US20090020195A1 - High Strength Spring Steel Wire and High Strength Spring and Methods of Production of the Same - Google Patents

High Strength Spring Steel Wire and High Strength Spring and Methods of Production of the Same Download PDF

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US20090020195A1
US20090020195A1 US12/224,185 US22418508A US2009020195A1 US 20090020195 A1 US20090020195 A1 US 20090020195A1 US 22418508 A US22418508 A US 22418508A US 2009020195 A1 US2009020195 A1 US 2009020195A1
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high strength
strength spring
tempering
spring
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Manabu Kubota
Masayuki Hashimura
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Nippon Steel Corp
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Nippon Steel Corp
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Publication of US20090020195A1 publication Critical patent/US20090020195A1/en
Priority to US13/199,203 priority Critical patent/US20110310924A1/en
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    • 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
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/34Methods of heating
    • C21D1/42Induction heating
    • 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
    • C21D9/52Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/14Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/60Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • C21D1/25Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Definitions

  • suspension springs and the like Due to the demands for lightening the weight of auto parts, suspension springs and the like are being asked to be raised in strength.
  • An important issue in raising the strength of suspension springs is improvement of the corrosion fatigue characteristics.
  • Suspension springs are painted for use, but pebbles etc. bounce against them while the automobile is moving, the parts of the springs contact each other, etc. resulting in unavoidable peeling of the paint, so corrosion and pitting are unavoidable.
  • suspension springs face tough corrosive conditions, so even if adding a small amount of alloy elements, no effect of suppression of corrosion can be expected any longer.
  • suspension springs in corrosion fatigue characteristics, it is considered effective not to control the corrosion and other surface reactions, but to control the mechanical properties of the steel material to improve the fatigue characteristics.
  • control of the precipitate precipitating at the time of tempering is important.
  • spring steel has a relatively large content of carbon, so a large amount of iron carbide inevitably precipitates as well.
  • the steel is tempered at a relatively low temperature, so the steel material greatly changes in properties due to changes in the state of the iron carbide precipitating at a low temperature.
  • the present invention solves the above-mentioned problems and has as its object the provision of high strength spring and high strength spring steel wire superior in corrosion fatigue characteristics suitable for the suspension spring of an automobile etc. and methods of production of the same.
  • the present invention provides a spring suppressing the precipitation of cementite (hereinafter sometimes simply indicated as ⁇ ) to suppress deterioration of corrosion fatigue characteristics and causing the precipitation of epsilon iron carbide (called “ ⁇ carbide”) to achieve a high strength and a material for the same, that is, a spring use steel wire, and furthermore methods or production suitably controlling the relationship between the temperature and time of tempering and the composition of ingredients of the steel.
  • ⁇ carbide epsilon iron carbide
  • a high strength spring steel wire characterized by containing, by mass %, C, 0.35 to 0.50%, Si: 1.00 to 3.00%, and Mn: 0.10 to 2.00%, restricting P to 0.015% or less and S to 0.015% or less, having a balance of Fe and unavoidable impurities, and, when raising the temperature in the range from 50° C. to 600° C. by 0.25° C./s and measuring the differential scanning calories, having the only peak of the exothermic reaction present at 450° C. or more.
  • a high strength spring steel wire as set forth in (1) characterized by further containing, by mass %, Ti: 0.100% or less and B: 0.0010 to 0.0100%, restricting N to 0.0100% or less, and having contents of Ti and N satisfying Ti ⁇ 3.5N.
  • a high strength spring as set forth in (1) or (2) characterized by further containing, by mass %, one or more of Mo: 0.05 to 1.00%, Cr: 0.05 to 1.50%, Ni: 0.05 to 1.00%, Cu: 0.05 to 1.00%, Nb: 0.010 to 0.100%, V: 0.05 to 0.20%, and Sb: 0.001 to 0.050%.
  • a high strength spring characterized by using as a material a high strength spring steel wire as set forth in any one of (1) to (3).
  • a high strength spring characterized by containing, by mass %, C, 0.35 to 0.50%, Si: 1.00 to 3.00%, and Mn: 0.10 to 2.00%, restricting P to 0.015% or less and S to 0.015% or less, having a balance of Fe and unavoidable impurities, and, when raising the temperature in the range from 50° C. to 600° C. by 0.25° C./s and measuring the differential scanning calories, having the only peak of the exothermic reaction present at 450° C. or more.
  • a high strength spring as set forth in (7) characterized by further containing, by mass %, Ti: 0.100% or less and B: 0.0010 to 0.0100%, restricting N to 0.0100% or less, and having contents of Ti and N satisfying Ti ⁇ 3.5N
  • a high strength spring as set forth in (5) or (6) characterized by further containing, by mass %, one or more of Mo: 0.05 to 1.00%, Cr: 0.05 to 1.50%, Ni: 0.05 to 1.00%, Cu: 0.05 to 1.00%, Nb: 0.010 to 0.100%, V: 0.05 to 0.20%, and Sb: 0.001 to 0.050%.
  • a method of production of high strength spring steel wire characterized by heating steel wire comprised of the ingredients as set forth in any one of (1) to (3) to 3 to 850 to 1000° C., quenching it, then tempering it under conditions where the tempering temperature T[K], tempering time t[s], and content Si % [mass %] of Si satisfy the following formula 1:
  • FIG. 1 is an example of the results of differential scanning calorimetry of a test piece after quenching and before tempering.
  • FIG. 2 is an example of the results of differential scanning calorimetry of a test piece after tempering.
  • the inventors intensively studied the various types of factors affecting the corrosion fatigue characteristics of high strength suspension spring and discovered the following, that is,
  • DSC Differential scanning calorimetry
  • DSC is a method of evaluating the precipitation behavior of metal materials by detection of the emission of heat and absorption of heat at the time of raising the temperature.
  • the temperatures of the peaks of exothermic reactions due to the precipitation of ⁇ carbide and the transition of ⁇ carbide to ⁇ change depending on the steel ingredients.
  • steel such as spring steel to which Si is added in an amount of 1% or more
  • a low temperature side peak is observed at 300° C. or less
  • a high temperature side peak is observed in a 300° C. or more temperature region.
  • the peak of exothermic reaction due to the precipitation of ⁇ carbide observed at 300° C. or less will be defined as the “first peak”
  • the peak of exothermic reaction due to transition of ⁇ carbide to ⁇ observed at 300° C. or more will be defined as the “second peak”.
  • the first peak and the second peak are both observed. This is for example a case of tempering by a lower temperature than the suitable conditions. The tempering is insufficient, so the yield ratio is low and the settling characteristic is inferior, so use as a spring is not possible.
  • C is an element required for obtaining a high strength, so it is necessary to add 0.35% or more.
  • the toughness falls.
  • the tempering temperature for obtaining the desired strength rises, the amount of production of cementite ( ⁇ ) increases, and it is no longer possible to obtain both high strength and high toughness, so the upper limit is preferably made 0.45% or less.
  • Si is an element effective for strengthening the steel and for improvement of the settling characteristic of the spring and is an important element for shifting the temperature at which the ⁇ carbide changes to ⁇ to the high temperature side. Due to the addition of Si, the temper embrittlement temperature region is shifted to the high temperature side. If performing the tempering under the conditions of formula 1, the precipitation of ⁇ carbide causes the strength to rise, suppresses the change to ⁇ to avoid temper embrittlement, and enables the achievement of both the high strength and high toughness:
  • T tempering temperature (K)
  • t tempering time (s)
  • Si % Si content [mass %].
  • Si must be added in an amount of 1.00% or more.
  • the upper limit has to be made 3.00%.
  • the preferred range is 1.50% to 2.50%.
  • Mn is an element effective for improvement of the hardenability. If added together with Si, the effect is exhibited of suppressing the transition from ⁇ carbide to ⁇ . To obtain this effect, Mn must be added in an amount of at least 0.10%, but if added over 2.00%, center segregation at the time of casting is assisted and the toughness falls. Therefore, the amount of Mn has to be made 0.10 to 2.00% in range. Note that the preferred range of the amount of Mn is 0.15 to 1.00%.
  • P, S: P and S are impurities.
  • P is an element which segregates at the old austenite grains and causes embrittlement of the grain boundaries and lowers the toughness.
  • the upper limits of P and S have to be limited to 0.015% or less. Further, P and S are preferably reduced as much as possible. The preferable upper limits are 0.010% or less.
  • Ti and B are preferably added to restrict the upper limit of N.
  • Ti is an element bonding with the N in the steel to cause precipitation of TiN and thereby fix the N, so contributes to the reduction of the amount of dissolved N. Due to the reduction of the amount of dissolved N, the formation of BN is prevented and the effect of improvement of the hardenability of B is obtained.
  • To fix the N in the steel it is preferable to add Ti in an amount of 3.5N or more. However, even if adding over 0.100% of Ti, the effect becomes saturated, so the upper limit should be made 0.100% or less. Further, to suppress the reduction in toughness due to the coarsening of the TiN and Ti(CN), the upper limit of the amount of Ti is preferably made 0.040% or less.
  • N is an impurity and is preferably restricted to 0.0100% or less. Further, the smaller the content of N, the smaller the amount of addition of Ti that is possible and the smaller the amount of TiN produced. Therefore, N is preferably reduced as much as possible. The preferable upper limit is 0.0060% or less.
  • B is an effective element for improvement of the hardenability of steel when added in a fine amount. It also has the effect of segregating at the old austenite grain boundaries to strengthen the crystal grain boundaries and improve the toughness.
  • B is added to steel containing the amount of C and the amount of Si in the range of the present invention, so addition of 0.0010% or more is preferable.
  • the preferred range of the amount of B is 0.0010 to 0.0030%. Note that to obtain the effect of addition of B, it is preferable to reduce the amount of dissolved N to prevent the formation of BN. Therefore, restriction of the amount of N and addition of Ti are extremely effective.
  • one or more types of elements of Mo, Cr, Ni, and Cu contributing to the improvement of the hardenability may be selectively included
  • Mo is preferably added in an amount of 0.05% or more to obtain the effect of improvement of the hardenability, but if added over 1.00%, the alloying cost becomes large and the economicalness is sometimes impaired. Therefore, the content of Mo is preferably made 0.05 to 1.00% in range. A more preferable range is 0.10 to 0.50%.
  • Cr is preferably added in an amount of 0.05% or more to obtain the effect of improvement of the hardenability, but if added over 1.50%, the toughness is sometimes impaired. Therefore, the content of Cr is preferably made 0.05 to 1.50% in range. A more preferable range is 0.10 to 0.80%.
  • Ni is preferably added in an amount of 0.05% or more to obtain the effect of improvement of the hardenability, but if added over 1.00%, the alloying cost becomes large and the economicalness is sometimes impaired. Therefore, the content of N is preferably made 0.05 to 1.00% in range. A more preferable range is 0.10 to 0.50%.
  • Cu is preferably added in an amount of 0.05% or more to obtain the effect of improvement of the hardenability, but if added over 1.00%, the hot ductility falls, the formation of cracks, scratches, etc. at the time of continuous casting and hot rolling is assisted, and the producibility of the steel is sometimes impaired. Therefore, the content of Cu is preferably made 0.05 to 1.00% in range. The preferable range is 0.10 to 0.50%.
  • Nb and V contributing to the increased fineness of the austenite crystal grains, may be included.
  • Nb is preferably added in an amount of 0.010% or more to obtain the effect of improvement of toughness by the increased fineness of the structure, but even if added over 0.010%, the effect is saturated. Therefore, the content of Nb is preferably 0.010 to 0.100% in range. A more preferable range is 0.015 to 0.040%.
  • V is preferably added in an amount of 0.05% or more to obtain the effect of improvement of toughness by the increased fineness of the structure, but even if added over 0.20%, the effect is saturated. Therefore, the content of V is preferably 0.05 to 0.20% in range. A more preferable range is 0.10 to 0.15%.
  • Sb is an element precipitating at the surface of the steel material and suppressing the decarburization at the time of heating for hot rolling, at the time of cooling after rolling, at the time of heating for quenching, etc.
  • Sb is an element precipitating at the surface of the steel material and suppressing the decarburization at the time of heating for hot rolling, at the time of cooling after rolling, at the time of heating for quenching, etc.
  • the content of Sb is preferably made 0.001 to 0.050% in range. A more preferable range is 0.002 to 0.020%.
  • the amount of Al is not defined, but it is also possible to add Al as a deoxidizing element.
  • Al is also an element forming a nitride and making the austenite crystal grains finer and contributes to the improvement of toughness through the increased fineness of the structure.
  • Al for deoxidation usually 0.010 to 0.100% is included.
  • Si, Mn, etc. may be used for deoxidation without adding Al.
  • Iron carbide To obtain a high strength spring steel and high strength spring superior in corrosion fatigue characteristics, it is necessary to form ⁇ carbide and suppress the transition to cementite ( ⁇ ).
  • ⁇ carbide is a finer iron carbide compared with ⁇ and is extremely effective for improvement of strength and has little detrimental effect on toughness.
  • the suitably tempered high strength spring steel and high strength spring of the present invention have ⁇ carbide and are suppressed in transition to ⁇ so are excellent in corrosion fatigue characteristics.
  • the iron carbide of the high strength spring and high strength spring steel of the present invention can be identified by the later explained differential scanning calorimetry.
  • Differential scanning calorimetry In differential scanning calorimetry, the temperature elevation rate is important.
  • the iron carbide of the high strength spring and high strength spring steel of the present invention is identified by a temperature elevation rate of 0.25° C./s.
  • the high strength spring and high strength spring steel of the present invention exhibit an exothermic reaction of only the second peak at 450° C. or more.
  • the temperature of the second peak changes due to the composition of ingredients of the steel, in particular the amount of Si.
  • the amount of Si is small, if less than 450° C., there is sometimes a second peak.
  • With tempering there is easy transition to ⁇ .
  • is excessively formed after tempering, so the toughness falls. Note that in steel with a temperature of the second peak of less than 450° C., even if performing the tempering under suitable conditions, part of the ⁇ carbide changes to ⁇ , so if compared with steel having a temperature of the second peak of 450° C. or more, the height of the second peak becomes lower.
  • the heating temperature of quenching of the spring and spring use steel wire is made 850° C. or more to make the structure austenitic, but if over 1000° C., coarsening of the austenite crystal grains is invited. Therefore, it is necessary to make the heating temperature at the quenching 850 to 1000° C. in range.
  • the preferable range is 900° C. to 990° C.
  • the heating may be performed by the method of furnace heating, high frequency induction heating, etc.
  • the heating time is usually 5 to 3600 s.
  • the method of quenching cooling may be oil cooling, water cooling, etc. Due to the quenching, a mainly martensite structure is obtained.
  • Tempering conditions To obtain both high strength and high toughness after quenching, tempering is performed under conditions of formula 1:
  • T tempering temperature (K)
  • t tempering time (s)
  • Si % Si content [mass %].
  • cooling after tempering may be performed by either air cooling or water cooling and is not particularly limited.
  • spring hot it is also possible not to form the spring hot, but to perform the quenching and tempering in the state of the rod shape to obtain spring use steel wire, form this into a spring cold, then perform stress relief annealing.
  • the springs produced by hot forming and cold forming are both shot peened, painted, set, and otherwise processed for use as suspension springs.
  • Converter produced steels having the compositions shown in Table 1 were produced by continuous casting and, in accordance with need, soaked and diffusion treated and cogged to obtain 162 mm square rolled materials. Next, hot rolling was performed to obtain wire material shapes of diameters of 13 mm. These were annealed in accordance with need, then cold drawn, then cut to predetermined lengths to obtain rods.
  • a spring shaped material and rod material were tempered under the conditions shown in Table 2.
  • the heating method in the tempering was made furnace heating or high frequency induction heating.
  • a tensile test piece with an 8 mm diameter of the parallel part and a U-notch test piece based on JIS Z 2242 (subsize, width 5 mm) were fabricated from a tempered rod and used for a tensile test and Charpy impact test.
  • the tensile strength and the 0.2% yield strength were measured and the yield ratio was found.
  • the tensile strength and yield ratio preferable as a suspension spring were defined as 1800 MPa or more and 0.85 or less. If satisfying these, the strength and settling characteristic are judged to be good when used as a suspension spring.
  • the test temperature in the Charpy impact test was made 20° C. Further, a sample with an impact value of 75 J/cm 2 or more was deemed good. Due to this, it was judged that the corrosion fatigue characteristics were improved.
  • test piece for differential scanning calorimetry (length 3 ⁇ width 3 ⁇ thickness 1 mm) was taken from the spring shaped material.
  • the DSC curve was measured under measurement conditions of the differential scanning calorimetry of an atmospheric gas: N 2 (30 ml/min), measurement temperature range: 50 to 600° C., cell: aluminum, and reference: ⁇ -Al 2 O 3 and with a temperature elevation rate of 0.25° C./s to find the temperatures of the exothermic peaks.
  • the steel materials of the Manufacturing Nos. 1 to 10 of the present invention are superior to the comparative examples in toughness and characteristics as suspension springs.
  • Manufacturing No. 11 has an amount of C over the range of the present invention, so a high impact value is not obtained.
  • Manufacturing No. 12 has an amount of C not satisfying the range of the present invention, so the tensile strength becomes lower as quenched and the tensile strength as a suspension spring cannot be obtained.
  • Manufacturing Nos. 13 to 15 have amounts of Si not satisfying the range of the present invention, so the temperatures of the second peaks are low, ⁇ forms in the steels, and high impact values cannot be obtained.
  • Manufacturing No. 16 has an amount of Mn over the range of the present invention, so a high impact value cannot be obtained.
  • Nos. 17 and 19 have high tempering temperatures and has tempering conditions over the ranges of the present invention, so cementite precipitates, the exothermic peaks in DSC are not clear, and high impact values cannot be obtained.
  • Manufacturing No. 18 has a low tempering temperature and therefore tempering conditions not reaching the range of the present invention, so the tempering is insufficient and ⁇ carbides are insufficiently formed, so even at less than 300° C., an exothermic peak is caused, the yield ratio is low, and use as a suspension spring is not possible.
  • Wire materials of diameters of 13 mm of Steel Nos. A to J shown in Table 1 hot rolled in the same way as Example 1 were used to evaluate the effect of suppression of decarburization by the addition of Sb.
  • the wire materials were straightened, then ground at their outer circumference to remove the effects of the initial surface layers and obtain 12 ⁇ rod test pieces.
  • the test pieces were heated to 870° C., was then held for 30 minutes, then were transferred to a 750° C. furnace, held there for 60 minutes, then air-cooled.
  • the heat treatment was all performed in the atmosphere.
  • the heat treatment conditions were heat treatment conditions very conducive to decarburization. After the heat treatment, the C cross-sections of the rod test pieces were cut, polished, and corroded by nitral and the depths of the decarburized layers of the surfaces were measured.

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US12/224,185 2007-02-22 2008-01-07 High Strength Spring Steel Wire and High Strength Spring and Methods of Production of the Same Abandoned US20090020195A1 (en)

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JP2007041810A JP5064060B2 (ja) 2007-02-22 2007-02-22 高強度ばね用鋼線及び高強度ばね並びにそれらの製造方法
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PCT/JP2008/050226 WO2008102573A1 (ja) 2007-02-22 2008-01-07 高強度ばね用鋼線及び高強度ばね並びにそれらの製造方法

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EP (1) EP2058414B1 (zh)
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Cited By (7)

* Cited by examiner, † Cited by third party
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US20110074079A1 (en) * 2009-09-29 2011-03-31 Chuo Hatsujo Kabushiki Kaisha Coil spring for automobile suspension and method of manufacturing the same
US20150004051A1 (en) * 2012-02-14 2015-01-01 Jfe Steel Corporation Spring steel
US9068615B2 (en) 2011-01-06 2015-06-30 Chuo Hatsujo Kabushiki Kaisha Spring having excellent corrosion fatigue strength
US9469895B2 (en) 2010-03-18 2016-10-18 Nhk Spring Co., Ltd. Spring steel and surface treatment method for steel material
US20170022580A1 (en) * 2009-12-22 2017-01-26 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) High-strength spring steel
US20180142333A1 (en) * 2015-05-15 2018-05-24 Nippon Steel & Sumitomo Metal Corporation Spring steel
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EP2058414A4 (en) 2016-11-23
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US20110310924A1 (en) 2011-12-22
EP2058414A1 (en) 2009-05-13
WO2008102573A1 (ja) 2008-08-28
BRPI0802242A2 (pt) 2011-08-30
CN101541995A (zh) 2009-09-23
EP2058414B1 (en) 2020-08-19
JP2008202124A (ja) 2008-09-04

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