TW201307612A - Hot dip Zn-Al based alloy plated steel sheet and manufacturing method thereof - Google Patents
Hot dip Zn-Al based alloy plated steel sheet and manufacturing method thereof Download PDFInfo
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- TW201307612A TW201307612A TW101128834A TW101128834A TW201307612A TW 201307612 A TW201307612 A TW 201307612A TW 101128834 A TW101128834 A TW 101128834A TW 101128834 A TW101128834 A TW 101128834A TW 201307612 A TW201307612 A TW 201307612A
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- steel sheet
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- dip
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 76
- 239000010959 steel Substances 0.000 title claims abstract description 76
- 229910007570 Zn-Al Inorganic materials 0.000 title claims abstract description 71
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 43
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229910018134 Al-Mg Inorganic materials 0.000 claims abstract description 30
- 229910018467 Al—Mg Inorganic materials 0.000 claims abstract description 30
- 230000005496 eutectics Effects 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000007747 plating Methods 0.000 claims description 113
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 238000007739 conversion coating Methods 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 abstract description 42
- 230000007797 corrosion Effects 0.000 abstract description 42
- 239000010410 layer Substances 0.000 description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010191 image analysis Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- -1 decane compound Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241001270131 Agaricus moelleri Species 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910018571 Al—Zn—Mg Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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
- C23C2/26—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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Coating With Molten Metal (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本發明是有關於一種較佳用作建築、土木、家電等的構件且耐腐蝕性優異的熱浸鍍Zn-Al系合金鋼板及其製造方法，本發明尤其是有關於一種鍍敷層的加工性及耐腐蝕性得到提高的熱浸鍍Zn-Al系合金鋼板。 The present invention relates to a hot-dip Zn-Al alloy steel sheet which is preferably used as a member of a building, a civil engineering, a home appliance, etc., and which is excellent in corrosion resistance, and a manufacturing method thereof, and the present invention relates to a processing of a plating layer. A hot dip Zn-Al alloy steel sheet having improved properties and corrosion resistance.
以往，對於在建築、土木、家電等領域使用的熱浸鍍Zn系鋼板，要求其耐腐蝕性優異。 In the past, hot-dip Zn-based steel sheets used in construction, civil engineering, and home appliances are required to have excellent corrosion resistance.
例如，於建築領域，是將熱浸鍍Zn系鋼板成形加工為既定形狀，用作屋頂、牆壁、或其他結構體等的結構構件。於此種用途中，除了要求耐腐蝕性優秀以外，亦要求加工性優異且要求加工部的耐腐蝕性優異，包含加工部的素材的耐腐蝕性是決定此結構構件的耐久性的重要要素。因此，自提高結構部件的耐久性的觀點而言，強烈要求提高用作素材的熱浸鍍Zn系鋼板的耐腐蝕性。該情形時，要求外觀的均一性、抗黑變性亦優異。此處，所謂黑變，是指鍍敷表面的一部分或整個面暗淡而產生灰黑色的變色的現象。 For example, in the field of construction, a hot-dip Zn-based steel sheet is formed into a predetermined shape and used as a structural member such as a roof, a wall, or another structure. In such an application, in addition to excellent corrosion resistance, it is required to have excellent workability and excellent corrosion resistance of the processed portion, and the corrosion resistance of the material including the processed portion is an important factor for determining the durability of the structural member. Therefore, from the viewpoint of improving the durability of the structural member, it is strongly required to improve the corrosion resistance of the hot dip Zn-based steel sheet used as a material. In this case, uniformity of appearance and excellent resistance to blackening are also required. Here, the term "blackening" refers to a phenomenon in which a part or the entire surface of the plating surface is dim and discoloration of gray-black is generated.
而且，熱浸鍍Zn系鋼板例如於海邊等飛來鹽分較多的苛刻環境下亦有優異的耐腐蝕性，故而於建築領域中大多是無塗裝地予以使用。 Further, the hot-dip Zn-based steel sheet is excellent in corrosion resistance even in a harsh environment in which a large amount of salt is emitted from the sea, and is often used in the field of construction without coating.
針對此種期望，例如於專利文獻1中記載有一種連續熱浸鍍Zn-Al-Mg鋼板。專利文獻1所記載的技術如下， 即，一種於鋼板表面形成有Al：4.0%~10%、Mg：1.0%~4.0%、剩餘部分包含Zn及不可避免的雜質的鍍敷層而成的連續熱浸鍍Zn-Al-Mg鋼板，將鍍敷後的冷卻速度控制為0.5℃/s以上，將鍍敷層形成為包含於Al/Zn/Zn2Mg的三元共晶組織的基底中混雜有初晶Al相的金屬組織的層，從而獲得具有良好的耐腐蝕性及表面外觀的鍍敷鋼板。 In view of such a desire, for example, Patent Document 1 describes a continuous hot dip Zn-Al-Mg steel sheet. The technique described in Patent Document 1 is a continuous process in which a plating layer containing Al: 4.0% to 10%, Mg: 1.0% to 4.0%, and the remaining portion containing Zn and unavoidable impurities is formed on the surface of the steel sheet. Hot-dip Zn-Al-Mg steel plate, the cooling rate after plating is controlled to 0.5 ° C / s or more, and the plating layer is formed to be mixed in the base of the ternary eutectic structure of Al / Zn / Zn 2 Mg A layer of a metal structure having a primary Al phase, thereby obtaining a plated steel sheet having good corrosion resistance and surface appearance.
而且，專利文獻2中，記載有一種具有金屬光澤的美麗的鍍敷外觀、且具有優異的抗黑變性的熱浸鍍Zn-Al系合金鋼板。該專利文獻2所記載的技術如下，將鋼板浸漬於熱浸鍍Zn-Al系合金浴之後，自該鍍敷浴中抽出鋼板，以1℃/s~15℃/s的範圍的冷卻速度對上述鋼板進行冷卻，直至上述鋼板達到250℃為止，於鋼板表面形成包含Al：1.0%~10%、Mg：0.2%~1.0%、Ni：0.005%~0.1%、且剩餘部分包含Zn及不可避免的雜質的熱浸鍍Zn-Al系合金層，藉此獲得具有金屬光澤的美麗的鍍敷外觀、且具有優異的抗黑變性的熱浸鍍Zn-Al系合金鋼板。而且，於專利文獻2所記載的技術中，若於上述特定的範圍內控制鍍敷後的冷卻速度，則藉由Mg與Ni的相輔作用而加快Ni向鍍敷最表層部的濃化。而且，於專利文獻2所記載的技術中，熱浸鍍Zn-Al系合金層於鍍敷層剖面，較佳以10面積%~30面積%含有Al-Zn-Mg金屬間化合物的3元共晶。進而，於專利文獻2所記載的技術中，作為鍍敷層的上層，可形成化成處理(chemical conversion treatment)層、底漆層(primer layer)、樹脂層，作為化成處理層，可應用 利用不含鉻的鈦系或鋯系等的處理液的無鉻處理。 Further, Patent Document 2 describes a hot-dip Zn-Al-based alloy steel sheet having a beautiful plating appearance of metallic luster and excellent blackening resistance. According to the technique described in Patent Document 2, after the steel sheet is immersed in a hot dip Zn-Al alloy bath, the steel sheet is taken out from the plating bath and cooled at a cooling rate in the range of 1 ° C / s to 15 ° C / s. The steel sheet is cooled until the steel sheet reaches 250 ° C, and includes Al: 1.0% to 10%, Mg: 0.2% to 1.0%, Ni: 0.005% to 0.1%, and the remaining portion contains Zn and is inevitably formed on the surface of the steel sheet. The hot-dip Zn-Al alloy layer of the impurity is hot-dipped, thereby obtaining a hot-dip Zn-Al alloy steel sheet having a beautiful plating appearance of metallic luster and excellent blackening resistance. Further, in the technique described in Patent Document 2, when the cooling rate after plating is controlled within the above-described specific range, the concentration of Ni to the outermost layer portion of the plating layer is accelerated by the complementary action of Mg and Ni. Further, in the technique described in Patent Document 2, the hot dip-plated Zn-Al alloy layer has a cross section of the plating layer, and preferably contains 10% by area to 30% by area of the Al-Zn-Mg intermetallic compound. crystal. Further, in the technique described in Patent Document 2, a chemical conversion treatment layer, a primer layer, and a resin layer can be formed as an upper layer of the plating layer, and can be applied as a chemical conversion treatment layer. The chromium-free treatment of a treatment liquid such as a titanium-based or zirconium-free metal containing no chromium is used.
其次，於專利文獻3中記載有一種熱浸鍍Zn-Al系合金鋼板，該熱浸鍍Zn-Al系合金鋼板是於鋼板的至少其中一表面上，形成熱浸鍍Zn-Al系合金層，進而於該鍍敷層的表面形成表面處理皮膜。上述專利文獻3所記載的技術中，熱浸鍍Zn-Al系合金層是形成為，以質量%計，含有Al：1.0%~10%、Mg：0.2%~1.0%、Ni：0.005%~0.1%，剩餘部分包含Zn及不可避免的雜質的熱浸鍍Zn-Al系合金層，進而，形成於該鍍敷層的表面的表面處理皮膜是形成為，利用以既定比例含有特定的含鈦水性液、鎳化合物及/或鈷化合物、及含氟化合物的表面處理組成物而成的表面處理皮膜，藉此與鍍敷組成的最佳化相輔，獲得優異的抗黑變性，並且藉由含氟化合物的作用提高反應性，從而於鍍敷表面形成緻密的反應層，進而藉由賦予表面處理皮膜自身較高的障壁性，從而獲得優異的耐腐蝕性。 Next, Patent Document 3 describes a hot dip Zn-Al alloy steel sheet which is formed on at least one surface of a steel sheet to form a hot dip Zn-Al alloy layer. Further, a surface treatment film is formed on the surface of the plating layer. In the technique described in the above Patent Document 3, the hot dip Zn-Al alloy layer is formed to contain Al: 1.0% to 10%, Mg: 0.2% to 1.0%, and Ni: 0.005% by mass%. 0.1%, a hot-dip Zn-Al alloy layer containing Zn and unavoidable impurities, and a surface-treated film formed on the surface of the plating layer is formed to contain a specific titanium content in a predetermined ratio A surface-treated film comprising a surface treatment composition of an aqueous liquid, a nickel compound and/or a cobalt compound, and a fluorine-containing compound, thereby obtaining excellent anti-blackening property by complementing the optimization of the plating composition, and by The action of the fluorine-containing compound enhances the reactivity, thereby forming a dense reaction layer on the surface of the plating, and further imparting excellent barrier properties by imparting a barrier property to the surface-treated film itself.
專利文獻1：日本專利第3179401號公報 Patent Document 1: Japanese Patent No. 3179401
專利文獻2：日本專利特開2008-138285號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-138285
專利文獻3：日本專利特開2008-291350號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-291350
然而，利用專利文獻1所記載的技術製造出的鍍敷鋼板存在如下問題，鍍敷層中含有大量氧化能力強於Zn的Al及Mg，若將該鍍敷鋼板以線圈或薄板狀態長期保存於 倉庫等內，則鍍敷表面的一部分或整個面有時會暗淡而產生灰黑色的變色(黑變現象)，從而導致商品價值下降。而且，專利文獻1所記載的技術存在如下問題，由於鍍敷層中含有大量的Mg，故而鍍敷層硬質化，施加成形加工的部位產生龜裂，加快了鍍敷層基底的腐蝕(紅鏽)。 However, the plated steel sheet manufactured by the technique described in Patent Document 1 has a problem in that a large amount of Al and Mg having a higher oxidation ability than Zn is contained in the plating layer, and the plated steel sheet is stored in a coil or a sheet for a long period of time. In a warehouse or the like, a part or the entire surface of the plating surface may be dim and a gray-black discoloration (blackening phenomenon) may occur, resulting in a decrease in the value of the product. Further, the technique described in Patent Document 1 has a problem in that the plating layer contains a large amount of Mg, so that the plating layer is hardened, and cracks are generated at the portion where the forming process is applied, which accelerates corrosion of the plating layer base (red rust) ).
而且，於專利文獻2所記載的技術中，藉由使鍍敷層中形成為含有Ni的Zn-Al-Mg系組成，主要用於提高抗黑變性，但存在如下問題，於Al-Mg-Ni-Zn系這樣的4元系中，根據鍍敷層組成而於鍍敷層表面形成化成處理皮膜時，存在化成處理反應不充分的情形，導致抑制黑變的效果變得不穩定。 Further, in the technique described in Patent Document 2, the Zn-Al-Mg-based composition containing Ni in the plating layer is mainly used for improving the blackening resistance, but the following problems occur in Al-Mg- In the quaternary system of the Ni-Zn system, when the chemical conversion treatment film is formed on the surface of the plating layer in accordance with the composition of the plating layer, the chemical conversion treatment reaction may be insufficient, and the effect of suppressing blackening becomes unstable.
進而，於專利文獻3所記載的技術中，是將鍍敷層形成為含有Ni的Zn-Al-Mg系組成，進而作為鍍敷層的上層是形成特殊的表面處理皮膜，從而提高抗黑變性，但存在如下問題，若鎳化合物及/或鈷化合物增多，則耐腐蝕性下降，故而難以同時實現抗黑變性與耐腐蝕性。 Further, in the technique described in Patent Document 3, the plating layer is formed into a Zn-Al-Mg-based composition containing Ni, and further, as the upper layer of the plating layer, a special surface-treated film is formed to improve the blackening resistance. However, there is a problem in that if the nickel compound and/or the cobalt compound are increased, the corrosion resistance is lowered, so that it is difficult to simultaneously achieve the blackening resistance and the corrosion resistance.
本發明的目的在於解決上述先前技術問題，提供一種抗黑變性及耐腐蝕性優異的熱浸鍍Zn-Al系合金鋼板及其製造方法。 An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a hot dip Zn-Al alloy steel sheet excellent in blackening resistance and corrosion resistance and a method for producing the same.
為達成上述目的，本發明者等人對涉及熱浸鍍Zn-Al系合金鋼板的抗黑變性及耐腐蝕性的各種要因，進行了銳意研討。結果發現：將形成於鋼板表面的鍍敷層，設為含有適當量的Ni的Zn-Al-Mg系組成，此外將鍍敷層的表面組織設為Zn-Al-Mg系的3元共晶以面積率計為1%~50% 存在的組織，藉此於之後的化成處理中在反應性優異的鍍敷層表面上，可形成良好的化成處理皮膜，且可穩定地提高抗黑變性，並且於成形加工時，可有效抑制鍍敷層的龜裂產生，從而顯著提高成形加工部的耐腐蝕性。 In order to achieve the above object, the inventors of the present invention have conducted intensive studies on various factors relating to blackening resistance and corrosion resistance of hot dip galvannealed Zn-Al alloy steel sheets. As a result, it was found that the plating layer formed on the surface of the steel sheet was composed of a Zn-Al-Mg system containing an appropriate amount of Ni, and the surface structure of the plating layer was set to a ternary eutectic of Zn-Al-Mg system. 1%~50% based on area ratio The existing structure can form a favorable chemical conversion treatment film on the surface of the plating layer excellent in reactivity in the subsequent chemical conversion treatment, and can stably improve the blackening resistance, and can effectively suppress plating during the forming process. The crack of the coating layer is generated, so that the corrosion resistance of the formed portion is remarkably improved.
而且，本發明者等人發現：形成如上所述的組成的Zn-Al-Mg系合金層之外，進而形成含有鉬酸鹽的化成處理皮膜而作為該鍍敷層的上層，藉此可與鍍敷層組成相輔而顯著抑制黑變，從而顯著提高抗黑變性。 Further, the inventors of the present invention have found that, in addition to the Zn-Al-Mg-based alloy layer having the above-described composition, a chemical conversion treatment film containing molybdate is formed as the upper layer of the plating layer, whereby The composition of the plating layer complements and significantly suppresses blackening, thereby significantly improving the anti-blackening property.
本發明是基於此種見解，進而加入研討而成的發明。亦即，本發明的要旨如下所示。 The present invention is based on such findings and is further incorporated into the invention. That is, the gist of the present invention is as follows.
(1)一種抗黑變性與耐腐蝕性優異的熱浸鍍Zn-Al系合金鋼板，其於鋼板的至少其中一表面，形成熱浸鍍Zn-Al系合金層，進而形成化成處理被膜而作為該熱浸鍍Zn-Al系合金層的上層而成，該熱浸鍍Zn-Al系合金鋼板的特徵在於：上述熱浸鍍Zn-Al系合金層以質量%計，具有含有Al：3.0%~6.0%、Mg：0.2%~1.0%及Ni：0.01%~0.10%，且剩餘部分含有Zn及不可避免的雜質的組成，該鍍敷層的表面組織以面積率計含有1%~50%的Zn-Al-Mg系三元共晶，上述化成處理被膜含有鉬酸鹽。 (1) A hot-dip galvannealed Zn-Al alloy steel sheet excellent in blackening resistance and corrosion resistance, wherein a hot-dip Zn-Al alloy layer is formed on at least one surface of the steel sheet to form a chemical conversion coating film. The hot dip Zn-Al alloy steel sheet is characterized in that the hot dip Zn-Al alloy steel layer contains Al: 3.0% by mass%. ~6.0%, Mg: 0.2% to 1.0%, and Ni: 0.01% to 0.10%, and the remainder contains Zn and unavoidable impurities. The surface structure of the plating layer is 1% to 50% by area ratio. The Zn-Al-Mg system is a ternary eutectic, and the chemical conversion coating film contains a molybdate.
(2)如請求項1所述的熱浸鍍Zn-Al系合金鋼板，其中上述含有鉬酸鹽的化成處理皮被膜的每單面的附著量為 0.05 g/m2~1.5 g/m2。 (2) The hot dip Zn-Al alloy steel sheet according to claim 1, wherein the deposition amount of the chemical conversion treatment film containing the molybdate is from 0.05 g/m 2 to 1.5 g/m 2 per one side. .
(3)一種抗黑變性與耐腐蝕性優異的熱浸鍍Zn-Al系合金鋼板的製造方法，將鋼板浸漬於以質量%計含有Al：3%~6%、Mg：0.2%~1.0%及Ni：0.01%~0.10%、且剩餘部分含有Zn及不可避免的雜質的組成的熱浸鍍Zn-Al系合金浴中，然後自同一鍍敷浴中抽出鋼板並使其冷卻，於該鋼板表面形成熱浸鍍Zn-Al系合金層，進而實施化成處理，形成化成處理皮被膜而作為該熱浸鍍Zn-Al系合金層的上層，該熱浸鍍Zn-Al系合金鋼板的製造方法的特徵在於：上述熱浸鍍Zn-Al系合金浴的溫度設為420℃~520℃，上述熱浸鍍Zn-Al系合金浴中所浸漬的上述鋼板的溫度設為420℃~600℃，且將上述鋼板的溫度調整為上述熱浸鍍Zn-Al系合金浴的溫度以上，而將上述鋼板浸漬於上述熱浸鍍Zn-Al系合金浴中，進而，自上述熱浸鍍Zn-Al系合金浴中抽出鋼板，然後對上述鋼板實施平均冷卻速度為1℃/s~100℃/s的冷卻，直至上述鋼板的表面溫度達到350℃為止，上述化成處理是使用含有鉬酸鹽的化成處理液而進行。 (3) A method for producing a hot dip Zn-Al alloy steel sheet excellent in blackening resistance and corrosion resistance, wherein the steel sheet is immersed in an Al content of 3% to 6% by mass%, and Mg: 0.2% to 1.0% And a hot-dip Zn-Al alloy bath in which Ni: 0.01% to 0.10% and the remaining portion contains Zn and unavoidable impurities, and then the steel sheet is taken out from the same plating bath and cooled, and the steel sheet is cooled. a hot dip Zn-Al alloy layer is formed on the surface, and a chemical conversion treatment is performed to form a chemically processed skin film as an upper layer of the hot dip Zn-Al alloy layer, and the hot dip Zn-Al alloy steel sheet is produced. The temperature of the hot dip Zn-Al alloy bath is 420 ° C to 520 ° C, and the temperature of the steel sheet immersed in the hot dip Zn-Al alloy bath is 420 ° C to 600 ° C. Further, the temperature of the steel sheet is adjusted to be higher than the temperature of the hot dip Zn-Al alloy bath, and the steel sheet is immersed in the hot dip Zn-Al alloy bath, and further, the hot dip Zn-Al plating is performed. The steel plate is extracted from the alloy bath, and then the steel plate is cooled to an average cooling rate of 1 ° C / s to 100 ° C / s until the upper The surface temperature reaches 350 deg.] C until the steel sheet, the above-described chemical conversion treatment using a chemical conversion treatment liquid containing molybdate performed.
(4)如請求項3所述的熱浸鍍Zn-Al系合金鋼板的製造方法，其中上述化成處理液的pH值為2~6。 (4) The method for producing a hot dip Zn-Al alloy steel sheet according to claim 3, wherein the chemical conversion treatment liquid has a pH of 2 to 6.
根據本發明，可容易且廉價地製造穩定地具有優異的抗黑變性的熱浸鍍Zn-Al系合金鋼板，於產業上實現顯著 效果。而且，根據本發明，鍍敷層的加工性得到提高，結果，成形加工時的鍍敷層的龜裂產生受到抑制，鍍敷基底的腐蝕被有效抑制，故而可提供成形加工後的耐腐蝕性優異的熱浸鍍Zn-Al系合金鋼板。 According to the present invention, a hot dip Zn-Al alloy steel sheet which stably exhibits excellent blackening resistance can be easily and inexpensively produced, and is industrially remarkable. effect. Moreover, according to the present invention, the workability of the plating layer is improved, and as a result, cracking of the plating layer during molding processing is suppressed, and corrosion of the plating substrate is effectively suppressed, so that corrosion resistance after forming processing can be provided. Excellent hot dip galvanized Zn-Al alloy steel plate.
本發明的熱浸鍍Zn-Al系合金鋼板(以下亦稱為「本發明鍍敷鋼板」)，於鋼板的至少其中一表面上，具有以質量%計，含有Al：3.0%~6.0%、Mg：0.2%~1.0%、Ni：0.01%~0.1%，且剩餘部分含有Zn及不可避免的雜質的熱浸鍍Zn-Al系合金層，進而具有含有鉬酸鹽的化成處理皮膜作為其上層。 The hot dip Zn-Al alloy steel sheet according to the present invention (hereinafter also referred to as "the plated steel sheet of the present invention") has Al: 3.0% to 6.0% by mass on at least one of the surfaces of the steel sheet. Mg: 0.2% to 1.0%, Ni: 0.01% to 0.1%, and the remaining portion contains a hot-dip Zn-Al alloy layer containing Zn and unavoidable impurities, and further has a chemical conversion treatment film containing molybdate as its upper layer .
首先，對熱浸鍍Zn-Al系合金層的組成限定理由進行說明。再者，以下將組成的質量%僅記述為%。 First, the reason for limiting the composition of the hot dip Zn-Al alloy layer will be described. In addition, the mass % of the composition is described below as only %.
Al：3.0%~6.0% Al: 3.0%~6.0%
當鍍敷層中所含的Al小於3.0%時，於鍍敷層與基底鋼板的界面會較厚地形成Fe-Al系合金層，故而加工性下降。另一方面，若Al超過6.0%而大量含有，則Zn的犧牲防腐蝕作用變小，耐腐蝕性下降，並且抗黑變性下降。而且，Zn-Al-Mg的3元共晶的形成變多，化成處理性變得不穩定，而且鍍敷層的加工性亦下降。因此，鍍敷層中的Al被限定於3.0%~6.0%的範圍內。進而，較佳為4.0%~5.5%的範圍。 When the Al contained in the plating layer is less than 3.0%, the Fe-Al alloy layer is formed thickly at the interface between the plating layer and the base steel sheet, and the workability is deteriorated. On the other hand, when Al is more than 6.0% and is contained in a large amount, the sacrificial anticorrosive action of Zn is small, the corrosion resistance is lowered, and the blackening resistance is lowered. Further, the formation of the ternary eutectic of Zn-Al-Mg is increased, the chemical conversion treatability is unstable, and the workability of the plating layer is also lowered. Therefore, Al in the plating layer is limited to a range of 3.0% to 6.0%. Further, it is preferably in the range of 4.0% to 5.5%.
Mg：0.2%~1.0% Mg: 0.2%~1.0%
Mg是為了提高耐腐蝕性而包含於鍍敷層中，但鍍敷 層中所含的Mg在小於0.2%時對耐腐蝕性的提高效果較少，另一方面，若Mg超過1.0%而大量含有，則Zn-Al-Mg系3元共晶的形成變多，鍍敷層的加工性下降。根據此種狀況，鍍敷層中的Mg被限定於0.2%~1.0%的範圍內。進而，較佳為0.3%~0.8%的範圍。 Mg is included in the plating layer in order to improve corrosion resistance, but plating When the amount of Mg contained in the layer is less than 0.2%, the effect of improving the corrosion resistance is small. On the other hand, if Mg is more than 1.0% and is contained in a large amount, the formation of the Zn-Al-Mg system ternary eutectic is increased. The workability of the plating layer is lowered. According to such a situation, Mg in the plating layer is limited to the range of 0.2% to 1.0%. Further, it is preferably in the range of 0.3% to 0.8%.
Ni：0.01%~0.10% Ni: 0.01%~0.10%
Ni是為了提高耐腐蝕性與抗黑變性而包含於鍍敷層中，但當鍍敷層中所含的Ni小於0.01%時，耐腐蝕性與抗黑變性的提高效果較少，另一方面，若Ni超過0.10%而大量含有，則鍍敷層的表面被過度活性化，變得易腐蝕，且初期容易出現白鏽。因此，鍍敷層中的Ni被限定於0.01%~0.10%的範圍內。 Ni is included in the plating layer in order to improve corrosion resistance and blackening resistance. However, when Ni contained in the plating layer is less than 0.01%, the effect of improving corrosion resistance and blackening resistance is small. When Ni is contained in a large amount in excess of 0.10%, the surface of the plating layer is excessively activated, and it is easily corroded, and white rust tends to occur at an initial stage. Therefore, Ni in the plating layer is limited to the range of 0.01% to 0.10%.
上述以外的剩餘部分包含Zn及不可避免的雜質。再者，作為雜質，有Si、Ca、Ti、V、Cr、Mn、Fe、Co、Cu、Sr、Zr、Nb、Mo等，且各成分可以0.01%為上限而含有。 The remainder other than the above contains Zn and unavoidable impurities. Further, as the impurities, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Cu, Sr, Zr, Nb, Mo, or the like may be contained, and each component may be contained in an upper limit of 0.01%.
進而，本發明鍍敷鋼板的表面所形成的鍍敷層具有上述組成，進而於鍍敷層表面具有以面積率計含有1%~50%的Zn-Al-Mg系三元共晶的組織。 Further, the plating layer formed on the surface of the plated steel sheet of the present invention has the above composition, and further has a structure containing 1% to 50% of a Zn-Al-Mg ternary eutectic in an area ratio on the surface of the plating layer.
本發明鍍敷鋼板的鍍敷層於表面具有Zn-Al-Mg系3元共晶以面積率計露出1%~50%的表面組織。藉由使鍍敷層表面存在(露出)既定量的Zn-Al-Mg系3元共晶，而可兼具耐腐蝕性與加工性。 The plating layer of the plated steel sheet of the present invention has a Zn-Al-Mg system ternary eutectic on the surface exposing 1% to 50% of the surface structure by area ratio. Corrosion resistance and workability can be achieved by presenting (exposed) a predetermined amount of Zn-Al-Mg system ternary eutectic on the surface of the plating layer.
亦即，當鍍敷層表面的Zn-Al-Mg系三元共晶在同表面的面積率小於1%時，耐腐蝕性的提高效果變少，另一 方面，若Zn-Al-Mg系三元共晶在表面上的面積率超過50%，則與化成處理的鍍敷層表面的反應性下降，難以獲得良好的化成處理皮膜，抗黑變性變得不穩定，並且鍍敷層的表面變得過硬，成形加工時容易產生龜裂。因此，鍍敷層的表面組織的Zn-Al-Mg系三元共晶被限定於面積率1%~50%的範圍內。再者，較佳為5%~40%。 That is, when the area ratio of the Zn-Al-Mg ternary eutectic on the surface of the plating layer is less than 1% on the same surface, the effect of improving corrosion resistance is less, and the other is less. When the area ratio of the Zn-Al-Mg ternary eutectic on the surface exceeds 50%, the reactivity with the surface of the plating layer of the chemical conversion treatment is lowered, and it is difficult to obtain a favorable chemical conversion treatment film, and the blackening resistance becomes It is unstable, and the surface of the plating layer becomes too hard, and cracks are likely to occur during molding. Therefore, the Zn-Al-Mg ternary eutectic of the surface structure of the plating layer is limited to an area ratio of 1% to 50%. Further, it is preferably 5% to 40%.
再者，鍍敷層表面的Zn-Al-Mg系三元共晶的面積率較佳以如下方式求出，即，例如利用掃描式電子顯微鏡(倍率：1000倍左右)觀察鍍敷層表面，隨機地對鍍敷層的表面組織進行數個視野拍攝，針對各視野(各照片)使用圖像處理軟體求出上述面積率。本發明中，是使各視野所得的面積率算術平均，並將該算術平均值設為此鍍敷層的Zn-Al-Mg系三元共晶的面積率。圖1中，表示本發明鍍敷鋼板的鍍敷層表面組織的一例。具有條紋模樣的結晶為Zn-Al-Mg系三元共晶。而且，圖2是利用EPMA(electron probe micro analyser，電子探針微量分析器)對圖1所示的鍍敷層表面分析Mg後對分析結果進行圖像解析，作為Zn-Al-Mg系三元共晶的表面分布狀況而表示的圖像解析圖。亦可藉由利用上述圖像解析圖，變成黑白2個灰階，而自直方圖算出的方法，求出Zn-Al-Mg系三元共晶的表面面積率。黑色部分為Zn-Al-Mg系三元共晶。 In addition, the area ratio of the Zn-Al-Mg ternary eutectic on the surface of the plating layer is preferably obtained by observing the surface of the plating layer by, for example, a scanning electron microscope (magnification: about 1000 times). The surface texture of the plating layer was randomly photographed in several fields, and the area ratio was obtained by using an image processing software for each field of view (each photograph). In the present invention, the area ratio obtained in each field of view is arithmetically averaged, and the arithmetic mean value is defined as the area ratio of the Zn-Al-Mg system ternary eutectic of the plating layer. Fig. 1 shows an example of the surface structure of a plating layer of a plated steel sheet of the present invention. The crystal having a stripe pattern is a Zn-Al-Mg system ternary eutectic. 2 is an image analysis of the surface of the plating layer shown in FIG. 1 by EPMA (electron probe micro analyser), and the image is analyzed as a Zn-Al-Mg system ternary. An image analysis diagram represented by the surface distribution of the eutectic. The surface area ratio of the Zn-Al-Mg ternary eutectic can also be obtained by the method of calculating from the histogram by using the above-described image analysis map to become two gray scales in black and white. The black portion is a Zn-Al-Mg system ternary eutectic.
本發明鍍敷鋼板中的熱浸鍍Zn-Al-Mg系合金層的附著量如通常般根據用途設定便可，無需特別限定，每單面較佳為30 g/m2~300 g/m2左右。鍍敷層的附著量為30 g/m2 以上時，鍍敷層厚度不會不足，可維持所期望的耐腐蝕性。另一方面，若上述附著量為300 g/m2以下，則鍍敷層厚度不會變的過於厚，鍍敷層不會剝離。 The amount of the hot-dip Zn-Al-Mg-based alloy layer in the plated steel sheet of the present invention can be set according to the application, and is not particularly limited, and is preferably 30 g/m 2 to 300 g/m per one side. 2 or so. When the adhesion amount of the plating layer is 30 g/m 2 or more, the thickness of the plating layer is not insufficient, and the desired corrosion resistance can be maintained. On the other hand, when the adhesion amount is 300 g/m 2 or less, the thickness of the plating layer does not become too thick, and the plating layer does not peel off.
本發明鍍敷鋼板中，具有含有鉬酸鹽的化成處理皮膜而作為熱浸鍍Zn-Al-Mg系合金層的上層。 The plated steel sheet of the present invention has a chemical conversion treatment film containing molybdate as an upper layer of a hot dip Zn-Al-Mg alloy layer.
作為鍍敷層的上層而形成的化成處理皮膜含有鉬酸鹽，藉由上述鉬酸鹽與Zn-Al-Mg系三元共晶的組合，而優化抗黑變性與耐腐蝕性。再者，作為鉬酸鹽，溶解於化成處理中便可，並無特別限定。作為鉬酸鹽的種類，可例示例如銨、鈉等鹽。化成處理皮膜中的鉬酸鹽的含量並無特別限定，就抗黑變性與耐腐蝕性的觀點而言，有利的是以鉬換算而於0.3質量%~3質量%的範圍內含有。 The chemical conversion treatment film formed as the upper layer of the plating layer contains molybdate, and the combination of the above molybdate and the Zn-Al-Mg ternary eutectic is optimized to resist blackening and corrosion resistance. Further, the molybdate is not particularly limited as long as it is dissolved in the chemical conversion treatment. As the kind of the molybdate, a salt such as ammonium or sodium can be exemplified. The content of the molybdate in the chemical conversion coating film is not particularly limited, and is preferably contained in the range of 0.3% by mass to 3% by mass in terms of molybdenum in terms of resistance to blackening and corrosion resistance.
而且，化成處理皮膜中除了含有鉬酸鹽之外，亦可含有鉻酸、磷酸鹽、或Ti、Zr、V、Mn、Ni、Co等的氟化物或鹽、矽烷化合物、金屬螯合劑、水性樹脂、矽溶膠等氧化物溶膠等。 Further, the chemical conversion treatment film may contain chromic acid, phosphate, or a fluoride or a salt of Ti, Zr, V, Mn, Ni, Co or the like, a decane compound, a metal chelating agent, or water, in addition to the molybdate. An oxide sol such as a resin or a ruthenium sol.
進而，化成處理皮膜的每單面的附著量根據用途適當決定便可，無需特別限定，若為0.05 g/m2以上則抗黑變性及耐腐蝕性不會下降，另一方面，若為1.5 g/m2以下，則皮膜形成量不會變多，不會導致製造成本升高。根據此種情況，化成處理皮膜的每單面的附著量較佳為設為0.05 g/m2~1.5 g/m2。 In addition, the amount of adhesion per one surface of the chemical conversion treatment film can be appropriately determined depending on the use, and is not particularly limited. When it is 0.05 g/m 2 or more, the blackening resistance and the corrosion resistance are not lowered. On the other hand, the amount is 1.5. When g/m 2 or less, the amount of film formation does not increase, and the manufacturing cost does not increase. In this case, the amount of adhesion per one side of the chemical conversion treatment film is preferably from 0.05 g/m 2 to 1.5 g/m 2 .
其次，對本發明鍍敷鋼板的較佳製造方法進行說明。 Next, a preferred method of producing the plated steel sheet of the present invention will be described.
例如利用連續式熱浸鍍Zn製造設備，將作為基板的 鋼板浸漬於熱浸鍍Zn-Al系合金浴中，然後抽出予以冷卻，於鋼板表面形成熱浸鍍Zn-Al系合金層。 For example, a continuous hot dip Zn plating apparatus will be used as a substrate. The steel sheet was immersed in a hot dip Zn-Al alloy bath, and then extracted and cooled to form a hot dip Zn-Al alloy layer on the surface of the steel sheet.
用作基板的鋼板的種類、組成並無特別限定，可根據用途，自周知的熱軋鋼板、冷軋鋼板中適當選擇。 The type and composition of the steel sheet used as the substrate are not particularly limited, and can be appropriately selected from known hot-rolled steel sheets and cold-rolled steel sheets depending on the application.
首先，作為基板的鋼板是利用例如連續式熱浸鍍Zn製造設備，加熱至所期望的加熱溫度為止。加熱溫度根據使用的鋼板而適當決定便可，並無特別限定，本發明中，將鋼板浸漬於鍍敷浴時，必須將鋼板溫度(板溫)調整為所期望的溫度，加熱溫度必須能確保至少於浸漬於鍍敷浴時的所期望的鋼板溫度(板溫)。 First, the steel sheet as the substrate is heated to a desired heating temperature by, for example, a continuous hot dip Zn plating apparatus. The heating temperature is not particularly limited as long as it is appropriately determined depending on the steel sheet to be used. In the present invention, when the steel sheet is immersed in the plating bath, the steel sheet temperature (plate temperature) must be adjusted to a desired temperature, and the heating temperature must be ensured. At least the desired steel sheet temperature (plate temperature) when immersed in the plating bath.
加熱至既定溫度的鋼板被浸漬於保持為既定組成、浴溫的熱浸鍍Zn-Al系合金浴中。 The steel sheet heated to a predetermined temperature is immersed in a hot dip Zn-Al alloy bath maintained at a predetermined composition and bath temperature.
浸漬鋼板的熱浸鍍Zn-Al系合金浴的組成如下，以質量%計，包含Al：3%~6%、Mg：0.2%~1.0%、Ni：0.01%~0.10%，且剩餘部分包含Zn及不可避免的雜質。而且，鍍敷浴的浴溫設為420℃~520℃。當鍍敷浴的浴溫小於420℃時，浴溫過低，存在鍍敷浴部分凝固的情形，無法進行既定的鍍敷處理。另一方面，若鍍敷浴的浴溫超過520℃變成高溫，則鍍敷浴的氧化變得顯著，浮渣(dross)的產生增加。因此，鍍敷浴的浴溫被限定於420℃~520℃的範圍的溫度。進而，鍍敷浴的浴溫較佳為450℃~500℃的範圍。 The composition of the hot dip Zn-Al alloy bath of the impregnated steel sheet is as follows, and includes, by mass%, Al: 3% to 6%, Mg: 0.2% to 1.0%, Ni: 0.01% to 0.10%, and the remainder includes Zn and unavoidable impurities. Further, the bath temperature of the plating bath is set to 420 ° C to 520 ° C. When the bath temperature of the plating bath is less than 420 ° C, the bath temperature is too low, and the plating bath partially solidifies, and the predetermined plating treatment cannot be performed. On the other hand, when the bath temperature of the plating bath exceeds 520 ° C and becomes a high temperature, oxidation of the plating bath becomes remarkable, and generation of dross increases. Therefore, the bath temperature of the plating bath is limited to a temperature in the range of 420 ° C to 520 ° C. Further, the bath temperature of the plating bath is preferably in the range of 450 ° C to 500 ° C.
而且，浸漬於鍍敷浴的鋼板的溫度(板溫)是於420℃~600℃的範圍內被調整為鍍敷浴的浴溫以上的溫度。浸漬 的鋼板的板溫在小於420℃或小於浴溫時，浴溫會逐漸變低，故而鍍敷浴的黏性變大，給操作帶來阻礙。另一方面，若浸漬的鋼板的板溫超過600℃，則浴溫逐漸上升，鍍敷固著性下降。因此，浸漬於鍍敷浴的鋼板的溫度(板溫)被限定於420℃~600℃的範圍的溫度，且被限定於鍍敷浴的浴溫以上。 Further, the temperature (plate temperature) of the steel sheet immersed in the plating bath is adjusted to a temperature equal to or higher than the bath temperature of the plating bath in the range of 420 ° C to 600 ° C. Impregnation When the sheet temperature of the steel sheet is less than 420 ° C or less than the bath temperature, the bath temperature is gradually lowered, so that the viscosity of the plating bath becomes large, which hinders the operation. On the other hand, when the plate temperature of the impregnated steel sheet exceeds 600 ° C, the bath temperature gradually rises, and the plating adhesion is lowered. Therefore, the temperature (plate temperature) of the steel sheet immersed in the plating bath is limited to a temperature in the range of 420 ° C to 600 ° C, and is limited to the bath temperature of the plating bath.
本發明中，將上述鍍敷浴設為上述範圍的浴溫，進而將浸漬於鍍敷浴的鋼板的溫度(板溫)調整為420℃~600℃的範圍的溫度，進而將浸漬於鍍敷浴的鋼板的溫度(板溫)調整為鍍敷浴的浴溫以上。藉此，於鍍敷浴與鋼板表面的界面產生合金元素的擴散，在鍍敷層與鋼板(基板)的界面上加快形成Ni濃化層。藉由Ni濃化層的形成，即便鍍敷層產生快到達基板的損傷時，或者因加工使得鍍敷層產生龜裂時，亦可確保耐腐蝕性。 In the present invention, the plating bath is set to a bath temperature in the above range, and the temperature (plate temperature) of the steel sheet immersed in the plating bath is further adjusted to a temperature in the range of 420 ° C to 600 ° C, and further immersed in plating. The temperature (plate temperature) of the steel plate of the bath was adjusted to be equal to or higher than the bath temperature of the plating bath. Thereby, diffusion of alloying elements occurs at the interface between the plating bath and the surface of the steel sheet, and the Ni-concentrated layer is accelerated at the interface between the plating layer and the steel sheet (substrate). By the formation of the Ni-concentrated layer, corrosion resistance can be ensured even when the plating layer is damaged to reach the substrate quickly, or when the plating layer is cracked by the processing.
將浸漬於鍍敷浴的鋼板自鍍敷浴中抽出予以冷卻。抽出之後的冷卻是以1℃/s~100℃/s的平均冷卻速度進行，直至鋼板的表面溫度到達350℃為止。至350℃為止的平均冷卻速度在小於1℃/s時，冷卻所需時間變長，故而生產性下降。另一方面，若平均冷卻速度超過100℃/s而變成急冷，則Zn-Al-Mg系三元結晶在表面上的面積率超過50%，化成處理的反應性與鍍敷層的加工性下降。根據此種情況，將鋼板自鍍敷浴中抽出之後的冷卻速度被限定於至350℃為止的平均為1℃/s~100℃/s。再者，較佳為2℃/s~70℃/s。 The steel sheet immersed in the plating bath was taken out from the plating bath and cooled. The cooling after the extraction is performed at an average cooling rate of 1 ° C / s to 100 ° C / s until the surface temperature of the steel sheet reaches 350 ° C. When the average cooling rate up to 350 ° C is less than 1 ° C / s, the time required for cooling becomes long, and productivity is lowered. On the other hand, when the average cooling rate exceeds 100 ° C / s and becomes quenched, the area ratio of the Zn-Al-Mg ternary crystal on the surface exceeds 50%, and the reactivity of the chemical conversion treatment and the workability of the plating layer are lowered. . In this case, the cooling rate after the steel sheet is extracted from the plating bath is limited to an average of 1 ° C/s to 100 ° C/s up to 350 ° C. Further, it is preferably 2 ° C / s to 70 ° C / s.
表面形成有鍍敷層的鋼板上接著實施化成處理，形成化成處理皮膜而作為鍍敷層的上層。 The steel sheet on which the plating layer is formed on the surface is subjected to a chemical conversion treatment to form a chemical conversion treatment film as an upper layer of the plating layer.
本發明中進行的化成處理使用的化成處理液是利用向水等溶劑中添加鉬酸鹽、且較佳調整為pH值=2~6的處理液。再者，化成處理液中除了含有鉬酸鹽之外，當然亦可含有鉻酸、磷酸鹽、Ti、Zr、V、Mn、Ni、Co等的氟化物、Ti、Zr、V、Mn、Ni、Co等的鹽、矽烷化合物、金屬螯合劑、水性樹脂及矽溶膠等氧化物溶膠中的任一種或2種以上。 The chemical conversion treatment liquid used in the chemical conversion treatment in the present invention is a treatment liquid obtained by adding a molybdate to a solvent such as water, and preferably adjusting the pH to 2 to 6. Further, in addition to the molybdate, the chemical conversion treatment liquid may of course contain fluorides such as chromic acid, phosphate, Ti, Zr, V, Mn, Ni, Co, etc., Ti, Zr, V, Mn, Ni. Any one or two or more kinds of oxide sols such as a salt of Co, a decane compound, a metal chelating agent, an aqueous resin, and a cerium sol.
而且，若化成處理液的pH值為2以上，則對鍍敷層表面的溶解性適度，化成處理皮膜正常地形成，且定著性、耐腐蝕性不會下降。另一方面，若pH值為6以下，則化成處理液的穩定性不會變差，且密著性、耐腐蝕性不會下降。因此，較佳為將化成處理液的pH值調成為2~6的範圍。更佳為4~5。 In addition, when the pH of the chemical conversion treatment liquid is 2 or more, the solubility on the surface of the plating layer is moderate, and the chemical conversion treatment film is formed normally, and the fixing property and the corrosion resistance are not lowered. On the other hand, when the pH is 6 or less, the stability of the chemical conversion treatment liquid does not deteriorate, and the adhesion and corrosion resistance do not decrease. Therefore, it is preferred to adjust the pH of the chemical conversion treatment solution to a range of 2 to 6. More preferably 4~5.
於常溫下將上述化成處理液塗佈至鍍敷層表面後，較佳將鋼板溫度加熱至60℃~120℃，使化成處理液乾燥而蒸發溶劑，從而形成作為鍍敷層的上層的化學處理皮膜。塗佈方法並無特別限定，可應用众所周知的任一種塗佈方法，即，輥塗、淋洗、浸漬氣體擦拭等連續處理的方法。而且，乾燥方法亦可應用众所周知的任一方法，即，暖風爐、電熱爐、感應加熱等。 After the chemical conversion treatment liquid is applied to the surface of the plating layer at normal temperature, the temperature of the steel sheet is preferably heated to 60 ° C to 120 ° C, and the chemical conversion treatment liquid is dried to evaporate the solvent to form a chemical treatment of the upper layer as a plating layer. Membrane. The coating method is not particularly limited, and any of various well-known coating methods, that is, a method of continuous treatment such as roll coating, rinsing, and immersion gas wiping, can be applied. Further, the drying method may be applied to any of the well-known methods, that is, a warm air furnace, an electric heating furnace, induction heating, or the like.
將冷軋鋼板(板厚：0.8mm、未退火(anneal))作為 基板，將該基板加熱至表1所示的浸漬時的鋼板溫度(板溫)後，浸漬於表1所示的各種組成、浴溫的熱浸鍍Zn-Al系合金浴中，抽出後予以冷卻，於基板表面形成表2所示的組成、附著量的熱浸鍍Zn-Al系合金層。再者，抽出後，以表1所示的自抽出後至350℃為止的平均、即以表1所示的冷卻速度進行冷卻。 Cold rolled steel sheets (sheet thickness: 0.8 mm, unannealed) were used as The substrate was heated to the steel sheet temperature (plate temperature) at the time of immersion shown in Table 1, and then immersed in a hot dip Zn-Al alloy bath of various compositions and bath temperatures shown in Table 1, and then extracted. After cooling, a hot-dip Zn-Al-based alloy layer having a composition and an adhesion amount shown in Table 2 was formed on the surface of the substrate. Further, after the extraction, the mixture was cooled to an average of 350 ° C after the extraction, that is, at a cooling rate shown in Table 1, as shown in Table 1.
接著，藉由輥塗，於所得的鍍敷鋼板的鍍敷層表面塗佈化成處理液(液溫：25℃)，然後利用220℃的暖風爐乾燥3秒鐘，實施形成0.6 g/m2的化成處理皮膜的化成處理。再者，所使用的化成處理液是藉由向溶劑(水)中以質量比計，添加10質量%的鉬酸鹽、鋯英石酸鹽、鈦酸鹽中的任一種，獲得具有表1所示的pH值的處理液。 Then, a chemical conversion treatment liquid (liquid temperature: 25 ° C) was applied onto the surface of the plating layer of the obtained plated steel sheet by roll coating, and then dried in a hot air oven at 220 ° C for 3 seconds to form 0.6 g/m. 2 conversion treatment chemical conversion treatment film. In addition, the chemical conversion treatment liquid to be used is obtained by adding any one of 10% by mass of molybdate, zirconate, and titanate in a mass ratio to a solvent (water). The pH of the treatment liquid shown.
針對所得的熱浸鍍Zn-Al系合金鋼板，首先實施鍍敷層表面的組織觀察、腐蝕試驗。試驗方法如下所示。 With respect to the obtained hot dip galvannealed Zn-Al alloy steel sheet, first, the structure observation and the corrosion test of the surface of the plating layer were carried out. The test method is as follows.
自所得的熱浸鍍Zn-Al系合金鋼板上獲取組織觀察用試驗片，利用掃描式電子顯微鏡(倍率：1000倍)，觀察鍍敷層表面的組織。而且，利用EPMA對鍍敷層表面分析Mg，對分析結果進行圖像解析，變成黑白兩種灰階，根據直方圖算出Zn-Al-Mg系三元共晶的面積率。 A test piece for observation of the structure was obtained from the obtained hot-dip galvannealed Zn-Al alloy steel sheet, and the structure of the surface of the plating layer was observed by a scanning electron microscope (magnification: 1000 times). Further, the surface of the plating layer was analyzed by EPMA using EPMA, and the analysis results were subjected to image analysis to obtain black and white gray scales, and the area ratio of the Zn-Al-Mg system ternary eutectic was calculated from the histogram.
接著，針對所得的熱浸鍍Zn-Al系合金鋼板，實施抗黑變性試驗，並評估抗黑變性。試驗方法如下所示。 Next, the obtained hot dip Zn-Al alloy steel sheet was subjected to an anti-blackening test, and the anti-blackening property was evaluated. The test method is as follows.
自所得的熱浸鍍Zn-Al系合金鋼板獲取試驗片(平 板：50×50 mm)，實施將該試驗片於溫度：80℃、相對濕度：95%的恆溫恆濕槽內保持24小時的試驗，於試驗前後測定試驗片表面的明度L，求出明度(brightness)L的差△L，對抗黑變性進行評估。評估基準如下所示。 A test piece was obtained from the obtained hot-dip Zn-Al alloy steel plate (flat Plate: 50 × 50 mm), the test piece was tested in a constant temperature and humidity chamber at a temperature of 80 ° C and a relative humidity of 95% for 24 hours, and the brightness L of the surface of the test piece was measured before and after the test to determine the brightness. (brightness) The difference ΔL of L is evaluated against blackening. The evaluation criteria are as follows.
評分3：△L：8以下(基本上無黑變產生的狀態) Score 3: ΔL: 8 or less (substantially no blackening state)
評估2：△L：超過8~小於15(略有黑變產生的狀態) Evaluation 2: △ L: more than 8 ~ less than 15 (slightly blackened state)
評分1：△L：15以上(黑變顯著產生的狀態) Score 1: △ L: 15 or more (state in which blackening is significantly generated)
而且，針對所得的熱浸鍍Zn-Al系合金鋼板，實施加工後的耐腐蝕性試驗，評估加工部的耐腐蝕性。試驗方法如下所示。 Further, the obtained hot dip galvannealed Zn-Al alloy steel sheet was subjected to a corrosion resistance test after the processing, and the corrosion resistance of the processed portion was evaluated. The test method is as follows.
自所得的熱浸鍍Zn-Al系合金鋼板上獲取彎曲試驗片，依據日本工業標準(Japanese Industrial Standards，JIS)G3317的規定，賦予內1.6 mmR-180°彎曲，然後依據JIS Z 2371的規定，實施鹽水噴霧試驗。鹽水噴霧條件設為，噴霧液：5質量%食鹽水、溫度：35℃、試驗時間：2000 h。試驗之後，利用數位相機(digital camera)觀察試驗片表面並拍攝，藉由圖像處理求出紅鏽產生率(面積率)，對加工部的耐腐蝕性進行評估。評估的基準如下所示。 A bending test piece was obtained from the obtained hot-dip Zn-Al alloy steel sheet, and was subjected to bending of 1.6 mm R-180° according to the Japanese Industrial Standards (JIS) G3317, and then according to JIS Z 2371, A salt spray test was performed. The salt spray conditions were as follows: spray liquid: 5% by mass saline, temperature: 35 ° C, test time: 2000 h. After the test, the surface of the test piece was observed by a digital camera and photographed, and the red rust generation rate (area ratio) was obtained by image processing, and the corrosion resistance of the processed portion was evaluated. The basis for the evaluation is as follows.
評分3：無紅鏽產生 Score 3: no red rust
評估2：有紅鏽產生，紅鏽產生率為50%以下 Assessment 2: Red rust is generated, and the red rust generation rate is 50% or less.
評分1：有紅鏽產生，紅鏽產生率超過50% Score 1: Red rust is generated, and the rate of red rust is over 50%.
所得的結果示於表2。 The results obtained are shown in Table 2.
本發明例均為抗黑變性優異、且加工部的耐腐蝕性亦優異的熱浸鍍Zn-Al系合金鋼板。另一方面，超出本發明的範圍的比較例中，抗黑變性下降，或者加工部的耐腐蝕性下降，或者兩者均下降。 Each of the examples of the present invention is a hot-dip galvannealed Zn-Al alloy steel sheet which is excellent in anti-blackening property and excellent in corrosion resistance of a processed portion. On the other hand, in the comparative example which is beyond the scope of the present invention, the blackening resistance is lowered, or the corrosion resistance of the processed portion is lowered, or both are lowered.
圖1是表示本發明的熱浸鍍Zn-Al系合金鋼板的鍍敷層表面組織的一例的掃描式電子顯微鏡組織照片。 Fig. 1 is a scanning electron microscope structure photograph showing an example of a surface structure of a plating layer of a hot dip Zn-Al alloy steel sheet according to the present invention.
圖2是表示圖1所示的鍍敷層表面組織的Zn-Al-Mg系3元共晶的表面分布狀態的圖像解析圖。 Fig. 2 is an image analysis diagram showing a state of surface distribution of a Zn-Al-Mg-based ternary eutectic of the surface structure of the plating layer shown in Fig. 1;
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| KR101568474B1 (en) * | 2013-10-30 | 2015-11-11 | 주식회사 포스코 | HOT DIP Zn ALLOY PLATED STEEL SHEET HAVING EXCELLENT BLACKENING-RESISTANCE AND SURFACE APPEARANCE AND METHOD FOR MANUFACTURING THE SAME |
| WO2016105157A1 (en) * | 2014-12-24 | 2016-06-30 | 주식회사 포스코 | Zinc alloy plated steel sheet having excellent phosphatability and spot weldability and method for manufacturing same |
| KR101758529B1 (en) | 2014-12-24 | 2017-07-17 | 주식회사 포스코 | Zn ALLOY PLATED STEEL SHEET HAVING EXCELLENT PHOSPHATABILITY AND SPOT WELDABILITY AND METHOD FOR MANUFACTURING SAME |
| KR101767788B1 (en) | 2015-12-24 | 2017-08-14 | 주식회사 포스코 | Plating steel material having excellent friction resistance and white rust resistance and method for manufacturing same |
| JP6515973B2 (en) * | 2016-10-11 | 2019-05-22 | Ｊｆｅスチール株式会社 | Surface treatment solution for zinc-based plated steel sheet, method for producing zinc-based plated steel sheet with surface treatment film, and zinc-based plated steel sheet with surface treatment film |
| AU2017342475B2 (en) * | 2016-10-11 | 2019-10-24 | Jfe Steel Corporation | Surface-treatment solution for zinc or zinc alloy coated steel sheet, method of producing zinc or zinc alloy coated steel sheet with surface-coating layer, and zinc or zinc alloy coated steel sheet with surface-coating layer |
| KR101879093B1 (en) | 2016-12-22 | 2018-07-16 | 주식회사 포스코 | Alloy plated steel having excellent corrosion resistance and surface quality, and method for manufacturing the same |
| JP6753369B2 (en) * | 2017-06-29 | 2020-09-09 | Ｊｆｅスチール株式会社 | Fused Zn-based galvanized steel sheet and its manufacturing method |
| KR20220054384A (en) * | 2019-08-30 | 2022-05-02 | 리엑스유니버시테이트 그로닝겐 | Method for Characterizing Forming Properties of Zinc Alloy Coatings on Metal Substrates |
| CN111155044B (en) * | 2019-12-13 | 2021-09-21 | 首钢集团有限公司 | Method for improving surface quality of zinc-aluminum-magnesium coated steel and zinc-aluminum-magnesium coating |
| CN111733410B (en) * | 2020-07-07 | 2022-08-02 | 奎克化学（中国）有限公司 | Chromium-free passivation solution for zinc-aluminum-magnesium steel plate and preparation method thereof |
| CN114472860A (en) * | 2021-12-30 | 2022-05-13 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Gradient cooling method for improving quality of zinc-aluminum-magnesium alloy |
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| JP2001262303A (en) * | 2000-03-21 | 2001-09-26 | Kawasaki Steel Corp | Method for producing alloyed galvanized steel sheet and galvannealed steel sheet excellent in hot dip metal coated property |
| JP2002371345A (en) * | 2001-06-13 | 2002-12-26 | Sumitomo Metal Ind Ltd | METHOD FOR MANUFACTURING HOT-DIP Zn-Al-Mg ALLOY PLATED STEEL SHEET |
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