CN116490626A - 汽车构造构件用镀敷钢板 - Google Patents
汽车构造构件用镀敷钢板 Download PDFInfo
- Publication number
- CN116490626A CN116490626A CN202180080366.2A CN202180080366A CN116490626A CN 116490626 A CN116490626 A CN 116490626A CN 202180080366 A CN202180080366 A CN 202180080366A CN 116490626 A CN116490626 A CN 116490626A
- Authority
- CN
- China
- Prior art keywords
- steel sheet
- plating layer
- plated steel
- plating
- percent
- 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.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 104
- 239000010959 steel Substances 0.000 title claims abstract description 104
- 238000007747 plating Methods 0.000 claims abstract description 112
- 239000000126 substance Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910017947 MgOx Inorganic materials 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims description 11
- 229910017107 AlOx Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 94
- 239000011777 magnesium Substances 0.000 description 52
- 238000005260 corrosion Methods 0.000 description 27
- 230000007797 corrosion Effects 0.000 description 27
- 238000001816 cooling Methods 0.000 description 23
- 239000011701 zinc Substances 0.000 description 22
- 239000012298 atmosphere Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000000137 annealing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052746 lanthanum Inorganic materials 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 239000008397 galvanized steel Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910018134 Al-Mg Inorganic materials 0.000 description 5
- 229910018467 Al—Mg Inorganic materials 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910018137 Al-Zn Inorganic materials 0.000 description 4
- 229910018573 Al—Zn Inorganic materials 0.000 description 4
- 229910017706 MgZn Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000005244 galvannealing Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—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
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
-
- 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
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
- C23C2/29—Cooling or quenching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C2/50—Controlling or regulating the coating processes
-
- 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
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Coating With Molten Metal (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
该汽车构造构件用镀敷钢板具有:钢板;镀敷层,其形成于所述钢板的表面的至少一部分;以及氧化物层,其形成于所述镀敷层的表面的至少一部分,所述镀敷层具有规定的化学组成,通过XPS在所述氧化物层的距表面在厚度方向上5.0nm的位置进行测定时,作为Mg的最大检测强度相对于Mg的氧化物或氢氧化物的最大检测强度之比的IMg/IMgOx为0.00以上且1.20以下。
Description
技术领域
本发明涉及汽车构造构件用镀敷钢板。
本申请基于2021年01月14日于日本申请的特愿2021-004012号来主张优先权,并将其内容援引于此。
背景技术
近年来,从防锈的观点出发在汽车构造构件中使用镀敷钢板,主要在日本国内市场中应用合金化热浸镀锌钢板等热浸镀锌钢板。合金化热浸镀锌钢板是通过对钢板实施热浸镀锌后进行合金化热处理,使Fe从钢板(基底钢板)扩散到镀敷层内,从而提高焊接性、涂装后耐腐蚀性的镀敷钢板。但是,对热浸镀锌钢板要求涂装后耐腐蚀性、耐红锈性等进一步的耐腐蚀性的提高。
作为提高热浸镀锌钢板的耐腐蚀性的方法,可举出向包含Zn的镀敷层添加Al等。例如,在建材领域中,作为高耐腐蚀性镀敷钢板,热浸镀Al-Zn系镀敷钢板被广泛实用化。这样的热浸镀Al-Zn系镀敷的镀敷层由以下的组织形成:从熔融状态最初结晶出的树枝状的α-(Zn,Al)相(Al初晶部:在Al-Zn系二元状态图等中,作为初晶而结晶出的α-(Zn,Al)相。不一定是富Al的相,而是作为Zn和Al的固溶体结晶。);以及形成于树枝状的Al初结晶部的间隙的由Zn相和Al相构成的组织(Zn/Al混相组织)。Al初晶部钝化,且Zn/Al混相组织与Al初晶部相比Zn浓度高,因此腐蚀集中于Zn/Al混相组织。结果,由于腐蚀在Zn/Al混相组织中呈虫蛀状进行,腐蚀进行路径变得复杂,因此腐蚀难以容易地到达基底钢板。由此,热浸镀Al-Zn系镀敷钢板与镀敷层的厚度相同的热浸镀锌钢板相比具有优异的耐腐蚀性。另外,以提高耐腐蚀性为目的,还在研究制成向Al-Zn系镀敷进一步添加Mg等元素的Zn-Al-Mg系镀敷钢板。
另一方面,对应用于汽车构造构件的镀敷钢板要求加工性。特别是,冲压成型在无涂装的状态下进行,因此重视模具与镀敷钢板之间的润滑性。因此,对应用于进行冲压成型的汽车构造构件的钢板要求优异的润滑性。
针对这样的技术问题,专利文献1中公开了一种加工性优异的润滑镀敷钢板,其特征在于,在钢板的表面形成含有Al:4~22质量%、Mg:1~5质量%、Ti:0.1质量%以下、Si:0.5质量%以下,剩余部分由Zn及不可避免的杂质构成的Zn合金镀敷层,在该镀敷层上形成由铬酸盐被膜或磷酸盐被膜、或含有水性树脂的树脂系被膜形成的基底处理层,进而在该基底处理层上以0.2~5g/m2的附着量形成被膜,该被膜通过涂布相对于水性树脂(a)的固体成分100%质量含有二氧化硅颗粒(b)5~50质量%、固体润滑剂(c)1~40质量%的水性润滑涂料并使其干燥而得到。
另外,在专利文献2中,公开了一种成型性优异的热浸镀锌钢板,具有含有Al:0.05~10质量%、根据需要含有Mg:0.01~5质量%,剩余部分由Zn及不可避免的杂质构成的镀锌层的热浸镀锌钢板,其特征在于,在该镀敷钢板表面的中心线平均粗糙度Ra为0.5~1.5μm,PPI(每1英寸(2.54cm)所含的1.27μm以上大小的峰的数量)为150~300,Pc(每1cm所含的0.5μm以上的大小的峰的数量)为Pc≥PPI/2.54+10。在专利文献2中示出了通过使Pc≥PPI/2.54+10,滑动性提高。
在先技术文献
专利文献
专利文献1:日本国特开2004-338397号公报
专利文献2:日本国特开2003-13192号公报
发明内容
发明要解决的技术问题
但是,在专利文献1中,作为镀敷工序后的后处理,需要进行水性润滑涂料的涂布、干燥,存在制造成本大这一技术问题。另外,在专利文献2中,存在仅通过粗糙度的改善无法得到充分的滑动性这一问题。
本发明鉴于以上技术问题而完成。本发明的目的在于提供一种润滑性优异的汽车构造构件用镀敷钢板,其是耐腐蚀性优异的Zn-Al-Mg系镀敷钢板(具备包含Zn、Al、Mg的镀敷的钢板)。
用于解决技术问题的技术手段
本发明人等对在Zn-Al-Mg系镀敷钢板中提高润滑性的方法进行了研究。结果发现,通过提高镀敷层中包含的Mg作为氧化物[MgO]或氢氧化物[Mg(OH)2]存在的比例,镀敷层的润滑性提高。
另外,除此之外发现,通过使镀敷层中包含的Al作为氧化物[Al2O3]或氢氧化物[Al(OH)3]存在的比例降低,还能够提高化学转化处理性。
本发明基于上述见解而完成。本发明的主旨如下所述。
[1]本发明的一个方案的汽车构造构件用镀敷钢板具有:钢板;镀敷层,其形成于所述钢板的表面的至少一部分;以及氧化物层,其形成于所述镀敷层的表面的至少一部分,所述镀敷层具有如下化学组成,以质量%计,含有:Al:0.5~35.0%、Mg:0.5~15.0%、Si:0~2.0%、Ca:0~2.0%、Fe:0~2.0%、La+Ce:合计为0~0.5%、Sb:0~0.5%、Pb:0~0.5%、Sr:0~0.5%、Sn:0~1.0%、Cu:0~1.0%、Ti:0~1.0%、Ni:0~1.0%、Mn:0~1.0%、Cr:0~1.0%、Nb:0~1.0%、Zr:0~1.0%、Mo:0~1.0%、Li:0~1.0%、Ag:0~1.0%、B:0~0.5%、Y:0~0.5%、以及P:0~0.5%,剩余部分由Zn及杂质构成,通过XPS在所述氧化物层的距表面在厚度方向上5.0nm的位置进行测定时,作为Mg的最大检测强度相对于Mg的氧化物或氢氧化物的最大检测强度之比的IMg/IMgOx为0.00以上且1.20以下。
[2]如上述[1]所记载的汽车构造构件用镀敷钢板,所述镀敷层的所述化学组成也可以以质量%计,含有Al:6.0~30.0%、Mg:3.0~11.0%。
[3]如上述[1]或[2]所记载的汽车构造构件用镀敷钢板,通过XPS在所述氧化物层的距所述表面在厚度方向上5.0nm的位置进行测定时,作为Al的最大检测强度相对于Al的氧化物或氢氧化物的最大检测强度之比的IAl/IAlOx也可以为0.77以上。
[4]如上述[1]至[3]的任意一项所记载的汽车构造构件用镀敷钢板,所述IMg/IMgOx也可以为0.00以上且0.80以下。
发明效果
根据本发明的上述方案,能够提供一种润滑性优异的汽车构造构件用镀敷钢板,其是具有包含Zn、Al、Mg的镀敷的钢板(Zn-Al-Mg系镀敷钢板)。另外,根据本发明的优选的方案,能够提供一种除润滑性之外,化学转化处理性也优异的汽车构造构件用镀敷钢板。
具体实施方式
本发明的一个方案的汽车构造构件用镀敷钢板(本实施方式的镀敷钢板)具有:钢板;镀敷层,其形成于钢板的表面的至少一部分;以及氧化物层,其形成于镀敷层的表面的至少一部分。另外,在本实施方式的镀敷钢板中,镀敷层的化学组成以质量%计,含有:Al:0.5~35.0%(优选为6.0~30.0%)、Mg:0.5~15.0%(优选为3.0~11.0%)、Si:0~2.0%、Ca:0~2.0%、Fe:0~2.0%、La+Ce:合计为0~0.5%、Sb:0~0.5%、Pb:0~0.5%、Sr:0~0.5%、Sn:0~1.0%、Cu:0~1.0%、Ti:0~1.0%、Ni:0~1.0%、Mn:0~1.0%、Cr:0~1.0%、Nb:0~1.0%、Zr:0~1.0%、Mo:0~1.0%、Li:0~1.0%、Ag:0~1.0%、B:0~0.5%、Y:0~0.5%、以及P:0~0.5%,剩余部分由Zn及杂质构成。
另外,在本实施方式的镀敷钢板中,通过XPS在所述氧化物层的表层部(例如,在厚度方向上距表面5.0nm的位置)进行测定时,作为Mg的最大检测强度相对于Mg的氧化物或氢氧化物的最大检测强度之比的IMg/IMgOx为0.00以上且1.20以下(优选为0.00以上且0.80以下)。
另外,本实施方式的镀敷钢板优选为,通过XPS在所述氧化物层的距所述表面在厚度方向上5.0nm的位置进行测定时,作为Al的最大检测强度(IAl)相对于Al的氧化物或氢氧化物的最大检测强度(IAlOx)之比的IAl/IAlOx为0.77以上。
<钢板>
本实施方式的镀敷钢板的镀敷层和氧化物层是重要的。因此,钢板(母材钢板)的种类没有特别限定,根据所应用的产品或所要求的强度、板厚等决定即可。例如,能够使用JIS G3193:2008中记载的热轧钢板、JIS G3141:2017中记载的冷轧钢板。
<镀敷层>
本实施方式的镀敷钢板在钢板的表面的至少一部分具备镀敷层。镀敷层可以形成于钢板的单面,也可以形成于两面。
镀敷层的附着量优选为每一面15~250g/m2。
[化学组成]
对本实施方式的镀敷钢板的镀敷层的化学组成进行说明。以下,与化学组成相关的%均为质量%。
Al:0.5~35.0%
Al是在包含铝(Al)、锌(Zn)、镁(Mg)的镀敷层中为了确保涂装后耐腐蚀性而有效的元素。为了充分得到上述效果,使Al含量为0.5%以上。Al含量优选为1.0%以上,更优选为6.0%以上。
另一方面,若Al含量超过35.0%,则涂装后耐腐蚀性、镀敷层的切断端面的耐腐蚀性降低。另外,Al氧化物的生成变多,氧化物层的MgO、Mg(OH)2的生成被阻碍。因此,Al含量为35.0%以下。Al含量优选为30.0%以下。
Mg:0.5~15.0%
Mg是具有提高镀敷层的耐腐蚀性的效果的元素。为了充分得到上述效果,使Mg含量为0.5%以上。Mg含量优选为1.0%以上,更优选为3.0%以上。
另一方面,若Mg含量超过15.0%,则涂装后耐腐蚀性降低,并且镀敷层的加工性降低。另外,由于Mg化合物不是在镀敷层中的表面附近而是在内侧形成,因此表面附近的MgO和Mg(OH)2(氧化物和氢氧化物)的生成被阻碍。另外,发生镀敷浴的浮渣产生量增大等制造方面的问题。因此,使Mg含量为15.0%以下。Mg含量优选为11.0%以下。
Si:0~2.0%
Si是与Mg一起形成化合物,有助于镀敷层的涂装后耐腐蚀性的提高的元素。另外,Si也是具有在钢板上形成镀敷层时抑制在钢板与镀敷层之间形成的合金层形成得过厚,提高钢板与镀敷层的密合性的效果的元素。因此也可以含有。Si不一定需要含有,下限为0%,但在得到上述效果的情况下,优选使Si含量为0.1%以上。
另一方面,若Si含量超过2.0%,则由于镀敷层中过剩的Si晶析或无法充分地形成层状组织等,导致涂装后耐腐蚀性降低。另外,镀敷层的加工性降低。因此,使Si含量为2.0%以下。Si含量更优选为1.5%以下。
Ca:0~2.0%
若镀敷层中含有Ca,则随着Mg含量的增加而在镀敷操作时容易形成的浮渣的形成量会减少,镀敷制造性提高。因此,也可以含有Ca。不一定需要含有Ca,下限为0%,但在得到上述效果的情况下,优选使Ca含量为0.1%以上。
另一方面,若Ca含量过剩则涂装后耐腐蚀性降低。另外,具有镀敷层的平面部的涂装后耐腐蚀性本身劣化的倾向,有时焊接部周围的耐腐蚀性也会劣化。因此,Ca含量为2.0%以下。Ca含量优选为1.0%以下。
Fe:0~2.0%
Fe在制造镀敷层时,从作为镀敷基材的钢板等作为杂质混入到镀敷层中。有时含有至2.0%左右,但是,如果在该范围内则对本实施方式的镀敷钢板的特性的不良影响小。因此,优选使Fe含量为2.0%以下。Fe含量更优选为1.5%以下,进一步优选为1.0%以下。
另一方面,如上所述,Fe作为杂质混入到镀敷层中。为了完全防止Fe的混入,要花费显著的成本,因此也可以使Fe含量为0.1%以上。
本实施方式的镀敷钢板的镀敷层的化学组成以具有上述化学组成,剩余部分为Zn及杂质为基本。
但是,本实施方式的镀敷钢板的镀敷层也可以进一步代替Zn的一部分,例如在以下范围内含有La、Ce、Sb、Pb、Cu、Sn、Ti、Sr、Ni、Mn、Cr、Nb、Zr、Mo、Li、Ag、B、Y、P(无论是有意地添加或作为杂质而含有)。由于这些元素也可以不一定含有,因此含量的下限为0%。
杂质的含量优选合计为5.0%以下,更优选为3.0%以下。
La+Ce:合计为0~0.5%
La及Ce是有助于镀敷层的耐腐蚀性提高的元素。因此,也可以含有La、Ce的1种或2种。不需要含有La及/或Ce,下限为0%,但在得到上述效果的情况下,La和Ce的合计含量优选为0.01%以上。
另一方面,若La和Ce的合计含量超过0.5%,则镀敷浴的粘性上升,镀敷浴的建浴本身大多变得困难,不能制造镀敷性状良好的镀敷钢板。因此,使La和Ce的合计含量为0.5%以下。
Sb:0~0.5%
Sr:0~0.5%
Pb:0~0.5%
若镀敷层中含有Sr、Sb、Pb,则镀敷层的外观变化,形成锌花,确认金属光泽的提高。因此,也可以含有。但是,若这些元素的含量超过0.5%,则形成各种金属间化合物相,加工性和耐腐蚀性恶化。另外,若这些元素的含量过剩,则镀敷浴的粘性上升,镀敷浴的建浴本身大多变得困难,不能制造镀敷性状良好的镀敷钢板。因此,使Sr含量为0.5%以下,使Sb含量为0.5%以下,使Pb含量为0.5%以下。
Sn:0~1.0%
Sn是在包含Zn、Al、Mg的镀敷层中,使Mg溶出速度上升的元素。若Mg的溶出速度上升,则平面部耐腐蚀性恶化。因此,使Sn含量为1.0%以下。
Cu:0~1.0%
Ti:0~1.0%
Ni:0~1.0%
Mn:0~1.0%
Cr:0~1.0%
Nb:0~1.0%
Zr:0~1.0%
Mo:0~1.0%
Li:0~1.0%
Ag:0~1.0%
B:0~0.5%
Y:0~0.5%
P:0~0.5%
这些元素是有助于耐腐蚀性的提高的元素。因此,也可以含有。另一方面,若这些元素的含量过剩,则镀敷浴的粘性上升,镀敷浴的建浴本身大多变得困难,不能制造镀敷性状良好的镀敷钢板。因此,使各元素的含量分别为1.0%以下。
镀敷层的化学组成通过以下方法测定。
首先,得到用含有抑制钢基(钢板)的腐蚀的抑制剂的酸将镀敷层剥离溶解而得到的酸液。接着,通过用ICP分析来测定得到的酸液,能够得到镀敷层的化学组成(在镀敷层与钢板之间形成有合金层的情况下,为镀敷层与合金层的合计的化学组成,但由于合金层薄因此影响小)。酸种只要是能够溶解镀敷层的酸,则没有特别限制。化学组成作为平均化学组成而测定。
[组织]
在本实施方式的镀敷钢板中,镀敷组织没有特别限定。根据本实施方式的镀敷钢板的镀敷层的化学组成,镀敷组织例如包含:(Al-Zn)枝晶、(Al-Zn)相/MgZn2相的层状组织、Zn相/MgZn2相的层状组织、Zn/Al/MgZn2的三元共晶组织、MgZn2相、枝晶或不定形的Zn相、Mg2Si相、及/或其他金属间化合物相。
<氧化物层>
本实施方式的镀敷钢板在镀敷层的表面的至少一部分具备氧化物层。氧化物层可以形成于单面,也可以形成于两面。
本发明人等对在Zn-Al-Mg系镀敷钢板中提高润滑性的方法进行了研究。结果发现,通过提高镀敷层中包含的Mg作为氧化物或氢氧化物存在的比例,从而镀敷层的润滑性提高。具体而言,发现通过XPS(X射线光电子分光法)在氧化物层的距表面在厚度方向上5.0nm的位置进行测定时,在作为Mg(金属状态)的最大检测强度(IMg)相对于Mg的氧化物或氢氧化物的最大检测强度(IMgOx)之比的IMg/IMgOx为0.00以上且1.20以下的情况下,润滑性提高。
其理由尚不明确,认为在与模具等接触的氧化物层的表层部中,通过IMg/IMgOx变低、即MgO(Mg的氧化物)或Mg(OH)2(Mg的氢氧化物)的存在比例变高,从而MgO或Mg(OH)2作为润滑材料而发挥功能,润滑性提高。在润滑性方面,无论是MgO、Mg(OH)2的任意一者均可得到效果,但在本实施方式的镀敷钢板中,认为主要是MgO。
以往,如果是表面(或,距表面大幅地薄于5nm的范围),则有时较多地形成MgO或Mg(OH)2。但是,本发明人等研究的结果,发现在距表面在厚度方向上5nm的位置(如以下说明那样,将镀敷层的表面沿深度方向削去5.0nm的位置),MgO(Mg的氧化物)或Mg(OH)2(Mg的氢氧化物)的存在比例变高是重要的。
另一方面,在氧化物层中,若Al2O3(Al氧化物)或Al(OH)3(Al氢氧化物)过剩地形成,则有时化学转化处理性降低。为了确保优异的化学转化处理性,通过XPS在距表面在厚度方向上5.0nm的位置进行测定时,作为Al(金属状态)的最大检测强度(IAl)相对于Al的氧化物或氢氧化物的最大检测强度(IAlOx)之比的IAl/IAlOx优选为0.77以上。不需要限定上限,但认为超过2.00的情况较少。
氧化物层的距表面在厚度方向上5.0nm的位置的IMg/IMgOx、IAl/IAlOx使用XPS进行测定。
具体而言,通过氩溅射等将镀敷层的表面沿深度方向削去5.0nm(只要在4.0~6.0nm的范围则允许),在该位置(深度5.0nm(深度4.0~6.0nm的范围即可)的位置)进行XPS测定。在XPS测定时,例如使用ULVAC-PHI公司制Quantera SXM型XPS分析装置或与此等同的装置,并采用以下条件。
X射线源:mono-Al Kα(1486.6eV)
真空度:9×10-10torr
离子种:Ar+
加速电压:4kV
速率:22.7nm/min(SiO2时)
进行XPS测定的结果,将能量范围为304~309eV的峰视为由Mg氧化物或Mg氢氧化物得到的峰,将300~303eV的峰视为由金属Mg得到的峰,测定各峰的最大检测强度,计算IMg/IMgOx。
关于IAl/IAlOx,将能量范围为73.5~76.5eV的峰视为由Al氧化物或Al氢氧化物得到的峰,将72.0~73.4eV的峰视为由金属Al得到的峰,根据各峰的最大强度计算IAl/IAlOx。
氧化物层的厚度没有特别限定,例如为超过5.0nm且50.0nm以下。
氧化物层的厚度通过以下方法测定。从镀敷钢板的表面以1~3nm间距向深度方向进行XPS测定,将到氧的最大强度成为最表面的最大强度的1/20为止的深度定义为氧化物层的厚度。
<制造方法>
对本实施方式的镀敷钢板的优选的制造方法进行说明。本实施方式的镀敷钢板不取决于制造方法,只要具有上述特征,则可得到其效果。但是,通过以下方法能够稳定地制造,因此优选。
具体而言,本实施方式的钢板能够通过包含以下工序(I)~(III)的制造方法来制造。
(I)对钢板进行还原退火的退火工序
(II)将钢板浸渍于包含Al、Mg、Zn的镀敷浴,制成镀敷原板的镀敷工序
(III)控制冷却工序:对于所述镀敷原板,在浴温~380℃的温度范围中,在露点为-10℃以上的惰性气体气氛中以10.0℃/秒以下的平均冷却速度进行冷却,在380~100℃的温度范围中,在露点为-20℃以下的气氛中以15℃/秒以上的平均冷却速度进行冷却。
以下,对各工序的优选的条件进行说明。
[退火工序]
在退火工序中,在镀敷工序之前,对通过公知的方法得到的钢板(热轧钢板或冷轧钢板)进行还原退火。退火条件可以是公知的条件,例如在露点为-10℃以上的5%H2-N2气体气氛下加热至750~900℃,保持30~240秒。
[镀敷工序]
在镀敷工序中,将钢板浸渍于镀敷浴而制成镀敷原板。镀敷浴优选包含Al:0.5~35.0%、Mg:0.5~15.0%、Si:0~2.0%、Ca:0~2.0%,剩余部分由Zn及杂质构成。镀敷浴进而也可以根据需要而包含La、Ce、Fe、Sb、Pb、Cu、Sn、Ti、Sr、Ni、Mn、Cr、Nb、Li、Ag。由于能够根据镀敷浴的组成推测所形成的镀敷层的组成,因此根据希望得到的镀敷层的化学组成来调整镀敷浴的组成即可。
[控制冷却工序]
在控制冷却工序中,将镀敷工序后的(从镀敷浴中提起的)镀敷原板用N2等擦拭气体调整镀敷附着量后,进行冷却。在冷却时,将从镀敷浴中提起的钢板(成为与镀敷浴温度同等的温度的)冷却至100℃。此时,将浴温~380℃的平均冷却速度设为10.0℃/秒以下,另外将浴温至380℃的冷却中的气氛设为惰性气体气氛,将其露点设为-10℃以上(第一冷却)。另外,将380~100℃的平均冷却速度设为15℃以上,将气氛的露点设为-20℃以下(第二冷却)。
若至380℃为止的平均冷却速度超过10.0℃/秒,则氧化变得不充分,在氧化物层中IMg/IMgOx变大。
另外,若气氛的露点小于-10℃,则Al的氧化物比MgO或Mg(OH)2更优先形成,在氧化物层中IMg/IMgOx变大。即使Al的氧化物形成,对提高润滑性也没有帮助。另外,在提高Al的最大检测强度相对于Al的氧化物或氢氧化物的最大检测强度之比,提高化学转化处理性的情况下,优选将气氛露点设为0℃以上。
关于气氛,机理未必明确,但在大气中,即使露点为-10℃以上,也无法得到规定的氧化物层。因此,将气氛设为惰性气体气氛。例如为N2气氛、Ar气氛、He气氛。但是,由于惰性气体单独露点低(不到-20℃以上),因此通过导入H2O来控制露点。
若380~100℃的平均冷却速度小于15℃,则氧化过剩地进行,ZnO等氧化物生长,在氧化物层中IMg/IMgOx变小。
另外,若该温度范围内的冷却时的气氛的露点超过-20℃,则氧化过剩地进行,ZnO等氧化物生长,在氧化物层中IMg/IMgOx变小。
第二冷却的冷却开始温度优选为380℃(优选在第一冷却完成后立即切换冷却速度),但如果至100℃为止的平均冷却速度为小于15℃/秒,则第2冷却的开始温度也可以为380~330℃的范围。
根据上述制造方法,可得到本实施方式的镀敷钢板。
实施例
以下,通过实施例更具体地说明本发明,但本发明并不限定于这些实施例。
作为供于退火、镀敷的钢板,准备板厚1.6mm的冷轧钢板(0.2%C-2.0%Si-2.3%Mn)。
将该钢板切断成100mm×200mm(×板厚)的大小后,使用间歇式的热浸镀敷试验装置持续进行退火及热浸镀敷。
在退火时,在氧浓度20ppm以下的炉内,在含有H2气体5%、剩余部分由N2构成的气体构成,露点为0℃的气氛下,在860℃下进行120秒退火。
退火后,用N2气体对钢板进行空冷,在钢板温度达到浴温+20℃时,将其浸渍于表1A所示的浴温的镀敷浴中约3秒。
对形成有镀敷层的镀敷原板,以浴温~380℃及380~100℃的平均冷却速度和气氛(气氛气体、露点)为表1B所示的条件的方式冷却至室温。钢板的温度在镀敷原板中心部使用点焊的热电偶进行测定。
所形成的镀敷层的组成如表1所示。
对得到的镀敷钢板,使用XPS并通过上述方法,测定氧化物层的厚度、氧化物层的距表面5nm的位置的IMg/IMgOx及IAl/IAlOx。
将结果示于表2。
[表1A]
[表1B]
[表2]
[润滑性]
另外,对于得到的镀敷钢板,按以下要领进行球盘试验,评价润滑性。在本试验中,将载荷P设为30N,将5mmφ的SUS球按压于样品,保持负荷有载荷P的状态使样品以旋转半径10mm、旋转速度1rpm旋转,测定朝向与SUS球成直角的方向的载荷F,将滑动距离为200mm时的F除以P,由此求出动摩擦系数。根据动摩擦系数,如以下那样进行评价,若为AA或A则判断为润滑性优异。
AA:动摩擦系数0.2以下
A:动摩擦系数超过0.2~0.4
B:动摩擦系数超过0.4
[化学转化处理性]
另外,对于得到的镀敷钢板,按以下要领对化学转化处理性进行评价。
从得到的镀敷钢板采集50×100mm(×板厚)的样品,按照(SD5350系统:日本Paint-Industries公司制标准)对该样品实施磷酸锌处理,形成化学转化处理被膜。通过对形成有化学转化处理被膜的镀敷钢板的表面进行SEM观察,从而测定了化学转化处理被膜的未覆盖的比例(面积%)。此时,在SEM观察视野中,将钢板露出的区域的面积率定义为未覆盖的比例。根据未覆盖的比例,如以下那样对化学转化处理性进行评价。
AA:无未覆盖
A:未覆盖5%以下
由表1A、表1B、表2可知,在作为发明例的No.2~8、10~13、19~22、24、26~30中,得到优异的润滑性。另外,在这些之内,Al/AlOx较大的No.3~8、10~13、19~22、24、26、28、29中,化学转化处理性也优异。
与此相对,在作为比较例的No.1、9、14~18、23、25、31、32中,镀敷层的化学组成或浴温~380℃、380~100℃的冷却条件中的至少一者偏离优选的范围,因此氧化物层的IMg/IMgOx变大,润滑性降低。
工业可利用性
根据本发明,能够提供一种润滑性优异的镀敷钢板,其是Zn-Al-Mg系镀敷钢板。由于该钢板的冲压成形性提高,因此能够适合应用于汽车构造构件。
Claims (4)
1.一种汽车构造构件用镀敷钢板,具有:
钢板;
镀敷层,其形成于所述钢板的表面的至少一部分;以及
氧化物层,其形成于所述镀敷层的表面的至少一部分;所述镀敷层具有如下化学组成,以质量%计,含有:
Al:0.5~35.0%、
Mg:0.5~15.0%、
Si:0~2.0%、
Ca:0~2.0%、
Fe:0~2.0%、
La+Ce:合计为0~0.5%、
Sb:0~0.5%、
Pb:0~0.5%、
Sr:0~0.5%、
Sn:0~1.0%、
Cu:0~1.0%、
Ti:0~1.0%、
Ni:0~1.0%、
Mn:0~1.0%、
Cr:0~1.0%、
Nb:0~1.0%、
Zr:0~1.0%、
Mo:0~1.0%、
Li:0~1.0%、
Ag:0~1.0%、
B:0~0.5%、
Y:0~0.5%、以及
P:0~0.5%,
剩余部分由Zn及杂质构成;
通过XPS在所述氧化物层的距表面在厚度方向上5.0nm的位置进行测定时,作为Mg的最大检测强度相对于Mg的氧化物或氢氧化物的最大检测强度之比的IMg/IMgOx为0.00以上且1.20以下。
2.如权利要求1所述的汽车构造构件用镀敷钢板,
所述镀敷层的所述化学组成,以质量%计,含有:
Al:6.0~30.0%、
Mg:3.0~11.0%。
3.如权利要求1或2所述的汽车构造构件用镀敷钢板,
通过XPS在所述氧化物层的距所述表面在厚度方向上5.0nm的位置进行测定时,作为Al的最大检测强度相对于Al的氧化物或氢氧化物的最大检测强度之比的IAl/IAlOx为0.77以上。
4.如权利要求1至3的任意一项所述的汽车构造构件用镀敷钢板,
所述IMg/IMgOx为0.00以上且0.80以下。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021-004012 | 2021-01-14 | ||
JP2021004012 | 2021-01-14 | ||
PCT/JP2021/048191 WO2022153840A1 (ja) | 2021-01-14 | 2021-12-24 | 自動車構造部材用めっき鋼板 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116490626A true CN116490626A (zh) | 2023-07-25 |
Family
ID=82448453
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202180080366.2A Pending CN116490626A (zh) | 2021-01-14 | 2021-12-24 | 汽车构造构件用镀敷钢板 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230383392A1 (zh) |
EP (1) | EP4230756A4 (zh) |
JP (1) | JPWO2022153840A1 (zh) |
KR (1) | KR20230095102A (zh) |
CN (1) | CN116490626A (zh) |
MX (1) | MX2023006041A (zh) |
WO (1) | WO2022153840A1 (zh) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3600804B2 (ja) | 2001-06-27 | 2004-12-15 | 新日本製鐵株式会社 | 成形性に優れた溶融亜鉛めっき鋼板 |
JP4157491B2 (ja) | 2003-04-25 | 2008-10-01 | 新日本製鐵株式会社 | 加工性に優れた非脱膜型潤滑めっき鋼板 |
JP5253090B2 (ja) * | 2008-10-28 | 2013-07-31 | 日新製鋼株式会社 | Mg、Al含有溶融Znめっき鋼板の製造方法 |
JP5748829B2 (ja) * | 2013-12-03 | 2015-07-15 | 日新製鋼株式会社 | 溶融Zn合金めっき鋼板およびその製造方法 |
BR112017019317A2 (pt) * | 2015-03-31 | 2018-05-08 | Nippon Steel & Sumitomo Metal Corporation | chapa de aço galvanizada |
JP2021004012A (ja) | 2019-06-27 | 2021-01-14 | 株式会社シマノ | 自転車用ドライビングシステム、および、自転車用フロントスプロケット組立体 |
CN114286869B (zh) * | 2019-08-29 | 2022-07-08 | 日本制铁株式会社 | 热冲压成形体 |
-
2021
- 2021-12-24 KR KR1020237017807A patent/KR20230095102A/ko unknown
- 2021-12-24 EP EP21919726.6A patent/EP4230756A4/en active Pending
- 2021-12-24 JP JP2022575510A patent/JPWO2022153840A1/ja active Pending
- 2021-12-24 WO PCT/JP2021/048191 patent/WO2022153840A1/ja active Application Filing
- 2021-12-24 CN CN202180080366.2A patent/CN116490626A/zh active Pending
- 2021-12-24 MX MX2023006041A patent/MX2023006041A/es unknown
- 2021-12-24 US US18/250,774 patent/US20230383392A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20230383392A1 (en) | 2023-11-30 |
EP4230756A1 (en) | 2023-08-23 |
EP4230756A4 (en) | 2024-04-24 |
KR20230095102A (ko) | 2023-06-28 |
MX2023006041A (es) | 2023-06-02 |
JPWO2022153840A1 (zh) | 2022-07-21 |
WO2022153840A1 (ja) | 2022-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3779941B2 (ja) | 塗装後耐食性と塗装鮮映性に優れた亜鉛めっき鋼板 | |
JP5482914B2 (ja) | 外観均一性に優れた高耐食性溶融亜鉛めっき鋼板およびその製造方法 | |
JP5830541B2 (ja) | めっき性、めっき密着性及びスポット溶接性に優れた溶融亜鉛めっき鋼板及びその製造方法 | |
EP3502299B1 (en) | Hot-rolled galvanizing steel sheet having excellent galling resistance, formability and sealer-adhesion property and method for manufacturing same | |
JP6350780B1 (ja) | 塗装後耐食性に優れた溶融Zn系めっき鋼板 | |
JPWO2020213686A1 (ja) | めっき鋼板 | |
WO2011052269A1 (ja) | 合金化溶融亜鉛めっき鋼板とその製造方法 | |
JP2013515863A (ja) | 表面特性に優れた熱間プレス用亜鉛めっき鋼板並びにこれを利用した熱間プレス成形部品及びその製造方法 | |
WO2014155944A1 (ja) | 溶融Al-Zn系めっき鋼板及びその製造方法 | |
JPS5891162A (ja) | 溶融亜鉛めつき鋼板の製造方法 | |
JP7401827B2 (ja) | 溶融Zn系めっき鋼板 | |
KR102649501B1 (ko) | 핫 스탬프 성형체 | |
WO2021039973A1 (ja) | ホットスタンプ成形体 | |
JP7453583B2 (ja) | Alめっきホットスタンプ鋼材 | |
CN116490626A (zh) | 汽车构造构件用镀敷钢板 | |
JP4452126B2 (ja) | 合金化溶融亜鉛めっき用鋼板 | |
WO1998030729A1 (fr) | Tole d'acier galvanise a chaud presentant peu de defauts par suite d'un placage defectueux, ainsi que d'excellentes caracteristiques d'adherence de depot par contact, et son procede de production | |
JPH06256925A (ja) | プレス成形性に優れた亜鉛−鉄合金化溶融亜鉛めっき鋼板 | |
JPH08170160A (ja) | Si含有高張力(合金化)溶融亜鉛めっき鋼板の製造方法 | |
JPH10140316A (ja) | 加工性に優れた溶融亜鉛めっき鋼板の製造方法 | |
WO2023238934A1 (ja) | Zn-Al-Mg系溶融めっき鋼板 | |
WO2022085287A1 (ja) | めっき鋼板 | |
TWI504754B (zh) | 含準晶體之鍍敷鋼板 | |
TWI512140B (zh) | 含準晶體之鍍敷鋼板 | |
CN117836461A (zh) | 热冲压成形体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |