WO2014208492A1 - 高炭素鋼線材及びその製造方法 - Google Patents
高炭素鋼線材及びその製造方法 Download PDFInfo
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
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- C21D6/00—Heat treatment of ferrous alloys
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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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
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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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
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/009—Pearlite
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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
Definitions
- the present invention relates to a steel cord used as a reinforcing material for a radial tire of an automobile, various industrial belts and hoses, and a high carbon steel wire material excellent in wire drawing workability suitable for applications such as a sawing wire and the production thereof. Regarding the method.
- This application claims priority based on Japanese Patent Application No. 2013-131959 filed in Japan on June 24, 2013 and Japanese Patent Application No. 2013-131196 filed in Japan on June 24, 2013. Is hereby incorporated by reference.
- steel cord steel wires used as reinforcing materials for automobile radial tires, various belts and hoses, or steel wires for sawing wires have a diameter of 4 to 4 mm after adjustment and cooling after hot rolling.
- a 6 mm wire is used as the material.
- This wire is formed into a steel wire having a diameter of 3 to 4 mm by primary wire drawing.
- an intermediate patenting treatment is performed on the steel wire, and the diameter of the steel wire is reduced to 1 to 2 mm by secondary wire drawing.
- the steel wire is subjected to a final patenting treatment and then subjected to brass plating.
- the steel wire having a diameter of 0.15 to 0.40 mm is obtained by final wet drawing.
- a steel cord is manufactured by twisting a plurality of high carbon steel wires obtained in this way into a twisted steel wire by twisting.
- Patent Documents 1 to 5 many proposals have been made to improve the wire drawing workability of a wire material that has undergone patenting.
- Patent Document 1 discloses a high carbon wire having a pearlite structure with an area ratio of 95% or more, an average nodule diameter of the pearlite structure of 30 ⁇ m or less, and an average lamella spacing of 100 nm or more.
- Patent Document 4 discloses a high-strength wire material to which B is added.
- the present invention provides a high carbon steel wire rod excellent in wire drawing workability and suitable for use in steel cords, sawing wires, and the like, and a method for producing the same.
- the purpose is to provide.
- the tensile strength and ductility of a high carbon steel wire mainly composed of a pearlite structure depend on the pearlite transformation temperature.
- the pearlite structure is a structure in which cementite and ferrite are arranged in layers, and the lamellar spacing which is the layer spacing greatly affects the tensile strength.
- the lamella spacing of the pearlite structure is determined by the transformation temperature when transforming from austenite to pearlite.
- the ductility of the wire is affected by the particle size of the pearlite block (pearlite block particle size) in the pearlite structure.
- the pearlite block particle size is also affected by the pearlite transformation temperature as well as the lamella spacing. For example, when the pearlite transformation temperature is high, the pearlite block particle size is large and the ductility is low.
- the pearlite transformation temperature when the pearlite transformation temperature is low, the pearlite block is small and the ductility is also improved. That is, when the pearlite transformation temperature is high, the tensile strength and ductility of the wire are low. On the other hand, when the pearlite transformation temperature is lowered, the tensile strength and ductility of the wire are increased. In order to improve the wire drawing workability of the wire, it is effective to reduce the tensile strength of the wire and increase the ductility. However, as described above, it is difficult to achieve both the tensile strength and the ductility of the wire regardless of whether the transformation temperature is high or low.
- a region having a depth of 1 mm or less from the surface of the wire toward the center is defined as a first surface layer portion, and a region having a depth of 30 ⁇ m or less from the surface of the wire toward the center is defined as a second surface layer portion.
- A In order to reduce the disconnection frequency, it is effective to make the structures of the first surface layer part and the second surface layer part mainly composed of a pearlite structure.
- (C) Increasing the lamella spacing in the pearlite structure of the first surface layer is effective in improving the wire drawing workability of the wire. Moreover, in the 1st surface layer part, the frequency of disconnection falls by making the area
- the tensile strength of the wire is 760 ⁇ Ceq. It is effective for improving the wire drawing workability of the wire to be +325 MPa or less.
- (F) It is effective in reducing the frequency of disconnection not to soften the hardness of the first and second surface layer portions of the wire.
- the occurrence frequency of disconnection is increased when the wire rod is subjected to strong processing such that the wire drawing strain exceeds 3.5.
- the Vickers hardness in the second surface layer portion is less than HV280, the frequency of disconnection increases.
- the high carbon steel wire according to one aspect of the present invention has, as chemical components, mass%, C: 0.60% to 1.20%, Si: 0.10% to 1.5%, Mn: 0.10% to 1.0%, P: 0.001% to 0.012%, S: 0.001% to 0.010%, Al: 0.0001% to 0.010%, N: 0.00.
- the area ratio of pearlite is 95% or more, and the balance is bainite, pseudo-pearlite, pro-eutectoid ferrite, A non-pearlite structure containing at least one proeutectoid cementite; the average block particle size of the pearlite is 15 ⁇ m to 35 ⁇ m, and the area ratio of the pearlite having a block particle size of 50 ⁇ m or more is 20% or less; In areas up to 1 mm deep The region where the lamellar spacing in the pearlite is 150 nm or less is 20% or less, and C (%), Si (%) and Mn (%) are respectively contained in unit mass% of C, Si, and Mn, Ceq.
- the chemical component may contain C: 0.70% to 1.10% in mass%, and the high carbon steel wire.
- the area ratio of the pearlite is 90% or more, and the balance may be the non-pearlite structure containing one or more of the bainite, the pseudo pearlite, and the pro-eutectoid ferrite,
- the average value of Vickers hardness may be HV280 to HV330 at a position 30 ⁇ m deep from the surface of the high carbon steel wire.
- the chemical components are mass%, C: 0.60% to 1.20%, Si: 0.1% to 1.5 %, Mn: 0.1% to 1.0%, P: 0.001% to 0.012%, S: 0.001% to 0.010%, Al: 0.0001% to 0.010%, N: A steel slab containing 0.0010% to 0.0050%, the balance being Fe and impurities, heated to 950 ° C.
- the wire is wound up at 700 ° C. to 900 ° C., and the wire is primarily cooled to 630 ° C. to 660 ° C. at a primary cooling rate of 15 ° C./second to 40 ° C./second, and the wire is heated at 660 ° C. to 630 ° C. for 15 seconds to The wire is held for 70 seconds, and the wire is subjected to secondary cooling from 25 ° C. to 300 ° C. at a secondary cooling rate of 5 ° C./second to 30 ° C./second.
- the difference in the primary cooling rate between the maximum cold speed part and the minimum cold speed part in the steel wire ring is 10 It may be not more than ° C / second.
- C 0.60% to 1.20%
- C is an element necessary for increasing the strength of the wire.
- the C content is less than 0.60%, it is difficult to stably impart strength to the final product, and at the same time, precipitation of pro-eutectoid ferrite is promoted at the austenite grain boundaries, and a uniform pearlite structure is formed. It becomes difficult to obtain. Therefore, the lower limit of the C content is set to 0.60%. In order to obtain a more uniform pearlite structure, the C content is preferably 0.70% or more.
- the C content exceeds 1.20%, net-form pro-eutectoid cementite is generated at the austenite grain boundaries and breakage is likely to occur during wire drawing, and the high carbon steel after the final wire drawing is also generated.
- the toughness and ductility of the wire is significantly degraded. Therefore, the upper limit of C content is 1.20%.
- the C content is preferably 1.10% or less.
- Si 0.10% to 1.5%
- Si is an element necessary for increasing the strength of the wire. Furthermore, it is an element that is useful as a deoxidizer, and is also an element that is necessary when targeting a wire that does not contain Al.
- the Si content is less than 0.10%, the deoxidation action is too small. Therefore, the lower limit for the Si content is 0.10%.
- the Si content exceeds 1.5%, precipitation of proeutectoid ferrite is promoted in the hypereutectoid steel. Furthermore, the limit working degree in wire drawing processing is lowered. Further, mechanical descaling, that is, wire drawing by MD becomes difficult. Therefore, the upper limit of Si content is 1.5%.
- Mn 0.10% to 1.0%
- Mn is an element necessary as a deoxidizer. It is also effective in improving the hardenability and increasing the strength of the wire. Furthermore, Mn has an effect of preventing hot embrittlement by fixing S in steel as MnS. If the Mn content is less than 0.10%, it is difficult to obtain the above effect. Therefore, the lower limit of the Mn content is 0.10%.
- Mn is an element that easily segregates. When the Mn content exceeds 1.0%, particularly, Mn is segregated in the central portion of the wire, and martensite and bainite are generated in the segregated portion, so that the wire drawing workability is lowered. Therefore, the upper limit of the Mn content is 1.0%.
- the total amount of the Si content and the Mn content in the wire is preferably 0.61% or more. If the total amount is less than 0.61%, the deoxidation effect and the hot embrittlement prevention effect may not be suitably obtained. Moreover, in order to obtain the effect as a deoxidizer, the total amount of Si content and Mn content is more preferably 0.64% or more, and further preferably 0.67% or more. On the other hand, when the total amount of the Si content and the Mn content exceeds 2.3%, segregation of Mn or Si to the center of the steel wire may become remarkable. Therefore, the total amount of Si content and Mn content is preferably 2.3% or less. In order to make the wire drawing process more suitable, the total amount of the Si content and the Mn content is more preferably 2.0% or less, and even more preferably 1.7% or less.
- P 0.001% to 0.012% P is an element that segregates at the grain boundaries and lowers the toughness of the wire. If the P content exceeds 0.012%, the ductility of the wire material is significantly deteriorated. Therefore, the upper limit of the P content is 0.012%. In addition, the lower limit of the P content is set to 0.001% in consideration of the current refining technology and manufacturing cost.
- S 0.001% to 0.010% S forms Mn and sulfide MnS to prevent hot embrittlement. If the S content exceeds 0.010%, the ductility of the wire material is significantly deteriorated. Therefore, the upper limit of the S content is set to 0.010%. Note that the lower limit of the S content is set to 0.001% in consideration of the current refining technology and manufacturing cost.
- Al 0.0001% to 0.010%
- Al is an element that generates hard non-deformable alumina-based nonmetallic inclusions and degrades the ductility of the wire. Therefore, the upper limit of the Al content is set to 0.010%. Note that the lower limit of the Al content is set to 0.0001% in consideration of the current refining technology and manufacturing cost.
- N 0.0010% to 0.0050%
- N is an element which, as solid solution N, promotes aging during wire drawing and deteriorates wire drawing workability. Therefore, the upper limit of N content is set to 0.0050%. The lower limit of the N content is set to 0.0010% in consideration of the current refining technology and manufacturing cost.
- the total amount of Al content and N content in the wire is preferably 0.007% or less. If the total amount exceeds 0.007%, the ductility of the wire may deteriorate due to the formation of metal inclusions.
- the lower limit of the total amount of Al content and N content is preferably 0.003%.
- the above elements are the basic components of the high carbon steel wire in the present embodiment, and the balance other than the above elements is Fe and impurities.
- this basic component instead of a part of the remaining Fe, in the high carbon steel wire in this embodiment, for the purpose of improving the mechanical properties of the wire such as strength, toughness and ductility, B, Cr, You may contain 1 type, or 2 or more types of elements of Ni, V, Cu, Mo, and Nb within the range mentioned later.
- B 0.0001% to 0.0015%
- the content of 0.0001% or more is preferable.
- the content exceeds 0.0015%, coarse boron carbide such as Fe 23 (CB) 6 is generated, and the wire drawing workability of the wire is deteriorated. Therefore, the upper limit of the B content is preferably 0.0015%.
- Cr 0.10% to 0.50% Cr is an element effective for reducing the lamella spacing of pearlite and improving the strength of the wire and the wire drawing workability.
- the content is preferably 0.10% or more.
- the Cr content exceeds 0.50%, the time until the pearlite transformation is completed becomes long, and a supercooled structure such as martensite or bainite may be generated in the wire. Furthermore, the mechanical descaling property is also deteriorated. Therefore, it is preferable that the upper limit of the Cr content is 0.50%.
- Ni 0.10 to 0.50% Ni does not contribute much to increasing the strength of the wire, but is an element that increases the toughness of the high carbon steel wire. In order to effectively exhibit such an action, the content is preferably 0.10% or more. On the other hand, when Ni is contained in excess of 0.50%, the time until the pearlite transformation is completed becomes long. For this reason, the upper limit of the Ni content is preferably 0.50%.
- V 0.05% to 0.50%
- V forms fine carbonitrides in the ferrite, thereby preventing the austenite grains from coarsening during heating and improving the ductility of the wire. It also contributes to an increase in strength after hot rolling.
- the content is preferably 0.05% or more.
- the upper limit of V content is preferably 0.50%.
- Cu 0.10% to 0.20%
- Cu has the effect of increasing the corrosion resistance of the high carbon steel wire.
- the content is preferably 0.10% or more.
- the upper limit of the Cu content is preferably 0.20%.
- Mo 0.10% to 0.20% Mo has the effect of increasing the corrosion resistance of the high carbon steel wire.
- the content is preferably 0.10% or more.
- the upper limit of the Mo content is 0.20%.
- Nb 0.05% to 0.10%
- Nb has the effect of increasing the corrosion resistance of the high carbon steel wire.
- the content is preferably 0.05% or more.
- the upper limit of Nb content is preferably 0.10%.
- the area ratio of non-pearlite structures such as pro-eutectoid ferrite, bainite, pseudo pearlite, and pro-eutectoid cementite in a cross section perpendicular to the longitudinal direction exceeds 5%. Then, cracks are likely to occur during wire drawing and wire drawing workability deteriorates. For this reason, the area ratio of a pearlite structure shall be 95% or more.
- the non-pearlite area ratio of the high carbon steel wire according to the present embodiment is the average area of the non-pearlite area ratio in each of the first surface layer portion, 1 / 2D portion, and 1 / 4D portion when D is the wire diameter.
- the pearlite area ratio indicates the average area ratio of the pearlite area ratio in each of the first surface layer portion, 1 / 2D portion, and 1 / 4D portion.
- the non-pearlite area ratio by the following method. That is, the C cross section of the high carbon steel wire, that is, the cross section perpendicular to the longitudinal direction is embedded with resin, then polished with alumina, corroded with saturated picral, and SEM observation is performed.
- a range of 1 mm or less from the surface of the wire toward the center is defined as the first surface layer portion.
- the observation areas in SEM observation are the first surface layer part, 1 / 4D part, and 1 / 2D part, where D is the wire diameter.
- the photograph of the area of 50 micrometers x 40 micrometers is taken at 45 places every 45 degrees by 3000 times of magnification.
- non-perlite structure pseudo pearlite part in which cementite is dispersed in granular form, bainite part in which plate-like cementite is dispersed at a coarse lamellar spacing of 3 times or more from the surroundings, and proeutectoid precipitated along old austenite grain boundaries
- the area ratios of the ferrite part and the pro-eutectoid cementite part are measured by image analysis. And the area ratio of each measured non-pearlite structure is totaled, and it is set as a non-pearlite area ratio.
- the area ratio of the pearlite structure is obtained by subtracting the non-pearlite area ratio from 100%.
- the second surface layer portion a region from the surface to the depth of 30 ⁇ m is defined as the second surface layer portion.
- the area ratio of the non-pearlite structure such as pro-eutectoid ferrite, bainite, and pseudo pearlite exceeds 10% in the second surface layer, the strength of the surface layer of the wire becomes non-uniform and cracks occur in the surface of the wire during wire drawing. It tends to occur and wire drawing processability may deteriorate.
- the area ratio of a pearlite structure shall be 90% or more.
- the balance other than the pearlite structure is preferably a non-pearlite structure containing at least one of bainite, pseudo-pearlite, and pro-eutectoid ferrite. More preferably, it is a non-pearlite structure composed of one or more selected from bainite, pseudo pearlite, and pro-eutectoid ferrite.
- the C section of the high carbon steel wire is embedded with resin, then polished with alumina, corroded with saturated picral, and observed with SEM.
- the second surface layer portion is photographed at 8 places at a central angle of 45 ° in the C cross section at a magnification of 2000 times.
- non-perlite structure pseudo pearlite part in which cementite is dispersed in granular form, bainite part in which plate-like cementite is dispersed at a coarse lamellar spacing of 3 times or more from the surroundings, and proeutectoid precipitated along old austenite grain boundaries
- the area ratio of each ferrite part is measured by image analysis.
- tissue is totaled and it is set as a non-pearlite area ratio.
- the area ratio of the pearlite structure is obtained by subtracting the non-pearlite area ratio from 100%.
- the perlite block is almost spherical.
- the pearlite block is a region where the crystal orientation of the ferrite can be regarded as the same, and the ductility of the wire improves as the average block grain size becomes finer.
- the average block particle size exceeds 35 ⁇ m, the ductility of the wire is reduced, and disconnection is likely to occur during wire drawing.
- the average block particle size is less than 15 ⁇ m, the tensile strength increases, and the deformation resistance increases during wire drawing, which increases the processing cost.
- the area ratio of the pearlite block having a block particle size of 50 ⁇ m or more exceeds 20%, the frequency of disconnection increases during wire drawing.
- the block particle diameter is a diameter of a circle having the same area as that occupied by the pearlite block.
- the block particle size of the pearlite block can be obtained by the following method.
- the C cross section of the wire is embedded in resin and then cut and polished.
- an area of 800 ⁇ m ⁇ 800 ⁇ m is analyzed by EBSD at the center of the C cross section.
- An interface having an azimuth difference of 9 ° or more in this region is defined as a pearlite block interface.
- the area surrounded by the interface is analyzed as one pearlite block.
- the average value of the equivalent circle diameters of the pearlite blocks is defined as the average block particle size.
- the area ratio of the region where the lamella spacing of the pearlite structure is 150 nm or less exceeds 20%, disconnection is likely to occur during wire drawing.
- the lamella spacing of the pearlite structure can be determined by the following method. First, the C section of the wire is etched with picral to reveal a pearlite structure. Next, in the first surface layer portion, photographs are taken at a magnification of 10000 times using FE-SEM at 8 positions every 45 ° of the central angle in the C cross section. And in each colony where the directions of the lamella are aligned, the lamella interval in each colony is obtained from the number of lamellas that intersect perpendicularly to the 2 ⁇ m line segment. Thus, the area ratio of the region where the lamella interval is 150 nm or less in the observation visual field is obtained by image analysis.
- the average value of the Vickers hardness at a position of 30 ⁇ m depth from the surface of the wire to the center is less than HV280, the frequency of occurrence of disconnection may increase during wire drawing. Therefore, it is preferable that the lower limit of the surface layer hardness at that position, that is, the Vickers hardness is HV280. On the other hand, if the Vickers hardness exceeds HV330, the wire drawing workability deteriorates due to wear of the die, so the upper limit is preferably set to HV330.
- surface layer hardness ie, Vickers hardness
- micro Vickers hardness meter is measured using a micro Vickers hardness meter at eight points at a central angle of 45 ° at a position of 30 ⁇ m in depth from the surface of the C cross section of the wire toward the center.
- the tensile test for determining the tensile strength of the wire is performed in accordance with JIS Z 2241. Sixteen 9B test pieces are continuously collected from the longitudinal direction of the wire, and the tensile strength is obtained. The tensile strength is evaluated using these average values. The standard deviation of tensile strength is obtained from 16 pieces of tensile strength data.
- the steel slab composed of the above-described chemical components is heated to 950 ° C. to 1130 ° C. and hot-rolled to obtain a wire, and the wire is wound at 700 ° C. to 900 ° C. , First cooling to 630 ° C. to 660 ° C. at a primary cooling rate of 15 ° C./second to 40 ° C./second, and then retaining in the temperature range of 660 ° C. to 630 ° C. for 15 seconds to 70 seconds, then 5 ° C. / Secondary cooling is performed from 25 ° C. to 300 ° C. at a secondary cooling rate of from 2 to 30 ° C./second.
- the high carbon steel wire according to the present embodiment can be manufactured by the above-described method.
- the maximum cooling speed portion in the steel wire ring that is, the primary cooling rate in the region where the primary cooling rate is the fastest and the minimum cooling speed portion, that is, the region where the primary cooling rate is the slowest.
- the difference is desirably 10 ° C./second or less.
- the heating temperature of the steel slab is less than 950 ° C.
- the deformation resistance during hot rolling becomes large and the productivity is hindered.
- the heating temperature exceeds 1130 ° C. the average block particle size of pearlite increases, or the non-pearlite area ratio of the second surface layer portion increases due to decarburization, and wire drawing workability decreases.
- the winding temperature is lower than 700 ° C.
- the scale peelability in mechanical descaling is deteriorated.
- the coiling temperature exceeds 900 ° C.
- the average block particle size of pearlite increases, and the wire drawing workability decreases.
- the primary cooling rate is less than 15 ° C./second, the average block particle size exceeds 35 ⁇ m.
- the primary cooling rate exceeds 40 ° C./second
- temperature control becomes difficult due to supercooling, and the variation in strength increases.
- the staying temperature range exceeds 660 ° C.
- the average block particle size of pearlite increases and the wire drawing workability deteriorates. If it is less than 630 degreeC, the intensity
- the residence time is less than 15 seconds, the region where the lamellar interval is 150 nm or less exceeds 20%.
- the residence time exceeds 70 seconds, the effect obtained by the residence is saturated.
- the secondary cooling rate is less than 5 ° C./second, the scale peeling due to mechanical descaling deteriorates.
- the conditions in the examples are condition examples adopted for confirming the feasibility and effects of the present invention, and the present invention is not limited to these condition examples.
- the present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
- Example 1 The steel billet having the chemical components shown in Table 1 was heated, then hot rolled to form a wire having a diameter of 5.5 mm, wound at a predetermined temperature, and then cooled by a stealmore facility.
- the wire drawing workability is obtained by removing the scale of the wire by pickling, preparing 10 4m long wires with a zinc phosphate coating by bondage treatment, and using a die with an approach angle of 10 degrees. Single-head drawing was performed with a reduction in area per pass of 16% to 20%. And the average value of the true strain of the limit which draws and breaks was calculated
- Example No. 2 shows manufacturing conditions, structure and mechanical properties. “Residence time” in Table 2 represents the residence time in the temperature range of 660 ° C. to 630 ° C.
- Example No. 2, 4, 6, 11, 14, and 16 did not satisfy the claims of the present invention.
- Example No. is an invention example of the same steel type. 1, Example No. 10, Example No. Compared with 13, the example which became a comparative example had a low strain for wire breaking.
- Example No. 4 Example No. In No.
- Example No. 16 the average block particle size of pearlite exceeded the upper limit of the present invention, and the area ratio of the pearlite block having a block particle size of 50 ⁇ m or more exceeded 20%.
- Example No. is an invention example of the same steel type. 3, Example No. Compared to 15, these comparative examples had a lower strain for wire breaking.
- Example No. No. 6 the standard deviation of tensile strength exceeded the preferred range of the present invention.
- Example 2 The steel billet having the chemical components shown in Table 3 was heated, then hot rolled into a wire having a diameter of 5.5 mm, wound at a predetermined temperature, and then cooled by a stealmore facility.
- the wire drawing workability is obtained by removing the scale of the wire by pickling, preparing 10 4m long wires with a zinc phosphate coating by bondage treatment, and using a die with an approach angle of 10 degrees. Single-head wire drawing was performed with a reduction in area per pass of 16% to 20%. And the average value of the true strain of the limit which draws and breaks was calculated
- Table 4 shows the manufacturing conditions, structure and mechanical properties. “Residence time” in Table 4 indicates the residence time in the temperature range of 660 ° C. to 630 ° C.
- the area ratio of the pearlite structure of the second surface layer portion is the area ratio of the pearlite structure in a region from the surface of the wire to the depth of 30 ⁇ m toward the center.
- the Vickers hardness of the second surface layer portion is the Vickers hardness at a position of a depth of 30 ⁇ m from the surface of the wire toward the center.
- Example No. 19, 22, 24, 26, 30, 32 did not satisfy the preferred scope of the present invention.
- Example No. is an invention example of the same steel type. 18, Example No. 21, Example No. 25, Example No. Compared with 12, the example which became a comparative example had the distortion which a wire-drawing disconnection was low.
- Example No. No. 29 the average value of the Vickers hardness of the second surface layer portion was lower than the preferred range of the present invention.
- Example No. 24 is an example in which the standard deviation of tensile strength exceeds the preferred range of the present invention.
- a high-strength, high-carbon steel wire material excellent in wire drawing workability and suitable for uses such as a steel cord and a sawing wire, and a method for producing the same are provided with high yield and low cost under high productivity. be able to. Therefore, the present invention has sufficient industrial applicability in the wire manufacturing industry.
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Abstract
Description
本願は、2013年6月24日に日本に出願された特願2013-131959号及び2013年6月24日に日本に出願された特願2013-131961号に基づき優先権を主張し、その内容をここに援用する。
通常、パーライト組織を主体とする高炭素鋼線材の、引張強さと延性とはパーライト変態温度に依存する。
パーライト組織は、セメンタイトとフェライトとが層状に並んだ組織であり、その層間隔であるラメラ間隔が引張強さに大きく影響する。また、パーライト組織のラメラ間隔は、オーステナイトからパーライトに変態する際の変態温度で決定される。パーライト変態温度が高い場合には、パーライト組織のラメラ間隔が大きく、線材の引張強さが低くなる。一方、パーライト変態温度が低い場合には、パーライト組織のラメラ間隔が小さく、線材の引張強さが高くなる。
また、線材の延性は、パーライト組織におけるパーライトブロックの粒径(パーライトブロック粒径)に影響される。また、このパーライトブロック粒径も、ラメラ間隔と同様にパーライト変態温度に影響される。例えば、パーライト変態温度が高い場合にはパーライトブロック粒径が大きく、延性が低くなる。一方、パーライト変態温度が低い場合にはパーライトブロックが小さく、延性も向上する。
即ち、パーライト変態温度が高い場合は、線材の引張強さ及び延性が低い。一方、パーライト変態温度が低くなると、線材の引張強さ及び延性が高くなる。線材の伸線加工性の向上には、線材の引張強さを低くして、延性を高くすることが有効である。しかしながら、上述の通り、変態温度が高い場合であっても、低い場合であっても、線材の引張強さと延性との両立は困難であった。
以下、線材の表面から中心に向けて深さ1mm以下までの領域を第1表層部とし、線材の表面から中心に向けて深さ30μm以下までの領域を第2表層部とする。
(a)断線頻度を低減するためには、第1表層部及び第2表層部の組織を、パーライト組織を主体とした組織にすることが有効である。第2表層部に初析フェライト組織や疑似パーライト組織、ベイナイト組織などの軟質組織が存在すると、伸線加工の際に変形が集中し亀裂の発生起点となる。したがって、伸線加工性の向上のためには、これらの軟質組織の抑制が有効である。
(b)断線頻度を低減するためには、線材の断面におけるパーライトブロックの平均ブロック粒径を15μm~35μmとすることが有効である。また、ブロック粒径が50μmを超える粗大なパーライトブロックの面積率が20%を超えると、断線する頻度が高くなる。
(c)第1表層部のパーライト組織におけるラメラ間隔を大きくすることが、線材の伸線加工性の向上に有効である。また、第1表層部において、ラメラ間隔が150nm以下の領域を20%以下とすることで、断線する頻度が低下する。
(d)線材の引張強さを760×Ceq.+325MPa以下とすることが、線材の伸線加工性の向上に有効である。
(e)線材の引張強さのバラツキを低下させることが、線材の伸線加工性の向上に有効である。特に、線材の引張強さの標準偏差を20MPa以下とすることで、断線頻度が低下する。
(f)線材の第1及び第2表層部の硬さを軟化させないことが、断線頻度の低減に有効である。脱炭や減炭などで第1及び第2表層部が軟化すると、線材に対して伸線加工歪みが3.5を超えるような強加工を行った際に、断線の発生頻度が高くなる。特に、第2表層部におけるビッカース硬さがHV280未満になると、断線する頻度が高くなる。
(1)本発明の一態様に係る高炭素鋼線材は、化学成分として、質量%で、C:0.60%~1.20%、Si:0.10%~1.5%、Mn:0.10%~1.0%、P:0.001%~0.012%、S:0.001%~0.010%、Al:0.0001%~0.010%、N:0.0010%~0.0050%を含有し、残部がFe及び不純物からなり;長手方向に垂直な断面において、パーライトの面積率が95%以上であり、残部が、ベイナイト、擬似パーライト、初析フェライト、初析セメンタイトの1種以上を含む非パーライト組織であり;前記パーライトの平均ブロック粒径が15μm~35μmであり、ブロック粒径が50μm以上の前記パーライトの面積率が20%以下であり;表面から深さ1mmまでの領域において、前記パーライトにおけるラメラ間隔が150nm以下である領域が20%以下であり、C(%)、Si(%)及びMn(%)をそれぞれ、C、Si、Mnの単位質量%での含有量として、Ceq.を式Aにより求めたとき、前記高炭素鋼線材の引張強さが760×Ceq.+325MPa以下であり、かつ、前記引張強さの標準偏差が20MPa以下である。
Ceq.=C(%)+Si(%)/24+Mn(%)/6・・・式A
(2)上記(1)に記載の高炭素鋼線材では、前記化学成分として、質量%で、C:0.70%~1.10%を含有してもよく、かつ、前記高炭素鋼線材の表面から深さ30μmまでの領域において、前記パーライトの面積率が90%以上であり、残部が、前記ベイナイト、前記擬似パーライト、前記初析フェライトの1種以上を含む前記非パーライト組織でもよく、かつ、前記高炭素鋼線材の表面から深さ30μmの位置において、ビッカース硬さの平均値がHV280~HV330でもよい。
(3)上記(1)または(2)に記載の高炭素鋼線材では、前記化学成分として、質量%で、B:0.0001%~0.0015%、Cr:0.10%~0.50%、Ni:0.10%~0.50%、V:0.05%~0.50%、Cu:0.10%~0.20%、Mo:0.10%~0.20%、Nb:0.05%~0.10%からなる群から選択される1種または2種以上をさらに含有してもよい。
(4)本発明の別の態様に係る高炭素鋼線材の製造方法では、化学成分が、質量%で、C:0.60%~1.20%、Si:0.1%~1.5%、Mn:0.1%~1.0%、P:0.001%~0.012%、S:0.001%~0.010%、Al:0.0001%~0.010%、N:0.0010%~0.0050%を含有し、残部がFe及び不純物からなる鋼片に対して、950℃~1130℃に加熱した後、熱間圧延を行って線材とし、前記線材を700℃~900℃で巻き取り、前記線材を15℃/秒~40℃/秒の1次冷却速度で630℃~660℃まで1次冷却し、前記線材を660℃~630℃で15秒~70秒間滞留させ、前記線材を5℃/秒~30℃/秒の2次冷却速度で25℃~300℃まで2次冷却を行う。
(5)上記(4)に記載の高炭素鋼線材の製造方法では、前記1次冷却において、鋼線リング内の最大冷速部と最小冷速部との前記1次冷却速度の差が10℃/秒以下であってもよい。
Cは、線材の強度を高めるのに必要な元素である。
C含有量が0.60%未満の場合には、強度を安定して最終製品に付与させることが困難であると同時に、オーステナイト粒界に初析フェライトの析出が促進され、均一なパーライト組織を得ることが困難となる。
そのため、C含有量の下限を0.60%とする。より均一なパーライト組織を得るためには、C含有量は0.70%以上が好ましい。
一方、C含有量が1.20%を超えると、オーステナイト粒界にネット状の初析セメンタイトが生成して伸線加工時に断線が発生しやすくなるだけでなく、最終伸線後における高炭素鋼線の靱性・延性が著しく劣化する。
そのため、C含有量の上限を1.20%とする。より確実に線材の靱性・延性の劣化を防ぐためには、C含有量は1.10%以下が好ましい。
Siは、線材の強度を高めるのに必要な元素である。
さらに、脱酸剤として有用な元素であり、Alを含有しない線材を対象とする際にも必要な元素である。
Si含有量が0.10%未満では、脱酸作用が過少である。そのため、Si含有量の下限を0.10%とする。
一方、Si含有量が1.5%を超えると、過共析鋼において、初析フェライトの析出が促進する。さらに、伸線加工での限界加工度が低下する。また、メカニカルデスケーリング、即ちMDによる伸線加工が困難になる。そのため、Si含有量の上限を1.5%とする。
MnもSiと同様、脱酸剤として必要な元素である。
また、焼き入れ性を向上させ、線材の強度を高めるのにも有効である。さらにMnは、鋼中のSをMnSとして固定して熱間脆化を防止する効果を有する。
Mn含有量が0.10%未満では前記の効果が得難い。そのため、Mn含有量の下限を0.10%とする。
一方、Mnは偏析しやすい元素である。Mn含有量が1.0%を超えると、特に、線材の中心部にMnが偏析し、その偏析部にはマルテンサイトやベイナイトが生成するので、伸線加工性が低下する。そのため、Mn含有量の上限を1.0%とする。
その合計量が0.61%未満では、前記脱酸効果、熱間脆化防止効果を好適に得られない場合がある。また、より脱酸剤としての効果を得るためには、Si含有量とMn含有量の合計量は0.64%以上がより好ましく、0.67%以上がさらに好ましい。
一方、Si含有量とMn含有量との合計量が2.3%を超えると、MnやSiの鋼線の中心部への偏析が顕著となる場合がある。そのため、Si含有量とMn含有量との合計量は2.3%以下が好ましい。より伸線加工を好適な状態とするためには、Si含有量とMn含有量との合計量は2.0%以下がより好ましく、1.7%以下がさらに好ましい。
Pは、粒界に偏析して線材の靱性を低下させる元素である。
P含有量が0.012%を超えると、線材の延性が著しく劣化する。そのため、P含有量の上限を0.012%とする。なお、P含有量の下限は、現状の精錬技術と製造コストとを考慮し、0.001%とする。
Sは、Mnと硫化物MnSを形成して熱間脆化を防止する。
S含有量が0.010%を超えると、線材の延性が著しく劣化する。そのため、S含有量の上限を0.010%とした。なお、S含有量の下限は、現状の精錬技術と製造コストとを考慮し、0.001%とする。
Alは、硬質非変形のアルミナ系非金属介在物を生成して、線材の延性を劣化させる元素である。そのため、Al含有量の上限を0.010%とした。なお、Al含有量の下限は、現状の精錬技術と製造コストとを考慮し、0.0001%とする。
Nは、固溶Nとして、伸線中の時効を促進させ、伸線加工性を劣化させる元素である。そのため、N含有量の上限を0.0050%とした。なお、N含有量の下限は、現状の精錬技術と製造コストを考慮し、0.0010%とする。
Bは、固溶状態でオーステナイト中に存在する場合、粒界に濃化してフェライト、擬似パーライト、ベイナイト等の非パーライト析出の生成を抑制し伸線加工性を向上させる。そのため、0.0001%以上の含有が好ましい。一方、0.0015%を超えて含有させると、粗大なFe23(CB)6などのボロン炭化物が生成し、線材の伸線加工性が劣化する。そのため、B含有量の上限を0.0015%とすることが好ましい。
Crは、パーライトのラメラ間隔を微細化し、線材の強度や伸線加工性等を向上させるのに有効な元素である。この様な作用を有効に発揮させるには0.10%以上の含有が好ましい。一方、Cr含有量が0.50%を超えると、パーライト変態が終了するまでの時間が長くなり、線材中にマルテンサイトやベイナイトなどの過冷組織が生じる恐れがある。さらに、メカニカルデスケーリング性も悪くなる。そのため、Cr含有量の上限を0.50%とすることが好ましい。
Niは、線材の強度上昇にはあまり寄与しないが、高炭素鋼線材の靭性を高める元素である。この様な作用を有効に発揮させるには0.10%以上の含有が好ましい。一方、Niを0.50%を超えて含有させるとパーライト変態が終了するまでの時間が長くなる。そのため、Ni含有量の上限を0.50%とすることが好ましい。
Vは、フェライト中に微細な炭窒化物を形成することにより、加熱時のオーステナイト粒の粗大化を防止して、線材の延性を向上させる。また、熱間圧延後の強度上昇にも寄与する。この様な作用を有効に発揮させるには、0.05%以上の含有が好ましい。しかし、Vを0.50%を超えて含有させると、炭窒化物の形成量が多くなり過ぎ、かつ、炭窒化物の粒子径も大きくなる。そのため、V含有量の上限を0.50%とすることが好ましい。
Cuは、高炭素鋼線の耐食性を高める効果がある。この様な作用を有効に発揮させるには0.10%以上の含有が好ましい。しかし、Cuを0.20%を超えて含有させると、Sと反応して粒界中にCuSを偏析して、線材の製造工程において、鋼塊や線材などに疵を発生させる。この様な悪影響を防止するためには、Cu含有量の上限を0.20%とすることが好ましい。
Moは、高炭素鋼線の耐食性を高める効果がある。この様な作用を有効に発揮させるには0.10%以上の含有が好ましい。一方、Moを0.20%を超えて含有させるとパーライト変態が終了するまでの時間が長くなる。そのため、Mo含有量の上限を0.20%とすることが好ましい。
Nbは、高炭素鋼線の耐食性を高める効果がある。この様な作用を有効に発揮させるには0.05%以上の含有が好ましい。一方、Nbを0.10%を超えて含有させるとパーライト変態が終了するまでの時間が長くなる。そのため、Nb含有量の上限を0.10%とすることが好ましい。
本実施形態に係る高炭素鋼線材の非パーライト面積率とは、Dを線径としたとき、第1表層部、1/2D部、1/4D部にそれぞれにおける非パーライトの面積率の平均面積率を示し、パーライト面積率とは、第1表層部、1/2D部、1/4D部にそれぞれにおけるパーライトの面積率の平均面積率を示す。
なお、表層硬さ、即ちビッカース硬さは、マイクロビッカース硬度計を用いて、線材のC断面の表面から中心に向けて深さ30μmの位置において、中心角45°おきに8箇所測定する。
Ceq.=C(%)+Si(%)/24+Mn(%)/6・・・式(1)
引張強さの標準偏差は16本の引張強さのデータより求める。
巻き取り温度が700℃を下回ると、メカニカルデスケーリングでのスケール剥離性が劣化する。また、巻き取り温度が900℃を上回ると、パーライトの平均ブロック粒径が大きくなり、伸線加工性が低下する。
1次冷却速度が15℃/秒を下回ると、平均ブロック粒径が35μmを超える。また、1次冷却速度が40℃/秒を上回ると、過冷却により温度制御が困難になり、強度のバラツキが大きくなる。
滞留する温度域が、660℃を超えるとパーライトの平均ブロック粒径が大きくなり、伸線加工性が劣化する。630℃未満では、線材の強度が高くなり、伸線加工性が劣化する。また、滞留時間が、15秒未満では、ラメラ間隔が150nm以下の領域が20%を超える。滞留時間が70秒を超えると、滞留により得られる効果が飽和する。
2次冷却速度が5℃/秒を下回ると、メカニカルデスケーリングでのスケール剥離が劣化する。また、2次冷却速度が30℃/秒を上回ると、効果が飽和する。
なお、1次冷却における最大冷速部と最小冷速部との1次冷却速度の差が、10℃/秒を超えると、強度が不均一となる場合があり好ましくない。
表1に示す化学成分を有する鋼のビレットを加熱後、熱間圧延により直径5.5mmの線材とし、所定の温度にて巻き取り後、ステルモア設備により冷却を行った。
表3に示す化学成分を有する鋼のビレットを加熱後、熱間圧延により直径5.5mmの線材とし、所定の温度にて巻き取り後、ステルモア設備により冷却を行った。
2:第1表層部
3:1/2D部
4:1/4D部
Claims (5)
- 化学成分として、質量%で、
C:0.60%~1.20%、
Si:0.10%~1.5%、
Mn:0.10%~1.0%、
P:0.001%~0.012%、
S:0.001%~0.010%、
Al:0.0001%~0.010%、
N:0.0010%~0.0050%
を含有し、
残部がFe及び不純物からなり;
長手方向に垂直な断面において、パーライトの面積率が95%以上であり、残部が、ベイナイト、擬似パーライト、初析フェライト、初析セメンタイトの1種以上を含む非パーライト組織であり;
前記パーライトの平均ブロック粒径が15μm~35μmであり、ブロック粒径が50μm以上の前記パーライトの面積率が20%以下であり;
表面から深さ1mmまでの領域において、前記パーライトにおけるラメラ間隔が150nm以下である領域が20%以下であり;
C(%)、Si(%)及びMn(%)をそれぞれ、C、Si、Mnの単位質量%での含有量として、Ceq.を下記式(1)により求めたとき、引張強さが760×Ceq.+325MPa以下であり、かつ、前記引張強さの標準偏差が20MPa以下である;
ことを特徴とする高炭素鋼線材。
Ceq.=C(%)+Si(%)/24+Mn(%)/6・・・式(1) - 前記化学成分として、質量%で、C:0.70%~1.10%を含有し、
かつ、前記高炭素鋼線材の表面から深さ30μmまでの領域において、前記パーライトの面積率が90%以上であり、残部が、前記ベイナイト、前記擬似パーライト、前記初析フェライトの1種以上を含む前記非パーライト組織であり、
かつ、前記高炭素鋼線材の表面から深さ30μmの位置において、ビッカース硬さの平均値がHV280~HV330である
ことを特徴とする請求項1に記載の高炭素鋼線材。 - 前記化学成分として、質量%で、B:0.0001%~0.0015%、Cr:0.10%~0.50%、Ni:0.10%~0.50%、V:0.05%~0.50%、Cu:0.10%~0.20%、Mo:0.10%~0.20%、Nb:0.05%~0.10%からなる群から選択される1種または2種以上をさらに含有することを特徴とする請求項1または請求項2に記載の高炭素線材。
- 化学成分が、質量%で、C:0.60%~1.20%、Si:0.1%~1.5%、Mn:0.1%~1.0%、P:0.001%~0.012%、S:0.001%~0.010%、Al:0.0001%~0.010%、N:0.0010%~0.0050%を含有し、残部がFe及び不純物からなる鋼片に対して、950℃~1130℃に加熱した後、熱間圧延を行って線材とし;
前記線材を700℃~900℃で巻き取り;
前記線材を15℃/秒~40℃/秒の1次冷却速度で630℃~660℃まで1次冷却し;
前記線材を660℃~630℃で15秒~70秒間滞留させ;
前記線材を5℃/秒~30℃/秒の2次冷却速度で25℃~300℃まで2次冷却を行う;
ことを特徴とする高炭素鋼線材の製造方法。 - 前記1次冷却において、鋼線リング内の最大冷速部と最小冷速部との前記1次冷却速度の差が10℃/秒以下であることを特徴とする請求項4に記載の高炭素鋼線材の製造方法。
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