CN107849628A - 用于制造没有lme问题的硬化部件的方法 - Google Patents
用于制造没有lme问题的硬化部件的方法 Download PDFInfo
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- CN107849628A CN107849628A CN201680044152.9A CN201680044152A CN107849628A CN 107849628 A CN107849628 A CN 107849628A CN 201680044152 A CN201680044152 A CN 201680044152A CN 107849628 A CN107849628 A CN 107849628A
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 68
- 239000011248 coating agent Substances 0.000 claims abstract description 65
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 50
- 239000010959 steel Substances 0.000 claims abstract description 50
- 239000011701 zinc Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 3
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910017372 Fe3Al Inorganic materials 0.000 claims description 2
- 229910019752 Mg2Si Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 229910001566 austenite Inorganic materials 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000011651 chromium Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 208000037656 Respiratory Sounds Diseases 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001338 liquidmetal Inorganic materials 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910018134 Al-Mg Inorganic materials 0.000 description 2
- 229910018467 Al—Mg Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004210 cathodic protection Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- 238000005240 physical vapour deposition Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018464 Al—Mg—Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 206010011376 Crepitations Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000001912 gas jet deposition Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 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
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000002784 sclerotic effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- 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
-
- 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
- B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
-
- 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
- B32B15/012—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 aluminium or an aluminium alloy
-
- 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
- C21D1/62—Quenching devices
- C21D1/673—Quenching devices for die quenching
-
- 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
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- 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
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- 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
- C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment 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
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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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
- C23C2/12—Aluminium or alloys based thereon
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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
- C23C2/26—After-treatment
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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
- C23C2/26—After-treatment
- C23C2/261—After-treatment in a gas atmosphere, e.g. inert or reducing atmosphere
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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
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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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
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
- C23C2/29—Cooling or quenching
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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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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- 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
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- Coating With Molten Metal (AREA)
Abstract
本发明涉及用于制造硬化部件的方法,包括以下步骤:A)提供预涂覆金属涂层的钢板,所述金属涂层包含2.0重量%至24.0重量%的锌,1.1重量%至7.0重量%的硅,当硅的量为1.1%至4.0%时任选的1.1重量%至8.0重量%的镁,以及任选的选自Pb、Ni、Zr或Hf的另外的元素,每种另外的元素以重量计的含量小于0.3重量%,余量为铝和不可避免的杂质以及残留元素,其中比率Al/Zn大于2.9;B)切割经涂覆的钢板以获得坯件;C)在840℃至950℃的温度下对所述坯件进行热处理以在钢中获得完全奥氏体显微组织;D)将所述坯件转移至压制工具中;E)使所述坯件热成形以获得部件;F)使步骤E)中获得的部件冷却以在钢中获得这样的显微组织:所述显微组织为马氏体或马氏体‑贝氏体或由至少75%的等轴铁素体、5%至20%的马氏体以及量小于或等于10%的贝氏体构成。
Description
本发明涉及用于从涂覆有金属涂层的钢板开始制造硬化部件的方法。本发明特别适合用于制造机动车辆。
通常使用基于锌的涂层,因为其由于阻挡层保护和阴极保护而允许抗腐蚀保护。阻挡层作用通过在钢表面上施加金属涂层而获得。因此,金属涂层防止钢与腐蚀性气氛之间的接触。阻挡层作用与涂层和基材的性质无关。相反,牺牲阴极保护基于这样的事实:锌与钢相比是较不贵重的金属。因此,如果发生腐蚀,则锌优先于钢被消耗。阴极保护在钢直接暴露于腐蚀性气氛的区域(例如其中在钢之前将消耗掉周围的锌的切割边缘)中是必需的。
然而,当对这样的经锌涂覆的钢板进行加热步骤,例如压制硬化或焊接时,在钢中观察到从涂层扩展的裂纹。事实上,偶尔,由于在加热步骤后在经涂覆的钢板中存在裂纹,所以存在金属机械性能的下降。这些裂纹在以下条件下出现:高温;除了应力之外,与具有低熔点的液体金属(例如,锌)接触;熔融金属与基材晶粒体(grain bulk)和晶界的不均匀扩散。这样的现象的名称为液体金属脆化(liquid metal embrittlement,LME),也称为液体金属辅助开裂(liquid metal assisted cracking,LMAC)。
专利申请US2013/0206824公开了用于由包含至少0.4重量%Mn的钢板生产具有金属防腐蚀涂层的钢组件的方法。将钢板产品在连续加热炉中在包含最高至25体积%H2,0.1体积%至10体积%NH3、H2O、N2,以及工艺相关杂质作为剩余部分的露点为-50℃至-5℃的退火气氛下在400℃至1100℃的温度下退火5秒至600秒。经退火的钢板具有5μm至200μm厚的颗粒尺寸比内部芯层的颗粒尺寸更细的硝化层。一经被金属保护层涂覆,就将坯件分离于经退火的钢板,加热至780℃至950℃的奥氏体化温度,热成形,并冷却以形成硬化组织。
在高温下,即使在钢板产品设置有金属涂层时产生的钢板中,硝化层也允许脆化的风险的最小化。可以施加至钢基材的金属涂层基于Zn、Al、Zn—Al、Zn—Mg、Zn—Ni、Zn—Fe、Al—Mg、Al—Si、Zn—Al—Mg或Zn—Al—Mg—Si。
然而,从工业观点出发,由于在渗氮处理期间存在氨气,因此必须重新设计作业线。事实上,该步骤必须在密闭箱中进行以防止该气体的泄露。该密闭箱难以生产,导致生产力成本的增加。而且,难以找到可以处理腐蚀性氨气的材料。此外,将渗氮处理添加至用于生产经涂覆的部件的方法。因此,该方法的持续时间被延长,导致生产力的损失。最后,在实现热浸镀锌后硝化层抑制锌涂层的可润湿性。
本发明的目的是提供用于制造没有LME问题的硬化部件的方法。特别地,其旨在使得可获得容易地实施的方法,以获得通过热成形产生的没有LME问题的部件。
该目的通过提供根据权利要求1所述的用于制造硬化部件的方法来实现。所述方法还可以包含权利要求2至23的特征。
本发明还涵盖了根据权利要求25所述的部件。所述部件还可以包含权利要求24和30的特征。
本发明还涵盖了根据权利要求31所述的这样的部件用于制造机动车辆的用途。
本发明的其他特征和优点将由本发明的以下详细描述变得明显。
为了举例说明本发明,将特别地参照以下附图描述多个实施方案和非限制性实例的试验:
图1示出根据本发明的包含2.0%至24.0%的锌、1.1重量%至7.0重量%的硅、以及当硅的量为1.1%至4.0%时任选的镁的组成的示意图。
名称“钢”或“钢板”意指用于压制硬化工艺的钢板,其具有允许部件实现大于或等于500MPa,优选大于或等于1000MPa,有利地大于或等于1500MPa的较高拉伸强度的组成。钢板的重量组成优选如下:0.03%≤C≤0.50%;0.3%≤Mn≤3.0%;0.05%≤Si≤0.8%;0.015%≤Ti≤0.2%;0.005%≤Al≤0.1%;0%≤Cr≤2.50%;0%≤S≤0.05%;0%≤P≤0.1%;0%≤B≤0.010%;0%≤Ni≤2.5%;0%≤Mo≤0.7%;0%≤Nb≤0.15%;0%≤N≤0.015%;0%≤Cu≤0.15%;0%≤Ca≤0.01%;0%≤W≤0.35%,余量为铁和来自钢制造的不可避免的杂质。
例如,钢板为具有以下组成的22MnB5:0.20%≤C≤0.25%;0.15%≤Si≤0.35%;1.10%≤Mn≤1.40%;0%≤Cr≤0.30%;0%≤Mo≤0.35%;0%≤P≤0.025%;0%≤S≤0.005%;0.020%≤Ti≤0.060%;0.020%≤Al≤0.060%;0.002%≤B≤0.004%,余量为铁和来自钢制造的不可避免的杂质。
钢板可以为具有以下组成的0.24%≤C≤0.38%;0.40%≤Mn≤3%;0.10%≤Si≤0.70%;0.015%≤Al≤0.070%;0%≤Cr≤2%;0.25%≤Ni≤2%;0.020%≤Ti≤0.10%;0%≤Nb≤0.060%;0.0005%≤B≤0.0040%;0.003%≤N≤0.010%;0.0001%≤S≤0.005%;0.0001%≤P≤0.025%;应理解,钛和氮的含量满足Ti/N>3.42;碳、锰、铬和硅的含量满足:
组成任选地包含以下中的一者或更多者:0.05%≤Mo≤0.65%;0.001%≤W≤0.30%;0.0005%≤Ca≤0.005%,余量为铁和来自钢制造的不可避免的杂质。
例如,钢板为具有以下组成的0.040%≤C≤0.100%;0.80%≤Mn≤2.00%;0%≤Si≤0.30%;0%≤S≤0.005%;0%≤P≤0.030%;0.010%≤Al≤0.070%;0.015%≤Nb≤0.100%;0.030%≤Ti≤0.080%;0%≤N≤0.009%;0%≤Cu≤0.100%;0%≤Ni≤0.100%;0%≤Cr≤0.100%;0%≤Mo≤0.100%;0%≤Ca≤0.006%,余量为铁和来自钢制造的不可避免的杂质。
钢板可以根据期望的厚度(其可以是例如0.7mm至3.0mm)通过热轧和任选地冷轧而获得。
本发明涉及用于制造没有LME问题的硬化部件的方法。首先,该方法包括提供预涂覆金属涂层的钢板,所述金属涂层包含2.0重量%至24.0重量%的锌,1.1重量%至7.0重量%的硅,当硅的量为1.1%至4.0%时任选的1.1重量%至8.0重量%的镁,以及任选的选自Pb、Ni、Zr或Hf的另外的元素,每种另外的元素以重量计的含量小于0.3重量%,余量为铝和不可避免的杂质以及残留元素,其中比率Al/Zn大于2.9。
图1示出涂层组合物。根据本发明,涂层包含当硅的量为1.1%至4.0%时任选的1.1重量%至8.0重量%的镁。任选的存在的镁在该图中以灰色表示。
不希望受任何理论约束,看起来如果不满足这些条件,则出现LME问题,这是因为富Zn相的量太高,并且液体锌可以朝向钢/涂层界面扩散并在钢中产生宏观裂纹。
优选地,金属涂层不包含选自以下的元素:Cr、Mn、Ti、Ce、La、Nd、Pr、Ca、Bi、In、Sn和Sb、或其组合。在另一优选实施方案中,金属涂层不包含任意以下成分(compound):Cr、Mn、Ti、Ce、La、Nd、Pr、Ca、Bi、In、Sn和Sb。事实上,不希望受任何理论约束,看起来当这些成分存在于涂层中时,存在涂层的特性(例如,电化学电位)改变的风险,原因是其与涂层的主要元素的可能相互作用。
优选地,比率Al/Zn为5至9。不希望受任何理论约束,已发现当比率Al/Zn不为5至9时,存在LME问题的减少不太显著的风险,因为锌不再在铝基体中的固溶体中且富Zn相开始形成。
优选地,比率Zn/Si为2.9至8。不希望受任何理论约束,已发现当Zn/Si比不为2.9至8时,存在LME问题的减少不太显著的风险,因为富Zn相在涂层中的比例有点过高。
有利地,涂层包含2.0重量%至5.0重量%,优选2.1重量%至4.9重量%的硅。在另一优选实施方案中,涂层包含1.5重量%至3.5重量%的硅。在另一优选实施方案中,涂层包含4.5重量%至5.5重量%的硅。
优选地,涂层包含5.0重量%至19.0重量%,优选5.0重量%至15.0重量%,有利地10.0重量%至15.0重量%的锌。
有利地,当硅的量为1.1重量%至4.0重量%时,涂层可以包含0.5重量%至3.0重量%,优选1.0重量%至2.9重量%的镁。在另一优选实施方案中,涂层包含3.1重量%至8.0重量%,优选4.0重量%至8重量%的镁。
有利地,涂层包含大于71重量%,优选大于76重量%的铝。
涂层可以通过本领域技术人员已知的任何方法沉积,例如热浸镀工艺、电镀工艺、物理气相沉积例如射流气相沉积或磁控溅射。优选地,涂层通过热浸镀工艺沉积。在该工艺中,将通过轧制获得的钢板浸在熔融金属浴中。
浴包含锌、硅、铝和任选的镁。其可以包含选自Pb、Ni、Zr或Hf的另外的元素,每种另外的元素以重量计的含量小于0.3重量%。这些另外的元素可以改善钢板上的涂层附着性、延展性等。
浴还可以包含不可避免的杂质和残留元素,其来自供给锭或来自钢板在熔融浴中的通过。残留元素可以是含量最高至3.0重量%的铁。
涂层的厚度通常为5μm至50μm,优选10μm至35μm,有利地12μm至18μm或26μm至31μm。浴温度通常为580℃至660℃。
在涂层的沉积之后,通常用喷嘴在经涂覆的钢板两侧喷射气体来擦拭(wipe)钢板。然后使经涂覆的钢板冷却。优选地,凝固开始和凝固结束之间的冷却速率大于或等于15℃·秒-1。有利地,凝固开始和结束之间的冷却速率大于或等于20℃·秒-1。
然后,可以实现光整冷轧(skin-pass),并允许对经涂覆的钢板进行加工硬化并给予其促进后续成形的粗糙度。可以施加脱脂和表面处理以改善例如附着结合或耐腐蚀性。
然后,切割经涂覆的钢板以获得坯件。在炉中在非保护气氛下在通常为840℃至950℃,优选880℃至930℃的奥氏体化温度Tm下对坯件施加热处理。有利地,在1分钟至12分钟,优选3分钟至9分钟的停留时间tm期间保持所述坯件。在热成形之前的热处理期间,涂层形成具有高耐腐蚀性、抗磨性(resistance to abration)、耐磨性(resistance to wear)和耐疲劳性的合金层。
在热处理之后,然后将坯件转移至热成形工具并在600℃至830℃的温度下热成形。热成形包括热冲压和辊轧成形。优选地,对坯件进行热冲压。然后使部件在热成形工具中冷却或在转移至特定冷却工具之后冷却。
根据钢组成以如下方式控制冷却速率:使得在热成形之后的最终显微组织主要包含马氏体,优选包含马氏体,或者马氏体和贝氏体,或者由至少75%的等轴铁素体、5%至20%的马氏体和量小于或等于10%的贝氏体构成。
如此,获得根据本发明的没有LME的硬化部件。
优选地,部件的涂层的显微组织包含相互扩散层Fe+Fe3Al、含有溶解的Si和Zn的AlFe金属间化合物相、二元Zn-Al相和富Si相。当镁存在于涂层中时,显微组织还包含Zn2Mg相和/或Mg2Si相。
在一个优选实施方案中,部件是具有可变厚度的压制硬化的钢部件,即本发明的压制硬化钢部件可以具有不均匀但可以变化的厚度。事实上,可以在最经受外部应力的区域中实现期望的机械抗性水平,并且可以节省压制硬化的部件的另一些区域中的重量,从而有助于车辆重量减轻。特别地,具有不均匀厚度的部件可以通过连续柔性轧制来生产,即,通过如下过程:其中轧制后获得的板厚度在轧制方向上是可变的,这与在轧制过程期间通过辊施加至板的载荷有关。
因此,在本发明的条件下,可以有利地制造具有变化的厚度的车辆部件以获得例如不等厚轧制板(tailored rolled blank)。具体地,部件可以是前纵梁(front rail)、座椅横向构件、门框下边梁(side sill)构件、前围挡板(dash panel)横向构件、前底板(front floor)加强件、后底板(rear floor)横向构件、后纵梁(rear rail)、B柱、门框或shotgun。
对于汽车应用,在磷酸盐化步骤之后,将部件浸在e-涂覆浴中。通常,磷酸盐层的厚度为1μm至2μm,e-涂层的厚度为15μm至25μm,优选小于或等于20μm。电泳层确保了另外的抗腐蚀保护。
在e-涂覆步骤之后,可以沉积另外的涂料层,例如涂料的底漆涂层、底涂层(basecoat layer)和顶涂层(top coat layer)。
在将e-涂层施加在部件上之前,预先将部件脱脂和磷酸盐化以确保电泳的附着性。
现在将在仅用于提供信息而进行的试验中说明本发明。这些试验不是限制性的。
实施例
对于所有样品,所使用的钢板为22MnB5。钢的组成如下:C=0.2252%;Mn=1.1735%;P=0.0126%,S=0.0009%;N=0.0037%;Si=0.2534%;Cu=0.0187%;Ni=0.0197%;Cr=0.180%;Sn=0.004%;Al=0.0371%;Nb=0.008%;Ti=0.0382%;B=0.0028%;Mo=0.0017%;As=0.0023%;V=0.0284%。
所有涂层通过热浸镀工艺沉积。
实施例1:抗裂性测试:
该测试用于确定在压制硬化处理期间在热成形之后可获得的裂纹的存在。
准备试验件1至10并使其经历抗裂性测试。
为此,切割经涂覆的试验件以获得坯件。然后在5分钟至10分钟的停留时间期间在900℃的温度下加热坯件。将坯件转移至压制工具中并热冲压以获得具有Ω形状的部件。然后,使部件冷却以通过马氏体转变获得硬化。
最后,切割部件的变形部分。然后,通过SEM(扫描电子显微术)分析裂纹的存在。0意指优异,换言之,根本没有裂纹;1意指存在深度为0μm至50μm的微裂纹;2意指非常差,换言之,存在深度大于50μm的宏观裂纹。结果示出于下表1中:
*:根据本发明的实施例。
根据本发明的所有试验件(试验件7至10)在热冲压期间表现出优异的性能。事实上,与试验件1至6相反,根据本发明的部件没有出现裂纹。
实施例2:工具退化测试:
该测试用于确定热冲压之后在压制工具中划痕和涂层涂污(coating smearing)的存在。
因此,在实施例1中制备的试验件1、2、4和7至10的热冲压之后,通过肉眼分析压制工具。0意指优异,换言之,没有工具降解并且在压制工具中没有涂层涂污;1意指在压制工具中存在划痕和轻微的涂层涂污;2意指非常差,换言之,在压制工具中存在严重划痕和大量涂层涂污。结果示出于下表2中:
*:根据本发明的实施例。
与试验件11至13相反,根据本发明的试验件14至17在压制工具中具有优异性能。
Claims (31)
1.一种用于制造硬化部件的方法,包括以下步骤:
A)提供预涂覆金属涂层的钢板,所述金属涂层包含2.0重量%至24.0重量%的锌,1.1重量%至7.0重量%的硅,当硅的量为1.1%至4.0%时任选的1.1重量%至8.0重量%的镁,以及任选的选自Pb、Ni、Zr或Hf的另外的元素,每种另外的元素以重量计的含量小于0.3重量%,余量为铝和不可避免的杂质以及残留元素,其中比率Al/Zn大于2.9;
B)切割经涂覆的钢板以获得坯件;
C)在840℃至950℃的温度下对所述坯件进行热处理以在所述钢中获得完全奥氏体显微组织;
D)将所述坯件转移至压制工具中;
E)使所述坯件热成形以获得部件;
F)使步骤E)中获得的部件冷却以在钢中获得这样的显微组织:所述显微组织为马氏体或马氏体-贝氏体或由至少75%的等轴铁素体、5%至20%的马氏体以及量小于或等于10%的贝氏体构成。
2.根据权利要求1所述的方法,其中比率Al/Zn为5至9。
3.根据权利要求1或2所述的方法,其中比率Zn/Si为2.9至8。
4.根据权利要求1至3中任一项所述的方法,其中所述涂层包含2.0重量%至5.0重量%的硅。
5.根据权利要求4所述的方法,其中所述涂层包含2.1重量%至4.9重量%的硅。
6.根据权利要求1至3中任一项所述的方法,其中所述涂层包含1.5重量%至3.5重量%的硅。
7.根据权利要求1至3中任一项所述的方法,其中所述涂层包含4.5重量%至5.5重量%的硅。
8.根据权利要求1至7中任一项所述的方法,其中所述涂层包含5.0重量%至19.0重量%的锌。
9.根据权利要求8所述的方法,其中所述涂层包含5.0重量%至15.0重量%的锌。
10.根据权利要求9所述的方法,其中所述涂层包含10.0重量%至15.0重量%的锌。
11.根据权利要求1至10中任一项所述的方法,其中所述涂层包含0.5重量%至3.0重量%的镁。
12.根据权利要求11所述的方法,其中所述涂层包含1.0重量%至2.9重量%的镁。
13.根据权利要求1至10中任一项所述的方法,其中所述涂层包含3.1重量%至8.0重量%的镁。
14.根据权利要求13所述的方法,其中所述涂层包含4.0重量%至8.0重量%的镁。
15.根据权利要求1至14中任一项所述的方法,其中所述涂层包含大于71重量%的铝。
16.根据权利要求1至15中任一项所述的方法,其中所述涂层包含大于76重量%的铝。
17.根据权利要求1至16中任一项所述的方法,其中所述涂层的厚度为5μm至50μm。
18.根据权利要求17所述的方法,其中所述厚度为10μm至35μm。
19.根据权利要求18所述的方法,其中所述厚度为12μm至18μm。
20.根据权利要求18所述的方法,其中所述厚度为26μm至31μm。
21.根据权利要求1至20中任一项所述的方法,其中所述涂层不包含选自以下的元素:Cr、Mn、Ti、Ce、La、Nd、Pr、Ca、Bi、In、Sn和Sb、或其组合。
22.根据权利要求1至21中任一项所述的方法,其中步骤C)在惰性气氛或包含空气的气氛中在1分钟至12分钟的停留时间期间进行。
23.根据权利要求1至22中任一项所述的方法,其中在步骤E)期间在600℃至830℃的温度下使所述坯件热成形。
24.一种能够由根据权利要求1至23中任一项所述的方法获得的涂覆有金属涂层的部件。
25.根据权利要求24所述的部件,其中所述金属涂层的显微组织包含相互扩散层Fe+Fe3Al、含有溶解的Si和Zn的AlFe金属间化合物相、二元Zn-Al相和富Si相。
26.根据权利要求24或25中任一项所述的部件,其中所述金属涂层的显微组织包含Zn2Mg相或Mg2Si相或二者。
27.根据权利要求24至26中任一项所述的部件,所述部件为具有可变厚度的压制硬化的钢部件。
28.根据权利要求27所述的部件,其中所述可变厚度通过连续柔性轧制过程产生。
29.根据权利要求24至28中任一项所述的部件,所述部件为不等厚轧制板。
30.根据权利要求24至29中任一项所述的部件,所述部件为前纵梁、座椅横向构件、门框下边梁构件、前围挡板横向构件、前底板加强件、后底板横向构件、后纵梁、B柱、门框或shotgun。
31.根据权利要求24至30中任一项所述的部件或能够根据权利要求1至23中任一项所述的方法获得的部件用于制造机动车辆的用途。
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PCT/IB2016/000983 WO2017017514A1 (en) | 2015-07-30 | 2016-07-11 | Method for the manufacture of a hardened part which does not have lme issues |
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KR102075278B1 (ko) | 2020-02-07 |
US20180223386A1 (en) | 2018-08-09 |
ES2909307T3 (es) | 2022-05-06 |
CA2991548A1 (en) | 2017-02-02 |
US20210395856A1 (en) | 2021-12-23 |
US20210395854A1 (en) | 2021-12-23 |
HUE058024T2 (hu) | 2022-06-28 |
MX2018001308A (es) | 2018-04-30 |
CA2991548C (en) | 2021-05-04 |
WO2017017514A1 (en) | 2017-02-02 |
JP6630431B2 (ja) | 2020-01-15 |
BR112018000450B1 (pt) | 2022-02-22 |
BR112018000450A2 (pt) | 2018-09-11 |
JP2018527462A (ja) | 2018-09-20 |
US20210395853A1 (en) | 2021-12-23 |
EP3329021A1 (en) | 2018-06-06 |
RU2685617C1 (ru) | 2019-04-22 |
US11162153B2 (en) | 2021-11-02 |
EP4006178A1 (en) | 2022-06-01 |
WO2017017484A1 (en) | 2017-02-02 |
EP3329021B1 (en) | 2022-02-23 |
UA119821C2 (uk) | 2019-08-12 |
PL3329021T3 (pl) | 2022-05-16 |
MA42520A (fr) | 2018-06-06 |
MA42520B1 (fr) | 2022-02-28 |
CN107849628B (zh) | 2020-09-22 |
KR20180022874A (ko) | 2018-03-06 |
US20210395855A1 (en) | 2021-12-23 |
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