WO2015099354A1 - 마그네슘-알루미늄 코팅 강판 및 그 제조 방법 - Google Patents
마그네슘-알루미늄 코팅 강판 및 그 제조 방법 Download PDFInfo
- Publication number
- WO2015099354A1 WO2015099354A1 PCT/KR2014/012489 KR2014012489W WO2015099354A1 WO 2015099354 A1 WO2015099354 A1 WO 2015099354A1 KR 2014012489 W KR2014012489 W KR 2014012489W WO 2015099354 A1 WO2015099354 A1 WO 2015099354A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- magnesium
- aluminum alloy
- steel sheet
- layer
- coating layer
- Prior art date
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- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 129
- 239000010959 steel Substances 0.000 title claims abstract description 129
- 238000004519 manufacturing process Methods 0.000 title description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 205
- 239000010410 layer Substances 0.000 claims abstract description 186
- 239000011247 coating layer Substances 0.000 claims abstract description 114
- 239000011777 magnesium Substances 0.000 claims abstract description 89
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 35
- 229910052782 aluminium Inorganic materials 0.000 claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001771 vacuum deposition Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 21
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 description 56
- 229910045601 alloy Inorganic materials 0.000 description 51
- 239000000956 alloy Substances 0.000 description 51
- 238000001704 evaporation Methods 0.000 description 28
- 230000008020 evaporation Effects 0.000 description 28
- 238000000151 deposition Methods 0.000 description 20
- 230000008021 deposition Effects 0.000 description 15
- 229910003023 Mg-Al Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000010960 cold rolled steel Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 238000010884 ion-beam technique Methods 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229910000905 alloy phase Inorganic materials 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910018084 Al-Fe Inorganic materials 0.000 description 5
- 229910018192 Al—Fe Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910015372 FeAl Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 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
- 238000009713 electroplating Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical group [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
-
- 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
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—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
- C22C38/04—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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/027—Graded interfaces
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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
-
- 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
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
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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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12729—Group IIA metal-base component
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- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the present invention relates to a magnesium-aluminum coated steel sheet and a method for producing such a steel sheet, and more particularly, to a steel sheet formed with a magnesium-aluminum coating layer in order to prevent corrosion of the steel sheet by galvanic coupling, and a method for producing such a steel sheet.
- a magnesium-aluminum coated steel sheet and a method for producing such a steel sheet, and more particularly, to a steel sheet formed with a magnesium-aluminum coating layer in order to prevent corrosion of the steel sheet by galvanic coupling, and a method for producing such a steel sheet.
- Steel has excellent physical properties and is used in various industries such as automobiles, home appliances, and construction. However, since steel is likely to cause corrosion by reacting with oxygen, it is necessary to apply a protective film to prevent such corrosion.
- These steels are processed in various forms such as plates, rods, tubes, etc.
- the thin steel sheet is one of the most commonly used forms of steel products in the industrial field.
- the protective film acts as a sacrificial anode to delay the corrosion of the steel sheet by coating a metal protective film having high reaction resistance with oxygen on the surface of the steel sheet.
- Representative metals used in the coating of such steel sheets are zinc and
- Aluminum, and the method used for coating this metal on a steel plate includes hot-dip plating, electroplating, and the like. Since the plating method is easy and inexpensive, it is currently used in most steel plate surface treatment processes.
- a method of increasing the plating amount of zinc may be considered in order to improve the corrosion resistance of the steel sheet.
- a method of lowering the plating rate is used, which causes a problem of lowering productivity.
- heterogeneous elements are not increased without increasing the zinc plating amount. Adding a method to improve the corrosion resistance of the existing galvanized steel sheet has been developed.
- Such hetero elements include aluminum and magnesium.
- Magnesium-aluminum coating layer which is a metal used to prevent corrosion of the steel plate, forms a coating layer of magnesium-aluminum using aluminum having excellent appearance characteristics and magnesium having excellent sacrificial anticorrosive properties, but gives a concentration gradient to the total magnesium content.
- An object of the present invention is to provide a steel sheet on which a steel sheet is formed and a method of manufacturing such steel sheet.
- the lower concentration may be used as the sacrificial anode due to the concentration gradient of magnesium formed in the coating layer.
- a first magnesium-aluminum alloy layer formed on an upper portion of the steel sheet
- It includes a coating layer formed of a second magnet-aluminum alloy layer formed on the first magnesium-aluminum alloy layer,
- the magnesium content of the first magnesium-aluminum alloy layer is higher than the magnesium content of the second magnesium-aluminum alloy layer.
- a steel plate on which a magnet-aluminum alloy coating layer is formed.
- the magnesium content of the first magnesium-aluminum alloy layer is
- magnesium content of the said 2nd magnesium-aluminum alloy layer is 5-40 increase%.
- the total magnesium content of the coating layer formed by the first magnesium-aluminum filler and the second magnesium-aluminum alloy layer is preferably 12.5% by weight or more.
- the thickness of the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer is preferably 0.5 to 30 kPa, respectively, and the first magnet-aluminum
- the total thickness of the coating layer formed on the steel sheet by the alloy layer and the second magnesium-aluminum alloy layer is more preferably 1 to 50 ⁇ .
- the total thickness of the coating layer formed on the steel sheet by the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer is even more preferably 5 / or less.
- ⁇ -phase and ⁇ -phase are mixed in the coating layer.
- the coating layer is any one part or the whole of the coating layer is formed in the crystal grain shape, the crystal grains of the coating layer is ⁇ phase and ⁇ phase (Al 3 Mg 2 ) respectively
- the area ratio of the ⁇ phase / ⁇ phase of the coating layer crystal grains is 10 to 70%, and the ⁇ phase and the ⁇ phase of the coating layer preferably have an XRD intensity ratio ⁇ (880) / ⁇ (1 1 1) of 0.01 to 1.5. .
- ⁇ (880) / ⁇ (1 1 1) 0.01 to 1.5.
- the magnesium content of the first magnesium aluminum alloy layer is higher than the magnesium content of the second magnesium aluminum alloy layer.
- Method j for forming a magnesium-aluminum alloy coating layer wherein the total magnesium content of the first magnesium-aluminum alloy layer is 20 to 95% by weight, the second magnesium-aluminum The total magnesium content of the alloy layer is preferably 5-40% by weight.
- the total magnesium content of the coating layer formed by the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer is 12.5% by weight or more. desirable.
- the first magnesium-aluminum alloy layer vacuum-deposited on the steel sheet has an iron contained in the first magnesium-aluminum alloy layer reacted with iron on the steel sheet by diffusion, and the iron-based alloy layer on the first magnesium-aluminum alloy layer. Vacuum deposition to a thickness capable of forming an aluminum alloy layer
- a method of forming a magnesium-aluminum alloy coating layer on a steel sheet is provided.
- the thicknesses of the first and second magnesium-aluminum alloy layers are preferably 0.5 to 30, respectively.
- the total thickness of the coating layer formed on the steel sheet by the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer is preferably 1 to 50.
- the total thickness of the coating layer formed on the steel sheet by the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer is more preferably 5 or less.
- the first and second magnesium-aluminum alloy layers are preferably vacuum deposited by magnetron sputtering.
- the first and second magnesium-aluminum alloy layers are vacuum-deposited by repeatedly reciprocating or rotating the magnesium-aluminum alloy source or the aluminum source or the steel plate disposed on the magnesium source.
- the first and second magnesium-aluminum alloy layers preferably change the magnesium content in the first and second magnesium-aluminum alloy layers by changing the current or voltage applied to the source.
- the method of forming a magnesium-aluminum alloy coating layer on a steel sheet is a method of phase transformation of the structure of the coating layer by heat-treating the steel sheet formed with the first and second magnesium-aluminum alloy coating layer in a heat treatment furnace It includes more. '
- the heat treatment is performed for 2 to 10 minutes at 350 600 ° C in an inert atmosphere. It is preferable to carry out.
- the first and second magnesium-aluminum alloy coating layers form at least one of an iron-aluminum alloy layer and a magnet-aluminum alloy layer.
- first and second magnesium-aluminum alloy coating layers form at least one of ⁇ phase or ⁇ phase (Al 3 Mg 2 ) by the heat treatment.
- the steel sheet having a magnesium-aluminum alloy coating layer having a magnesium concentration gradient may have the same or more corrosion resistance while having a thickness thinner than that of a galvanized layer of a conventional galvanized steel sheet, and at the same time a colorful color and Can exhibit aesthetics
- a steel sheet having a magnesium-aluminum alloy coating layer having a magnesium concentration gradient according to an embodiment of the present invention is sacrificed by galvanically coupling two magnesium-aluminum alloy layers having a magnesium concentration gradient by using a potential difference between the alloy layers. Because of the anticorrosion method, a steel sheet excellent in corrosion resistance can be provided.
- a steel sheet having a magnesium-aluminum alloy coating layer having a magnesium concentration gradient simultaneously contains aluminum having excellent surface color characteristics, thereby providing a steel sheet having a beautiful surface with excellent corrosion resistance. can do.
- the steel sheet provided with a magnesium-aluminum alloy coating layer formed with a magnesium concentration gradient may further provide a steel sheet which improves corrosion resistance characteristics by heat treatment and simultaneously maintains an elegant surface.
- FIG. 1 is a schematic diagram of a vacuum coating equipment used to deposit a magnesium-aluminum alloy layer used in an embodiment according to the present invention on a steel sheet.
- FIG. 2 is a schematic diagram of a vacuum coating equipment for depositing pure magnesium and pure aluminum on a two-layer magnesium-aluminum alloy layer substrate 14 as a deposition source, which is another embodiment of the present invention.
- 3A is a schematic diagram showing the first coating layer 22 and the second coating layer 23 deposited on the cold rolled steel sheet 21 according to Examples 1 and 3 of the present invention.
- 3B is a schematic diagram showing the results of heat treatment according to Examples 2 and 4 of the present invention.
- Example 4A is a scanning electron micrograph of Example 1 of the present invention.
- Example 4b is a scanning electron micrograph of Example 2 of the present invention.
- Example 5 is a graph evaluating corrosion resistance of each Example and Comparative Example according to the present invention.
- a magnesium-aluminum alloy layer having a different magnesium content is deposited in multiple layers on the upper portion of the steel sheet.
- the concentration of magnesium at is formed higher than the magnesium content in another magnet-aluminum alloy layer relatively far from the steel sheet.
- the multilayer magnesium-aluminum alloy layer thus formed is formed on the steel sheet.
- Forming a single coating layer as a whole and by heat-treating this coating layer can further increase the corrosion resistance characteristics by the phase transformation of the crystal structure of the coating.
- the magnesium-aluminum alloy layer of the multiple layers deposited on the steel sheet has galvanic coupling of the alloy layer itself by varying the magnesium content in each alloy layer, so that the outer alloy layer acts as a sacrificial layer. .
- the magnesium-aluminum alloy coating layer includes aluminum, although the regenerated anticorrosive property is weak aluminum, but this sacrificial anticorrosive property enhances the role of magnesium, and the surface color of the aluminum itself is brilliant. Make it work.
- the magnesium-aluminum alloy layer to be deposited may be deposited in multiple layers, but for the convenience of description, the deposition in two layers will be described in detail.
- magnesium is first deposited on the steel sheet-aluminum alloy layer has a magnesium content contained in the alloy layer is preferably from 20 to 95 increased 0/0.
- the reason for limiting the magnesium content in the first alloy layer is that when the magnesium content is 20wt% or less, the sacrificial anticorrosive property is lowered, and when the magnesium content is 95wt% or more, the effect of improving the characteristics by alloying disappears.
- the magnesium content in the second magnesium-aluminum alloy layer deposited on the first alloy layer is preferably 5 to 40% by weight.
- the reason for limiting the magnesium content in the second alloy layer as described above is that when the magnesium content is 5 wt% or less, the effect of alloying improves, and when the wt% or more is 40 wt% or more, the durability of the coating surface is reduced.
- the total magnesium content in the coating layer formed by the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer is preferably 12.5 increase of 0 / ° or more.
- the reason for limiting the content in the entire coating layer as described above is that the sacrificial anticorrosive properties of the coating layer are deteriorated when the total magnesium content is 12.5 increase 0 / ° or less.
- first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer preferably have a thickness of 0.5 to 30, respectively. This is because when the thickness of the coating layer is 0.5 or less, the corrosion resistance is not sufficient, and when the thickness of the coating layer is 30 or more, problems such as peeling due to increased stress occur.
- the total thickness of the coating layer formed on the steel sheet by the first magnesium-aluminum alloy layer and the second magnesium-3 ⁇ 4 aluminum alloy layer is preferably 1 to 50, and more preferably 5 or less.
- FIG. 1 shows a schematic diagram of a vacuum coating equipment used to deposit a magnesium-aluminum alloy layer onto a steel sheet.
- a vacuum coating method can be used.
- This vacuum coating method has a high process cost compared to the conventional plating method, but can be competitive in productivity because it can quickly produce a thin coating layer.
- a cold rolled steel sheet may be used as a substrate on which a multilayer of a magnesium-aluminum alloy is coated according to an embodiment of the present invention.
- the cold-rolled steel sheet is preferably a carbon content of 0.3 wt. 0 /. Or less preferably a low carbon steel of, and used as automobile steel sheet or steel sheet or building material steel sheet for household appliances for automobiles.
- a plasma vacuum deposition method may be used to form a multilayer of magnesium-aluminum alloy.
- the deposition source used is a magnesium-aluminum alloy and these deposition sources may be provided in plural.
- a plurality of magnesium-aluminum alloy deposition sources that is, a source, are simultaneously mounted in a deposition apparatus and operated by applying a current or a voltage to reciprocate or electrophorically move a sputtered source on a sputtered source. Form a coating layer.
- Each of the second alloy evaporators 6 is provided, and a substrate holder 3 for mounting and transporting a steel plate, that is, a substrate 4, is provided above the vacuum chamber 1.
- the substrate holder 3 for mounting and transporting a steel plate, that is, a substrate 4, is provided above the vacuum chamber 1.
- the substrate transfer guide (2) can be moved to the prisoner. And a linear ion beam source 9 can be mounted on the side of the vacuum chamber 1 to clean the substrate 4.
- the first alloy evaporator (5) forming a magnesium-aluminum alloy vapor
- the second alloy evaporation source (6) is equipped with magnet-aluminum alloy targets (7,8) having different component contents from each other so that the alloy vapor generated from this target is coated on the substrate.
- substrate 4 using the above vacuum deposition equipment is as follows.
- a crab alloy target 7 and a second alloy target 8 are installed in the first alloy evaporator 5 and the second alloy evaporator 6, respectively, and the substrate 4 is attached to the substrate holder 3.
- the substrate 4 is placed on the first alloy evaporator 5, and then evacuated using a vacuum pump (not shown) so that the degree of vacuum is 10 -5 Torr or less.
- the substrate 4 is cleaned using the linear ion beam source 9, and then a plasma is generated in the first alloy evaporation source 5 to coat the substrate 4 with the lower layer first.
- the substrate 4 is positioned on the second alloy evaporation source 6, and then a plasma is generated in the second alloy source 6 to coat the second layer film.
- the magnesium-aluminum alloy is used as the deposition source used to deposit the coating layer of the magnesium-aluminum alloy, but the present invention is not limited thereto.
- a magnesium-aluminum alloy layer can be deposited on the substrate (1).
- a method of depositing two layers of magnesium-aluminum alloy layers on the substrate 14 using pure magnesium and pure aluminum as a deposition source is as follows.
- an aluminum target 17 having a purity of 99.995% was mounted on the aluminum evaporation source 15, and a magnesium target 18 having a purity of 99.99% was mounted on the magnesium evaporation source 16, and two evaporation sources were installed in close proximity to each other.
- a substrate 14 made of a cold rolled steel sheet was installed in the substrate holder 13, and then evacuated.
- the vacuum is less than 10 -5 Torr, the substrate 14 is placed over the linear ion beam source 19 for cleaning of the substrate 14, and then the linear ion beam source 19 is used to Impurities and oxide films are removed.
- Cleanliness of the substrate 14 is controlled by ion beams in an argon gas atmosphere.
- the substrate 14 may be moved to the left or right using the substrate transfer guide 12.
- the substrate transfer guide 12 is used to position the substrate 14 over two evaporation sources installed side by side, while applying power to the aluminum evaporation source 15 and simultaneously to the magnesium evaporation source 16. By applying electric power, two evaporation sources are simultaneously generated to coat the underlying magnesium-aluminum alloy worms on the substrate 14.
- the substrate 14 can be alternately coated left and right on the two evaporation sources to be coated with aluminum and magnesium alternately to control the magnesium content in the magnesium-aluminum alloy layer.
- the vacuum heat treatment furnace may be a heat treatment furnace formed by continuously connecting the preheating furnace, the heat treatment furnace and the crack furnace. At this time, the preheating furnace, the heat treatment furnace, and the cracking furnace have a barrier to block the space of each furnace at each connection part and a steel sheet is used for the barrier. It is preferred that a door is formed for movement.
- Such a heat treatment furnace may evacuate in a vacuum state and then supply a noble gas such as nitrogen gas to the atmosphere gas.
- the steel sheet formed with the magnesium-aluminum alloy coating layer is first charged into a preheating furnace, and then the steel sheet is heated to a heat treatment silver and moved to a heat treatment furnace in a state where the temperature is stabilized to perform heat treatment.
- Heat treatment of the steel sheet on which the alloy coating layer is formed is preferably performed at 350 to 600 ° C. for 2 to 10 minutes.
- bun stress increases in the coating layer-heat-treated when magnesium performed in less than two minutes or less 350 ° C - failure to the respective components diffusion in the aluminum alloy layer cheungbun magnesium Due to this, the coating layer may peel off.
- This heat treatment is preferably carried out at 350 ° C for 10 minutes or 400 ° C for 4 minutes.
- the iron component of the steel sheet diffuses into the coating layer at the interface between the steel sheet and the coating layer to form an AbcFey layer, and in the magnesium-aluminum alloy coating layer, the phase changes to a magnesium-aluminum alloy layer.
- x is preferably 1 to 3 and y is preferably 0.5 to 1.5, and the thickness of the AlxFey layer is preferably 0.2 to 1 ⁇ .
- the xy value is in a range that shows brittleness in Al-Fe alloy phase due to diffusion so that alloy phases having poor mechanical properties (eg FeAl 2 , Fe 2 Al 5 , FeAl 3, etc.) are not produced.
- alloy phases having poor mechanical properties eg FeAl 2 , Fe 2 Al 5 , FeAl 3, etc.
- Al-Fe phases for example, Fe 3 Al, FeAl, etc.
- X to 1 to 3 and y to 0.5 to 1.5 are limited to this range because they improve the adhesion between the steel sheet and the magnesium-aluminum alloy layer.
- the layer thickness of the Al-Fe alloy phase is limited to 0.2 to 1, and as the thickness of the Al-Fe layer is increased, A1 is relatively limited, and the Fe content is increased, resulting in brittle Al-Fe alloy phase. This is because the mechanical properties of the coating layer can be reduced.
- the AlxFey layer formed on the interface between the steel sheet and the coating layer is an aluminum-iron alloy layer containing a small amount of magnesium and the AlxFey layer is in the direction of the coating layer in the steel sheet It is preferable that it consists of 1-50% of the thickness of a magnesium-aluminum coating layer.
- AlxFey layer is limited to 1 to 50% of the coating thickness is that if the AkFey layer is formed to be more than 50% of the thickness of the coating layer, the Fe content may increase and an alloy phase having poor mechanical properties may be generated.
- the magnesium-aluminum alloy layer phase-changed by heat treatment is in a state in which ⁇ and ⁇ phases are common.
- the a phase means the aluminum phase of the face centered cubic lattice (FCC)
- the ⁇ phase means Al 3 Mg 2 of the face centered cubic lattice.
- the ratio of ⁇ and ⁇ phases is 0.01 to 1.5 as XRD intensity ratio, ⁇ (880) / ⁇ (11 1).
- the ratio of ⁇ and ⁇ phases in the magnesium-aluminum alloy layer is set to 0.01 to 1.5 as ( ⁇ / ⁇ ) in the Mg-Al alloy phase ( ⁇ phase) generated according to the Mg content when the Mg-Al coating layer is heat treated. This is to limit the Mg content in which the ⁇ phase is generated because the XD peak intensity is different. .
- the magnesium-aluminum alloy layer phase-changed by heat treatment forms grains such as columnar crystals, and such crystal grains are preferably 0.2 to 1 urn.
- the size of the crystal grains is limited to 0.2-1, which is not easy to form under the control of heat treatment conditions when the crystal grain size of the Mg-Al alloy layer is 0.2 or less. This is because separation occurs in layers, which is undesirable.
- the crystal grains of the magnesium-aluminum alloy layer thus formed have an area ratio of 10 to 70% of the ⁇ phase / ⁇ phase.
- the area ratio of the ⁇ phase / ⁇ phase in the crystal grains of the magnesium-aluminum alloy is the area ratio of the ⁇ phase / ⁇ phase in the crystal grains of the magnesium-aluminum alloy
- the reason for limiting the content to 10 to 70% is not preferable because the Mg-Al alloy phase ( ⁇ phase) is not formed when out of this range.
- the steel sheets used in Examples and Comparative Examples to be described below are all C; 0.12 weight 0 / ⁇ or less (except 0%), ⁇ : 0.50 increment% or less (except 0%), ⁇ ; 0.04 weight% (except 0%) and S; A steel sheet containing 0.040 weight 0 / ° (except 0%) and the balance Fe and other unavoidable impurities and rolled to a thickness of 0.8 mm through hot and cold rolling was used.
- a thin steel sheet having a width of 300 mm and a thickness of 0.8 mm was used as the substrate 4.
- the 20% increase in the magnesium alloy first evaporation source (5) is an aluminum weight of 80 0/0,
- the second alloy evaporation source 6 was provided with a second alloy target 8 having 5 wt% magnesium and 95 wt% aluminum.
- the exhaust vacuum within the vacuum chamber (1) to remove impurities and oxide films which vacuum is present in the substrate (4) using the following linear ion source pan (9) is 10-5. Torr or less.
- the cleaning of the substrate 4 was carried out four times, while adjusting the conditions of the ion beam to 3 kV and 400 mA in an argon gas atmosphere of 5 ⁇ 10 -4 Torr and moving the substrate 4 to the left and right using the substrate transfer guide 2. ⁇ during
- Example 2 a specimen in which the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer were successively deposited on a cold rolled steel sheet according to Example 1 was charged into a heat treatment furnace, and then, in a 400 ° C. atmosphere under a nitrogen atmosphere, Heat treatment was performed for minutes.
- Example 3 the first magnesium-aluminum alloy layer and the second magnesium-aluminum alloy layer were sequentially increased by using the deposition apparatus described in FIG.
- the deposition source used here was not a magnesium-aluminum alloy but a single metal target of aluminum and magnesium.
- the aluminum metal used as the aluminum evaporation source is 99.995% purity
- Magnesium metal used as a magnesium evaporation source has a purity of 99.99%.
- Such aluminum and magnesium were mounted with aluminum targets 17 and magnesium targets 18, respectively, and these targets were placed adjacent to each other.
- the inside of the vacuum chamber 1 was evacuated in the state in which the board
- the degree of vacuum to remove impurities and oxide films present on the substrate 14 by operating the linear ion beam source (19) for cleaning of the substrate 14 in a state that is reached in less than 10-5 torr.
- the cleaning of the substrate 14 is performed by adjusting the conditions of the ion beam to 3 kV and 400 mA in an argon gas atmosphere of 5 ⁇ 10 ⁇ 4 Torr, and moving the substrate 14 from side to side using the substrate transfer guide 12. Conducted for a time.
- the substrate 14 is placed on two evaporation sources installed side by side using the substrate transfer guide 12 in the state where the substrate 14 is cleaned. Then, 8 kW of power is applied to the aluminum evaporation source 15. A power of 3 kW was applied to the magnesium evaporation source 16 to generate two plasma sources at the same time to deposit a first magnesium-aluminum alloy layer film on the substrate 14.
- the substrate 14 was alternately coated on both evaporation sources while moving left and right, and the magnesium content of the first magnesium-aluminum alloy layer was controlled to be 40wt%. At this time, the film thickness of the first magnesium-aluminum alloy layer was 2.5 kPa.
- the first magnesium-aluminum alloy layer was deposited on the substrate 14, and then the second magnesium-aluminum alloy layer was continuously deposited.
- the deposition conditions of the second magnesium-aluminum alloy layer lowered the power of the magnesium evaporation source 16 to lkW so that the magnesium content of the second magnesium-aluminum alloy layer was reduced.
- the amount was adjusted to 10 wt%.
- the film thickness of the second magnet-aluminum alloy layer was 2.5 // m.
- Example 4 comprises a first magnesium-aluminum alloy layer on a cold rolled steel sheet according to Example 3 A specimen in which 2 magnesium-aluminum alloy layers were continuously deposited was charged into a heat treatment furnace, and then heat treated for 10 minutes in a 400 ° C. atmosphere under a nitrogen atmosphere.
- Example 3 in the same manner as the substrate 14 to the aluminum remaining conditions other than vacuum evaporation point such that only a thickness of 5 (100 parts by weight 0/0) was carried out in the same manner as in Example 3.
- Comparative Example 2 pure zinc was coated on the cold rolled steel sheets used in Examples 1 to 4 by a conventional electroplating method to a thickness of 5.6? 1.
- Example 3 a magnesium-aluminum alloy layer was deposited on a cold rolled steel sheet in the same manner as in Example 1, but without a concentration gradient of magnesium, that is, without forming the first and second magnesium-aluminum alloy layers, one layer of magnet -The remaining conditions were carried out in the same manner as in Example 1 except that the aluminum alloy layer was vacuum deposited on the cold rolled steel sheet to have a thickness of 5 ⁇ .
- FIG. 3A is a schematic diagram showing the first coating layer 22 and the low second coating layer 23 deposited on the cold rolled steel sheet 21 according to the first and third embodiments described above.
- 3B is a schematic diagram showing the results of heat treatment according to the second and fourth embodiments described above.
- the first Mg-Al alloy layer 22 and the second Mg-Al alloy layer 23 deposited on the steel sheet are formed of the lower layer and the upper layer. It is characterized by a clear interface.
- the so-called magnesium concentration gradient gradually increases from the top to the bottom (tilt).
- the layer 24 is formed.
- FIG. 4A is a scanning electron micrograph of Example 1, in which two alloy layers are clearly formed on the steel plate 30.
- reference numeral 31 denotes the first Mg-Al alloy layer
- reference numeral 32 denotes the second Mg-Al alloy layer.
- the first Mg-Al alloy layer 31 is in a state in which crystal growth is not obvious and the structure is dense.
- the second Mg-Al alloy layer 32 the columnar crystal structure is developed. It can be seen.
- This phenomenon is because the crystal growth structure depends on the magnesium content in the alloy deposition layer.
- Figure 4b is a scanning electron micrograph of Example 2 shows the shape of the alloy layer 41 deposited on the steel sheet 40, the boundary of the two alloy layers are diluted and combined into one by heat treatment. This phenomenon is judged that the first and second Mg-Al alloy layers on the steel sheet 40 are diffused into each other by the heat treatment process, and then aggregated into one. The upper portion of the combined coating layer 41 forms a so-called concentration gradient (tilt) layer in which the magnesium content is small and the magnesium content increases toward the substrate.
- concentration gradient tilt
- Figure 5 is a graph evaluating the corrosion resistance for each of the specimens according to Examples 1 to 4 and Comparative Examples 1 to 3.
- the corrosion resistance was evaluated using the salt spray test (ASTM B-117) and evaluated based on the initial red blue development time.
- the occurrence time is more than 400 hours, exhibiting excellent corrosion resistance.
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DE112014005865.3T DE112014005865T5 (de) | 2013-12-24 | 2014-12-17 | Magnesium-Aluminium-beschichtetes Stahlblech und dessen Herstellungsverfahren |
US15/108,260 US10106866B2 (en) | 2013-12-24 | 2014-12-17 | Magnesium-aluminum coated steel sheet |
CN201480065205.6A CN105793463B (zh) | 2013-12-24 | 2014-12-17 | 镁铝涂层钢板及其制造方法 |
JP2016538023A JP6295329B2 (ja) | 2013-12-24 | 2014-12-17 | マグネシウム−アルミニウムコーティング鋼板およびその製造方法 |
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KR101696046B1 (ko) * | 2014-12-23 | 2017-01-13 | 주식회사 포스코 | 밀착성이 우수한 도금 강판 및 그 제조 방법 |
US10577686B2 (en) * | 2017-06-09 | 2020-03-03 | The Boeing Company | Corrosion resistant and low embrittlement aluminum alloy coatings on steel by magnetron sputtering |
WO2019024021A1 (zh) * | 2017-08-02 | 2019-02-07 | 深圳市柔宇科技有限公司 | 成膜设备及成膜方法 |
KR102043782B1 (ko) * | 2017-12-26 | 2019-11-12 | 주식회사 포스코 | 방향성 전기강판 및 방향성 전기강판의 제조방법 |
EP3901328A4 (en) | 2018-12-18 | 2021-10-27 | Posco | ALLOY COATED STEEL SHEET AND ITS MANUFACTURING PROCESS |
US11661665B2 (en) * | 2020-04-30 | 2023-05-30 | The Boeing Company | Aluminum and aluminum alloy electroplated coatings |
CN112663008B (zh) * | 2020-11-30 | 2022-12-23 | 江苏理工学院 | 一种利用射频磁控制备镁铝复合板的方法 |
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CN105793463A (zh) | 2016-07-20 |
US20160326607A1 (en) | 2016-11-10 |
CN105793463B (zh) | 2018-11-09 |
DE112014005865T5 (de) | 2016-12-01 |
US10106866B2 (en) | 2018-10-23 |
KR101527144B1 (ko) | 2015-06-10 |
JP2017508865A (ja) | 2017-03-30 |
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