WO2012091409A2 - 도금 방법 및 아연 도금 공정 - Google Patents
도금 방법 및 아연 도금 공정 Download PDFInfo
- Publication number
- WO2012091409A2 WO2012091409A2 PCT/KR2011/010154 KR2011010154W WO2012091409A2 WO 2012091409 A2 WO2012091409 A2 WO 2012091409A2 KR 2011010154 W KR2011010154 W KR 2011010154W WO 2012091409 A2 WO2012091409 A2 WO 2012091409A2
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- Prior art keywords
- plasma
- plating
- laser
- surface treatment
- atmosphere
- Prior art date
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- 238000007747 plating Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 58
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 35
- 239000011701 zinc Substances 0.000 title claims abstract description 35
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 108
- 239000010959 steel Substances 0.000 claims abstract description 108
- 230000001678 irradiating effect Effects 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000004381 surface treatment Methods 0.000 claims description 52
- 239000012298 atmosphere Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 32
- 229910000937 TWIP steel Inorganic materials 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 22
- 238000007789 sealing Methods 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 210000004894 snout Anatomy 0.000 claims description 10
- 229910000794 TRIP steel Inorganic materials 0.000 claims description 9
- 238000005246 galvanizing Methods 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000005211 surface analysis Methods 0.000 description 17
- 229910001873 dinitrogen Inorganic materials 0.000 description 16
- 238000003763 carbonization Methods 0.000 description 7
- 238000010924 continuous production Methods 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000010953 base metal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 206010040925 Skin striae Diseases 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
-
- 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
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
- C21D1/38—Heating by cathodic discharges
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/82—Descaling by thermal stresses
-
- 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
- C21D11/00—Process control or regulation for heat treatments
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
-
- 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/003—Apparatus
- C23C2/0034—Details related to elements immersed in bath
- C23C2/00342—Moving elements, e.g. pumps or mixers
- C23C2/00344—Means for moving substrates, e.g. immersed rollers or immersed bearings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/003—Apparatus
- C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
- C23C2/004—Snouts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
- C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a method for plating a steel sheet and a zinc plating process using the same.
- at least one of Mn oxide, A1 oxide, and Si oxide formed on the surface during annealing of high strength steel may be used for plasma or full plasma and laser. It is about a plating method to remove through and a zinc plating process using the same.
- TWIP steel TWinning Induced Plasticity Steel
- TRIP Traransformation Induced Plasticity Steel
- Such AHSS forms Si / Mn / Al-based oxides of several tens of nm as the Si / Mn / Al contained in the high strength steel is diffused to the surface of the steel sheet during annealing.
- Such Si / Mn / Al type oxide prevents adhesion of molten zinc during hot dip galvanizing and causes unplating.
- Mn oxide and A1 oxide are present on the surface of the TWIP steel to prevent zinc from adhering to the TWIP steel.
- FIGS. 3 and 4 show surface analysis and depth profiles of TRIP steel. It can be seen that the Si-based oxide and Mn-based oxide are present on the surface of the TRIP steel. Similarly, zinc plating is difficult.
- the Si / Mn / Al oxide film is arranged in the form of islands or networks on the surface of the high-strength steel, the bonding strength is difficult to remove it.
- the present invention is a plating method and plating apparatus for high strength steel which can irradiate at least one of laser and plasma to the surface of AHSS to remove Si / Mn / Al-based oxides on the AHSS surface or to modify the surface, thereby allowing a post-treatment process such as zinc plating.
- the purpose is to provide.
- an object of the present invention is to provide a plating method of high strength steel which can be effectively applied to the plating continuous process by removing the Si / Mn / Al-based oxide on the AHSS surface effectively in a short time.
- the present invention is a plating method and plating that can be plated in a continuous process after annealing The purpose is to provide a process.
- the present invention provides the following plating method and zinc plating process.
- the present invention is a heating step of heating a high strength steel; A surface treatment step of irradiating plasma to remove at least one of Mn-based oxide, A1-based oxide, and Si-based oxide formed on the surface of the high strength steel formed in the heating step; And it provides a plating method comprising a plating step of plating the surface-treated high strength steel.
- the plasma in the surface treatment step may be irradiated at a temperature of 200 ⁇ 900 ° C on the high-strength steel surface.
- the plasma is irradiated in a nitrogen atmosphere of 200 ⁇ 800 ° C in the surface treatment step
- the atmosphere gas may be supplied as a feeding gas of the plasma in the surface treatment step.
- the plasma arc may be irradiated onto the high-strength steel surface together with the plasma.
- the surface treatment step is performed in a chamber that is blocked from the outside, the surface treatment step is to inhale the gas inside the chamber to increase the irradiation distance of the plasma to lower the pressure inside the chamber to irradiate the plasma Can be.
- the surface treatment step may be irradiated with a seed oil laser having a wavelength of less than 1064nm to the high-strength steel to remove the oxide film together with plasma irradiation.
- the laser black having a spot size of 1 ⁇ or less may be a laser beam having a width of less than limn.
- the surface treatment may irradiate the laser to the same point as the plasma.
- the present invention provides a TWIP or TRIP steel galvanized by the plating method described above.
- the present invention provides an annealing plant; An atmosphere chamber installed at the rear of the annealing plant to remove at least one of Mn oxide, A1 oxide, and Si oxide formed on the surface of the steel sheet during annealing, and having a nitrogen atmosphere of 200 to 800 ° C. formed therein; And a plasma generator disposed in the atmosphere chamber to remove the oxide film and irradiate the steel plate with plasma. And it provides a galvanizing process comprising a plating facility for galvanizing the steel sheet passed through the surface treatment equipment.
- the atmosphere chamber may include an atmosphere gas suction unit, and the atmosphere gas suction unit may be connected to a feeding gas supply unit of the plasma generator to use the atmosphere gas as a feeding gas of the plasma generator.
- the steel sheet includes a blocking portion for sealing the atmosphere hamber while allowing entry and exit of the steel plate
- the atmosphere chamber includes an atmosphere gas suction unit, a communication port for supplying the atmosphere gas, and a pressure sensor for measuring the internal pressure, and the atmosphere chamber.
- the internal pressure can be kept below atmospheric pressure.
- the blocking part includes a sealing, the sealing shaft and the rotating shaft of the sealing roll is formed of a conductive material, the rotating shaft is grounded to the cathode, the atmosphere The steel sheet passing through the chamber is grounded to the cathode, and the plasma generator may be spaced apart from the steel sheet to irradiate the plasma arc with the plasma.
- the plasma generator is located in the front or rear, and further comprising a laser generator for irradiating a laser to the surface of the steel sheet, the laser generator may be a double laser laser irradiation device having a wavelength of less than 1064nm. .
- the surface treatment facility may be disposed within a snout between the annealing facility and the plating facility.
- the present invention provides a method and plating of high-strength steel that can irradiate at least one of the laser and plasma to the surface of the AHSS to remove Si / Mn / Al-based oxides on the AHSS surface, or to modify the surface to perform a post-treatment process such as zinc plating. Provide the device.
- the present invention provides a high-strength steel plating method that can be effectively applied to the plating continuous process by removing the Si / Mn / Al-based oxide on the AHSS surface effectively in a short time.
- the present invention provides a plating method and a plating process capable of plating in a continuous process after annealing.
- 1 and 2 are graphs showing surface analysis and depth profiles of TWIP steels.
- 3 and 4 are graphs showing surface analysis and depth profiles of TRIP steel.
- 5 shows an example of a surface treatment apparatus for removing an oxide film of high strength steel with a plasma irradiation apparatus.
- 6 and 7 are graphs showing the surface analysis and the depth profile of the TWIP steel when the plasma was irradiated for 1 second at a distance of 3 m from the base metal with a 350 W atmospheric plasma irradiation apparatus.
- FIG. 8 is a graph showing a depth profile of a TWIP steel when the plasma is irradiated for 20 seconds at a distance of 3 mm from the base metal using a 350 W atmospheric plasma irradiation apparatus.
- 9 and 10 show an example of a plasma generator for irradiating plasma and arc together.
- 11 and 12 are graphs showing the surface analysis and the depth profile of the TWIP steel when the plasma and the arc were irradiated with the atmospheric pressure plasma irradiation apparatus.
- 13 and 14 are graphs showing the surface analysis and the depth profile of TRIP steel when the plasma and the arc are irradiated with the atmospheric pressure plasma irradiation apparatus.
- 15 is a schematic diagram of a surface treatment apparatus for removing an oxide film from high strength steel with a laser irradiation apparatus.
- 16 and 17 are graphs showing the surface analysis and the depth profile of the TWIP steel after irradiating the surface of the TWIP steel with a seedable oil laser 25W.
- FIG. 18 is a surface photograph when irradiating a pulse laser in an air atmosphere
- FIG. 19 is a surface photograph when irradiating a fill laser in a nitrogen atmosphere.
- FIG. 20 is a schematic diagram of a conventional zinc plating process
- FIG. 21 is a schematic diagram of a zinc plating process according to the present invention.
- Nitrogen gas communication port 340 Blocking part
- the oxide layer generated on the surface of the high strength steel during the annealing process is formed as an island (TWIP steel) or a network (TRIP) in a thin layer of several tens to hundreds of nm.
- TWIP steel island
- TRIP network
- the Si / Mn / Al-based oxide is 10 times more than the Fe oxide layer, a new approach is required to remove the oxide.
- the Si / Mn / Al oxide, oxide film, and oxide layer means an oxide, oxide film, and oxide layer containing at least one of Si oxide, Mn oxide, and A1 oxide. Removal of Si / Mn / Al-based Oxides Using Polazma
- the surface treatment apparatus used in the present invention is shown in FIG.
- the plasma generator 20 was arranged above the base material S of the support part 25, and was comprised so that the plasma P from the plasma generator 20 could be irradiated to the base material surface.
- the plasma P decreases as the distance 1 from the plasma generator 20 decreases, and when the temperature of the plasma P decreases, the plasma P decreases.
- the distance (L) between the plasma generator 20 and the base material (S) in the plasma generator 20 of the same output (350W) was investigated using this point, and the irradiation results are shown in Table 1 below. Is shown.
- the base material (S) used TWIP steel.
- the improvement of plating quality after plasma irradiation means that the zinc plating quality is improved compared to before plasma irradiation when zinc-plated specimen is plasma-plated.
- 'O' is a significant improvement
- ' ⁇ ' Means some improvement
- 'X' means no improvement.
- the temperature of the plasma at least on the surface of the base material is preferably up to 900 ° C.
- 6 and 7 are graphs showing the surface analysis and the depth profile of the TWIP steel when the plasma was irradiated for 1 second with the substrate and the distance of 3 inches with the 350 W atmospheric plasma irradiation apparatus. have. Although not significantly different from the surface analysis and depth profile (see FIGS. 1 and 2) of the TWIP steel before the irradiation, it can be seen that the amount of Mn and Al oxides on the surface was reduced.
- FIG. 6 shows that the amplitude of Mnl and A12 is lower than that of FIG. 1, but the amplitude of Fe 3 is increased.
- the Mn / Al oxide is Decreases and Fe is exposed to the surface instead.
- the fraction of the Mnl and A12 of the 'depth as can be determined by in case the profile in FIG. 2, when the base material and the distance to the atmospheric pressure plasma irradiation apparatus 3 ⁇ with investigating 1 seconds plasma sputter time early (surface) Since it decreased, it can be seen from this that the Mn / Al-based oxide on the surface of the base material was reduced. That is, since the fraction of Mn / Al was relatively reduced compared to the fraction of Fe, it can be seen from this that Mn / Al-based oxides on the surface of the base material were reduced.
- FIG. 8 shows a graph showing the depth profile of the TWIP steel when the plasma was irradiated for 20 seconds at a distance of 3 m from the base metal with a 350 W atmospheric plasma irradiation apparatus (Invention Example 3 in Table 1). Looking at the graph of Figure 8 it can be seen that the Mn / Al-based oxides are reduced compared to FIG.
- the plasma arc was generated around the nozzle.
- the plasma arc can damage the surface of the base material, and since the plasma arc is generated only around the plasma nozzle, the plasma arc can be irradiated only when it is very close to the plasma generator, and is not usually used with the plasma.
- Si / Mn / Al-based oxide on the surface of high strength steel it is formed in an island or network shape on the surface, which means that the oxide layer is located at a relatively high position relative to the base material surface.
- plasma arc since it is supplied to a high position similar to lightning, this point was used to remove the plasma arc energy to the Si / Mn / Al-based oxide.
- the experimental plasma generator (output: 350W) is generated only around the plasma nozzle, and by grounding the base material to the cathode, the ions are accelerated to maximize the ion impact effect, and the plasma arc surface of the base material.
- Pulled down. 9 shows a surface treatment apparatus for irradiating a plasma
- FIG. 10 shows a surface treatment apparatus for irradiating a plasma arc together with a plasma. Is shown.
- the plasma arc A is irradiated only up to a short distance 11 as compared to the plasma irradiation distance.
- the base material S is grounded to the cathode 30. Accordingly, the plasma P is accelerated, and the distance 12 at which the plasma arc is irradiated with the plasma acceleration is also increased.
- nitrogen gas was used as a feeding gas of the plasma generator 20 to prevent oxidation on the surface of the base material.
- 11 and 12 are graphs showing the surface analysis and the depth profile of the TWIP steel when the plasma and the arc were irradiated with the 350W atmospheric pressure plasma irradiation apparatus together for 10 seconds.
- Mn was reduced by about 66% by irradiation for 10 seconds, and by about 10 seconds in the case of A1. It can be seen that about 90% is reduced. 12, the atomic fraction of Mn and A1 on the surface was greatly reduced, and the atomic fraction of Fe was increased.
- FIGS. 13 and 14 are the surface analysis results of the TRIP steel before the irradiation
- the results of FIGS. 13 and 14 showed that Si and Mn were reduced to an extent difficult to find in the graph by irradiating the plasma and the plasma arc together for 10 seconds.
- the atomic fractions of Mn and Si on the surface were greatly reduced, and the atomic fractions of Fe were increased.
- the plating property of the TRIP steel was increased after irradiation.
- the support part supporting the base material is composed of a conductive member, and the support part is grounded. By grounding the support in this way, the base material can be freely moved or arranged.
- Figure 15 shows a surface treatment apparatus including a laser irradiation apparatus according to the present invention.
- the surface treatment apparatus disposed the laser generator 10 above the base material S of the support part 25 and irradiated a laser onto the surface of the base material, and moved the laser generator 10 to move the surface of the base material surface.
- the laser (L) was irradiated. After the laser was irradiated, the surface of the irradiated specimen was analyzed and galvanized.
- Nd YAG 1064nm Pulse and Continuous Wave Laser were alternately tested as a laser, and the experiment was performed while changing the output and irradiation speed.
- the improvement of plating quality after laser irradiation means that the zinc plating quality is improved compared to before laser irradiation when zinc-coated specimens are coated.
- 'O' is a significant improvement
- 'X' Means no improvement.
- the seed oil can remove the Si / Mn / Al oxide.
- the seed oil (Inventive Example 5) is plated compared to the Fils laser (Comparative Example 2).
- the degree of improvement in performance was significantly different, and therefore, the use of a seed oil laser is advantageous for removing Si / Mn / Al oxides.
- 16 and 17 show graphs illustrating the surface analysis and depth profile of the TWIP steel after irradiating the surface of the TWIP steel with a seedable oil laser 25W.
- the spot size of the laser is set to be smaller than or equal to li ⁇ or the laser beam width is lower than or equal to Ira.
- the spot size of the laser is set to be smaller than or equal to li ⁇ or the laser beam width is lower than or equal to Ira.
- the experiment was performed while changing the wavelength of the laser to 1064nm, 532nm, 355nm, it was confirmed that the removal of Si / Mn / Al oxide in all 1064nm, 532nm, 355nm.
- the laser wavelength is preferably 1064iim.
- the steel sheet 100 of the rolled coil is continuously heated through a pay-off reel (not shown) and a welding machine (not shown), and then heat-treated in the annealing facility 110 that rises to a maximum temperature of 70Crc to 800 ° C to remove residual stress.
- the heated steel sheet 100 is drawn into the plating bath 130 filled with the plating liquid, that is, the molten zinc 130a, while being maintained at a suitable temperature for zinc plating.
- the equipment connected between the annealing equipment 110 and the plating bath 130 of the zinc plating equipment, to prevent the surface oxidation as the steel sheet heat-treated at high temperature to the atmosphere Snout 120 is provided for this purpose.
- the inside of the known snout 120 is filled with a activating gas in order to prevent plating failure of the steel sheet due to surface oxidation.
- the plated steel sheet 100 passing through the heating furnace 110, the snout 120, and the sink roll 132 and the stabilizing 134 of the plating bath 130 is air disposed directly above the plating bath.
- the demand is adjusted to the desired plating amount.
- the plated steel sheet after the plating amount adjustment is completed is cut through a temper rolling mill (not shown), cut by a cutter (not shown) through proper surface roughness and shape correction, and then wound on a tension reel (not shown) for final plating. It is produced as a coil product.
- the Si / Mn / Al-based oxide film is formed on the surface during heat treatment during annealing, so the zinc plating process for high strength steel of the present invention in which a surface treatment apparatus is disposed in the snout between the annealing facility and the zinc plating facility is illustrated. 21 is shown. Since the galvanizing process of the present invention is disposed in the snout, it can be applied only by changing the snout in a conventional installation, and thus has high utilization.
- the steel sheet 200 of the high strength steel (eg, TWIP, TRIP) coil is continuously passed through a pay-off reel (not shown) and a welding machine (not shown), and then heat-treated at the annealing facility 210 to form Si / Mn / Al.
- the oxide film is formed, and the steel sheet 200 on which the oxide film is formed passes through the surface treatment facility disposed inside the snout 220 and then is introduced into the plating bath 230 filled with the molten zinc 230a of the zinc plating facility.
- the plasma generating apparatus may remove the Si / Mn / Al based oxide film formed on the surface of the high strength steel sheet in a short time.
- 310 , 311) and laser The generators 320 and 321 are arranged on both sides, respectively.
- a window 322, 323 is installed in the middle of the laser light emitted from the laser generators 320, 321, and a pump 336 for supplying a feeding gas is connected to the plasma generators 310, 311.
- the thickness of Si / Mn oxides is 50 nm or less in the case of TRIP steels. Therefore, depending on the grade of steel and oxide, the laser generators 320 and 321 are not mounted. It may not.
- a sealing 342 and a blocking portion 340 for fixing it, separating the space inside and outside of the surface treatment facility 300, and rises from the plating bath 230 To block the ingress of zinc vapor and foreign substances.
- a nitrogen gas communication port 330 is formed at an outer wall thereof, and a pump 332 and a nitrogen gas storage part 333 are connected to the nitrogen gas communication hole 330. Nitrogen from the gas storage unit 333 may be supplied into the surface treatment facility 300 to initially form a nitrogen atmosphere.
- the blocking portion 340 is formed on the outer wall of the surface treatment equipment 300, the suction port 335 for sucking the nitrogen gas therein, the nitrogen supplied from the nitrogen gas communication port in the suction port 335
- the high temperature nitrogen gas heated by the steel plate 200 is sucked in.
- a pump 336 may be connected to the suction port 335 to suck nitrogen gas, and the sucked nitrogen gas may be supplied to the feeding gas of the plasma generators 310 and 311 or may be discharged to the outside.
- the sucked gas contains Si / Mn / Al-based oxide gas evaporated from the surface of the steel plate 200, the gas is sucked to the plasma generators 310 and 311. Can be supplied. If necessary, the sucked gas is sent to a treatment facility, and the plasma generator may be supplied with nitrogen gas from the nitrogen gas storage unit 333.
- the pump 336 connected to the hop inlet 335 supplies high temperature nitrogen gas to the plasma generators 310 and 311, so that the plasma generators 310 and 311 supply nitrogen gas at room temperature as the feeding gas. High energy plasma can be irradiated. Therefore, the performance of the high output plasma generator can be obtained through the low output plasma generator.
- the suction port 335 may not only supply a feeding gas of the plasma generators 310 and 311, but also simultaneously maintain a pressure inside the surface treatment facility 300 to be lower than atmospheric pressure.
- a pressure inside the surface treatment facility 300 By maintaining the pressure inside the surface treatment facility 300 to be lower than atmospheric pressure, the plasma irradiation distance and the plasma arc irradiation distance of the plasma generators 310 and 311 are increased, which is caused by the fluctuation of the steel plate 200. (310, 311) and the steel plate 200 is prevented from colliding or rubbing.
- a sensor 360 for measuring the internal pressure is disposed in the surface treatment facility 300 to measure the internal pressure in real time and provide the internal pressure value to the controller 390.
- the controller 390 is connected to the plasma generators 310 and 311, the laser generators 320 and 321, the pumps 332 and 336, and the sensor 360, and inputs information about the sensor 360 and the steel grade. And the plasma generators 310, 311, the laser generators 320, 321, and the pumps 332, 336 in accordance with the user's operation.
- the seal 342 is made of a chargeable material
- the ground terminal 343 is attached to the roll out 341 of the seal 342 (see Fig. 22), and the ground terminal is grounded with a negative electrode.
- the steel sheet 200 entering the surface treatment facility 300 while contacting the sealing roll 340 and the sealing roll 340 is negatively grounded.
- the distance of the plasma arc irradiated from the plasma generators 310 and 311 becomes relatively shorter than when grounded. Therefore, in order to irradiate the plasma arc on the surface of the steel sheet 200, the distance between the steel sheet 200 and the full plasma generators 310 and 311 should be maintained at a relatively narrow distance. Therefore, when the plasma generating apparatuses 310 and 311 are arranged at such a narrow distance, physical friction or collision with the steel sheet 200 cannot be avoided, and therefore, it is difficult to irradiate the steel sheet with the plasma arc.
- the sealing 340 is used as the ground, but it is possible to include a contact with the steel sheet 200 inside the surface treatment facility, and to mount the steel plate by attaching a ground terminal to the shaft of the roll.
- the plasma generating apparatuses 310 and 311 have a temperature of 200 to 90 rc irradiated to the steel sheet, and are spaced apart from the steel sheet so that the plasma arc can be irradiated together.
- 200 is grounded to the cathode, so that the plasma arc can be irradiated with the plasma from the plasma generators 310 and 311 onto the steel sheet, so that the oxide film formed on the surface of the steel sheet 200 can be quickly removed.
- Plasma generators (310, 311) are arranged in plurality are connected along the width of the steel sheet so that the plasma and the plasma arc can be irradiated to the entire width of the steel sheet at once It is preferable.
- the laser generators 320 and 321 irradiate a laser beam parallel to the width direction of the steel sheet 200.
- the laser beam is irradiated with a 1064 TM Nd-YAG double oil laser to quickly remove the oxide film formed on the surface of the steel sheet.
- the width of the laser beam is preferably 1 kW or less so as to prevent carbonization.
- a portion where the laser is irradiated by the laser generators 320 and 321 and a portion where the plasma is generated by the plasma generators 310 and 311 coincide with each other. Therefore, it is possible to continuously remove the oxide film formed on the surface of the steel sheet through which the laser beam, the plasma, and the plasma arc are irradiated to the oxide film at one point of the steel sheet 200.
- the inside of the surface treatment facility 300 is maintained at 8 (xrc or less), since an additional heating device is required when maintaining the temperature above 80 CTC, which is the highest temperature in the annealing facility.
- the inside of the surface treatment facility 300 is maintained at a temperature of 200 ° C or more, which means that the steel sheet 200 introduced into the zinc bath 230 should have a temperature of about 460 ° C.
- the surface treatment facility 300 If the internal temperature is low, it is necessary to raise the temperature of the steel sheet 200 introduced into the zinc bath 230 through an additional heating device, the sequence of the zinc plating process of the present invention is as follows.
- the steel sheet 200 released from the coil passes through the annealing facility 210 and then flows into the surface treatment facility 300.
- the steel plate 200 is grounded to the cathode by the sealing 342 while passing the sealing 342 separating the inside and the outside of the surface treatment facility 300.
- the interior of the surface treatment facility 300 is maintained in a low pressure (below atmospheric pressure) nitrogen atmosphere through feedback control by the intake port 335, the nitrogen gas communication port 330, and the sensor 360.
- the steel sheet 200 is irradiated with a laser beam, a plasma, and a plasma arc on both surfaces. Accordingly, the Si / Mn / AI-based oxide film formed on the surface of the steel sheet 200 in the annealing facility 210 is removed, and the surface of the steel sheet 200 is sealed through the sealing 342 in a state capable of galvanizing.
- Exit 300 Thereafter, the steel sheet 200 passing through the surface treatment facility 300 is introduced into the plating tank 230, and the plated steel sheet passing through the sink roll 232 and the stabilizing 234 of the plating tank 230 ( 200 is adjusted to the amount of plating desired by the demand in the air knife 240 disposed directly above the plating bath.
- the plated steel sheet after the plating amount adjustment is completed is cut through a temper rolling mill (not shown), cut by a cutter (not shown) through proper surface roughness and shape correction, and then wound on a tension reel (not shown) for final plating. Produced as a coiled product.
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- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Plasma & Fusion (AREA)
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Abstract
Description
Claims
Priority Applications (3)
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CN201180068529.1A CN103517995B (zh) | 2010-12-27 | 2011-12-27 | 镀覆方法和镀锌方法 |
JP2013547332A JP5879365B2 (ja) | 2010-12-27 | 2011-12-27 | メッキ方法及び亜鉛メッキ設備 |
US13/997,829 US9321077B2 (en) | 2010-12-27 | 2011-12-27 | Plating method |
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KR10-2010-0136019 | 2010-12-27 | ||
KR1020100136019A KR101242953B1 (ko) | 2010-12-27 | 2010-12-27 | 도금 방법 및 아연 도금 장치 |
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US (1) | US9321077B2 (ko) |
JP (1) | JP5879365B2 (ko) |
KR (1) | KR101242953B1 (ko) |
CN (1) | CN103517995B (ko) |
WO (1) | WO2012091409A2 (ko) |
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WO2016105163A1 (ko) * | 2014-12-24 | 2016-06-30 | 주식회사 포스코 | 용접성 및 가공부 내식성이 우수한 아연합금도금강재 및 그 제조방법 |
MX2017008452A (es) | 2014-12-24 | 2017-11-09 | Posco | Material de acero emplacado con aleacion de zinc que tiene caracteristicas excelentes de soldado y resistencia a la corrosion de partes procesadas y metodo de manufactura del mismo. |
DE102018211108B4 (de) * | 2018-07-05 | 2023-06-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zum Modifizieren und anschließendem Ausbilden einer Oberflächenbeschichtung auf einem metallischen Bauteil |
AT520637B1 (de) * | 2018-07-31 | 2019-06-15 | Andritz Ag Maschf | Verfahren zur verbesserung der beschichtbarkeit eines metallbandes |
KR102290782B1 (ko) * | 2019-09-26 | 2021-08-18 | 주식회사 포스코 | 내구성이 우수한 고강도 코팅강판의 제조방법 |
EP4334488A1 (en) | 2021-05-06 | 2024-03-13 | Tata Steel Nederland Technology B.V. | A system and a method for plasma surface treatment |
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2011
- 2011-12-27 CN CN201180068529.1A patent/CN103517995B/zh not_active Expired - Fee Related
- 2011-12-27 US US13/997,829 patent/US9321077B2/en not_active Expired - Fee Related
- 2011-12-27 JP JP2013547332A patent/JP5879365B2/ja not_active Expired - Fee Related
- 2011-12-27 WO PCT/KR2011/010154 patent/WO2012091409A2/ko active Application Filing
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JP2001140051A (ja) * | 1999-11-12 | 2001-05-22 | Kawasaki Steel Corp | 溶融めっき鋼帯及び合金化溶融めっき鋼帯の製造方法並びに溶融めっき装置 |
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Also Published As
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KR101242953B1 (ko) | 2013-03-12 |
WO2012091409A3 (ko) | 2012-10-04 |
JP2014506300A (ja) | 2014-03-13 |
US9321077B2 (en) | 2016-04-26 |
CN103517995A (zh) | 2014-01-15 |
KR20120074067A (ko) | 2012-07-05 |
JP5879365B2 (ja) | 2016-03-08 |
US20130288073A1 (en) | 2013-10-31 |
CN103517995B (zh) | 2016-01-20 |
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