EP2832891A1 - Steel wire rod with excellent shavability for high-strength spring, and high-strength spring - Google Patents

Steel wire rod with excellent shavability for high-strength spring, and high-strength spring Download PDF

Info

Publication number
EP2832891A1
EP2832891A1 EP13768751.3A EP13768751A EP2832891A1 EP 2832891 A1 EP2832891 A1 EP 2832891A1 EP 13768751 A EP13768751 A EP 13768751A EP 2832891 A1 EP2832891 A1 EP 2832891A1
Authority
EP
European Patent Office
Prior art keywords
wire rod
steel wire
less
content
pearlite
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.)
Granted
Application number
EP13768751.3A
Other languages
German (de)
French (fr)
Other versions
EP2832891A4 (en
EP2832891B1 (en
Inventor
Hiroshi Oura
Nao Yoshihara
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.)
Kobe Steel Ltd
Original Assignee
Kobe Steel Ltd
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 Kobe Steel Ltd filed Critical Kobe Steel Ltd
Publication of EP2832891A1 publication Critical patent/EP2832891A1/en
Publication of EP2832891A4 publication Critical patent/EP2832891A4/en
Application granted granted Critical
Publication of EP2832891B1 publication Critical patent/EP2832891B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/06Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
    • C21D8/065Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/02Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20Ferrous alloys, e.g. steel alloys containing chromium with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32Ferrous alloys, e.g. steel alloys containing chromium with boron
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/004Dispersions; Precipitations
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/009Pearlite

Definitions

  • the present invention relates to a steel wire rod for a high-strength spring that is usable as material for the high-strength springs (especially, valve spring) used in parts of vehicles, including a clutch, an engine, a fuel injector, a suspension mechanism, and the like, and also to a high-strength spring using the steel wire rod for a high-strength spring. More particularly, the present invention is directed to a steel wire rod for a high-strength spring that can exhibit excellent shavability in a shaving process.
  • Springs applied under the environment described above are used with a high stress applied thereto over a long time of period. For this reason, such springs are required to have high fatigue resistance. In order to improve the fatigue resistance, it is required to impart the excellent surface properties to the spring, and to appropriately control inclusions in the spring. Regarding the surface properties, the spring molded is subjected to a planarization process and a hardening process by shot peening, nitriding, or the like. When a flaw on the order of several tens of micrometers in size remains or occurs in the spring, a break might be caused starting from the surface flaw in use of the spring.
  • a shaving process (hereinafter referred to as a "SV process") is performed to remove a decarburized part of a surface layer of the wire rod having been rolled, and a fine flaw on the surface layer of the wire rod.
  • the SV process is a process which involves cutting the surface layer of the wire rod over its entire periphery in a depth direction by about several hundreds of micrometers using a chipper die.
  • a wire rod having unsatisfactory SV workability (shavability) might be broken in the SV process, which disadvantageously results in a crack of the chipper die, an uneven surface of the wire rod, a shorter life time of a tool, and the like.
  • a breaker is provided for improving the discharge of shavings produced by minutely cutting the wire rod.
  • the shavings In cutting the wire rod having the unsatisfactory SV workability, the shavings might be stuck in the breaker, excessively increasing a load on motor for driving the breaker. As a result, the device might sometimes stop, which decreases the yield of products or wire rods.
  • Improvement of the SV workability of a wire rod can significantly increase the yield of the wire rods and improve the quality of the wire rod.
  • the mainstream techniques for improving the SV workability include control of the microstructure of the wire rod, control of the composition of inclusions, and the like. Various types of such techniques have been already proposed.
  • Patent Literature (PTL) 1 has proposed that the shavability of a wire rod is improved by making austenite crystal grain size coarse.
  • the steel needs to be formed of fine crystal grains.
  • the crystal grains of the wire rod preferably have a fine grain size.
  • the composition of an oxide-based inclusion, and the size and distribution density of the oxide-based inclusion existing in the surface layer can be defined to improve the SV workability.
  • the alloy-based carbide or nitride which significantly influences the ductility and toughness of the microstructure tends to cause the reduction in the SV workability at present.
  • PTL 3 has proposed that the SV workability is improved by defining the mechanical characteristics of steel.
  • the amount of added alloys is so much that a spring steel includes precipitation of alloy-based carbides or nitrides in a large amount.
  • the spring steel can satisfy only the mechanical characteristics, but cannot improve the SV workability.
  • the SV process is performed on the spring so as to remove a decarburized layer or surface flaw of a rolled rod.
  • the SV process includes a skin pass step of enhancing the circularity of the rolled rod to prevent side cutting, and a shaving step of shaving using a chipper die. It is necessary that cooling conditions for rolling on a conveyor are properly controlled to prevent a rolled rod microstructure from containing a supercooled phase (bainite, martensite).
  • the shaving process with the chipper die requires that the overall length of a coil having a weight of 2 tons can be shaved with a stable surface quality, for example, with no mark made by the die. For this reason, the rolled rod microstructure needs to have excellent shavability. For example, the rolled rod microstructure does not contain a supercooled phase that might cause break of a wire. Additionally, the chipper die needs to be less likely to be cracked, and a load on a tool should be small. Shavings generated when shaving the wire rod with the chipper die are discharged by being cut finely by a breaker. Thus, the shavings needs to be easily cut by the breaker, that is, the wire rod needs to have excellent discharge of shavings.
  • the present invention has been made in order to solve such problems in the related art.
  • the object of the present invention is to provide a wire rod for a high-strength spring that can exhibit the excellent SV workability without any break of the wire in an SV process, while having excellent shavability and discharging property of shavings, and also to provide a high-strength spring obtained by using such a wiring rod for a high-strength spring as material.
  • the present invention has achieved the objects described above, and provides a steel wire rod for a high-strength spring, which is a steel wire rod having been hot-rolled.
  • the steel wire rod includes as a chemical composition: C in a content of 0.4% or more and less than 1.2%; Si in a content of 1.5% to 3.0%; Mn in a content of 0.5% to 1.5%; Cr in a content of 0.02% to 0.5%; and Al in a content of 0.010% or less, in mass percent, with the remainder being iron and inevitable impurities, wherein the steel wire rod has a phase with an area fraction of pearlite of 90% or more, an average grain size number Pave of pearlite nodules satisfies the following formula (1), a total decarburized depth of the surface layer is 0.20 mm or less, and a content of Cr-based alloy carbides is 7.5% or less relative to a mass of the steel wire rod: 6.0 ⁇ Pave ⁇ 12.0
  • the steel wire rod for a high-strength spring according to the present invention further effectively includes: at least one of (a) V in a content of 0.5% or less (excluding 0%), and Nb in a content of 0.5% or less (excluding 0%); (b) Mo in a content of 0.5% or less (excluding 0%); (c) Ni in a content of 1.0% or less (excluding 0%); (d) Cu in a content of 0.5% or less (excluding 0%); and (e) B in a content of 0.010% or less (excluding 0%), as necessary. Accordingly, the characteristics of the steel wire rod for a high-strength spring can be improved depending on the components included therein.
  • the present invention includes a high-strength spring obtained from the steel wire rod for a high-strength spring described above.
  • the present invention optimizes the manufacturing conditions by appropriately adjusting the chemical composition so as to form a microstructure having an area fraction of pearlite of 90% or more, to set an average grain size number Pave of pearlite nodules in a predetermined range, and to control the total decarburized depth of the surface layer and the content of Cr-based alloy carbides. Accordingly, the present invention can achieve the steel wire rod for a high-strength spring that can exhibit the excellent SV workability without any break of the wire in the SV process, while having excellent shavability and discharging property of shavings. Such a steel wire rod for a high-strength spring is very useful as the material for manufacturing a high-strength spring.
  • the inventors have studied the characteristics of steel wire rods for a high-strength spring to achieve the above objects from various points of view. As a result, it has been revealed that a chemical composition and microstructure of a rolled rod, the grain size number of pearlite nodules, a decarburized depth of a surface layer, and a Cr-based alloy carbide content of the rolled rod surface layer are appropriately controlled to provide a steel wire rod that can drastically improve the SV workability without any break of the wire in an SV process, while having excellent shavability and discharging property of shavings.
  • the shavability and the discharge property of shavings are hereinafter referred to as the "SV workability". N ow, requirements specified by the invention will be described.
  • the steel wire rod (steel wire rod obtained after hot-rolling: rolled wire rod) of the invention has a microstructure with an area fraction of pearlite of 90 % or more.
  • the rolled wire rod having the microstructure with an area fraction of pealite of 90% or more means a rolled wire rod in which an area fraction of ferrite and supercooled phases formed of bainite and martensite that occupy a cross section of the rolled wire rod is 10% or less.
  • the rolled wire rod having an area fraction of pealite of 90% or more can be subjected to the SV processing while having no break of the wire during the SV processing.
  • a rolled wire rod has a supercooled phase containing bainite, martenside, and the like at an area fraction of 10% or more, the rolled wire rod will have the reduced ductility/toughness, and as a result, might degrade the SV workability, for example, might be broken in the SV processing.
  • an area fraction of pearlite is preferably 90 area% or more.
  • the area fraction of pealite is more preferably 92 area% or more (most preferably, 95 area% or more).
  • An average grain size number of pearlite nodules (hereinafter sometimes referred to as a "pearlite nodule size”) Pave significantly affects the ductility of the rolled wire rod.
  • a rolled wire rod with a small pearlite nodule size has poor ductility, which might cause a break of the wire in the SV processing.
  • the pearlite nodule size becomes larger, the ductility of the wire is improved.
  • a placing temperature in the hot rolling is required to be excessively reduced, and cooling equipment with an excessive heating capacity is necessary for rapid cooling. Thus, this is difficult to implement in real life.
  • the average pearlite nodule size Pave is set to satisfy the following formula: 6.0 ⁇ Pave ⁇ 12.0 , preferably , 7.0 ⁇ Pave ⁇ 11.0.
  • Total decarburized depth of surface layer 0.20 mm or less
  • a decarburized surface layer is normally removed by the SV process.
  • the ductility of shavings generated in the SV process becomes higher, which results in deterioration of separability of shavings by the chip breaker and reduction in discharge of the shavings, thereby degrading the SV workability.
  • the deep decarburized surface layer is likely to remain even after the SV process, which drastically reduces a fatigue strength of a spring. Accordingly, the total decarburized depth of the surface layer is set to 0.20 mm or less, and preferably 0.15 mm or less (more preferably, 0.10 mm or less).
  • Cr-based alloy carbides are much harder than iron-based carbides. Thus, even a small amount of Cr-based alloy carbides causes cracks of a tip of a chipper blade, which reduces a life time of a chipper die and the discharge of shavings, thereby degrading the SV workability. Accordingly, an upper limit of the Cr-based alloy carbide content relative to the entire mass of steel wire rod is set to 7.5 mass%.
  • the Cr-based alloy carbide content is preferably 5.0 % or less (more preferably, 4.0 % or less).
  • the Cr-based alloy carbides of interest in the invention are carbides that basically contain Cr as a principal component.
  • the Cr-based alloy carbides may contain a composite alloy carbide thereof.
  • the Cr-based alloy carbides sometimes contain a very small amount of nitride or carbonitride.
  • the procedure for manufacturing the steel wire rod for a high-strength spring will be as follows. First, a steel billet having a predetermined chemical composition is hot-rolled into a desired wire diameter. An excessively high heating temperature in rolling makes the wire rod microstructure brittle due to an increase in grain size of a prior austenite, thereby reducing the SV workability. In contrast, an excessively low heating temperature increases a deformation resistance of the steel rod, causing a high load on a rolling machine, which leads to reduction of the productivity.
  • the heating temperature before the rolling is preferably not less than 900°C nor more than 1100°C, and more preferably not less than 950°C nor more than 1050°C.
  • the steel wire rod having been hot-rolled is placed in the form of coil on a cooling conveyor.
  • the temperature at this time exceeds 1100°C
  • the prior austenite grain size is increased to make the grains of the prior austenite coarse, which might c ause the brittleness of the microstructure together with the grain coarsening of the pealite nodules.
  • the placing temperature is below 860°C, the decarburized surface layer is more likely to be deep, which might increase the deformation resistance, leading to a defect in the winding shape.
  • the placing temperature is preferably in a range of 860°C to 1100°C.
  • the placing temperature can be controlled in such a range to thereby suppress the grain coarsening of the pearlite nodules and the formation of the decarburized surface layer.
  • the placing temperature is more preferably in a range of not less than 900°C nor more than 1050°C.
  • the rolled steel wire rod After placing the steel wire rod on the conveyor, the rolled steel wire rod is cooled down to 600°C at an average cooling rate of 1.0°C/sec or more (preferably, 3.5°C/sec or more) and 10°C/sec or less (preferably, at 8°C/sec), which is an end temperature of pearlite transformation, whereby a rolled steel microstructure having a phase containing pearlite as a principal element is obtained while preventing the grain coarsening of the pearlite nodules.
  • the steel wire rod is cooled in a temperature range decreasing from less than 600°C to 400°C at the average cooling rate of 3°C/sec or more (preferably, 3.5°C/sec or more) and 10°C/sec or less (preferably, 8°C/sec or less), and then continuously cooled to 400°C or less (preferably, 375°C or less), whereby the rolled steel wire rod with excellent SV workability can be obtained while preventing the precipitation of Cr-based alloy carbides in the phase containing pearlite as the principal element.
  • the steel wire rod for a high-strength spring in the invention needs to have its chemical composition controlled appropriately so as to exhibit the characteristics of a final product (specifically, a high-strength spring).
  • the range of content of each of components (elements) in the chemical composition is specified for the following reason.
  • Carbon (C) element is effective for ensuring the strength basically required for steel and increasing the strength and settling resistance of a spring produced from the steel. For this reason, the carbon content needs to be 0.4% or more. The strength and settling resistance of the spring is improved as the carbon content is increased. However, if the carbon content is excessive, the coarse cementite will precipitate in a great amount, which reduces the ductility/toughness of the wire rod, thus adversely affecting the workability and characteristics of the spring. From this aspect, the carbon content needs to be less than 1.2%.
  • the lower limit of carbon content is preferably 0.5% or more, and the upper limit of carbon content is preferably 1.0% or less.
  • Si element is necessary for deoxidation of the steel and also for ensuring the strength, hardness, and settling resistance of the spring. To exhibit these effects, the Si content needs to be 1.5% or more. I f the Si content is excessive, however, the steel is hardened, and additionally, the ductility/toughness of the steel wire rod is reduced, and the amount of the decarburized surface layer is increased, which degrades the SV workability and the fatigue properties of the steel wire rod. Accordingly, the Si content needs to be 3.0% or less.
  • the lower limit of Si content is preferably 1.6% or more (more preferably, 1.7% or more), and the upper limit of Si content is preferably 2.8% or less (more preferably, 2.5% or less).
  • Manganese (Mn) element is also necessary for deoxidation of the steel, as with Si, and increases the hardenability to contribute to improve the spring strength in addition to fixing S element in the steel as a compound MnS. To exhibit these effects, the Mn content needs to be 0.5% or more. If the Mn content is excessive, however, the hardenability of the steel wire rod becomes excessively high, which allows the supercooled phase of martensite, bainite, and the like to be easily formed. Accordingly, the Mn content needs to be 1.5% or less.
  • the lower limit of Mn content is preferably 0.6% or more (more preferably, 0.7% or more), and the upper limit of Mn content is preferably 1.4% or less (more preferably, 1.3% or less).
  • Chromium (Cr) element improves the spring strength by enhancing the hardenability and the resistance to temper softening, and effectively reduces the activity of carbon to thereby prevent decarburization upon rolling and heat treatment. If the Cr content is excessive, however, the Cr-based alloy carbides, nitride, and carbonitride are precipitated much, thus degrading the SV workability. Accordingly, the Cr content needs to be 0.5% or less (preferably, the upper limit of Cr content is 0.45% or less, (more preferably, 0.40% or less)). To exhibit the above effects, the Cr content is 0.02% or more. The lower limit of Cr content is preferably 0.05% or more (more preferably, 0.10% or more).
  • Aluminum (Al) element is a deoxidizing element, and forms an Al 2 O 3 inclusion and an AlN inclusion in the steel. Such inclusions significantly reduce the fatigue life of the spring. For this reason, the Al content should be reduced as much as possible. From this aspect, the Al content needs to be 0.010% or less, preferably 0.008% or less, and more preferably 0.005% or less.
  • the steel wire rod for a high-strength spring in the present invention may contain at least one of (a) V in a content of 0.5% or less (excluding 0%), and Nb in a content of 0.5% or less (excluding 0%); (b) Mo in a content of 0.5% or less (excluding 0%); (c) Ni in a content of 1.0% or less (excluding 0%); (d) Cu in a content of 0.5% or less (excluding 0%); and (e) B in a content of 0.010% or less (excluding 0%), as necessary. Accordingly, the characteristics of the steel wire rod are improved depending on the components included therein.
  • the preferable range of content of each of components (elements) in the chemical composition is specified for the following reason.
  • each of the V content and the Nb content is preferably 0.5% or less.
  • the lower limit of each of V and Nb content is preferably 0.05% or more (more preferably, 0.10% or more), and the upper limit thereof is preferably 0.45% or less (more preferably, 0.40% or less).
  • Molybdenum (Mo) element effectively contributes to improve the spring strength due to secondary precipitation hardening induced in stress relief annealing after molding of the spring. If the Mo content is excessive, however, composite alloy carbides containing the Mo element and Cr element are precipitated in a large amount, which degrades the SV workability. Accordingly, the Mo content is preferably 0.5% or less. To exhibit the above effects, the Mo content is preferably 0.05% or more. The lower limit of Mo content is preferably 0.10% or more, and the upper limit of Mo content is preferably 0.45% or less (more preferably 0.40% or less).
  • Nickel (Ni) element contributes to improve the ductility/toughness and resistance to corrosion after the quenching-tempering process, while suppressing the decarbonization in the hot-rolling process. If the Ni content is excessive, however, the hardenability is excessively improved, whereby a supercooled phase containing martensite, bainite, and the like are more likely to be formed. Further, in the quenching-tempering process of the manufacturing procedure of an oil tempered wire (OT wire), retained austenaite is formed in an excessively large amount, which might drastically reduce the settling resistance of the spring. Accordingly, the Ni content is preferably 1.0% or less.
  • the lower limit of Ni content is preferably 0.05% or more (more preferably, 0.10% or more), and the upper limit of Ni content is preferably 0.9% or less (more preferably, 0.8% or less).
  • Copper (Cu) element contributes to improve the corrosion resistance, while suppressing the decarbonization in the hot-rolling process. If the Cu content is excessive, however, the hot ductility of the steel wire rod is reduced to possibly cause a crack in the hot-rolling process. Accordingly, the additive amount of Cu is preferably 0.5% or less.
  • the lower limit of Cu content is preferably 0.05% or more (more preferably, 0.1% or more), and the upper limit of Cu content is preferably 0.45% or less (more preferably, 0.40% or less).
  • B element effectively improves the hardenability and also improves the ductility/toughness by cleaning the austenite grain boundary. If the B content is excessive, however, composite compounds of Fe and B are precipitated to possibly cause cracks in the hot-rolling process. The hardenability is excessively improved, whereby the supercooled phase containing martensite, bainite, and the like are more likely to be formed. Accordingly, the B content is preferably 0.010% or less.
  • the lower limit of B content is preferably 0.0010% or more (more preferably 0.0015% or more, and most preferably, 0.0020% or more), and the upper limit of B content is preferably 0.0080% or less (more preferably, 0.0060% or less).
  • the high-strength steel wire rod of the invention is intended to be obtained after the hot-rolling process. Further, such a high-strength steel wire rod will be subjected to shaving, annealing, pre-wire-drawing (pickling), wire-drawing, coiling, quenching-tempering, surface treatment, and the like to thereby form the high-strength spring.
  • the thus-obtained high-strength spring exhibits the excellent characteristics.
  • each of the thus-obtained coils was examined on its pearlite area fraction, pearlite nodule size, total decarburized depth of the surface layer, a content of Cr-based alloy carbide, and SV workabilities.
  • each coil examined had the entire weight of 2 tons.
  • each one ring was cut from an end of each 2 ton coil for examination of each kind of workability, and then the ring was separated into 8 parts in its circumferential direction (corresponding to 8 parts in the longitudinal direction of the wire rod) as shown in Fig. 1 to produce samples. The measured values of the respective samples were averaged to determine a representative value of each coil.
  • the pearlite area fractions of the respective 8 parts of the rolled wire rod were measured using a light microscope at a surface layer (two fields of view) of each part and in positions of D/4 thereof (where D represents the diameter of the wire rod: two fields of view) and D/2 thereof (the center between the above-mentioned D/4 positions: one fields of view) (that is, five fields of view in total).
  • D represents the diameter of the wire rod: two fields of view
  • D/2 thereof the center between the above-mentioned D/4 positions: one fields of view
  • the hot-rolled wire rod was embedded in an appropriate material or the like and its cross section was polished and subjected to chemical corrosion using picric acid.
  • P indicates a phase having a pearlite area fraction of 90% or more
  • P + B + M" or “B + M” represents the formation of bainite or martensite together with the pearlite phase having a pearlite area fraction of less than 90%
  • the pearlite nodule sizes of the respective 8 parts of the rolled wire rod were measured using a light microscope at a surface layer (two fields of view) of each part and in positions of D/4 thereof (where D represents the diameter of the wire rod: two fields of view) and D/2 thereof (the center between the above-mentioned D/4 positions: one fields of view) (that is, five fields of view in total).
  • D represents the diameter of the wire rod: two fields of view
  • D/2 thereof the center between the above-mentioned D/4 positions: one fields of view
  • the term "pearlite nodule” refers to a region in which ferrite grains of the pearlite phase have the same orientation.
  • the measurement method for the pearlite nodules are as follows.
  • the grain size numbers of the pearlite nodules in five fields of view of each of 8 parts were measured, and averaged to thereby calculate an average value Pave of the pearlite nodule size every coil.
  • the grain size number of the pearlite nodules was measured in conformance with "Measurement of Austenite grain number" defined by JISG0551.
  • Fig. 3 which is a cross-sectional view exemplarily showing decarburation observation positions
  • the total decarburized depth of the layers were measured at 8 points of the surface layer of each of the 8 parts of the hot-rolled wire rod by use of the light microscopy.
  • the hot-rolled wire rod was embedded in the appropriate material, and its cross section was polished, and then subjected to chemical corrosion using picric acid and observed.
  • the maximum depth among 8 points was measured at each part, and further the deepest total decarburized depth of the layer among the 8 parts was defined as the total decarburized depth of the layer of the coil.
  • the total decarburized depth of the layer was determined in conformance with "Measurement of depth of decarburized layer of steel" defined by JISG0558.
  • the amount of Cr-based alloy carbides was determined by electrolytic extraction. First, scales of the rolled wire rod of each sample were removed with a sandpaper and washed with acetone. Then, the sample was immersed in an electrolytic solution (for example, an ethanol solution containing acetylaceton in a content of 10 mass%) (whereby the electrolytic quantity from the wire rod surface layer was set to approximately 0.4 to 0.5 g, and then the sample was taken). Then, metal Fe of a mother phase was decomposed by electric current, and alloy deposits (carbides, and nitrides and carbonitrides in a small amount) of the steel existing in the electrolytic solution were taken as residues.
  • an electrolytic solution for example, an ethanol solution containing acetylaceton in a content of 10 mass
  • the content of Cr-based alloy carbides was determined by dividing the mass of residues by the electrolytic quantity.
  • the alloy deposits measured include mainly Cr-based alloy carbides, but may also contain a composite alloy carbide of Cr and V, Nb, Mo, or the like upon adding a selected element.
  • a filter for taking the residue a filter with a mesh diameter of 0.1 ⁇ m (for example, a membrane filter manufactured by Advantic Toyo Kaisha, Ltd) was used.
  • the SV workability was evaluated in the following manner. A sample coil was subjected to a SV process without a heat treatment, and then the SV workability was evaluated by the presence or absence of a break in the SV process, the load on the breaker that is installed on an inlet side of a chipper die to cut shavings, the presence or absence of a crack in the chipper die, and the like.
  • Samples of Test No. 1 to No. 15 satisfied the requirements defined by the invention.
  • Samples of Test No. 16 to No. 23 satisfied the required chemical compositions (steels B1, B2, C1, C2, E1, G1, G2, and L1), but did not satisfy the manufacturing conditions required to obtain the steel of the invention.
  • Samples of Test No. 24 to No. 31 had the chemical compositions (steels P to W) departing from the scope of the invention.
  • the sample of Test No. 16 was placed at the high placing temperature after the rolling. As a result, this sample had coarse pearlite nodules of the rolled rod microstructure and got a break in the SV process.
  • the sample of Test No. 17 was placed at the low placing temperature after the rolling. As a result, this sample had the deep decarburized surface layer in the rolled wire rod, leading to an increase in load on the breaker.
  • Test No. 18 and 21 were cooled at low average cooling rate down to a temperature of 600°C after being placed on the conveyor. As a result, these samples had the coarse pearlite nodules of the rolled rod microstructure, and got a break in the SV process.
  • the samples of Test No. 19 and 22 were cooled at a low average cooling rate in a range decreasing from a temperature lower than 600°C to 400°C. As a result, the content of Cr-based alloy cabides contained in these samples was increased, leading to an increase in load on the breaker with a crack occurring in a chipper.
  • the sample of Test No. 20 was cooled at a high average cooling rate down to 600°C after being placed on the conveyer. As a result, the resultant steel wire rod of the sample did not become a single pearlite phase, and a martenite or bainite phase was formed in the steel wire rod, whereby the sample got a break in the SV process.
  • the sample of Test No. 23 was cooled at a high average cooling rate in a range descreasing from a temperature lower than 600°C to 400°C. As a result, the resultant steel wire rod of the sample did not become a single pearlite phase, and a martenite or bainite phase was formed in the steel wire rod, whereby the sample got a break in the SV process.
  • Test No. 24 used the steel (steel P shown in Table 2) in which a Si content was excessive, so that the total decarburized depth of the surface layer of the rolled steel wire rod was very deep, resulting in an increase in load on the breaker.
  • Test No. 25, 26, and 31 were examples using steels (steels Q, R, and W shown in Table 2) in which a content of each component (Mn, Ni, B) was excessive.
  • the resultant steel wire rod of each of these samples had the excessively increased hardenability, and did not become a single pearlite phase, and a martenite or bainite phase was formed in the steel wire rod, whereby these samples got a break in the SV process.
  • Test No. 27 to No. 30 were examples using steels (steels S, T, U, and V shown in Table 2) in which a content of each component (Cr, V, Mo, Nb) was excessive.
  • the resultant steel wire rod of each of these samples had increased content of Cr-based alloy carbides, leading to an increase in load on the breaker with a crack occurring in a chipper.
  • Fig. 4 illustrates variations in current through the breaker in the sample of Test No. 2 (example of the invention), and showed that the current values were stable.
  • Fig. 5 illustrates variations in current through the breaker in the sample of Test No. 27 (comparative example), and shows that the load on the breaker partly increased (specifically, the load on breaker as illustrated in a part enclosed by a broken line in the figure was high and the current value in the part was large).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical 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)
  • Springs (AREA)

Abstract

This steel wire rod for a high-strength spring is a hot-rolled steel wire rod which has a prescribed chemical composition and a texture such that the area fraction of pearlite is 90% or more; and the average grain size number of pearlite nodules, namely Pave, satisfies the relationship (1) 6.0 ≤ Pave ≤ 12.0. In the hot-rolled steel wire rod, the total decarburized depth of the surface layer is 0.20 mm or less, and the content of Cr-based alloy carbides is 7.5% or lower relative to the mass of the steel wire rod. The wire rod for a high strength spring and a high-strength spring obtained using the same as the raw material exhibit excellent shavability and ensure excellent discharge of shavings and excellent SV processing which is not accompanied with the breaking of wire.

Description

    Technical Field
  • The present invention relates to a steel wire rod for a high-strength spring that is usable as material for the high-strength springs (especially, valve spring) used in parts of vehicles, including a clutch, an engine, a fuel injector, a suspension mechanism, and the like, and also to a high-strength spring using the steel wire rod for a high-strength spring. More particularly, the present invention is directed to a steel wire rod for a high-strength spring that can exhibit excellent shavability in a shaving process.
  • Background Art
  • Springs applied under the environment described above are used with a high stress applied thereto over a long time of period. For this reason, such springs are required to have high fatigue resistance. In order to improve the fatigue resistance, it is required to impart the excellent surface properties to the spring, and to appropriately control inclusions in the spring. Regarding the surface properties, the spring molded is subjected to a planarization process and a hardening process by shot peening, nitriding, or the like. When a flaw on the order of several tens of micrometers in size remains or occurs in the spring, a break might be caused starting from the surface flaw in use of the spring.
  • Thus, a shaving process (hereinafter referred to as a "SV process") is performed to remove a decarburized part of a surface layer of the wire rod having been rolled, and a fine flaw on the surface layer of the wire rod. The SV process is a process which involves cutting the surface layer of the wire rod over its entire periphery in a depth direction by about several hundreds of micrometers using a chipper die. A wire rod having unsatisfactory SV workability (shavability) might be broken in the SV process, which disadvantageously results in a crack of the chipper die, an uneven surface of the wire rod, a shorter life time of a tool, and the like. Further, a breaker is provided for improving the discharge of shavings produced by minutely cutting the wire rod. In cutting the wire rod having the unsatisfactory SV workability, the shavings might be stuck in the breaker, excessively increasing a load on motor for driving the breaker. As a result, the device might sometimes stop, which decreases the yield of products or wire rods.
  • Improvement of the SV workability of a wire rod can significantly increase the yield of the wire rods and improve the quality of the wire rod. The mainstream techniques for improving the SV workability include control of the microstructure of the wire rod, control of the composition of inclusions, and the like. Various types of such techniques have been already proposed.
  • For example, Patent Literature (PTL) 1 has proposed that the shavability of a wire rod is improved by making austenite crystal grain size coarse. However, in order to achieve a spring steel with high fatigue strength, the steel needs to be formed of fine crystal grains. Moreover, taking into consideration the productivity, including the SV workability, wire-drawing workability, and the like, the crystal grains of the wire rod preferably have a fine grain size.
  • As disclosed in PTL 2, the composition of an oxide-based inclusion, and the size and distribution density of the oxide-based inclusion existing in the surface layer can be defined to improve the SV workability. However, the alloy-based carbide or nitride which significantly influences the ductility and toughness of the microstructure tends to cause the reduction in the SV workability at present.
  • On the other hand, PTL 3 has proposed that the SV workability is improved by defining the mechanical characteristics of steel. In the technique, however, the amount of added alloys is so much that a spring steel includes precipitation of alloy-based carbides or nitrides in a large amount. As a result, the spring steel can satisfy only the mechanical characteristics, but cannot improve the SV workability.
  • Citation List Patent Document
    • PTL 1: Japanese Unexamined Patent Publication No. 2000-256785
    • PTL 2: Japanese Unexamined Patent Publication No. 2010-222604
    • PTL3: Japanese Unexamined Patent Publication No. 2000-239797
    Summary of Invention Technical Problem
  • In particular, spring valves are required to have a high fatigue strength and a high fatigue life. In order to satisfy these characteristics, a spring needs to have good surface properties. The SV process is performed on the spring so as to remove a decarburized layer or surface flaw of a rolled rod. The SV process includes a skin pass step of enhancing the circularity of the rolled rod to prevent side cutting, and a shaving step of shaving using a chipper die. It is necessary that cooling conditions for rolling on a conveyor are properly controlled to prevent a rolled rod microstructure from containing a supercooled phase (bainite, martensite).
  • The shaving process with the chipper die requires that the overall length of a coil having a weight of 2 tons can be shaved with a stable surface quality, for example, with no mark made by the die. For this reason, the rolled rod microstructure needs to have excellent shavability. For example, the rolled rod microstructure does not contain a supercooled phase that might cause break of a wire. Additionally, the chipper die needs to be less likely to be cracked, and a load on a tool should be small. Shavings generated when shaving the wire rod with the chipper die are discharged by being cut finely by a breaker. Thus, the shavings needs to be easily cut by the breaker, that is, the wire rod needs to have excellent discharge of shavings.
  • The present invention has been made in order to solve such problems in the related art. The object of the present invention is to provide a wire rod for a high-strength spring that can exhibit the excellent SV workability without any break of the wire in an SV process, while having excellent shavability and discharging property of shavings, and also to provide a high-strength spring obtained by using such a wiring rod for a high-strength spring as material.
  • Solution to Problem
  • The present invention has achieved the objects described above, and provides a steel wire rod for a high-strength spring, which is a steel wire rod having been hot-rolled. The steel wire rod includes as a chemical composition: C in a content of 0.4% or more and less than 1.2%; Si in a content of 1.5% to 3.0%; Mn in a content of 0.5% to 1.5%; Cr in a content of 0.02% to 0.5%; and Al in a content of 0.010% or less, in mass percent, with the remainder being iron and inevitable impurities, wherein the steel wire rod has a phase with an area fraction of pearlite of 90% or more, an average grain size number Pave of pearlite nodules satisfies the following formula (1), a total decarburized depth of the surface layer is 0.20 mm or less, and a content of Cr-based alloy carbides is 7.5% or less relative to a mass of the steel wire rod: 6.0 Pave 12.0
    Figure imgb0001
  • The steel wire rod for a high-strength spring according to the present invention further effectively includes: at least one of (a) V in a content of 0.5% or less (excluding 0%), and Nb in a content of 0.5% or less (excluding 0%); (b) Mo in a content of 0.5% or less (excluding 0%); (c) Ni in a content of 1.0% or less (excluding 0%); (d) Cu in a content of 0.5% or less (excluding 0%); and (e) B in a content of 0.010% or less (excluding 0%), as necessary. Accordingly, the characteristics of the steel wire rod for a high-strength spring can be improved depending on the components included therein.
  • The present invention includes a high-strength spring obtained from the steel wire rod for a high-strength spring described above.
  • Advantageous Effects of Invention
  • The present invention optimizes the manufacturing conditions by appropriately adjusting the chemical composition so as to form a microstructure having an area fraction of pearlite of 90% or more, to set an average grain size number Pave of pearlite nodules in a predetermined range, and to control the total decarburized depth of the surface layer and the content of Cr-based alloy carbides. Accordingly, the present invention can achieve the steel wire rod for a high-strength spring that can exhibit the excellent SV workability without any break of the wire in the SV process, while having excellent shavability and discharging property of shavings. Such a steel wire rod for a high-strength spring is very useful as the material for manufacturing a high-strength spring.
  • Brief Description of Drawings
    • [Fig. 1] Fig. 1 is an explanatory diagram showing a sampling method (ring division positions) of samples for evaluation.
    • [Fig. 2] Fig. 2 is an exemplary cross-sectional view showing a microstructure observation position of a wire rod.
    • [Fig. 3] Fig. 3 is an exemplary cross-sectional view showing surface decarbonization observation position of the wire rod.
    • [Fig. 4] Fig. 4 is a graph showing variations in current through a breaker in a test No. 2 (example of the invention).
    • [Fig. 5] Fig. 5 is a graph showing variations in breaker current in a test No. 27 (comparative example).
    Description of Embodiments
  • The inventors have studied the characteristics of steel wire rods for a high-strength spring to achieve the above objects from various points of view. As a result, it has been revealed that a chemical composition and microstructure of a rolled rod, the grain size number of pearlite nodules, a decarburized depth of a surface layer, and a Cr-based alloy carbide content of the rolled rod surface layer are appropriately controlled to provide a steel wire rod that can drastically improve the SV workability without any break of the wire in an SV process, while having excellent shavability and discharging property of shavings. The shavability and the discharge property of shavings are hereinafter referred to as the "SV workability". N ow, requirements specified by the invention will be described.
  • [Microstructure with area fraction of pearlite of 90% or more]
  • The steel wire rod (steel wire rod obtained after hot-rolling: rolled wire rod) of the invention has a microstructure with an area fraction of pearlite of 90 % or more. The rolled wire rod having the microstructure with an area fraction of pealite of 90% or more means a rolled wire rod in which an area fraction of ferrite and supercooled phases formed of bainite and martensite that occupy a cross section of the rolled wire rod is 10% or less. The rolled wire rod having an area fraction of pealite of 90% or more can be subjected to the SV processing while having no break of the wire during the SV processing. In contrast, if a rolled wire rod has a supercooled phase containing bainite, martenside, and the like at an area fraction of 10% or more, the rolled wire rod will have the reduced ductility/toughness, and as a result, might degrade the SV workability, for example, might be broken in the SV processing.
  • Ferrite does not reduce the SV workability so much as the supercooled phases of bainite, martensite, or the like, and may be partly contained in the wire rod microstructure. If the ferrite content of the steel wire rod is excessive, however, the microstructure of the wire rod becomes heterogeneous, which is not preferable in terms of the SV workability. From this aspect, in the steel wire rod of the invention, an area fraction of pearlite is preferably 90 area% or more. The area fraction of pealite is more preferably 92 area% or more (most preferably, 95 area% or more).
  • [Average grain size number of pearlite nodules Pave: 6.0 ≤ Pave ≤ 12.0]
  • An average grain size number of pearlite nodules (hereinafter sometimes referred to as a "pearlite nodule size") Pave significantly affects the ductility of the rolled wire rod. A rolled wire rod with a small pearlite nodule size has poor ductility, which might cause a break of the wire in the SV processing. As the pearlite nodule size becomes larger, the ductility of the wire is improved. However, to make the pearlite nodules much finer, a placing temperature in the hot rolling is required to be excessively reduced, and cooling equipment with an excessive heating capacity is necessary for rapid cooling. Thus, this is difficult to implement in real life.
    From this aspect, the average pearlite nodule size Pave is set to satisfy the following formula: 6.0 Pave 12.0 , preferably , 7.0 Pave 11.0.
    Figure imgb0002
  • [Total decarburized depth of surface layer: 0.20 mm or less]
  • A decarburized surface layer is normally removed by the SV process. However, when the decarburized surface layer is deep, the ductility of shavings generated in the SV process becomes higher, which results in deterioration of separability of shavings by the chip breaker and reduction in discharge of the shavings, thereby degrading the SV workability. Further, the deep decarburized surface layer is likely to remain even after the SV process, which drastically reduces a fatigue strength of a spring. Accordingly, the total decarburized depth of the surface layer is set to 0.20 mm or less, and preferably 0.15 mm or less (more preferably, 0.10 mm or less).
  • [Content of Cr-based alloy carbides relative to mass of steel wire rod ≤ 7.5 mass%]
  • Cr-based alloy carbides are much harder than iron-based carbides. Thus, even a small amount of Cr-based alloy carbides causes cracks of a tip of a chipper blade, which reduces a life time of a chipper die and the discharge of shavings, thereby degrading the SV workability. Accordingly, an upper limit of the Cr-based alloy carbide content relative to the entire mass of steel wire rod is set to 7.5 mass%. The Cr-based alloy carbide content is preferably 5.0 % or less (more preferably, 4.0 % or less). The Cr-based alloy carbides of interest in the invention are carbides that basically contain Cr as a principal component. When the steel wire rod further contains a carbide formation element, such as V, Nb, or Mo, the Cr-based alloy carbides may contain a composite alloy carbide thereof. The Cr-based alloy carbides sometimes contain a very small amount of nitride or carbonitride.
  • To manufacture such a steel wire rod for a high-strength spring described above, manufacturing conditions also need to be appropriately controlled. The procedure for manufacturing the steel wire rod for a high-strength spring will be as follows. First, a steel billet having a predetermined chemical composition is hot-rolled into a desired wire diameter. An excessively high heating temperature in rolling makes the wire rod microstructure brittle due to an increase in grain size of a prior austenite, thereby reducing the SV workability. In contrast, an excessively low heating temperature increases a deformation resistance of the steel rod, causing a high load on a rolling machine, which leads to reduction of the productivity. Thus, the heating temperature before the rolling is preferably not less than 900°C nor more than 1100°C, and more preferably not less than 950°C nor more than 1050°C.
  • Subsequently, the steel wire rod having been hot-rolled is placed in the form of coil on a cooling conveyor. When the temperature at this time (placing temperature) exceeds 1100°C, the prior austenite grain size is increased to make the grains of the prior austenite coarse, which might c ause the brittleness of the microstructure together with the grain coarsening of the pealite nodules. On the other hand, when the placing temperature is below 860°C, the decarburized surface layer is more likely to be deep, which might increase the deformation resistance, leading to a defect in the winding shape. Accordingly, the placing temperature is preferably in a range of 860°C to 1100°C. The placing temperature can be controlled in such a range to thereby suppress the grain coarsening of the pearlite nodules and the formation of the decarburized surface layer. The placing temperature is more preferably in a range of not less than 900°C nor more than 1050°C.
  • After placing the steel wire rod on the conveyor, the rolled steel wire rod is cooled down to 600°C at an average cooling rate of 1.0°C/sec or more (preferably, 3.5°C/sec or more) and 10°C/sec or less (preferably, at 8°C/sec), which is an end temperature of pearlite transformation, whereby a rolled steel microstructure having a phase containing pearlite as a principal element is obtained while preventing the grain coarsening of the pearlite nodules. Sequentially, the steel wire rod is cooled in a temperature range decreasing from less than 600°C to 400°C at the average cooling rate of 3°C/sec or more (preferably, 3.5°C/sec or more) and 10°C/sec or less (preferably, 8°C/sec or less), and then continuously cooled to 400°C or less (preferably, 375°C or less), whereby the rolled steel wire rod with excellent SV workability can be obtained while preventing the precipitation of Cr-based alloy carbides in the phase containing pearlite as the principal element.
  • The steel wire rod for a high-strength spring in the invention needs to have its chemical composition controlled appropriately so as to exhibit the characteristics of a final product (specifically, a high-strength spring). The range of content of each of components (elements) in the chemical composition is specified for the following reason.
  • [C: 0.4% or more and less than 1.2%]
  • Carbon (C) element is effective for ensuring the strength basically required for steel and increasing the strength and settling resistance of a spring produced from the steel. For this reason, the carbon content needs to be 0.4% or more. The strength and settling resistance of the spring is improved as the carbon content is increased. However, if the carbon content is excessive, the coarse cementite will precipitate in a great amount, which reduces the ductility/toughness of the wire rod, thus adversely affecting the workability and characteristics of the spring. From this aspect, the carbon content needs to be less than 1.2%. The lower limit of carbon content is preferably 0.5% or more, and the upper limit of carbon content is preferably 1.0% or less.
  • [Si: 1.5% to 3.0%]
  • Silicon (Si) element is necessary for deoxidation of the steel and also for ensuring the strength, hardness, and settling resistance of the spring. To exhibit these effects, the Si content needs to be 1.5% or more. I f the Si content is excessive, however, the steel is hardened, and additionally, the ductility/toughness of the steel wire rod is reduced, and the amount of the decarburized surface layer is increased, which degrades the SV workability and the fatigue properties of the steel wire rod. Accordingly, the Si content needs to be 3.0% or less. The lower limit of Si content is preferably 1.6% or more (more preferably, 1.7% or more), and the upper limit of Si content is preferably 2.8% or less (more preferably, 2.5% or less).
  • [Mn: 0.5% to 1.5%]
  • Manganese (Mn) element is also necessary for deoxidation of the steel, as with Si, and increases the hardenability to contribute to improve the spring strength in addition to fixing S element in the steel as a compound MnS. To exhibit these effects, the Mn content needs to be 0.5% or more. If the Mn content is excessive, however, the hardenability of the steel wire rod becomes excessively high, which allows the supercooled phase of martensite, bainite, and the like to be easily formed. Accordingly, the Mn content needs to be 1.5% or less. The lower limit of Mn content is preferably 0.6% or more (more preferably, 0.7% or more), and the upper limit of Mn content is preferably 1.4% or less (more preferably, 1.3% or less).
  • [Cr: 0.02% to 0.5%]
  • Chromium (Cr) element improves the spring strength by enhancing the hardenability and the resistance to temper softening, and effectively reduces the activity of carbon to thereby prevent decarburization upon rolling and heat treatment. If the Cr content is excessive, however, the Cr-based alloy carbides, nitride, and carbonitride are precipitated much, thus degrading the SV workability. Accordingly, the Cr content needs to be 0.5% or less (preferably, the upper limit of Cr content is 0.45% or less, (more preferably, 0.40% or less)). To exhibit the above effects, the Cr content is 0.02% or more. The lower limit of Cr content is preferably 0.05% or more (more preferably, 0.10% or more).
  • [Al: 0.010% or less]
  • Aluminum (Al) element is a deoxidizing element, and forms an Al2O3 inclusion and an AlN inclusion in the steel. Such inclusions significantly reduce the fatigue life of the spring. For this reason, the Al content should be reduced as much as possible. From this aspect, the Al content needs to be 0.010% or less, preferably 0.008% or less, and more preferably 0.005% or less.
  • Basic components of the steel wire rod for a high-strength spring according to the present invention have been described above, in which the remainder includes iron and inevitable impurities (for example, P, S, and the like). The steel wire rod for a high-strength spring in the present invention may contain at least one of (a) V in a content of 0.5% or less (excluding 0%), and Nb in a content of 0.5% or less (excluding 0%); (b) Mo in a content of 0.5% or less (excluding 0%); (c) Ni in a content of 1.0% or less (excluding 0%); (d) Cu in a content of 0.5% or less (excluding 0%); and (e) B in a content of 0.010% or less (excluding 0%), as necessary. Accordingly, the characteristics of the steel wire rod are improved depending on the components included therein. The preferable range of content of each of components (elements) in the chemical composition is specified for the following reason.
  • [At least one of V: 0.5% or less (excluding 0%), and Nb: 0.5% or less (excluding 0%)]
  • Both vanadium (V) and niobium (Nb) elements have the effect of making the crystal grains finer in the hot-rolling process as well as the quenching-tempering process, to thereby improve the ductility/toughness of the steel wire rod. Among them, vanadium (V) element effectively contributes to improve the spring strength due to secondary precipitation hardening induced in stress relief annealing after molding of the spring. If the V content is excessive, however, composite alloy carbides containing the V or Nb element and the Cr element are precipitated in a large amount, which degrades the SV workability. Accordingly, each of the V content and the Nb content is preferably 0.5% or less. To exhibit the effects described above, the lower limit of each of V and Nb content is preferably 0.05% or more (more preferably, 0.10% or more), and the upper limit thereof is preferably 0.45% or less (more preferably, 0.40% or less).
  • [Mo: 0.5% or less (excluding 0%)]
  • Molybdenum (Mo) element effectively contributes to improve the spring strength due to secondary precipitation hardening induced in stress relief annealing after molding of the spring. If the Mo content is excessive, however, composite alloy carbides containing the Mo element and Cr element are precipitated in a large amount, which degrades the SV workability. Accordingly, the Mo content is preferably 0.5% or less. To exhibit the above effects, the Mo content is preferably 0.05% or more. The lower limit of Mo content is preferably 0.10% or more, and the upper limit of Mo content is preferably 0.45% or less (more preferably 0.40% or less).
  • [Ni: 1.0% or less (excluding 0%)]
  • Nickel (Ni) element contributes to improve the ductility/toughness and resistance to corrosion after the quenching-tempering process, while suppressing the decarbonization in the hot-rolling process. If the Ni content is excessive, however, the hardenability is excessively improved, whereby a supercooled phase containing martensite, bainite, and the like are more likely to be formed. Further, in the quenching-tempering process of the manufacturing procedure of an oil tempered wire (OT wire), retained austenaite is formed in an excessively large amount, which might drastically reduce the settling resistance of the spring. Accordingly, the Ni content is preferably 1.0% or less. The lower limit of Ni content is preferably 0.05% or more (more preferably, 0.10% or more), and the upper limit of Ni content is preferably 0.9% or less (more preferably, 0.8% or less).
  • [Cu: 0.5% or less (excluding 0%)]
  • Copper (Cu) element contributes to improve the corrosion resistance, while suppressing the decarbonization in the hot-rolling process. If the Cu content is excessive, however, the hot ductility of the steel wire rod is reduced to possibly cause a crack in the hot-rolling process. Accordingly, the additive amount of Cu is preferably 0.5% or less. The lower limit of Cu content is preferably 0.05% or more (more preferably, 0.1% or more), and the upper limit of Cu content is preferably 0.45% or less (more preferably, 0.40% or less).
  • [B: 0.010% or less (excluding 0%)]
  • Boron (B) element effectively improves the hardenability and also improves the ductility/toughness by cleaning the austenite grain boundary. If the B content is excessive, however, composite compounds of Fe and B are precipitated to possibly cause cracks in the hot-rolling process. The hardenability is excessively improved, whereby the supercooled phase containing martensite, bainite, and the like are more likely to be formed. Accordingly, the B content is preferably 0.010% or less. The lower limit of B content is preferably 0.0010% or more (more preferably 0.0015% or more, and most preferably, 0.0020% or more), and the upper limit of B content is preferably 0.0080% or less (more preferably, 0.0060% or less).
  • The high-strength steel wire rod of the invention is intended to be obtained after the hot-rolling process. Further, such a high-strength steel wire rod will be subjected to shaving, annealing, pre-wire-drawing (pickling), wire-drawing, coiling, quenching-tempering, surface treatment, and the like to thereby form the high-strength spring. The thus-obtained high-strength spring exhibits the excellent characteristics.
  • EXAMPLES
  • The present invention will be described in more detail using experimental examples below. It should be noted that, however, these examples are never construed to limit the scope of the invention; and various modifications and changes may be made without departing from the scope and spirit of the invention and should be considered to be within the scope of the invention.
  • Steel ingots having chemical compositions given in the following Tables 1 and 2 were made in a converter and then bloomed into steel billets having a cross section of 155 mm by 155 mm. The steel billets were heated to 1000°C and hot-rolled. Then, the rolled steel was cooled at conveyor placing temperatures given in Tables 3 and 4 (that is, placing temperature after the hot-rolling) at an average cooling rate (specifically, at average cooling rates in a range from the placing temperature to 600°C, and in another range from a temperature less than 600°C to 400°C), thereby producing coils having a diameter of 8.0 mm and an individual weight of 2 ton (test No. 1 to No. 31). [Table 1]
    Steel Chemical compositions* (in mass%)
    C Si Mn Ni Cr V Cu Mo Nb B Al
    A 0.81 1.56 0.75 - 0.22 - - - - - 0.003
    B 0.69 1.89 0.81 - 0.06 - - - - - 0.004
    C 0.55 2.11 1.05 - 0.16 - - - - - 0.002
    D 1.12 1.89 0.79 - 0.33 - 0.34 - - - 0.003
    E 0.44 2.09 0.93 0.25 0.47 - - - 0.0031 0.0031 0.003
    F 0.78 2.51 1.38 0.22 0.31 - - 0.22 - - 0.002
    G 0.61 2.01 1.05 - 0.29 0.22 - - - - 0.006
    H 0.83 1.82 0.77 - 0.11 - 0.18 - 0.41 - 0.003
    I 0.77 2.51 1.40 - 0.08 - - - 0.23 - 0.003
    J 0.71 1.85 0.68 - 0.22 0.18 - - - 0.0051 0.004
    K 0.63 2.81 1.13 0.71 0.37 0.41 - - - - 0.003
    L 0.53 1.77 0.81 - 0.28 - 0.41 - 0.08 - 0.002
    M 0.49 1.66 0.88 0.42 0.16 - - 0.18 - - 0.002
    N 0.58 1.95 1.00 - 0.18 - 0.22 - -0.0037 0.0037 0.003
    O 0.62 2.31 1.28 - 0.06 0.08 - - - 0.0024 0.005
    * The remainder being iron and inevitable impurities
    [Table 2]
    Steel Chemical compositions* (in mass%)
    C Si Mn Ni Cr V Cu Mo Nb B Al
    B1 0.69 1.89 0.81 - 0.06 - - - - - 0.004
    B2 0.69 1.89 0.81 - 0.06 - - - - - 0.004
    C1 0.55 2.11 1.05 - 0.16 - - - - - 0.002
    C2 0.55 2.11 1.05 - 0.16 - - - - - 0.002
    E1 0.44 2.09 0.93 0.25 0.47 - - - - 0.0031 0.004
    G1 0.61 2.01 1.05 - 0.29 0.22 - - - - 0.003
    G2 0.61 2.01 1.05 - 0.29 0.22 - - - - 0.002
    L1 0.53 1.77 0.81 - 0.28 - 0.41 - 0.08 - 0.002
    P 071 3.22 1.12 - 0.35 - - 0.31 - - 0.001
    G 0.84 1.76 1.72 - 0.18 0.08 0.22 - 0.15 - 0.002
    R 0.88 2.05 1.13 1.21 0.27 0.22 - - - 0.0035 0.003
    S 0.58 1.95 0.81 - 0.71 - - 0.21 - 0.0028 0.005
    T 0.68 1.66 0.98 0.31 0.41 0.75 0.21 - 0.19 - 0.003
    U 0.47 2.51 1.41 0.12 0.08 - - 0.75 - - 0.008
    V 0.73 1.88 1.05 - 0.34 0.18 - 0.65 - 0.005
    W 0.59 1.86 0.61 - 0.18 0.17 - - 0.34 0.0135 0.003
    * The remainder being iron and inevitable impurities
    [Table 3]
    Test No. Steel Placing temperature after rolling (°C) Average cooling rate (°C/sec)
    From placing temperature to 600°C From less than 600°C to 400°C
    1 A 950 2.5 4.0
    2 B 900 3.0 3.5
    3 C 890 3.5 4.0
    4 D 940 3.5 3.5
    5 E 1030 6.5 5.0
    6 F 910 2.0 3.5
    7 G 880 4.0 4.0
    8 H 930 4.0 4.0
    9 I 930 3.5 7.0
    10 J 910 4.0 5.0
    11 K 960 5.0 3.5
    12 L 900 3.5 4.0
    13 M 890 3.5 4.0
    14 N 910 3.0 5.0
    15 O 900 4.0 3.5
    [Table 4]
    Test No. Steel Placing temperature after rolling (°C) Average cooling rate (°C/sec)
    From placing temperature to 600°C From less than 600°C to 400°C
    16 B1 1130 4.0 3.5
    17 B2 840 3.0 5.
    18 C1 920 0.5 5.0
    19 C2 930 3.0 2.0
    20 E1 910 11.5 4.0
    21 G1 950 0.5 3.5
    22 G2 910 3.0 1.5
    23 L1 920 4.0 11.0
    24 P 880 3.5 4.0
    25 Q 910 3.0 6.5
    26 R 890 2.5 3.5
    27 S 950 4.0 4.5
    28 T 940 3.0 3.5
    29 U 920 3.5 4.5
    30 V 890 2.5 3.5
    31 W 880 3.0 4.5
  • Then, each of the thus-obtained coils was examined on its pearlite area fraction, pearlite nodule size, total decarburized depth of the surface layer, a content of Cr-based alloy carbide, and SV workabilities. In examination of the SV workability, each coil examined had the entire weight of 2 tons. Regarding properties other than the SV workability, each one ring was cut from an end of each 2 ton coil for examination of each kind of workability, and then the ring was separated into 8 parts in its circumferential direction (corresponding to 8 parts in the longitudinal direction of the wire rod) as shown in Fig. 1 to produce samples. The measured values of the respective samples were averaged to determine a representative value of each coil.
  • As shown in Fig. 2 (which is a cross-sectional view exemplarily showing the microstructure observation positions), the pearlite area fractions of the respective 8 parts of the rolled wire rod were measured using a light microscope at a surface layer (two fields of view) of each part and in positions of D/4 thereof (where D represents the diameter of the wire rod: two fields of view) and D/2 thereof (the center between the above-mentioned D/4 positions: one fields of view) (that is, five fields of view in total). In more detail, the hot-rolled wire rod was embedded in an appropriate material or the like and its cross section was polished and subjected to chemical corrosion using picric acid. Then, images of the wire rod microstructure in a region of 200 µm x 200 µm were taken by the light microscope under a magnification of 400 times. Each image was binarized using an image analysis software ("image pro plus" manufactured by Media Cybemetics, inc.), whereby pearlite area fractions in the images were determined and then calculated to obtain an average pearlite area fraction. In this way, the pearlite area fractions in the respective five fields of view for each of the eight parts were determined and averaged to thereby calculate the average pearlite area fraction per coil. In the presence of a decarburized surface layer, the whole decarburized parts defined under JIS G0558-4 were omitted from the parts of interest for measurement. Herein, P indicates a phase having a pearlite area fraction of 90% or more, and "P + B + M" or "B + M" represents the formation of bainite or martensite together with the pearlite phase having a pearlite area fraction of less than 90%.
  • As shown in Fig. 2, the pearlite nodule sizes of the respective 8 parts of the rolled wire rod were measured using a light microscope at a surface layer (two fields of view) of each part and in positions of D/4 thereof (where D represents the diameter of the wire rod: two fields of view) and D/2 thereof (the center between the above-mentioned D/4 positions: one fields of view) (that is, five fields of view in total). As used herein, the term "pearlite nodule" refers to a region in which ferrite grains of the pearlite phase have the same orientation. The measurement method for the pearlite nodules are as follows. First, the hot-rolled wire rod of each coil was embedded in an appropriate material, and its cross section was polished and then subjected to corrosion using a mixture of a concentrated nitric acid solution (62%): alcohol = 1 : 100 (in volume ratio) (at this time, pearlite nodule grains seemed to emerge from the section due to a difference in amount of corrosion from that on the crystal surface of the ferrite grain), whereby the grain size number of the pearlite nodules was measured. Specifically, the grain size numbers of the pearlite nodules in five fields of view of each of 8 parts were measured, and averaged to thereby calculate an average value Pave of the pearlite nodule size every coil. The grain size number of the pearlite nodules was measured in conformance with "Measurement of Austenite grain number" defined by JISG0551.
  • As shown in Fig. 3 (which is a cross-sectional view exemplarily showing decarburation observation positions), the total decarburized depth of the layers were measured at 8 points of the surface layer of each of the 8 parts of the hot-rolled wire rod by use of the light microscopy. Specifically, the hot-rolled wire rod was embedded in the appropriate material, and its cross section was polished, and then subjected to chemical corrosion using picric acid and observed. The maximum depth among 8 points was measured at each part, and further the deepest total decarburized depth of the layer among the 8 parts was defined as the total decarburized depth of the layer of the coil. The total decarburized depth of the layer was determined in conformance with "Measurement of depth of decarburized layer of steel" defined by JISG0558.
  • The amount of Cr-based alloy carbides was determined by electrolytic extraction. First, scales of the rolled wire rod of each sample were removed with a sandpaper and washed with acetone. Then, the sample was immersed in an electrolytic solution (for example, an ethanol solution containing acetylaceton in a content of 10 mass%) (whereby the electrolytic quantity from the wire rod surface layer was set to approximately 0.4 to 0.5 g, and then the sample was taken). Then, metal Fe of a mother phase was decomposed by electric current, and alloy deposits (carbides, and nitrides and carbonitrides in a small amount) of the steel existing in the electrolytic solution were taken as residues. Thus, the content of Cr-based alloy carbides (by mass%) was determined by dividing the mass of residues by the electrolytic quantity. The alloy deposits measured include mainly Cr-based alloy carbides, but may also contain a composite alloy carbide of Cr and V, Nb, Mo, or the like upon adding a selected element. As a filter for taking the residue, a filter with a mesh diameter of 0.1 µm (for example, a membrane filter manufactured by Advantic Toyo Kaisha, Ltd) was used.
  • The SV workability was evaluated in the following manner. A sample coil was subjected to a SV process without a heat treatment, and then the SV workability was evaluated by the presence or absence of a break in the SV process, the load on the breaker that is installed on an inlet side of a chipper die to cut shavings, the presence or absence of a crack in the chipper die, and the like.
  • [Evaluation criteria of SV workability]
    1. (1) Presence or absence of break: In applying the SV process to an entire coil having a weight of 2 tons, a coil that did not get a break was evaluated as the good SV workability, indicated by O, and a coil that got one or more breaks was evaluated as the bad SV workability, indicated by x.
    2. (2) Load on breaker: Variations in current (from 0 to 10 A) through the breaker for each coil was measured at intervals of 1 sec for sampling by use of a data logger. In the SV process, data on the coil except for TOP and BOT thereof each having a weight of 10 kg was used. A coil in which any part of 60-point moving average of measured data did not exceed 9 A was evaluated as the good SV workability, indicated by O, and a coil in which a part of 60-point moving average of measured data exceeded 9A was evaluated as the bad SV workability, indicated by x (see Figs. 4 and 5 to be described later).
    3. (3) Crack of chipper die: The whole coil having a weight of 2 tons was subjected to the SV process, followed by removing the chipper die. The presence or absence of cracks in a wire contact part of the chipper die was checked by a stereoscopic microscope. A coil that did not cause any crack (crack of the chipper) in the wire contact part of the chipper die was evaluated as the good SV workability, indicated by O, and a coil that caused a crack in the wire contact part of the chipper die was evaluated as the bad SV workability, indicated by x.
  • The evaluation results are shown in Tables 5 and 6 below together with the rolled wire rod microstructures (pearlite area fraction, average size Pave of pearlite nodules), and the content of Cr-based alloy carbides. [Table 5]
    Test No. Steel Rolled wire rod microstructure Total decarburized depth (mm) Cr-based alloy carbide content (in mass%) SV workability
    Main microstructure** Pave Presence or absence of break Load on breaker Crack of chipper
    1 A P 8.5 0.07 3.8
    2 B P 8.0 0.11 1.1
    3 C P 9.5 0.08 2.6
    4 D P 9.5 0.06 5.2
    5 E P 9.0 0.05 3.8
    6 F P 9.5 0.09 4.2
    7 G P 11.0 0.15 2.5
    8 H P 8.5 0.04 1.8
    9 I P 8.5 0.10 1.3
    10 J P 8.5 0.07 3.5
    11 K P 9.5 0.06 4.6
    12 L p 9.5 0.11 2.7
    13 M P 9.0 0.11 2.1
    14 N P 9.5 0.09 1.6
    15 O P 9.0 0.11 0.9
    **: P: Pearlite
    [Table 6]
    Test No. Steel Rolled wire rod microstructure Total decarburized depth (mm) Cr-based alloy carbide content (in mass%) SV workability
    Main microstructure** Pave Presence or absence of break Load on breaker Crack of chipper
    16 B1 P 5.5 0.05 1.1 × - -
    17 B2 P 8.5 0.24 1.3 ×
    18 C1 P 5.5 0.10 2.8 × - -
    19 C2 P 9.5 0.08 9.1 × ×
    20 E1 B+M - 0.01 0.2 × - -
    21 G1 P 5.5 0.12 5.7 × - -
    22 G2 P 9.0 0.14 8.5 × ×
    23 L1 P+B+M 10.5 0.12 1.1 × - -
    24 P P 9.5 0.28 3.7 ×
    25 Q P+B+M 9.0 0.05 2.3 × - -
    26 R P+B+M 9.5 0.07 4.8 × - -
    27 S P 10.0 0.14 10.8 × ×
    28 T P 10.5 0.06 9.5 × ×
    29 U P 9.0 0.08 9.7 × ×
    30 V P 10.0 0.11 10.5 × ×
    31 W P+B+M 9.0 0.16 2.8 × - -
    **: P: Pearlite, B: Bainite, M: Martensite
  • Samples of Test No. 1 to No. 15 (see Table 5) satisfied the requirements defined by the invention. Samples of Test No. 16 to No. 23 (see Table 6) satisfied the required chemical compositions (steels B1, B2, C1, C2, E1, G1, G2, and L1), but did not satisfy the manufacturing conditions required to obtain the steel of the invention. Samples of Test No. 24 to No. 31 (see Table 6) had the chemical compositions (steels P to W) departing from the scope of the invention.
  • These results can lead to the following conclusion. First, the samples of Tests No. 1 to 15 satisfied the requirements defined by the invention. There steel wire rods got very good results regarding all items on the SV workability (including the presence or absence of the break, the load on the breaker, and the crack of the chipper).
  • In contrast, the sample of Test No. 16 was placed at the high placing temperature after the rolling. As a result, this sample had coarse pearlite nodules of the rolled rod microstructure and got a break in the SV process. The sample of Test No. 17 was placed at the low placing temperature after the rolling. As a result, this sample had the deep decarburized surface layer in the rolled wire rod, leading to an increase in load on the breaker.
  • The samples of Test No. 18 and 21 were cooled at low average cooling rate down to a temperature of 600°C after being placed on the conveyor. As a result, these samples had the coarse pearlite nodules of the rolled rod microstructure, and got a break in the SV process. The samples of Test No. 19 and 22 were cooled at a low average cooling rate in a range decreasing from a temperature lower than 600°C to 400°C. As a result, the content of Cr-based alloy cabides contained in these samples was increased, leading to an increase in load on the breaker with a crack occurring in a chipper.
  • The sample of Test No. 20 was cooled at a high average cooling rate down to 600°C after being placed on the conveyer. As a result, the resultant steel wire rod of the sample did not become a single pearlite phase, and a martenite or bainite phase was formed in the steel wire rod, whereby the sample got a break in the SV process. The sample of Test No. 23 was cooled at a high average cooling rate in a range descreasing from a temperature lower than 600°C to 400°C. As a result, the resultant steel wire rod of the sample did not become a single pearlite phase, and a martenite or bainite phase was formed in the steel wire rod, whereby the sample got a break in the SV process.
  • The sample of Test No. 24 used the steel (steel P shown in Table 2) in which a Si content was excessive, so that the total decarburized depth of the surface layer of the rolled steel wire rod was very deep, resulting in an increase in load on the breaker.
  • The samples of Test No. 25, 26, and 31 were examples using steels (steels Q, R, and W shown in Table 2) in which a content of each component (Mn, Ni, B) was excessive. As a result, the resultant steel wire rod of each of these samples had the excessively increased hardenability, and did not become a single pearlite phase, and a martenite or bainite phase was formed in the steel wire rod, whereby these samples got a break in the SV process.
  • The samples of Test No. 27 to No. 30 were examples using steels (steels S, T, U, and V shown in Table 2) in which a content of each component (Cr, V, Mo, Nb) was excessive. As a result, the resultant steel wire rod of each of these samples had increased content of Cr-based alloy carbides, leading to an increase in load on the breaker with a crack occurring in a chipper.
  • Fig. 4 illustrates variations in current through the breaker in the sample of Test No. 2 (example of the invention), and showed that the current values were stable. In contrast, Fig. 5 illustrates variations in current through the breaker in the sample of Test No. 27 (comparative example), and shows that the load on the breaker partly increased (specifically, the load on breaker as illustrated in a part enclosed by a broken line in the figure was high and the current value in the part was large).

Claims (7)

  1. A steel wire rod for high-strength springs, the steel wire rod having been hot-rolled and exhibiting excellent shavability, the steel wire rod comprising, as a chemical composition: C in a content of 0.4% or more and less than 1.2%; Si in a content of 1.5% to 3.0%; Mn in a content of 0.5% to 1.5%; Cr in a content of 0.02% to 0.5%; and Al in a content of 0.010% or less, in mass percent, with the remainder being iron and inevitable impurities, wherein
    the steel wire rod has a microstructure with an area fraction of pearlite of 90% or more, an average grain size number Pave of pearlite nodules satisfies the following formula (1), a total decarburized depth of the surface layer is 0.20 mm or less, and a content of Cr-based alloy carbides is 7.5% or less relative to an entire mass of the steel wire rod: 6.0 Pave 12.0
    Figure imgb0003
  2. The steel wire rod for high-strength springs according to claim 1, further comprising at least one of V in a content of 0.5% or less (excluding 0%), and Nb in a content of 0.5% or less (excluding 0%).
  3. The steel wire rod for high-strength springs according to claim 1, further comprising Mo: 0.5% or less (excluding 0%).
  4. The steel wire rod for high-strength springs according to claim 1, further comprising Ni: 1.0% or less (excluding 0%).
  5. The steel wire rod for high-strength springs according to claim 1, further comprising Cu: 0.5% or less (excluding 0%).
  6. The steel wire rod for high-strength springs according to claim 1, further comprising B: 0.010% or less (excluding 0%).
  7. A high-strength spring obtained using the steel wire rod for high-strength springs according to any one of claims 1 to 6.
EP13768751.3A 2012-03-30 2013-03-25 Steel wire rod with excellent shavability for high-strength spring, and high-strength spring Not-in-force EP2832891B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012083005A JP5796782B2 (en) 2012-03-30 2012-03-30 High strength spring steel wire rod and high strength spring with excellent skin machinability
PCT/JP2013/058564 WO2013146675A1 (en) 2012-03-30 2013-03-25 Steel wire rod with excellent shavability for high-strength spring, and high-strength spring

Publications (3)

Publication Number Publication Date
EP2832891A1 true EP2832891A1 (en) 2015-02-04
EP2832891A4 EP2832891A4 (en) 2016-04-27
EP2832891B1 EP2832891B1 (en) 2019-02-20

Family

ID=49259926

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13768751.3A Not-in-force EP2832891B1 (en) 2012-03-30 2013-03-25 Steel wire rod with excellent shavability for high-strength spring, and high-strength spring

Country Status (6)

Country Link
EP (1) EP2832891B1 (en)
JP (1) JP5796782B2 (en)
KR (1) KR101601582B1 (en)
CN (1) CN104169453B (en)
MX (1) MX2014011610A (en)
WO (1) WO2013146675A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3279358A4 (en) * 2015-03-31 2018-08-15 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Heat-treated steel wire having excellent bendability
US10385430B2 (en) 2014-03-31 2019-08-20 Kobe Steel, Ltd. High-strength steel material having excellent fatigue properties
US20220112753A1 (en) * 2019-02-26 2022-04-14 Nv Bekaert Sa Helical compression spring for an actuator for opening and closing a door or a tailgate of a car
US11761054B2 (en) 2017-09-29 2023-09-19 Posco Co., Ltd Wire rod and steel wire for springs having excellent corrosion fatigue resistance properties, and method for producing same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6479527B2 (en) 2015-03-27 2019-03-06 株式会社神戸製鋼所 Bolt wire with excellent pickling property and delayed fracture resistance after quenching and tempering, and bolt
JP6453693B2 (en) * 2015-03-31 2019-01-16 株式会社神戸製鋼所 Heat treated steel wire with excellent fatigue characteristics
CN110573638A (en) * 2017-03-28 2019-12-13 住友电气工业株式会社 Wire and spring

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2932943B2 (en) * 1993-11-04 1999-08-09 株式会社神戸製鋼所 High corrosion resistance and high strength steel for springs
JP3599551B2 (en) * 1998-01-09 2004-12-08 株式会社神戸製鋼所 Wire with excellent drawability
JP2000239797A (en) 1998-12-21 2000-09-05 Kobe Steel Ltd Steel for spring excellent in workability and production of steel wire for spring
JP3739958B2 (en) 1999-03-09 2006-01-25 新日本製鐵株式会社 Steel with excellent machinability and its manufacturing method
JP3435112B2 (en) * 1999-04-06 2003-08-11 株式会社神戸製鋼所 High carbon steel wire excellent in longitudinal crack resistance, steel material for high carbon steel wire, and manufacturing method thereof
JP4088220B2 (en) * 2002-09-26 2008-05-21 株式会社神戸製鋼所 Hot-rolled wire rod with excellent wire drawing workability that can omit heat treatment before wire drawing
JP4476846B2 (en) * 2005-03-03 2010-06-09 株式会社神戸製鋼所 High strength spring steel with excellent cold workability and quality stability
CN101208446B (en) * 2005-06-29 2012-07-04 新日本制铁株式会社 High-strength wire rod having superior rod drawability, and manufacturing method therefor
JP2007327084A (en) * 2006-06-06 2007-12-20 Kobe Steel Ltd Wire rod having excellent wire drawability and its production method
EP2083094B1 (en) * 2006-10-12 2019-06-05 Nippon Steel & Sumitomo Metal Corporation High-strength steel wire excelling in ductility and process for producing the same
JP4310359B2 (en) * 2006-10-31 2009-08-05 株式会社神戸製鋼所 Steel wire for hard springs with excellent fatigue characteristics and wire drawability
CN101624679B (en) * 2007-07-20 2011-08-17 株式会社神户制钢所 Steel wire material for spring and its producing method
JP5121360B2 (en) * 2007-09-10 2013-01-16 株式会社神戸製鋼所 Spring steel wire rod excellent in decarburization resistance and wire drawing workability, and method for producing the same
JP5329272B2 (en) 2009-03-19 2013-10-30 株式会社神戸製鋼所 Spring steel
CN101928892B (en) * 2010-08-27 2012-05-02 南京钢铁股份有限公司 Spring steel round steel and production process thereof
US9097306B2 (en) * 2010-08-30 2015-08-04 Kobe Steel, Ltd. Steel wire rod for high-strength spring excellent in wire drawability, manufacturing method therefor, and high-strength spring

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10385430B2 (en) 2014-03-31 2019-08-20 Kobe Steel, Ltd. High-strength steel material having excellent fatigue properties
EP3279358A4 (en) * 2015-03-31 2018-08-15 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Heat-treated steel wire having excellent bendability
US11761054B2 (en) 2017-09-29 2023-09-19 Posco Co., Ltd Wire rod and steel wire for springs having excellent corrosion fatigue resistance properties, and method for producing same
US20220112753A1 (en) * 2019-02-26 2022-04-14 Nv Bekaert Sa Helical compression spring for an actuator for opening and closing a door or a tailgate of a car

Also Published As

Publication number Publication date
JP2013213238A (en) 2013-10-17
EP2832891A4 (en) 2016-04-27
CN104169453A (en) 2014-11-26
MX2014011610A (en) 2014-10-17
WO2013146675A1 (en) 2013-10-03
KR20140129262A (en) 2014-11-06
CN104169453B (en) 2016-03-30
KR101601582B1 (en) 2016-03-08
JP5796782B2 (en) 2015-10-21
EP2832891B1 (en) 2019-02-20

Similar Documents

Publication Publication Date Title
KR101600146B1 (en) Steel wire material for high-strength spring which has excellent wire-drawing properties and process for production thereof, and high-strength spring
EP2832891B1 (en) Steel wire rod with excellent shavability for high-strength spring, and high-strength spring
JP6210155B2 (en) Rail vehicle wheel and method for manufacturing rail vehicle wheel
KR101031679B1 (en) Method of producing steel wire material for spring
KR100839726B1 (en) High strength spring steel wire with excellent coiling properties and hydrogen embrittlement resistance
JP5162875B2 (en) High strength wire rod excellent in wire drawing characteristics and method for producing the same
KR101235448B1 (en) Steel for heat treatment
KR100711370B1 (en) Steel wire for high strength spring excellent in workability and high strength spring
EP2816131A1 (en) Rolled rod steel for hot forging, hot-forged roughly shaped material, and common rail and process for producing same
EP1900837A1 (en) High-strength wire rod excelling in wire drawing performance and process for producing the same
EP3112491A1 (en) Rolled material for high strength spring, and wire for high strength spring
EP1897964A1 (en) High-strength wire rod excelling in wire drawing performance and process for producing the same
KR101750668B1 (en) Steel for spring, and method for producing spring
KR20150105476A (en) High-strength cold-rolled steel sheet having excellent bendability
CN100453684C (en) Cold formable spring steel wire excellent in cold cutting capability and fatigue properties and manufacturing process thereof
KR20150126699A (en) Case-hardening steel material and case-hardening steel member
CN109689911B (en) Case hardening steel, method for producing same, and method for producing gear member
CN108315637B (en) High carbon hot-rolled steel sheet and method for producing same
EP2784169A1 (en) Rolled steel bar for hot forging
EP2990500B1 (en) Steel sheet
KR101660616B1 (en) Steel wire rod with excellent spring workability for high-strength spring, process for manufacturing same, and high-strength spring
US10385430B2 (en) High-strength steel material having excellent fatigue properties
KR20170118882A (en) Heat treated wire with excellent fatigue properties
CN107429359B (en) Hot-rolled rod and wire material, component, and method for producing hot-rolled rod and wire material
CN112585290B (en) High-strength steel sheet and method for producing same

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: 20141009

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: 20160331

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/06 20060101ALI20160323BHEP

Ipc: C22C 38/04 20060101ALI20160323BHEP

Ipc: C22C 38/40 20060101ALI20160323BHEP

Ipc: C22C 38/20 20060101ALI20160323BHEP

Ipc: F16F 1/02 20060101ALI20160323BHEP

Ipc: C22C 38/32 20060101ALI20160323BHEP

Ipc: C22C 38/22 20060101ALI20160323BHEP

Ipc: C21D 9/02 20060101ALI20160323BHEP

Ipc: C22C 38/54 20060101ALI20160323BHEP

Ipc: C22C 38/34 20060101AFI20160323BHEP

Ipc: C22C 38/46 20060101ALI20160323BHEP

Ipc: C21D 8/06 20060101ALI20160323BHEP

Ipc: C22C 38/26 20060101ALI20160323BHEP

Ipc: C22C 38/44 20060101ALI20160323BHEP

Ipc: C22C 38/24 20060101ALI20160323BHEP

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

R17P Request for examination filed (corrected)

Effective date: 20141009

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 38/44 20060101ALI20180813BHEP

Ipc: C22C 38/46 20060101ALI20180813BHEP

Ipc: C22C 38/06 20060101ALI20180813BHEP

Ipc: C22C 38/22 20060101ALI20180813BHEP

Ipc: C22C 38/40 20060101ALI20180813BHEP

Ipc: C22C 38/04 20060101ALI20180813BHEP

Ipc: C21D 9/02 20060101ALI20180813BHEP

Ipc: C22C 38/26 20060101ALI20180813BHEP

Ipc: C22C 38/24 20060101ALI20180813BHEP

Ipc: F16F 1/02 20060101ALI20180813BHEP

Ipc: C22C 38/34 20060101AFI20180813BHEP

Ipc: C22C 38/20 20060101ALI20180813BHEP

Ipc: C22C 38/54 20060101ALI20180813BHEP

Ipc: C21D 8/06 20060101ALI20180813BHEP

Ipc: C22C 38/32 20060101ALI20180813BHEP

INTG Intention to grant announced

Effective date: 20180829

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

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: DE

Ref legal event code: R096

Ref document number: 602013051014

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1098271

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

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

Ref country code: DE

Payment date: 20190327

Year of fee payment: 7

Ref country code: GB

Payment date: 20190320

Year of fee payment: 7

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

Ref country code: SE

Payment date: 20190311

Year of fee payment: 7

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190220

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: 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: 20190520

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: 20190220

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: 20190620

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: 20190220

Ref country code: NL

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: 20190220

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

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: 20190220

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: 20190220

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: 20190620

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: 20190521

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: 20190520

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: 20190220

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

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: 20190220

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: 20190220

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: 20190220

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: 20190220

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: 20190220

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: 20190220

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: 20190220

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: 20190220

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013051014

Country of ref document: DE

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

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: 20190220

Ref country code: LU

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

Effective date: 20190325

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: 20190220

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

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: 20190220

26N No opposition filed

Effective date: 20191121

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

Ref country code: LI

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

Effective date: 20190331

Ref country code: CH

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

Effective date: 20190331

Ref country code: IE

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

Effective date: 20190325

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

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: 20190220

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: 20190220

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

Ref country code: AT

Payment date: 20200225

Year of fee payment: 8

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

Ref country code: BE

Payment date: 20200217

Year of fee payment: 8

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

Ref country code: MT

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

Effective date: 20190325

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

Ref country code: FR

Payment date: 20200214

Year of fee payment: 8

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602013051014

Country of ref document: DE

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

Ref country code: DE

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

Effective date: 20201001

Ref country code: SE

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

Effective date: 20200326

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200325

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

Ref country code: GB

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

Effective date: 20200325

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

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: 20190220

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

Ref country code: HU

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

Effective date: 20130325

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1098271

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210325

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210331

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 NON-PAYMENT OF DUE FEES

Effective date: 20210325

Ref country code: FR

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

Effective date: 20210331

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: 20190220

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: 20210331

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1098271

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190220