WO2020230880A1 - Steel wire and hot-rolled wire material - Google Patents
Steel wire and hot-rolled wire material Download PDFInfo
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- WO2020230880A1 WO2020230880A1 PCT/JP2020/019393 JP2020019393W WO2020230880A1 WO 2020230880 A1 WO2020230880 A1 WO 2020230880A1 JP 2020019393 W JP2020019393 W JP 2020019393W WO 2020230880 A1 WO2020230880 A1 WO 2020230880A1
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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
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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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
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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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
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
Definitions
- the present disclosure relates to steel wire and hot rolled wire.
- the present application claims priority based on Japanese Patent Application No. 2019-092640 filed in Japan on May 16, 2019, the contents of which are incorporated herein by reference.
- cold forging is excellent in dimensional accuracy and productivity of molded products, it is possible to switch from conventional hot forging to cold forging when molding mechanical parts such as steel bolts, screws, and nuts. It is expanding. Further, parts such as bolts and nuts are often used for structural purposes, and for this reason, alloying elements such as C, Mn, and Cr are added to impart strength.
- the shape of parts has become complicated for the purpose of reducing parts manufacturing costs and improving the functionality of parts. Therefore, the steel material used for cold forging is required to be soft and have extremely high ductility. Therefore, conventionally, the hot-rolled material has been softened by heat treatment such as spheroidizing annealing to improve workability.
- the workability of cold forging steel includes deformation resistance that affects the mold load and ductility that affects the occurrence of machining cracks. Although the required characteristics differ depending on the use of the steel material, it is usual that both deformation resistance and ductility, or one of them, is required.
- Patent Document 1 a region in which the average particle size of ferrite grains is 2 to 5.5 ⁇ m, the major axis is 3 ⁇ m or less, and the ratio of cementite having an aspect ratio of 3 or less is 70% or more with respect to all cementite is defined from the surface. It is disclosed that the cold workability is improved by setting the wire diameter to 10% or more.
- Patent Document 2 the standard deviation of the cementite distance divided by the average value of the cementite distance is set to 0.50 or less, that is, by making the distance between cementites substantially uniform, during cold forging.
- a steel wire having a reduced deformation resistance and a reduced cracking has been disclosed.
- an average particle size of the ferrite grains is not less than 15 [mu] m, 0.8 [mu] m or less average grain size of globular carbides, the maximum particle size 4.0 ⁇ m or less, 1 mm 2 per 0.5 ⁇ 10 6 ⁇ the number of and C% ⁇ 5.0 ⁇ 10 6 ⁇ C% number particle size is cold forgeability that excellent disclosed by the maximum distance between 0.1 ⁇ m or more globular carbides and 10 ⁇ m or less.
- Patent Document 1 The method disclosed in Patent Document 1 is effective for processing in which the crack generation position is near the surface of the rolled wire, but is workable for processing in which the crack generation position is inside the rolled wire.
- the improvement effect is small.
- the rolled wire is cut and then cold forged. Therefore, in many cases, the vicinity of the surface of the rolled wire does not become the crack generation position, and the effect is limited.
- Patent Document 3 has a problem that the Cr content is 0.20% or less, the hardenability is low, and the strength of the parts after quenching and tempering becomes unstable as the wire diameter becomes large. ..
- the means for solving the above problems include the following aspects. ⁇ 1> Ingredient composition is mass%, C: 0.10 to 0.60%, Si: 0.01-0.50%, Mn: 0.20 to 1.00%, P: 0.030% or less, S: 0.050% or less, Cr: 0.85 to 1.50%, Al: 0.001 to 0.080%, N: 0.0010 to 0.0200%, and the balance: Fe and impurity elements.
- Ingredient composition is mass%, C: 0.10 to 0.60%, Si: 0.01-0.50%, Mn: 0.20 to 1.00%, P: 0.030% or less, S: 0.050% or less, Cr: 0.85 to 1.50%, Al: 0.001 to 0.080%, N: 0.0010 to 0.0200%, and the balance: Fe and impurity elements.
- a cross section that includes the central axis of the steel wire and is parallel to the central axis. More than 95 area% of the metallographic structure is composed of ferrite and spherical carbides.
- the spherical carbide has an average aspect ratio of 2.5 or less for the spherical carbide having a diameter equivalent to a circle of 0.1 ⁇ m or more, and the content (mass%) of C contained in the steel wire is represented by [C].
- a circle number of equivalent diameter 0.1 ⁇ m or more of the globular carbides is 1.5 ⁇ 10 6 ⁇ [C] ⁇ 7.0 ⁇ 10 6 ⁇ [C] number / mm 2, the steel wire. ⁇ 2> The above.
- the average particle size of the spherical carbide having a diameter equivalent to a circle of 0.1 ⁇ m or more is 0.50 ⁇ m or less, and the maximum particle size of the spherical carbide is 3.00 ⁇ m or less.
- Steel wire
- a steel wire containing an alloying element and having excellent cold forging property, and a hot-rolled wire rod for manufacturing the steel wire are provided.
- the numerical range represented by using “-” means a range including the numerical values before and after “-” as the lower limit value and the upper limit value.
- the numerical range when "greater than” or “less than” is added to the numerical values before and after “to” means a range in which these numerical values are not included as the lower limit value or the upper limit value.
- the upper limit value or the lower limit value of the numerical range described stepwise may be replaced with the upper limit value or the lower limit value of the numerical range described stepwise. , Or you may replace it with the value shown in the examples.
- the content of elements in the component composition may be expressed as an elemental amount (for example, C amount, Si amount, etc.).
- “%” means “mass%”.
- the term “process” is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
- the "cross section including the central axis of the steel wire and parallel to the central axis” includes the central axis of the steel wire and is cut along the longitudinal direction (that is, the drawing direction) of the steel wire. A cross section parallel to the axial direction (also referred to as an L cross section) is shown.
- the "central axis” indicates a virtual line extending in the axial direction through the center point of the cross section orthogonal to the axial direction (longitudinal direction) of the steel wire.
- the "surface layer portion of the steel wire” indicates a region having a depth of up to 500 ⁇ m from the surface (outer peripheral surface) of the steel wire toward the central axis (in the radial direction).
- the notation “numerical value XD” is a position at a depth X times the diameter D from the surface of the steel wire toward the central axis (in the radial direction), where D is the diameter of the steel wire. Is shown. For example, "0.25D” indicates a position at a depth of 0.25 times the diameter D.
- the steel wire according to the present disclosure is a steel wire having a predetermined component composition and having a metal structure satisfying the following (1) and (2).
- (2) The ferrite has an average particle size of 10.0 ⁇ m or more, and the spherical carbide has an average aspect ratio of a spherical carbide having a circular equivalent diameter of 0.1 ⁇ m or more (hereinafter, simply referred to as “average aspect ratio of spherical carbide”).
- the number (which may be referred to) is 2.5 or less, and the number of pieces per 1 mm 2 in the L cross section is 1.5 ⁇ 10 6 ⁇ [C] to 7.0 ⁇ 10 6 ⁇ [C] ([[].
- C] represents the content (mass%) of carbon (C) contained in the steel wire).
- the steel wire according to the present disclosure is a steel wire having excellent cold forging properties due to the above configuration.
- the steel wire according to the present disclosure was found based on the following findings.
- the present inventors can achieve both coarse graining of ferrite grains and miniaturization of carbides even in steel containing 0.85% or more of Cr, and reduce deformation resistance. And succeeded in achieving improvement in ductility at the same time.
- the structure of the hot-rolled material shall be a structure mainly composed of bainite having a small proeutectoid ferrite fraction.
- strain is applied to the steel wire by wire drawing with a total surface reduction rate of 20% or more.
- C Performing spheroidizing annealing at a temperature of Ac 1 or less, Found to be important.
- the reason why the cold forging property of the steel wire having a structure composed of coarse ferrite grains and fine spherical carbides is excellent is that the coarse carbides that are likely to generate molding cracks and the spherical carbide grains having a large aspect ratio. It is considered that the occurrence of cracks can be suppressed by making the diameter finer, and the strength is lowered and the deformation resistance is reduced by making the ferrite grain size coarse.
- the steel wire according to the present disclosure can be formed into a complicated shape part by cold forging, and the product yield can be obtained. And productivity are improved. Further, with the steel wire according to the present disclosure, it is possible to integrally mold a complex-shaped part having high strength, which has been difficult in the past. That is, the steel wire according to the present disclosure can be suitably used for machine structural steel used as a material for machine parts such as bolts, screws, and nuts.
- the steel wire according to the present disclosure can suppress molding cracks, it contributes to high functionality by complicating the shape of parts and improvement of productivity of mechanical parts, and is extremely useful in industry.
- the composition and metallographic structure of the steel wire according to the present disclosure will be specifically described.
- the composition of the steel wire according to the present disclosure is, in mass%, C: 0.10 to 0.60%, Si: 0.01 to 0.50%, Mn: 0.20 to 1.00%, P: 0.030% or less, S: 0.050% or less, Cr: 0.85 to 1.50%, Al: 0.001 to 0.080%, N: 0.0010 to 0.0200%, and the balance: It consists of Fe and impurity elements.
- the steel wire according to the present disclosure may contain an element other than the above instead of a part of Fe, and the component composition is mass%, for example, Ti: 0 to 0.050%, B: 0 to 0.
- Mo 0 to 0.50%
- Ni 0 to 1.00%
- Cu 0 to 0.50%
- V 0 to 0.50%
- Nb 0 to 0.050%
- Ca One or more of 0 to 0.0050%, Mg: 0 to 0.0050%, and Zr: 0 to 0.0050% may be satisfied.
- Ti, B, Mo, Ni, Cu, V, Nb, Ca, Mg, and Zr are arbitrary elements. That is, these elements do not have to be contained in the steel wire.
- the reason for limiting the range of the amount of each element contained in the steel wire will be described.
- C 0.10 to 0.60% C is contained in order to secure the strength as a mechanical part. If the amount of C is less than 0.10%, it is difficult to secure the required strength as a mechanical part. On the other hand, when the amount of C exceeds 0.60%, ductility, toughness, and cold forging property deteriorate. Therefore, the amount of C was set to 0.10 to 0.60%.
- the amount of C may be 0.15% or more, 0.20% or more, or 0.25% or more.
- the amount of C may be 0.55% or less, 0.50% or more, or 0.40% or less.
- Si 0.01 to 0.50%
- Si is an element that functions as a deoxidizing element, imparts hardenability, improves temper softening resistance, and imparts the strength required for mechanical parts. If the amount of Si is less than 0.01%, these effects are insufficient. When the amount of Si exceeds 0.50%, the ductility and toughness of the mechanical parts are deteriorated, and the deformation resistance of the steel wire is increased to deteriorate the cold forging property. Therefore, the amount of Si was set to 0.01 to 0.50%.
- the amount of Si may be 0.03% or more, 0.05% or more, or 0.10% or more.
- the amount of Si may be 0.35% or less, 0.30% or less, or 0.25% or less.
- Mn 0.20 to 1.00% Mn is an element necessary for imparting hardenability and imparting strength required for mechanical parts. If the amount of Mn is less than 0.20%, the effect is insufficient. If the amount of Mn exceeds 1.00%, the toughness of the mechanical parts deteriorates, the deformation resistance of the steel wire increases, and the cold forging property deteriorates. Therefore, the amount of Mn was set to 0.20 to 1.00%.
- the amount of Mn may be 0.25% or more, 0.30% or more, or 0.35% or more.
- the Mn content may be 0.90% or less, 0.85% or less, or 0.80% or less.
- P 0.030% or less
- P is contained in the steel wire as an impurity. It is desirable to reduce P because it segregates at the grain boundaries of mechanical parts after quenching and tempering and deteriorates toughness. Therefore, the upper limit of the amount of P is 0.030%.
- the upper limit of the preferable amount of P is 0.020%.
- the upper limit of the more preferable amount of P is 0.015% or less, or 0.012% or less.
- the lower limit of the amount of P is preferably 0% (that is, it is preferable not to include it), but it exceeds 0% (or 0.0001% or more or 0.005% or more) from the viewpoint of reducing the de-P cost. There should be.
- S (S: 0.050% or less) S is contained in the steel wire as a sulfide such as MnS. These sulfides improve the machinability of steel wire.
- the upper limit of the amount of S is set to 0.050%.
- the upper limit of the preferable amount of S is 0.030%.
- a more preferable upper limit of the amount of S is 0.015% or 0.010%.
- the lower limit of the amount of S is preferably 0% (that is, it is preferable not to include it), but it exceeds 0% (or 0.0001% or more or 0.005% or more) from the viewpoint of reducing the cost of removing S. There should be.
- Cr 0.85 to 1.50%
- Cr is an element required to improve hardenability and impart the required strength to mechanical parts. Further, by containing Cr, the shape of the carbide after annealing becomes spherical, and the cold workability is improved. If the amount of Cr is less than 0.85%, the effect is insufficient. When the amount of Cr exceeds 1.50%, the spheroidizing time becomes long, the manufacturing cost increases, the deformation resistance of the steel wire increases, and the cold forging property deteriorates. Therefore, the amount of Cr was set to 0.85 to 1.50%.
- the amount of Cr may be 0.87% or more, 0.90% or more, or 0.95% or more.
- the amount of Cr may be 1.40% or less, 1.30% or less, or 1.20% or less.
- Al has the effect of functioning as a deoxidizing element and forming AlN to refine austenite crystal grains and improve the toughness of mechanical parts. Further, Al has an effect of fixing the solid solution N, suppressing dynamic strain aging, and reducing deformation resistance. If the amount of Al is less than 0.001%, these effects are insufficient. If the amount of Al exceeds 0.080%, the effect may be saturated and the manufacturability may be lowered. Therefore, the amount of Al was set to 0.001 to 0.080%.
- the amount of Al may be 0.010% or more, 0.020% or more, or 0.025% or more.
- the amount of Al may be 0.060% or less, 0.050% or less, or 0.040% or less.
- N (N: 0.0010 to 0.0200%) N has the effect of forming a nitride with Al, Ti, Nb, V and the like, making austenite crystal grains finer, and improving the toughness of mechanical parts. If the amount of N is less than 0.0010%, the amount of nitride precipitated is insufficient and no effect can be obtained. When the amount of N exceeds 0.0200%, the deformation resistance of the steel wire becomes high due to the dynamic strain aging due to the solid solution N, and the workability deteriorates. Therefore, the amount of N was set to 0.0010 to 0.0200%. The range of the amount of N may be 0.0020% or more, 0.0025% or more, or 0.0030% or more. The amount of N may be 0.0080% or less, less than 0.0050%, or 0.0040% or less.
- the steel wire according to the present disclosure has Ti: 0 to 0.050%, B: 0 to 0.0050%, Mo: 0 to 0.50%, Ni: 0 to 0 to improve the characteristics described below.
- 1.00%, Cu: 0 to 0.50%, V: 0 to 0.50%, Nb: 0 to 0.050%, Ca: 0 to 0.0050%, Mg: 0 to 0.0050%, And Zr: 0 to 0.0050% may contain one or more.
- the steel wire according to the present disclosure can solve the problem without containing these elements. Therefore, the lower limit of the content of these arbitrary elements is 0%.
- Ti functions as a deoxidizing element. Furthermore, Ti has the effect of forming nitrides and carbides to refine austenite crystal grains to improve the toughness of mechanical parts, the effect of promoting the formation of solid solution B, and the effect of enhancing hardenability, and solid solution N. It has the effect of fixing and suppressing dynamic strain aging and reducing deformation resistance. If the amount of Ti exceeds 0.050%, these effects may be saturated and coarse oxides or nitrides may be generated to deteriorate the fatigue strength of mechanical parts. Therefore, the amount of Ti may be contained in the range of more than 0 to 0.050%. The amount of Ti may be 0.005% or more, or 0.010% or more. The amount of Ti may be 0.030% or less, or 0.025% or less.
- B has the effect of segregating into grain boundaries as a solid solution B to improve hardenability and impart the required strength to mechanical parts.
- the amount of B may be contained in the range of more than 0 to 0.0050%.
- the amount of B may be 0.0003% or more, or 0.0005% or more.
- the amount of B may be 0.0030% or less, or 0.0020% or less.
- Mo 0 to 0.50%
- Mo has the effect of improving hardenability and imparting the required strength to mechanical parts.
- the amount of Mo may be contained in the range of more than 0 to 0.50%.
- the amount of Mo may be 0.10% or more, or 0.15% or more.
- the amount of Mo may be 0.40% or less, or 0.30% or less.
- Ni 0 to 1.00%
- Ni has the effect of improving hardenability and imparting the required strength to mechanical parts.
- the amount of Ni may be contained in the range of more than 0 to 1.00%.
- the amount of Ni may be 0.02% or more, or 0.10% or more.
- the amount of Ni may be 0.50% or less, or 0.30% or less.
- Cu has the effect of improving hardenability, imparting the necessary strength to mechanical parts, and improving corrosion resistance.
- the amount of Cu may be contained in the range of more than 0 to 0.50%.
- the amount of Cu may be 0.02% or more, or 0.10% or more.
- the amount of Cu may be 0.40% or less, or 0.35% or less.
- V has the effect of precipitating carbide VC and increasing the strength of mechanical parts.
- the amount of V may be contained in the range of more than 0 to 0.50%.
- the amount of V may be 0.01% or more, or 0.05% or more.
- the amount of V may be 0.20% or less, or 0.15% or less.
- Nb has the effect of precipitating carbides and nitrides to increase the strength of mechanical parts, the effect of finely granulating austenite grains to improve toughness, the effect of reducing solid solution N, and the effect of reducing deformation resistance. is there.
- the amount of Nb may be contained in the range of more than 0 to 0.050%.
- the amount of Nb may be 0.001% or more, or 0.005% or more.
- the amount of Nb may be 0.030% or less, or 0.020% or less.
- Ca, Mg and Zr may be used for the purpose of deoxidation. These elements have the effect of making oxides finer and improving fatigue strength. On the other hand, if the content of each of these elements exceeds 0.050%, the effect is saturated and coarse oxides are generated, which may deteriorate the fatigue characteristics. Therefore, the Ca amount, the Mg amount, and the Zr amount may each be contained in the range of more than 0 to 0.050%.
- the amount of Ca, the amount of Mg, and the amount of Zr may be 0.0001% or more and 0.0005% or more, respectively.
- the amount of Ca, the amount of Mg, and the amount of Zr may be 0.030% or less, or 0.020% or less, respectively.
- the balance is Fe and impurity elements.
- the impurity element refers to, for example, a component contained in a raw material or a component that is unintentionally mixed in a manufacturing process and is not intentionally contained. Further, the impurity element includes a component contained in an amount within a range that does not affect the performance of the steel wire even if the component is intentionally contained.
- the impurity element examples include O and the like.
- O exists in the steel wire as an oxide such as Al and Ti. If the amount of O is high, coarse oxides are formed, which causes a decrease in fatigue strength of mechanical parts. Therefore, the amount of O is preferably suppressed to 0.01% or less.
- the metal structure of the steel wire according to the present disclosure is composed of ferrite and spherical carbide (spherical cementite) in a cross section (L cross section) parallel to the central axis and including the central axis of the steel wire. Will be done. If the metal structure contains a martensite structure, a bainite structure, a pearlite structure, or the like, the deformation resistance increases, the ductility decreases, and the cold forging property deteriorates. Therefore, it is preferable that these structures are not included.
- the cross section including the central axis of the steel wire and parallel to the central axis, 97 area% or more, 98 area% or more, or 99 area% or more of the metal structure.
- it may be composed of ferrite and spherical carbide (spherical cementite).
- the fact that 95 area% or more of the metal structure is composed of ferrite and spherical carbide in the L cross section means that 95 area% or more of the metal structure is formed of ferrite and spherical carbide when the L cross section is observed. means.
- the area% of ferrite and spherical carbide is calculated by the following procedure. After mirror-polishing the cross section (L cross section) including the central axis of the steel wire and parallel to the central axis, the sample is immersed in nital (5% nitric acid + 95% ethanol solution) at room temperature for 20 seconds to reveal the metal structure. Using this sample, a scanning electron microscope (SEM) was used to measure a depth of 250 ⁇ m (the central part of the surface layer in the depth direction) and a depth of 0.25D (of the steel wire) from the surface (outer peripheral surface of the steel wire).
- SEM scanning electron microscope
- the area% of ferrite and spherical carbide can be obtained by subtracting the total area of martensite, bainite and pearlite from the entire imaging field as the area of ferrite and spherical carbide, and dividing this value by the area of the imaging field. it can.
- the pearlite structure was a structure in which carbides having an aspect ratio (major axis / minor axis) of more than 5.0 were present in layers.
- the lower limit of the average particle size of the ferrite grains is preferably 10.0 ⁇ m.
- the preferable lower limit of the average particle size of the ferrite grains is 11.5 ⁇ m.
- a more preferable lower limit of the average particle size of the ferrite grains is 13.0 ⁇ m.
- the upper limit of the average particle size of the ferrite grains was set to 30.0 ⁇ m.
- the upper limit of the average particle size of the preferred ferrite grains is 20.0 ⁇ m.
- the average particle size of ferrite grains can be measured by an electron backscattering diffraction (EBSD) method. Specifically, as shown in FIG. 1, a depth portion 250 ⁇ m from the surface of a cross section (L cross section) including the central axis C of the steel wire 10 and parallel to the central axis C (central portion in the depth direction of the surface layer portion).
- EBSD electron backscattering diffraction
- the measurement step is 1.0 ⁇ m in a region of 500 ⁇ m in the depth direction (diametrical direction) and 500 ⁇ m in the central axis direction, that is, in a region of 500 ⁇ m square shown by A1, A2, and A3 in FIG.
- the crystal orientation of bcc-Fe at each measurement point in the region is measured.
- a boundary having an orientation difference of 15 degrees or more is defined as a ferrite grain boundary.
- a region of 5 pixels or more surrounded by the ferrite grain boundaries is defined as a ferrite grain.
- Johnson-Saltykov's measurement method (“Measurement Morphology", Uchida Otsuru Farm Shinsha, S47.7.30), which is a method for determining the average particle size of a grain population on the premise of mixing ferrite grains. , Original work: RT DeHoff. F.N.Rbiness. P189). This is performed for two samples, and the average value of the average particle diameters measured in a total of six measurement regions is taken as the average particle diameter of the ferrite grains.
- the spherical carbide means cementite having an aspect ratio of 5.0 or less represented by the major axis / minor axis of the carbide.
- the aspect ratio (major axis / minor axis) of the spherical carbide becomes large, cracks are generated from around the strained carbide and it becomes easy to crack.
- the average aspect ratio of the spherical carbide having a circle equivalent diameter of 0.1 ⁇ m or more exceeds 2.5, the ductility is lowered and processing cracks are likely to occur.
- the upper limit of the average aspect ratio of spherical carbide having a circle equivalent diameter of 0.1 ⁇ m or more is set to 2.5.
- the preferable upper limit of the average aspect ratio of the spherical carbide having a circle equivalent diameter of 0.1 ⁇ m or more is 2.0.
- a more preferable upper limit of the average aspect ratio of the spherical carbide having a circle equivalent diameter of 0.1 ⁇ m or more is 1.8.
- the particle size of the spherical carbide is not particularly specified.
- the maximum particle size of the spherical carbide affects the occurrence of molding cracks. When the maximum particle size is reduced, it is possible to prevent cracks from being generated around the strained carbide, and it is possible to more effectively prevent cracks in the steel wire.
- the upper limit of the maximum particle size of the spherical carbide may be 3.00 ⁇ m.
- the preferable upper limit of the maximum particle size of the spherical carbide is 2.00 ⁇ m.
- a more preferable upper limit of the maximum particle size of the spherical carbide is 1.50 ⁇ m.
- the upper limit of the average particle size of the spherical carbide may be 0.50 ⁇ m.
- the preferable upper limit of the average particle size of the spherical carbide is 0.40 ⁇ m.
- a more preferable upper limit of the average particle size of the spherical carbide is 0.32 ⁇ m.
- the average particle size of the spherical carbide means the average number of circle-equivalent diameters of the spherical carbide. The number average is calculated after excluding spherical carbides with a circle equivalent diameter of less than 0.1 ⁇ m.
- [C] indicates the C content in the steel wire represented by mass%.
- Circle preferable lower limit of the number of 1 mm 2 per equivalent diameter 0.1 ⁇ m or more globular carbide, 3.0 ⁇ 10 6 ⁇ [C ] number, or 3.5 ⁇ 10 is a 6 ⁇ [C] number.
- Circle equivalent diameter preferred upper limit is 6.5 ⁇ 10 6 ⁇ the number of 1 mm 2 per 0.1 ⁇ m or more globular carbides [C] number, or 6.0 ⁇ 10 6 ⁇ [C] number.
- the maximum particle size of the spherical carbide, the average particle size of the spherical carbide, the aspect ratio of the spherical carbide, and the number density of the spherical carbide can be obtained by image analysis of a scanning electron microscope (SEM) photograph.
- the sample is placed in picral (5% picric acid + 95% ethanol solution) at room temperature for 50 seconds. Immerse to reveal the metallographic structure.
- the 250 ⁇ m depth part (the central part in the depth direction of the surface layer part), the 0.25D depth part, and the 0.5D depth part from the surface of the steel wire are set to be the center of the measurement field of view.
- a metal structure of a total of 15 fields of view is photographed at a magnification of 5000 times in a region of 20 ⁇ m in the depth direction and 25 ⁇ m in the central axis direction.
- image analysis software name: Nireco's small general-purpose image processing analysis system LUZEX_AP
- the average number of circle-equivalent diameters of spherical carbides of 0.1 ⁇ m or more is defined as the average particle size of spherical carbides, and the maximum particle size in the measurement field is defined as the maximum particle size of spherical carbides.
- the circle-equivalent diameter of the spherical carbide is the diameter of a circle having an area equal to the area of the spherical carbide.
- the aspect ratio of the spherical carbide of 0.1 ⁇ m or more is obtained by the length of the major axis / the length of the minor axis.
- the number density of spherical carbides is obtained by dividing the number of spherical carbides having a circle-equivalent diameter of 0.1 ⁇ m or more by the area of the measurement field of view.
- Step wire manufacturing method> An example of a method for manufacturing a steel wire according to the present disclosure will be described. However, the method for manufacturing a steel wire described below does not limit the steel wire according to the present disclosure. That is, regardless of the manufacturing method, the steel wire satisfying the above requirements is the steel wire according to the present disclosure.
- An example of the method for manufacturing a steel wire according to the present disclosure is The process of drawing a wire mainly composed of bainite with a total surface reduction rate of 20 to 50%, The process of annealing the wire drawn wire by holding it at 650 ° C or higher and Ac 1 temperature (° C) or lower for 3 hours or longer and cooling it. To be equipped.
- a step of holding the cooled wire rod in a temperature range of 400 ° C. to less than 500 ° C. for 20 seconds or more (first holding step) and Further, a wire rod mainly composed of bainite may be produced by a step of holding the wire rod that has undergone the first holding step within a temperature range of 500 ° C. to 600 ° C. for 30 seconds or longer (second holding step).
- first holding step a step of holding the wire rod that has undergone the first holding step within a temperature range of 500 ° C. to 600 ° C. for 30 seconds or longer.
- Heating process In the heating step, the steel piece having the component composition of the steel wire according to the present disclosure is heated to 950 to 1150 ° C. If the heating temperature is less than 950 ° C., the deformation resistance during hot rolling increases and the rolling cost increases. When the heating temperature exceeds 1150 ° C., decarburization of the surface becomes remarkable, and the surface hardness of the final product decreases.
- the heated steel pieces are hot rolled at a finish rolling temperature of 850 to 1000 ° C. If the finish rolling temperature is less than 850 ° C., the ferrite grains become finer and a structure having an average grain size of 10.0 to 30.0 ⁇ m cannot be obtained after the annealing step. When the finish rolling temperature exceeds 1000 ° C., the transformation completion time in the first holding step becomes long, and the manufacturing cost increases.
- the finish rolling temperature refers to the surface temperature of the wire rod immediately after finish rolling.
- the wire rod at 850 to 1000 ° C. is cooled from 850 ° C. to 550 ° C. at an average cooling rate of 30 to 250 ° C./s to less than 400 to 500 ° C.
- the wire rod after hot rolling may be wound into a ring shape and immersed in a molten salt tank so as to have the above average cooling rate. If the average cooling rate is less than 30 ° C./s, the area ratio of ferrite and spherical carbides tends to decrease after the annealing step, and the number density of spherical carbides tends to decrease.
- the cooling rate refers to the surface cooling rate of the wire rod.
- First holding step In the first holding step, the cooled wire rod is held at 400 ° C. to less than 500 ° C. for 20 seconds or more. If the holding temperature is less than 400 ° C., the strength after the annealing step becomes high and the cold forging property deteriorates. When the holding temperature is 500 ° C. or higher, the transformation completion time in the first holding step becomes remarkably long, and the untransformed portion remains after the first holding step and the second holding step. The untransformed portion causes disconnection in the wire drawing process and deteriorates the cold forging property after the annealing process.
- the holding time in the first holding step is less than 20 seconds, untransformed portions remain after the first holding step and after the second holding step, which causes disconnection in the wire drawing process and cold after the annealing step. Deteriorates forgeability. From the viewpoint of manufacturing cost, the upper limit of the holding time is preferably 120 seconds.
- the first holding step is carried out, for example, by immersing the wire rod in the molten salt tank.
- the wire rod that has undergone the first holding step is held at 500 ° C. to 600 ° C. for 30 seconds or longer. If the holding temperature is less than 500 ° C., the strength of the wire rod is high, which causes disconnection in the wire drawing process. If the holding temperature is 600 ° C. or higher, the manufacturing cost increases. From the viewpoint of manufacturing cost, the upper limit of the holding time is preferably 150 seconds.
- the second holding step is carried out, for example, by immersing in a molten salt tank.
- the wire rod cooled to room temperature suppresses proeutectoid ferrite and pearlite, and has a structure mainly composed of bainite.
- the area ratio of bainite measured in the C cross section is 50% or more, and the area ratio of martensite is 0% or more.
- the area ratio of martensite may be 0%, preferably more than 0%.
- the structure of the wire rod produced by hot rolling and cooling by a normal method using subeutectoid steel with a carbon content of 0.50% or less is a mixed structure of ferrite and pearlite.
- carbon in the steel is unevenly distributed in the pearlite portion. Therefore, after spheroidizing annealing, the carbides are unevenly distributed in the portion that was pearlite before annealing, and the ductility is lowered.
- the structure of the wire is a bainite structure or martensite structure in which ferrite is suppressed, carbon in the steel is uniformly distributed, so that carbides are uniformly dispersed after spheroidizing annealing, and ductility is improved.
- Martensite is effective in improving ductility because it makes carbides after spheroidizing annealing finer, but on the other hand, it increases deformation resistance because it makes the ferrite grain size after annealing finer. Therefore, in order to improve the ductility of the steel wire after spheroidizing annealing and reduce the deformation resistance, it is effective to make the structure of the wire rod mainly composed of bainite.
- bainite in the present disclosure includes as with pearlitic ferrite phase (alpha) and cementite phase (Fe 3 C) are.
- pearlite is a structure in which ferrite phases and cementite phases are alternately and continuously laminated in layers.
- bainite is a structure in which lath (needle-shaped lower structure) is contained in grains and granular or needle-shaped carbides are dispersed. In this respect, pearlite and bainite are distinguished.
- the area ratio (area%) of bainite, ferrite, and martensite of the wire is determined by the following procedure.
- the C cross section of the wire rod to be measured (hereinafter sometimes referred to as "object") is mirror-polished, and then the object is immersed in picral (5% picric acid + 95% ethanol solution) at room temperature for 50 seconds. To reveal the organization.
- the diameter of the object is referred to as D.
- D the diameter of the object.
- the visual field shape is a rectangle having a length of 80 ⁇ m in the depth direction and a length of 120 ⁇ m in the circumferential direction, and the center of the visual field is aligned with the above-mentioned measurement position.
- the visual field shape is a rectangle having a length of 80 ⁇ m in the depth direction and a length of 120 ⁇ m in the circumferential direction, and the center of the visual field is aligned with the above-mentioned measurement position.
- One point on the central axis One point on the central axis that overlaps with the central axis (depth position with a depth of 0.5D from the surface) is defined as the measurement point on the central axis.
- the visual field shape is a square with a length and width of 80 ⁇ m centered on the central axis.
- cementite and ferrite having (length of major axis) / (length of minor axis) of 5.0 or more are alternately and continuously laminated in layers, and these layers are laminated.
- a tissue containing no granular or acicular cementite between the two was designated as pearlite.
- pearlite includes pseudo pearlite.
- the pseudo-pearlite was a structure in which the divided cementites were arranged in a row, did not contain granular or needle-like carbides between the rows, and did not contain a lath (needle-shaped substructure) in the grains.
- Bainite had a structure in which laths were contained in the grains and granular or needle-like carbides were dispersed between the laths and in the laths.
- each structure of bainite, ferrite, martensite, pearlite, austenite, and proeutectoid cementite in the photographed microstructure is visually marked. Then, the area of the region of each tissue is obtained by image analysis (software name: Nireco's small general-purpose image processing analysis system LUZEX_AP). In addition, the above-mentioned series of operations is performed on at least two samples, the area ratio of the structure in these samples is measured and calculated, the average value thereof is obtained, and the average value is the area% of each structure of the wire rod in the present disclosure. And.
- the region that is corroded by nital but weakly corroded by piclar is determined to be martensite, and the region where both nital and picral are weakly corroded is determined to be ferrite. Then, the region of each tissue is visually marked by the above method, and the area% of each tissue is obtained by image analysis.
- the C cross section of the wire rod or steel wire to be measured is mirror-polished.
- the tissue is then exposed by immersion in Nital at room temperature for 20 seconds.
- a histological photograph of the entire area in the nine regions in the C cross section is taken using SEM at a magnification of 5000 times.
- a structure in which laths (needle-shaped substructures) were present in the grains and granules or needle-like carbides were present was determined to be bainite.
- the "nine regions in the C cross section" are (1) four locations on the surface layer portion, (2) four locations at a depth position of 0.25D, and (3) one location on the central axis. Is.
- wire drawing process In the wire drawing process, after the second holding step, the wire rod cooled to room temperature is drawn with a total surface reduction rate of 20 to 50%.
- a total surface reduction rate of 20 to 50%.
- spheroidization of carbides is promoted during the annealing step, and growth of ferrite grains is promoted. If the total surface reduction rate during wire drawing is less than 20%, these effects are insufficient and the cold forging property deteriorates. Even if the total surface reduction rate exceeds 50%, the effect may be saturated and the steel wire diameter may become smaller, which may limit the application.
- the steel wire diameter (diameter) according to the present disclosure is not particularly limited and may be determined according to the intended use. However, when used as a material for mechanical parts such as bolts, screws and nuts, for example, the diameter is Wire drawing is performed so that the steel wire has a diameter of 3.5 to 16.0 mm.
- the steel wire obtained by wire drawing is held at 650 ° C. or higher and Ac 1 temperature (° C.) or lower for 3 hours or longer to cool.
- Ac 1 723-10.7 ⁇ [Mn] + 29.1 ⁇ [Si] + 16.9 ⁇ [Cr].
- the annealing temperature is less than 650 ° C.
- the average particle size of the ferrite grains is less than 10 ⁇ m, and the cold forging property deteriorates.
- the annealing temperature exceeds Ac 1 , the average particle size of the ferrite grains becomes less than 10 ⁇ m, the number of carbides decreases, and the cold forging property may deteriorate.
- the holding time is less than 3 hours, the average particle size of the ferrite grains is less than 10 ⁇ m, and the cold forging property deteriorates.
- the steel wire according to the present disclosure can be suitably manufactured.
- the method for producing the steel wire according to the present disclosure is not particularly limited.
- the method for producing a steel wire composed of the above steps is only a preferable example for obtaining the steel wire according to the present disclosure.
- the wire rod according to the present disclosure is a hot-rolled wire rod for manufacturing the steel wire according to the present disclosure.
- the wire rod according to the present disclosure inevitably has substantially the same chemical composition as the steel wire according to the present disclosure.
- the metal structure of the wire rod according to the present disclosure and various aspects of spherical carbide are not particularly limited.
- a preferable example of the metal structure of the wire rod is that the area ratio of bainite is 50% or more and the area ratio of martensite is 0% or more in the C cross section.
- the present disclosure relates to a wire rod having such a metal structure by applying strain to the steel wire by wire drawing with a total surface reduction rate of 20% or more, and further performing spheroidizing annealing at a temperature of Ac 1 or less. Steel wire can be obtained.
- the steel wires of test numbers 1 to 16, 32 to 36, and 41 shown in Tables 2-1 to 2-4 were manufactured as follows.
- the steel pieces were heated and then hot-rolled, and the obtained wire rod was wound into a ring shape and immersed in a molten salt tank installed behind the hot-rolling line and cooled to 470 to 520 ° C. ..
- the wire rod immersed in the molten salt tank was first held and second held in the molten salt bath of two tanks. Then, the wire rod cooled to room temperature (25 ° C.) was wire-drawn at the total surface reduction rate shown in Table 2-1 and Table 2-2, and after the wire was drawn, it was heated and annealed.
- the annealing treatment of the steel wires of test numbers 1 to 12, 15, 32 and 35 was held at 710 ° C. for 5 hours and then air-cooled, and the annealing treatment of the steel wire of test number 16 was held at 760 ° C. for 5 hours. After air cooling, the annealing treatment of the steel wire of test number 33 was held at 740 ° C.
- the annealing treatment of the steel wire of test number 34 was held at 695 ° C. for 5 hours and then air cooled.
- the annealing treatment of the steel wire of 36 was held at 730 ° C. for 5 hours and then air-cooled, and the annealing treatment of the steel wire of Test No. 41 was carried out after holding at 735 ° C. for 5 hours and then air-cooled.
- the steel wire of test number 31 was manufactured as follows. First, the steel pieces were heated and then hot-rolled, and the obtained wire rod was wound into a ring shape and cooled to 470 ° C. by impulse cooling. Then, the obtained wire rod was immersed in two molten salt tanks for first holding and second holding. Then, the wire rod cooled to room temperature (25 ° C.) was drawn at the total surface reduction rate shown in Table 2-2, held at 710 ° C. for 5 hours after the wire drawing, and then air-cooled.
- the steel wires of test numbers 17 to 28 and 37 to 40 shown in Tables 2-1 to 2-4 were manufactured as follows. First, the steel pieces were heated and then hot-rolled, and the obtained wire rod was wound into a ring shape and cooled by an impulse. Then, the wire rod cooled to room temperature (25 ° C.) was wire-drawn at the total surface reduction rate shown in Table 2-1 and Table 2-2, and after the wire was drawn, it was heated and annealed. The steel wires of test numbers 17 to 28 and 37 to 40 were annealed at 760 ° C. for 5 hours, cooled to 660 ° C. at a cooling rate of 15 ° C./h, and then air-cooled. Through these steps, the steel wires shown in test numbers 17 to 28 and 37 to 40 were manufactured.
- the steel wire of test number 29 shown in Table 3-1 and Table 3-2 was manufactured as follows. After heating the steel pieces, they were hot-rolled, and the obtained wire rod was wound into a ring shape and cooled by an impulse. Then, the wire rod cooled to room temperature (25 ° C.) was heated to 850 ° C. and quenched, and then heated to 650 ° C. and tempered. Then, the wire was drawn at the total surface reduction rate shown in Table 3-1 and then heated and annealed after the wire was drawn.
- the steel wire of test number 30 shown in Table 4-1 and Table 4-2 was manufactured as follows. After heating the steel pieces, they were hot-rolled, and the obtained wire rod was wound into a ring shape and cooled by an impulse. Then, the wire rod cooled to room temperature (25 ° C.) was heated and subjected to the first annealing treatment. Then, the wire rod cooled to room temperature (25 ° C.) was wire-drawn at the total surface reduction rate shown in Table 4-1 and heated after the wire drawing to be subjected to the second annealing treatment. The first annealing treatment and the second annealing treatment were carried out at 760 ° C. for 5 hours, then cooled to 660 at a cooling rate of 15 ° C./h, and then air-cooled.
- the particle size (described as “average particle size” in the table) and the maximum particle size of spherical carbide having a circle-equivalent diameter of 0.1 ⁇ m or more are the methods described above. Measured according to. The results are shown in the table.
- number / C% is the number of spherical carbides with a circular equivalent diameter of 0.1 ⁇ m or more observed per 1 mm 2 L cross section of each steel wire, and the C content (C content) contained in the steel wire. %) Divided by.
- the deformation resistance and limit compressibility of the steel wire were measured by a compression test.
- the annealed steel wire was drawn with a surface reduction rate of 8% to prepare a columnar test piece having a diameter D and a height of 1.5 D from the drawn steel wire.
- the compression test method is a compression test in which the end face is constrained by a die with concentric grooves based on the standards of the Cold Forging Subcommittee of the Japan Society for Plasticity Processing (Plasticity and Processing, vol.22, No.211, 1981, p139). Was done.
- the deformation resistance was the equivalent stress when processed at an equivalent strain of 1.6 and a compressibility of 73.6% according to Kosakada's method (K. Osakada: Ann.
- the critical compressibility is a curvature of 0.15 mm, a depth of 0.8 mm, and an angle in the circumferential axial direction of a cylindrical test piece having a diameter of 5.0 mm and a height of 7.5 mm manufactured from the drawn steel wire by machining.
- a compression test was performed using a test piece having a 30 ° notch. When cracks with a length of 0.5 mm or more were observed, it was determined that cracks had occurred, and the maximum compressibility at which cracks did not occur was defined as the limit compressibility.
- the table shows the measurement results of deformation resistance and critical compressibility, and also shows the comparison results with ordinary steel wires (test numbers 17 to 28 and 37 to 40).
- Deformation resistance and / or the steel wire with the test number described as "equivalent” to the limit compressibility has a deformation resistance within ⁇ 20 MPa and less than ⁇ 20 MPa as compared with the normal steel wire (test numbers 17 to 28 and 37 to 40).
- the critical compressibility is within ⁇ 2%.
- the steel wire with the test number described as "good” had better characteristics than the normal steel wire, and the steel wire with the test number described as "poor” was inferior to the normal steel wire.
- the steel wires of test numbers 1 to 12, 33 to 36, and 41 that satisfy all the requirements specified in the present disclosure are compared with the normal steel wires (test numbers 17 to 28 and 37 to 40) in terms of deformation resistance.
- the steel wires of test numbers 1 to 12, 33 to 36, and 41 that satisfy all the requirements specified in the present disclosure are superior in the critical compressibility to the normal steel wire.
- the structure before wire drawing that is, the structure of the wire rod
- it had a structure mainly composed of bainite (see Table 5 described later).
- the ordinary steel wires 17 to 28 and 37 to 40 are manufactured under manufacturing conditions in which it is presumed that the structure before wire drawing does not become a structure mainly composed of bainite.
- the structure before wire drawing that is, the structure of the wire rod
- it was not mainly bainite see Table 5 described later.
- the steel wire could not be manufactured because the wire was broken during the wire drawing. It is presumed that this is because the holding temperature in the first holding step was too high and the hardness of the wire before wire drawing became excessive.
- the steel wire 14 the steel wire could not be manufactured because the wire was broken during the drawing.
- the metallographic structure of the wire rod as the raw material was also evaluated.
- the evaluation method was as described above in the present specification.
- the evaluation results are shown in Table 5.
- the wire rods which are the materials of the steel wires of test numbers 1 to 12, 33 to 36, and 41 that satisfy all the requirements specified in the present disclosure, have a bainite area ratio of 50% or more in the C cross section before wire drawing. Therefore, the area ratio of martensite was 0% or more.
- the wire rods of test numbers 13 and 14 in which the wire was broken during the wire drawing process the amount of bainite was insufficient and the amount of martensite was large.
- the wire rod of Test No. 19 for steel wire in which the average aspect ratio of the spherical carbide exceeds the upper limit of the present disclosure and the number density of the spherical carbide is less than the lower limit of the present disclosure includes both bainite and martensite. There wasn't.
- the wire rods of test numbers 22 and 24 on the steel wire having an average ferrite grain size below the lower limit of the present disclosure contained both bainite and martensite, but the amount was insufficient.
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Abstract
Description
本願は、2019年5月16日に、日本に出願された特願2019-092640号に基づき優先権を主張し、その内容をここに援用する。 The present disclosure relates to steel wire and hot rolled wire.
The present application claims priority based on Japanese Patent Application No. 2019-092640 filed in Japan on May 16, 2019, the contents of which are incorporated herein by reference.
<1>
成分組成が、質量%で、
C :0.10~0.60%、
Si:0.01~0.50%、
Mn:0.20~1.00%、
P :0.030%以下、
S :0.050%以下、
Cr:0.85~1.50%、
Al:0.001~0.080%、
N :0.0010~0.0200%、並びに
残部:Fe及び不純物元素であり、
鋼線の中心軸を含み、かつ、前記中心軸に平行な断面において、
金属組織の95面積%以上が、フェライト及び球状炭化物からなり、
前記フェライトは、平均粒径が10.0~30.0μmであり、
前記球状炭化物は、円相当径0.1μm以上の球状炭化物の平均アスペクト比が2.5以下であり、かつ、前記鋼線に含まれるCの含有量(質量%)を[C]で表した場合に、円相当径0.1μm以上の前記球状炭化物の個数が1.5×106×[C]~7.0×106×[C]個/mm2である、鋼線。
<2>
前記断面において、前記円相当径0.1μm以上の球状炭化物の平均粒径が0.50μm以下であり、かつ、前記球状炭化物の最大粒径が3.00μm以下である、<1>に記載の鋼線。
<3>
前記成分組成が、質量%で、
Ti:0~0.050%、
B :0~0.0050%、
Mo:0~0.50%、
Ni:0~1.00%、
Cu:0~0.50%、
V :0~0.50%、
Nb:0~0.050%、
Ca:0~0.0050%、
Mg:0~0.0050%、及び
Zr:0~0.0050%、
の1つ又は2つ以上を満たす、<1>又は<2>に記載の鋼線。
<4>
<1>~<3>のいずれか一項に記載の鋼線の製造用の熱間圧延線材。 The means for solving the above problems include the following aspects.
<1>
Ingredient composition is mass%,
C: 0.10 to 0.60%,
Si: 0.01-0.50%,
Mn: 0.20 to 1.00%,
P: 0.030% or less,
S: 0.050% or less,
Cr: 0.85 to 1.50%,
Al: 0.001 to 0.080%,
N: 0.0010 to 0.0200%, and the balance: Fe and impurity elements.
In a cross section that includes the central axis of the steel wire and is parallel to the central axis.
More than 95 area% of the metallographic structure is composed of ferrite and spherical carbides.
The ferrite has an average particle size of 10.0 to 30.0 μm.
The spherical carbide has an average aspect ratio of 2.5 or less for the spherical carbide having a diameter equivalent to a circle of 0.1 μm or more, and the content (mass%) of C contained in the steel wire is represented by [C]. case, a circle number of equivalent diameter 0.1μm or more of the globular carbides is 1.5 × 10 6 × [C] ~ 7.0 × 10 6 × [C] number / mm 2, the steel wire.
<2>
The above. <1>, wherein in the cross section, the average particle size of the spherical carbide having a diameter equivalent to a circle of 0.1 μm or more is 0.50 μm or less, and the maximum particle size of the spherical carbide is 3.00 μm or less. Steel wire.
<3>
When the component composition is mass%,
Ti: 0 to 0.050%,
B: 0 to 0.0050%,
Mo: 0 to 0.50%,
Ni: 0 to 1.00%,
Cu: 0 to 0.50%,
V: 0 to 0.50%,
Nb: 0 to 0.050%,
Ca: 0 to 0.0050%,
Mg: 0 to 0.0050%, and Zr: 0 to 0.0050%,
The steel wire according to <1> or <2>, which satisfies one or more of the above.
<4>
The hot-rolled wire rod for manufacturing the steel wire according to any one of <1> to <3>.
なお、本明細書中において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。また、「~」の前後に記載される数値に「超」または「未満」が付されている場合の数値範囲は、これら数値を下限値または上限値として含まない範囲を意味する。
本明細書中に段階的に記載されている数値範囲において、ある段階的な数値範囲の上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよく、また、実施例に示されている値に置き換えてもよい。
また、成分組成の元素の含有量は、元素量(例えば、C量、Si量等)と表記する場合がある。
また、成分組成の元素の含有量について、「%」は「質量%」を意味する。
また、「工程」との用語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。
また、「鋼線の中心軸を含み、かつ、前記中心軸に平行な断面」とは、鋼線の中心軸を含み、鋼線の長手方向(つまり伸線方向)に沿って切断した、中心軸方向と平行な断面(L断面とも称する。)を示す。
また、「中心軸」とは、鋼線の軸方向(長手方向)と直交する断面の中心点を通り、軸方向に延びる仮想線を示す。
また、「鋼線の表層部」とは、鋼線の表面(外周面)から、中心軸に向かって(径方向に向かって)、500μmまでの深さの領域を示す。
また、「数値XD」との表記は、鋼線の直径をDとしたとき、鋼線の表面から、中心軸に向かって(径方向に向かって)、直径DのX倍の深さの位置を示す。例えば、「0.25D」は、直径Dの0.25倍の深さの位置を示す。 An embodiment which is an example of the present disclosure will be described.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value. In addition, the numerical range when "greater than" or "less than" is added to the numerical values before and after "to" means a range in which these numerical values are not included as the lower limit value or the upper limit value.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range described stepwise may be replaced with the upper limit value or the lower limit value of the numerical range described stepwise. , Or you may replace it with the value shown in the examples.
In addition, the content of elements in the component composition may be expressed as an elemental amount (for example, C amount, Si amount, etc.).
Further, regarding the content of the element in the component composition, "%" means "mass%".
Further, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
Further, the "cross section including the central axis of the steel wire and parallel to the central axis" includes the central axis of the steel wire and is cut along the longitudinal direction (that is, the drawing direction) of the steel wire. A cross section parallel to the axial direction (also referred to as an L cross section) is shown.
Further, the "central axis" indicates a virtual line extending in the axial direction through the center point of the cross section orthogonal to the axial direction (longitudinal direction) of the steel wire.
Further, the "surface layer portion of the steel wire" indicates a region having a depth of up to 500 μm from the surface (outer peripheral surface) of the steel wire toward the central axis (in the radial direction).
Further, the notation "numerical value XD" is a position at a depth X times the diameter D from the surface of the steel wire toward the central axis (in the radial direction), where D is the diameter of the steel wire. Is shown. For example, "0.25D" indicates a position at a depth of 0.25 times the diameter D.
(1)L断面において、金属組織の95面積%以上がフェライトと球状炭化物から構成される。
(2)前記フェライトは、平均粒径が10.0μm以上であり、前記球状炭化物は、円相当径0.1μm以上の球状炭化物の平均アスペクト比(以下、単に「球状炭化物の平均アスペクト比」と称する場合がある。)が2.5以下で、かつ、L断面において1mm2当たりの個数が1.5×106×[C]~7.0×106×[C]個である([C]は、鋼線に含まれる炭素(C)の含有量(質量%)を表す)。 The steel wire according to the present disclosure is a steel wire having a predetermined component composition and having a metal structure satisfying the following (1) and (2).
(1) In the L cross section, 95 area% or more of the metal structure is composed of ferrite and spherical carbide.
(2) The ferrite has an average particle size of 10.0 μm or more, and the spherical carbide has an average aspect ratio of a spherical carbide having a circular equivalent diameter of 0.1 μm or more (hereinafter, simply referred to as “average aspect ratio of spherical carbide”). The number (which may be referred to) is 2.5 or less, and the number of pieces per 1 mm 2 in the L cross section is 1.5 × 10 6 × [C] to 7.0 × 10 6 × [C] ([[]. C] represents the content (mass%) of carbon (C) contained in the steel wire).
(a)熱間圧延材の組織を、初析フェライト分率が小さいベイナイトを主体とする組織とすること、
(b)熱間圧延後に、総減面率20%以上の伸線加工などで鋼線にひずみを付与すること、
(c)Ac1以下の温度で球状化焼鈍を行うこと、
が重要であることを見出した。 Specifically, in a steel containing 0.85% or more of Cr, in order to achieve both coarse graining of ferrite grains and miniaturization of carbides,
(A) The structure of the hot-rolled material shall be a structure mainly composed of bainite having a small proeutectoid ferrite fraction.
(B) After hot rolling, strain is applied to the steel wire by wire drawing with a total surface reduction rate of 20% or more.
(C) Performing spheroidizing annealing at a temperature of Ac 1 or less,
Found to be important.
以下、本開示に係る鋼線の成分組成及び金属組織について具体的に説明する。 Since the steel wire according to the present disclosure can suppress molding cracks, it contributes to high functionality by complicating the shape of parts and improvement of productivity of mechanical parts, and is extremely useful in industry.
Hereinafter, the composition and metallographic structure of the steel wire according to the present disclosure will be specifically described.
本開示に係る鋼線の成分組成は、質量%で、C:0.10~0.60%、Si:0.01~0.50%、Mn:0.20~1.00%、P:0.030%以下、S:0.050%以下、Cr:0.85~1.50%、Al:0.001~0.080%、N:0.0010~0.0200%、並びに残部:Fe及び不純物元素からなる。
ただし、本開示に係る鋼線はFeの一部に代えて上記以外の元素を含んでもよく、成分組成が、質量%で、例えば、Ti:0~0.050%、B:0~0.0050%、Mo:0~0.50%、Ni:0~1.00%、Cu:0~0.50%、V:0~0.50%、Nb:0~0.050%、Ca:0~0.0050%、Mg:0~0.0050%、及びZr:0~0.0050%の1つ又は2つ以上を満たしてもよい。Ti、B、Mo、Ni、Cu、V、Nb、Ca、Mg、及び、Zrは、任意元素である。つまり、これらの元素は、鋼線に含まれなくてもよい。
以下、鋼線に含まれる各元素量の範囲を限定した理由を説明する。 <Ingredient composition>
The composition of the steel wire according to the present disclosure is, in mass%, C: 0.10 to 0.60%, Si: 0.01 to 0.50%, Mn: 0.20 to 1.00%, P: 0.030% or less, S: 0.050% or less, Cr: 0.85 to 1.50%, Al: 0.001 to 0.080%, N: 0.0010 to 0.0200%, and the balance: It consists of Fe and impurity elements.
However, the steel wire according to the present disclosure may contain an element other than the above instead of a part of Fe, and the component composition is mass%, for example, Ti: 0 to 0.050%, B: 0 to 0. 0050%, Mo: 0 to 0.50%, Ni: 0 to 1.00%, Cu: 0 to 0.50%, V: 0 to 0.50%, Nb: 0 to 0.050%, Ca: One or more of 0 to 0.0050%, Mg: 0 to 0.0050%, and Zr: 0 to 0.0050% may be satisfied. Ti, B, Mo, Ni, Cu, V, Nb, Ca, Mg, and Zr are arbitrary elements. That is, these elements do not have to be contained in the steel wire.
Hereinafter, the reason for limiting the range of the amount of each element contained in the steel wire will be described.
Cは、機械部品としての強度を確保するため含有させる。C量が0.10%未満では機械部品としての必要な強度を確保することが困難である。一方、C量が0.60%を超えると延性、靱性、及び冷間鍛造性が劣化する。そのため、C量は、0.10~0.60%とした。C量を0.15%以上、0.20%以上、または0.25%以上としてもよい。C量を0.55%以下、0.50%以上、または0.40%以下としてもよい。 (C: 0.10 to 0.60%)
C is contained in order to secure the strength as a mechanical part. If the amount of C is less than 0.10%, it is difficult to secure the required strength as a mechanical part. On the other hand, when the amount of C exceeds 0.60%, ductility, toughness, and cold forging property deteriorate. Therefore, the amount of C was set to 0.10 to 0.60%. The amount of C may be 0.15% or more, 0.20% or more, or 0.25% or more. The amount of C may be 0.55% or less, 0.50% or more, or 0.40% or less.
Siは、脱酸元素として機能するとともに、焼入れ性を付与し、焼戻し軟化抵抗を向上させて、機械部品に必要な強度を付与するのに有効な元素である。Si量が0.01%未満ではこれらの効果が不十分である。Si量が0.50%を超えると、機械部品の延性、靱性が劣化するとともに、鋼線の変形抵抗を上昇させて冷間鍛造性を劣化させる。そのため、Si量は、0.01~0.50%とした。Si量を0.03%以上、0.05%以上、または0.10%以上としてもよい。Si量を0.35%以下、0.30%以下、または0.25%以下としてもよい。 (Si: 0.01 to 0.50%)
Si is an element that functions as a deoxidizing element, imparts hardenability, improves temper softening resistance, and imparts the strength required for mechanical parts. If the amount of Si is less than 0.01%, these effects are insufficient. When the amount of Si exceeds 0.50%, the ductility and toughness of the mechanical parts are deteriorated, and the deformation resistance of the steel wire is increased to deteriorate the cold forging property. Therefore, the amount of Si was set to 0.01 to 0.50%. The amount of Si may be 0.03% or more, 0.05% or more, or 0.10% or more. The amount of Si may be 0.35% or less, 0.30% or less, or 0.25% or less.
Mnは、焼入れ性を付与し、機械部品に必要な強度を付与するのに必要な元素である。Mn量が0.20%未満では効果が不十分である。Mn量が1.00%を超えると、機械部品の靱性が劣化するとともに、鋼線の変形抵抗が上昇し冷間鍛造性を劣化させる。そのため、Mn量は、0.20~1.00%とした。Mn量を0.25%以上、0.30%以上、または0.35%以上としてもよい。Mn含有量を0.90%以下、0.85%以下、または0.80%以下としてもよい。 (Mn: 0.20 to 1.00%)
Mn is an element necessary for imparting hardenability and imparting strength required for mechanical parts. If the amount of Mn is less than 0.20%, the effect is insufficient. If the amount of Mn exceeds 1.00%, the toughness of the mechanical parts deteriorates, the deformation resistance of the steel wire increases, and the cold forging property deteriorates. Therefore, the amount of Mn was set to 0.20 to 1.00%. The amount of Mn may be 0.25% or more, 0.30% or more, or 0.35% or more. The Mn content may be 0.90% or less, 0.85% or less, or 0.80% or less.
Pは、不純物として鋼線に含有される。Pは焼入れ焼戻し後の機械部品の結晶粒界に偏析し、靱性を劣化させるため低減させることが望ましい。このため、P量の上限は、0.030%とした。好ましいP量の上限は0.020%である。より好ましいP量の上限は0.015%以下、または0.012%以下である。なお、P量の下限は、0%がよいが(つまり含まないことがよいが)、脱Pコストを低減する観点から、0%超え(又は0.0001%以上もしくは0.005%以上)であることがよい。 (P: 0.030% or less)
P is contained in the steel wire as an impurity. It is desirable to reduce P because it segregates at the grain boundaries of mechanical parts after quenching and tempering and deteriorates toughness. Therefore, the upper limit of the amount of P is 0.030%. The upper limit of the preferable amount of P is 0.020%. The upper limit of the more preferable amount of P is 0.015% or less, or 0.012% or less. The lower limit of the amount of P is preferably 0% (that is, it is preferable not to include it), but it exceeds 0% (or 0.0001% or more or 0.005% or more) from the viewpoint of reducing the de-P cost. There should be.
Sは、MnS等の硫化物として鋼線に含有される。これらの硫化物は鋼線の被削性を向上させる。S量が0.050%を超えると鋼線の冷間鍛造性を劣化させるとともに、焼入れ焼戻し後の機械部品の靱性を劣化させる。このため、S量の上限は0.050%とした。好ましいS量の上限は、0.030%である。より好ましいS量の上限は、0.015%または0.010%である。なお、S量の下限は、0%がよいが(つまり含まないことがよいが)、脱Sコストを低減する観点から、0%超え(又は0.0001%以上もしくは0.005%以上)であることがよい。 (S: 0.050% or less)
S is contained in the steel wire as a sulfide such as MnS. These sulfides improve the machinability of steel wire. When the amount of S exceeds 0.050%, the cold forging property of the steel wire is deteriorated and the toughness of the mechanical parts after quenching and tempering is deteriorated. Therefore, the upper limit of the amount of S is set to 0.050%. The upper limit of the preferable amount of S is 0.030%. A more preferable upper limit of the amount of S is 0.015% or 0.010%. The lower limit of the amount of S is preferably 0% (that is, it is preferable not to include it), but it exceeds 0% (or 0.0001% or more or 0.005% or more) from the viewpoint of reducing the cost of removing S. There should be.
Crは、焼入れ性を向上させて、機械部品に必要な強度を付与するのに必要な元素である。さらに、Crを含有することにより、焼鈍後の炭化物の形状が球状になり、冷間加工性を向上させる。Cr量が0.85%未満では効果が不十分である。Cr量が1.50%を超えると、球状化時間が長時間となり、製造コストを増加させるとともに、鋼線の変形抵抗が上昇し冷間鍛造性を劣化させる。そのため、Cr量は、0.85~1.50%とした。Cr量を0.87%以上、0.90%以上、または0.95%以上としてもよい。Cr量を1.40%以下、1.30%以下、または1.20%以下としてもよい。 (Cr: 0.85 to 1.50%)
Cr is an element required to improve hardenability and impart the required strength to mechanical parts. Further, by containing Cr, the shape of the carbide after annealing becomes spherical, and the cold workability is improved. If the amount of Cr is less than 0.85%, the effect is insufficient. When the amount of Cr exceeds 1.50%, the spheroidizing time becomes long, the manufacturing cost increases, the deformation resistance of the steel wire increases, and the cold forging property deteriorates. Therefore, the amount of Cr was set to 0.85 to 1.50%. The amount of Cr may be 0.87% or more, 0.90% or more, or 0.95% or more. The amount of Cr may be 1.40% or less, 1.30% or less, or 1.20% or less.
Alは、脱酸元素として機能するとともに、AlNを形成してオーステナイト結晶粒を細粒化し、機械部品の靱性を向上させる効果がある。また、Alは、固溶Nを固定して動的ひずみ時効を抑制し、変形抵抗を低減する効果がある。Al量が0.001%未満ではこれらの効果が不十分である。Al量が0.080%を超えると効果が飽和するとともに製造性を低下させることがある。そのため、Al量は0.001~0.080%とした。Al量を0.010%以上、0.020%以上、または0.025%以上としてもよい。Al量を0.060%以下、0.050%以下、または0.040%以下としてもよい。 (Al: 0.001 to 0.080%)
Al has the effect of functioning as a deoxidizing element and forming AlN to refine austenite crystal grains and improve the toughness of mechanical parts. Further, Al has an effect of fixing the solid solution N, suppressing dynamic strain aging, and reducing deformation resistance. If the amount of Al is less than 0.001%, these effects are insufficient. If the amount of Al exceeds 0.080%, the effect may be saturated and the manufacturability may be lowered. Therefore, the amount of Al was set to 0.001 to 0.080%. The amount of Al may be 0.010% or more, 0.020% or more, or 0.025% or more. The amount of Al may be 0.060% or less, 0.050% or less, or 0.040% or less.
Nは、Al、Ti、Nb、V等と窒化物を形成し、オーステナイト結晶粒を細粒化し、機械部品の靱性を向上させる効果がある。N量が0.0010%未満では窒化物の析出量が不足し、効果が得られない。N量が0.0200%を超えると固溶Nによる動的ひずみ時効により鋼線の変形抵抗が高くなり加工性を劣化させる。そのため、N量は、0.0010~0.0200%とした。N量の範囲を0.0020%以上、0.0025%以上、または0.0030%以上としてもよい。N量を0.0080%以下、0.0050%未満、または0.0040%以下としてもよい。 (N: 0.0010 to 0.0200%)
N has the effect of forming a nitride with Al, Ti, Nb, V and the like, making austenite crystal grains finer, and improving the toughness of mechanical parts. If the amount of N is less than 0.0010%, the amount of nitride precipitated is insufficient and no effect can be obtained. When the amount of N exceeds 0.0200%, the deformation resistance of the steel wire becomes high due to the dynamic strain aging due to the solid solution N, and the workability deteriorates. Therefore, the amount of N was set to 0.0010 to 0.0200%. The range of the amount of N may be 0.0020% or more, 0.0025% or more, or 0.0030% or more. The amount of N may be 0.0080% or less, less than 0.0050%, or 0.0040% or less.
Tiは、脱酸元素として機能する。さらにTiには、窒化物や炭化物を形成しオーステナイト結晶粒を細粒化し、機械部品の靱性を向上させる効果、固溶Bの生成を促進し、焼入れ性を高める効果、および、固溶Nを固定して動的ひずみ時効を抑制し、変形抵抗を低減する効果がある。Ti量が0.050%を超えると、これらの効果が飽和するとともに、粗大な酸化物又は窒化物を生成して、機械部品の疲労強度を劣化させることがある。そのため、Ti量は0超~0.050%の範囲で含有させてもよい。Ti量を0.005%以上、または0.010%以上としてもよい。Ti量を0.030%以下、または0.025%以下としてもよい。 (Ti: 0 to 0.050%)
Ti functions as a deoxidizing element. Furthermore, Ti has the effect of forming nitrides and carbides to refine austenite crystal grains to improve the toughness of mechanical parts, the effect of promoting the formation of solid solution B, and the effect of enhancing hardenability, and solid solution N. It has the effect of fixing and suppressing dynamic strain aging and reducing deformation resistance. If the amount of Ti exceeds 0.050%, these effects may be saturated and coarse oxides or nitrides may be generated to deteriorate the fatigue strength of mechanical parts. Therefore, the amount of Ti may be contained in the range of more than 0 to 0.050%. The amount of Ti may be 0.005% or more, or 0.010% or more. The amount of Ti may be 0.030% or less, or 0.025% or less.
Bは、固溶Bとして粒界に偏析して、焼入れ性を向上させて、機械部品に必要な強度を付与する効果がある。一方、B量が0.0050%を超えると、粒界に炭化物を生成して伸線加工性を劣化させることがある。そのため、B量は0超~0.0050%の範囲で含有させてもよい。B量を0.0003%以上、または0.0005%以上としてもよい。B量を0.0030%以下、又は0.0020%以下としてもよい。 (B: 0 to 0.0050%)
B has the effect of segregating into grain boundaries as a solid solution B to improve hardenability and impart the required strength to mechanical parts. On the other hand, if the amount of B exceeds 0.0050%, carbides may be generated at the grain boundaries to deteriorate the wire drawing workability. Therefore, the amount of B may be contained in the range of more than 0 to 0.0050%. The amount of B may be 0.0003% or more, or 0.0005% or more. The amount of B may be 0.0030% or less, or 0.0020% or less.
Moは、焼入れ性を向上させて、機械部品に必要な強度を付与する効果がある。一方、Mo量が0.50%を超えると、合金コストが増加するとともに、鋼線の変形抵抗が上昇し冷間鍛造性を劣化させる。そのため、Mo量は、0超~0.50%の範囲で含有させてもよい。Mo量を0.10%以上、または0.15%以上としてもよい。Mo量を0.40%以下、又は0.30%以下としてもよい。 (Mo: 0 to 0.50%)
Mo has the effect of improving hardenability and imparting the required strength to mechanical parts. On the other hand, when the amount of Mo exceeds 0.50%, the alloy cost increases and the deformation resistance of the steel wire increases, which deteriorates the cold forging property. Therefore, the amount of Mo may be contained in the range of more than 0 to 0.50%. The amount of Mo may be 0.10% or more, or 0.15% or more. The amount of Mo may be 0.40% or less, or 0.30% or less.
Niは、焼入れ性を向上させて、機械部品に必要な強度を付与する効果がある。一方、Ni量が1.00%を超えると合金コストが増加する。そのため、Ni量は0超~1.00%の範囲で含有させてもよい。Ni量を0.02%以上、または0.10%以上としてもよい。Ni量を0.50%以下、又は0.30%以下としてもよい。 (Ni: 0 to 1.00%)
Ni has the effect of improving hardenability and imparting the required strength to mechanical parts. On the other hand, if the amount of Ni exceeds 1.00%, the alloy cost increases. Therefore, the amount of Ni may be contained in the range of more than 0 to 1.00%. The amount of Ni may be 0.02% or more, or 0.10% or more. The amount of Ni may be 0.50% or less, or 0.30% or less.
Cuは、焼入れ性を向上させて、機械部品に必要な強度を付与するとともに耐食性を向上させる効果がある。一方、Cu量が0.50%を超えると合金コストが増加する。そのため、Cu量は0超~0.50%の範囲で含有させてもよい。Cu量を0.02%以上、又は0.10%以上としてもよい。Cu量を0.40%以下、又は0.35%以下としてもよい。 (Cu: 0 to 0.50%)
Cu has the effect of improving hardenability, imparting the necessary strength to mechanical parts, and improving corrosion resistance. On the other hand, if the amount of Cu exceeds 0.50%, the alloy cost increases. Therefore, the amount of Cu may be contained in the range of more than 0 to 0.50%. The amount of Cu may be 0.02% or more, or 0.10% or more. The amount of Cu may be 0.40% or less, or 0.35% or less.
Vは、炭化物VCを析出させて、機械部品の強度を高める効果がある。一方、V量が0.50%を超えて含有すると合金コストが増加する。そのため、V量は0超~0.50%の範囲で含有させてもよい。V量を0.01%以上、又は0.05%以上としてもよい。V量を0.20%以下、又は0.15%以下としてもよい。 (V: 0 to 0.50%)
V has the effect of precipitating carbide VC and increasing the strength of mechanical parts. On the other hand, if the amount of V exceeds 0.50%, the alloy cost increases. Therefore, the amount of V may be contained in the range of more than 0 to 0.50%. The amount of V may be 0.01% or more, or 0.05% or more. The amount of V may be 0.20% or less, or 0.15% or less.
Nbは、炭化物や窒化物を析出させて、機械部品の強度を高める効果、オーステナイト結晶粒を細粒化して靱性を向上させる効果、固溶Nを低減して、変形抵抗を低減する効果等がある。一方、Nb量が0.050%を超えるとこれらの効果が飽和するとともに冷間鍛造性を劣化させることがある。そのため、Nb量は0超~0.050%の範囲で含有させてもよい。Nb量を0.001%以上、又は0.005%以上としてもよい。Nb量を0.030%以下、又は0.020%以下としてもよい。 (Nb: 0 to 0.050%)
Nb has the effect of precipitating carbides and nitrides to increase the strength of mechanical parts, the effect of finely granulating austenite grains to improve toughness, the effect of reducing solid solution N, and the effect of reducing deformation resistance. is there. On the other hand, if the amount of Nb exceeds 0.050%, these effects may be saturated and the cold forging property may be deteriorated. Therefore, the amount of Nb may be contained in the range of more than 0 to 0.050%. The amount of Nb may be 0.001% or more, or 0.005% or more. The amount of Nb may be 0.030% or less, or 0.020% or less.
(Mg:0~0.0050%)
(Zr:0~0.0050%)
Ca、Mg、Zrは、脱酸を目的に用いてもよい。これらの元素は酸化物を微細にして疲労強度を向上させる効果がある。一方、これら元素それぞれの含有量が0.050%を超えると、効果が飽和するとともに、粗大な酸化物を生成し、疲労特性を劣化させることがある。そのため、Ca量、Mg量、及びZr量はそれぞれ0超~0.050%の範囲で含有させてもよい。Ca量、Mg量、及びZr量それぞれを0.0001%以上、0.0005%以上としてもよい。Ca量、Mg量、及びZr量それぞれを0.030%以下、又は0.020%以下としてもよい。 (Ca: 0 to 0.0050%)
(Mg: 0 to 0.0050%)
(Zr: 0 to 0.0050%)
Ca, Mg and Zr may be used for the purpose of deoxidation. These elements have the effect of making oxides finer and improving fatigue strength. On the other hand, if the content of each of these elements exceeds 0.050%, the effect is saturated and coarse oxides are generated, which may deteriorate the fatigue characteristics. Therefore, the Ca amount, the Mg amount, and the Zr amount may each be contained in the range of more than 0 to 0.050%. The amount of Ca, the amount of Mg, and the amount of Zr may be 0.0001% or more and 0.0005% or more, respectively. The amount of Ca, the amount of Mg, and the amount of Zr may be 0.030% or less, or 0.020% or less, respectively.
本開示に係る鋼線の成分組成において、残部はFe及び不純物元素である。
ここで、不純物元素とは、例えば原材料に含まれる成分、または、製造の工程で意図せず混入する成分であって、意図的に含有させたものではない成分を指す。さらに、不純物元素は、意図的に含有させた成分であっても、鋼線の性能に影響を与えない範囲の量で含有する成分も含む。 (Remaining: Fe and impurity elements)
In the composition of the steel wire according to the present disclosure, the balance is Fe and impurity elements.
Here, the impurity element refers to, for example, a component contained in a raw material or a component that is unintentionally mixed in a manufacturing process and is not intentionally contained. Further, the impurity element includes a component contained in an amount within a range that does not affect the performance of the steel wire even if the component is intentionally contained.
次に、本開示に係る鋼線の金属組織の限定理由について述べる。
本開示に係る鋼線では、鋼線の中心軸を含み、かつ、前記中心軸に平行な断面(L断面)において、金属組織の95面積%以上が、フェライトと球状炭化物(球状セメンタイト)で構成される。金属組織中にマルテンサイト組織、ベイナイト組織、パーライト組織などが含まれると、変形抵抗が増大するとともに延性が低下し、冷間鍛造性が劣化するため、これらの組織が含まれないことが好ましい。従って、本開示に係る鋼線では、鋼線の中心軸を含み、かつ、中心軸に平行な断面(L断面)において、金属組織の97面積%以上、98面積%以上、又は99面積%以上が、フェライトと球状炭化物(球状セメンタイト)で構成されてもよい。なお、L断面において金属組織の95面積%以上がフェライトと球状炭化物から構成されるとは、L断面を観察したときに、金属組織の95面積%以上がフェライトと球状炭化物から形成されることを意味する。 <Metal structure>
Next, the reasons for limiting the metal structure of the steel wire according to the present disclosure will be described.
In the steel wire according to the present disclosure, 95 area% or more of the metal structure is composed of ferrite and spherical carbide (spherical cementite) in a cross section (L cross section) parallel to the central axis and including the central axis of the steel wire. Will be done. If the metal structure contains a martensite structure, a bainite structure, a pearlite structure, or the like, the deformation resistance increases, the ductility decreases, and the cold forging property deteriorates. Therefore, it is preferable that these structures are not included. Therefore, in the steel wire according to the present disclosure, in the cross section (L cross section) including the central axis of the steel wire and parallel to the central axis, 97 area% or more, 98 area% or more, or 99 area% or more of the metal structure. However, it may be composed of ferrite and spherical carbide (spherical cementite). The fact that 95 area% or more of the metal structure is composed of ferrite and spherical carbide in the L cross section means that 95 area% or more of the metal structure is formed of ferrite and spherical carbide when the L cross section is observed. means.
-フェライト粒の平均粒径-
フェライト粒の粗粒化は、変形抵抗を低下させ、冷間鍛造の際の金型寿命を向上させる。フェライト粒の平均粒径が10.0μm未満では、変形抵抗の低減効果が小さい。このため、フェライト粒の平均粒径の下限を10.0μmとするとよい。フェライト粒の平均粒径の好ましい下限は11.5μmである。フェライト粒の平均粒径のより好ましい下限は13.0μmである。一方、30.0μmを超えるフェライト粒径を得ようとする場合、焼鈍時間が長くなり製造コストが増加する。このためフェライト粒の平均粒径の上限を30.0μmとした。好ましいフェライト粒の平均粒径の上限は、20.0μmである。 (Ferrite grain)
-Average grain size of ferrite grains-
Coarse-grained ferrite grains reduce deformation resistance and improve die life during cold forging. When the average particle size of the ferrite grains is less than 10.0 μm, the effect of reducing the deformation resistance is small. Therefore, the lower limit of the average particle size of the ferrite grains is preferably 10.0 μm. The preferable lower limit of the average particle size of the ferrite grains is 11.5 μm. A more preferable lower limit of the average particle size of the ferrite grains is 13.0 μm. On the other hand, when trying to obtain a ferrite grain size exceeding 30.0 μm, the annealing time becomes long and the manufacturing cost increases. Therefore, the upper limit of the average particle size of the ferrite grains was set to 30.0 μm. The upper limit of the average particle size of the preferred ferrite grains is 20.0 μm.
フェライト粒の平均粒径は電子線後方散乱回折(EBSD:Electron Back Scattering Diffraction)法により測定できる。具体的には、図1に示すように、鋼線10の中心軸Cを含み中心軸Cに平行な断面(L断面)の表面から250μm深さ部(表層部の深さ方向の中央部位)、0.25D深さ部(鋼線の表面から鋼線の中心に向かう方向に鋼線の直径Dの0.25倍の深さの部分)、0.5D深さ部(鋼線の中心部分)を中心に、深さ方向(径方向)に500μm、中心軸方向に500μmの領域、すなわち、図1においてA1、A2、A3で示されるそれぞれ500μm四方の領域において、測定ステップを1.0μmとして領域内の各測定点でのbcc-Feの結晶方位を測定する。ここで、方位差が15度以上の境界をフェライト粒界と定義する。そして、このフェライト粒界に囲まれた5ピクセル以上の領域をフェライト粒とする。フェライト粒の平均粒径を、混粒が前提となる粒集団の平均粒径の求め方であるJohnson-Saltykovの測定方法(「計量形態学」内田老鶴圃新社、S47.7.30発行、原著:R.T.DeHoff.F.N.Rbiness.P189参照)を用いて得た。これを2つのサンプルについて行い、合計6つの測定領域で測定した平均粒径の平均値をフェライト粒の平均粒径とする。 -Measurement method of ferrite grains-
The average particle size of ferrite grains can be measured by an electron backscattering diffraction (EBSD) method. Specifically, as shown in FIG. 1, a depth portion 250 μm from the surface of a cross section (L cross section) including the central axis C of the
-球状炭化物の平均アスペクト比-
球状炭化物とは、炭化物の長径/短径で表されるアスペクト比が5.0以下のセメンタイトを意味する。球状炭化物のアスペクト比(長径/短径)が大きくなると、ひずみを受けた炭化物の周囲からクラックが発生し割れやすくなる。特に、円相当径0.1μm以上の球状炭化物の平均アスペクト比が2.5を超えると、延性が低下し加工割れが発生しやすくなる。このため、円相当径0.1μm以上の球状炭化物の平均アスペクト比の上限を2.5とした。円相当径0.1μm以上の球状炭化物の平均アスペクト比の好ましい上限は2.0である。円相当径0.1μm以上の球状炭化物の平均アスペクト比のより好ましい上限は1.8である。 (Spherical carbide)
-Average aspect ratio of spherical carbide-
The spherical carbide means cementite having an aspect ratio of 5.0 or less represented by the major axis / minor axis of the carbide. When the aspect ratio (major axis / minor axis) of the spherical carbide becomes large, cracks are generated from around the strained carbide and it becomes easy to crack. In particular, when the average aspect ratio of the spherical carbide having a circle equivalent diameter of 0.1 μm or more exceeds 2.5, the ductility is lowered and processing cracks are likely to occur. Therefore, the upper limit of the average aspect ratio of spherical carbide having a circle equivalent diameter of 0.1 μm or more is set to 2.5. The preferable upper limit of the average aspect ratio of the spherical carbide having a circle equivalent diameter of 0.1 μm or more is 2.0. A more preferable upper limit of the average aspect ratio of the spherical carbide having a circle equivalent diameter of 0.1 μm or more is 1.8.
上述の要件が満たされる限り、球状炭化物の粒径は特に規定されない。ただし、球状炭化物の最大粒径は、成形割れの発生に影響する。最大粒径が小さくなると、ひずみを受けた炭化物の周囲からクラックが発生することを防止し、鋼線の割れを一層効果的に防止することができる。例えば、球状炭化物の最大粒径が3.00μm以下である場合、延性が一層向上し、冷鍛割れを一層防止しやすくなる。このため、球状炭化物の最大粒径の上限を3.00μmとしてもよい。球状炭化物の最大粒径の好ましい上限は2.00μmである。球状炭化物の最大粒径のより好ましい上限は1.50μmである。 -Maximum particle size of spherical carbide-
As long as the above requirements are met, the particle size of the spherical carbide is not particularly specified. However, the maximum particle size of the spherical carbide affects the occurrence of molding cracks. When the maximum particle size is reduced, it is possible to prevent cracks from being generated around the strained carbide, and it is possible to more effectively prevent cracks in the steel wire. For example, when the maximum particle size of the spherical carbide is 3.00 μm or less, the ductility is further improved and it becomes easier to prevent cold forging cracks. Therefore, the upper limit of the maximum particle size of the spherical carbide may be 3.00 μm. The preferable upper limit of the maximum particle size of the spherical carbide is 2.00 μm. A more preferable upper limit of the maximum particle size of the spherical carbide is 1.50 μm.
また、球状炭化物の平均粒径を0.50μm以下にすると、延性が一層向上し、冷鍛割れを一層防止しやすくなる。このため球状炭化物の平均粒径の上限を0.50μmとしてもよい。球状炭化物の平均粒径の好ましい上限は0.40μmである。球状炭化物の平均粒径のより好ましい上限は0.32μmである。 -Average particle size of spherical carbide-
Further, when the average particle size of the spherical carbide is 0.50 μm or less, the ductility is further improved and it becomes easier to prevent cold forging cracks. Therefore, the upper limit of the average particle size of the spherical carbide may be 0.50 μm. The preferable upper limit of the average particle size of the spherical carbide is 0.40 μm. A more preferable upper limit of the average particle size of the spherical carbide is 0.32 μm.
鋼線の中心軸を含み、且つ中心軸に平行な断面(L断面)の1mm2当たりにおいて、円相当径0.1μm以上の球状炭化物(本明細書において「1mm2当たりの球状炭化物」と称する場合がある。)の個数が1.5×106×[C]個未満の場合、冷間鍛造の際に、炭化物の周囲にクラックが発生し、加工割れが発生する場合がある。このため、1mm2当たりの円相当径0.1μm以上の球状炭化物の下限を1.5×106×[C]個とした。ここで、[C]は、質量%で表される鋼線中のC含有量を示す。円相当径0.1μm以上の球状炭化物の1mm2当たりの個数の好ましい下限は、3.0×106×[C]個、又は3.5×106×[C]個である。 -Number density of spherical carbides-
Spherical carbide having a circle equivalent diameter of 0.1 μm or more per 1 mm 2 of a cross section (L cross section) including the central axis of the steel wire and parallel to the central axis (referred to as “spherical carbide per 1 mm 2 ” in the present specification). If there is a.) If the number is less than 1.5 × 10 6 × [C] number of the time of cold forging, there is a crack is generated around carbides, machining cracks occur. For this reason, the lower limit of the circle equivalent diameter 0.1μm or more globular carbides per 1 mm 2 and 1.5 × 10 6 × [C] number. Here, [C] indicates the C content in the steel wire represented by mass%. Circle preferable lower limit of the number of 1 mm 2 per equivalent diameter 0.1μm or more globular carbide, 3.0 × 10 6 × [C ] number, or 3.5 × 10 is a 6 × [C] number.
球状炭化物の最大粒径、球状炭化物の平均粒径、球状炭化物のアスペクト比、球状炭化物の個数密度は走査型電子顕微鏡(SEM)写真を画像解析することにより求められる。 -Measuring method of spherical carbide-
The maximum particle size of the spherical carbide, the average particle size of the spherical carbide, the aspect ratio of the spherical carbide, and the number density of the spherical carbide can be obtained by image analysis of a scanning electron microscope (SEM) photograph.
本開示に係る鋼線の製造方法の一例について説明する。ただし、以下に説明する鋼線の製造方法は、本開示に係る鋼線を限定するものではない。即ち、その製造方法に関わらず、上述の要件を満たす鋼線は、本開示に係る鋼線である。 <Steel wire manufacturing method>
An example of a method for manufacturing a steel wire according to the present disclosure will be described. However, the method for manufacturing a steel wire described below does not limit the steel wire according to the present disclosure. That is, regardless of the manufacturing method, the steel wire satisfying the above requirements is the steel wire according to the present disclosure.
ベイナイトを主体とする線材を、総減面率20~50%で伸線加工する工程と、
伸線加工された線材を、650℃以上Ac1温度(℃)以下で3時間以上保持して冷却することにより焼鈍する工程と、
を備える。この鋼線の製造方法において、
上記本開示に係る鋼線の成分組成を有する鋼片を、950~1150℃に加熱する工程と、
加熱された鋼片を、仕上げ圧延温度850~1000℃で熱間圧延して線材を得る工程と、
熱間圧延後、850~1000℃である線材を、850℃から550℃までの平均冷却速度を30~250℃/sとして、400~500℃未満の温度範囲まで冷却する工程と、
冷却された線材を、400℃~500℃未満の温度範囲内に20秒以上保持する工程(第1保持工程)と、
さらに、第1保持工程を経た線材を、500℃~600℃の温度範囲内に30秒以上保持する工程(第2保持工程)と
によって、ベイナイトを主体とする線材を製造してもよい。以下、各工程について詳細に説明する。 An example of the method for manufacturing a steel wire according to the present disclosure is
The process of drawing a wire mainly composed of bainite with a total surface reduction rate of 20 to 50%,
The process of annealing the wire drawn wire by holding it at 650 ° C or higher and Ac 1 temperature (° C) or lower for 3 hours or longer and cooling it.
To be equipped. In the method of manufacturing this steel wire,
The step of heating the steel piece having the composition of the steel wire according to the present disclosure to 950 to 1150 ° C.
A process of hot-rolling a heated steel piece at a finish rolling temperature of 850 to 1000 ° C. to obtain a wire rod.
After hot rolling, the wire rod at 850 to 1000 ° C. is cooled to a temperature range of less than 400 to 500 ° C. with an average cooling rate of 30 to 250 ° C./s from 850 ° C. to 550 ° C.
A step of holding the cooled wire rod in a temperature range of 400 ° C. to less than 500 ° C. for 20 seconds or more (first holding step) and
Further, a wire rod mainly composed of bainite may be produced by a step of holding the wire rod that has undergone the first holding step within a temperature range of 500 ° C. to 600 ° C. for 30 seconds or longer (second holding step). Hereinafter, each step will be described in detail.
加熱工程では、上記本開示に係る鋼線の成分組成を有する鋼片を、950~1150℃に加熱する。加熱温度が950℃未満では、熱間圧延の際の変形抵抗が増大し圧延コストが嵩む。加熱温度が1150℃を超えると表面の脱炭が顕著となり、最終製品の表面硬さが低下する。 (Heating process)
In the heating step, the steel piece having the component composition of the steel wire according to the present disclosure is heated to 950 to 1150 ° C. If the heating temperature is less than 950 ° C., the deformation resistance during hot rolling increases and the rolling cost increases. When the heating temperature exceeds 1150 ° C., decarburization of the surface becomes remarkable, and the surface hardness of the final product decreases.
熱間圧延工程では、加熱された鋼片を、仕上げ圧延温度850~1000℃で熱間圧延する。仕上げ圧延温度が850℃未満では、フェライト粒が細粒化し、焼鈍工程後にフェライト粒の平均粒径が10.0~30.0μmの組織が得られない。仕上げ圧延温度が1000℃を超えると、第1保持工程における変態完了時間が長くなり、製造コストが増加する。なお、仕上げ圧延温度とは、仕上げ圧延直後の線材の表面温度を指す。 (Hot rolling process)
In the hot rolling step, the heated steel pieces are hot rolled at a finish rolling temperature of 850 to 1000 ° C. If the finish rolling temperature is less than 850 ° C., the ferrite grains become finer and a structure having an average grain size of 10.0 to 30.0 μm cannot be obtained after the annealing step. When the finish rolling temperature exceeds 1000 ° C., the transformation completion time in the first holding step becomes long, and the manufacturing cost increases. The finish rolling temperature refers to the surface temperature of the wire rod immediately after finish rolling.
冷却工程では、熱間圧延後、850~1000℃である線材を、850℃から550℃までを30~250℃/sの平均冷却速度で、400~500℃未満まで冷却する。例えば、熱間圧延後の線材をリング状に巻取って、上記平均冷却速度となるように溶融塩槽に浸漬すればよい。平均冷却速度が30℃/s未満では、焼鈍工程後にフェライトと球状炭化物の面積率の低下や、球状炭化物の個数密度の低下を招き易い。一方、平均冷却速度が250℃/s以上とするには製造コストが嵩む。なお、冷却速度とは、線材の表面冷却速度を指す。850℃から550℃までの平均冷却速度とは、300℃(=850℃-550℃)を、線材の表面温度を850℃から550℃まで低下させるのに要した時間で割って得られる値である。 (Cooling process)
In the cooling step, after hot rolling, the wire rod at 850 to 1000 ° C. is cooled from 850 ° C. to 550 ° C. at an average cooling rate of 30 to 250 ° C./s to less than 400 to 500 ° C. For example, the wire rod after hot rolling may be wound into a ring shape and immersed in a molten salt tank so as to have the above average cooling rate. If the average cooling rate is less than 30 ° C./s, the area ratio of ferrite and spherical carbides tends to decrease after the annealing step, and the number density of spherical carbides tends to decrease. On the other hand, if the average cooling rate is 250 ° C./s or more, the manufacturing cost increases. The cooling rate refers to the surface cooling rate of the wire rod. The average cooling rate from 850 ° C to 550 ° C is the value obtained by dividing 300 ° C (= 850 ° C-550 ° C) by the time required to reduce the surface temperature of the wire from 850 ° C to 550 ° C. is there.
第1保持工程では、冷却された線材を、400℃~500℃未満で20秒以上保持する。保持温度が400℃未満では、焼鈍工程後の強度が高くなり、冷間鍛造性を劣化させる。保持温度が500℃以上では、第1保持工程における変態完了時間が著しく長くなり、第1保持工程、及び第2保持工程後に未変態部分が残存する。未変態部分は、伸線加工工程において断線の原因となるとともに、焼鈍工程後の冷間鍛造性を劣化させる。 (First holding step)
In the first holding step, the cooled wire rod is held at 400 ° C. to less than 500 ° C. for 20 seconds or more. If the holding temperature is less than 400 ° C., the strength after the annealing step becomes high and the cold forging property deteriorates. When the holding temperature is 500 ° C. or higher, the transformation completion time in the first holding step becomes remarkably long, and the untransformed portion remains after the first holding step and the second holding step. The untransformed portion causes disconnection in the wire drawing process and deteriorates the cold forging property after the annealing process.
第2保持工程では、第1保持工程を経た線材を、500℃~600℃に30秒以上保持する。保持温度が500℃未満では線材の強度が高いため、伸線加工工程において断線の原因となる。保持温度が600℃以上では、製造コストが増加する。製造コストの観点から、保持時間の上限は、150秒がよい。第2保持工程は、例えば、溶融塩槽への浸漬により実施する。 (Second holding step)
In the second holding step, the wire rod that has undergone the first holding step is held at 500 ° C. to 600 ° C. for 30 seconds or longer. If the holding temperature is less than 500 ° C., the strength of the wire rod is high, which causes disconnection in the wire drawing process. If the holding temperature is 600 ° C. or higher, the manufacturing cost increases. From the viewpoint of manufacturing cost, the upper limit of the holding time is preferably 150 seconds. The second holding step is carried out, for example, by immersing in a molten salt tank.
(1)表層部における4箇所
当該対象物の表面からの深さが250μmの深さ位置(表層部の深さ方向の中央部位)における、対象物の周方向に90°おきに4箇所を、表層部における測定箇所とする。視野形状は、深さ方向の長さが80μm、周方向の長さが120μmの長方形とし、視野の中心を、上述の測定位置に一致させる。
(2)0.25Dの深さ位置における4箇所
当該対象物の表面からの深さが0.25Dの深さ位置における、対象物の周方向に90°おきに4箇所を、0.25Dの深さ位置における測定箇所とする。視野形状は、深さ方向の長さが80μm、周方向の長さが120μmの長方形とし、視野の中心を、上述の測定位置に一致させる。
(3)中心軸における1箇所
中心軸と重なる部分(表面からの深さが0.5Dの深さ位置)の1箇所を、中心軸における測定箇所とする。視野形状は中心軸を中心とした縦横80μmの正方形とする。 Next, at nine points on the C cross section of the object, a microstructure photograph at a magnification of 1000 times is taken using a scanning electron microscope (SEM). The specific positions of the nine measurement points are as described below. Hereinafter, the diameter of the object is referred to as D.
(1) Four locations on the surface layer At a depth position of 250 μm from the surface of the object (the central portion in the depth direction of the surface layer), four locations at 90 ° intervals in the circumferential direction of the object. It is the measurement point on the surface layer. The visual field shape is a rectangle having a length of 80 μm in the depth direction and a length of 120 μm in the circumferential direction, and the center of the visual field is aligned with the above-mentioned measurement position.
(2) Four locations at a depth of 0.25D At a depth of 0.25D from the surface of the object, four locations at 90 ° intervals in the circumferential direction of the object are 0.25D. The measurement point at the depth position. The visual field shape is a rectangle having a length of 80 μm in the depth direction and a length of 120 μm in the circumferential direction, and the center of the visual field is aligned with the above-mentioned measurement position.
(3) One point on the central axis One point on the central axis that overlaps with the central axis (depth position with a depth of 0.5D from the surface) is defined as the measurement point on the central axis. The visual field shape is a square with a length and width of 80 μm centered on the central axis.
伸線加工工程では、第2保持工程後、室温に冷却された線材を、総減面率20~50%で伸線加工する。伸線加工を行うことで、焼鈍工程の際に炭化物の球状化を促進するとともに、フェライト粒の成長を促進する。伸線加工の際の総減面率が20%未満では、これらの効果が不十分で冷間鍛造性が劣化する。総減面率が50%を超えても効果が飽和するとともに、鋼線径が小さくなり用途が制限される可能性がある。 (Wire drawing process)
In the wire drawing process, after the second holding step, the wire rod cooled to room temperature is drawn with a total surface reduction rate of 20 to 50%. By performing wire drawing, spheroidization of carbides is promoted during the annealing step, and growth of ferrite grains is promoted. If the total surface reduction rate during wire drawing is less than 20%, these effects are insufficient and the cold forging property deteriorates. Even if the total surface reduction rate exceeds 50%, the effect may be saturated and the steel wire diameter may become smaller, which may limit the application.
焼鈍工程では、伸線加工によって得られた鋼線を、650℃以上Ac1温度(℃)以下で3時間以上保持して冷却する。ここで、Ac1=723-10.7×[Mn]+29.1×[Si]+16.9×[Cr]である。焼鈍温度が650℃未満では、フェライト粒の平均粒径が10μm未満となり冷間鍛造性が劣化する。焼鈍温度がAc1を超えると、フェライト粒の平均粒径が10μm未満となり、また、炭化物の個数が減少し、冷間鍛造性が劣化する可能性がある。保持時間が3時間未満では、フェライト粒の平均粒径が10μm未満となり冷間鍛造性が劣化する。 (Annealing process)
In the annealing step, the steel wire obtained by wire drawing is held at 650 ° C. or higher and Ac 1 temperature (° C.) or lower for 3 hours or longer to cool. Here, Ac 1 = 723-10.7 × [Mn] + 29.1 × [Si] + 16.9 × [Cr]. If the annealing temperature is less than 650 ° C., the average particle size of the ferrite grains is less than 10 μm, and the cold forging property deteriorates. When the annealing temperature exceeds Ac 1 , the average particle size of the ferrite grains becomes less than 10 μm, the number of carbides decreases, and the cold forging property may deteriorate. If the holding time is less than 3 hours, the average particle size of the ferrite grains is less than 10 μm, and the cold forging property deteriorates.
表1に示す成分組成を有する鋼種A~Pの鋼片を用いて、後述の表2-1~表4-2に示す条件で、次の通り、鋼線を製造した。なお、表1において「-」で示した部分は、その欄における元素を意図的に添加していないことを意味する。
また、表2-1~表4-2において、下線部分は、本開示において必須とする範囲から外れているか、任意であるものの好ましい範囲から外れていることを意味する。 [Manufacturing of steel wire]
Using steel pieces of steel grades A to P having the component compositions shown in Table 1, steel wires were produced as follows under the conditions shown in Tables 2-1 to 4-2 described later. In addition, the part indicated by "-" in Table 1 means that the element in the column was not intentionally added.
Further, in Tables 2-1 to 4-2, the underlined portions mean that they are out of the range required in the present disclosure, or are optional but out of the preferable range.
まず、鋼片を加熱した後、熱間圧延して、得られた線材をリング状に巻取り、衝風冷却により470℃まで冷却した。その後、得られた線材を2槽の溶融塩槽に浸漬して第1保持、及び第2保持した。その後、室温(25℃)まで冷却した線材を表2-2に示す総減面率で伸線加工し、伸線後に710℃に5時間保持した後、空冷して行った。 The steel wire of test number 31 was manufactured as follows.
First, the steel pieces were heated and then hot-rolled, and the obtained wire rod was wound into a ring shape and cooled to 470 ° C. by impulse cooling. Then, the obtained wire rod was immersed in two molten salt tanks for first holding and second holding. Then, the wire rod cooled to room temperature (25 ° C.) was drawn at the total surface reduction rate shown in Table 2-2, held at 710 ° C. for 5 hours after the wire drawing, and then air-cooled.
まず、鋼片を加熱した後、熱間圧延して、得られた線材をリング状に巻き取り、衝風冷却した。その後、室温(25℃)まで冷却した線材を表2-1及び表2-2に示す総減面率で伸線加工し、伸線後に加熱して焼鈍処理した。なお、試験番号17~28、37~40の鋼線の焼鈍処理は、760℃に5時間保持した後、冷却速度15℃/hで660℃まで冷却し、その後空冷して行った。
これら工程を経て、試験番号17~28、37~40に示す鋼線を製造した。 The steel wires of test numbers 17 to 28 and 37 to 40 shown in Tables 2-1 to 2-4 were manufactured as follows.
First, the steel pieces were heated and then hot-rolled, and the obtained wire rod was wound into a ring shape and cooled by an impulse. Then, the wire rod cooled to room temperature (25 ° C.) was wire-drawn at the total surface reduction rate shown in Table 2-1 and Table 2-2, and after the wire was drawn, it was heated and annealed. The steel wires of test numbers 17 to 28 and 37 to 40 were annealed at 760 ° C. for 5 hours, cooled to 660 ° C. at a cooling rate of 15 ° C./h, and then air-cooled.
Through these steps, the steel wires shown in test numbers 17 to 28 and 37 to 40 were manufactured.
鋼片を加熱した後、熱間圧延して、得られた線材をリング状に巻き取り、衝風冷却した。その後、室温(25℃)まで冷却した線材を850℃に加熱し焼入れし、650℃に加熱し焼戻した。その後、表3-1に示す総減面率で伸線加工し、伸線後に加熱して焼鈍処理した。 The steel wire of test number 29 shown in Table 3-1 and Table 3-2 was manufactured as follows.
After heating the steel pieces, they were hot-rolled, and the obtained wire rod was wound into a ring shape and cooled by an impulse. Then, the wire rod cooled to room temperature (25 ° C.) was heated to 850 ° C. and quenched, and then heated to 650 ° C. and tempered. Then, the wire was drawn at the total surface reduction rate shown in Table 3-1 and then heated and annealed after the wire was drawn.
鋼片を加熱した後、熱間圧延して、得られた線材をリング状に巻き取り、衝風冷却した。その後、室温(25℃)まで冷却した線材を加熱し第1焼鈍処理した。その後、室温(25℃)まで冷却した線材を表4-1に示す総減面率で伸線加工し、伸線後に加熱して第2焼鈍処理した。なお、第1焼鈍処理、及び第2焼鈍処理は、760℃に5時間保持した後、冷却速度15℃/hで660まで冷却し、その後空冷して行った。 The steel wire of test number 30 shown in Table 4-1 and Table 4-2 was manufactured as follows.
After heating the steel pieces, they were hot-rolled, and the obtained wire rod was wound into a ring shape and cooled by an impulse. Then, the wire rod cooled to room temperature (25 ° C.) was heated and subjected to the first annealing treatment. Then, the wire rod cooled to room temperature (25 ° C.) was wire-drawn at the total surface reduction rate shown in Table 4-1 and heated after the wire drawing to be subjected to the second annealing treatment. The first annealing treatment and the second annealing treatment were carried out at 760 ° C. for 5 hours, then cooled to 660 at a cooling rate of 15 ° C./h, and then air-cooled.
これらの鋼線に対して、伸線加工で断線した試験番号13、14以外の鋼線については金属組織の観察を行い、圧縮試験を行った。 [Evaluation]
For these steel wires, the metallographic structure of the steel wires other than the test numbers 13 and 14 that were broken by the wire drawing process was observed, and a compression test was performed.
焼鈍後の鋼線を、減面率8%で伸線加工し、伸線後の鋼線から直径D、高さ1.5Dの円柱状の試験片を作製した。
圧縮試験方法は日本塑性加工学会冷間鍛造分科会基準(塑性と加工,vol.22,No.211,1981,p139)に基づき同心円状に溝がついた金型により端面を拘束して圧縮試験を行った。
変形抵抗は、小坂田の方法(K.Osakada:Ann.CIRP,30-1(1981),p135)による相当ひずみ1.6、圧縮率73.6%で加工した際の相当応力とした。
限界圧縮率は、前記伸線後鋼線から機械加工で作製した直径5.0mm、高さ7.5mmの円柱状試験片の周部軸方向に曲率0.15mm、深さ0.8mm、角度30°の切欠きを有する試験片を用いて、圧縮試験を行った。長さ0.5mm以上の割れが観察されたとき割れ発生と認定し、割れが発生しない最大の圧縮率を限界圧縮率とした。 The deformation resistance and limit compressibility of the steel wire were measured by a compression test.
The annealed steel wire was drawn with a surface reduction rate of 8% to prepare a columnar test piece having a diameter D and a height of 1.5 D from the drawn steel wire.
The compression test method is a compression test in which the end face is constrained by a die with concentric grooves based on the standards of the Cold Forging Subcommittee of the Japan Society for Plasticity Processing (Plasticity and Processing, vol.22, No.211, 1981, p139). Was done.
The deformation resistance was the equivalent stress when processed at an equivalent strain of 1.6 and a compressibility of 73.6% according to Kosakada's method (K. Osakada: Ann. CIRP, 30-1 (1981), p135).
The critical compressibility is a curvature of 0.15 mm, a depth of 0.8 mm, and an angle in the circumferential axial direction of a cylindrical test piece having a diameter of 5.0 mm and a height of 7.5 mm manufactured from the drawn steel wire by machining. A compression test was performed using a test piece having a 30 ° notch. When cracks with a length of 0.5 mm or more were observed, it was determined that cracks had occurred, and the maximum compressibility at which cracks did not occur was defined as the limit compressibility.
通常鋼線17~28、及び37~40は、伸線前の組織がベイナイトを主体とした組織にならないと推定される製造条件のもとで製造されたものである。これら通常鋼線の一部に関して、伸線前の組織(即ち線材の組織)を評価したところ、ベイナイト主体ではなかった(後述する表5参照)。
試験番号13では、伸線中に断線が生じたので、鋼線を製造することができなかった。これは、第1保持工程における保持温度が高すぎたので、伸線前の線材の硬度が過剰になったからであると推定される。
鋼線14では、伸線中に断線が生じたので、鋼線を製造することができなかった。これは、第1保持工程における保持時間が短すぎたので、伸線前の線材の硬度が過剰になったからであると推定される。
試験番号15の鋼線では、フェライト及び球状炭化物の合計面積率が不足し、さらにフェライトの平均粒径が小さすぎたので、変形抵抗及び限界圧縮率が通常鋼線よりも劣った。これは、伸線加工における総減面率が不足したからであると推定される。
試験番号16の鋼線では、円相当径0.1μm以上の球状炭化物の個数が不足し、さらにフェライトの平均粒径が小さすぎたので、変形抵抗及び限界圧縮率が通常鋼線よりも優れたものとはならなかった。これは、伸線加工後の焼鈍における焼鈍温度がAc1点を上回っていたからであると推定される。
試験番号31の鋼線では、フェライト及び球状炭化物の合計面積率が不足し、さらに円相当径0.1μm以上の球状炭化物の個数が不足したので、変形抵抗及び限界圧縮率が通常鋼線よりも優れたものとはならなかった。これは、仕上圧延後の平均冷却速度が不足したからであると推定される。
試験番号32の鋼線では、フェライト及び球状炭化物の合計面積率が不足し、さらにフェライトの平均粒径が小さすぎたので、変形抵抗が通常鋼線に劣り、限界圧縮率が通常鋼線よりも優れたものとはならなかった。これは、第2保持工程を行わなかったからであると推定される。 From the above results, the steel wires of test numbers 1 to 12, 33 to 36, and 41 that satisfy all the requirements specified in the present disclosure are compared with the normal steel wires (test numbers 17 to 28 and 37 to 40) in terms of deformation resistance. Was equivalent or superior. Furthermore, it can be seen that the steel wires of test numbers 1 to 12, 33 to 36, and 41 that satisfy all the requirements specified in the present disclosure are superior in the critical compressibility to the normal steel wire. When the structure before wire drawing (that is, the structure of the wire rod) was evaluated for a part of these steel wires, it had a structure mainly composed of bainite (see Table 5 described later).
The ordinary steel wires 17 to 28 and 37 to 40 are manufactured under manufacturing conditions in which it is presumed that the structure before wire drawing does not become a structure mainly composed of bainite. When the structure before wire drawing (that is, the structure of the wire rod) was evaluated for a part of these ordinary steel wires, it was not mainly bainite (see Table 5 described later).
In test number 13, the steel wire could not be manufactured because the wire was broken during the wire drawing. It is presumed that this is because the holding temperature in the first holding step was too high and the hardness of the wire before wire drawing became excessive.
In the steel wire 14, the steel wire could not be manufactured because the wire was broken during the drawing. It is presumed that this is because the holding time in the first holding step was too short and the hardness of the wire before wire drawing became excessive.
In the steel wire of test number 15, the total area ratio of ferrite and spherical carbide was insufficient, and the average particle size of ferrite was too small, so that the deformation resistance and the critical compressibility were inferior to those of the normal steel wire. It is presumed that this is because the total surface reduction rate in wire drawing was insufficient.
In the steel wire of test number 16, the number of spherical carbides having a diameter equivalent to a circle of 0.1 μm or more was insufficient, and the average grain size of ferrite was too small, so that the deformation resistance and the critical compression ratio were superior to those of the normal steel wire. It didn't become a thing. It is presumed that this is because the annealing temperature in the annealing after the wire drawing process exceeded the Ac1 point.
In the steel wire of test number 31, the total area ratio of ferrite and spherical carbide was insufficient, and the number of spherical carbides with a circular equivalent diameter of 0.1 μm or more was insufficient. Therefore, the deformation resistance and the limit compressibility were higher than those of the normal steel wire. It didn't turn out to be excellent. It is presumed that this is because the average cooling rate after finish rolling was insufficient.
In the steel wire of test number 32, the total area ratio of ferrite and spherical carbide was insufficient, and the average particle size of ferrite was too small. Therefore, the deformation resistance was inferior to that of the normal steel wire, and the critical compression ratio was higher than that of the normal steel wire. It didn't turn out to be excellent. It is presumed that this is because the second holding step was not performed.
一方、伸線加工時に断線が生じた試験番号13及び14の線材では、ベイナイト量が不足し、かつマルテンサイト量が大きかった。
球状炭化物の平均アスペクト比が本開示の上限を超え、かつ球状炭化物の個数密度が本開示の下限未満であった鋼線にかかる、試験番号19の線材では、ベイナイト及びマルテンサイトの両方が含まれなかった。
平均フェライト粒径が本開示の下限未満であった鋼線にかかる、試験番号22及び24の線材では、ベイナイト及びマルテンサイトの両方が含まれていたものの、その量が不足していた。 The wire rods, which are the materials of the steel wires of test numbers 1 to 12, 33 to 36, and 41 that satisfy all the requirements specified in the present disclosure, have a bainite area ratio of 50% or more in the C cross section before wire drawing. Therefore, the area ratio of martensite was 0% or more.
On the other hand, in the wire rods of test numbers 13 and 14 in which the wire was broken during the wire drawing process, the amount of bainite was insufficient and the amount of martensite was large.
The wire rod of Test No. 19 for steel wire in which the average aspect ratio of the spherical carbide exceeds the upper limit of the present disclosure and the number density of the spherical carbide is less than the lower limit of the present disclosure includes both bainite and martensite. There wasn't.
The wire rods of test numbers 22 and 24 on the steel wire having an average ferrite grain size below the lower limit of the present disclosure contained both bainite and martensite, but the amount was insufficient.
C 中心軸
D 鋼線の直径 10 Steel wire C Central axis D Diameter of steel wire
Claims (4)
- 成分組成が、質量%で、
C :0.10~0.60%、
Si:0.01~0.50%、
Mn:0.20~1.00%、
P :0.030%以下、
S :0.050%以下、
Cr:0.85~1.50%、
Al:0.001~0.080%、
N :0.0010~0.0200%、並びに
残部:Fe及び不純物元素であり、
鋼線の中心軸を含み、かつ、前記中心軸に平行な断面において、
金属組織の95面積%以上が、フェライト及び球状炭化物からなり、
前記フェライトは、平均粒径が10.0~30.0μmであり、
前記球状炭化物は、円相当径0.1μm以上の球状炭化物の平均アスペクト比が2.5以下であり、かつ、前記鋼線に含まれるCの含有量(質量%)を[C]で表した場合に、円相当径0.1μm以上の前記球状炭化物の個数が1.5×106×[C]~7.0×106×[C]個/mm2である、鋼線。 Ingredient composition is mass%,
C: 0.10 to 0.60%,
Si: 0.01-0.50%,
Mn: 0.20 to 1.00%,
P: 0.030% or less,
S: 0.050% or less,
Cr: 0.85 to 1.50%,
Al: 0.001 to 0.080%,
N: 0.0010 to 0.0200%, and the balance: Fe and impurity elements.
In a cross section that includes the central axis of the steel wire and is parallel to the central axis.
More than 95 area% of the metallographic structure is composed of ferrite and spherical carbides.
The ferrite has an average particle size of 10.0 to 30.0 μm.
The spherical carbide has an average aspect ratio of 2.5 or less for the spherical carbide having a diameter equivalent to a circle of 0.1 μm or more, and the content (mass%) of C contained in the steel wire is represented by [C]. case, a circle number of equivalent diameter 0.1μm or more of the globular carbides is 1.5 × 10 6 × [C] ~ 7.0 × 10 6 × [C] number / mm 2, the steel wire. - 前記断面において、前記円相当径0.1μm以上の球状炭化物の平均粒径が0.50μm以下であり、かつ、前記球状炭化物の最大粒径が3.00μm以下である、請求項1に記載の鋼線。 The first aspect of claim 1, wherein in the cross section, the average particle size of the spherical carbide having a diameter equivalent to a circle of 0.1 μm or more is 0.50 μm or less, and the maximum particle size of the spherical carbide is 3.00 μm or less. Steel wire.
- 前記成分組成が、質量%で、
Ti:0~0.050%、
B :0~0.0050%、
Mo:0~0.50%、
Ni:0~1.00%、
Cu:0~0.50%、
V :0~0.50%、
Nb:0~0.050%、
Ca:0~0.0050%、
Mg:0~0.0050%、及び
Zr:0~0.0050%、
の1つ又は2つ以上を満たす、請求項1又は請求項2に記載の鋼線。 When the component composition is mass%,
Ti: 0 to 0.050%,
B: 0 to 0.0050%,
Mo: 0 to 0.50%,
Ni: 0 to 1.00%,
Cu: 0 to 0.50%,
V: 0 to 0.50%,
Nb: 0 to 0.050%,
Ca: 0 to 0.0050%,
Mg: 0 to 0.0050%, and Zr: 0 to 0.0050%,
The steel wire according to claim 1 or 2, which satisfies one or more of the above. - 請求項1~3のいずれか一項に記載の鋼線の製造用の熱間圧延線材。 The hot-rolled wire rod for manufacturing the steel wire according to any one of claims 1 to 3.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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KR1020217030894A KR102588222B1 (en) | 2019-05-16 | 2020-05-15 | Steel wire and hot rolled wire rod |
CN202080026373.XA CN113710821B (en) | 2019-05-16 | 2020-05-15 | Steel wire and hot rolled wire rod |
JP2021519499A JP7151885B2 (en) | 2019-05-16 | 2020-05-15 | steel wire |
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KR (1) | KR102588222B1 (en) |
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WO2023190994A1 (en) * | 2022-03-31 | 2023-10-05 | 日本製鉄株式会社 | Wire rod |
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CN114959462B (en) * | 2022-05-08 | 2023-04-18 | 江阴兴澄特种钢铁有限公司 | Steel for new energy automobile motor shaft and manufacturing method thereof |
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JP2001011575A (en) * | 1999-06-30 | 2001-01-16 | Nippon Steel Corp | Bar steel and steel wire for machine structure excellent in cold workability and its production |
JP2013234349A (en) * | 2012-05-08 | 2013-11-21 | Nippon Steel & Sumitomo Metal Corp | Steel wire rod/steel bar having excellent cold-workability, and method for producing the same |
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JPH0426716A (en) * | 1990-05-23 | 1992-01-29 | Nippon Steel Corp | Short-time spheroidization annealing method for steel bar and wire |
JPH0713257B2 (en) * | 1990-05-30 | 1995-02-15 | 新日本製鐵株式会社 | Method for manufacturing soft wire without as-rolled surface abnormal phase |
JP3527641B2 (en) | 1998-08-26 | 2004-05-17 | 株式会社神戸製鋼所 | Steel wire with excellent cold workability |
JP2003183733A (en) | 2001-12-14 | 2003-07-03 | Sumitomo Metal Ind Ltd | Method for manufacturing wire rod |
JP4669317B2 (en) | 2005-05-10 | 2011-04-13 | 新日本製鐵株式会社 | Steel wire excellent in cold forgeability and manufacturing method thereof |
JP5292698B2 (en) * | 2006-03-28 | 2013-09-18 | Jfeスチール株式会社 | Extremely soft high carbon hot-rolled steel sheet and method for producing the same |
JP4952236B2 (en) * | 2006-12-25 | 2012-06-13 | Jfeスチール株式会社 | High carbon hot rolled steel sheet and manufacturing method thereof |
JP5026626B2 (en) * | 2010-03-02 | 2012-09-12 | 新日本製鐵株式会社 | Steel wire excellent in cold forgeability and manufacturing method thereof |
JP5549640B2 (en) * | 2011-05-18 | 2014-07-16 | Jfeスチール株式会社 | High carbon steel sheet and method for producing the same |
CN104040003B (en) * | 2012-01-06 | 2016-05-11 | 杰富意钢铁株式会社 | High-carbon hot-rolled steel sheet and manufacture method thereof |
JP5655986B2 (en) * | 2012-06-08 | 2015-01-21 | 新日鐵住金株式会社 | Steel wire rod or bar |
JP6149927B2 (en) * | 2013-04-10 | 2017-06-21 | 新日鐵住金株式会社 | Rolled round steel for steering rack bar and steering rack bar |
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- 2020-05-15 JP JP2021519499A patent/JP7151885B2/en active Active
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Patent Citations (2)
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JP2001011575A (en) * | 1999-06-30 | 2001-01-16 | Nippon Steel Corp | Bar steel and steel wire for machine structure excellent in cold workability and its production |
JP2013234349A (en) * | 2012-05-08 | 2013-11-21 | Nippon Steel & Sumitomo Metal Corp | Steel wire rod/steel bar having excellent cold-workability, and method for producing the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2023190994A1 (en) * | 2022-03-31 | 2023-10-05 | 日本製鉄株式会社 | Wire rod |
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KR102588222B1 (en) | 2023-10-13 |
JP7151885B2 (en) | 2022-10-12 |
KR20210130212A (en) | 2021-10-29 |
CN113710821B (en) | 2023-06-23 |
CN113710821A (en) | 2021-11-26 |
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