WO2023181820A1 - 連続焼鈍装置及び連続溶融亜鉛めっき装置、並びに鋼板の製造方法 - Google Patents
連続焼鈍装置及び連続溶融亜鉛めっき装置、並びに鋼板の製造方法 Download PDFInfo
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- WO2023181820A1 WO2023181820A1 PCT/JP2023/007690 JP2023007690W WO2023181820A1 WO 2023181820 A1 WO2023181820 A1 WO 2023181820A1 JP 2023007690 W JP2023007690 W JP 2023007690W WO 2023181820 A1 WO2023181820 A1 WO 2023181820A1
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- steel sheet
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- rolled steel
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/562—Details
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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
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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- C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
- C21D3/02—Extraction of non-metals
- C21D3/06—Extraction of hydrogen
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- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C21D9/573—Continuous furnaces for strip or wire with cooling
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Definitions
- the present invention relates to a continuous annealing device, a continuous hot-dip galvanizing device, and a method for manufacturing steel sheets.
- the present invention is particularly directed to a continuous annealing apparatus and a continuous annealing apparatus for producing a steel plate having a small amount of hydrogen inherent in the steel and having excellent hydrogen embrittlement resistance, which is suitably used in the fields of automobiles, home appliances, and building materials.
- the present invention relates to a hot-dip galvanizing apparatus and a method for manufacturing steel sheets.
- the steel sheets are annealed in a reducing atmosphere containing hydrogen.
- Hydrogen enters. Hydrogen inherent in a steel sheet reduces formability such as ductility, bendability, stretch flangeability, etc. of the steel sheet. Further, hydrogen inherent in the steel plate may cause the steel plate to become brittle and cause delayed fracture. Therefore, a treatment is required to reduce the amount of hydrogen in the steel sheet.
- the amount of hydrogen in the steel can be reduced by leaving the product coil manufactured in a continuous annealing device and a continuous hot-dip galvanizing device at room temperature.
- room temperature it takes time for hydrogen to move from the inside of the steel sheet to the surface and desorb from the surface, so it takes several weeks or more to sufficiently reduce the amount of hydrogen in the steel. . Therefore, the space and time required for such dehydrogenation treatment pose problems in the manufacturing process.
- Patent Document 1 discloses that a steel sheet, a hot-dip galvanized steel sheet, or an alloyed hot-dip galvanized steel sheet after annealing is held in a temperature range of 50° C. or more and 300° C. or less for 1800 seconds or more and 43200 seconds or less. A method of reducing the amount of hydrogen is disclosed.
- Patent Document 1 there are concerns about changes in mechanical properties such as an increase in yield strength and temper embrittlement due to structural changes due to heating.
- the present invention provides a continuous annealing apparatus and a continuous hot-dip galvanizing system that can produce steel sheets with excellent hydrogen embrittlement resistance without impairing production efficiency or changing mechanical properties.
- the purpose of the present invention is to provide an apparatus and a method for manufacturing steel sheets.
- a steel plate is annealed in a reducing atmosphere containing hydrogen, and then cooled from the annealing temperature to room temperature.
- CAL continuous annealing line
- CGL continuous hot-dip galvanizing line
- a payoff reel for discharging cold-rolled steel sheets from cold-rolled coils The annealing furnace continuously anneales the cold-rolled steel sheet by passing the sheet through the sheet, in which a heating zone, a soaking zone, and a cooling zone are located from the upstream side in the sheet passing direction, and in the heating zone and the soaking zone, reduction containing hydrogen is formed.
- an annealing furnace for annealing the cold-rolled steel sheet in a neutral atmosphere and cooling the cold-rolled steel sheet in the cooling zone; downstream equipment that continues to pass the cold rolled steel sheet discharged from the annealing furnace; a tension reel that winds up the cold-rolled steel sheet that is being passed through the downstream equipment; a magnetic field application device that applies a steady magnetic field along the width direction of the cold-rolled steel sheet to the cold-rolled steel sheet that is being passed from the cooling zone to the tension reel; Continuous annealing equipment with
- the magnetic field application device includes an electromagnet located outside the widthwise end of the cold-rolled steel sheet, and the electromagnet has a magnetic pole surface facing the widthwise end surface of the cold-rolled steel sheet.
- the continuous annealing apparatus according to any one of [3] to [3].
- the magnetic field application device includes a pair of electromagnets located outside both ends of the cold-rolled steel sheet in the width direction, and each of the pair of electromagnets has a magnetic pole surface facing the end surface of the cold-rolled steel sheet in the width direction.
- the continuous annealing apparatus according to any one of [1] to [3] above, wherein one of the magnetic pole faces is a north pole and the other is a south pole.
- a hot-dip galvanizing bath is located downstream of the annealing furnace in the sheet passing direction and immerses the cold-rolled steel sheet to apply hot-dip galvanization to the cold-rolled steel sheet; Continuous hot dip galvanizing equipment.
- the downstream equipment includes an alloying furnace that is located downstream of the hot-dip galvanizing bath in the sheet-threading direction and heat-alloys the hot-dip galvanized steel sheet by passing the cold-rolled steel sheet through the hot-dip galvanizing bath.
- Continuous hot-dip galvanizing equipment includes an alloying furnace that is located downstream of the hot-dip galvanizing bath in the sheet-threading direction and heat-alloys the hot-dip galvanized steel sheet by passing the cold-rolled steel sheet through the hot-dip galvanizing bath.
- the magnetic field application device includes a pair of electromagnets located outside both ends of the cold-rolled steel sheet in the width direction, and each of the pair of electromagnets has a magnetic pole surface facing the end surface of the cold-rolled steel sheet in the width direction.
- the continuous hot-dip galvanizing apparatus according to any one of [7] to [12] above, wherein one of the magnetic pole surfaces is an N pole and the other is an S pole.
- (A) A step of paying out the cold rolled steel sheet from the cold rolled coil using a payoff reel, (B) The cold rolled steel sheet is passed through an annealing furnace in which a heating zone, a soaking zone, and a cooling zone are located from the upstream side in the sheet passing direction, and (B-1) In the heating zone and the soaking zone, Annealing the cold rolled steel sheet in a reducing atmosphere containing hydrogen, (B-2) cooling the cold rolled steel sheet in the cooling zone, performing continuous annealing; (C) a step of continuously passing the cold rolled steel sheet discharged from the annealing furnace; (D) a step of winding up the cold-rolled steel sheet with a tension reel to form a product coil; in this order, After step (B-2) and before step (D), a magnetic field application step of applying a steady magnetic field along the width direction of the cold rolled steel sheet to the cold rolled steel sheet during sheet passing.
- Manufacturing method of steel plate including.
- Step (C) is (C-1) a step of immersing the cold rolled steel sheet in a hot dip galvanizing bath located downstream of the annealing furnace in the sheet passing direction to apply hot dip galvanization to the cold rolled steel sheet.
- the step (C) is subsequent to the step (C-1) and includes (C-2) passing the cold rolled steel sheet through an alloying furnace located downstream of the hot dip galvanizing bath in the sheet passing direction.
- a magnetic field application device including an electromagnet located outside the widthwise end of the cold rolled steel sheet, the electromagnet having a magnetic pole face facing the widthwise end surface of the cold rolled steel sheet, The method for manufacturing a steel plate according to any one of [16] to [25] above, wherein the steady magnetic field is applied.
- the magnetic field application step includes a pair of electromagnets located outside both ends of the cold rolled steel sheet in the width direction, and each of the pair of electromagnets has a magnetic pole surface facing the end surface of the cold rolled steel sheet in the width direction. and the steady magnetic field is applied by a magnetic field applying device in which one of the magnetic pole faces is a north pole and the other is a south pole, according to any one of [16] to [25] above. manufacturing method of steel plate.
- the cold-rolled steel sheet contains, in mass%, C: 0.030-0.800%, Si: 0.01-3.00%, Mn: 0.01-10.00%, P: 0.001-0.100%, S: 0.0001-0.0200%, N: 0.0005 to 0.0100%, and Al: 0.001 to 2.000%,
- the component composition further comprises, in mass%, Ti: 0.200% or less, Nb: 0.200% or less, V: 0.500% or less, W: 0.500% or less, B: 0.0050% or less, Ni: 1.000% or less, Cr: 1.000% or less, Mo: 1.000% or less, Cu: 1.000% or less, Sn: 0.200% or less, Sb: 0.200% or less, Ta: 0.100% or less, Ca: 0.0050% or less, Mg: 0.0050% or less, The method for producing a steel sheet according to [29] above, containing at least one element selected from the group consisting of Zr: 0.1000% or less, and REM: 0.0050% or less.
- the cold rolled steel sheet has a mass percentage of C: 0.001-0.400%, Si: 0.01-2.00%, Mn: 0.01 to 5.00%, P: 0.001-0.100%, S: 0.0001-0.0200%, Cr: 9.0-28.0%, Ni: 0.01 to 40.0%, N: 0.0005 to 0.500%, and Al: 0.001 to 3.000%,
- the component composition further comprises, in mass%, Ti: 0.500% or less, Nb: 0.500% or less, V: 0.500% or less, W: 2.000% or less, B: 0.0050% or less, Mo: 2.000% or less, Cu: 3.000% or less, Sn: 0.500% or less, Sb: 0.200% or less, Ta: 0.100% or less, Ca: 0.0050% or less, Mg: 0.0050% or less, The method for producing a steel plate according to [31] above, containing at least one element selected from the group consisting of Zr: 0.1000% or less, and REM: 0.0050% or less.
- steel sheets with excellent hydrogen embrittlement resistance can be manufactured without impairing production efficiency or changing mechanical properties. be able to.
- FIG. 1 is a schematic diagram of a continuous annealing apparatus 100 according to an embodiment of the present invention.
- 1 is a schematic diagram of a continuous hot-dip galvanizing apparatus 200 according to an embodiment of the present invention.
- FIG. 3 is a schematic diagram of a continuous hot-dip galvanizing apparatus 300 according to another embodiment of the present invention.
- It is a schematic diagram which shows the structure of a pair of electromagnets 60A and 60B as a magnetic field application device used in each embodiment of this invention, and the magnetic force line generated from the said electromagnets 60A and 60B.
- (A) and (B) are diagrams schematically showing an example of how a pair of electromagnets 60A and 60B are installed as magnetic field generators for a cold rolled steel sheet S during sheet passing in each embodiment of the present invention. be.
- One embodiment of the present invention relates to continuous annealing equipment (Continuous Annealing Line: CAL), and another embodiment of the present invention relates to continuous hot-dip galvanizing equipment (Continuous hot-dip Galvanizing Line: CGL) It is.
- a method for manufacturing a steel plate according to an embodiment of the present invention is realized by a continuous annealing line (CAL) or a continuous hot-dip galvanizing line (CGL).
- CAL continuous annealing line
- CGL continuous hot-dip galvanizing line
- a continuous annealing apparatus (CAL) 100 includes a payoff reel 10 for discharging a cold-rolled steel sheet S from a cold-rolled coil C, and a payoff reel 10 for discharging a cold-rolled steel sheet S from a cold-rolled coil C; an annealing furnace 20 for continuous annealing; a downstream facility 30 for continuously passing the cold rolled steel sheet S discharged from the annealing furnace 20; and a tension reel 50.
- a heating zone 22, a soaking zone 24, and a cooling zone 26 are located from the upstream side in the sheet passing direction, and in the heating zone 22 and soaking zone 24, the cold rolled steel sheet S is annealed in a reducing atmosphere containing hydrogen. , the cold rolled steel sheet S is cooled in the cooling zone 26.
- the annealing furnace 20 of the CAL 100 has an overaging treatment zone 28 downstream of the cooling zone 26, it is not essential.
- the cold rolled steel sheet S is subjected to an overaging treatment.
- a product coil of cold rolled annealed steel plate (CR) is manufactured by CAL 100.
- the method of manufacturing a steel plate according to the first embodiment realized by a continuous annealing apparatus (CAL) 100 is as follows: (A) A cold rolled steel plate (steel strip) (B-1 ) In the heating zone 22 and the soaking zone 24, the cold rolled steel sheet S is annealed in a reducing atmosphere containing hydrogen, and (B-2) in the cooling zone 26, the cold rolled steel sheet S is cooled, performing continuous annealing; C) A step of continuously passing the cold rolled steel sheet S discharged from the annealing furnace 20, and (D) A step of winding up the cold rolled steel sheet S using the tension reel 50 to form a product coil P, in this order.
- This embodiment is a method for manufacturing a product coil of cold rolled annealed steel plate (CR) using CAL100.
- a continuous hot-dip galvanizing apparatus (CGL) 200 includes a payoff reel 10 for discharging a cold-rolled steel sheet S from a cold-rolled coil C; An annealing furnace 20 that continuously anneales the sheet, a downstream facility 30 that continues to pass the cold-rolled steel sheet S discharged from the annealing furnace 20, and a downstream facility 30 that winds up the cold-rolled steel sheet S being passed through the annealing furnace 20 to form a product.
- the tension reel 50 has a coil P.
- a heating zone 22, a soaking zone 24, and a cooling zone 26 are located from the upstream side in the sheet passing direction, and in the heating zone 22 and soaking zone 24, the cold rolled steel sheet S is annealed in a reducing atmosphere containing hydrogen. , the cold rolled steel sheet S is cooled in the cooling zone 26.
- the CGL 200 is located downstream of the annealing furnace 20 in the sheet passing direction as a downstream facility 30, and has a hot-dip galvanizing bath 31 in which the cold-rolled steel sheet S is immersed to apply hot-dip galvanization to the cold-rolled steel sheet S; It further includes an alloying furnace 33, which is located downstream of the plating bath 31 in the sheet passing direction, and heats and alloys the hot-dip galvanizing by passing the cold-rolled steel sheet S therethrough.
- the CGL 200 produces a product coil of alloyed hot-dip galvanized steel (GA) with an alloyed galvanized layer.
- a product coil of a hot-dip galvanized steel sheet (GI) in which the galvanized layer is not alloyed is manufactured.
- a method for manufacturing a steel sheet according to a second embodiment realized by a continuous hot-dip galvanizing apparatus (CGL) 200 includes (A) a method of manufacturing a cold-rolled steel sheet (steel strip) from a cold-rolled coil C using a payoff reel 10; ) A step of discharging the S, and (B) passing the cold rolled steel sheet S into the annealing furnace 20 in which the heating zone 22, the soaking zone 24, and the cooling zone 26 are located from the upstream side in the sheet passing direction.
- the cold rolled steel sheet S is annealed in a reducing atmosphere containing hydrogen
- the cold rolled steel sheet S is cooled, performing continuous annealing.
- step (C) is (C-1) a step of immersing the cold rolled steel sheet S in the hot dip galvanizing bath 31 located downstream of the annealing furnace 20 in the sheet passing direction to apply hot dip galvanization to the cold rolled steel sheet S. and (C-2) passing the cold-rolled steel sheet S through the alloying furnace 33 located downstream of the hot-dip galvanizing bath 31 in the sheet-threading direction, and heating and alloying the hot-dip galvanizing.
- This embodiment is a method for manufacturing a product coil of an alloyed hot-dip galvanized steel sheet (GA) in which a galvanized layer is alloyed using CGL200.
- a continuous hot dip galvanizing apparatus (CGL) 300 has the same configuration as the CGL 200 except that it does not include an alloying furnace 33.
- the CGL 300 produces a product coil of hot-dip galvanized steel (GI) in which the galvanized layer is not alloyed.
- GI hot-dip galvanized steel
- the method for manufacturing a steel plate according to the third embodiment in which step (C-1) is performed and step (C-2) is not performed is realized, for example, by CGL300 without the alloying furnace 33, and also by CGL200.
- This can also be achieved by simply passing the steel plate S through the alloying furnace 33 without performing heating and alloying.
- This embodiment is a method for manufacturing a product coil of hot-dip galvanized steel sheet (GI) in which the galvanized layer is not alloyed using CGL200 or CGL300.
- GI hot-dip galvanized steel sheet
- Step (A) Referring to FIGS. 1 to 3, a payoff reel 10 pays out a cold rolled steel sheet S from a cold rolled coil C. That is, in step (A), the cold rolled steel sheet S is paid out from the cold rolled coil C by the payoff reel 10.
- the discharged cold rolled steel sheet S passes through the welding machine 11, the cleaning equipment 12, and the entrance looper 13, and is supplied to the annealing furnace 20.
- the upstream equipment between the payoff reel 10 and the annealing furnace 20 is not limited to the welding machine 11, the cleaning equipment 12, and the entrance looper 13, and may be any known or arbitrary equipment.
- an annealing furnace 20 continuously anneals a cold-rolled steel sheet S by passing it therethrough.
- a heating zone 22, a soaking zone 24, and a cooling zone 26 are located from the upstream side in the sheet passing direction, and in the heating zone 22 and soaking zone 24, the cold rolled steel sheet S is annealed in a reducing atmosphere containing hydrogen. , the cold rolled steel sheet S is cooled in the cooling zone 26.
- step (B) continuous annealing is performed by passing the cold rolled steel sheet S through the annealing furnace 20 in which the heating zone 22, soaking zone 24, and cooling zone 26 are located from the upstream side in the sheet passing direction.
- Cooling zone 26 may be composed of a plurality of cooling zones. Further, a preheating zone may be provided on the upstream side of the heating zone 22 in the sheet passing direction.
- the annealing furnace 20 of the CAL 100 shown in FIG. 1 has an overaging treatment zone 28 downstream of the cooling zone 26, it is not essential.
- each zone is illustrated as a vertical furnace, but the present invention is not limited to this, and a horizontal furnace may be used. In the case of a vertical furnace, adjacent bands communicate through throats (throttles) that connect the tops or bottoms of each band.
- the cold rolled steel sheet S can be directly heated using a burner, or the cold rolled steel sheet S can be indirectly heated using a radiant tube (RT) or an electric heater. Further, heating by induction heating, roll heating, electric resistance heating, direct current heating, salt bath heating, electron beam heating, etc. is also possible.
- the average temperature inside the heating zone 22 is preferably 500 to 800°C. At the same time that the gas from the soaking zone 24 flows into the heating zone 22, reducing gas is separately supplied.
- a H 2 -N 2 mixed gas is usually used, for example, a gas having a composition of 1 to 35% by volume of H 2 and the balance consisting of one or both of N 2 and Ar and unavoidable impurities (with a low dew point). : about -60°C).
- the cold rolled steel sheet S can be indirectly heated using a radiant tube (RT).
- the average temperature inside the soaking zone 24 is preferably 600 to 950°C.
- a reducing gas is supplied to the soaking zone 24.
- a H 2 -N 2 mixed gas is usually used, for example, a gas having a composition of 1 to 35% by volume of H 2 and the balance consisting of one or both of N 2 and Ar and unavoidable impurities (with a low dew point). : about -60°C).
- cooling zone 26 In the cooling zone 26, the cold rolled steel sheet S is cooled by either gas, a mixture of gas and water, or water. When the cold rolled steel sheet S leaves the annealing furnace 20, it is cooled to about 100 to 400°C in CAL and to about 470 to 530°C in CGL.
- a plurality of cooling nozzles are provided in the cooling zone 26 along the steel plate conveyance path.
- the cooling nozzle is a circular tube that is longer than the width of the steel plate, as described in, for example, Japanese Patent Application Publication No. 2010-185101, and is installed so that the extending direction of the circular tube is parallel to the width direction of the steel plate.
- the circular tube is provided with a plurality of through holes at predetermined intervals along the extending direction of the circular tube at a portion facing the steel plate, and water in the circular tube is injected toward the steel plate from the through holes.
- the cooling nozzles are provided in pairs to face each other on the front and back sides of the steel plate, and a plurality of pairs (for example, 5 to 10 pairs) of the cooling nozzles are arranged at predetermined intervals along the steel plate conveyance path to form one cooling zone. Configure. It is preferable that about 3 to 6 cooling zones be arranged along the steel plate conveyance path.
- cold rolled steel sheet S leaving cooling zone 26 is subjected to at least one of isothermal holding, reheating, furnace cooling, and natural cooling.
- the rolled steel sheet S leaves the annealing furnace 20 it is cooled to about 100 to 400°C.
- step (C) the cold rolled steel sheet S discharged from the annealing furnace 20 is continuously passed through the downstream equipment 30.
- CAL 100 includes an outlet looper 35 and a temper rolling mill 36 as downstream equipment 30.
- the CGL 200 includes a hot dip galvanizing bath 31, a gas wiping device 32, an alloying furnace 33, a cooling device 34, an exit looper 35, and a temper rolling mill 36 as downstream equipment 30.
- the CGL 300 includes a hot dip galvanizing bath 31, a gas wiping device 32, a cooling device 34, an exit looper 35, and a temper rolling mill 36 as downstream equipment 30.
- the downstream equipment 30 is not limited to these, and may be any known or arbitrary equipment.
- the downstream equipment 30 can include a tension leveler, chemical conversion equipment, surface conditioning equipment, oiling equipment, and inspection equipment.
- hot-dip galvanizing bath 31 is located downstream of annealing furnace 20 in the sheet passing direction, and immerses cold-rolled steel sheet S to apply hot-dip galvanization to cold-rolled steel sheet S. That is, in step (C-1), the cold-rolled steel sheet S is immersed in the hot-dip galvanizing bath 31 located downstream of the annealing furnace 20 in the sheet-threading direction to apply hot-dip galvanization to the cold-rolled steel sheet S.
- the snout 29 connected to the most downstream zone of the annealing furnace (the cooling zone 26 in FIGS.
- Hot-dip galvanizing may be performed according to a standard method.
- Gas is blown onto the cold rolled steel sheet S from a pair of gas wiping devices 32 arranged to sandwich the cold rolled steel sheet S pulled up from the hot dip galvanizing bath 31 to adjust the amount of molten zinc deposited on both sides of the cold rolled steel sheet S. be able to.
- the alloying furnace 33 is located downstream of the hot dip galvanizing bath 31 and the gas wiping device 32 in the sheet passing direction, passes the cold rolled steel sheet S, and heats and alloys the hot dip galvanizing. . That is, in step (C-2), the cold rolled steel sheet S is passed through the alloying furnace 33 located downstream of the hot dip galvanizing bath 31 and the gas wiping device 32 in the sheet passing direction, and the hot dip galvanizing is heated and alloyed. do. Alloying treatment may be performed according to a conventional method.
- the heating means in the alloying furnace 33 is not particularly limited, and examples thereof include heating with high temperature gas and induction heating.
- the alloying furnace 33 is an optional facility in the CGL, and the alloying process is an optional step in the method for manufacturing a steel plate using the CGL.
- the cooling device 34 is located downstream of the gas wiping device 32 and the alloying furnace 33 in the sheet passing direction.
- the cold-rolled steel sheet S can be cooled by passing the cold-rolled steel sheet S through the cooling device 34.
- the cooling device 34 cools the cold rolled steel sheet S by water cooling, air cooling, gas cooling, mist cooling, or the like.
- Step (D) Referring to FIGS. 1 to 3, the cold rolled steel sheet S that has passed through the downstream equipment 30 is finally wound up by a tension reel 50 as a winding device to become a product coil P.
- the CAL 100 of the first embodiment, the CGL 200 of the second embodiment, and the CGL 300 of the third embodiment are used for cold-rolled steel sheets S that are being passed from the cooling zone 26 to the tension reel 50. It is important to have a magnetic field applying device 60 that applies a steady magnetic field along the width direction of the steel plate S. That is, in the method for manufacturing a steel sheet according to the first, second, and third embodiments, after step (B-2) and before step (D), the cold rolled steel sheet S is Therefore, it is important to include a magnetic field application step in which a steady magnetic field is applied along the width direction of the cold rolled steel sheet S.
- the hydrogen contained in the cold-rolled steel sheet S during annealing can be sufficiently and efficiently reduced, and a steel sheet with excellent hydrogen embrittlement resistance can be manufactured. Furthermore, since the application of a steady magnetic field is incorporated into the steel plate manufacturing process (inline) using CAL100, CGL200, or CGL300, production efficiency is not impaired. Furthermore, since hydrogen is desorbed not by heating but by applying a steady magnetic field, there is no concern that the mechanical properties of the steel sheet will change.
- Magnetic field application device 60 Each embodiment of the present invention can be realized by installing a magnetic field application device 60 as shown in FIG. 4 and FIGS. A steady magnetic field is applied to the cold rolled steel sheet S during threading using the device 60.
- magnetic field application device 60 includes a pair of electromagnets 60A and 60B located on the outer sides of both widthwise ends of cold-rolled steel sheet S, respectively.
- the electromagnets 60A and 60B each include iron cores 62A and 62B, coils 64A and 64B around which these iron cores 62A and 62B are wound, and a drive power source (not shown) for passing current through these coils 64A and 64B.
- the electromagnets 60A, 60B can be magnetized and a steady magnetic field can be generated.
- the axial direction of the coils 64A, 64B coincides with the width direction of the cold rolled steel sheet S.
- the pair of electromagnets 60A and 60B each have magnetic pole faces 66A and 66B that face the widthwise end face of the cold rolled steel sheet S with a predetermined distance therebetween.
- the pair of magnetic pole surfaces 66A and 66B are located at the same position in the passing direction of the cold-rolled steel sheet S, and face each other with the cold-rolled steel sheet S in between. Therefore, as shown in FIG. 4, the main magnetic flux of the steady magnetic field generated by the pair of electromagnets 60A and 60B is directed from the magnetic pole face 66A (N pole) to the magnetic pole face 66B (S pole), and in that direction. coincides with the width direction of the cold rolled steel sheet S. Thereby, a steady magnetic field can be applied uniformly along the width direction of the cold rolled steel sheet S. As shown in FIGS.
- continuous direct current means a direct current whose current value is maintained continuously (preferably constant) rather than in a pulsed manner.
- a steady magnetic field means a magnetic field that is maintained continuously rather than in a pulsed manner, and includes a magnetic field formed by a stationary magnet and a magnetic field formed by an electromagnet supplied with continuous direct current. including.
- the installation mode of the pair of electromagnets 60A and 60B is preferably as described above, the installation mode is not limited as long as a steady magnetic field with a magnetic flux component in the width direction of the cold rolled steel sheet S is generated.
- the configuration of the magnetic field application device 60 is not limited to the pair of electromagnets 60A and 60B as long as a steady magnetic field with a magnetic flux component in the width direction of the cold rolled steel sheet S is generated.
- the magnetic field applying device 60 may be only one of the electromagnet 60A and the electromagnet 60B. If the magnetic field formed by one of the electromagnets has enough strength to apply a magnetic field along the width direction of the cold rolled steel sheet S to the entire width of the cold rolled steel sheet S, only one of the electromagnets may be used.
- the position of the magnetic field application device 60 is as long as it can apply a magnetic field to the cold rolled steel sheet S being passed from the cooling zone 26 to the tension reel 50. Not limited.
- a magnetic field application device 60 can be provided in the cooling zone 26.
- the magnetic field application step can be performed in step (B-2). Note that the entire magnetic field application device 60 does not need to be located inside the cooling zone 26, and at least the electromagnets 60A and 60B may be located inside the cooling zone 26.
- the magnetic field application device 60 can be provided at a position where the downstream equipment 30 can apply a magnetic field to the cold rolled steel sheet S being passed through.
- the magnetic field application step can be performed in step (C). Specifically, (i) between the overaging treatment zone 28 and the exit looper 35, (ii) within the exit looper 35, (iii) between the exit looper 35 and the temper rolling mill 36, (iv) )
- a magnetic field applying device 60 can be provided between at least one of the temper rolling mill 36 and the tension reel 50.
- the magnetic field application device 60 may be provided both in the cooling zone 26 and at a position where the downstream equipment 30 can apply a magnetic field to the cold rolled steel sheet S being passed. That is, the magnetic field application step may be performed in both step (B-2) and step (C). Further, the magnetic field application device 60 may be provided in the overaging treatment zone 28 to perform the magnetic field application step during the overaging treatment.
- the preferred position of the magnetic field application device 60 that is, the preferred implementation of the magnetic field application step.
- the magnetic field application device 60 can be provided at a first position upstream of the hot-dip galvanizing bath 31 at a position where it can apply a magnetic field to the cold-rolled steel sheet S that is being passed.
- the magnetic field application step can be performed before step (C-1).
- the magnetic field application device 60 can be provided in the cooling zone 26.
- the entire magnetic field application device 60 does not need to be located inside the cooling zone 26, and at least the electromagnets 60A and 60B need only be located inside the cooling zone 26. Furthermore, at least the electromagnets 60A and 60B of the magnetic field application device 60 can be installed inside the snout 29.
- the magnetic field applying device 60 can be provided at a second position downstream of the hot-dip galvanizing bath 31 where it can apply a magnetic field to the cold-rolled steel sheet S that is being passed.
- the magnetic field application step can be performed after step (C-1). Specifically, (i) between the hot dip galvanizing bath 31 and the gas wiping device 32, (ii) between the gas wiping device 32 and the alloying furnace 33, (iii) inside the alloying furnace 33, (iv) An air cooling zone between the alloying furnace 33 and the cooling device 34, (v) between the cooling device 34 and the exit looper 35, (vi) inside the exit looper 35, (vii) between the exit looper 35 and temper rolling.
- a magnetic field applying device 60 can be provided at least one of (viii) between the temper rolling mill 36 and the tension reel 50. In particular, it is preferable to provide the magnetic field application device 60 in the air cooling zone (iv).
- the magnetic field application device 60 is provided at the first position rather than the second position. That is, the magnetic field application step is preferably performed before step (C-1) rather than after step (C-1). However, the magnetic field application device 60 may be provided at both the first position and the second position. That is, the magnetic field application step may be performed both before and after step (C-1).
- the magnetic field application device 60 can be provided at a first position upstream of the hot-dip galvanizing bath 31 at a position where it can apply a magnetic field to the cold-rolled steel sheet S that is being passed.
- the magnetic field application step can be performed before step (C-1).
- the magnetic field application device 60 can be provided in the cooling zone 26.
- the entire magnetic field application device 60 does not need to be located inside the cooling zone 26, and at least the electromagnets 60A and 60B need only be located inside the cooling zone 26. Furthermore, at least the electromagnets 60A and 60B of the magnetic field application device 60 can be installed inside the snout 29.
- the magnetic field applying device 60 can be provided at a second position downstream of the hot-dip galvanizing bath 31 where it can apply a magnetic field to the cold-rolled steel sheet S that is being passed.
- the magnetic field application step can be performed after step (C-1). Specifically, (i) an air cooling zone between the hot dip galvanizing bath 31 and the gas wiping device 32, (ii) an air cooling zone between the gas wiping device 32 and the cooling device 34, and (iii) a cooling device 34 and the outlet looper. 35, (iv) inside the exit looper 35, (v) between the exit looper 35 and the temper rolling mill 36, and (vi) between the temper rolling mill 36 and the tension reel 50.
- a magnetic field applying device 60 can be provided in the magnetic field application device 60 . In particular, it is preferable to provide the magnetic field application device 60 in the air cooling zone (ii).
- the magnetic field application device 60 is provided at the first position rather than the second position. That is, the magnetic field application step is preferably performed before step (C-1) rather than after step (C-1). However, the magnetic field application device 60 may be provided at both the first position and the second position. That is, the magnetic field application step may be performed both before and after step (C-1).
- the magnetic flux density in the width direction of the cold rolled steel sheet S is preferably 0.1 T or more, It is more preferably 0.2T or more, and even more preferably 0.5T or more.
- the magnetic flux density in the width direction of the cold rolled steel sheet S is preferably 15T or less, more preferably 14T or less.
- the magnetic flux density in the width direction of the cold rolled steel sheet S can be adjusted by adjusting the number of turns of the coil and the current value.
- Magnetic flux density in the width direction of the cold-rolled steel sheet S can be measured in-line by installing a Tesla meter near the width-direction end face of the cold-rolled steel sheet S during threading and near the magnetic field generation surface of the magnetic field application device 60. It can be measured by Alternatively, once the number of turns of the coil in the magnetic field application device 60 and the magnitude of the current value are determined, the "magnetic flux density in the width direction of the cold-rolled steel sheet S" can be determined in advance off-line.
- the time for applying the magnetic field to the cold rolled steel sheet S is preferably 1 second or more, more preferably 5 seconds or more, and 10 seconds or more. It is more preferable to set it to more than a second.
- the time for applying the magnetic field to the cold rolled steel sheet S is preferably 3600 seconds or less, more preferably 1800 seconds or less, and even more preferably 900 seconds or less.
- the time period for which a magnetic field is applied to the cold-rolled steel sheet S means the time period during which a magnetic field is applied to each position in the sheet width direction of the cold-rolled steel sheet S, and each position is connected to a plurality of magnetic field application devices 60.
- a magnetic field When a magnetic field is applied from , it means the cumulative time.
- the cumulative time during which each portion of the cold-rolled steel sheet S faces the pair of electromagnets 60A and 60B can be defined as the magnetic field application time.
- the magnetic field application time can be adjusted by the threading speed of the cold rolled steel sheet S and the position of the magnetic field application device 60 (for example, the number of the pair of electromagnets 60A, 60B shown in FIG. 4 along the threading direction). .
- the cold rolled steel sheets S supplied to CAL100, CGL200, and CGL300 are not particularly limited.
- the cold-rolled steel plate S preferably has a thickness of less than 6 mm, and includes, for example, a high-strength steel plate having a tensile strength of 590 MPa or more and a stainless steel plate.
- composition of cold-rolled steel sheet high-strength steel sheet
- mass % is simply written as "%”.
- C 0.030-0.800% C has the effect of increasing the strength of the steel plate. From the viewpoint of obtaining this effect, the amount of C is set to 0.030% or more, preferably 0.080% or more. However, when the amount of C is excessive, the steel sheet becomes extremely brittle regardless of the amount of hydrogen in the steel sheet. Therefore, the amount of C should be 0.800% or less, preferably 0.500% or less.
- Si 0.01-3.00% Si has the effect of increasing the strength of the steel plate. From the viewpoint of obtaining this effect, the amount of Si is set to 0.01% or more, preferably 0.10% or more. However, when the amount of Si is excessive, the steel plate becomes brittle and its ductility decreases, red scale etc. occur and the surface quality deteriorates, and the plating quality deteriorates. Therefore, the amount of Si should be 3.00% or less, preferably 2.50% or less.
- Mn 0.01-10.00% Mn has the effect of increasing the strength of the steel plate through solid solution strengthening. From the viewpoint of obtaining this effect, the amount of Mn is set to 0.01% or more, preferably 0.5% or more. However, when the amount of Mn is excessive, unevenness tends to occur in the steel structure due to segregation of Mn, and hydrogen embrittlement originating from the unevenness may become apparent. Therefore, the Mn content should be 10.00% or less, preferably 8.00% or less.
- P 0.001 ⁇ 0.100%
- P is an element that has a solid solution strengthening effect and can be added depending on the desired strength. From the viewpoint of obtaining such effects, the amount of P is set to 0.001% or more, preferably 0.003% or more. However, when the amount of P is excessive, weldability deteriorates, and when alloying zinc plating, the alloying speed decreases, impairing the quality of the zinc plating. Therefore, the amount of P should be 0.100% or less, preferably 0.050% or less.
- S 0.0001-0.0200% S segregates at grain boundaries and makes the steel brittle during hot working, and also exists as a sulfide and reduces local deformability. Therefore, the amount of S is set to 0.0200% or less, preferably 0.0100% or less, and more preferably 0.0050% or less. On the other hand, due to production technology constraints, the S content is set to 0.0001% or more.
- N 0.0005-0.0100%
- N is an element that deteriorates the aging resistance of steel. Therefore, the amount of N is set to 0.0100% or less, preferably 0.0070% or less. The smaller the amount of N, the more preferable it is, but due to constraints on production technology, the amount of N is set to 0.0005% or more, preferably 0.0010% or more.
- Al acts as a deoxidizing agent and is an element effective in improving the cleanliness of steel. From the viewpoint of obtaining this effect, the amount of Al is set to 0.001% or more, preferably 0.010% or more. However, if the amount of Al is excessive, cracks may occur during continuous casting. Therefore, the amount of Al should be 2.000% or less, preferably 1.200% or less.
- the remainder other than the above components is Fe and inevitable impurities. However, it may optionally contain at least one element selected from the following.
- Ti 0.200% or less Ti contributes to increasing the strength of the steel sheet through precipitation strengthening of the steel and fine grain strengthening by suppressing the growth of ferrite crystal grains. Therefore, when adding Ti, the amount of Ti is preferably 0.005% or more, more preferably 0.010% or more. However, when the amount of Ti is excessive, a large amount of carbonitrides may precipitate, leading to a decrease in formability. Therefore, when adding Ti, the amount of Ti should be 0.200% or less, preferably 0.100% or less.
- Nb 0.200% or less
- V 0.500% or less
- W 0.500% or less
- Nb, V, and W are effective for precipitation strengthening of steel. Therefore, when adding Nb, V, and W, the content of each element is preferably 0.005% or more, more preferably 0.010% or more. However, if each content is excessive, a large amount of carbonitrides may precipitate and formability may deteriorate. Therefore, when adding Nb, the amount of Nb should be 0.200% or less, preferably 0.100% or less. When V and W are added, the content of each element is 0.500% or less, preferably 0.300% or less.
- B 0.0050% or less B is effective in strengthening grain boundaries and increasing the strength of steel sheets. Therefore, when adding B, the amount of B is preferably 0.0003% or more. However, when the amount of B is excessive, moldability may deteriorate. Therefore, when adding B, the amount of B should be 0.0050% or less, preferably 0.0030% or less.
- Ni 1.000% or less
- Ni is an element that increases the strength of steel through solid solution strengthening. Therefore, when adding Ni, the amount of Ni is preferably 0.005% or more. However, when the amount of Ni is excessive, the area ratio of hard martensite becomes excessive, which increases the number of microvoids at the grain boundaries of martensite during a tensile test, and further propagates cracks, resulting in ductile may decrease. Therefore, when adding Ni, the amount of Ni should be 1.000% or less.
- Cr 1.000% or less
- Mo 1.000% or less Cr and Mo have the effect of improving the balance between strength and formability. Therefore, when adding Cr and Mo, the content of each element is preferably 0.005% or more. However, if each content is excessive, the area ratio of hard martensite becomes excessive, and during the tensile test, microvoids at grain boundaries of martensite increase, and crack propagation progresses. Ductility may decrease. Therefore, when adding Cr and Mo, the content of each element should be 1.000% or less.
- Cu 1.000% or less
- Cu is an element effective in strengthening steel. Therefore, when adding Cu, the amount of Cu is preferably 0.005% or more. However, when the amount of Cu is excessive, the area ratio of hard martensite becomes excessive, microvoids at grain boundaries of tempered martensite increase during a tensile test, and crack propagation progresses. Ductility may decrease. Therefore, when adding Cu, the amount of Cu is 1.000% or less.
- Sn 0.200% or less
- Sb 0.200% or less
- Sn and Sb suppress decarburization in an area of several tens of ⁇ m on the steel plate surface layer caused by nitriding and oxidation of the steel plate surface, and improve strength and material stability. It is effective in ensuring sex. Therefore, when adding Sn and Sb, the content of each element is preferably 0.002% or more. However, if each content is excessive, toughness may decrease. Therefore, when adding Sn and Sb, the content of each element should be 0.200% or less.
- Ta 0.100% or less Ta, like Ti and Nb, generates alloy carbides and alloy carbonitrides and contributes to high strength.
- Nb carbide and Nb carbonitride by partially forming a solid solution in Nb carbide and Nb carbonitride to form composite precipitates such as (Nb, Ta) (C, N), coarsening of the precipitates is significantly suppressed and precipitation It is thought that this has the effect of stabilizing the contribution to strength due to reinforcement. Therefore, when adding Ta, the amount of Ta is preferably 0.001% or more. However, even if Ta is added excessively, the precipitate stabilizing effect may become saturated, and the alloy cost also increases. Therefore, when adding Ta, the amount of Ta should be 0.100% or less.
- Ca 0.0050% or less
- Mg 0.0050% or less
- Zr 0.1000% or less
- REM Rare Earth Metal
- Ca, Mg, Zr and REM change the shape of the sulfide. It is an effective element for spheroidizing and improving the adverse effects of sulfide on formability.
- the content of each element is preferably 0.0005% or more. However, when each content is excessive, inclusions and the like increase, and surface and internal defects may occur. Therefore, when adding these elements, the content of each element should be 0.0050% or less.
- composition of cold rolled steel sheet stainless steel sheet
- mass % is simply written as “%”.
- C 0.001-0.400%
- C is an essential element for obtaining high strength in stainless steel. However, during tempering in steel manufacturing, it combines with Cr and precipitates as carbides, which deteriorates the corrosion resistance and toughness of the steel. If the C content is less than 0.001%, sufficient strength cannot be obtained, and if it exceeds 0.400%, the deterioration becomes noticeable. Therefore, the amount of C is set to 0.001 to 0.400%.
- Si 0.01 ⁇ 2.00%
- Si is an element useful as a deoxidizing agent. From the viewpoint of obtaining this effect, the amount of Si is set to 0.01% or more. However, when the amount of Si is excessive, Si dissolved in the steel deteriorates the workability of the steel. Therefore, Si should be 2.00% or less.
- Mn 0.01-5.00% Mn has the effect of increasing the strength of steel. From the viewpoint of obtaining this effect, the amount of Mn is set to 0.01% or more. However, when the amount of Mn is excessive, the workability of the steel decreases. Therefore, the Mn content is set to 5.00% or less.
- P is an element that promotes grain boundary destruction due to grain boundary segregation. Therefore, it is desirable that the amount of P be as low as possible, and should be 0.100% or less, preferably 0.030% or less, and more preferably 0.020% or less. On the other hand, due to production technology constraints, the amount of P is set to 0.001% or more.
- S 0.0001-0.0200%
- S exists as sulfide inclusions such as MnS and reduces ductility, corrosion resistance, etc. Therefore, the S amount is desirably low, and is set to 0.0200% or less, preferably 0.0100% or less, and more preferably 0.0050% or less.
- the S content is set to 0.0001% or more.
- Cr 9.0 ⁇ 28.0%
- Cr is a basic element constituting stainless steel, and is also an important element that exhibits corrosion resistance.
- the Cr content is set to 9.0 to 28.0%.
- Ni 0.01-40.0% Ni is an element that improves the corrosion resistance of stainless steel. If the amount of Ni is less than 0.01%, the effect will not be fully exhibited. On the other hand, when the amount of Ni is excessive, not only the formability is deteriorated but also stress corrosion cracking is likely to occur. Therefore, the Ni amount is set to 0.01 to 40.0%.
- N 0.0005-0.500% N is an element harmful to improving the corrosion resistance of stainless steel. Therefore, the amount of N is set to 0.500% or less, preferably 0.200% or less. The smaller the amount of N, the more preferable it is, but due to constraints on production technology, the amount of N is set to 0.0005% or more.
- Al 0.001-3.000%
- Al has the effect of suppressing the peeling of oxide scale. From the viewpoint of obtaining these effects, the amount of Al is set to 0.001% or more. However, when the amount of Al is excessive, a decrease in elongation and a deterioration in surface quality occur. Therefore, the amount of Al is set to 3.000% or less.
- the remainder other than the above components is Fe and inevitable impurities. However, it may optionally contain at least one element selected from the following.
- Ti 0.500% or less Ti combines with C, N, and S to improve corrosion resistance, intergranular corrosion resistance, and deep drawability. However, when the amount of Ti exceeds 0.500%, the toughness deteriorates due to solid solution Ti. Therefore, when adding Ti, the amount of Ti should be 0.500% or less.
- Nb 0.500% or less Like Ti, Nb combines with C, N, and S to improve corrosion resistance, intergranular corrosion resistance, and deep drawability. In addition to improving workability and high-temperature strength, it also suppresses crevice corrosion and promotes repassivation. However, excessive addition causes hardening and deteriorates moldability. Therefore, when adding Nb, the amount of Nb should be 0.500% or less.
- V 0.500% or less V suppresses crevice corrosion. However, excessive addition deteriorates moldability. Therefore, when adding V, the amount of V should be 0.500% or less.
- W 2.000% or less W contributes to improving corrosion resistance and high temperature strength.
- excessive addition leads to deterioration of toughness and increase in cost during production of steel sheets. Therefore, when adding W, the amount of W should be 2.000% or less.
- B 0.0050% or less B improves the secondary workability of the product by segregating at grain boundaries. However, excessive addition results in deterioration of workability and corrosion resistance. Therefore, when adding B, the amount of B should be 0.0050% or less.
- Mo 2.000% or less
- Mo is an element that improves corrosion resistance and particularly suppresses crevice corrosion.
- excessive addition deteriorates moldability. Therefore, when adding Mo, the amount of Mo should be 2.000% or less.
- Cu 3.000% or less
- Cu is an austenite stabilizing element and is effective in refining crystal grains through phase transformation. It also inhibits crevice corrosion and promotes repassivation. However, excessive addition deteriorates toughness and formability. Therefore, when adding Cu, the amount of Cu is 3.000% or less.
- Sn 0.500% or less Sn contributes to improving corrosion resistance and high temperature strength. However, excessive addition may cause slab cracking during steel sheet production. Therefore, when adding Sn, the amount of Sn should be 0.500% or less.
- Sb 0.200% or less Sb segregates at grain boundaries and has the effect of increasing high-temperature strength. However, excessive addition may cause cracks during welding due to Sb segregation. Therefore, when adding Sb, the amount of Sb should be 0.200% or less.
- Ta 0.100% or less Ta combines with C and N and contributes to improving toughness. However, if excessively added, the effect becomes saturated, leading to an increase in manufacturing costs. Therefore, when adding Ta, the amount of Ta was set to 0.100% or less.
- Ca 0.0050% or less
- Mg 0.0050% or less
- Zr 0.1000% or less
- REM Rare Earth Metal
- Ca, Mg, Zr and REM change the shape of the sulfide. It is an effective element for spheroidizing and improving the adverse effects of sulfide on formability.
- the content of each element is preferably 0.0005% or more. However, when each content is excessive, inclusions and the like increase, and surface and internal defects may occur. Therefore, when adding these elements, the content of each element should be 0.0050% or less.
- the amount of diffusible hydrogen in the product coil is preferably 0.50 mass ppm or less, more preferably 0.30 mass ppm or less, and 0.50 mass ppm or less. More preferably, the content is 20 mass ppm or less. Note that there is no particular lower limit to the amount of diffusible hydrogen in the product coil, but due to constraints on production technology, the amount of diffusible hydrogen in the product coil may be 0.01 mass ppm or more.
- the method for measuring the amount of diffusible hydrogen in the product coil is as follows.
- a test piece with a length of 30 mm and a width of 5 mm is taken from the product coil.
- the hot-dip galvanized layer or alloyed hot-dip galvanized layer of the test piece is removed by grinding or alkali.
- the amount of hydrogen released from the test piece is measured by thermal desorption spectrometry (TDS). Specifically, the test piece was continuously heated from room temperature to 300°C at a heating rate of 200°C/h, then cooled to room temperature, and the cumulative amount of hydrogen released from the test piece from room temperature to 210°C was measured. , the amount of diffusible hydrogen in the product coil.
- a steel having a composition having the elements shown in Table 1 with the remainder consisting of Fe and unavoidable impurities was melted in a converter and made into a slab by a continuous casting method. The obtained slab was hot rolled and cold rolled to obtain a cold rolled coil.
- some standards produce product coils of cold-rolled annealed steel (CR) by CAL as shown in Figure 1, while other standards produce product coils of cold-rolled annealed steel (CR) without heat alloying by CGL as shown in Figure 2.
- production coils of hot-dip galvanized steel (GI) were produced, and for the remaining levels, production coils of alloyed galvanized steel (GA) were produced by CGL shown in FIG.
- Magnetic flux densities (in the sheet width direction) shown in Table 2 are applied to the cold-rolled steel sheet during threading using the magnetic field application device shown in FIGS. 4 and 5 (A) and (B).
- a steady magnetic field was applied along the width direction of the cold-rolled steel sheet under the following conditions: and magnetic field application time.
- Magnetic field application location indicates the area where the magnetic field application process in CAL or CGL was performed, that is, the location where the magnetic field application device was installed.
- (B-2)" means that in CAL and CGL, a magnetic field application device was installed in the cooling zone, and the magnetic field application process was performed in the cooling zone of step (B-2).
- (C) means that the magnetic field application device is installed at a position where it can apply a magnetic field to the cold-rolled steel sheet being passed through the downstream equipment, and is located downstream of the cooling zone and upstream of the tension reel. Specifically, (i) between the overaging treatment zone 28 and the outlet looper 35, (ii) inside the outlet looper 35, (iii) between the outlet looper 35 and the temper rolling mill 36, ( iv) This means that a magnetic field application device is installed at at least one location between the temper rolling mill 36 and the tension reel 50. That is, "(C)” means that in CAL, a magnetic field application step was performed at step (C), specifically, at least one of the above (i) to (iv).
- Before (C-1) is a position downstream of the cooling zone and upstream of the hot-dip galvanizing bath in CGL, specifically, a magnetic field application device is installed in the snout 29, and from step (B-2) This means that the magnetic field application step was performed after and before step (C-1).
- "After (C-1)” refers to a position downstream of the hot-dip galvanizing bath and upstream of the tension reel in the CGL, specifically, (i) between the hot-dip galvanizing bath 31 and the gas wiping device 32; ii) between the gas wiping device 32 and the alloying furnace 33; (iii) within the alloying furnace 33; (iv) between the alloying furnace 33 and the cooling device 34; (v) between the cooling device 34 and the outlet.
- the tensile test was conducted in accordance with JIS Z 2241 (2011) using a JIS No. 5 test piece whose tensile direction was perpendicular to the rolling direction of the steel plate, and the TS (tensile strength) and EL (total elongation) was measured.
- the hydrogen embrittlement resistance was evaluated from the above tensile test as follows. When the value obtained by dividing the EL of the steel sheet after applying the magnetic field measured above by the EL' when the hydrogen content in the steel of the same steel sheet is 0.00 mass ppm is 0.70 or more, the hydrogen embrittlement resistance is good. It was determined that In addition, EL' reduces the hydrogen in the steel by leaving the same steel plate in the atmosphere for a long time, and then after confirming that the amount of hydrogen in the steel is 0.00 mass ppm by TDS. , was measured by performing a tensile test.
- steel sheets with excellent hydrogen embrittlement resistance can be manufactured without impairing production efficiency or changing mechanical properties. be able to.
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Abstract
Description
[1]冷延コイルから冷延鋼板を払い出すペイオフリールと、
前記冷延鋼板を通板させて連続焼鈍する焼鈍炉であって、通板方向上流側から加熱帯、均熱帯、及び冷却帯が位置し、前記加熱帯及び前記均熱帯では、水素を含む還元性雰囲気で前記冷延鋼板を焼鈍し、前記冷却帯では前記冷延鋼板を冷却する焼鈍炉と、
前記焼鈍炉から排出された前記冷延鋼板を引き続き通板させる下流設備と、
前記下流設備を通板中の前記冷延鋼板を巻き取るテンションリールと、
前記冷却帯から前記テンションリールまでを通板中の前記冷延鋼板に対して、前記冷延鋼板の板幅方向に沿って定常磁場を印加する磁場印加装置と、
を有する連続焼鈍装置。
前記下流設備として、前記焼鈍炉の通板方向下流に位置し、前記冷延鋼板を浸漬させて、前記冷延鋼板に溶融亜鉛めっきを施す溶融亜鉛めっき浴と、
を有する連続溶融亜鉛めっき装置。
(B)通板方向上流側から加熱帯、均熱帯、及び冷却帯が位置する焼鈍炉内に、前記冷延鋼板を通板させて、(B-1)前記加熱帯及び前記均熱帯では、水素を含む還元性雰囲気で前記冷延鋼板を焼鈍し、(B-2)前記冷却帯では前記冷延鋼板を冷却する、連続焼鈍を行う工程と、
(C)前記焼鈍炉から排出された前記冷延鋼板を引き続き通板させる工程と、
(D)テンションリールにより前記冷延鋼板を巻き取って、製品コイルとする工程と、
をこの順に有し、
工程(B-2)以降、かつ、工程(D)より前において、通板中の前記冷延鋼板に対して、前記冷延鋼板の板幅方向に沿って定常磁場を印加する磁場印加工程を含む鋼板の製造方法。
C :0.030~0.800%、
Si:0.01~3.00%、
Mn:0.01~10.00%、
P :0.001~0.100%、
S :0.0001~0.0200%、
N :0.0005~0.0100%、及び
Al:0.001~2.000%を含み、
残部がFe及び不可避的不純物からなる成分組成を有する、上記[16]~[28]のいずれか一項に記載の鋼板の製造方法。
Ti:0.200%以下、
Nb:0.200%以下、
V :0.500%以下、
W :0.500%以下、
B :0.0050%以下、
Ni:1.000%以下、
Cr:1.000%以下、
Mo:1.000%以下、
Cu:1.000%以下、
Sn:0.200%以下、
Sb:0.200%以下、
Ta:0.100%以下、
Ca:0.0050%以下、
Mg:0.0050%以下、
Zr:0.1000%以下、及び
REM:0.0050%以下
からなる群から選ばれる少なくとも一種の元素を含有する、上記[29]に記載の鋼板の製造方法。
C :0.001~0.400%、
Si:0.01~2.00%、
Mn:0.01~5.00%、
P :0.001~0.100%、
S :0.0001~0.0200%、
Cr:9.0~28.0%、
Ni:0.01~40.0%、
N :0.0005~0.500%、及び
Al:0.001~3.000%を含み、
残部がFe及び不可避的不純物からなる成分組成を有するステンレス鋼板である、上記[16]~[27]のいずれか一項に記載の鋼板の製造方法。
Ti:0.500%以下、
Nb:0.500%以下、
V :0.500%以下、
W :2.000%以下、
B :0.0050%以下、
Mo:2.000%以下、
Cu:3.000%以下、
Sn:0.500%以下、
Sb:0.200%以下、
Ta:0.100%以下、
Ca:0.0050%以下、
Mg:0.0050%以下、
Zr:0.1000%以下、及び
REM:0.0050%以下
からなる群から選ばれる少なくとも一種の元素を含有する、上記[31]に記載の鋼板の製造方法。
[工程(A)]
図1~3を参照して、ペイオフリール10は、冷延コイルCから冷延鋼板Sを払い出す。すなわち、工程(A)では、ペイオフリール10により冷延コイルCから冷延鋼板Sを払い出す。払い出された冷延鋼板Sは、溶接機11、クリーニング設備12、及び入側ルーパー13を通過し、焼鈍炉20へと供給される。ただし、ペイオフリール10と焼鈍炉20との間の上流設備は、これら溶接機11、クリーニング設備12、及び入側ルーパー13に限定されることはなく、公知の又は任意の装置であってよい。
[工程(B)]
図1~3を参照して、焼鈍炉20は、冷延鋼板Sを内部に通板させて連続焼鈍する。焼鈍炉20では、通板方向上流側から加熱帯22、均熱帯24、及び冷却帯26が位置し、加熱帯22及び均熱帯24では、水素を含む還元性雰囲気で冷延鋼板Sを焼鈍し、冷却帯26では冷延鋼板Sを冷却する。すなわち、工程(B)では、通板方向上流側から加熱帯22、均熱帯24、及び冷却帯26が位置する焼鈍炉20内に、冷延鋼板Sを通板させて連続焼鈍を行う。冷却帯26は、複数の冷却帯から構成されてもよい。また、加熱帯22の通板方向上流側に予熱帯があってもよい。なお、図1に示すCAL100の焼鈍炉20は、冷却帯26の下流に過時効処理帯28を有することが好ましいが、必須ではない。図1~3では、各帯はいずれも縦型炉として図示したが、これに限定されず、横型炉でもよい。縦型炉の場合、隣り合う帯は、それぞれの帯の上部同士または下部同士を接続するスロート(絞り部)を介して連通する。
加熱帯22では、バーナーを用いて、冷延鋼板Sを直接加熱することや、ラジアントチューブ(RT)又は電気ヒーターを用いて、冷延鋼板Sを間接加熱することができる。また、誘導加熱、ロール加熱、電気抵抗加熱、直接通電加熱、ソルトバス加熱、エレクトロンビーム加熱等での加熱も可能である。加熱帯22の内部の平均温度は500~800℃とすることが好ましい。加熱帯22には、均熱帯24からのガスが流れ込むと同時に、別途還元性ガスが供給される。還元性ガスとしては、通常H2-N2混合ガスが用いられ、例えばH2:1~35体積%、残部がN2及びArの一方又は両方並びに不可避的不純物からなる組成を有するガス(露点:-60℃程度)が挙げられる。
均熱帯24では、ラジアントチューブ(RT)を用いて、冷延鋼板Sを間接加熱することができる。均熱帯24の内部の平均温度は600~950℃とすることが好ましい。均熱帯24には還元性ガスが供給される。還元性ガスとしては、通常H2-N2混合ガスが用いられ、例えばH2:1~35体積%、残部がN2及びArの一方又は両方並びに不可避的不純物からなる組成を有するガス(露点:-60℃程度)が挙げられる。
冷却帯26では、ガス、ガスと水の混合、及び水のいずれかによって冷延鋼板Sが冷却される。冷延鋼板Sは、焼鈍炉20を出る段階で、CALでは100~400℃程度、CGLでは470~530℃程度にまで冷却される。冷却帯26には、鋼板搬送路に沿って複数の冷却ノズルが設けられる。冷却ノズルは、例えば特開2010-185101号公報に記載されるような、鋼板幅よりも長い円管であり、円管の延在方向が鋼板の幅方向と平行になるように設置される。円管には、鋼板と対向する部位に、円管の延在方向に沿って所定の間隔で複数の貫通穴が設けられ、円管内の水が当該貫通穴から鋼板に向かって噴射される。冷却ノズルは、鋼板の表裏に対向するように一対に設けられ、さらに一対の冷却ノズルが鋼板搬送路に沿って所定間隔で複数対(例えば5~10対)配置されて、1つの冷却ゾーンを構成する。そして、当該冷却ゾーンは鋼板搬送路に沿って3~6つ程度配置することが好ましい。
図1を参照して、CAL100において、過時効処理帯28では、冷却帯26を出た冷延鋼板Sが等温保持、再加熱、炉冷、及び放冷の少なくとも一つの処理に供され、冷延鋼板Sは、焼鈍炉20を出る段階で、100~400℃程度にまで冷却される。
[工程(C)]
図1~3を参照して、工程(C)では、焼鈍炉20から排出された冷延鋼板Sを下流設備30に引き続き通板させる。図1を参照して、CAL100は、下流設備30として出側ルーパー35及び調質圧延機36を有する。図2を参照して、CGL200は、下流設備30として、溶融亜鉛めっき浴31、ガスワイピング装置32、合金化炉33、冷却装置34、出側ルーパー35、及び調質圧延機36を有する。図3を参照して、CGL300は、下流設備30として、溶融亜鉛めっき浴31、ガスワイピング装置32、冷却装置34、出側ルーパー35、及び調質圧延機36を有する。ただし、下流設備30はこれらに限定されることはなく、公知の又は任意の装置であってよい。例えば、下流設備30としては、テンションレベラー、化成処理設備、表面調整設備、オイリング設備、及び検査設備を挙げることができる。
(工程(C-1))
図2,3を参照して、溶融亜鉛めっき浴31は、焼鈍炉20の通板方向下流に位置し、冷延鋼板Sを浸漬させて、冷延鋼板Sに溶融亜鉛めっきを施す。すなわち、工程(C-1)では、焼鈍炉20の通板方向下流に位置する溶融亜鉛めっき浴31に冷延鋼板Sを浸漬させて、冷延鋼板Sに溶融亜鉛めっきを施す。焼鈍炉の最下流の帯(図2,3では冷却帯26)と連結したスナウト29は、冷延鋼板Sが通過する空間を区画する、通板方向に垂直な断面が矩形状の部材であり、その先端が溶融亜鉛めっき浴31に浸漬しており、以って焼鈍炉20と溶融亜鉛めっき浴31とが接続されている。溶融亜鉛めっきは定法に従って行えばよい。
(工程(C-2))
図2を参照して、合金化炉33は、溶融亜鉛めっき浴31及びガスワイピング装置32の通板方向下流に位置し、冷延鋼板Sを通板させて、溶融亜鉛めっきを加熱合金化する。すなわち、工程(C-2)では、溶融亜鉛めっき浴31及びガスワイピング装置32の通板方向下流に位置する合金化炉33に冷延鋼板Sを通板させて、溶融亜鉛めっきを加熱合金化する。合金化処理は定法に従って行えばよい。合金化炉33における加熱手段は特に限定されず、例えば、高温のガスによる加熱や誘導加熱が挙げられる。ただし、合金化炉33は、CGLにおける任意の設備であり、合金化工程は、CGLを用いた鋼板の製造方法における任意の工程である。
図2,3を参照して、冷却装置34は、ガスワイピング装置32及び合金化炉33の通板方向下流に位置する。冷却装置34に冷延鋼板Sを通板させて、冷延鋼板Sを冷却することができる。冷却装置34は、冷延鋼板Sを水冷、空冷、ガス冷却、ミスト冷却等で冷却する。
[工程(D)]
図1~3を参照して、下流設備30を通過した冷延鋼板Sは、最終的に、巻取り装置としてのテンションリール50により巻き取られて、製品コイルPとなる。
上記第一の実施形態のCAL100、第二の実施形態のCGL200、及び第三の実施形態のCGL300は、冷却帯26からテンションリール50までを通板中の冷延鋼板Sに対して、冷延鋼板Sの板幅方向に沿って定常磁場を印加する磁場印加装置60を有することが肝要である。すなわち、上記第一、第二、及び第三の実施形態による鋼板の製造方法は、工程(B-2)以降、かつ、工程(D)より前において、通板中の冷延鋼板Sに対して、冷延鋼板Sの板幅方向に沿って定常磁場を印加する磁場印加工程を含むことが肝要である。これにより、焼鈍で冷延鋼板S中に含有された水素を十分に効率良く低減させることができ、耐水素脆化特性に優れた鋼板を製造することができる。また、定常磁場の印加は、CAL100、CGL200又はCGL300による鋼板の製造過程(インライン)に組み込まれるため、生産効率を損なうことがない。また、加熱による水素の脱離ではなく、定常磁場の印加による水素の脱離であるため、鋼板の機械的特性を変化させる懸念もない。
本発明の各実施形態は、図4及び図5(A),(B)に示すような磁場印加装置60をCAL100、CGL200又はCGL300に設置することにより実現でき、磁場印加工程は、当該磁場印加装置60を用いて通板中の冷延鋼板Sに定常磁場を印加する。図4を参照して、磁場印加装置60は、冷延鋼板Sの幅方向両端部の外側にそれぞれ位置する一対の電磁石60A,60Bを含む。電磁石60A,60Bは、それぞれ、鉄心62A,62Bと、これら鉄心62A,62Bを巻回するコイル64A,64Bと、これらコイル64A,64Bに電流を流すための駆動電源(図示せず)と、を有する。駆動電源をONにして、コイル64A,64Bに直流の連続電流を流すことにより、電磁石60A,60Bを磁化させることができ、定常磁場を発生させることができる。コイル64A,64Bの軸方向は、冷延鋼板Sの板幅方向と一致する。一対の電磁石60A,60Bは、それぞれ冷延鋼板Sの幅方向端面と所定の間隔をあけて対向する磁極面66A,66Bを有する。コイル64A,64Bに流す電流の方向を制御することで、片方の磁極面66AをN極とし、他方の磁極面66BをS極とすることができる。一対の磁極面66A,66Bは、冷延鋼板Sの通板方向の同じ位置にあり、かつ、冷延鋼板Sを挟んで対向している。このため、図4に示すように、一対の電磁石60A,60Bにより発生する定常磁場は、その主たる磁束が磁極面66A(N極)から磁極面66B(S極)に向かうことになり、その方向が冷延鋼板Sの幅方向と一致する。これにより、冷延鋼板Sの板幅方向に沿って均一に定常磁場を印加することができる。そして、図5(A),(B)に示すように、このような一対の電磁石60A,60Bを通板方向に沿って複数配置することによって、冷延鋼板Sに磁場を印加する時間を十分に確保することができる。なお、本明細書において、「直流の連続電流」とは、電流値がパルス的ではなく連続的に(好ましくは一定に)維持される直流電流を意味する。また、本明細書において「定常磁場」とは、パルス的ではなく連続的に維持される磁場を意味し、静止した磁石が形成する磁場と、直流の連続電流が供給された電磁石が形成する磁場とを含む。
水素の拡散を促進して、冷延鋼板S中に含有された水素を十分に脱離する観点から、冷延鋼板Sの板幅方向への磁束密度は0.1T以上であることが好ましく、0.2T以上であることがより好ましく、0.5T以上であることがさらに好ましい。他方で、一般的な磁場印加装置の性能を考慮して、冷延鋼板Sの板幅方向への磁束密度は、15T以下であることが好ましく、14T以下であることがより好ましい。冷延鋼板Sの板幅方向への磁束密度は、コイルの巻き数や電流値を調整することにより、調整することができる。「冷延鋼板Sの板幅方向への磁束密度」は、通板中の冷延鋼板Sの幅方向端面近傍、かつ、磁場印加装置60の磁場発生面近傍にテスラメータを設置することにより、インラインで測定することができる。あるいは、磁場印加装置60におけるコイルの巻き数と、電流値の大きさが決まれば、オフラインで「冷延鋼板Sの板幅方向への磁束密度」を予め把握することもできる。
冷延鋼板Sから水素をより十分に低減させる観点から、磁場印加工程において、冷延鋼板Sに対する磁場の印加時間は1秒以上とすることが好ましく、5秒以上とすることがより好ましく、10秒以上とすることがさらに好ましい。他方、生産性を阻害しない観点から、冷延鋼板Sに対する磁場の印加時間は3600秒以下とすることが好ましく、1800秒以下とすることがより好ましく、900秒以下とすることがさらに好ましい。本明細書において、「冷延鋼板Sに対する磁場の印加時間」とは、冷延鋼板Sの板幅方向の各位置に磁場が印可される時間を意味し、各位置が複数の磁場印加装置60から磁場を印加される場合には、その積算時間を意味する。図4を参照して、一対の電磁石60A,60Bを用いる場合には、冷延鋼板Sの一対の電磁石60A,60Bと対向する部分は、磁場が印可されているとみなすことができる。よって、冷延鋼板Sの各部位が一対の電磁石60A,60Bと対向している時間の積算を磁場印加時間とすることができる。磁場印加時間は、冷延鋼板Sの通板速度と、磁場印加装置60の位置(例えば、図4に示す一対の電磁石60A,60Bの通板方向に沿った数)とによって調整することができる。
本実施形態において、CAL100、CGL200及びCGL300に供給される冷延鋼板Sは特に限定されない。冷延鋼板Sは、板厚6mm未満であることが好ましく、例えば、590MPa以上の引張強さを有する高強度鋼板や、ステンレス鋼板を挙げることができる。
冷延鋼板Sが高強度鋼板である場合の成分組成について説明する。以下、「質量%」は単に「%」と記す。
Cは、鋼板の強度を上昇させる効果を有する。この効果を得る観点から、C量は0.030%以上とし、好ましくは0.080%以上とする。しかし、C量が過剰の場合、鋼板中の水素量によらず鋼板が著しく脆化する。よって、C量は0.800%以下とし、好ましくは0.500%以下とする。
Siは、鋼板の強度を上昇させる効果を有する。この効果を得る観点から、Si量は0.01%以上とし、好ましくは0.10%以上とする。しかし、Si量が過剰の場合、鋼板が脆化して延性が低下したり、赤スケールなどが発生して表面性状が劣化したり、めっき品質が低下する。よって、Si量は3.00%以下とし、好ましくは2.50%以下とする。
Mnは、固溶強化により鋼板の強度を上昇させる効果を有する。この効果を得る観点から、Mn量は0.01%以上とし、好ましくは0.5%以上とする。しかし、Mn量が過剰の場合、Mnの偏析に起因して鋼組織にムラが生じやすくなり、ムラを起点とした水素脆性が顕在化する場合がある。よって、Mn量は10.00%以下とし、好ましくは8.00%以下とする。
Pは、固溶強化の作用を有し、所望の強度に応じて添加できる元素である。こうした効果を得る観点から、P量は0.001%以上とし、好ましくは0.003%以上とする。しかし、P量が過剰の場合、溶接性が劣化し、亜鉛めっきを合金化する場合には、合金化速度が低下して、亜鉛めっきの品質を損なう。よって、P量は0.100%以下とし、好ましくは0.050%以下とする。
Sは、粒界に偏析して熱間加工時に鋼を脆化させるとともに、硫化物として存在して局部変形能を低下させる。そのため、S量は0.0200%以下とし、好ましくは0.0100%以下とし、より好ましくは0.0050%以下とする。一方、生産技術上の制約から、S量は0.0001%以上とする。
Nは、鋼の耐時効性を劣化させる元素である。そのため、N量は0.0100%以下とし、好ましくは0.0070%以下とする。N量は少ないほど好ましいが、生産技術上の制約から、N量は0.0005%以上とし、好ましくは0.0010%以上とする。
Alは、脱酸剤として作用し、鋼の清浄度に有効な元素である。この効果を得る観点から、Al量は0.001%以上とし、好ましくは0.010%以上とする。しかし、Al量が過剰の場合、連続鋳造時に鋼片割れが発生する可能性がある。よって、Al量は2.000%以下とし、好ましくは1.200%以下とする。
Tiは、鋼の析出強化やフェライト結晶粒の成長抑制による細粒強化にて、鋼板の強度上昇に寄与する。よって、Tiを添加する場合、Ti量は0.005%以上とすることが好ましく、0.010%以上とすることがよりこのましい。しかし、Ti量が過剰の場合、炭窒化物が多量に析出し、成形性が低下する場合がある。よって、Tiを添加する場合、Ti量を0.200%以下とし、好ましくは0.100%以下とする。
Nb、V、及びWは、鋼の析出強化に有効である。よって、Nb、V、及びWを添加する場合、各元素の含有量は0.005%以上とすることが好ましく、0.010%以上とすることがより好ましい。しかし、各含有量が過剰の場合、炭窒化物が多量に析出し、成形性が低下する場合がある。よって、Nbを添加する場合、Nb量は0.200%以下とし、好ましくは0.100%以下とする。V及びWを添加する場合、各元素の含有量は0.500%以下とし、好ましくは0.300%以下とする。
Bは、粒界の強化や鋼板の高強度化に有効である。よって、Bを添加する場合、B量は0.0003%以上とすることが好ましい。しかし、B量が過剰の場合、成形性が低下する場合がある。よって、Bを添加する場合、B量は0.0050%以下とし、好ましくは0.0030%以下とする。
Niは、固溶強化により鋼の強度を上昇させる元素である。よって、Niを添加する場合、Ni量は0.005%以上とすることが好ましい。しかし、Ni量が過剰の場合、硬質なマルテンサイトの面積率が過大となり、引張試験時に、マルテンサイトの結晶粒界でのマイクロボイドが増加し、さらに、亀裂の伝播が進行してしまい、延性が低下する場合がある。よって、Niを添加する場合、Ni量は1.000%以下とする。
Cr及びMoは、強度と成形性のバランスを向上させる作用を有する。よって、Cr及びMoを添加する場合、各元素の含有量は0.005%以上とすることが好ましい。しかし、各含有量が過剰の場合、硬質なマルテンサイトの面積率が過大となり、引張試験時に、マルテンサイトの結晶粒界でのマイクロボイドが増加し、さらに、亀裂の伝播が進行してしまい、延性が低下する場合がある。よって、Cr及びMoを添加する場合、各元素の含有量は1.000%以下とする。
Cuは、鋼の強化に有効な元素である。よって、Cuを添加する場合、Cu量は0.005%以上とすることが好ましい。しかし、Cu量が過剰の場合、硬質なマルテンサイトの面積率が過大となり、引張試験時に、焼戻しマルテンサイトの結晶粒界でのマイクロボイドが増加し、さらに、亀裂の伝播が進行してしまい、延性が低下する場合がある。よって、Cuを添加する場合、Cu量は1.000%以下とする。
Sn及びSbは、鋼板表面の窒化や酸化によって生じる鋼板表層の数十μm程度の領域の脱炭を抑制することや、強度や材質安定性の確保に有効である。よって、Sn及びSbを添加する場合、各元素の含有量は0.002%以上とすることが好ましい。しかし、各含有量が過剰の場合、靭性が低下する場合がある。よって、Sn及びSbを添加する場合、各元素の含有量は0.200%以下とする。
Taは、TiやNbと同様に、合金炭化物や合金炭窒化物を生成して高強度化に寄与する。加えて、Nb炭化物やNb炭窒化物に一部固溶し、(Nb、Ta)(C、N)のような複合析出物を生成することで、析出物の粗大化を著しく抑制し、析出強化による強度への寄与を安定化させる効果があると考えられる。よって、Taを添加する場合、Ta量は0.001%以上とすることが好ましい。しかし、Taを過剰に添加しても析出物安定化効果が飽和する場合がある上、合金コストも増加する。よって、Taを添加する場合、Ta量は0.100%以下とする。
Ca、Mg、Zr及びREMは、硫化物の形状を球状化し、成形性への硫化物の悪影響を改善するために有効な元素である。これらの元素を添加する場合には、各元素の含有量は0.0005%以上とすることが好ましい。しかし、各含有量が過剰の場合、介在物等が増加し、表面及び内部欠陥が発生する場合がある。よって、これらの元素を添加する場合、各元素の含有量は0.0050%以下とする。
冷延鋼板Sがステンレス鋼板である場合の成分組成について説明する。以下、「質量%」は単に「%」と記す。
Cは、ステンレス鋼において高強度を得るために欠かせない元素である。しかし、鋼製造における焼戻し時にCrと結合して炭化物として析出し、これが鋼の耐食性及び靭性を劣化させる。C量が0.001%未満では十分な強度が得られず、0.400%を超えると前記劣化が顕著になる。このため、C量は0.001~0.400%とする。
Siは、脱酸剤として有用な元素である。この効果を得る観点から、Si量は0.01%以上にする。しかし、Si量が過剰の場合、鋼中に固溶したSiは鋼の加工性を低下させる。よって、Siは2.00%以下とする。
Mnは、鋼の強度を高める効果を有する。この効果を得る観点から、Mn量は0.01%以上とする。しかし、Mn量が過剰の場合、鋼の加工性が低下する。よって、Mn量は5.00%以下とする。
Pは、粒界偏析による粒界破壊を助長する元素である。このため、P量は低い方が望ましく、0.100%以下とし、好ましくは0.030%以下とし、より好ましくは0.020%以下とする。一方、生産技術上の制約からP量0.001%以上とする。
Sは、MnSなどの硫化物系介在物として存在して、延性や耐食性等を低下させる。このため、S量は低い方が望ましく、0.0200%以下とし、好ましくは0.0100%以下とし、より好ましくは0.0050%以下とする。一方、生産技術上の制約からS量は0.0001%以上とする。
Crはステンレス鋼を構成する基本的な元素で、しかも耐食性を発現する重要な元素である。180℃以上の苛酷な環境における耐食性を考慮した場合、Cr量が9.0%未満では十分な耐食性が得られず、28.0%を超えると効果は飽和し経済性の点で問題が生じる。このため、Cr量は9.0~28.0%とする。
Niはステンレス鋼の耐食性を向上させる元素である。Ni量が0.01%未満ではその効果が十分に発揮されない。一方、Ni量が過剰の場合、成形性を劣化させる他、応力腐食割れが生じやすくなる。このため、Ni量は0.01~40.0%とする。
Nはステンレス鋼の耐食性向上に有害な元素である。そのため、N量は0.500%以下とし、好ましくは0.200%以下とする。N量は少ないほど好ましいが、生産技術上の制約から、N量は0.0005%以上とする。
Alは、脱酸剤として作用する他、酸化スケールの剥離を抑制する効果がある。これらの効果を得る観点から、Al量は0.001%以上とする。しかし、Al量が過剰の場合、伸びの低下及び表面品質の劣化が起きる。よって、Al量は3.000%以下とする。
Tiは、C、N、及びSと結合して耐食性、耐粒界腐食性、及び深絞り性を向上させる。ただし、Ti量が0.500%超えの場合、固溶Tiにより靭性が劣化する。よって、Tiを添加する場合、Ti量は0.500%以下とする。
Nbは、Tiと同様に、C、N、及びSと結合して耐食性、耐粒界腐食性、及び深絞り性を向上させる。また、加工性の向上や高温強度の向上に加え、隙間腐食の抑制や再不働態化を促進させる。ただし、過度の添加は硬質化をもたらし成形性を劣化させる。よって、Nbを添加する場合、Nb量は0.500%以下とする。
Vは、隙間腐食を抑制させる。しかし、過度の添加は成形性を劣化させる。よって、Vを添加する場合、V量は0.500%以下とする。
Wは、耐食性と高温強度の向上に寄与する。ただし、過度の添加は、鋼板製造時の靭性劣化やコスト増に繋がる。よって、Wを添加する場合、W量は2.000%以下とする。
Bは、粒界に偏析することで製品の二次加工性を向上させる。ただし、過度の添加は加工性、耐食性の低下をもたらす。よって、Bを添加する場合、B量は0.0050%以下とする。
Moは耐食性を向上させ、特に隙間腐食を抑制する元素である。ただし、過度の添加は成形性を劣化させる。よって、Moを添加する場合、Mo量は2.000%以下とする。
Cuは、NiやMn同様、オーステナイト安定化元素であり、相変態による結晶粒の微細化に有効である。また、隙間腐食の抑制や再不動態化を促進させる。ただし、過度の添加は靭性及び成形性を劣化させる。よって、Cuを添加する場合、Cu量は3.000%以下とする。
Snは、耐食性と高温強度の向上に寄与する。ただし、過度の添加は鋼板製造時のスラブ割れを生じさせるおそれがある。よって、Snを添加する場合、Sn量は0.500%以下とする。
Sbは、粒界に偏析して高温強度を上げる作用を有する。ただし、過度の添加はSb偏析により溶接時に割れが生じるおそれがある。よって、Sbを添加する場合、Sb量は0.200%以下とする。
Taは、CやNと結合して靭性の向上に寄与する。ただし、過度の添加により、その効果は飽和し、製造コストの増加につながる。よって、Taを添加する場合、Ta量は0.100%以下とした。
Ca、Mg、Zr及びREMは、硫化物の形状を球状化し、成形性への硫化物の悪影響を改善するために有効な元素である。これらの元素を添加する場合には、各元素の含有量は0.0005%以上とすることが好ましい。しかし、各含有量が過剰の場合、介在物等が増加し、表面及び内部欠陥が発生する場合がある。よって、これらの元素を添加する場合、各元素の含有量は0.0050%以下とする。
本実施形態において、良好な延性を確保するためには、製品コイルの拡散性水素量は0.50質量ppm以下とすることが好ましく、0.30質量ppm以下とすることがより好ましく、0.20質量ppm以下とすることがさらに好ましい。なお、製品コイルの拡散性水素量の下限は特に規定しないが、生産技術上の制約から、製品コイルの拡散性水素量は0.01質量ppm以上となりうる。
「(B-2)」は、CAL及びCGLにおいて、冷却帯に磁場印加装置を設置し、工程(B-2)の冷却帯で磁場印加工程を行ったことを意味する。
「(C)」は、CALにおいて、下流設備を通板中の冷延鋼板に磁場を印加可能な位置に磁場印加装置を設置したことを意味し、冷却帯より下流かつテンションリールより上流の位置、具体的には、(i)過時効処理帯28と出側ルーパー35との間、(ii)出側ルーパー35内、(iii)出側ルーパー35と調質圧延機36との間、(iv)調質圧延機36とテンションリール50との間、の少なくとも1箇所に磁場印加装置を設置したことを意味する。すなわち、「(C)」は、CALにおいて、工程(C)、具体的には、上記(i)~(iv)の少なくとも1箇所にて磁場印加工程を行ったことを意味する。
「(C-1)前」は、CGLにおいて、冷却帯より下流で溶融亜鉛めっき浴よりも上流の位置、具体的には、スナウト29に磁場印加装置を設置し、工程(B-2)より後かつ工程(C-1)より前に磁場印加工程を行ったことを意味する。
「(C-1)後」は、CGLにおいて、溶融亜鉛めっき浴より下流かつテンションリールより上流の位置、具体的には、(i)溶融亜鉛めっき浴31とガスワイピング装置32との間、(ii)ガスワイピング装置32と合金化炉33との間、(iii)合金化炉33内、(iv)合金化炉33と冷却装置34との間の空冷ゾーン、(v)冷却装置34と出側ルーパー35との間、(vi)出側ルーパー35内、(vii)出側ルーパー35と調質圧延機36との間、(viii)調質圧延機36とテンションリール50との間、の少なくとも1箇所に磁場印加装置を設置し、工程(C-1)より後に、具体的には、上記(i)~(viii)の少なくとも1箇所にて磁場印加工程を行ったことを意味する。
200 連続溶融亜鉛めっき装置
300 連続溶融亜鉛めっき装置
10 ペイオフリール
11 溶接機
12 クリーニング設備
13 入側ルーパー
20 焼鈍炉
22 加熱帯
24 均熱帯
26 冷却帯
28 過時効処理帯
29 スナウト
30 下流設備
31 溶融亜鉛めっき浴
32 ガスワイピング装置
33 合金化炉
34 冷却装置
35 出側ルーパー
36 調質圧延機
50 テンションリール
60 磁場印加装置
60A 電磁石(磁場印加装置)
60B 電磁石(磁場印加装置)
62A 鉄心
62B 鉄心
64A コイル
64B コイル
66A 磁極面(N極)
66B 磁極面(S極)
C 冷延コイル
S 冷延鋼板
P 製品コイル
Claims (33)
- 冷延コイルから冷延鋼板を払い出すペイオフリールと、
前記冷延鋼板を通板させて連続焼鈍する焼鈍炉であって、通板方向上流側から加熱帯、均熱帯、及び冷却帯が位置し、前記加熱帯及び前記均熱帯では、水素を含む還元性雰囲気で前記冷延鋼板を焼鈍し、前記冷却帯では前記冷延鋼板を冷却する焼鈍炉と、
前記焼鈍炉から排出された前記冷延鋼板を引き続き通板させる下流設備と、
前記下流設備を通板中の前記冷延鋼板を巻き取るテンションリールと、
前記冷却帯から前記テンションリールまでを通板中の前記冷延鋼板に対して、前記冷延鋼板の板幅方向に沿って定常磁場を印加する磁場印加装置と、
を有する連続焼鈍装置。 - 前記磁場印加装置は、前記冷却帯に設けられる、請求項1に記載の連続焼鈍装置。
- 前記磁場印加装置は、前記下流設備を通板中の前記冷延鋼板に磁場を印加可能な位置に設けられる、請求項1又は2に記載の連続焼鈍装置。
- 前記磁場印加装置は、前記冷延鋼板の幅方向端部の外側に位置する電磁石を含み、前記電磁石は前記冷延鋼板の幅方向端面と対向する磁極面を有する、請求項1~3のいずれか一項に記載の連続焼鈍装置。
- 前記磁場印加装置は、前記冷延鋼板の幅方向両端部の外側にそれぞれ位置する一対の電磁石を含み、前記一対の電磁石は、それぞれ前記冷延鋼板の幅方向端面と対向する磁極面を有し、前記磁極面のうち片方がN極であり、他方がS極である、請求項1~3のいずれか一項に記載の連続焼鈍装置。
- 前記磁場印加装置は、前記冷延鋼板の板幅方向への磁束密度が0.1~15Tとなるように設定された、請求項1~5のいずれか一項に記載の連続焼鈍装置。
- 請求項1に記載の連続焼鈍装置と、
前記下流設備として、前記焼鈍炉の通板方向下流に位置し、前記冷延鋼板を浸漬させて、前記冷延鋼板に溶融亜鉛めっきを施す溶融亜鉛めっき浴と、
を有する連続溶融亜鉛めっき装置。 - 前記磁場印加装置は、前記溶融亜鉛めっき浴より上流を通板中の前記冷延鋼板に磁場を印加可能な位置に設けられる、請求項7に記載の連続溶融亜鉛めっき装置。
- 前記磁場印加装置は、前記溶融亜鉛めっき浴より下流を通板中の前記冷延鋼板に磁場を印加可能な位置に設けられる、請求項7又は8に記載の連続溶融亜鉛めっき装置。
- 前記下流設備として、前記溶融亜鉛めっき浴の通板方向下流に位置し、前記冷延鋼板を通板させて、前記溶融亜鉛めっきを加熱合金化する合金化炉を有する、請求項7に記載の連続溶融亜鉛めっき装置。
- 前記磁場印加装置は、前記溶融亜鉛めっき浴より上流を通板中の前記冷延鋼板に磁場を印加可能な位置に設けられる、請求項10に記載の連続溶融亜鉛めっき装置。
- 前記磁場印加装置は、前記溶融亜鉛めっき浴より下流を通板中の前記冷延鋼板に磁場を印加可能な位置に設けられる、請求項10又は11に記載の連続溶融亜鉛めっき装置。
- 前記磁場印加装置は、前記冷延鋼板の幅方向端部の外側に位置する電磁石を含み、前記電磁石は前記冷延鋼板の幅方向端面と対向する磁極面を有する、請求項7~12のいずれか一項に記載の連続溶融亜鉛めっき装置。
- 前記磁場印加装置は、前記冷延鋼板の幅方向両端部の外側にそれぞれ位置する一対の電磁石を含み、前記一対の電磁石は、それぞれ前記冷延鋼板の幅方向端面と対向する磁極面を有し、前記磁極面のうち片方がN極であり、他方がS極である、請求項7~12のいずれか一項に記載の連続溶融亜鉛めっき装置。
- 前記磁場印加装置は、前記冷延鋼板の板幅方向への磁束密度が0.1~15Tとなるように設定された、請求項7~14のいずれか一項に記載の連続溶融亜鉛めっき装置。
- (A)ペイオフリールにより冷延コイルから冷延鋼板を払い出す工程と、
(B)通板方向上流側から加熱帯、均熱帯、及び冷却帯が位置する焼鈍炉内に、前記冷延鋼板を通板させて、(B-1)前記加熱帯及び前記均熱帯では、水素を含む還元性雰囲気で前記冷延鋼板を焼鈍し、(B-2)前記冷却帯では前記冷延鋼板を冷却する、連続焼鈍を行う工程と、
(C)前記焼鈍炉から排出された前記冷延鋼板を引き続き通板させる工程と、
(D)テンションリールにより前記冷延鋼板を巻き取って、製品コイルとする工程と、
をこの順に有し、
工程(B-2)以降、かつ、工程(D)より前において、通板中の前記冷延鋼板に対して、前記冷延鋼板の板幅方向に沿って定常磁場を印加する磁場印加工程を含む鋼板の製造方法。 - 前記磁場印加工程は、工程(B-2)にて行われる、請求項16に記載の鋼板の製造方法。
- 前記磁場印加工程は、工程(C)にて行われる、請求項16又は17に記載の鋼板の製造方法。
- 工程(C)は、(C-1)前記焼鈍炉の通板方向下流に位置する溶融亜鉛めっき浴に前記冷延鋼板を浸漬させて、前記冷延鋼板に溶融亜鉛めっきを施す工程を含む、請求項16に記載の鋼板の製造方法。
- 前記磁場印加工程は、工程(C-1)より前に行われる、請求項19に記載の鋼板の製造方法。
- 前記磁場印加工程は、工程(C-1)より後に行われる、請求項19又は20に記載の鋼板の製造方法。
- 前記工程(C)は、前記工程(C-1)に続き、(C-2)前記溶融亜鉛めっき浴の通板方向下流に位置する合金化炉に前記冷延鋼板を通板させて、前記溶融亜鉛めっきを加熱合金化する工程を含む、請求項19に記載の鋼板の製造方法。
- 前記磁場印加工程は、工程(C-1)より前に行われる、請求項22に記載の鋼板の製造方法。
- 前記磁場印加工程は、工程(C-1)より後に行われる、請求項22又は23に記載の鋼板の製造方法。
- 前記磁場印加工程において、前記冷延鋼板の板幅方向への磁束密度を0.1~15Tとする、請求項16~24のいずれか一項に記載の鋼板の製造方法。
- 前記磁場印加工程では、前記冷延鋼板の幅方向端部の外側に位置する電磁石を含み、前記電磁石は前記冷延鋼板の幅方向端面と対向する磁極面を有する磁場印加装置により、前記定常磁場が印可される、請求項16~25のいずれか一項に記載の鋼板の製造方法。
- 前記磁場印加工程では、前記冷延鋼板の幅方向両端部の外側にそれぞれ位置する一対の電磁石を含み、前記一対の電磁石は、それぞれ前記冷延鋼板の幅方向端面と対向する磁極面を有し、前記磁極面のうち片方がN極であり、他方がS極である磁場印加装置により、前記定常磁場が印可される、請求項16~25のいずれか一項に記載の鋼板の製造方法。
- 前記冷延鋼板が、590MPa以上の引張強さを有する高強度鋼板である、請求項16~27のいずれか一項に記載の鋼板の製造方法。
- 前記冷延鋼板は、質量%で、
C :0.030~0.800%、
Si:0.01~3.00%、
Mn:0.01~10.00%、
P :0.001~0.100%、
S :0.0001~0.0200%、
N :0.0005~0.0100%、及び
Al:0.001~2.000%を含み、
残部がFe及び不可避的不純物からなる成分組成を有する、請求項16~28のいずれか一項に記載の鋼板の製造方法。 - 前記成分組成が、さらに、質量%で、
Ti:0.200%以下、
Nb:0.200%以下、
V :0.500%以下、
W :0.500%以下、
B :0.0050%以下、
Ni:1.000%以下、
Cr:1.000%以下、
Mo:1.000%以下、
Cu:1.000%以下、
Sn:0.200%以下、
Sb:0.200%以下、
Ta:0.100%以下、
Ca:0.0050%以下、
Mg:0.0050%以下、
Zr:0.1000%以下、及び
REM:0.0050%以下
からなる群から選ばれる少なくとも一種の元素を含有する、請求項29に記載の鋼板の製造方法。 - 前記冷延鋼板は、質量%で、
C :0.001~0.400%、
Si:0.01~2.00%、
Mn:0.01~5.00%、
P :0.001~0.100%、
S :0.0001~0.0200%、
Cr:9.0~28.0%、
Ni:0.01~40.0%、
N :0.0005~0.500%、及び
Al:0.001~3.000%を含み、
残部がFe及び不可避的不純物からなる成分組成を有するステンレス鋼板である、請求項16~27のいずれか一項に記載の鋼板の製造方法。 - 前記成分組成が、さらに、質量%で、
Ti:0.500%以下、
Nb:0.500%以下、
V :0.500%以下、
W :2.000%以下、
B :0.0050%以下、
Mo:2.000%以下、
Cu:3.000%以下、
Sn:0.500%以下、
Sb:0.200%以下、
Ta:0.100%以下、
Ca:0.0050%以下、
Mg:0.0050%以下、
Zr:0.1000%以下、及び
REM:0.0050%以下
からなる群から選ばれる少なくとも一種の元素を含有する、請求項31に記載の鋼板の製造方法。 - 前記製品コイルは、0.50質量ppm以下の拡散性水素量を有する、請求項16~32のいずれか一項に記載の鋼板の製造方法。
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| WO2023181820A1 true WO2023181820A1 (ja) | 2023-09-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2023/007690 Ceased WO2023181820A1 (ja) | 2022-03-25 | 2023-03-01 | 連続焼鈍装置及び連続溶融亜鉛めっき装置、並びに鋼板の製造方法 |
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| Country | Link |
|---|---|
| US (1) | US20250171872A1 (ja) |
| EP (1) | EP4474497A4 (ja) |
| JP (1) | JP7380965B1 (ja) |
| KR (1) | KR20240162098A (ja) |
| CN (1) | CN118946671A (ja) |
| MX (1) | MX2024011171A (ja) |
| WO (1) | WO2023181820A1 (ja) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20240144275A (ko) * | 2022-03-25 | 2024-10-02 | 제이에프이 스틸 가부시키가이샤 | 탈수소 장치 및 강판의 제조 시스템, 그리고 강판의 제조 방법 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56169719A (en) * | 1980-06-02 | 1981-12-26 | Nippon Steel Corp | Continuous vibrating method for metal plate |
| JPS6312555A (ja) * | 1986-07-01 | 1988-01-19 | Mitsubishi Heavy Ind Ltd | 搬送金属板のステアリング装置 |
| JPH10130739A (ja) * | 1996-10-28 | 1998-05-19 | Fuji Photo Film Co Ltd | 磁場熱処理方法及び装置 |
| JP2010185101A (ja) | 2009-02-12 | 2010-08-26 | Jfe Steel Corp | 連続焼鈍炉のガスジェット冷却装置 |
| WO2019188642A1 (ja) | 2018-03-30 | 2019-10-03 | Jfeスチール株式会社 | 高強度鋼板およびその製造方法 |
| WO2023286440A1 (ja) * | 2021-07-14 | 2023-01-19 | Jfeスチール株式会社 | 連続焼鈍装置及び連続溶融亜鉛めっき装置、並びに鋼板の製造方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3661116A (en) * | 1970-11-23 | 1972-05-09 | Bethlehem Steel Corp | Magnetic stabilizing means for strip |
| US4655166A (en) * | 1979-12-26 | 1987-04-07 | Hitachi, Ltd. | Apparatus for preventing oscillation of running strip |
| KR930000171A (ko) * | 1991-06-25 | 1993-01-15 | 사이또오 히로시 | 강대의 연속 이동방법 |
| US12571068B2 (en) * | 2020-07-14 | 2026-03-10 | Jfe Steel Corporation | Continuous annealing line, continuous hot-dip galvanizing line, and steel sheet production method |
-
2023
- 2023-03-01 US US18/844,156 patent/US20250171872A1/en active Pending
- 2023-03-01 EP EP23774419.8A patent/EP4474497A4/en active Pending
- 2023-03-01 CN CN202380029116.5A patent/CN118946671A/zh active Pending
- 2023-03-01 JP JP2023555692A patent/JP7380965B1/ja active Active
- 2023-03-01 KR KR1020247033711A patent/KR20240162098A/ko active Pending
- 2023-03-01 MX MX2024011171A patent/MX2024011171A/es unknown
- 2023-03-01 WO PCT/JP2023/007690 patent/WO2023181820A1/ja not_active Ceased
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56169719A (en) * | 1980-06-02 | 1981-12-26 | Nippon Steel Corp | Continuous vibrating method for metal plate |
| JPS6312555A (ja) * | 1986-07-01 | 1988-01-19 | Mitsubishi Heavy Ind Ltd | 搬送金属板のステアリング装置 |
| JPH10130739A (ja) * | 1996-10-28 | 1998-05-19 | Fuji Photo Film Co Ltd | 磁場熱処理方法及び装置 |
| JP2010185101A (ja) | 2009-02-12 | 2010-08-26 | Jfe Steel Corp | 連続焼鈍炉のガスジェット冷却装置 |
| WO2019188642A1 (ja) | 2018-03-30 | 2019-10-03 | Jfeスチール株式会社 | 高強度鋼板およびその製造方法 |
| WO2023286440A1 (ja) * | 2021-07-14 | 2023-01-19 | Jfeスチール株式会社 | 連続焼鈍装置及び連続溶融亜鉛めっき装置、並びに鋼板の製造方法 |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP4474497A4 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2023181820A1 (ja) | 2023-09-28 |
| CN118946671A (zh) | 2024-11-12 |
| KR20240162098A (ko) | 2024-11-14 |
| JP7380965B1 (ja) | 2023-11-15 |
| MX2024011171A (es) | 2024-09-23 |
| EP4474497A1 (en) | 2024-12-11 |
| EP4474497A4 (en) | 2025-05-28 |
| US20250171872A1 (en) | 2025-05-29 |
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