CN106795613A - 具有Al涂层的扁钢产品及其制造方法和钢部件及其制造方法 - Google Patents
具有Al涂层的扁钢产品及其制造方法和钢部件及其制造方法 Download PDFInfo
- Publication number
- CN106795613A CN106795613A CN201580047395.3A CN201580047395A CN106795613A CN 106795613 A CN106795613 A CN 106795613A CN 201580047395 A CN201580047395 A CN 201580047395A CN 106795613 A CN106795613 A CN 106795613A
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- Prior art keywords
- flat product
- weight
- protective coating
- steel
- thermoforming
- 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.)
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 85
- 239000010959 steel Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 title claims description 39
- 239000011253 protective coating Substances 0.000 claims abstract description 56
- 238000005275 alloying Methods 0.000 claims abstract description 41
- 238000003856 thermoforming Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 17
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000004224 protection Effects 0.000 claims description 4
- 229910001566 austenite Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims 2
- 238000007654 immersion Methods 0.000 claims 1
- 230000002784 sclerotic effect Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 27
- 239000001257 hydrogen Substances 0.000 abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 27
- 239000010410 layer Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000007731 hot pressing Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000712 Boron steel Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910015372 FeAl Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- PALQHNLJJQMCIQ-UHFFFAOYSA-N boron;manganese Chemical compound [Mn]#B PALQHNLJJQMCIQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101000856234 Clostridium acetobutylicum (strain ATCC 824 / DSM 792 / JCM 1419 / LMG 5710 / VKM B-1787) Butyrate-acetoacetate CoA-transferase subunit A Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
-
- 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
-
- 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
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- 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
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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
- B32B15/18—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
- 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
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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
-
- 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
- C21D7/00—Modifying the physical properties of iron or steel by deformation
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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
- 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
-
- 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
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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
- 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
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
- C21D8/0284—Application of a separating or insulating coating
-
- 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
- C21D8/0421—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 characterised by the working steps
-
- 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
- C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
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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
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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
- C22C21/02—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
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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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C21/10—Alloys based on aluminium with zinc 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
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- C22C21/12—Alloys based on aluminium with copper 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
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
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- 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
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
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- 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
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- 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
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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Abstract
本发明涉及一种用于热成型的扁钢产品及其制造方法,该扁钢产品由钢基底和涂覆在钢基底上的、基于Al的保护涂层而组成,钢基底由具有0.1‑3重量%的Mn和最高0.01重量%的B的钢制成,保护涂层可选地含有总共最大20重量%的其他合金元素,还涉及一种钢部件及其制造方法。按照本发明的扁钢产品实现了,在热成型所需要的加热过程中使氢吸收最小化。这按照本发明由此得以实现,即,保护涂层含有总共0.1‑0.5重量%的至少一种的碱土金属或过渡金属作为额外的合金成分,其中,在扁钢产品的热成型过程中在所述保护涂层的外侧的表面上形成一种碱土金属或过渡金属的氧化物。
Description
技术领域
本发明涉及一种用于热成型的扁钢产品,该扁钢产品由钢基底和涂覆在钢基底上的、基于Al的保护涂层而组成,钢基底由具有0.1-3重量%的Mn和0.0005-0.01重量%的B的钢制成,保护涂层可选地含有总共最大20重量%的其他合金元素。
本发明同样还涉及一种用于制造按照本发明的扁钢产品的方法。
另外,本发明还涉及一种通过热压淬火制成的钢部件。
本发明还涉及一种用于制造这类钢部件的方法。
背景技术
“扁钢产品”的概念在此为所有的轧制产品,其长度较其厚度而言大很多。为此,钢带和钢板以及由其获得的切割件和扁坯都属于扁钢产品。
当在此作出合金的含量的规定时,只要没有其他说明,则合金的含量总是以“重量%”理解。
按照本发明的扁钢产品的钢基底由所谓的“MnB钢”组成。这类钢在EN 10083-3中标准化。这些钢具有良好的可硬化性并且在热压期间允许可靠的过程实施,通过该过程实施以经济的方式实现了,无需额外冷却,在热成型过程中仍在工具中产生马氏体硬化。这种钢的典型实例是以名称22MnB5已知的钢,其可以在2004年的德国钢编码(Stahlschlüssel)中以材料编号1.5528找到。
市场可购买到的完全镇静的22MnB5钢除了含有铁和不可避免的杂质之外通常还含有(以重量%计的):0.10-0.250%的C、1.0-1.4%的Mn、0.35-0.4%的Si、最多0.03%的P、最多0.01%的S、最多0.040%的Al、最多0.15%的Ti、最多0.1%的Nb、总计至多0.5%的Cr+Mo以及最多0.005%的B。
对于热轧的并且设置有Al涂层的MnB钢板,其通过热压淬火用于制造钢部件,在EP0 971 044 Bl中说明了一种合金规格,根据该合金标准,MnB钢除了含有铁和不可避免的杂质之外还含有(以重量%计的):大于0.20%但小于0.5%的碳含量、大于0.5%但小于3%的锰含量、大于0.1%但小于0.5%的硅含量、大于0.01%但小于1%的铬含量、小于0.2%的钛含量、小于0.1%的铝含量、小于0.1%的磷含量、小于0.05%的硫含量、大于0.0005%但小于0.08%的硼含量。Al涂层为所谓的AlSi涂层,其由9-10重量%的Si、2-3.5重量%的铁和余量的铝组成。将这种组成和涂覆的扁钢产品加热到大于700℃的加热温度,然后放入到压制模具中,在此热成型成钢部件并在此快速地冷却,以使得该扁钢产品的钢基底中产生硬化组织结构。
在发货状态下,所有的锰硼钢种是少氢的。其可扩散氢的含量分别在目前的0.1ppm的检测限以下。MnB钢由此基本上仅表现出较低的氢致裂纹的倾向。
但是在实际中发现,在基于铝的保护涂层涂覆的锰硼钢在潮湿的炉气氛中的热成型过程中会导致钢基底中的氢聚集。对此的原因已确定为金属-水蒸气反应。当在含有水蒸气的气氛条件下在加热炉中将用于热成型的、设置有Al涂层的扁钢产品加热到较高的温度时,会导致该反应。在此,位于炉气氛中的水蒸气在材料表面上反应形成氢气和金属氧化物。所形成的氢气扩散到钢材中并在此可以通过其优选在高固有拉应力的区域中的浓集而导致延迟的失效。如果局部达到非常高的氢浓度,这削弱了钢基材组织结构的晶界上的结合,以使得在使用中由于出现的应力而导致沿着晶界的开裂。
为了避免由于在炉中的表面反应而导致的氢渗入,通常使用露点调节剂。在此的目的是,限制在炉气氛中的水蒸气供应。
这类措施的一个例子为在EP 1 767 286 A1中描述的方法。在该方法中,设置有Al或Zn涂层的扁钢产品为了其热成型而在干燥的气氛中(其氢气含量不高于6体积%、优选不超过1体积%并且其露点保持在最高10℃)加热到一个温度,该温度至少等于Ac3温度并且最高等于1100℃。这样加热的扁钢产品的钢基底优选由MnB钢组成,其具有0.05-0.5重量%的C、0.5-3重量%的Mn和最多0.05重量%的B,而在其为了改善腐蚀保护作用的Al和Zn涂层中可以分别含有0.1-1重量%的Cr、0.5-10重量%的Mg、0.1-1重量%的Ti或1-5重量%的Sn。在此,Al涂层优选是具有3-15重量%Si的AlSi涂层。铁通常可以以0.05-0.5重量%的含量作为杂质存在于Al涂层中。然而,EP 1 767 286 A1中提出的实施例都不涉及除了不可避免的Fe杂质还包含额外的合金成分的AlSi涂层。
特别是在其中规定高空气湿度的区域中,为了提供足够量的干燥空气或干燥氮气所必要的花费会引起显著的运行开支。
发明内容
在该现有技术的背景下,本发明的目的在于,提供一种开头所述的扁钢产品,其中使热成型需要的加热过程中的氢吸收最小化。此外还应说明一种用于制造这类扁钢产品的方法、由该扁钢产品热成型的钢部件和一种用于制造这类钢部件的方法。
本发明关于扁钢产品的目的由此得以实现,即,根据权利要求1来形成一类扁钢产品。
用于制造按照本发明的扁钢产品的方法在权利要求9中说明。
解决了上述目的的钢部件的特征在于,其由按照本发明的扁钢产品而制成。
用于制造这类钢部件的方法最终可由权利要求11中得出。
本发明的有利的设计方案在从属权利要求中说明并随后类似于一般发明构思一样详细地说明。
按照本发明的扁钢产品包括钢基底和涂覆在钢基底上的、基于Al的保护涂层,该钢基底由具有0.1-3重量%的Mn和0.0005-0.01重量%的B的钢组成,保护涂层可选地含有总共最大20重量%的其他合金元素。
按照本发明,基于Al的保护涂层含有总共0.1-0.5重量%的至少一种的碱土金属或过渡金属作为额外的合金成分,其中,在扁钢产品的热成型过程中在保护涂层的外侧的表面上形成一种碱土金属或过渡金属的氧化物。
基于Al的保护涂层优选含有总共0.1-0.5重量%的Mg作为额外的合金成分,其中,在扁钢产品的热成型之后在至少700℃的加热温度条件下在保护涂层的外侧的表面上形成氧化镁(MgO)。
按照本发明地以较少的量加入Al涂层的额外的合金成分的特征在于比保护涂层的主要成分Al更高的亲氧性。在已经存在这样少量的碱土金属或过渡金属的条件下,在保护涂层上产生薄的氧化层,该氧化层覆盖了位于其和钢基底之间的铝。
该薄层阻碍在对于扁钢产品的热成型而言必要的加热过程中铝与湿气的反应,该湿气存在于为了加热扁钢产品所使用的炉的气氛中。这样有效地防止了涂层的铝的氧化和与此伴随的氢的释放,释放的氢能扩散到涂层和扁钢产品的钢基底中。这令人意外地特别是适用于,当Al基涂层由于加热而局部变成熔液并撕开其表面时,从而熔液状的涂层材料与炉气氛接触。特别是在较长的退火持续时间的情况下,相对于常规设置有Al涂层的扁钢产品,在按照本发明的扁钢产品中表现出在由扁钢产品热成型的部件中更低的氢浓度。
为了制造按照本发明的扁钢产品,本发明提出了两种不同的途径。
按照本发明为了制造按照本发明的扁钢产品而优选的方法途径设置为,由此制造按照本发明的扁钢产品,即,准备以由钢制成的扁钢产品的形式的钢基底并为该钢基底涂覆一个基于Al的保护涂层,其中,钢具有0.1-3重量%的Mn和最高0.01重量%的B,特别是0.0005-0.01重量%的B,保护涂层含有0.1-0.5重量%的至少一种选自碱土金属或过渡金属组成的组的合金成分以及可选地含有总共最大20重量%的其他合金元素。还为该涂层过程提供热浸镀层,其中此处使用热浸镀层的熔池,按照本发明预设的额外的合金成分已经加合金到该熔池。
替代性地,按照本发明的扁钢产品也可以以这样的方法途径制造,其中,准备以由钢制成的扁钢产品的形式的钢基底,其中,钢具有0.1-3重量%的Mn和最高0.01重量%、特别是0.0005-0.01重量%的B并且剩余为以已知的方式用于调整其特性的其他合金成分,随后为该钢基底涂覆一个基于Al的保护涂层,其中,该保护涂层可选地含有其含量总共最大25重量%的其他合金元素,并且随后在获得的保护涂层上涂覆一个层,该层由至少一种选自碱土金属或过渡金属组成的组的合金成分而构成,其中,这样设定所涂覆的层的厚度,以使得额外的合金成分相对于保护涂层和涂覆的层的总重量的含量为0.1-0.5重量%。对此适合的层厚度通常在5-35μm、特别是10-25μm的范围内。在此,该方法变型的特征在于,其实现了施加具有所述额外的合金成分的这种层厚度,这些额外的合金成分可以以已知的方式有针对性地混合到涂层中,从而调整涂层的特殊性质。
在制造按照本发明的扁钢产品的过程中特别是可以设置为,选自碱土金属或过渡金属组成的组的、额外的合金成分通过Mg形成。
基于Al的保护涂层特别是可以经济地通过热浸镀层(专业术语中也称为“火镀”)而涂覆在钢基底上。
每一种已知的方法都适用于涂覆由按照本发明设置的额外的合金成分组成的层,通过这些方法实现了足够薄的层沉积在基于Al的涂层上。在此,这些方法包括已知的PVD(物理气相沉积)或CVD(化学气相沉积)方法。同样能够考虑的是,通过根据滚压包层的类型辊涂Al箔将附加层施加到钢基底上。
出于本发明的目的而在按照本发明的扁钢产品的保护涂层中额外设置的碱土金属首选是镁,其中替代性或补充性地也可以是钙、锶、钠或钡。
在过渡金属中可以使用例如Zr和Ti。这些过渡金属与存在于或渗透到Al基保护涂层中的氢形成金属类的氢化物,该氢化物的分解持续的时间显然比将扁钢产品加热至加热温度的时间更长(为了热成型而需将扁钢产品加热到该加热温度),从而该扁钢产品在相应的热成型开始时具有所要求的热成型温度。因此,为了达到在700-900℃范围内的热成型温度,与之相应地,加热温度实际上为至少700℃。
为了阻碍扁钢产品的氢吸收而按照本发明设置的额外的合金元素的总量应在0.1-0.5重量%的范围内。
试验已经显示,即使少量的至少一种根据本发明设置的额外的合金成分也足以用于本发明的目的。在此,尽可能少含量的按照本发明的额外的合金成分被证明是有利的,因为额外的合金成分的氧化快速结束,保护涂层的表面相应快速地钝化并且由于额外的合金成分没有过量的氢形成。
因此,根据本发明用于阻碍扁钢产品的吸收氢的额外的合金成分的含量优选限制为小于0.5重量%、特别小于0.45重量%或至多0.4重量%。这特别是在这样的背景下适用,即,在此试验已经表明,即使在高达0.35重量%的含量下仍实现了对于按照本发明的目的而言足够的良好效果。
当Al涂层作为热浸涂层而涂覆并且将按照本发明设置的量的额外的合金成分被合金化到熔池中时,除了理想地防止氢吸收之外,该添加还具有这样的优点,即,使由熔池中这些额外的合金成分的存在而引起的在熔池上产生大量熔渣的风险最小化。增加的熔渣形成可能损害涂层质量。
作为阻碍氢吸收特别适宜的额外的合金成分被证实为镁,其可以很好地合金化到此处谈及类型的Al保护涂层中。所加入的Mg的量理想地这样调整,即,使得保护涂层中存在至少0.1重量%且不超过0.5重量%的Mg,其中,由于上面已经阐述的原因,小于0.5重量%、特别是小于0.45重量%或最多0.4重量%或最多0.35重量%的Mg含量在实践中被证明特别有利于本发明的目的。
在本发明的Al涂层中为了按照本发明的目的钙可以作为额外的合金成分以0.01-0.5重量%的含量存在,其中,由于已经阐明的原因,最高0.02重量%的低Ca含量可能是有利的。
出于相同的原因,锶也可以以0.005-0.25重量%的含量作为额外的合金元素存在于按照本发明的保护涂层中。在此同样有利的是,将Sr的含量限制为最大0.15重量%、特别最大0.10重量%。
作为用于按照本发明的目的的额外的合金成分,钡可以以0.005-0.25重量%的含量加入按照本发明的保护涂层中,其中,出于已说明的原因,已经证明0.005-0.05重量%的Ba含量是特别有利的。
如果为了按照本发明的目的将锆和钛作为额外的合金元素添加到保护涂层中,这可以分别以0.15-0.7重量%的含量进行,其中,由于已经阐明的原因,最高0.5重量%、特别最高0.4重量%或最高0.35重量%的含量是特别有利的。
按照本发明的扁钢产品的保护涂层通常是AlSi涂层,其除了Al之外包含3-15重量%的Si。这种AlSi涂层的典型Si含量在9-12重量%的范围内,其中,实践中已知的标准化额定AlSi涂层含有10重量%。
除了或代替Si含量,在基于Al的保护涂层中还含有其他合金成分。特别是最大5重量%的Fe,其作为涂层中的杂质或者用于实现涂层在扁钢产品的钢基底上的理想的连接而加入。涂层中杂质的含量可以为最大0.5重量%。
如上所述地,按照本发明设置的额外的合金成分最晚在扁钢产品的加热过程中通过加载在炉气氛中的水在保护涂层的表面上形成薄氧化层,其阻碍了氢向钢基底中的渗入并阻碍了进一步释放氢气的保护涂层的铝氧化。在由按照本发明的扁钢产品热成型的钢部件中,该层的厚度仅为最大200nm厚,其中,在实际中,最大100nm的层厚度被证实是足够的。
按照本发明的钢部件可以由此制成,即,按照本发明的扁钢产品以上述方式制成,随后将扁钢产品加热至热成型温度,其中,该加热在环境气氛的条件下或在减少H2O的气氛条件下进行,并最后将加热的扁钢产品热成型为钢部件。
该热成型在此可以以已知的方式这样实施,即,使热成型温度这样高,以使得钢基底的组织结构是奥氏体的,并且扁钢产品在成型(两个阶段的过程)之后或在成型过程中、即在成型工具中(一个阶段的过程)淬火,从而在扁钢产品的钢基底的组织结构中形成硬化组织结构。
附图说明
随后,借助实施例进一步说明本发明。附图中:
图1以示意图示出了存在于按照本发明的钢部件上的保护涂层的层结构;
图2示出了一个图表,该图表反映了在热浸镀层之后但在热压淬火之前按照本发明的扁钢产品的近表面层的GDOES测量的结果;
图3示出了一个图表,该图表再次反映了在热压淬火之后按照本发明的扁钢产品的近表面层的GDOES测量的结果;
图4示出了一个图表,其中相互比较了设置有常规的AlSi保护涂层和设置有按照本发明的保护涂层的扁钢产品的经过不同的退火持续时间而出现的氢吸收。
具体实施方式
针对为了证实本发明的作用而实施的试验使用了由MnB钢组成的钢板组成的四个样品E1、E2、E3、V,这些样品的组成在表1中说明。
C | Si | Mn | P | S | Al | Ti | Cr+Mo | B |
0.22 | 0.25 | 1.16 | 0.014 | 0.002 | 0.038 | 0.023 | 0.21 | 0.0026 |
剩余铁和不可避免的杂质,以重量%计。
表1
在该时间点上不含氢的样品E1、E2、E3和V分别通过热浸镀层而设置有AlSi保护涂层,其组成在表2中说明。
样品 | Si | Mg | Fe |
E1 | 10 | 0.4 | 最高3 |
E2 | 10 | 0.3 | 最高3 |
E3 | 10 | 0.05 | 最高3 |
V | 10 | - | 最高3 |
剩余铁和不可避免的杂质,以重量%计。
表2
保护涂层的最小涂覆重量分别为120g/m2。
这样设置有保护涂层的扁钢产品样品E1、E2、E3、V分别在炉中连续经过360s、600s或者800s的退火持续时间GD(参见图4)在标准化气氛(其露点为14.0℃)的条件下加热至900℃。随后将这些样品在4-6秒的转移时间内转移到热压成型工具中并在此热成型成为一个部件。在热成型的过程中,各个样品快速地冷却,以使得在它们的钢基底的组织结构中产生硬化组织结构。
如在图1中示意性示出的,在按照本发明的样品E1、E2、E3中,在退火处理的过程中产生在邻接保护涂层S的表面O的薄MgO层“M”,其除了MgO之外还含有Al2O3,其中这些样品位于钢基底“S”上的、包括FeAl(Si)化合物的保护涂层“C”分别含有Mg作为额外的合金成分。层M使位于其下方的、包括FeAl(Si)化合物的AlSi层“A”相对于潮湿的炉气氛“P”得到隔离并且这样防止了层A的铝的过度氧化。
对于样品E1在图2中示出了在热浸镀层之后和热压淬火之前保护涂层的GDOES分析的结果,并且在图3中示出了热压淬火之后保护涂层的GDOES分析结果。还表明,在热压淬火之前和之后,在AlSi涂层上存在薄Mg层。
图2和图3的比较显示,在压硬化之前镁组分基本上均匀地分布在层内(图2),而相反地在压硬化之后聚集在近表面的层中(图3)。
以这种方式由样品E1,E2,E3和V制成的钢部件中,确定氢含量Hdiff,该氢含量是指在热处理过程中扩散到钢基底中的氢。
图4中比较了对于不同时长退火的样品E1,E2,E3和V的测试结果。已显示,按照本发明的保护涂层即使当Mg仅以非常小的量存在于保护涂层中时也产生氢吸收的决定性的降低。
Claims (14)
1.一种用于热成型的扁钢产品,所述扁钢产品由钢基底和涂覆在所述钢基底上的、基于Al的保护涂层而组成,所述钢基底由具有0.1-3重量%的Mn和最高0.01重量%的B的钢制成,所述保护涂层可选地含有总共最大20重量%的其他合金元素,其特征在于,所述保护涂层含有总共0.1-0.5重量%的至少一种的碱土金属或过渡金属作为额外的合金成分,其中,在所述扁钢产品的热成型过程中在所述保护涂层的外侧的表面上形成一种碱土金属或过渡金属的氧化物。
2.根据权利要求1所述的扁钢产品,其特征在于,所述保护涂层含有总共0.1-0.5重量%的Mg作为额外的合金成分,其中,在所述扁钢产品的热成型之后在至少700℃的加热温度条件下在所述保护涂层的外侧的表面上形成氧化镁(MgO)。
3.根据权利要求1所述的扁钢产品,其特征在于,所述保护涂层是具有3-15重量%的Si含量的AlSi涂层。
4.根据上述权利要求中任意一项所述的扁钢产品,其特征在于,所述保护涂层含有最大5重量%的Fe。
5.根据权利要求2至4中任意一项所述的扁钢产品,其特征在于,所述保护涂层的Mg含量为最大0.4重量%。
6.根据上述权利要求中任意一项所述的扁钢产品,其特征在于,所述保护涂层通过热浸镀层而涂覆。
7.一种钢部件,其通过根据上述权利要求中任意一项所述的扁钢产品的热成型而制成。
8.根据权利要求7所述的钢部件,其特征在于,在形成所述保护涂层相对于周围环境封闭的层中存在额外的合金成分,所述层具有最大200nm的厚度。
9.一种用于制造根据权利要求1至8中任意一项所述的扁钢产品的方法,其包括以下的操作步骤:
-提供一种以由钢制成的扁钢产品形式的钢基底,所述钢具有0.1-3重量%的Mn和最高0.01重量%的B;
-对所述钢基底涂覆基于Al的保护涂层,所述保护涂层含有0.1-0.5重量%的至少一种从碱土金属或过渡金属的组中选出的合金成分以及可选地含有总共最大20重量%的其他的合金成分。
10.根据权利要求9所述的方法,其特征在于,至少一种从碱土金属或过渡金属的组中选出的合金成分通过Mg形成。
11.根据权利要求10所述的方法,其特征在于,所述保护涂层通过热浸镀层涂覆在所述钢基底上。
12.一种用于制造根据权利要求7或8所述的钢部件的方法,其包括以下的操作步骤:
-通过使用根据权利要求10或11所述的方法制造扁钢产品;
-将所述扁钢产品加热至用于热成型的加热温度,其中,所述加热在环境气氛的条件下或在减少H2O的气氛条件下进行;
-将所述扁钢产品热成型为所述钢部件。
13.根据权利要求12所述的方法,其特征在于,所述加热温度这样高,以使得所述扁钢产品在所述成型开始时具有热成型温度,在所述热成型温度下,所述钢基底的组织结构是奥氏体的,并且所述扁钢产品在成型之后或在成型过程中淬火,从而在所述扁钢产品的钢基底的组织结构中形成硬化组织结构。
14.根据权利要求13所述的方法,其特征在于,所述加热温度为至少700℃。
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KR20170048542A (ko) | 2017-05-08 |
ES2804776T3 (es) | 2021-02-09 |
WO2016034476A1 (de) | 2016-03-10 |
PL3189174T3 (pl) | 2020-11-16 |
US20170260601A1 (en) | 2017-09-14 |
PL2993248T3 (pl) | 2020-11-30 |
MX2017002797A (es) | 2017-06-15 |
EP3189174A1 (de) | 2017-07-12 |
ES2813870T3 (es) | 2021-03-25 |
BR112017004225A2 (pt) | 2017-12-05 |
EP2993248A1 (de) | 2016-03-09 |
JP2017536472A (ja) | 2017-12-07 |
CN106795613B (zh) | 2019-12-17 |
US10669603B2 (en) | 2020-06-02 |
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