CN109112454A - 耐高温锌基镀层钢板及其制造方法、热成型方法和部件 - Google Patents
耐高温锌基镀层钢板及其制造方法、热成型方法和部件 Download PDFInfo
- Publication number
- CN109112454A CN109112454A CN201710493875.3A CN201710493875A CN109112454A CN 109112454 A CN109112454 A CN 109112454A CN 201710493875 A CN201710493875 A CN 201710493875A CN 109112454 A CN109112454 A CN 109112454A
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- CN
- China
- Prior art keywords
- steel plate
- hot
- coating
- zinc
- high temperature
- 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.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 56
- 239000010959 steel Substances 0.000 title claims abstract description 56
- 239000011701 zinc Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims description 49
- 238000000576 coating method Methods 0.000 claims description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 238000004017 vitrification Methods 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000003856 thermoforming Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 3
- 239000011224 oxide ceramic Substances 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910001021 Ferroalloy Inorganic materials 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 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 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- -1 zinc-aluminium magnesium Chemical compound 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IRPDISVJRAYFBI-UHFFFAOYSA-N nitric acid;potassium Chemical compound [K].O[N+]([O-])=O IRPDISVJRAYFBI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- LIBWRRJGKWQFSD-UHFFFAOYSA-M sodium;2-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC=C1S([O-])(=O)=O LIBWRRJGKWQFSD-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- 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
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D37/00—Tools as parts of machines covered by this subclass
- B21D37/16—Heating or cooling
-
- 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
- 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
- C23C22/34—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 fluorides or complex fluorides
-
- 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
- C23C22/73—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 characterised by the process
-
- 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
-
- 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
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Abstract
本发明公开一种耐高温锌基镀层钢板及其制造方法、热成型方法和部件，由于陶瓷化学转化膜的存在，耐受了加热至850～950℃的高温，气氛中的氧通过陶化膜与镀层缓慢反应，形成更多的氧化物，进一步阻止了锌层的蒸发，热冲压之后镀层完全转变成铁合金层，没有镀层蒸发现象，无硬质的Fe‑Al金属间化合物。
Description
技术领域
本发明涉及一种镀层钢板，特别涉及一种耐高温锌基镀层钢板及其制造方法、热成型方法和部件。
背景技术
现代的汽车制造业要求减重、节能、安全性的结合，热压成型钢的出现满足了这方面的要求，因此得到了极大的发展。
但是在热冲压的加热以及冲压过程中，钢板在几百度的温度下暴露于空气中会发生比较严重的表面氧化，冲压完成后需要进行清理以及防腐处理，消耗人力和成本。为解决此问题，各种解决方案先后被提出，包括在钢板表面涂覆防腐涂料、热浸镀铝硅镀层、锌铁合金镀层、锌镍镀层，这些方法各有优缺点。
锌基镀层钢板在热压成型领域也得到了较多的应用，但是有几个问题依然没有得到较好的解决，包括锌层的液相腐蚀问题、锌液的高温蒸发问题。现有技术中有在镀锌钢板表面涂覆高温防氧化涂料的方法，但是钢板涂覆高温防氧化涂料操作不方便，在经济上也不适合。
发明内容
为了克服上述缺陷，本发明提供了一种耐高温锌基镀层钢板及其制造方法、热成型方法和部件，具备纯锌镀层对钢板的保护作用，同时又解决了纯锌镀层液相侵蚀及易于蒸发等缺点。
本发明目的是通过下面的技术方案实现的：
一种耐高温锌基镀层钢板，其特征在于：含有锌及锌合金热浸镀层，热浸镀层表面具有陶瓷化学转化膜；所述的陶瓷化学转化膜厚度为10-1000纳米；所述的陶瓷转化膜包括ZrO2、ZrOF2、Zr2OF2、及MgO、Al2O3、ZnO三种中的一种或几种。
所述的热浸镀层含有Si、Ti、Mn、Ca、Na、K、B中的一种或几种元素。
所述的热浸镀层中锌的质量百分含量60％以上。
一种耐高温锌基镀层钢板的制造方法，其特征在于：将含有锌及锌合金热浸镀层钢板进入陶化液中，或者将陶化液均匀涂覆到含有锌及锌合金热浸镀层钢板表面，经过50～130℃的温度烘干，在烘干的过程中溶液与钢板表面发生化学反应，在镀层表面生成一层陶瓷化学转化膜；所述的陶化液为含有锆的化合物的溶液。
一种耐高温锌基镀层钢板的热成型的方法为：在含氧气氛中将钢板加热至850～950℃，在650℃以下的温度区间加热速度控制在15℃/s以下，在850～950℃的温度区间保温3-15分钟，之后进行热成型，热成型过程中的冷却速率大于20℃/s，冷却终点温度控制在50～350℃。在650℃以下的温度区间加热速度控制在15℃/s以下，可以保证在加热的过程中镀层表面的陶化层不被破坏。
所述的进入陶化液中是通过线下以单张钢板的方式进行。
所述的将陶化液均匀涂覆到含有锌及锌合金热浸镀层钢板表面是在连续热浸镀生产线上通过辊涂、喷淋后再烘干的方法进行的。
所述的陶化液，包括锆化物、氧化剂、硅烷偶联剂、成膜促进剂、PH值调节剂、缓蚀剂，PH值控制在2-5。
一种耐高温锌基镀层钢板制得的部件，热成型后钢板表面由钢基体到表面依次为铁基固溶体层、金属间化合物层和氧化物-陶瓷化学转化膜结合层，所述的金属间化合物层以Fe-Zn化合物为主；所述的氧化物以氧化锌为主。
铁基的固溶体层，由镀层中的元素扩散溶解于铁基体之中，但是没有改变铁的晶格结构，该层为铁基体与镀层之间的过渡层；金属间化合物层，铁元素扩散进入镀层并与镀层中的元素之间反应形成金属间化合物，该层以Fe-Zn化合物为主，同时含有镀层中的其它元素；氧化物-陶瓷化学转化膜结合层，该层是镀层中的元素在热冲压的加热和保温过程中与空气中的扩散进入镀层中的氧反应生成的氧化物。
对含有铝、镁等合金元素的锌合金镀锌板进行化学转化处理的过程中，由于镀层中的Al、Mg等合金元素在镀锌钢板的镀层表面富集，镀层表面的Al、Mg元素的含量远大于其在镀层中的平均含量，且这些元素由于本身的化学活性较大，会参与到化学转化处理过程中，形成氧化物和盐类存在于化学转化膜中。
在锆盐的化成处理中，表面转化膜中包含有ZrO2、ZrOF2、Zr2OF2，以及依据镀层中锌合金组分不同而变化的MgO、Al2O3、ZnO等，在随后的热冲压成型过程中，无定形陶瓷氧化锆、氧化铝、氧化镁等会形成对锌合金层的保护，阻止锌的蒸发，使得镀层与钢基体形成完整均一的铁锌合金。且由于化成转化的薄膜与镀层有着良好的结合，可以提高镀层钢板在热冲压过程中的成形性能，提高钢板的润滑、流动能力，便于复杂成形。
本发明一种耐高温锌基镀层热压成型钢板，适用于C-Mn钢，典型的如22MnB5、30MnB5等，或者其它适用于热冲压的钢。正是由于陶瓷化学转化膜的存在，耐受了加热至850～950℃的高温，气氛中的氧通过陶化膜与镀层缓慢反应，形成更多的氧化物，进一步阻止了锌层的蒸发，热冲压之后镀层完全转变成铁合金层，没有镀层蒸发现象，无硬质的Fe-Al金属间化合物。
具体实施方式
下面结合具体实施例进行说明：
实施例1：
镀层为锌铝镁合金的热压成型钢板，镀层的成分组成为：2％Mg、3％Al、其余为Zn，钢板为22MnB5，采用陶化工艺进行在线处理，将陶化液辊涂到镀层钢板表面，之后进行烘干。烘干温度为85℃，该陶瓷膜的厚度为100纳米，主要由ZrO2、ZrOF2、Zr2OF2、MgO、Al2O3、ZnO、SiO2构成，尤其以纳米氧化锆、氧化铝、氧化镁为主。热浸镀层含有Si、Ti、F、Na等元素；陶化液的主要成分为：氟锆盐、双氧水、氟钛酸、氟化锆、酒石酸、硝酸钠、单宁酸、KH550。
热冲压工艺，在含有氧的气氛中，在650℃以下的温度区间加热速度控制在10℃/s，在920℃的温度区间保温5分钟，之后进行热冲压，热冲压过程中的冷却速率为35℃/s，冷却终点温度控制在200℃。
镀层在加热的过程中没有蒸发现象，并完全转变成铁合金。
实施例2：
镀层为锌铝镁合金的热压成型钢板，镀层的成分组成为：1.5％Mg、2％Al、其余为Zn，钢板为22MnB5，采用陶化工艺进行离线处理，将镀层钢板浸没到陶化液中，取出之后进行烘干。烘干温度为130℃，该陶瓷膜的厚度为1000纳米，主要由ZrO2、ZrOF2、Zr2OF2、MgO、Al2O3、ZnO、SiO2构成，尤其以纳米氧化锆、氧化铝、氧化镁为主。热浸镀层含有Si、Ti、F、Na、K等元素；陶化液的主要成分为：氟锆盐、双氧水、氟钛酸、氟化锆、酒石酸、氟硼酸钠、硝酸钾、月桂醇聚氧乙烯醚、KH550。
热冲压工艺，在含有氧的气氛中，在650℃以下的温度区间加热速度控制在8℃/s，在950℃的温度区间保温4分钟，之后进行热冲压，热冲压过程中的冷却速率为40℃/s，冷却终点温度控制在100℃。
镀层在加热的过程中没有蒸发现象，并完全转变成铁合金。
实施例3：
镀层为锌铝合金的热压成型钢板，镀层的成分组成为：4.7％Al、其余为Zn，钢板为30MnB5，采用陶化工艺进行离线处理，将镀层钢板浸没到陶化液中，取出之后进行烘干。烘干温度为110℃，该陶瓷膜的厚度为400纳米，主要由ZrO2、ZrOF2、Zr2OF2、Al2O3、ZnO、SiO2构成，尤其以纳米氧化锆、氧化铝为主。热浸镀层含有Si、Ti、Mn、Na、F等元素；陶化液的主要成分为：氟锆盐、高锰酸钾、氟钛酸、过硫酸钠、硝基苯磺酸钠、氟化锆、柠檬酸钠、KH560。
热冲压工艺，在含有氧的气氛中，在650℃以下的温度区间加热速度控制在8℃/s，在950℃的温度区间保温4分钟，之后进行热冲压，热冲压过程中的冷却速率为40℃/s，冷却终点温度控制在100℃。
镀层在加热的过程中没有蒸发现象，并完全转变成铁合金。
实施例4：
镀层为锌镁合金的热压成型钢板，镀层的成分组成为：2.5％Mg、0.2％Al、其余为Zn，钢板为20MnB5，采用陶化工艺进行在线处理，将陶化液喷淋到镀层钢板表面，之后进行烘干。烘干温度为95℃，该陶瓷膜的厚度为90纳米，主要由ZrO2、ZrOF2、Zr2OF2、Al2O3、ZnO、SiO2构成，尤其以纳米氧化锆、氧化铝、氧化镁、氧化锰为主。热浸镀层含有Si、Ti、Mn、F、K等元素；陶化液的主要成分为：氟锆盐、氧化锆、高锰酸钾、高氯酸钾、氟钛酸、氟化锆、硝酸、柠檬酸钠、KH560。
热冲压工艺，在含有氧的气氛中，在650℃以下的温度区间加热速度控制在13℃/s，在850℃的温度区间保温14分钟，之后进行热冲压，热冲压过程中的冷却速率为50℃/s，冷却终点温度控制在50℃。
镀层在加热的过程中没有蒸发现象，并完全转变成铁合金。
实施例5：
镀层为锌的热压成型钢板，镀层的成分组成为：0.23％Al、其余为Zn，钢板为：0.25％C,0.5％Si，2.0Mn，0.3％Mo，0.05％Ti，0.5％Cr，采用陶化工艺进行离线处理，将镀层钢板浸没到陶化液中，取出之后进行烘干。烘干温度为120℃，该陶瓷膜的厚度为800纳米，主要由ZrO2、ZrOF2、Zr2OF2、Al2O3、ZnO、SiO2构成，尤其以纳米氧化锆、氧化铝、氧化锌为主。热浸镀层含有Si、Ti、B、F、K、Na等元素；陶化液的主要成分为：氟锆盐、四氯化锆、硝酸钾、氟钛酸、硼酸、氟化锆、柠檬酸钠、KH560。
热冲压工艺，在含有氧的气氛中，在650℃以下的温度区间加热速度控制在6℃/s，在890℃的温度区间保温7分钟，之后进行热冲压，热冲压过程中的冷却速率为25℃/s，冷却终点温度控制在300℃。
镀层在加热的过程中没有蒸发现象，并完全转变成铁合金。
Claims (6)
1.一种耐高温锌基镀层钢板，其特征在于：含有锌及锌合金热浸镀层，热浸镀层表面具有陶瓷化学转化膜；所述的陶瓷化学转化膜厚度为10-1000纳米；所述的陶瓷转化膜包括ZrO2、ZrOF2、Zr2OF2、及MgO、Al2O3、ZnO三种中的一种或几种。
2.根据权利要求1所述的耐高温锌基镀层钢板，其特征在于：所述的热浸镀层含有Si、Ti、Mn、Ca、Na、K、B中的一种或几种元素。
3.根据权利要求1所述的耐高温锌基镀层钢板，其特征在于：所述的热浸镀层中锌的质量百分含量60％以上。
4.一种根据权利要求1-3任意一项权利要求所述的耐高温锌基镀层钢板的制造方法，其特征在于：将含有锌及锌合金热浸镀层钢板进入陶化液中，或者将陶化液均匀涂覆到含有锌及锌合金热浸镀层钢板表面，经过50～130℃的温度烘干，在烘干的过程中溶液与钢板表面发生化学反应，在镀层表面生成一层陶瓷化学转化膜；所述的陶化液为含有锆的化合物的溶液。
5.一种根据权利要求1-3任意一项权利要求所述的耐高温锌基镀层钢板的热成型方法，其特征在于：在含氧气氛中将钢板加热至850～950℃，在650℃以下的温度区间加热速度控制在15℃/s以下，在850～950℃的温度区间保温3-15分钟，之后进行热成型，热成型过程中的冷却速率大于20℃/s，冷却终点温度控制在50～350℃。
6.一种根据权利要求1-3任意一项权利要求所述的耐高温锌基镀层钢板制得的部件，其特征在于：热成型后钢板表面由钢基体到表面依次为铁基固溶体层、金属间化合物层和氧化物-陶瓷化学转化膜结合层；所述的金属间化合物层以Fe-Zn化合物为主；所述的氧化物以氧化锌为主。
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| CN103184446A (zh) * | 2013-03-22 | 2013-07-03 | 常州大学 | 一种环保型无磷陶化膜形成溶液及其制备方法与应用 |
| CN104894545A (zh) * | 2015-04-28 | 2015-09-09 | 常州市春雷浩宇化工有限公司 | 一种硅烷陶化剂及其制备方法 |
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| CN113025937A (zh) * | 2021-02-07 | 2021-06-25 | 首钢集团有限公司 | 一种热浸镀锌钢板及其制备方法 |
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