range of 0.9 % to 1.2%.
  • the stainless steel wire contains these constitutional elements, and the components are adjusted such that the MdS value is in a range of 15 to 60, and the stainless steel wire includes Fe and unavoidable impurities as the balance.
  • the unavoidable impurities include O: 0.001% to 0.01%, Zr: 0.0001% to 0.01%, Sn: 0.001% to 0.1%, Pb: 0.00005% to 0.01%, Bi: 0.00005% to 0.01%, Zn: 0.0005% to 0.01%, materials contained in a raw material and a heat resistance material, which are mixed in stainless steel during manufacturing of normal stainless steel, and a total amount of the elements and the materials of 2.0% or less is allowable.
  • the embodiment can contain at least one selected from the following elements.
  • a first group includes V, Nb, Ti, W, and Ta, and these elements respectively form fine carbonitrides. Accordingly, these elements contribute to increasing strength and improving heat setting resistance by refining grains.
  • the effects can be obtained by adding at least one selected from V: 0.01% to 1.0% (preferably 0.05% to 0.6%), Nb: 0.01% to 1.0% (preferably 0.05% to 0.4%), Ti: 0.01% to 1.0% (preferably 0.02% to 0.2%), W: 0.05% to 2.0% (preferably 0.05% to 0.5%), and Ta: 0.05% to 2.0% (preferably 0.1% to 0.5%).
  • V 0.01% to 1.0%
  • Nb 0.01% to 1.0%
  • Ti 0.01% to 1.0%
  • W 0.05% to 2.0%
  • Ta 0.05% to 2.0%
  • a second group includes the following elements, and these elements increase the corrosion resistance, toughness, and workability of the stainless steel wire as an incidental effect. Therefore, at least one selected from the following elements may be added as required.
  • Cu is an effective element in improving corrosion resistance, and Cu is added as required. However, in the case where the added amount of Cu is more than 0.8%, the amount of work hardening is small. Thus, the steel wire is softened and also heat setting resistance is decreased. Therefore, the upper limit of the amount of Cu is set to 0.8% or less.
  • the amount of Cu is preferably in a range of 0.1% to 0.6%.
  • Co secures ductility and toughness to improve heat setting resistance
  • 0.1% or more of Co is added as required.
  • the upper limit of the amount of Co is set to 2.0%.
  • the amount of Co is preferably in a range of 0.5% to 1.5%.
  • B improves the hot manufacturability and toughness of the stainless steel
  • 0.0005% or more of B is added as required.
  • the added amount of B is more than 0.015%, boride is formed, and thus, conversely, ductility and toughness are decreased and manufacturability is deteriorated.
  • the upper limit of the amount of B is set to 0.015%.
  • the amount of B is preferably in a range of 0.001% to 0.01%.
  • Ca, Mg, and REM are selected. These elements can be contained for deoxidation, and one or more of Ca: 0.0005% to 0.01%, Mg: 0.0005% to 0.01%, and REM: 0.0005% to 0.1% are added as required. However, in the case where the added amount of each element is more than each upper limit, coarse inclusions are generated and thus, manufacturability is decreased.
  • the amounts of P and S are preferably adjusted in specific ranges as other elements.
  • the allowable ranges are P: 0.015% to 0.045%, and S: 0.0001% to 0.01%.
  • a reduction of the content more than required leads a rather cost increase.
  • nonmetallic inclusions or the like cause deterioration in quality.
  • an element can be selected from a single group and added, and an element can be selected from two or more groups and added.
  • the stainless steel wire of the embodiment thus constituted is manufactured by, for example, the following method.
  • a cast steel having the predetermined component composition is subjected to casting and hot rolling to form a wire rod.
  • the diameter of the wire rod is reduced while the wire rod is subjected to cold working repeatedly.
  • Solution treatment may be performed between the cold working steps.
  • a stainless steel wire having a target wire diameter can be formed.
  • the cold working includes the wire drawing and rolling, and, for example, continuous wire drawing using a drawing die or a roller die, and rolling using a rolling roller are employed.
  • a total working ratio may be in a range of 60% to 90%.
  • the amount of deformation induced martensite ( ⁇ ') in the matrix and the tensile strength defined in the embodiment can be realized and the torsion value and proof stress ratio of the stainless steel wire defined in the embodiment can be realized in the same manner.
  • the total working ratio of the final cold working is preferably in a range of about 65% to 85%, and more preferably in a range of 70% to 83%, and the final cold working may be performed within a range in which the total working ratio is relatively suppressed.
  • a working temperature is preferably adjusted so that the surface temperature of the steel wire on the inlet side of a final finish die or a final roll is in a range of 70°C or lower (preferably in a range of 10°C to 50°C).
  • the working ratio in the final finish die or the final rolling is set to be in a range of 20% or less, and preferably in a range of 10% or less, and uniform hard working of the surface layer is preferably performed.
  • heat setting resistance can be further improved.
  • the surface temperature of the steel wire on the inlet side of the final finish die and the working ratio in the final finish die or in the final rolling are controlled; and thereby, heat setting resistance is further improved.
  • the mechanism is not clear at this point.
  • the inventors have found that the steel wire in the case where these conditions were controlled and the steel wire the case where these conditions were not controlled were respectively subjected to aging treatment, and the vicinities of the surface layers of the steel wires after the aging treatment were observed and compared to each other. As a result, it has been found that fine compounds were uniformly distributed in the steel wire in the case where the conditions were controlled. Thus, it can be assumed that the fine compounds being more uniformly precipitated in the vicinities of the surface layer of the steel wire have influence on further improvement of heat setting resistance.
  • the working ratio is expressed by a change ratio of the area of the transverse cross section of the stainless steel wire by the working and is calculated by the following expression.
  • Working ratio % cross section area before working ⁇ cross section area after working / cross section area before working ⁇ 100
  • the spring product is made of the stainless steel wire of the embodiment and can be formed in various shapes such as a coil spring, a torsion spring, and a linear spring. Further, spring properties can be improved by performing aging treatment which will be further described later.
  • the spring properties are set based on an environment temperature of 200°C, and the residual shearing strain at the temperature is in a range of 0.008% or less.
  • the heat setting resistance of the spring properties is expressed by a load loss in some cases.
  • a load loss is calculated by dividing a load difference between applied loads corresponding to the heights of the spring before and after the test by an applied load before the test.
  • the load loss measured by the method varies depending on the shape of the spring and is not always standard. Therefore, in the embodiment, instead of the load loss, the residual shearing strain ratio is used.
  • the environment temperature is also set to 200°C as described above.
  • a residual shearing strain ⁇ is defined as follows.
  • a predetermined spring is deformed by applying a fixed load or a torque to the spring.
  • the load or the torque is released.
  • a shearing strain ratio remaining when the load or the torque is released is a residual shearing strain ⁇ , and is calculated by, for example, the following Expression (7). That is, for example, a case in which the spring is a compression coil spring will be described. As shown in FIG. 2 , a predetermined compression load is applied to the coil spring, and a height of the spring is displaced from S to S1. While the state is maintained, the spring is heated to 200°C. Next, the spring is cooled to room temperature and the compression load is released.
  • a height of the spring when the compression load is released is set to S0, and a load when the height of the spring is returned from S1 to S0 is used to calculate a load loss ( ⁇ P).
  • ⁇ P load loss
  • the height of the spring S1 when the compression load is applied is set to a predetermined set height.
  • FIG. 2(c) shows a spring after being heated in a state in which a predetermined compression load is applied and then cooled and the compression load has been released, and the height of the spring is S0.
  • FIG. 2(a) shows a spring before a test in which a predetermined compression load is applied, and the height of the spring is S. With respect to each spring shown in FIGS.
  • a load required for displacement to the height of S1 is measured using a spring load testing machine.
  • a difference between the required loads of the springs is calculated and the value is set to a load loss ( ⁇ P).
  • a spring product in which the residual shearing strain is in a range of 0.008% or less and the heat setting resistance is excellent has an advantage of the heat setting treatment being omitted.
  • the residual shearing strain is more preferably in a range of 0.005% or less.
  • a spring product is subjected to heat treatment at a predetermined temperature in advance, and fine compound particles are uniformly precipitated particularly in the vicinity of the surface layer in the structure of the stainless steel wire.
  • a heating time is preferably set to be in a range of about 3 minutes to 10 hours in a temperature range of 300°C to 600°C.
  • FIG. 3 it is possible to form and distribute fine and hard compounds.
  • the residual shearing strain of the high-strength spring defined in the embodiment can be realized.
  • it is desirable that the components thereof are adjusted in advance so that the aforementioned compounds are precipitated to form precipitation hardening stainless steel by subjecting the stainless steel wire to hard working.
  • the more preferable condition of the aging treatment is as follows.
  • the shape and the distribution state of the compound particles precipitated by the aging treatment are influenced by the volume and the shape of the spring product. It is desirable that a setting temperature and a heating time are adjusted considering the volume and the shape of the spring product.
  • the setting temperature and the heating time are desirably adjusted such that an aging treatment factor in the following Expression (3) becomes in a range of 100 to 10000, and preferably in a range of 150 to 3000.
  • Aging treatment factor temperature ° C ⁇ treatment time min / 2 ⁇ equivalent wire diameter of spring mm ⁇ deployed length mm of spring
  • the deployed length means a total length of a stainless steel wire constituting the spring product.
  • a heating temperature of the aging treatment is lower than 300°C, a sufficient amount of the compounds are not formed even in the case where the wire is heated for a long period of time.
  • a heating temperature of the aging treatment is higher than 600°C, the stainless steel wire is softened and the strength is decreased. It is recommended that the aging treatment is more preferably performed at a temperature of about 400°C to 580°C.
  • the formation and the precipitation state of the compounds depend on the heating time, and the particle size and the density change. Therefore, heating is preferably performed for at least 3 minutes or longer. Proper ranges of the heating temperature and the heating time are set by the aforementioned Expression (3) including the condition.
  • the proper range of the heating temperature is more preferably in a range of 400°C to 550°C.
  • the aforementioned compounds are very fine, it is difficult to define the presence of the compounds specifically throughout most of the aforementioned condition range of the aging treatment. However, it is possible to confirm the presence of the compounds with a three-dimensional atom probe or a transmission electron microscope. Particularly, as the temperature of the aging treatment increases and the heating time becomes longer, the compounds grows gradually, and thus, the presence of the compounds formed under a treatment condition close to the upper limit can be confirmed with a transmission type electron microscope.
  • FIG. 3(a) is an enlarged image of the transverse cross section of the stainless steel wire obtained by the aging treatment at 600°C for 30 minutes at high magnification. Fine compounds of NiAl having an average particle size of 50 nm or less are precipitated at a high density in the matrix of the martensite.
  • FIG. 3(b) is an electron beam diffraction image thereof and it has been confirmed that the compounds have a B2 structure.
  • the average particle size of the compounds is expressed by, for example, an average value of particle sizes of respective compound particles confirmed in an arbitrary observation visual field of the diffraction image, and a more proper particle size is in a range of 20 nm or less.
  • FIG. 3(a) is a bright field image of a thin film sample collected from the stainless steel wire obtained by a transmission electron microscope and is an image of the deformation induced martensite structure.
  • FIG. 3(b) is a diffraction image (which is obtained by Fourier-transforming the structure of the sample) in the region, and the presence of NiAl having the B2 structure as shown in FIG. 3(d) and a BCC structure of the deformation induced martensite can be confirmed.
  • FIG 3(c) shows a dark field image in which only the NiAl precipitates having the B2 structure are projected. It is observed that the compound particles tend to be distributed more uniformly by controlling the aforementioned surface temperature of the steel wire on the inlet side of the final finish die and the working ratio in the final finish die or the final rolling.
  • the shape and the distribution state of the compounds are highly dependent on the heating temperature and the heating condition, the working condition and the constitutional elements of the steel wire.
  • the reaction is facilitated by high temperature heating and long-time heating, and thus, the particle sizes of the compounds can be increased and the density can be increased. Accordingly, it is desirable that while a preliminary test is performed, the treatment is performed so as to obtain a desired compound configuration.
  • a preheating adjustment (heat setting) step is performed before a spring is used.
  • the spring product that can be obtained by the embodiment has high strength and excellent heat setting resistance. Therefore, cost reduction can be expected by omitting the preheating adjustment (heat setting) step.
  • the properties of a spring product made of a piano wire are deteriorated in a warm temperature region in which the wire is in a slightly heated state.
  • the stainless steel wire of the embodiment is suitable for a spring product which is heat-resistant in the warm temperature region in which the wire is in a slightly heated state.
  • the stainless steel wire of the embodiment is expected to be applied to heat resistance uses such as use in a general high temperature environment of 400°C or higher, and thus, the utilization range is extended.
  • Steel having these components was melted in a vacuum melting furnace and casted to form a cast steel having a diameter of ⁇ 178 mm.
  • the cast steel was subjected to hot forging to form a steel bar having a diameter of ⁇ 62 mm.
  • the steel bar was heated to 1250°C and extruded using a hot extrusion simulator to form a wire rod having a diameter of ⁇ 10.7 mm.
  • the wire rod was subjected to solution treatment and pickling, and then, the wire rod was subjected to wire drawing to form a wire rod having a diameter of ⁇ 5.5 mm.
  • the wire rod was used as a raw material and worked into a soft wire having a diameter of rod of 2.2 mm while cold wire drawing and solution treatment were repeatedly performed.
  • a fine hard wire (drawn steel wire) having a wire diameter of ⁇ 1.0 mm was formed by the final cold wire drawing.
  • the final cold wire drawing was performed under conditions where a final total wire drawing ratio was set to 80%.
  • a reduction (working ratio) of the final wire drawing die was adjusted to be in a range of 8% to 25%, and the surface temperature of the steel wire on the inlet side of the die was controlled to be in a range of 0°C to 80°C.
  • a Ni plating layer having a thickness of 1.2 ⁇ m was formed on the surface of the steel wire (drawn steel wire) after the working.
  • the tensile strength and the 0.2% proof stress were measured according to JIS-Z2241.
  • the amount of the deformation induced martensite was measured by the magnetic method described in the [Measurement of Amount of Martensite].
  • the torsion value was measured by the methods described in the [Torsion Test 1] and [Torsion Test 2]. The results are shown in Tables 3 and 4.
  • each stainless steel wire (drawn steel wire) after the final wire drawing in Example 1 was cut to have a length of 150 mm; and thereby, samples were obtained. Then, each of the samples was subjected to aging treatment at 500°C for 30 minutes.
  • the aging treatment factor expressed by the above-described Expression (3) was 612.
  • the aging-treated steel wires of Invention Examples according to the embodiment had excellent high-strength properties in which the tensile strength was in a range of 2100 MPa to 2600 MPa, the proof stress ratio was in a range of 80% to 95%, and the rigidity was in a range of 77000 MPa or more.
  • precipitated compounds consisting of NiAl particles having average particle sizes of about 3 nm to 10 nm were able to be confirmed.
  • each stainless steel wire (drawn steel wire) before aging treatment was subjected to coiling working to form a compression coil spring having an average coil diameter: 7 mm, an effective coiling number: 4.5, a spring free length: 25 mm, and a deployed length: 100 mm.
  • aging treatment was performed at 500°C for 30 minutes.
  • the heat setting resistance of an actual spring product was evaluated.
  • the heat setting resistance (residual shearing strain ⁇ ) was measured by the method described in the [Method for Manufacturing Spring Product]. Specifically, while maintaining a state in which a compression stress of 600 MPa was applied, the spring product was held at 200°C for 96 hours. Then, the residual shearing strain ⁇ was calculated by Expression (7).
  • the peak of the tensile strength was observed particularly around a temperature of 450°C to 550°C, and the strength was slightly softened at 600°C.
  • the residual shearing strain of almost 0.008% or less was obtained in all Invention Examples but in the temperature range increased up to around 600°C, the properties were slightly deteriorated.
  • the residual strain properties were in a range of 0.005% or less, which was very preferable.
  • each of steels A and D in Table 1 was subjected to wire drawing by the method described in Example 1 to obtain a soft wire having a wire diameter of ⁇ 1.8 mm.
  • a metallic soap lubricant was applied to the surface of the soft wire, and then, working of diameter reduction was performed by a cold wire drawing apparatus to form a fine hard wire having a wire diameter of 1.0 mm.
  • cold rolling was performed by a multistage rolling apparatus, and pressing to a thickness of 0.2 mm was finally performed to manufacture a hard flat wire.
  • the optimal cooling method was employed such that the surface temperature of the steel wire on the inlet side of the rolling roll in the final finish was 45°C.
  • the lubricant attached on the surface was removed with a solvent so as to evaluate the properties when a flat wire was worked into a spring product.
  • aging treatment was performed at 500°C for 30 minutes as was the case with Example 2, and the properties of the flat wire were evaluated before and after the heat treatment.
  • Table 8 Test Items Steel type A Steel type D Before heat treatment After heat treatment Before heat treatment After heat treatment After heat treatment Amount of deformation induced ⁇ ' (Vol.%) 90 - 89 - Tensile strength (N/mm 2 ) 2030 2550 1910 2350 Proof stress ratio (%) 92 89 91 88 Residual shearing strain (%) 0.009 0.004 0.007 0.004
  • the tensile strength was evaluated by the tensile test method as was the case with Example 1.
  • the residual shearing strain was evaluated as the properties at a temperature of 200°C as was the case with Example 3 in the following manner. Torsion stress was applied to both ends of the flat wire having a predetermined length. The wire was heated to 200°C while maintaining this state. Next, the wire was cooled to room temperature and the torsion stress was released. The residual shearing strain was evaluated based on a change in the return angle at this time.
  • the residual shearing strain of the flat wire was calculated using a load loss, an elastic coefficient, and a cross section area as was the case with the spring.
  • a load loss was calculated as described below.
  • An arbitrary distance was set as a gage length in a range of, for example, about 5 times to 50 times of the width of the flat wire.
  • a predetermined stress was applied to the both ends of the flat wire having the gage length to twist the wire.
  • the wire was heated to 200°C while maintaining this state. Next, the wire was cooled to room temperature and the stress was released.
  • the flat stainless steel wire has excellent mechanical properties which can be used as, for example, a spring material for a wave spring.
  • the surface properties were preferable since the bright surface having excellent smoothness due to fine grains was obtained.
  • the stainless steel wire according to the embodiment has a tensile strength of 1800 MPa to 2200 MPa in a state in which the wire is subjected to wire drawing.
  • the amount of deformation induced martensite is in a range of 80 vol% to 99 vol%. Therefore, spring properties are greatly improved by the subsequent aging treatment. Particularly, high strength and excellent heat setting resistance can be obtained.
  • the stainless steel wire according to the embodiment can be applied to, for example, a compression coil spring, a tension coil spring, a torsion spring, and other various spring products, and a spring product having high strength and excellent heat setting resistance can be obtained.
  • the stainless steel wire is suitably applied to a spring product used in a warm temperature region in a heated state of the periphery of an engine or an electrical system of an automobile, and a heat resistant spring for home electric appliances.
  • the embodiment can also be used in various linear products, such as a heat-resistant high-strength rope, a heat resistant shaft, a heat resistant pin, and the like, which are used in a high temperature region and have high strength and heat resistance, and the embodiment is industrially useful.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Articles (AREA)
EP13767507.0A 2012-03-29 2013-03-27 High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same Active EP2832876B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012076870 2012-03-29
JP2013062817A JP6259579B2 (ja) 2012-03-29 2013-03-25 耐熱へたり性に優れた高強度ステンレス鋼線、高強度ばね並びにその製造方法
PCT/JP2013/058992 WO2013146876A1 (ja) 2012-03-29 2013-03-27 耐熱へたり性に優れた高強度ステンレス鋼線、高強度ばね及びその製造方法

Publications (3)

Publication Number Publication Date
EP2832876A1 EP2832876A1 (en) 2015-02-04
EP2832876A4 EP2832876A4 (en) 2015-12-16
EP2832876B1 true EP2832876B1 (en) 2019-11-20

Family

ID=49260125

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13767507.0A Active EP2832876B1 (en) 2012-03-29 2013-03-27 High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same

Country Status (7)

Country Link
EP (1) EP2832876B1 (ja)
JP (1) JP6259579B2 (ja)
KR (1) KR101615844B1 (ja)
CN (1) CN104136645B (ja)
HK (1) HK1205769A1 (ja)
TW (1) TWI491745B (ja)
WO (1) WO2013146876A1 (ja)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103789641A (zh) * 2014-01-16 2014-05-14 安徽省杨氏恒泰钢管扣件加工有限公司 一种高强度不锈钢钢管材料及其制备方法
KR101891018B1 (ko) 2014-05-29 2018-08-22 신닛테츠스미킨 카부시키카이샤 열처리 강재 및 그 제조 방법
JP6108032B2 (ja) 2014-05-29 2017-04-05 新日鐵住金株式会社 熱処理鋼材及びその製造方法
RU2586934C1 (ru) * 2015-06-08 2016-06-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Уральский государственный университет" (национальный исследовательский университет) (ФГБОУ ВПО "ЮУрГУ" (НИУ)) Аустенитная коррозионно-стойкая хромоникелевая сталь с улучшенной обрабатываемостью резанием
CN105112800A (zh) * 2015-09-01 2015-12-02 广西南宁智翠科技咨询有限公司 一种抗氧化抗拉弹簧丝
CN105483502A (zh) * 2015-12-03 2016-04-13 浙江腾龙精线有限公司 一种弹簧线的生产方法
JP6222504B1 (ja) * 2016-06-01 2017-11-01 株式会社特殊金属エクセル 準安定オーステナイト系ステンレス鋼帯または鋼板並びにその製造方法
CN106011629A (zh) * 2016-07-06 2016-10-12 安徽红桥金属制造有限公司 一种高强度韧性的汽车悬架弹簧钢及其制备方法
CN106167880A (zh) * 2016-07-14 2016-11-30 龙泉市卓越刀剑有限公司 一种宝剑外置安全锁扣制作方法
JP6782601B2 (ja) * 2016-10-05 2020-11-11 日鉄ステンレス株式会社 耐温間リラクセーション特性に優れる高強度ステンレス鋼線およびその製造方法、ならびにばね部品
CN107761010B (zh) * 2017-10-17 2019-06-14 中国华能集团公司 一种具有优异高温强度与稳定性的管材料及其制备方法
CN107739995B (zh) * 2017-10-17 2019-09-24 中国华能集团公司 一种低成本高强度的管材料及其制备方法
CN109778079B (zh) * 2017-11-13 2020-06-16 路肯（上海）医疗科技有限公司 一种医疗器械用不锈钢、制作方法、热处理方法和应用
JP7049142B2 (ja) * 2018-03-15 2022-04-06 日鉄ステンレス株式会社 マルテンサイト系ステンレス鋼板およびその製造方法並びにばね部材
SE541925C2 (en) 2018-04-26 2020-01-07 Suzuki Garphyttan Ab A stainless steel
CN110499455B (zh) * 2018-05-18 2021-02-26 宝武特种冶金有限公司 一种时效硬化奥氏体不锈钢及其制备方法
KR102404122B1 (ko) * 2018-06-11 2022-05-31 닛테츠 스테인레스 가부시키가이샤 스테인리스 강선용 선재, 스테인리스 강선 및 그 제조 방법, 및, 스프링 부품
CN111043204A (zh) * 2019-12-27 2020-04-21 太仓卡兰平汽车零部件有限公司 一种电动撑杆阻尼器用不锈钢波簧
JP6906649B1 (ja) * 2020-03-05 2021-07-21 株式会社オリジン トルクリミッタの製造方法
CN114787406B (zh) * 2020-05-13 2023-08-08 日铁不锈钢株式会社 奥氏体系不锈钢材及其制造方法以及板簧
CN111618120A (zh) * 2020-05-21 2020-09-04 东莞市万欣金属制品有限公司 一种提高316l不锈钢棒材强度的生产方法
CN111593260B (zh) * 2020-06-17 2021-09-24 大连理工大学 一种b2纳米粒子共格析出强化的超高强度马氏体时效不锈钢及制备方法
CN112126868A (zh) * 2020-09-14 2020-12-25 高燕仪 一种减少废料的发条制作加工用生产方法
CN116323994A (zh) * 2021-02-24 2023-06-23 日铁不锈钢株式会社 奥氏体系不锈钢钢材及其制造方法以及板簧
EP4341453A1 (en) * 2021-05-21 2024-03-27 NV Bekaert SA A straight stainless steel wire for flexible card clothing
CN113699461A (zh) * 2021-08-30 2021-11-26 南通普创医疗科技有限公司 介入医疗用高强度不锈钢丝及其制备方法
CN114686774B (zh) * 2022-03-08 2022-12-02 四川大学 一种高强高韧纳米析出强化超细晶马氏体奥氏体双相钢及其制备方法
CN115044838A (zh) * 2022-06-29 2022-09-13 东北大学 一种复合强化型超高强韧马氏体不锈钢及其制备方法
TWI833286B (zh) * 2022-07-15 2024-02-21 日商日鐵不銹鋼股份有限公司 高強度不鏽鋼線及彈簧
KR102570361B1 (ko) 2022-07-19 2023-08-25 닛테츠 스테인레스 가부시키가이샤 고강도 스테인리스 강선 및 스프링
DE102023117976A1 (de) 2022-08-23 2024-02-29 Schaeffler Technologies AG & Co. KG Elektromechanischer Aktuator
WO2024041687A1 (de) 2022-08-23 2024-02-29 Schaeffler Technologies AG & Co. KG Elektromechanischer aktuator
CN115927976A (zh) * 2022-11-27 2023-04-07 安徽海螺川崎装备制造有限公司 一种经济型预热器挂板及其生产方法
CN115927973B (zh) * 2023-01-03 2024-03-22 中国原子能科学研究院 一种马氏体不锈钢及其制备方法及应用

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE651249A (ja) * 1963-08-02 1964-11-16
FR1402682A (fr) * 1963-08-02 1965-06-11 Armco Steel Corp Aciers inoxydables au chrome-nickel aluminium et leur application
JPS6036649A (ja) * 1983-08-05 1985-02-25 Nisshin Steel Co Ltd 靭性に優れたマルテンサイト系析出硬化型ステンレス鋼
JPS61114415A (ja) * 1984-11-08 1986-06-02 日立電線株式会社 導電用クラツドばね材
JPS6220857A (ja) * 1985-07-19 1987-01-29 Daido Steel Co Ltd 高強度ステンレス鋼
JPH0768584B2 (ja) * 1986-06-09 1995-07-26 日新製鋼株式会社 ばね特性に優れたばね用ステンレス鋼材の製造方法
JPH02310339A (ja) * 1989-05-24 1990-12-26 Kawasaki Steel Corp 強度、バネ特性及び成形性に優れたマルテンサイト系ステンレス鋼
JP3482053B2 (ja) 1995-11-24 2003-12-22 日本金属株式会社 耐熱ばね用ステンレス鋼及びその製造方法
JPH1068050A (ja) 1996-08-27 1998-03-10 Hitachi Metals Ltd 耐熱へたり性に優れたばね用ステンレス鋼
JP3492531B2 (ja) * 1998-10-05 2004-02-03 住友電工スチールワイヤー株式会社 耐熱ステンレス鋼
JP4489928B2 (ja) * 2000-11-09 2010-06-23 新日鐵住金ステンレス株式会社 高強度オーステナイト系ステンレス鋼線
SE526881C2 (sv) 2001-12-11 2005-11-15 Sandvik Intellectual Property Utskiljningshärdbar austenitisk legering, användning av legeringen samt framställning av en produkt av legeringen
WO2003095693A1 (fr) * 2002-05-08 2003-11-20 Nippon Steel Corporation Fil d'acier inoxydable tres solide aux bonnes qualites de tenacite a la ductilite et module de rigidite, et procede de production
JP4163055B2 (ja) 2003-06-24 2008-10-08 日本精線株式会社 耐熱ばね用ステンレス鋼線、及びそれを用いた耐熱ばね製品
JP4519513B2 (ja) * 2004-03-08 2010-08-04 新日鐵住金ステンレス株式会社 剛性率に優れた高強度ステンレス鋼線およびその製造方法
JP4319083B2 (ja) * 2004-04-14 2009-08-26 新日鐵住金ステンレス株式会社 剛性率に優れたばね向け高強度鋼線用の準安定オーステナイト系ステンレス鋼線
JP4790539B2 (ja) * 2006-08-18 2011-10-12 日本精線株式会社 高強度高弾性型ステンレス鋼及びステンレス鋼線
JP5154122B2 (ja) * 2007-03-29 2013-02-27 日本精線株式会社 高強度ステンレス鋼及びこれを用いた高強度ステンレス鋼線
JP5091732B2 (ja) * 2008-03-17 2012-12-05 日新製鋼株式会社 耐へたり性および曲げ性に優れた低Ｎｉばね用ステンレス鋼
JP5744678B2 (ja) * 2010-10-07 2015-07-08 新日鐵住金ステンレス株式会社 耐疲労性に優れた析出硬化型の準安定オーステナイト系ステンレス鋼線およびその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
CN104136645B (zh) 2016-06-29
WO2013146876A1 (ja) 2013-10-03
KR101615844B1 (ko) 2016-04-26
TWI491745B (zh) 2015-07-11
JP2013227662A (ja) 2013-11-07
HK1205769A1 (en) 2015-12-24
EP2832876A1 (en) 2015-02-04
CN104136645A (zh) 2014-11-05
EP2832876A4 (en) 2015-12-16
KR20140117568A (ko) 2014-10-07
JP6259579B2 (ja) 2018-01-10
TW201346044A (zh) 2013-11-16

Similar Documents

Publication Publication Date Title
EP2832876B1 (en) High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same
EP2226406B1 (en) Stainless austenitic low Ni alloy
JP5791791B2 (ja) 高弾性限非磁性鋼材の製造方法
US20070125456A1 (en) High strength spring steel wire with excellent coiling properties and hydrogen embrittlement resistance
EP2586886B1 (en) High-tension/hot-rolled steel sheet having excellent workability, and method for producing same
EP2083094A1 (en) High-strength steel wire excelling in ductility and process for producing the same
KR102509847B1 (ko) 고강도 저열팽창 합금선
EP1801255A1 (en) Cold formable spring steel wire excellent in cold cutting capability and fatigue properties and manufacturing process thereof
EP3342891B1 (en) Steel sheet
EP3124638B1 (en) Stabilizer steel having high strength and excellent corrosion resistance, vehicle stabilizer employing same, and method for manufacturing same
JP5154122B2 (ja) 高強度ステンレス鋼及びこれを用いた高強度ステンレス鋼線
EP3378964A1 (en) Wire rod for steel wire, and steel wire
JP5155634B2 (ja) 耐水素性ばね用ステンレス鋼線及びそれを用いた耐水素性ばね製品
EP2194154A1 (en) Two-way shape-recovery alloy
EP3486345A1 (en) Steel wire
EP3156511A1 (en) Steel for mechanical structure for cold working, and method for producing same
JP4790539B2 (ja) 高強度高弾性型ステンレス鋼及びステンレス鋼線
EP3115478B1 (en) High-carbon steel wire having superior wire drawing properties and method for producing same
WO2014157146A1 (ja) オーステナイト系ステンレス鋼板およびそれを用いた高強度鋼材の製造方法
JP2002256395A (ja) 捻回特性に優れた高強度低熱膨張合金およびその合金線
JP5080215B2 (ja) 等方性と伸びおよび伸びフランジ性に優れた高強度冷延鋼板
WO2023105852A1 (ja) 冷間鍛造性及び、耐水素脆化特性又は耐食性と非磁性に優れるステンレス鋼
KR20180117129A (ko) 압연 선재
WO2015144661A2 (de) Bauteile aus einer stahllegierung und verfahren zur herstellung hochfester bauteile
JP3216824B2 (ja) 高強度低熱膨張合金

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20141016

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20151113

RIC1 Information provided on ipc code assigned before grant

Ipc: C21D 6/00 20060101ALI20151109BHEP

Ipc: B21C 1/00 20060101ALI20151109BHEP

Ipc: C22C 38/00 20060101AFI20151109BHEP

Ipc: C22C 38/58 20060101ALI20151109BHEP

Ipc: C22C 38/46 20060101ALI20151109BHEP

Ipc: C22C 38/04 20060101ALI20151109BHEP

Ipc: C22C 38/48 20060101ALI20151109BHEP

Ipc: C21D 9/52 20060101ALI20151109BHEP

Ipc: C22C 38/44 20060101ALI20151109BHEP

Ipc: C22C 38/50 20060101ALI20151109BHEP

Ipc: C21D 9/02 20060101ALI20151109BHEP

Ipc: C22C 38/02 20060101ALI20151109BHEP

Ipc: F16F 1/02 20060101ALI20151109BHEP

Ipc: C21D 8/06 20060101ALI20151109BHEP

Ipc: C22C 38/06 20060101ALI20151109BHEP

Ipc: C22C 38/42 20060101ALI20151109BHEP

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1205769

Country of ref document: HK

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190527

RIN1 Information on inventor provided before grant (corrected)

Inventor name: AKIURA TSUNEO

Inventor name: TOHJOH MASAYUKI

Inventor name: TOYODA GOU

Inventor name: TAKANO KOHJI

Inventor name: KAJIMURA HARUHIKO

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: NIPPON SEISEN CO., LTD.

Owner name: NIPPON STEEL & SUMIKIN STAINLESS STEEL CORPORATION

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013063121

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1204266

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191215

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200220

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200220

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200221

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200320

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200412

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1204266

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191120

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013063121

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20200821

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200327

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200331

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602013063121

Country of ref document: DE

Owner name: NIPPON STEEL STAINLESS STEEL CORPORATION, JP

Free format text: FORMER OWNERS: NIPPON SEISEN CO., LTD., OSAKA, JP; NIPPON STEEL & SUMIKIN STAINLESS STEEL CORPORATION, TOKYO, JP

Ref country code: DE

Ref legal event code: R081

Ref document number: 602013063121

Country of ref document: DE

Owner name: NIPPON SEISEN CO., LTD., JP

Free format text: FORMER OWNERS: NIPPON SEISEN CO., LTD., OSAKA, JP; NIPPON STEEL & SUMIKIN STAINLESS STEEL CORPORATION, TOKYO, JP

REG Reference to a national code

Ref country code: NL

Ref legal event code: HC

Owner name: NIPPON STEEL STAINLESS STEEL CORPORATION; JP

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: NIPPON STEEL & SUMIKIN STAINLESS STEEL CORPORATION

Effective date: 20210816

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230519

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240311

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240325

Year of fee payment: 12

Ref country code: GB

Payment date: 20240328

Year of fee payment: 12