EP3533898A1 - Fil machine et procédé pour le fabriquer - Google Patents
Fil machine et procédé pour le fabriquer Download PDFInfo
- Publication number
- EP3533898A1 EP3533898A1 EP17866036.1A EP17866036A EP3533898A1 EP 3533898 A1 EP3533898 A1 EP 3533898A1 EP 17866036 A EP17866036 A EP 17866036A EP 3533898 A1 EP3533898 A1 EP 3533898A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wire rod
- pro
- eutectoid cementite
- content
- wire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 150
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 claims abstract description 150
- 229910001562 pearlite Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims description 72
- 229910000831 Steel Inorganic materials 0.000 claims description 36
- 239000010959 steel Substances 0.000 claims description 36
- 238000004804 winding Methods 0.000 claims description 34
- 238000005098 hot rolling Methods 0.000 claims description 19
- 229910000859 α-Fe Inorganic materials 0.000 claims description 18
- 229910001563 bainite Inorganic materials 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 3
- 229910001566 austenite Inorganic materials 0.000 description 47
- 238000000034 method Methods 0.000 description 29
- 230000007423 decrease Effects 0.000 description 27
- 230000000694 effects Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 238000005491 wire drawing Methods 0.000 description 21
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 230000003247 decreasing effect Effects 0.000 description 13
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- 230000009466 transformation Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910000677 High-carbon steel Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000734 martensite Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
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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
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/573—Continuous furnaces for strip or wire with cooling
- C21D9/5732—Continuous furnaces for strip or wire with cooling of wires; of rods
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- 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
- C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a wire rod and a manufacturing method thereof.
- High strength steel wires such as steel cords and sawing wires are typically manufactured by wire-drawing a high carbon steel wire rod having a C content of about 0.7% to 0.9%. Since high carbon steel has high strength, wire breaks tend to occur during wire-drawing. When the working strain is increased by wire-drawing, the drawn wire undergoes high-strengthening and decreases in ductility, and thus wire breaks particularly tend to occur. Wire breaks during wire-drawing significantly reduce productivity. Therefore, there is a demand for a high carbon steel wire rod (that is, a high carbon steel wire rod having good drawability) which is less likely to break during wire-drawing.
- steel wires For example, steel cords require high-strengthening for a weight reduction of tires and improvement of fuel economy of automobiles.
- Sawing wires require high-strengthening and a reduction in diameter in order to prevent wire breaks during cutting of a silicon wafer and reduce a cutting margin.
- high carbon steel particularly hyper-eutectoid steel containing C in an amount more than that of eutectoid steel is used.
- the "hot rolled wire rod” means the wire rod as hot-rolled after hot rolling which has not been subjected to a reheating treatment.
- Patent Document 1 discloses that the drawability of a hot rolled wire rod is improved by defining the pearlite lamellar spacing of the hot rolled wire rod.
- Patent Document 1 the influence of pro-eutectoid cementite on drawability is not examined.
- Patent Document 1 a step of setting a cooling rate from winding to a predetermined temperature to 20 °C/s or more and thereafter performing heating is provided, and thus the manufacturing process is complex. Furthermore, there are problems that the load on the cooling capacity after the winding is large and the manufacturing costs increase.
- Patent Document 2 aims at improving the drawability of a hot rolled wire rod by limiting the tensile strength, reduction in area after breaking, nodule diameter, and the like of the hot rolled wire rod.
- Patent Document 1 in Patent Document 2, the influence of pro-eutectoid cementite on the drawability is not examined. If the reduction in area after breaking, nodule diameter, and the like limited in Patent Document 2 are realized in a wire rod having a large C content, a large amount of pro-eutectoid cementite precipitates, and there may be a case that the drawability decreases.
- Patent Document 3 the drawability of a wire rod is improved by refining austenite grains of the wire rod after hot rolling and causing the area fraction, aspect ratio, and the like of pro-eutectoid cementite after cooling to be in predetermined ranges.
- the improvement of drawability and a reduction in manufacturing costs due to a reduction in the load during wire-drawing are expected.
- an object of the present invention is to provide a wire rod which contains C in an amount more than that of eutectoid steel, is obtained without a reheating treatment after hot rolling, and has excellent drawability, and a manufacturing method thereof.
- the present inventors produced high carbon steel hot rolled wire rods (hereinafter, sometimes referred to as "wire rods") in which the metallographic structure and tensile strength were controlled under various manufacturing conditions, using steels having a C content of 0.90% to 1.15%.
- the inventors evaluated the drawability of the wire rods, and examined the influence of the structure and tensile strength of the wire rods on the drawability.
- the inventors obtained findings that the drawability of a wire rod is improved by controlling the tensile strength in a predetermined range depending on the C content and the Cr content, limiting the area fraction and thickness of pro-eutectoid cementite, and furthermore controlling the total length of the pro-eutectoid cementite per unit area.
- drawability refers to a property that can be drawn without wire breaks.
- the drawability of a wire rod is evaluated by true strain at the time of occurrence of breaking during wire-drawing.
- the wire rod according to the aspects is useful as a material of a high strength steel wire such as a steel cord used as a reinforcing material for tires and hoses, and a sawing wire used for cutting a silicon wafer or the like.
- the C is an essential element for securing the strength of a steel wire.
- the lower limit of the C content is set to 0.90%.
- a preferable lower limit of the C content is 0.96%, or 1.00%.
- the upper limit of the C content is set at 1.15%.
- a preferable upper limit of the C content is 1.10% or 1.08%.
- the Si has an effect of increasing the strength of ferrite in pearlite.
- the lower limit of the Si content is set to 0.10%.
- a preferable lower limit of the Si content is 0.15%, or 0.20%.
- the upper limit of the Si content is set to 0.50%.
- a preferable upper limit of the Si content is 0.40%, or 0.35%.
- Mn has an effect of delaying the transformation from austenite to pro-eutectoid cementite and pro-eutectoid ferrite, and is an element useful for obtaining a structure primarily containing pearlite.
- the lower limit of the Mn content is set to 0.10%.
- a preferable lower limit of the Mn content is set to 0.20% or 0.30%.
- Mn has an effect of improving the hardenability of steel.
- the upper limit of the Mn content is set to 0.80%.
- a preferable upper limit of the Mn content is 0.70%, 0.60%, or 0.50%.
- Cr has an effect of increasing the work hardening rate of pearlite in steel. As the work hardening rate of the pearlite increases, higher tensile strength can be obtained in wire-drawing with low strain.
- Cr since Cr has an effect of delaying the transformation from austenite to pro-eutectoid cementite and pro-eutectoid ferrite, Cr is an element useful for obtaining a structure primarily containing pearlite.
- the lower limit of the Cr content is set to 0.10%.
- a preferable lower limit of the Cr content is 0.15% or 0.20%.
- the upper limit of the Cr content is set at 0.50%.
- a preferable upper limit of the Cr content is 0.40% or 0.35%.
- Both Mn and Cr are elements having effects of improving the hardenability of steel and delaying the transformation to pro-eutectoid cementite.
- a non-pearlite structure such as pro-eutectoid cementite, bainite, and martensite
- the lower limit of the total amount of Mn and Cr is preferably 0.40% or 0.45%.
- the upper limit of the total amount of Mn and Cr is preferably 0.60% or 0.55%.
- the wire rod according to this embodiment may further selectively contain one or two or more of Ni, Co, Mo and B described below. In a case where these elements are not contained, the amount of these elements is 0%.
- Ni has an effect of delaying the transformation from austenite to pro-eutectoid cementite and pro-eutectoid ferrite and is thus an element useful for obtaining a structure primarily containing pearlite.
- Ni is also an element having an effect of increasing the toughness of a drawn wire.
- a more preferable lower limit of the Ni content is 0.15% or 0.20%.
- the upper limit of the Ni content is 0.50%.
- a more preferable upper limit of the Ni content is 0.30% or 0.25%.
- Co has an effect of limiting precipitation of pro-eutectoid ferrite in a rolled wire rod.
- Co has an effect of improving the ductility of the drawn wire.
- a more preferable lower limit of the Co content is 0.20%, 0.30%, or 0.40%.
- the upper limit of the Co content is 1.00%.
- a more preferable upper limit of the Co content is 0.90% or 0.80%.
- Mo has an effect of delaying the transformation from austenite to pro-eutectoid cementite and pro-eutectoid ferrite and is an element useful for obtaining a structure primarily containing pearlite.
- a more preferable lower limit of the Mo content is 0.08%.
- the Mo content exceeds 0.20%, the hardenability becomes excessive, and a supercooled structure such as bainite and martensite is generated in a cooling process after hot rolling, or the drawability of the wire rod decreases in some cases. Therefore, it is preferable to set the upper limit of the Mo content to 0.20%.
- a more preferable upper limit of the Mo content is 0.15% or 0.11%.
- B has an effect of being concentrated at grain boundaries and thus limiting precipitation of pro-eutectoid ferrite.
- a more preferable lower limit of the B content is 0.0005%, 0.0007%, 0.0008%, or 0.0009%.
- B when B is excessively contained, B may form carbides such as Fe 23 (CB) 6 in austenite, so that there may be a case where the drawability of the wire rod decreases. Therefore, it is preferable to set the upper limit of the B content to 0.0030%. A more preferable upper limit of the B content is 0.0020%.
- the wire rod according to this embodiment contains the above-described base elements and one or two or more of Ni, Co, Mo, and B as necessary, and the remainder substantially consists of Fe and impurities. There may be a case where P and S are contained in the wire rod according to this embodiment as impurities incorporated during the production of molten steel.
- the upper limit of the P content is set to 0.020%.
- a preferable upper limit of the P content is 0.014%, or 0.010%.
- P may be incorporated as impurities during the production of molten steel in some cases, but there is no need to particularly limit the lower limit thereof, and the lower limit thereof is 0%.
- the lower limit of the P content may be set to 0.003% or 0.005%.
- the upper limit of the S content is set to 0.010%.
- a preferable upper limit of the S content is 0.008%, 0.007%, or 0.005%.
- S may be incorporated as impurities during the production of molten steel in some cases, but there is no need to particularly limit the lower limit thereof, and the lower limit thereof is 0%.
- the lower limit of the S content may be set to 0.001% or 0.003%.
- the wire rod according to this embodiment contains pearlite as the primary structure, and the residual structure contains any one or two or more of pro-eutectoid cementite, intergranular ferrite, and bainite.
- the pro-eutectoid cementite, intergranular ferrite, and bainite as the residual structures may become the propagation path of fracture in some cases, and as the area fraction of the residual structures increases, the drawability of the wire rod decreases in some cases.
- the area fraction of the pearlite is set to 90.0% or more and the area fraction of the pro-eutectoid cementite is set to 1.00% or less.
- a preferable area fraction of the pearlite is 93.0% or more, 95.0% or more, or 97.0% or more.
- a preferable area fraction of the pro-eutectoid cementite is 0.50% or less, or 0.20% or less.
- the area fraction of the pearlite may be 100%.
- the area fraction of the pearlite In order to cause the area fraction of the pearlite to be 100% in the structure observed in the central part within (1/5)R from the center of the cross section of the wire rod, superior cooling capacity is required, and there are a case where the facility cost increases, a case where the drawability decreases due to an increase in the tensile strength of the wire rod, and a case where the cost increases due to secondary work caused by an increase in the load during wire-drawing. Therefore, in the structure observed in the central part within (1/5)R from the center of the cross section of the wire rod, the area fraction of the pearlite may be less than 100%.
- the pro-eutectoid cementite does not reduce the drawability of the wire rod.
- the structure observed in the central part within (1/5)R from the center of the cross section of the wire rod in order to cause the area fraction of the pro-eutectoid cementite to be 0%, excellent cooling capacity is required, and there may be a case where the facility cost increases. Therefore, in the structure observed in the central part within (1/5)R from the center of the cross section of the wire rod, the area fraction of the pro-eutectoid cementite may be more than 0%.
- the pro-eutectoid cementite in the wire rod is a cause of wire breaks during wire-drawing.
- a decrease in the drawability can be limited by appropriately adjusting the relationship with prior austenite grain boundaries. Specifically, by reducing the thickness of the pro-eutectoid cementite and shortening the total length of the pro-eutectoid cementite per unit area, a decrease in the drawability of the wire rod can be limited.
- FIG. 1 is a schematic view showing the state of pro-eutectoid cementite precipitated at a prior austenite grain boundary.
- FIG. 2 is a view showing a method of measuring the thickness and length of pro-eutectoid cementite 10a in FIG. 1.
- FIGS. 3 and 4 are views showing methods of measuring the thickness and length of pro-eutectoid cementite 10b and 10c in FIG. 1 , respectively.
- Pro-eutectoid cementite precipitates in a shape along the prior austenite grain boundary. Specifically, as shown in FIG. 1 , pro-eutectoid cementite 10a to 10d precipitate along a prior austenite grain boundary 20. For each of the pro-eutectoid cementite, the length is defined in a direction along the prior austenite grain boundary, and the thickness is defined in a direction perpendicular to the prior austenite grain boundary.
- the thickness of the pro-eutectoid cementite is measured at three points at intervals at which the length is quartered in the direction along the prior austenite grain boundary, and the average of the measured values is defined as the thickness of the pro-eutectoid cementite.
- the measurement points are different from typical cases, for example, in a case of branch points and end portions, these points are not included in the average. That is, in FIG 2 , the length of the pro-eutectoid cementite 10a is L1, and the thickness of the pro-eutectoid cementite 10a is the average of T1, T2, and T3.
- the sum of the lengths of the branches is defined as the length of the pro-eutectoid cementite. That is, in FIG. 3 , the length of the pro-eutectoid cementite 10b is the sum of OA, OB and OC.
- the thickness of the pro-eutectoid cementite is measured in each of the branches at three points at intervals at which the length is quartered in the direction along the prior austenite grain boundary as described above, and the average of the measured values is defined as the thickness of the pro-eutectoid cementite. That is, in FIG.
- the thickness of the pro-eutectoid cementite 10b is the average of TA1, TA2, TA3, TB1, TB2, TB3, TC1, TC2, and TC3.
- the length of pro-eutectoid cementite having a shape bent along the prior austenite grain boundary is measured along the prior austenite grain boundary. That is, in FIG. 4 , the length of the pro-eutectoid cementite 10c is the sum of O'D and O'E.
- the thickness is divided at the bent part and is measured at three points in each part at intervals at which the length is quartered in the direction along the prior austenite grain boundary, and the average of the measured values is defined as the thickness of the pro-eutectoid cementite. That is, in FIG. 4 , the thickness of the pro-eutectoid cementite 10c is the average of TD1, TD2, TD3, TE1, TE2, and TE3.
- the total length of the pro-eutectoid cementite in FIG. 1 is the sum of the lengths of the pro-eutectoid cementite 10a to 10d.
- the average thickness of the pro-eutectoid cementite is set to 0.25 ⁇ m or less, and the total length of the pro-eutectoid cementite per unit area is set to be less than 40.0 mm/mm 2
- a preferable average thickness of the pro-eutectoid cementite is 0.20 ⁇ m or less.
- a preferable total length of the pro-eutectoid cementite per unit area is 30.0 mm/mm 2 or less, 20.0 mm/mm 2 or less, or 10.0 mm/mm 2 or less.
- the drawability of the wire rod may be further reduced by reducing the degree of occupation of the pro-eutectoid cementite in the prior austenite grain boundary.
- the degree of occupation of the pro-eutectoid cementite in the prior austenite grain boundary is evaluated by the product of the total length of the pro-eutectoid cementite per unit area and the prior austenite grain size as shown on the left side of Formula (A). It is preferable that the left side of Formula (A) is less than 1.2. More preferably, the left side of Formula (A) is less than 1.0. Total length mm / mm 2 of pro-eutectoid cementite per unit area ⁇ prior austenite graine size mm ⁇ 1.2
- the tensile strength (MPa) of the wire rod according to this embodiment is defined by Formula (1) according to the C content (mass%) and Cr content (mass%).
- a preferable constant term of the right side of Formula (1) is +150 (MPa). In other words, it is preferable that the tensile strength of the wire rod satisfies Formula (2).
- a more preferable constant term of the left side of Formula (1) is +80 (MPa), and a more preferable constant term of the right side is +150 (MPa). In other words, it is more preferable that the tensile strength of the wire rod satisfies Formula (3).
- a more preferable constant term of the left side of Formula (1) is +90 (MPa), and a more preferable constant term of the right side is +140 (MPa). In other words, it is more preferable that the tensile strength of the wire rod satisfies Formula (4).
- TS represents the tensile strength of the wire rod
- C content (%) represents the amount of C contained in the wire rod by mass%
- Cr content (%) represents the amount of Cr contained in the wire rod by mass%
- the diameter of the wire rod affects the cooling rate after winding, and accordingly affects the metallographic structure, tensile strength, and the like of the wire rod.
- the diameter of the wire rod exceeds 5.5 mm, the cooling rate at the central part of the wire rod becomes slow, so that there may be a case where pro-eutectoid cementite is generated in a large amount in the wire rod.
- the diameter of the wire rod is less than 3.0 mm, it becomes difficult to manufacture the wire rod, and the production efficiency decreases, so that there may be a case where the cost of the wire rod increases. Therefore, the wire diameter of the wire rod according to this embodiment is set to 3.0 to 5.5 mm.
- the area fraction of pearlite and pro-eutectoid cementite is measured by the following method.
- the wire rod is cut, and the wire rod is embedded in a resin so that a cross section perpendicular to the longitudinal direction of the wire rod can be observed.
- the wire rod embedded in the resin is polished with abrasive paper and alumina abrasive grains, and is further mirror-finished to obtain a sample.
- the observed section of the sample (that is, the cross section of the wire rod) is corroded with a nital solution or a picral solution and then the observed section of the sample is observed with a scanning electron microscope (SEM).
- the nital solution is a mixed solution of nitric acid and ethyl alcohol. Corrosion of the observed section of the sample is performed by a method of immersing the observed section in the nital solution having a concentration of 5% or less and a temperature of about 15°C to 30°C for several seconds to one minute, a method of wiping the observed section with absorbent cotton soaked with the nital solution having the above concentration and temperature, or the like.
- the picral solution is a mixed solution of picric acid and ethyl alcohol.
- Corrosion of the observed section of the sample is performed by a method of immersing the observed section in the picral solution having a concentration of about 5% and a temperature of about 40°C to 60°C for 30 seconds to two minutes. After the corrosion, the observed section of the sample is immediately washed with water thoroughly, and is quickly dried with cold air or hot air.
- a central part (a region within (1/5)R from the center of the wire rod with the radius of the wire rod as R) of the sample is photographed in a plurality of visual fields at a magnification of 2,000-fold or more so that the total observation visual field area is 0.08 mm 2 or more.
- image analysis software such as particle analysis software
- the average thickness and length of the pro-eutectoid cementite are measured using the SEM photographs.
- the average thickness of the pro-eutectoid cementite is obtained by obtaining the thicknesses of all pro-eutectoid cementite in the SEM photographs and calculating the average value thereof.
- the thickness of the pro-eutectoid cementite is obtained by measuring the thickness in a direction perpendicular to a prior austenite grain boundary. In the case of the cementite 10a in FIG. 2 , the thicknesses T1, T2, and T3 are measured, and the average thereof is taken as the thickness of the pro-eutectoid cementite.
- the length (mm) of the pro-eutectoid cementite is measured by drawing a line imaging the prior austenite grain boundary based on the shapes of the pro-eutectoid cementite in the SEM photographs and measuring the length along the line.
- a straight line imaging the prior austenite grain boundary is drawn along the major axis direction thereof and the length L1 is measured along the straight line.
- a line imagining the prior austenite grain boundary is drawn according to the shape, and the length of the pro-eutectoid cementite is measured along the line.
- the lengths of the branches are added.
- the total length (mm/mm 2 ) of the pro-eutectoid cementite per unit area is set to a value obtained by dividing the sum of the lengths of pro-eutectoid cementite in a measurement visual field which is measured, by the area of the visual field.
- the total length (mm/mm 2 ) of the pro-eutectoid cementite per unit area is the sum of the lengths of the pro-eutectoid cementite observed per unit area.
- a region including the pro-eutectoid cementite may be photographed at a higher magnification and the average thickness and length of the pro-eutectoid cementite may be measured.
- the prior austenite grain size is measured using a wire rod which is quenched by water-cooling several rings from the final end of a coil immediately after winding after hot rolling.
- the quenched wire rod is cut, and the wire rod is embedded in a resin so that a cross section thereof can be observed.
- the wire rod embedded in the resin is polished with abrasive paper and alumina, and is further mirror-finished to obtain a sample.
- the observed section of the sample (that is, the cross section of the wire rod) is corroded with an alkaline picric acid solution to reveal prior austenite grain boundaries.
- Corrosion of the observed section of the sample is performed by immersing the observed section of the sample in the alkaline picric acid solution having a temperature of about 75°C to 90°C for 10 to 20 minutes. After the corrosion, the observed section of the sample is immediately washed with water thoroughly, and is quickly dried with cold air or hot air.
- the alkaline picric acid solution used for the corrosion of the observed section is a mixed solution of 2 parts of picric acid, 5 parts of sodium hydroxide, and 100 parts of water by weight.
- a central part (a region within (1/5)R from the center of the wire rod with the radius of the wire rod as R) of the observed section of the sample is photographed in a plurality of visual fields at a magnification of 400-fold or more so that the total observation visual field area is 0.15 mm 2 or more.
- prior austenite grain sizes are measured.
- ten or more straight lines with a length of 400 ⁇ m are drawn at intervals of 100 ⁇ m so as not to overlap each other, and the grain sizes are evaluated by the number of grains trapped by straight lines of 4 mm or more in total.
- the tensile strength of the wire rod is measured by the following method.
- three or more samples are taken from a front part, a middle part, and a tail part of the wire rod coil. Using the taken samples, a tension test is conducted according to JIS Z 2241: 2011. The tensile strength of the wire rod is obtained by calculating the average value of the tensile strengths of all the samples.
- the manufacturing method described below is merely an example, and is not limited by the following procedures and methods, and any method can be adopted as long as the method can realize the configuration of the wire rod according to this embodiment.
- Materials to be subjected to hot rolling can be obtained under typical manufacturing conditions.
- steel having the above-mentioned elements is cast, and the cast piece is subjected to a soaking treatment (a heat treatment for reducing segregation occurring in casting) to be retained at about 1100°C to 1200°C for 10 to 20 hours, and the cast piece is subjected to blooming, thereby obtaining a steel piece having a suitable size for hot rolling (a steel piece before hot rolling generally called a billet).
- a soaking treatment a heat treatment for reducing segregation occurring in casting
- hot rolling is performed under the following conditions.
- the steel piece is heated to 900°C to 1200°C and the start temperature of finish rolling is controlled to 750°C to 950°C.
- the temperature of the wire rod during the hot rolling indicates the surface temperature of the wire rod.
- the temperature of the wire rod during the hot rolling can be measured using a radiation thermometer.
- the temperature of the wire rod after the finish rolling is higher than the start temperature of the finish rolling due to deformation heating.
- the winding temperature is controlled to 800°C to 940°C.
- austenite grain sizes of the wire rod are refined, so that there are a case where pro-eutectoid cementite, intergranular ferrite, and bainite tend to precipitate, and a case where the mechanical descaling properties of the wire rod decrease.
- the winding temperature exceeds 940°C, the austenite grain sizes of the wire rod become excessively large, so that there may be a case where the drawability of the wire rod decreases.
- a preferable winding temperature is 830°C to 920°C.
- a more preferable winding temperature is 850°C to 900°C.
- the prior austenite grain size of the wire rod is caused to be 15 to 60 ⁇ m by controlling the start temperature of the finish rolling and the winding temperature as described above.
- a more preferable prior austenite grain size is 20 to 45 ⁇ m.
- the cooling rate after the winding is an important factor for controlling the structure and tensile strength of the wire rod.
- the cooling after the winding is divided into three temperature ranges and the average cooling rate in each of the temperature ranges is controlled.
- the average cooling rate to 650°C after the winding is less than 6.0 °C/s, there may be a case where it is difficult to limit the precipitation of pro-eutectoid cementite.
- the average cooling rate to 650°C after the winding exceeds 15.0 °C/s, there may be a case where transformation from austenite to bainite, a decrease in drawability due to high-strengthening, and a decrease in the mechanical descaling properties of the wire rod are incurred.
- the average cooling rate to 650°C after the winding exceeds 15.0 °C/s, large-scale cooling facilities are necessary, so that there may be a case where the facility cost increases. Therefore, after the winding, the average cooling rate to 650°C is set to 6.0 to 15.0 °C/s. After the winding, a preferable average cooling rate to 650°C is 7.0 to 10.0°C/s.
- the average cooling rate is controlled to 1.0 to 3.0 °C/s in order to transform austenite in the wire rod into pearlite.
- the average cooling rate at 650°C to 600°C is less than 1.0 °C/s, there may be a case where the drawability of the wire rod decrease due to a decrease in the tensile strength of the wire rod or an increase in the thickness of the pro-eutectoid cementite.
- a preferable average cooling rate at 650°C to 600°C is 1.5 to 2.8 °C/s.
- the average cooling rate is set to 10.0 °C/s or more for cooling to 300°C or less. This is because the tensile strength of the wire rod decreases in some cases when the wire rod is retained at a temperature near the transformation temperature even after the transformation from austenite to pearlite.
- a preferable average cooling rate at 600°C to 300°C is 15.0°C/s or more. When the average cooling rate at 600°C to 300°C is set to be higher than 50 °C/s, excellent cooling facilities are necessary, resulting in an increase in facility costs. Therefore, the upper limit of the average cooling rate at 600°C to 300°C may be set to 50°C/s or less.
- the temperature of the wire rod during the cooling may be measured with the radiation thermometer.
- cooling of the wire rod after hot rolling is performed after winding in a coil form.
- the wire rod wound in a coil form has a dense part where there are many overlaps of the wire rod and a sparse part where there are few overlaps of the wire rod.
- the temperature of the wire rod after being wound is measured at a part of the wire rod wound in a coil form, where there are many overlaps of the wire rod (dense part).
- the structure and tensile strength of the wire rod can be within the ranges of the present invention.
- Table 1 shows the chemical compositions of steels and manufacturing conditions.
- Table 2 shows the evaluation results of the structures of wire rods and the evaluation results of tensile properties and drawability. Cooling rates 1 to 3 in Table 1 are as follows. The average cooling rate was controlled by adjusting the air volume of a blast. In Tables 1 and 2, numerical values outside the ranges of the present invention are underlined.
- Nos. A1 to A22 in Table 1 are examples of the present invention.
- Nos. B1 to B13 in Table 1 are comparative examples in which one or more of the compositions and the manufacturing conditions were outside appropriate ranges.
- a billet was heated to 1000°C to 1200°C in a heating furnace, and thereafter the start temperature of finish rolling was set to 750°C to 950°C.
- the temperature of a wire rod increased by deformation heating was controlled and wound into a coil form at a winding temperature shown in Table 1. Cooling after the winding was performed at an average cooling rate to 650°C after the winding (cooling rate 1 in Table 1), an average cooling rate from 650°C to 600°C (cooling rate 2 in Table 1), and an average cooling rate from 600°C to 300°C (cooling rate 3 in Table 1) under conditions shown in Table 1.
- a wire rod having the wire diameter shown in Table 1 was obtained.
- the area fraction of the pearlite and the area fraction of the pro-eutectoid cementite of the wire rod were measured by the following method.
- the wire rod was cut, and the wire rod was embedded in a resin so that a cross section perpendicular to the longitudinal direction could be observed.
- the wire rod embedded in the resin was polished with abrasive paper and alumina abrasive grains, and was further mirror-finished to obtain a sample.
- the observed section of the sample (that is, the cross section of the wire rod) was corroded with a nital solution or a picral solution and then the observed section of the sample was observed with a scanning electron microscope (SEM).
- the nital solution used was a mixed solution of nitric acid and ethyl alcohol.
- Corrosion of the observed section of the sample was performed by a method of immersing the observed section in the nital solution having a concentration of 5% or less and a temperature of about 15°C to 30°C for several seconds to one minute, a method of wiping the observed section with absorbent cotton soaked with the nital solution having the above concentration and temperature, or the like.
- the picral solution used was a mixed solution of picric acid and ethyl alcohol.
- Corrosion of the observed section of the sample was performed by a method of immersing the observed section in the picral solution having a concentration of about 5% and a temperature of about 40°C to 60°C for 30 seconds to two minutes. After the corrosion, the observed section of the sample was immediately washed with water thoroughly, and was quickly dried with cold air or hot air.
- a central part (a region within (1/5)R from the center of the wire rod with the radius of the wire rod as R) of the sample was photographed in a plurality of visual fields at a magnification of 2,000-fold or more so that the total observation visual field area was 0.08 mm 2 or more.
- image analysis software such as particle analysis software
- the area fraction of the pearlite and pro-eutectoid cementite of the central part of the wire rod was obtained.
- Luzex registered trademark, manufactured by NIRECO CORPORATION.
- the metallographic structure observed in the central part was a composite structure of one or two or more of pearlite, pro-eutectoid cementite, intergranular ferrite, and bainite.
- the average thickness and length of the pro-eutectoid cementite were measured using the SEM photographs.
- the average thickness of the pro-eutectoid cementite was obtained by measuring the thicknesses of all pro-eutectoid cementite in the SEM photographs and calculating the average value thereof.
- the thickness of the pro-eutectoid cementite was obtained by measuring the thickness in a direction perpendicular to a prior austenite grain boundary. In a case of cementite having the same shape as the cementite 10a in FIG. 2 , the thicknesses T1, T2, and T3 were measured, and the average thereof was taken as the thickness of the pro-eutectoid cementite.
- the length of the pro-eutectoid cementite was measured by drawing a line imaging the prior austenite grain boundary based on the shapes of the pro-eutectoid cementite in the SEM photographs and measuring the length along the line.
- a straight line imaging the prior austenite grain boundary was drawn along the major axis direction thereof and the length L1 was measured along the straight line.
- the total length (mm/mm 2 ) of the pro-eutectoid cementite per unit area was the sum of the lengths of the pro-eutectoid cementite observed per unit area.
- a region including the pro-eutectoid cementite was photographed at a magnification of 3,000 to 5,000-fold and the average thickness and length of the pro-eutectoid cementite were measured.
- the prior austenite grain size was measured using a wire rod which was quenched by water-cooling several rings from the final end of a coil immediately after winding after hot rolling.
- the quenched wire rod was cut, was embedded in a resin so as to observe a cross section thereof, and thereafter polished with alumina to obtain a sample. Thereafter, the polished sample was corroded with an alkaline picric acid solution to reveal prior austenite grain boundaries. Corrosion of the observed section of the sample was performed by immersing the observed section of the sample in the alkaline picric acid solution having a temperature of about 75°C to 90°C for 10 to 20 minutes. After the corrosion, the observed section of the sample was immediately washed with water thoroughly, and was quickly dried with cold air or hot air.
- the alkaline picric acid solution used for the corrosion of the observed section was a mixed solution of 2 parts of picric acid, 5 parts of sodium hydroxide, and 100 parts of water by weight.
- the observed section of the sample was corroded by immersing the observed section of the sample in the alkaline picric acid solution having a temperature of about 75°C to 90°C for 10 to 20 minutes. After the corrosion, the observed section of the sample was immediately washed with water thoroughly, and was quickly dried with cold air or hot air. Thereafter, using an optical microscope, a central part (a region within (1/5)R from the center of the wire rod with the radius of the wire rod as R) of the observed section of the sample was photographed in a plurality of visual fields at a magnification of 400-fold or more so that the total observation visual field area was 0.18 mm 2 or more. Using the SEM photographs and the cutting method described in JIS G 0551: 2013, prior austenite grain sizes were measured. In the cutting method, 15 or more straight lines with a length of 400 ⁇ m were drawn at intervals of 100 ⁇ m so as not to overlap each other, and the grain sizes were evaluated by the number of grains trapped by straight lines of 6 mm or more in total.
- the tensile strength was measured by the following method.
- three rings were taken from each of a front part (a place closer to the tail end side than the front end side by 50 rings), a middle part (within 100 rings from the middle between the front end and the tail end in the coil), and a tail part (a place closer to the front end side than the tail end by 50 rings), and eight samples were taken from each ring at equal intervals, so that a total of 72 samples were taken.
- a tension test was conducted according to JIS Z 2241: 2011.
- the tensile strength of the wire rod was obtained by calculating the average value of the tensile strengths obtained from the 72 samples.
- the tension test was conducted with a sample length of 400 mm, a crosshead speed of 10 mm/min, and a chuck distance of 200 mm.
- the drawability of the wire rod was evaluated by the following method. Ten rings were taken from the wire rod, were pickled to remove scale, and were subjected to a lime coating treatment. Thereafter, wire-drawing (dry wire-drawing) was performed thereon without a patenting treatment. The reduction of area per one pass during the wire-drawing was set to 17% to 23%. A case where wire-drawing was performed and the true strain at the time of a wire break was 2.9 or more was determined as passed due to excellent drawability. On the other hand, a case where wire-drawing was performed and the true strain at the time of a wire break was less than 2.9 was determined as failed due to poor drawability. The true strain was obtained by calculating -2 ⁇ In (diameter of drawn wire / diameter of wire rod). Here, "In" is the natural logarithm.
- All of Nos. A1 to A22 are examples of the present invention, and showed excellent drawability that enables wire-drawing with a true strain of 2.9 or more without a patenting treatment.
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JPS583929A (ja) * | 1981-07-01 | 1983-01-10 | Daido Steel Co Ltd | 鋼線材の製造方法 |
JP2926195B2 (ja) * | 1991-02-06 | 1999-07-28 | 新日本製鐵株式会社 | 伸線加工性に優れた高炭素鋼線の製造方法 |
JP2544867B2 (ja) * | 1992-04-21 | 1996-10-16 | 新日本製鐵株式会社 | 過共析鋼線材の製造方法 |
JPH06228642A (ja) * | 1993-02-01 | 1994-08-16 | Nippon Steel Corp | 過共析鋼線材の製造方法 |
JP3487957B2 (ja) * | 1995-04-24 | 2004-01-19 | 新日本製鐵株式会社 | 伸線加工性の優れた線材 |
JP2001164337A (ja) * | 1999-12-09 | 2001-06-19 | Nippon Steel Corp | 遅れ破壊特性の優れた高張力鋼材及びその製造方法 |
JP2001181789A (ja) | 1999-12-22 | 2001-07-03 | Nippon Steel Corp | 伸線加工性に優れた細径高炭素鋼熱間圧延線材 |
JP4003450B2 (ja) * | 2001-12-13 | 2007-11-07 | 住友金属工業株式会社 | 鋼線材、鋼線及びその製造方法 |
JP3997867B2 (ja) * | 2002-09-04 | 2007-10-24 | 住友金属工業株式会社 | 鋼線材とその製造法及び当該鋼線材を用いる鋼線の製造法 |
JP4088220B2 (ja) * | 2002-09-26 | 2008-05-21 | 株式会社神戸製鋼所 | 伸線前の熱処理が省略可能な伸線加工性に優れた熱間圧延線材 |
JP2005206853A (ja) * | 2004-01-20 | 2005-08-04 | Kobe Steel Ltd | 伸線加工性に優れた高炭素鋼線材およびその製造方法 |
US8142577B2 (en) * | 2005-06-29 | 2012-03-27 | Nippon Steel Corporation | High strength wire rod excellent in drawability and method of producing same |
CN101765672B (zh) * | 2008-03-25 | 2012-05-23 | 新日本制铁株式会社 | 延性优良的线材及高强度钢线以及它们的制造方法 |
JP5179331B2 (ja) | 2008-12-02 | 2013-04-10 | 株式会社神戸製鋼所 | 伸線加工性およびメカニカルデスケーリング性に優れた熱間圧延線材およびその製造方法 |
KR101253852B1 (ko) * | 2009-08-04 | 2013-04-12 | 주식회사 포스코 | 고인성 비조질 압연재, 신선재 및 그 제조방법 |
WO2011089782A1 (fr) * | 2010-01-25 | 2011-07-28 | 新日本製鐵株式会社 | Matériau de fil métallique, fil d'acier et procédé de fabrication du matériau de fil métallique |
EP2557191B1 (fr) * | 2010-04-08 | 2016-07-27 | Nippon Steel & Sumitomo Metal Corporation | Matériau de fil pour fil de scie et procédé de fabrication de ce dernier |
JP4958998B1 (ja) * | 2010-12-27 | 2012-06-20 | 株式会社神戸製鋼所 | 鋼線材及びその製造方法 |
JP6615485B2 (ja) | 2015-04-28 | 2019-12-04 | 山下ゴム株式会社 | 液封防振装置 |
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US20210395868A1 (en) * | 2018-10-16 | 2021-12-23 | Nippon Steel Corporation | Hot-rolled wire rod |
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