WO2014141831A1 - ばね用鋼線およびその製造方法 - Google Patents
ばね用鋼線およびその製造方法 Download PDFInfo
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- WO2014141831A1 WO2014141831A1 PCT/JP2014/053837 JP2014053837W WO2014141831A1 WO 2014141831 A1 WO2014141831 A1 WO 2014141831A1 JP 2014053837 W JP2014053837 W JP 2014053837W WO 2014141831 A1 WO2014141831 A1 WO 2014141831A1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/02—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
- C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
- C21D1/10—Surface hardening by direct application of electrical or wave energy; by particle radiation by electric induction
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2251/00—Treating composite or clad material
- C21D2251/02—Clad material
Definitions
- the present invention relates to a spring steel wire having improved sag resistance and fatigue characteristics and a method for producing the same.
- forced cooling is performed by repeating a rapid heating and quenching cycle of a surface layer portion and performing self-cooling using a temperature difference between the surface layer portion and the center portion.
- a technique has been proposed in which the crystal grain of the surface layer portion is refined without performing the step, and the center section is repeatedly subjected to thermal cycling until it exceeds the A1 transformation point, thereby making the entire cross section a martensitic structure.
- Patent Document 2 pattern quenching is performed by heating and quenching under heating conditions (temperature, cooling rate) such that only the surface side of the steel wire becomes quenched martensite, and the steel wire is reheated and tempered.
- heating conditions temperature, cooling rate
- a technique for generating surface compressive residual stress due to transformation strain of surface martensite by applying warm coiling has been proposed.
- High design stress is required to reduce the size and weight of the suspension spring.
- it is necessary to increase the strength of the spring material from the viewpoint of sag resistance and durability.
- the strength is increased, the sensitivity to delayed fracture and the sensitivity to defects such as corrosion pits generated by snow melting materials increase, so a large amount of elements such as Ni, Cu, Cr, Ti, V, etc. are added to the above.
- Alloys with reduced susceptibility to environmental embrittlement have been developed.
- such an alloy has a problem that it is less versatile and has a higher material cost than SUP7, SUP12, and the like.
- crystal grain refinement is effective as a technique for improving environmental embrittlement. Rapid heating and rapid cooling are effective for crystal grain refinement, and a technique using induction hardening is employed. Further, in order to use a spring with a high stress design for weight reduction, it is necessary to increase hardness in order to ensure sag resistance. However, increasing the hardness increases the crack propagation rate and deteriorates fatigue properties.
- an object of the present invention is to provide a spring steel wire and a manufacturing method thereof that can improve sag resistance and fatigue characteristics by a manufacturing process without depending on the addition of an alloy element.
- the inventors of the present invention have come up with the idea of further subjecting the surface contour portion to induction hardening after induction hardening as a method for improving environmental embrittlement by the manufacturing process.
- This makes it possible to reduce the hardness of the crack propagation site while increasing the surface hardness by utilizing the HAZ softening phenomenon by contour quenching, while making the crystal grains of the surface layer portion of the steel wire ultrafine.
- both sag resistance and improved fatigue characteristics can be achieved.
- the present invention has been made on the basis of the above knowledge, and is a spring steel wire having a structure obtained by quenching and tempering, the first layer on the surface, the second layer on the inner side of the first layer,
- the second layer is composed of a third layer that reaches the center on the middle side of the second layer, and the second layer has a lower hardness than the first layer and the third layer.
- a corrosion pit due to pitting corrosion is formed on the surface of the spring, an initial crack is generated at the bottom of the corrosion pit, and the crack propagates and progresses to a rapid fracture.
- a second layer made of a tempered structure softer than the first and third layers, which are hard tempered structures is provided.
- the second layer acts as a barrier layer for crack propagation. Therefore, in the present invention, corrosion fatigue characteristics (environmental embrittlement characteristics) can be improved.
- the entire surface has an average hardness substantially equal to that of the surface. Therefore, in the present invention, the sag resistance can be improved.
- the present invention is a method for producing the spring steel wire, the quenching step of heating the entire steel wire to a temperature higher than the austenite transformation point, and quenching only the surface layer of the steel wire from the austenite transformation point
- the center portion is provided with a contour quenching step in which the center portion is cooled from a temperature lower than the tempering temperature in the next step, and a tempering step in which the entire steel wire is heated.
- the fatigue characteristics are improved by the second layer, and effects such as improved sag resistance are obtained by the first and third layers having high hardness.
- FIG. 1 is a cross-sectional view showing a spring steel wire according to an embodiment.
- This steel wire for spring is composed of a third layer 3, a second layer 2 and a first layer from the center.
- the first layer 1 preferably has a smaller average crystal grain size than the second layer 2.
- the first layer 1 has a structure mainly composed of tempered martensite or troostite.
- the prior austenite grain size is preferably # 12.0 to 14.0 and the hardness is preferably 500 to 700 HV.
- the grain size number is less than # 12.0, the effect of the crystal grain boundary as a hydrogen trap site becomes insufficient.
- the hardness is less than 500 HV, the sag resistance is lowered, and when it exceeds 700 HV, the corrosion durability and the hydrogen embrittlement resistance are lowered.
- the second layer 2 has a structure mainly composed of sorbite, and preferably has a prior austenite grain size of # 9.0 to 11.5 and a hardness of 400 to 650 HV.
- the third layer 3 is a structure mainly composed of tempered martensite or troostite, and it is desirable that the prior austenite grain size is # 9.0 to 11.5 and the hardness is 500 to 700 HV. If the hardness is less than 500 HV, the tensile strength is low and the sag resistance is reduced.
- the thickness of the first layer 1 is preferably 0.3 to 1.5 mm.
- the thickness is less than 0.3 mm, the improvement of hydrogen embrittlement characteristics due to the refinement of crystal grains is not sufficiently exhibited.
- the thickness exceeds 1.5 mm, the distance from the bottom of the corrosion pit to the second layer 2 is long, and crack propagation is likely to proceed, so that the corrosion durability is lowered.
- the thickness of the second layer 2 is preferably 0.5 to 3.0 mm. If the thickness is less than 0.5 mm, the softening layer thickness is small, so the effect of improving the crack growth life is small. On the other hand, when the thickness exceeds 3.0 mm, the sag resistance decreases.
- the manufacturing method of the embodiment includes a quenching process in which the entire steel wire is heated to a temperature higher than the austenite transformation point and then quenching, and only the surface layer of the steel wire is heated to a temperature higher than the austenite transformation point, and the lower layer is centered
- the center portion has a temperature gradient due to heat transfer in the direction, and includes a contour quenching process for quenching from a temperature lower than a tempering temperature in the next process, and a tempering process for heating the entire steel wire.
- a material supply means for winding the steel wire is disposed at the beginning of the line, and a winding device for winding the steel wire is disposed at the end of the line.
- the steel wire is passed through a high frequency heating coil and then through a cooling jacket. In the cooling jacket, the steel wire is cooled by contacting the coolant with the steel wire.
- the entire steel wire is heated to a temperature higher than the austenite transformation point (T AC3 ). Then, after holding at that temperature for a predetermined time, austenite is transformed into martensite by rapid cooling.
- the temperature gradually decreases from the surface layer toward the center, and the temperatures T1, T2, and T3 are within the temperature condition range shown in FIG. That is, in the contour quenching step, only the first layer, which is the surface layer of the steel wire, is heated to a temperature (T1) higher than the austenite transformation point (T AC3 ). Specifically, T1 is 800 to 1000 ° C. The third layer in the center is heated to a temperature (T3) lower than the tempering temperature (T temp ) in the next step. Thereby, at least a part of the third layer becomes tempered martensite or troostite.
- the second layer is heated to a temperature (T2) that is lower than the austenite transformation point (T AC3 ) and higher than the tempering temperature (T temp ) in the next step.
- T2 the austenite transformation point
- T temp the tempering temperature
- the heating temperature gradually decreases from the surface layer toward the center, so that such heating is possible.
- at least a part of the second layer has an organization mainly composed of sorbite. It is known that tempering at a temperature exceeding 500 to 600 ° C. results in sorbite and softening remarkably.
- the first layer transforms from austenite to martensite.
- the austenite crystal grains are refined by rapid heating in the quenching process, and the austenite crystal grains are further refined by rapid heating in the quenching (contour quenching) process.
- the steel wire is tempered, and the martensite of the first layer becomes, for example, troostite or tempered martensite. Those crystal grains become very fine by rapid heating twice.
- the second layer is a structure mainly composed of sorbite without change after contour quenching, and is a softer layer than the first layer.
- the third layer is a structure mainly composed of troostite and tempered martensite, and the crystal grains are approximately the same as those of the second layer. Since the second layer is heated (tempered) at a higher temperature than the third layer in the contour quenching step, the second layer is a softer layer than the third layer.
- the material of the steel wire is not limited to spring steel, and all types of steel that can be quenched can be adopted.
- steel types that can be quenched include those containing 0.05 to 0.8% by mass of C.
- C 0.05 to 0.8%
- Si 0.1 to 2.5%
- Mn 0.1 to 2.5%
- Cr 0.1 to 2.5%
- Cr 0.1 to 2.5%
- Cr 0.1 to 2.5%
- Cr nickel
- Cu chromium
- Example 1 A steel wire made of SUP12 material having a diameter of 12.6 mm was heated to 960 ° C. by a high-frequency heating coil and cooled with water (quenching process). Next, the steel wire was heated so that the first layer would be 900 ° C. and the third layer would be 470 ° C. or less, and immediately after reaching the target temperature, it was water-cooled (contour quenching step). The steel wire was then tempered at 470 ° C.
- Comparative Example 1 A sample of Comparative Example 1 was produced under the same conditions as Example 1 except that no contour quenching was performed.
- Comparative Example 2 The sample of Comparative Example 2 was prepared under the same conditions as in Example 1 except that the material of the steel wire was changed to SUP12 with 0.02% Ti and 0.3% Mo added and no contour quenching was performed. .
- Example 1 Measurement of Physical Properties The following measurements were performed on the samples of Example 1 and Comparative Example 2. For Examples 1 and 2, the thickness, crystal grain size, and hardness of the first layer, the second layer, and the third layer, and for Comparative Examples 1 and 2, for any internal location, While measuring the thickness, the metal structure was observed. The results are shown in Table 1.
- Example 1 to Comparative Example 2 were cold-formed into coil springs, and were annealed, shot peened and painted under the same conditions.
- the coil spring had an average coil diameter of 100 mm, an effective winding number of 6.5, and a free book of 355 mm. Holes with a diameter of 1 mm are formed on the surface of the coil spring at regular intervals, and after four cycles of composite corrosion cycle test (CCT test) are performed on the coil spring in accordance with JASO C6041, the coil spring is moved vertically.
- CCT test composite corrosion cycle test
- a durability test was performed with 150,000 vibrations.
- the present invention is applicable to any spring incorporated in an industrial product.
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Abstract
Description
第1層1は焼戻しマルテンサイトまたはトルースタイトを主体とする組織であり、旧オーステナイト結晶粒度は#12.0~14.0、硬さは500~700HVであることが望ましい。粒度番号が#12.0を下回ると結晶粒界の水素トラップサイトとしての効果が不十分となる。また、硬さが500HV未満では耐へたり性が低下し、700HVを超えると腐食耐久性および耐水素脆性が低下する。
以下、実施例を参照して本発明をさらに詳細に説明する。
[実施例1,2]
直径12.6mmのSUP12材からなる鋼線を高周波加熱コイルにより960℃まで加熱しし、水冷した(焼入れ工程)。次いで、第1層が900℃、第3層が470℃以下となるように鋼線を加熱し、目標温度に達したら直ちに水冷した(輪郭焼入れ工程)。次いで、鋼線を470℃で焼戻しを行った。
輪郭焼入れを行わなかった以外は実施例1と同じ条件で比較例1の試料を作製した。
鋼線の材質をSUP12にTiを0.02%、Moを0.3%添加したものに変更するとともに輪郭焼入れを行わなかった以外は実施例1と同じ条件で比較例2の試料を作製した。
実施例1~比較例2の試料に対して以下の測定を行った。
実施例1,2については、第1層、第2層、および第3層に対して、比較例1,2については内部の任意の箇所に対して、層の厚さ、結晶粒度、および硬さを測定するとともに、金属組織を観察した。その結果を表1に示す。
[腐食耐久テスト]
実施例1~比較例2の試料を冷間でコイルばねに成形し同一の条件で焼鈍・ショットピーニング及び塗装を施した。コイルばねは、平均コイル径:100mm、有効巻き数6.5巻、自由帳:355mmとした。このコイルばねの塗装表面に一定間隔で直径1mmの穴を空け、このコイルばねに対してJASO C6041に準拠して複合腐食サイクル試験(CCT試験)を4サイクル行った後、コイルばねを上下方向に15万回加振する耐久試験を行った。これらCCT試験と耐久試験とを交互に行い、コイルばねが折損するまでの耐久回数を調べた。なお、耐久試験は、応力(τ)=588±300(MPa)となる条件と、応力(τ)=588±126(MPa)となる条件で行った。
上記コイルばねを塗装しないで応力が1274MPaとなるように圧縮して締結保持し、これを1%希硫酸に浸漬して折損に至るまでの時間を調査した。
以上の破壊試験の結果を表2に示す。表2に示すように、振幅が300MPaでの腐食耐久テストでは、実施例2のコイルばねはCCT試験中に折損したが、それでも比較例1,2と比較すると優れた耐久性を示した。これは、実施例1,2では軟質な第2層を備えているからである。また、実施例1,2では、一定時間に達しても遅れ破壊に至らなかった。実施例1,2の第1層の結晶粒度が#13.0および#12.5と極めて微細な結果、水素脆化特性が向上したためである。なお、比較例2において遅れ破壊に至らなかったのは、比較例2のコイルばねの材質がSUP12に結晶粒微細化元素であるTiを0.02%、Moを0.3%添加したものであることから、結晶粒度が細かく水素脆化特性に優れた合金であったためである。
Claims (6)
- 焼入れ焼戻しにより得られる組織を有するばね用鋼線であって、
表面の第1層と、該第1層よりも中側の第2層と、該第2層よりも中側で中心に至る第3層とからなり、該第2層は第1層および第3層よりも硬さが低いことを特徴とするばね用鋼線。 - 前記第1層は前記第2層と比べて平均結晶粒径が小さいことを特徴とする請求項1に記載のばね用鋼線。
- 前記第1層および前記第3層の硬さは500~700HVであり、前記第2層の硬さが400~650HVであることを特徴とする請求項1または2に記載のばね用鋼線。
- 前記第1層の厚さが0.3~1.5mmであることを特徴とする請求項1~3のいずれかに記載のばね用鋼線。
- 前記第2層の厚さが0.5~3.0mmであることを特徴とする請求項1~3のいずれかに記載のばね用鋼線。
- 請求項1~5のいずれかに記載のばね用鋼線の製造方法であって、鋼線の全体をオーステナイト変態点よりも高い温度に加熱してから焼入れする焼入れ工程と、
鋼線の表層のみオーステナイト変態点よりも高い温度に加熱し、中心部は次工程での焼戻し温度よりも低い温度の状態から冷却する輪郭焼入れ工程と、
鋼線の全体を加熱する焼戻し工程と
を備えたことを特徴とするばね用鋼線の製造方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14762227.8A EP2942413B1 (en) | 2013-03-12 | 2014-02-19 | Steel wire for spring and method for manufacturing same |
US14/767,996 US10294540B2 (en) | 2013-03-12 | 2014-02-19 | Steel wire for spring and method for manufacturing same |
CN201480013237.1A CN105008573B (zh) | 2013-03-12 | 2014-02-19 | 弹簧用钢丝及其制造方法 |
JP2015505343A JP6053916B2 (ja) | 2013-03-12 | 2014-02-19 | ばね用鋼線およびその製造方法 |
BR112015021826-1A BR112015021826B1 (pt) | 2013-03-12 | 2014-02-19 | Arame de aço para mola e método para fabricação do mesmo |
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JP2016191098A (ja) * | 2015-03-31 | 2016-11-10 | 株式会社神戸製鋼所 | 加工性に優れた熱処理鋼線の製造方法 |
EP3315625A4 (en) * | 2015-06-29 | 2018-12-26 | NTN Corporation | Machine part |
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CN107723598B (zh) * | 2017-10-23 | 2019-01-04 | 中国石油天然气集团公司 | 一种改善疲劳性能的耐硫化氢腐蚀油管及其生产方法 |
JP7203910B1 (ja) | 2021-07-01 | 2023-01-13 | 日本発條株式会社 | コイルばね、懸架装置およびコイルばねの製造方法 |
CN115011784B (zh) * | 2022-07-29 | 2024-02-27 | 安阳双兴线材制品有限公司 | 一种热处理工艺 |
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JP2004315968A (ja) * | 2003-03-28 | 2004-11-11 | Kobe Steel Ltd | 加工性に優れた高強度ばね用鋼線および高強度ばね |
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EP2942413A1 (en) | 2015-11-11 |
JP6587993B2 (ja) | 2019-10-09 |
EP2942413B1 (en) | 2018-08-08 |
BR112015021826A2 (pt) | 2017-07-18 |
EP3409809A1 (en) | 2018-12-05 |
JP2017048466A (ja) | 2017-03-09 |
CN105008573B (zh) | 2017-03-22 |
EP3409809B1 (en) | 2020-08-19 |
JPWO2014141831A1 (ja) | 2017-02-16 |
CN105008573A (zh) | 2015-10-28 |
JP2019007081A (ja) | 2019-01-17 |
US10294540B2 (en) | 2019-05-21 |
US20150376731A1 (en) | 2015-12-31 |
EP2942413A4 (en) | 2016-10-19 |
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