EP3369838A1 - Tôle d'acier plaquée d'alliage de zinc présentant une excellente aptitude au cintrage, et son procédé de fabrication - Google Patents
Tôle d'acier plaquée d'alliage de zinc présentant une excellente aptitude au cintrage, et son procédé de fabrication Download PDFInfo
- Publication number
- EP3369838A1 EP3369838A1 EP16860213.4A EP16860213A EP3369838A1 EP 3369838 A1 EP3369838 A1 EP 3369838A1 EP 16860213 A EP16860213 A EP 16860213A EP 3369838 A1 EP3369838 A1 EP 3369838A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc alloy
- steel sheet
- plated steel
- alloy plated
- single phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 121
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 118
- 239000010959 steel Substances 0.000 title claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000005452 bending Methods 0.000 title description 22
- 239000011701 zinc Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910018134 Al-Mg Inorganic materials 0.000 claims abstract description 17
- 229910018467 Al—Mg Inorganic materials 0.000 claims abstract description 17
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 17
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- 238000007747 plating Methods 0.000 claims description 75
- 239000011777 magnesium Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 229910017708 MgZn2 Inorganic materials 0.000 claims description 25
- 239000007921 spray Substances 0.000 claims description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 230000005496 eutectics Effects 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 2
- 229910017488 Cu K Inorganic materials 0.000 abstract 1
- 229910017541 Cu-K Inorganic materials 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 101000912181 Arabidopsis thaliana Cysteine synthase, mitochondrial Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 101710178035 Chorismate synthase 2 Proteins 0.000 description 2
- 101710152694 Cysteine synthase 2 Proteins 0.000 description 2
- 101710109085 Cysteine synthase, chloroplastic/chromoplastic Proteins 0.000 description 2
- 101000921780 Solanum tuberosum Cysteine synthase Proteins 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- TUBQDCKAWGHZPF-UHFFFAOYSA-N 1,3-benzothiazol-2-ylsulfanylmethyl thiocyanate Chemical compound C1=CC=C2SC(SCSC#N)=NC2=C1 TUBQDCKAWGHZPF-UHFFFAOYSA-N 0.000 description 1
- 229910019805 Mg2Zn11 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
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Images
Classifications
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- 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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
-
- 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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
-
- 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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
-
- 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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
- C23C2/20—Strips; Plates
-
- 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
- C23C2/26—After-treatment
-
- 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
- C23C2/26—After-treatment
- C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
-
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- 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 disclosure relates to a zinc alloy plated steel sheet having high bending workability and a method for manufacturing the zinc alloy plated steel sheet.
- a zinc plating method for suppressing the corrosion of iron by cathodic protection has high anti-corrosion efficiency and economic feasibility, and thus has been widely used in manufacturing steel materials having high corrosion resistance.
- hot-dip zinc plated steel sheets manufactured by dipping a steel material into molten zinc to form a plating layer, are obtainable through simple manufacturing processes and are relatively inexpensive, as compared to electro-zinc plated steel sheets, and thus, demand therefor has increased in a wide range of industries, such as the automotive industry, the home appliance industry, and the construction industry.
- the zinc alloy plated steel sheet includes large amounts of Zn-Al-Mg-based intermetallic compounds in a plating layer thereof as a result of thermodynamic reaction between zinc (Zn), aluminum (Al), and magnesium (Mg), and such intermetallic compounds may cause cracks in the plating layer during a bending process because of high hardness of the intermetallic compounds, thereby lowering the bending workability of the zinc alloy plated steel sheet.
- aspects of the present disclosure may provide a zinc alloy plated steel sheet having high bending workability and a method for manufacturing the zinc alloy plated steel sheet.
- a method for manufacturing a zinc alloy plated steel sheet may include: preparing a zinc alloy plating bath including magnesium (Mg) and aluminum (Al); obtaining a zinc alloy plated steel sheet by dipping a base steel sheet into the zinc alloy plating bath to plate the base steel sheet; wiping the zinc alloy plated steel sheet with gas to adjust a plating weight; and after adjusting the plating weight of the zinc alloy plated steel sheet, cooling the zinc alloy plated steel sheet by spraying droplets of water or an aqueous solution onto the zinc alloy plated steel sheet and then using air, wherein when the droplets are sprayed, a droplet spray start temperature ranges from 405°C to 425°C, a droplet spray stop temperature ranges from 380°C to 400°C.
- a droplet spray start temperature ranges from 405°C to 425°C
- a droplet spray stop temperature ranges from 380°C to 400°C.
- an embodiment of the present disclosure provides a zinc alloy plated steel sheet having high bending workability as well as high corrosion resistance.
- the zinc alloy plated steel sheet of the embodiment has high surface quality.
- the zinc alloy plated steel sheet of the embodiment has high scratch resistance.
- the zinc alloy plated steel sheet includes a base steel sheet and a zinc alloy plating layer.
- the base steel sheet is not limited to a particular type.
- a hot-rolled steel sheet or a cold-rolled steel sheet commonly used as a base steel sheet of a zinc alloy plated steel sheet may be used.
- hot-rolled steel sheets have a large amount of surface oxide scale that lowers plating adhesion and thus plating quality, and thus a hot-rolled steel sheet from which oxide scale has been previously removed using an acid solution may be used as the base steel sheet.
- the zinc alloy plating layer may be formed on one or each side of the base steel sheet.
- the zinc alloy plating layer may include, by wt%, aluminum (Al): 0.5% to 3%, magnesium (Mg): 0.5% to 3%, and the balance of zinc (Zn) and inevitable impurities.
- magnesium (Mg) reacts with zinc (Zn) and aluminum (Al) and forms a Zn-Al-Mg-based intermetallic compound, thereby functioning as a key element improving the corrosion resistance of the zinc alloy plated steel sheet. If the content of magnesium (Mg) is excessively low, the Zn-Al-Mg-based intermetallic compound is not present in sufficient amounts in the microstructure of the zinc alloy plating layer, and thus corrosion resistance may not be sufficiently improved. Therefore, the amount of magnesium (Mg) in the zinc alloy plating layer may be 0.5 wt% or greater, preferably 1.0 wt% or greater.
- the amount of magnesium (Mg) in the zinc alloy plating layer may be 3 wt% or less, preferably 2.9 wt% or less.
- Aluminum (Al) suppresses the formation of Mg oxide dross and reacts with zinc (Zn) and magnesium (Mg) to form the Zn-Al-Mg-based intermetallic compound in the zinc alloy plating layer, thereby functioning as a key element improving the corrosion resistance of the zinc alloy plated steel sheet. If the content of aluminum (Al) is excessively low, the formation of Mg dross is not sufficiently suppressed, and the Zn-Al-Mg-based intermetallic compound is not present in sufficient amounts in the microstructure of the zinc alloy plating layer, which may result in insufficient improvements in corrosion resistance.
- the amount of aluminum (Al) in the zinc alloy plating layer may be 0.5 wt% or greater, preferably 0.6 wt% or greater.
- the content of aluminum (Al) is excessively high, the effect of improving corrosion resistance is saturated, and the durability of plating equipment may be negatively affected because of a high plating bath temperature.
- the Zn-Al-Mg-based intermetallic compound having high harness may be formed in excessively large amounts in the microstructure of the zinc alloy plating layer, and thus bending workability may be lowered. Therefore, the amount of aluminum (Al) in the zinc alloy plating layer may be 3 wt% or less, preferably 2.6 wt% or less.
- the contents of magnesium (Mg) and aluminum (Al) in the zinc alloy plating layer may satisfy the following Formula 1. If [Mg]/[Al] is 1.0 or less, scratch resistance may deteriorate, and if [Mg]/[Al] is greater than 4.0, Mg-based dross may be formed in large amounts in a hot-dip plating bath to lower workability. 1.0 ⁇ Mg / Al ⁇ 4.0 where [Mg] and [Al] refer to the weight percentages (wt%) of corresponding elements, respectively.
- the zinc alloy plating layer may include a Zn single phase structure as a microstructure and the Zn-Al-Mg-based intermetallic compound.
- the Zn-Al-Mg-based intermetallic compound is not limited to a particular type.
- the Zn-Al-Mg-based intermetallic compound may include at least one selected from the group consisting of a Zn/Al/MgZn 2 ternary eutectic structure, a Zn/MgZn 2 binary eutectic structure, a Zn-Al binary eutectic structure, and an MgZn 2 single phase structure.
- the inventors have conducted in-depth research into improving the bending workability of zinc alloy plated steel sheets and found that if a Zn single phase structure having a hexagonal close packing (HCP) structure is grown in a (0001) orientation in the microstructure of the zinc alloy plating layer, ductility increases owing to easy slippage, and thus cracks are markedly reduced in a bending process.
- HCP hexagonal close packing
- the degree (f) of (0001) preferred orientation may preferably be adjusted to be 50% or greater, more preferably 60% or greater.
- f % I basal / I total ⁇ 100 where I total refers to the integral of all diffraction peaks of the Zn single phase structure when an X-ray diffraction pattern is measured within the range of 2 theta from 10° to 100° using a Cu-K ⁇ source, and I basal refers to the integral of diffraction peaks of the Zn single phase structure relating to a basal plane.
- the inventors have found that if the Zn single phase structure coarsely formed in the zinc alloy plating layer is refined in size, it is also helpful to reduce cracking during a bending process.
- the average grain diameter of the Zn single phase structure may be preferably adjusted to be 15 ⁇ m or less, more preferably 12 ⁇ m or less, and even more preferably 10 ⁇ m or less.
- the "average grain diameter" of the Zn single phase structure refers to the average of equivalent circular diameters of the Zn single phase structure measured by observing a thicknesswise cross-section of the zinc alloy plating layer.
- the zinc alloy plated steel sheet of the present disclosure has high corrosion resistance and bending workability as well.
- the zinc alloy plated steel sheet of the present disclosure may have a good appearance.
- the number of black spots per unit area may be equal to or less than 0.1/cm 2 on the surface of the zinc alloy plated steel sheet.
- the area fraction of the Zn single phase structure may preferably be 40% or less (excluding 0%) on the surface of the zinc alloy plating layer. That is, the appearance of the zinc alloy plated steel sheet may be improved by maximizing the fraction of the Zn-Al-Mg-based intermetallic compound present on the surface of the zinc alloy plating layer.
- the zinc alloy plated steel sheet of the present disclosure may also have high scratch resistance.
- the sum of the area fractions of the Zn/MgZn 2 binary eutectic structure and the Zn/Al/MgZn 2 ternary eutectic structure may be 50% or greater (excluding 100%), and the area fraction of the MgZn 2 single phase structure may be 10% or less (including 0%).
- the MgZn 2 single phase structure has high hardness and thus causes cracks during a machining process, and thus the area fraction of the MgZn 2 single phase structure may be adjusted to be as low as possible.
- the zinc alloy plated steel sheet of the present disclosure may be manufactured by various methods without limitation. However, for example, when the zinc alloy plating layer solidifies from a molten state, the zinc alloy plating layer may be cooled by spraying droplets thereon and then cooled with air to obtain the above-described degree of preferred orientation and average grain diameter.
- droplets may be sprayed by a charge spray method to attach the droplets by electrostatic attraction between the droplets and the zinc alloy plated steel sheet.
- This charge spray method may be helpful in forming fine, uniform droplets and reducing the amount of droplets colliding with and bouncing off the zinc alloy plated steel sheet after being sprayed on the zinc alloy plated steel sheet, thereby facilitating rapid cooling of the zinc alloy plating layer from the molten state and having a positive effect on the growth of the Zn single phase structure in the (0001) orientation and refinement of the Zn single phase structure.
- the droplets may be droplets of a phosphate aqueous solution capable of rapidly cooling the zinc alloy plating layer from the molten state through an endothermic reaction and thus effective in growing the Zn single phase structure in the (0001) orientation and refining the Zn single phase structure.
- the phosphate aqueous solution may include an aqueous solution of ammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), an aqueous solution of sodium ammonium hydrogen phosphate (NaNH 4 HPO 4 ), an aqueous solution of zinc dihydrogen phosphate (Zn(H 2 PO 4 ) 2 ), and an aqueous solution of calcium phosphate (Ca 3 (PO 4 ) 2 ).
- the content of the phosphate aqueous solution may be 1 wt% to 3 wt%. If the content of the phosphate aqueous solution is less than 1 wt%, the effect of the phosphate aqueous solution may not be sufficient. If the content of the phosphate aqueous solution is greater than 3 wt%, the effect of the phosphate aqueous solution is saturated, and nozzle clogging may occur in a continuous production process, lowering productivity.
- droplets when the droplets may be sprayed at a droplet spray start temperature of 405°C to 425°C, and more preferably 410°C to 420°C.
- droplet spray start temperature refers to a surface temperature of the zinc alloy plated steel sheet at the start time of droplet spraying. If the droplet spray start temperature is less than 405°C, solidification of the Zn single phase structure may have already started, and thus black spots may be formed on the surface of the zinc alloy plated steel sheet. Conversely, if the droplet spray start temperature is greater than 425°C, droplets may not effectively undergo an endothermic reaction, and thus it may be difficult to obtain an intended structure.
- the droplets may be sprayed at a droplet spray stop temperature of 380°C to 400°C, and more preferably 390°C to 400°C.
- droplet spray stop temperature refers to a surface temperature of the zinc alloy plated steel sheet at a point in time at which spraying of droplets stops. If the droplet spray stop temperature is greater than 400°C, an endothermic reaction by the droplets may occur ineffectively, and thus it may be difficult to obtain an intended structure.
- a Mg 2 Zn 11 phase may be formed due to over cooling while the Zn/MgZn 2 binary eutectic phase and the Zn/Al/MgZn 2 ternary phase start to solidify, and thus many black spots may be formed, decreasing the degree of (0001) preferred orientation of the Zn single phase structure.
- the difference between the droplet spray start temperature and the droplet spray stop temperature may be 15°C or greater. If the difference is less than 15°C, the droplets may not undergo an effective endothermic reaction, and thus it may be difficult to obtain an intended structure.
- the droplets may be sprayed in an amount of 50 g/m 2 to 100 g/m 2 . If the spraying amount of the droplets is less than 50 g/m 2 , the effect of the droplets may be insufficient, and if the spraying amount of the droplets is greater than 100 g/m 2 , the effect of the droplets may be saturated.
- Low carbon cold-rolled steel sheets each having a thickness of 0.8 mm, a width of 100 mm, and a length of 200 mm were prepared as base steel sheets for plating test samples, and then foreign substances such as rolling oil were removed from the surfaces of the base steel sheets by dipping the base steel sheets into acetone and washing the base steel sheets with ultrasonic waves. Thereafter, a 750°C reducing atmosphere heat treatment commonly performed to guarantee mechanical characteristics of steel sheets in the hot-dipping plating field was performed on the base steel sheets, and then the base steel sheets were dipped into plating baths (bath temperature: 460°C) having compositions shown in Table 1 below to fabricate zinc alloy plated steel sheets.
- bath temperature: 460°C plating baths
- Comparative Sample 5 was prepared by performing a gas wiping process on a zinc alloy plated steel sheet fabricated using the same plating bath as that used to fabricate Inventive Sample 1 to adjust a plating weight to be 70 g/m 2 on each side, and then cooling the zinc alloy plated steel sheet using a general cooling device at an average cooling rate of 12°C/sec until the plating layer of the zinc alloy plated steel sheet was completely solidified (at about 300°C or less).
- the microstructures of the fabricated zinc alloy plated steel sheets were observed using an FE-SEM (SUPRA-55VP, Zeiss) as illustrated in FIGS. 1 and 2 , and the average grain diameter of a Zn single phase structure of each of the zinc alloy plated steel sheets was measured as shown in Table 2 below.
- f % I basal / I total ⁇ 100
- I total refers to the integral of all diffraction peaks of the Zn single phase structure when an X-ray diffraction pattern was measured within the range of 2 theta from 10° to 100° using a Cu-K ⁇ source
- I basal refers to the integral of diffraction peaks of the Zn single phase structure relating to a basal plane.
- a salt spray test (based on KS-C-0223) was performed on each of the zinc alloy plated steel sheets to facilitate corrosion, and then the time taken until the area fraction of red rust on the surface of each plating layer was 5% was measured.
- Comparative Samples 1 to 5 had high corrosion resistance, Comparative Samples 1 to 5 had poor bending workability because the (f) values thereof were less than 50%.
- FIG. 1A and 1B are views illustrating results of an observation of a surface microstructure of Inventive Sample 1 of the present disclosure and an observation of a surface microstructure of Comparative Sample 5
- FIGS. 2A and 2B are views illustrating results of an observation of a cross-sectional microstructure of Inventive Sample 1 of the present disclosure and an observation of a cross-sectional microstructure of Comparative Sample 5.
- FIG. 3 is a view illustrating results of X-ray diffractometer (XRD) analysis of Inventive Sample 1.
- XRD X-ray diffractometer
- Low carbon cold-rolled steel sheets each having a thickness of 0.8 mm, a width of 100 mm, and a length of 200 mm were prepared as base steel sheets for plating test samples, and then foreign substances such as rolling oil were removed from the surfaces of the base steel sheets by dipping the base steel sheets into acetone and washing the base steel sheets with ultrasonic waves. Thereafter, a 750°C reducing atmosphere heat treatment commonly performed to guarantee mechanical characteristics of steel sheets in the hot-dipping plating field was performed on the base steel sheets, and then the base steel sheets were dipped into plating baths having compositions shown in Table 3 below to fabricate zinc alloy plated steel sheets. Thereafter, each of the zinc alloy plated steel sheets was wiped with gas to adjust a plating weight to be 70 g/m 2 on each side. Then, the zinc alloy plated steel sheets were cooled under the same conditions as Inventive Sample 1 of Example 1.
- a friction test (linear friction test) was performed by rubbing the surface of each of the zinc alloy plated steel sheets 20 times with a tool head at a constant pressure.
- a target load was 333.3 kgf
- a pressure was 3.736 MPa
- the tool head traveled 200 mm per rub
- the speed of the tool head was 20 mm/s.
- each of the zinc alloy plated steel sheets was inserted into a salt spray tester, and the time taken until the occurrence of red rust was measured according to international standard ASTM B117-11. In that time, a 5% salt solution (35°C, pH 6.8) was sprayed at a rate of 2 ml/80 cm 2 per hour.
- a 5% salt solution 35°C, pH 6.8 was sprayed at a rate of 2 ml/80 cm 2 per hour.
- each of Comparative Samples A, B, D, and E had poor appearance because the area fraction of a Zn single phase structure present on the surface of a plating layer was excessively high, and each of Comparative Samples A to G had poor scratch resistance because the area fractions of a Zn/MgZn 2 binary eutectic structure and a Zn/Al/MgZn 2 ternary eutectic structure are excessively low.
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KR20150148793 | 2015-10-26 | ||
PCT/KR2016/012098 WO2017074030A1 (fr) | 2015-10-26 | 2016-10-26 | Tôle d'acier plaquée d'alliage de zinc présentant une excellente aptitude au cintrage, et son procédé de fabrication |
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EP3369838A1 true EP3369838A1 (fr) | 2018-09-05 |
EP3369838A4 EP3369838A4 (fr) | 2018-09-05 |
EP3369838B1 EP3369838B1 (fr) | 2019-08-21 |
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US (1) | US20180320260A1 (fr) |
EP (1) | EP3369838B1 (fr) |
JP (1) | JP6983153B2 (fr) |
KR (1) | KR101819381B1 (fr) |
CN (1) | CN108350555A (fr) |
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WO2021038102A1 (fr) | 2019-08-30 | 2021-03-04 | Rijksuniversiteit Groningen | Procédé de caractérisation de propriétés de formabilité d'un revêtement d'alliage de zinc sur un substrat métallique |
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KR101847567B1 (ko) | 2015-12-24 | 2018-04-10 | 주식회사 포스코 | 미세하고 균일한 도금 조직을 갖는 도금 강판 |
WO2018131171A1 (fr) * | 2017-01-16 | 2018-07-19 | 新日鐵住金株式会社 | Matériau de type acier plaqué |
EP3957766A4 (fr) * | 2019-04-19 | 2022-08-24 | Nippon Steel Corporation | Tôle d'acier plaquée |
MY197182A (en) * | 2019-06-26 | 2023-05-30 | Posco | Plated steel wire and manufacturing method for the same |
CN111155044B (zh) * | 2019-12-13 | 2021-09-21 | 首钢集团有限公司 | 一种提高锌铝镁镀层钢表面质量的方法、锌铝镁镀层 |
WO2021176768A1 (fr) * | 2020-03-03 | 2021-09-10 | Jfeスチール株式会社 | Élément pressé à chaud, procédé pour sa fabrication et tôle d'acier plaquée pour un pressage à chaud |
KR102453011B1 (ko) * | 2020-12-21 | 2022-10-12 | 주식회사 포스코 | 실러 접착성이 우수한 도금 강판 및 이의 제조방법 |
TW202405204A (zh) * | 2022-06-10 | 2024-02-01 | 日商日本製鐵股份有限公司 | Zn-Al-Mg系熔融鍍敷鋼板 |
KR102672418B1 (ko) * | 2022-07-29 | 2024-06-07 | 현대제철 주식회사 | 도금강판 및 그 제조방법 |
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KR100324893B1 (ko) * | 1996-12-13 | 2002-08-21 | 닛신 세이코 가부시키가이샤 | 내식성및표면외관이양호한융용아연-알루미늄-마그네슘도금강판및그제조법 |
JP3179401B2 (ja) * | 1996-12-13 | 2001-06-25 | 日新製鋼株式会社 | 耐食性および表面外観の良好な溶融Zn−Al−Mgめっき鋼板およびその製造法 |
JP3149129B2 (ja) * | 1997-03-04 | 2001-03-26 | 日新製鋼株式会社 | 耐食性および表面外観の良好な溶融Zn−Al−Mg系めっき鋼板およびその製造法 |
JP3888784B2 (ja) * | 1998-09-21 | 2007-03-07 | 日新製鋼株式会社 | 溶融Zn基めっき鋼板のエッジしわ防止法 |
JP4522552B2 (ja) * | 2000-07-10 | 2010-08-11 | 日新製鋼株式会社 | 耐黒変性ミニマイズドスパングル溶融亜鉛めっき鋼板並びに処理液およびその使用法 |
JP3580261B2 (ja) * | 2001-03-23 | 2004-10-20 | 住友金属工業株式会社 | 溶融Zn−Al−Mgめっき鋼板およびその製造方法 |
JP3732141B2 (ja) * | 2001-11-09 | 2006-01-05 | 新日本製鐵株式会社 | 加工後の耐食性に優れた溶融亜鉛−Al系合金めっき鋼板及びその製造方法 |
JP4546884B2 (ja) * | 2004-07-07 | 2010-09-22 | 新日本製鐵株式会社 | 加工部耐食性に優れる表面処理めっき鋼板 |
US7914851B2 (en) * | 2004-12-28 | 2011-03-29 | Posco | Method of manufacturing hot-dipped galvanized steel sheet |
KR20120075235A (ko) * | 2010-12-28 | 2012-07-06 | 주식회사 포스코 | 고내식 용융아연합금 도금강판과 그 제조방법 |
CN103429781B (zh) * | 2011-01-20 | 2016-08-17 | Posco公司 | 具有优良的深冲性能和超低温粘合脆性的热浸镀锌钢板及其制备方法 |
KR101417304B1 (ko) * | 2012-07-23 | 2014-07-08 | 주식회사 포스코 | 내식성 및 표면외관이 우수한 용융아연합금 도금강판 및 그 제조방법 |
KR20150052376A (ko) * | 2013-10-30 | 2015-05-14 | 주식회사 포스코 | 내식성이 우수한 용융아연합금 도금강판 및 그 제조방법 |
-
2016
- 2016-10-26 JP JP2018521248A patent/JP6983153B2/ja active Active
- 2016-10-26 US US15/770,615 patent/US20180320260A1/en not_active Abandoned
- 2016-10-26 EP EP16860213.4A patent/EP3369838B1/fr active Active
- 2016-10-26 KR KR1020160140342A patent/KR101819381B1/ko active IP Right Grant
- 2016-10-26 CN CN201680064509.XA patent/CN108350555A/zh active Pending
Cited By (1)
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WO2021038102A1 (fr) | 2019-08-30 | 2021-03-04 | Rijksuniversiteit Groningen | Procédé de caractérisation de propriétés de formabilité d'un revêtement d'alliage de zinc sur un substrat métallique |
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KR20170049422A (ko) | 2017-05-10 |
KR101819381B1 (ko) | 2018-01-18 |
JP2018532889A (ja) | 2018-11-08 |
EP3369838B1 (fr) | 2019-08-21 |
CN108350555A (zh) | 2018-07-31 |
EP3369838A4 (fr) | 2018-09-05 |
JP6983153B2 (ja) | 2021-12-17 |
US20180320260A1 (en) | 2018-11-08 |
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