CN115003848B - 具有含锰防腐蚀覆层的钢部件 - Google Patents
具有含锰防腐蚀覆层的钢部件 Download PDFInfo
- Publication number
- CN115003848B CN115003848B CN202180010920.XA CN202180010920A CN115003848B CN 115003848 B CN115003848 B CN 115003848B CN 202180010920 A CN202180010920 A CN 202180010920A CN 115003848 B CN115003848 B CN 115003848B
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- China
- Prior art keywords
- manganese
- alloy layer
- iron
- containing alloy
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- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 181
- 239000010959 steel Substances 0.000 title claims abstract description 181
- 239000011572 manganese Substances 0.000 title claims abstract description 150
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 144
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 238000005260 corrosion Methods 0.000 title claims abstract description 79
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 230000007797 corrosion Effects 0.000 title claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 198
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 141
- 239000000956 alloy Substances 0.000 claims abstract description 141
- 229910052742 iron Inorganic materials 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims description 60
- 239000011651 chromium Substances 0.000 claims description 52
- 239000010949 copper Substances 0.000 claims description 50
- 238000005275 alloying Methods 0.000 claims description 48
- 229910052802 copper Inorganic materials 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 46
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 44
- 239000011135 tin Substances 0.000 claims description 44
- 229910052718 tin Inorganic materials 0.000 claims description 44
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 42
- 229910052804 chromium Inorganic materials 0.000 claims description 42
- 229910052782 aluminium Inorganic materials 0.000 claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011701 zinc Substances 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052791 calcium Inorganic materials 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 229910052712 strontium Inorganic materials 0.000 claims description 24
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 24
- 229910052726 zirconium Inorganic materials 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000003856 thermoforming Methods 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 14
- 229910000734 martensite Inorganic materials 0.000 claims description 11
- 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 claims description 10
- 238000005240 physical vapour deposition Methods 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 19
- 239000010410 layer Substances 0.000 description 98
- 239000000047 product Substances 0.000 description 30
- PALQHNLJJQMCIQ-UHFFFAOYSA-N boron;manganese Chemical compound [Mn]#B PALQHNLJJQMCIQ-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 229910000712 Boron steel Inorganic materials 0.000 description 7
- 238000013461 design Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 229910001562 pearlite Inorganic materials 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 229910001338 liquidmetal Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910000851 Alloy steel 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
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- 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
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- 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
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
- 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
- C22C22/00—Alloys based on manganese
-
- 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- 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
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
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Abstract
本发明涉及一种钢部件(13),其包括钢基板(15),其具有存在于该钢基板(15)的至少一侧上的防腐蚀覆层(17)。这里,该防腐蚀覆层(17)包括含锰合金层(19)。这里含锰合金层(19)形成防腐蚀覆层最靠近表面的合金层。此外,含锰合金层(19)包括铁和另一种金属。
Description
技术领域
本发明涉及一种具有含锰防腐蚀覆层的钢部件、一种用于生产该钢部件的扁钢产品以及一种用于生产该钢部件或该扁钢产品的方法。
背景技术
此处提到的“扁钢产品”是指钢带、钢板或由其制成的坯料等。
为了提供现代车身构造中所需的低重量、最大强度和保护效果的组合,如今在碰撞情况下可能承受特别高负载的车身区域中使用由超高强度钢热压成型的部件。
在热模压硬化,也称为热成型中,从冷轧或热轧钢带上分离出来的钢坯被加热到通常高于相应钢的奥氏体化温度的变形温度,并在加热状态下放入成型压力机的工具中。在随后的成形过程中,金属板裁切件或由其形成的部件通过与冷的工具的接触而经历快速冷却。冷却速率在此这样设置,使得在部件中产生硬化组织结构。将该组织结构转变为马氏体组织结构。
适用于热模压硬化的典型钢是钢A-E,其化学成分列于表5。
在实践中,含锰钢通常不耐湿腐蚀的缺点与已知的特别适用于热模压硬化的锰硼钢的优点相抵触。与低合金钢相比,在增加的氯离子浓度的作用下,导致局部有限但强烈的腐蚀的强烈趋势使得恰恰在车身结构中难以使用属于高合金钢板材料组的钢。此外,含锰钢容易产生表面腐蚀,这同样也限制了其应用范围。
此外,从研究中得知,对于用于车身中的复杂碰撞相关结构部件的Mn-B调质钢而言,在不利条件下,例如在氢气输入增加和拉伸应力增加的情况下,在这些钢的生产或进一步加工过程中潜在存在氢脆的风险或存在氢致延迟开裂的风险。在退火处理过程中,钢基体在奥氏体组织结构状态下的更高吸收能力会促进氢的引入。
现有技术中存在各种旨在减少调温状态期间含锰钢的氢吸收或也为此类钢提供保护钢免受腐蚀侵袭的金属覆层的建议。在此分为主动和被动腐蚀保护系统。
主动防腐蚀系统通常通过连续施加含锌防腐蚀覆层来生产。另一方面,被动腐蚀保护系统通常通过施加含铝覆层,尤其是铝硅涂层(AlSi)来生产,该涂层对腐蚀侵袭具有良好的阻隔效果。
然而,使用含锌防腐蚀覆层的缺点是锌的熔点相对较低,约为419℃。在热成型过程中,液态的含锌覆层会渗入基材并在此导致严重的开裂(所谓的液态金属脆化)。
目前的含铝防腐蚀覆层也有多个不利方面。因此,由于涂层材料的高熔化温度,用于生产AlSi涂层的热浸涂层设备的能耗相对较高。此外,锰硼钢上的这些涂层只能在一定程度上进行冷成型。由于硬的Fe-Al-Si金属间相,在冷成型过程中导致涂层剥落。这限制了成型度。因此,AlSi涂层通常需要直接热成型。与阴极浸漆相结合,可使漆层在AlSi涂层的表面上具有良好的附着力,可实现良好的腐蚀侵袭阻隔效果。此外,对于这种涂层变体方案,须考虑到钢材料中的氢输入,其使得在不利的工艺条件下,有必要在连续炉上使用露点控制来进行模压硬化工艺。与露点控制相关的能耗会导致部件制造中的额外成本。
从US 2017/0029955已知用于热成型的各种涂层,其中也提到了含有锰的合金层。
发明内容
以此为出发点,本发明的目的在于提供一种替代性的涂层,该涂层适用于热成型并充分保护热成型钢部件免受腐蚀。
该目的通过包含钢基板的钢部件实现,其具有存在于该钢基板的至少一侧上的防腐蚀覆层。这里,该防腐蚀覆层包括含锰合金层,其中含锰合金层形成防腐蚀覆层最靠近表面的合金层,并且其中含锰合金层包括铁和另一种金属。
在本申请的意义中,如果某元素的质量分数大于0.5重量%,则称该层包括或包含该元素。含锰合金层因此包含大于0.5重量%的锰质量分数、大于0.5重量%的铁质量分数和同样大于0.5重量%的另一种金属质量分数。
在下文中,质量分数以通常的方式用元素符号缩写,即以下适用:Mn>0.5重量%和Fe>0.5重量%。如果金属没有指定,则其他金属的质量分数缩写为X。因此,X>0.5重量%适用。
特别地,该目的通过包含钢基板的钢部件实现,该钢基板具有存在于该钢基板的至少一侧上的防腐蚀覆层。这里,该防腐蚀覆层包括含锰合金层,其中含锰合金层形成防腐蚀覆层最靠近表面的合金层,并且其中该含锰合金层包括:
-锰
-铝、铬、铜、锡中的另一种金属
-选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜、锡的合金元素,规定来自该组的所有合金元素的总比例小于2重量%
-其余为铁和不可避免的杂质。
或者,该任务也通过钢部件的特殊配置(以下称为Cu-Zn变体)来解决。在这种情况下,钢部件包括钢基板,其具有至少存在于钢基板一侧上的防腐蚀覆层。所述防腐蚀覆层包括含锰合金层,所述含锰合金层包括:
-锰
-铜、锡中的另一种金属
-选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜、锡的合金元素,规定来自该组的所有合金元素的总比例小于2重量%
-其余为铁和不可避免的杂质。
在Cu-Zn变体方案的优选扩展方案中,含锰合金层形成防腐蚀覆层最接近表面的合金层。
在Cu-Zn变体方案的一种特殊扩展方案中,防腐蚀覆层具有至少一个另外的功能层,该另外的功能层布置得比含锰合金层更靠近表面。
如上所述的钢部件的钢基板通常是具有马氏体组织结构的钢,优选具有马氏体组织结构的锰硼钢。
特别优选地,钢基板是来自钢A-E组的钢,其化学分析在表5中给出。在此表5应理解为,对于钢A-E组中的每种钢,元素比例均以重量百分比给出。这里给出了最小和最大重量百分比。例如,钢A因此具有碳含量C:0.05重量%-0.10重量%。如果下限为0,则该元素被认为是选择性的。表中没有条目,则表示对于该元素没有限制。对于元素铬和钼,钢C-E中只给定了铬和钼元素含量之和的上限。除了表中列出的元素外,钢A-E还可以包含其他选择性元素,例如Cu、N、Ni、V、Sn、Ca。余量分别由铁组成。
令人惊讶的是,这种含铁和锰的三元合金体系显示出特别好的防腐蚀阻隔效果。此外,防腐蚀覆层在此还充当牺牲阳极或保护阳极。与开头提到的含锌防腐蚀覆层相比,根据本发明的防腐蚀覆层具有更高的熔点,因此其非常适合热成型并且显著降低了液态金属脆化。
在一个优选的实施方案变体中,含锰合金层包含超过10重量%的锰,特别是超过20重量%的锰,优选超过30重量%,特别优选超过40重量%的锰。这一方面保证了合金层的熔点足够高,另一方面实现了主动的腐蚀保护。此外,高锰含量会由于在表面形成氧化锰而导致表面变暗。这改善了熔炉中的能量吸收,从而又节省了能源。
在钢部件的特定设计方案中,含锰合金层接触钢基板。这意味着含锰合金层也是防腐蚀覆层中唯一的合金层,因为其既是最接近表面的合金层,又与钢基板直接接触(Cu-Zn变体方案中至少在一个特殊的扩展方案中就是这种情况)。在任何情况下,与钢基板的直接接触都在腐蚀保护中支持作为牺牲阳极的效果。
钢部件的进一步扩展变体方案包括在防腐蚀覆层表面上具有氧化层的防腐蚀覆层。氧化层是通过与大气中的氧气反应而自发形成的。如果含锰合金层也是最靠近表面的合金层,则氧化层主要包含锰氧化物、其它金属的氧化物和/或选择性合金元素的氧化物。如果另外的功能层比含锰合金层更靠近表面布置,则氧化层主要包含另外的功能层的材料的氧化物。氧化层的厚度通常为20nm至300nm,优选为50nm至200nm,并且额外保护钢部件免受腐蚀。
在钢部件的特殊设计方案中,含锰合金层的电化学势比钢基板的电化学势更负。由此实现了合金层作为牺牲阳极的效果,从而实现了对钢基板的主动腐蚀保护。在此,钢基板和含锰合金层的电化学势差尤其大于50mV,尤其是大于100mV,优选150mV,特别优选大于200mV。已经表明,电化学势的高差异导致特别好的主动耐腐蚀保护。
根据DIN标准“DIN 50918(3.1部分)(1978.06)”(“均质混合电极上的静息电位测量”)测定电化学势。如果在下文中给出的是电化学势的绝对值而不是差值,则是指对标准氢电极的参考。
含锰合金层的另一种金属选自铝、铬、铜和锡。试验表明,由铁、锰和来自组铝、铬、铜和锡的一种元素组成的三元合金系统特别适用于防腐蚀保护。此外,这些元素相对无毒且价格合理。此外,熔点足够高以充分降低热成型过程中的液态金属脆化。此外,所有这些组合都显示出良好的主动防腐蚀保护。
含锰合金层选择性地包括一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜和锡的合金元素,规定该组所有合金元素的总比例低于2重量%。与来自铝、铬、铜和锡的组中的其他金属相比,选择性的合金元素也可以以小于0.5重量%的比例存在。
合金化添加这些元素的优点是其形成氧化物并且当其与水蒸气形成氧化物时释放的氢相对较少。因此,在热成型过程中,相对较少的氢渗透到含锰合金层和基板中。因此,这种合金化添加可防止氢脆。
同时,在如此之少的合金化添加量(总重量小于2重量%)下,这些元素对电化学性能,即阴极保护的影响很小或没有影响。因此,在没有这种合金化添加的实施例中进行电化学研究也是合理的。
在优选的变体方案中,含锰合金层不包含除铁和所提及的其他金属之外的另外的元素。因此,所有另外的元素的质量分数小于0.5重量%。
在特殊设计方案中,含锰合金层的铁含量大于2.0重量%,尤其是大于3.0重量%,优选5.0重量%,特别优选10.0重量%。一定量的铁比例在热成型过程中自动扩散到合金层中。
在一个特殊的设计方案中,含锰合金层包含铁和铝,其中铁含量小于24重量%,尤其是小于20重量%,优选小于15重量%,特别优选小于12重量%,并且锰含量大于40重量%。尤其是对于铁含量小于12重量%和锰含量大于40重量%的变体方案,已经表明,电化学势结果小于-400mV。对于由具有-250mV电化学势的锰硼钢制成的钢基板,含锰合金层因此确保了非常好的主动防腐蚀保护。
上述具有马氏体组织结构的锰硼钢,尤其是根据表5的钢A-E,其电化学势在-250mV±100mV范围内,分别取决于确切的化学组成。含锰合金层的优点在此及下文中结合钢基板进行示例性说明,该钢基板的钢的电化学势为-250mV。这同样适用于具有在-250mV±100mV范围内的不同化学势的其他钢基板。
在进一步的特殊设计方案中,含锰合金层含有铁和锡,其中铁含量小于20重量%,并且锡含量小于30重量%,在该变体方案中,锡含量优选大于6重量%。已经表明,对于具有这种相对组成的含锰合金层,电化学势始终小于-250mV,因此对所提到的锰硼钢产生了主动防腐蚀保护。
在进一步的特殊设计方案中,含锰合金层包含铁和铜,其中铁含量与铜含量之比大于0.05。已经表明,对于具有这种质量比的含锰合金层,存在始终小于-250mV的电化学势,从而对所提到的锰硼钢产生主动防腐蚀保护。
尤其已经表明,如果铁含量Fe和铜含量Cu满足以下关系是有利的:
Fe<45重量%-1.18Cu。
在这种情况下,电化学势甚至始终小于-500mV,这与上述锰硼钢结合导致更好的主动防腐蚀保护。
在一个优选的变体方案中,铁含量Fe和铜含量Cu还满足以下关系:
Fe<20重量%-0.66Cu。
在这种情况下,电化学势甚至始终小于-650mV,这与上述锰硼钢结合导致进一步更好的主动防腐蚀保护。
在另一个特殊设计方案中,含锰合金层含有铁和铬,其中铁含量Fe和铬含量Cr满足如下关系:
20重量%<铁+铬<50重量%。
在该范围内,电化学势始终低于-350mV,这与上述锰硼钢结合导致非常好的主动防腐蚀保护。
钢部件尤其如此扩展,使得在880℃的温度下,含锰合金层至少70体积%,优选至少80体积%处于固态聚集体状态。由此可以以简单的方式进行热成型,而不会出现液化层粘附到工具上或液态金属变脆的情况。
上述钢部件尤其是模压硬化钢部件,优选机动车辆的钢部件,优选选自保险杠横梁、侧面防撞梁、支柱和车身加强件。
根据本发明的目的还通过一种用于生产如上所述的钢部件的扁钢产品来实现。在此,扁钢产品包括钢基板,其具有存在于该钢基板的至少一侧上的防腐蚀覆层,其中该防腐蚀覆层包括含锰合金层,并且其中含锰合金层形成防腐蚀覆层最靠近表面的合金层。该含锰合金层包括:
-锰
-铝、铬、铜、锡中的另一种金属
-任选一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜、锡的合金元素,规定来自该组的所有合金元素的总比例小于2重量%
-其余为铁和不可避免的杂质。
替代性地,该目的也通过扁钢产品的特殊设计方案(以下称为Cu-Zn变体方案)来解决。在此,扁钢产品包括钢基板,其具有存在于该钢基板的至少一侧上的防腐蚀覆层,其中该防腐蚀覆层包括含锰合金层。该含锰合金层包括:
-锰
-铜、锡中的另一种金属
-任选一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜、锡的合金元素,规定来自该组的所有合金元素的总比例小于2重量%
-其余为铁和不可避免的杂质。
在Cu-Zn变体方案的优选扩展方案中,含锰合金层形成防腐蚀覆层最接近表面的合金层。与钢基板的直接接触在防腐蚀保护中支持作为牺牲阳极的效果。
在Cu-Zn变体方案的一种特殊扩展方案中,防腐蚀覆层具有至少一个另外的功能层,该另外的功能层布置得比含锰合金层更靠近表面。
扁钢产品尤其可以用于生产如上所述的钢部件。因此,扁钢产品具有上面结合钢部件解释的相应优点。
扁钢产品的含锰合金层可以已经具有一定的铁比例。然而,这通常比热成型钢部件低几个百分点。替代性地,扁钢产品的含锰合金层也可以是不含铁的。在这两种情况下,在热成型过程中铁含量都会增加,因为铁从钢基板扩散到含锰合金层中。扩散到含锰合金层中的铁的确切比例可以通过热成型过程中的工艺参数来控制。热成型时的温度越高,钢板产品在该温度下保持的时间越长,铁越多地扩散到含锰合金层中。
在优选的实施变体方案中,扁钢产品的含锰合金层包含超过10重量%的锰,尤其是超过20重量%的锰,优选超过30重量%,特别优选超过40重量%的锰,尤其是超过50重量%的锰。这一方面确保了合金层的熔点足够高。另一方面确保了即使在热成型后锰含量也足够高,以确保主动防腐蚀保护。
在扁钢产品的特殊设计方案中,含锰合金层接触钢基板。由此,含锰合金层也是防腐蚀覆层中唯一的合金层,因为其既是最接近表面的合金层,又与钢基板直接接触(Cu-Zn变体方案中至少在一个特殊的扩展方案中就是这种情况)。在任何情况下,与钢基板的直接接触都在腐蚀保护中支持作为牺牲阳极的效果。
在扁钢产品的进一步扩展方案中,钢基板是具有铁氧体-珠光体组织结构的钢,优选是具有铁氧体-珠光体组织结构的锰硼钢,特别优选是这样一种具有铁氧体-珠光体组织结构的锰硼钢,其通过热硬化处理形式的热处理可以转化为马氏体组织结构。由此,该钢基板尤其适用于通过热成型生产前述钢部件。
根据本发明的目的还通过一种用于生产上述扁钢产品的方法来实现。在此,该方法至少包括以下步骤:
-制造或提供钢基板,其中该钢基板的组织结构可以通过热成型转化为马氏体组织结构,
-施加含锰合金层来形成防腐蚀覆层,其中该含锰合金层包括:
i.锰
ii.铝、铬、铜、锡中的另一种金属
iii.选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜、锡、铁的合金元素,规定来自该组的所有合金元素的总比例小于2重量%。
vi.其余为铁和不可避免的杂质
并且其中含锰合金层(19)形成防腐蚀覆层最靠近表面的合金层。
替代性地,根据本发明的目的通过用于制造上述扁钢产品(Cu-Zn变体方案)的方法的特殊设计方案来实现。在此该方法至少包括以下步骤:
-制造或提供钢基板,其中该钢基板的组织结构可以通过热成型转化为马氏体组织结构,
-施加含锰合金层来形成防腐蚀覆层,其中该含锰合金层包括:
i.锰
ii.铜、锡中的另一种金属
iii.选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜、锡、铁的合金元素,规定来自该组的所有合金元素的总比例小于2重量%
vi.其余为铁和不可避免的杂质。
这里,这些方法具有与上面关于扁钢产品或钢部件解释的相同的优点。
尤其地,该生产方法以这样一种方式扩展,即含锰合金层通过选自下组的方法施加:
电解沉积、物理气相沉积(PVD)、浸没工艺、化学气相沉积、浆料工艺、热喷涂、辊轧包覆及其组合。
在提到的含锰合金层的情况下,物理气相沉积(Physical Vapour Deposition)是特别有利的,因为在该方法中没有将氢引入基板中。此外,PVD方法可以使用高熔点合金进行涂层,这例如在热浸镀工艺中并不容易。
根据本发明的目的还通过一种用于生产上述钢部件的方法来实现。在此,该钢部件的生产方法至少包括以下步骤:
-提供先前解释的扁钢产品或生产先前解释的扁钢产品,尤其是根据上述方法,
-对所提供或制造的扁钢产品进行热成型,形成钢部件。
所提供或制造的扁钢产品的热成型优选设计成包括以下步骤:
-在炉温为830℃至980℃,优选830℃至910℃的炉中加热扁钢产品,其中扁钢产品在炉内的停留时间至少为1分钟且至多为18分钟
-从炉中取出扁钢产品并放入成型工具
-在成型工具中将扁钢产品成型为钢部件。
为避免更大的热损失,炉和成型工具之间的转移时间通常不超过10秒。
选择性地,扁钢产品可以在成型期间以20-1000K/s,优选25-500K/s的冷却速率在成型工具中冷却,以硬化钢基板。
替代性地,扁钢产品可以首先在成型工具中成型为钢部件,然后可以以20-1000K/s,优选25-500K/s的冷却速率冷却钢部件,以硬化钢基材。
通常,扁钢产品在室温下放置在炉中,因此停留时间t可以包括加热阶段和炉温下的保持阶段。
制造钢部件的方法尤其这样进行扩展,即所提供或制造的扁钢产品作为钢基板包含具有这样的组织结构的钢,该组织结构可以通过热处理转化为马氏体组织结构,优选具有铁氧体-珠光体组织结构的钢,特别优选具有铁氧体-珠光体组织结构的锰硼钢,并且热成型包括:
-热硬化处理,其中组织结构转变为马氏体组织结构,
并且优选
-在热硬化处理之前、期间和/或之后进行机械处理,优选机械成型。
上述钢部件的制造方法尤其进一步这样进行扩展,即在热成型过程中铁从钢基板扩散到含锰合金层中,从而产生含锰合金层,该含锰合金层包含选自铝、铬、铜、锡的另一种金属,以及选择性的一种或几种来自镁、钙、锶、锆、锌、硅、铝、铬、铜、锡的合金元素,规定来自该组的所有合金元素的总比例低于2重量%,其余为铁和不可避免的杂质。在此,含锰合金层的电化学势尤其比钢基板的电化学势更负,其中钢基板与含锰合金层的电化学势差值尤其大于50mV,尤其大于100mV,优选150mV,特别优选大于200mV。
上述钢部件的生产方法尤其这样进行扩展,使得热成型至少包括以下步骤:
-热处理,其中所提供或制造的部件的组织结构保持在Ac3以上的温度,直到组织结构完全或部分转变为奥氏体组织结构,
-在热处理之前、期间和/或之后将部件机械成型,
-在机械成型过程中和/或之后将部件从高于Ac3的温度优选冷却到低于100℃的温度,从而形成马氏体组织结构,优选冷却速率>20K/s。
附图说明
参考附图更详细地解释本发明。图中
图1示出了具有防腐蚀覆层的钢部件的示意图;
图2示出了含铝的含锰合金层的电化学势;
图3示出了含锡的含锰合金层的电化学势;
图4示出了含铜的含锰合金层的电化学势;
图5示出了含铬的含锰合金层的电化学势。
具体实施方式
图1示出了钢部件13的示意图。钢部件13包括钢基板15和防腐蚀覆层17。防腐蚀覆层17包括含锰合金层19。含锰合金层19是防腐蚀覆层17最靠近表面的合金层。并且含锰合金层19接触钢基板15。因此,含锰合金层是防腐蚀覆层17的唯一合金层。
此外,防腐蚀覆层17包括在防腐蚀覆层17的表面上的氧化层20。氧化层20是通过与大气中的氧气反应而自发形成的,并且主要包含氧化锰和另一种金属的氧化物。
在与防腐蚀覆层17的接触区域中,钢基板15形成铁氧体接缝21。铁氧体接缝21为含铁量高的扩散层,厚度在1μm至6μm之间,其可在热成型时形成。在本申请的意义中,铁氧体接缝21被认为是钢基板15的一部分。根据热成型期间工艺参数的设计,铁氧体接缝21的厚度可以变化或者也可以没有铁氧体接缝21。
图2示出了含铝的含锰合金层的电化学势。电化学势根据铝含量和铁含量以灰度表示。剩余的质量比例分别由锰形成。基础测量值在表1中示出。
图3示出了含锡的含锰合金层的电化学势。电化学势根据锡含量和铁含量以灰度表示。剩余的质量比例分别由锰形成。基础测量值在表2中示出。
图4示出了含铜的含锰合金层的电化学势。电化学势根据铜含量和铁含量以灰度表示。剩余的质量比例分别由锰形成。基础测量值在表3中示出。附图标记23示出作为下列范围边界的线
Fe<45重量%-1.18Cu
因此,线23下方左侧的点满足此关系。相应地,附图标记25示出作为下列范围边界的线
Fe<20重量%-0.66Cu
图5示出了含铬的含锰合金层的电化学势。电化学势根据铬含量和铁含量以灰度表示。剩余的质量比例相应由锰形成。基础测量值如表4所示。
表1
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表2
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表3
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表4
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Claims (15)
1.包含钢基板(15)的钢部件(13),所述钢基板具有存在于所述钢基板(15)的至少一侧上的防腐蚀覆层(17),其中所述防腐蚀覆层(17)包括含锰合金层(19),
其特征在于,
所述含锰合金层(19)形成防腐蚀覆层(17)的最靠近表面的合金层,并且其中所述含锰合金层(19)包括超过40重量%的锰,
以及,
所述含锰合金层(19)包含铁和铝,铁含量小于12重量%,锰含量大于40重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铬、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)含有铁和锡,铁含量小于20重量%,锡含量小于30重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铜,铁含量与铜含量之比大于0.05,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铬,铁含量Fe和铬含量Cr满足:20重量%<Fe+Cr<50重量%,Fe≥0.5重量%,Cr≥1重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质,
其中所述含锰合金层(19)的电化学势比钢基板(15)的电化学势更负。
2.根据权利要求1所述的钢部件(13),
其中所述含锰合金层(19)接触所述钢基板(15)。
3.根据权利要求1所述的钢部件(13),其中铁含量Fe和铜含量Cu满足以下关系:
Fe<45重量%-1.18Cu。
4.根据权利要求1所述的钢部件(13),
其中钢基板(15)和含锰合金层(19)的电化学势差大于50mV。
5.根据权利要求1所述的钢部件(13),
其中钢基板(15)和含锰合金层(19)的电化学势差大于100mV。
6.根据权利要求1所述的钢部件(13),
其中钢基板(15)和含锰合金层(19)的电化学势差大于150mV。
7.根据权利要求1所述的钢部件(13),
其中钢基板(15)和含锰合金层(19)的电化学势差大于200mV。
8.用于借助热成型生产根据权利要求1至7中任意一项所述的钢部件(13)的扁钢产品,
所述扁钢产品包括钢基板(15),所述钢基板具有存在于所述钢基板(15)的至少一侧上的防腐蚀覆层(17),其中所述防腐蚀覆层(17)包括含锰合金层(19),
其特征在于,
所述含锰合金层(19)形成防腐蚀覆层(17)的最靠近表面的合金层,
并且其中所述含锰合金层(19)包括超过40重量%的锰,
以及,
所述含锰合金层(19)包含铁和铝,铁含量小于12重量%,锰含量大于40重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铬、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)含有铁和锡,铁含量小于20重量%,锡含量小于30重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铜,铁含量与铜含量之比大于0.05,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铬,铁含量Fe和铬含量Cr满足:20重量%<Fe+Cr<50重量%,Fe≥0.5重量%,Cr≥1重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质,
其中所述含锰合金层(19)的电化学势比钢基板(15)的电化学势更负。
9.用于生产根据权利要求8所述的扁钢产品的方法,所述方法具有以下步骤:
-制造或提供钢基板(15),其中所述钢基板(15)的组织结构能够通过热成型转化为马氏体组织结构,
-施加含锰合金层(19)来形成防腐蚀覆层(17),
其中所述含锰合金层(19)包括超过40重量%的锰,
以及,
所述含锰合金层(19)包含铁和铝,铁含量小于12重量%,锰含量大于40重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铬、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)含有铁和锡,铁含量小于20重量%,锡含量小于30重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铜,铁含量与铜含量之比大于0.05,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铬,铁含量Fe和铬含量Cr满足:20重量%<Fe+Cr<50重量%,Fe≥0.5重量%,Cr≥1重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质,
其中所述含锰合金层(19)的电化学势比钢基板(15)的电化学势更负,
-并且其中所述含锰合金层(19)形成防腐蚀覆层的最靠近表面的合金层。
10.根据权利要求9所述的方法,其中所述含锰合金层(19)通过选自以下组的方法施加:
电解沉积、物理气相沉积(PVD)、浸没工艺、化学气相沉积、浆料工艺、热喷涂、辊轧包覆及其组合。
11.用于生产如权利要求1至7中任意一项所述的钢部件(13)的方法,所述方法具有以下步骤:
-提供根据权利要求8所述的扁钢产品或通过根据权利要求9或10中任意一项所述的方法生产扁钢产品,
-对所提供或生产的扁钢产品进行热成型,形成钢部件(13)。
12.根据权利要求11所述的方法,其中在热成型过程中铁从钢基板(15)扩散到含锰合金层(19)中,从而产生含锰合金层(19),
其中所述含锰合金层(19)包括超过40重量%的锰,
以及,
所述含锰合金层(19)包含铁和铝,铁含量小于12重量%,锰含量大于40重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铬、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)含有铁和锡,铁含量小于20重量%,锡含量小于30重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、铜的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铜,铁含量与铜含量之比大于0.05,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铬、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质;或者
所述含锰合金层(19)包含铁和铬,铁含量Fe和铬含量Cr满足:20重量%<Fe+Cr<50重量%,Fe≥0.5重量%,Cr≥1重量%,并且含有选择性一种或多种选自镁、钙、锶、锆、锌、硅、铝、铜、锡的合金元素,所述合金元素的总比例小于2重量%,其余为铁和不可避免的杂质,其中,所述含锰合金层(19)的电化学势比钢基板(15)的电化学势更负,
其中钢基板与含锰合金层的电化学势差值大于50mV。
13.根据权利要求12所述的方法,
其中钢基板和含锰合金层的电化学势差大于100mV。
14.根据权利要求12所述的方法,
其中钢基板和含锰合金层的电化学势差大于150mV。
15.根据权利要求12所述的方法,
其中钢基板和含锰合金层的电化学势差大于200mV。
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