US3791801A - Electroplated steel sheet - Google Patents
Electroplated steel sheet Download PDFInfo
- Publication number
- US3791801A US3791801A US00165751A US3791801DA US3791801A US 3791801 A US3791801 A US 3791801A US 00165751 A US00165751 A US 00165751A US 3791801D A US3791801D A US 3791801DA US 3791801 A US3791801 A US 3791801A
- Authority
- US
- United States
- Prior art keywords
- deposit
- steel sheet
- zinc
- molybdenum
- metal
- 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.)
- Expired - Lifetime
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 58
- 239000010959 steel Substances 0.000 title claims abstract description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 17
- 239000011733 molybdenum Substances 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 239000010937 tungsten Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011133 lead Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000011135 tin Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- -1 hydrated oxides) Chemical compound 0.000 abstract description 4
- 239000003973 paint Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 229910017313 Mo—Co Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002003 electron diffraction Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 150000003752 zinc compounds Chemical class 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910015338 MoNi Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910008947 W—Co Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005244 galvannealing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/934—Electrical process
- Y10S428/935—Electroplating
-
- 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.]
- Y10T428/1266—O, S, or organic compound in metal component
-
- 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.]
- Y10T428/1266—O, S, or organic compound in metal component
- Y10T428/12667—Oxide of transition metal or Al
-
- 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.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- ABSTRACT An electroplated steel plate product with a zinc-rich deposit on the steel surface, said deposit comprising an oxide of molybdenum and tungsten (including hydrated oxides), and/or the total amount in the oxide being about 0.05 to about 2 weight percent of the deposit.
- the deposit may further include at least one additional material selected from the group consisting of iron, nickel, cobalt, tin and lead, and compound of said metal, the total metal content of the said additional material being about 0.5 to about 15 weight percent of the deposit.
- the present invention relates to electroplated steel products and a method of producing an electroplated steel plate or sheet having excellent corrosion resistance and formability suitable for coating paint or synthetic resin enamel on the surface thereof.
- Zinc is electrochemically so active that the phenomenon of white rust or self dissolution of zinc coating easily occurs, especially in corrosive circumstances, such as wet, salty or acidic atmospheres. Though its corrosion resistance can be improved by applying some organic coatings, in many cases its paint adhesion property is not satisfactory.
- the galvannealed steel sheet (the surface layer of which consists of a zinc-iron alloy) has better paint adhesion and corrosion resistance than a conventional electrogalvanized steel sheet, but a zinciron alloy layer has rather poor formability, and therefore, after forming, the paint adhesion deteriorates because of the fractures of the zinc-iron alloy layer.
- the present invention is based upon the technological discovery that the passive properties of a zinc-rich deposit with at least one oxide of molybdenum and/or tungsten is effective to restrain the dissolution of zinc under corrosive conditions so that excellent corrosion resistance and paint adhesion can be obtained.
- the present invention contemplates providing an electroplated steel product with a zinc-rich deposit on the steel surface, the deposit comprising (1) an oxide (and as used herein, this term includes hydrated oxides) of molybdenum and tungsten, and/or (2) in addition, the deposit may also include at least one of the metals or metal compounds selected from the group consisting of iron, nickel, cobalt, tin and lead, so as to give to the finished product excellent corrosion resistance and formability.
- the base metal employed in the present invention the plate, cut sheet,
- base metal refers to such a plate, cut sheet, or strip of steel or iron, which hereinafter for convenience, is referred to as a sheet.
- the electroplated steel sheet contemplated herein is produced by cathodically electroplating thesteel sheet in an aqueous solution which comprises mainly water soluble, or bath soluble zinc compounds, and at least one compound of molybdenum or tungsten.
- another method of producing the electroplated steel sheet is by cathodically electroplating the steel sheet in an aqueous solution which comprises mainly a water soluble, or bath soluble zinc compound, and at least one compound of molybdenum or tungsten, and further includes at least one water soluble or bath soluble metal compound of iron, nickel, cobalt, tin or lead.
- composition of the deposit of the present invention is classified into two main groups, namely, (1) the deposit which comprises at least one of the oxides of molybdenum and tungsten, the total metal amount in said oxides being about 0.05 to about 2 weight percent of the deposit, and the balance zinc, and (2) the deposit which comprises at least one of the oxides of molybdenum and tungsten, the total metal amount in said oxides being about 0.05 to about 2 weight percent of the deposit, and further includes at least one metal or metal compound of the group consisting of iron, nickel, cobalt, tin and lead, the total metal amount of the additional metal or metal compound being about 0.5 to about 15 weight percent of the deposit, and the balance zinc.
- the electroplated steel sheet produced according to the present invention can be surface coated with conventional coating materials, such as paint, varnish, lac quer and other organic finishes, among which are acryl based paint, melamine based paint, epoxy based paint, vinyl based paint, vinyl chloride based paint, oil based paint and other paints.
- conventional coating materials such as paint, varnish, lac quer and other organic finishes, among which are acryl based paint, melamine based paint, epoxy based paint, vinyl based paint, vinyl chloride based paint, oil based paint and other paints.
- roller coating As to the methods of applying these coating materials to the electroplated steel sheet of the present invention, there can be utilized roller coating, spray coating, knife coating, laminating, injection coating, electrostatic coating, and others.
- the electroplated steel sheet according to the present invention is produced by the following method.
- the steel sheet is subjected to a conventional pretreatment such as pickling with acids after degreasing with alkalis, or pickling with acids only, or degreasing with alkalis only, and rinsing with water. Then, the steel sheet is put into an electrolytic bath and cathodically plated.
- the composition of the bath is mainly water soluble or bath soluble zinc compounds, (for example,
- another bath composition for the present invention is mainly water soluble or bath soluble zinc compounds, at least one water soluble or bath soluble 'compound of molybdenum and tungsten, and further,
- At least one water soluble or bath soluble compound of iron, nickeLcobalt, tinor lead, for example, iron sulfate, nickel sulfate, cobalt sulfate, stannous sulfate, iron nitrate, nickel nitrate, cobalt nitrate, lead nitrate, iron chloride, nickel chloride, cobalt chloride, tin chloride, cobalt acetate, lead acetate).
- the electrolysis operation should be controlled so that the composition of deposit is within the range of the composition of deposit of the present invention.
- the appearance of the treated surface with regard to the deposit formed changes with the kind or amount of the additional element.
- the color of the deposit changes depending upon the conditions of electrolysis, for example, blue, gray, brown or black. The deeper the degree of tint, the better the corrosion resistance, the formability and paint adhesion.
- the composition of the deposit is not within the range of the composition of the present invention, the formability becomes poor, as hereinafter described.
- EXAMPLE 1 A 0.45 mm thick low carbon steel sheet was cathodically cleaned for 15 seconds at a current density of 3 A/sq.dm at 70C in a sodium hydroxide (70 g/liter) solution, and rinsed with water, then pickled for 5 seconds at room temperature in a sulfuric acid (70 g/liter) solution, and again rinsed with water. Then the steel sheet was put in an electrolytic bath and direct current was applied, wherein the steel sheet acted as the cathode and zinc acted as the anode.
- the composition of the bath was: zinc sulfate 250 g/liter, aluminum sulfate 20 g/liter, ammonium molybdate 4 g/liter and sodium sulfate 30 g/liter.
- the temperature was 45C, current density was 20 A/sq.dm and treating time was 16 seconds.
- the amount of the deposit formed was g/sq.m.
- the color of the deposit formed was blue-gray.
- the total molybdenum metal amount in the molybdenum oxides was'0.5 weight percent of the deposit. The properties of the sample are indicated as No. 5 in the Table given hereinafter.
- EXAMPLE 2 The same low carbon steel sheet as described in Example l was subjected to the same pre-treatment, as described in Example 1. After that, the steel sheet was cathodically treated for seconds at 45C at a current density of A/sq.dm in an electrolyte containing 250 g/liter zinc sulfate, 0.5 g/liter ammonium molybdate and 30 g/liter cobalt sulfate. The amount of the deposit formed was 10 g/sq.m.
- the deposit formed was composed of Zn, Zn (OH) ZnO, M00 M0 0 Co(OH) C00, and other minor constituents, and the total molybdenum metal amount in the molybdenum oxides and total cobalt metal amount was 0.5 and 3.0 weight percent of the deposit, respectively.
- the salt spray test provided by 118 (Japanese lndustrial Standard) Z 2371 was applied (first) to the electroplated steel sheet produced according to the present invention; (second) to a conventional zinc-cobalt alloy plated steel sheet (coating weight 10 g/sq.m) containing 2 weight percent of cobalt; and, (third) to a conventional electrogalvanized steel sheet (coating weight 10 g/sq.m).
- the (first) electroplated steel sheet according to the present invention showed no red, rusty spots after 12 hours; in the case of the (third) conventional electrogalvanized steel sheet, to percent of the total surface was covered with red, rusty spots.
- the (second) conventional zinc-cobalt alloy plated steel sheet showed rusty spots which covered 50 percent of the total surface. From the results of successive tests, the electroplated steel sheet according to the present invention was proved to withstand about 4 times longer in corrosion resistance tests in comparison with conventional electrogalvanized steel sheets.
- the conventional electrogalvanized steel sheet was then treated in a phosphate based solution and rinsed with water, then treated in the chromate based solution.
- the conventional electrogalvanized steel sheet which has 20 mg/sq.dm of phosphate film on the surface by the conventional phosphating treatment and 0.2 mg/sq.dm of elemental chromium in chromate film overlaid by the conventional chromating treatment, revealed as many blisters as those of the zinc-cobalt alloy plated steel sheet after 500 hours of paint adhesion test described in (c) in Note: 3 of the Table, whereas the electroplated steel sheet according to the present invention showed no evidence of blisters.
- the electroplated steel sheet according to the present invention which is coated with 70 mg/sq.dm of acryl based adhesive agent and then with 0.2 mm thick polyvinyl chloride thereon, had much higher resistance to the degradation of film adhesion in the said running water exposure test than the conventional electrogalvanized steel sheet.
- the properties of this sample are indicated as No. l l in the Table.
- Example 2 The amount of the of the electron-diffraction analysis, it was found that posit formed was g/sq.m.
- Example 1 The low carbon steel sheet as described in Example In the case ofgroup Ofthe combmatlonfomppsb l was subjected to the same pre-treatment as described i zg gigig zi ggig f w grj 5:3 ?:2232: in Example 1.
- the steel sheet was cathodil bdenum Oxides i as low as 0 O4 ht ercent of cally treated for 16 seconds at 45C at a current density j de 08 (listed as No 3 in the'Tablwgthepmol of 20 A/sq.dm in the electrolyte containing 250 g/liter h d ff d y of zinc sulfate, 0.5 g/liter of ammonium molybdate and 25 g 1 i the pzfpemeshwere poor 50 g/liter of nickel sulfate.
- the amount of the deposit i a accorHmg to t 6 s formed was l0 g/sqm.
- the color of the deposit formed nona g g processf' rg t e was gray.
- analy- 22 33 .3 l jz z j fi 3 gj z fi g s g; thazt ii g fa g iff coglpoied ing to the present invention resulted in excellent corroz s ki 2 tztal 2 i' i s; sion resistance and good resistance to the degradation of paint adhesion.
- amontmthe dmlbd m th t a t t of the deposit respectively.
- B means that some blisters were found on the cross hatched part.
- .C means that many blisters were found on the cross hatched part.
- the electroplated steel sheet has excellent resistance against degradation of paint adhesion, has good formability, and good corrosion resistance, is because of the effect of metal oxides in the deposit formed.
- the behavior of the metal oxides and metal compounds which produce the excellent properties hereinbefore described is believed to be that when some corrosive substances permeate through the paint layer perpendicularly to the electroplated steel sheet, the oxides and compounds of such metals as molybdenum, tungsten, iron, nickel, cobalt, tin, and lead are effective to prevent the propagation of zinc dissolution along the horizontal directions and thus prevent the direct reaction of the steel base with corrosive substances.
- An electroplated steel product having a zinc-rich deposit onthe steel surface said product is formed in for 500 hours according to HS 2 2371. Then, blisters on the cross hatched part were observed. The results are classified into 3 classes:
- an acidic aqueous electrolytic bath comprising at least one of the oxides, of molybdenum and tungsten, the total amount of metal in said oxide being from 0.05 to 2 weight percent of the deposit.
- An electroplated stccl product with a zinc-rich deposit on the steel surface comprising at least one oxide material selected from the group consisting of the oxides of molybdenum and tungsten, the total amount of molybdenum and tungsten being about 0.05 to about 2 weight percent of the deposit, and further, including at least one additional material selected from the group consisting of iron, nickel, cobalt, tin and lead, and oxides and hydroxides of said metals, the total metal content of the said additional material being about 0.5 to about 15 weight percent of the deposit said product having been formed by electro-deposition in an acidic aqueous electrolytic bath.
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Abstract
An electroplated steel plate product with a zinc-rich deposit on the steel surface, said deposit comprising an oxide of molybdenum and tungsten (including hydrated oxides), and/or the total amount in the oxide being about 0.05 to about 2 weight percent of the deposit. In addition, the deposit may further include at least one additional material selected from the group consisting of iron, nickel, cobalt, tin and lead, and compound of said metal, the total metal content of the said additional material being about 0.5 to about 15 weight percent of the deposit.
Description
United States Patent [191 Ariga et al.
[ ELECTROPLATED STEEL SHEET [75] Inventors: Keiji Ariga; Satoshi Morishita;
Katsumi Kanda; Takashi Mizobe, all of Yamaguchi-Ken. Japan [73] Assignee: Toyo Kohan Co., Ltd., Tokyo, Japan [22] Filed: July 23, 1971 [21] Appl. No.: 165,751
[ 1 =,-,-122/.t1?61 1 3 ZLZ94L5M B. [51] Int. Cl. C23b 11/00, C23d 5/00 [58] Field of Search... 204/43 Z, 55 R, 56; 29/1965 [5 6] References Cited UNITED STATES PATENTS 2,233,500 3/1941 Westbrook 204/43 Z X 2,900,313 8/1959 Saubestre et al.. 204/43 Z 3,317,412 5/1967 Dahlmann 204/55 R FOREIGN PATENTS OR APPLICATIONS 1,043,618 9/1966 Great Britain 204/55 R [451 Feb. 12, 1974 Primary Examiner-F. C. Edmundson Attorney, Agent, or FirmGeorge B. Oujevolk [57] ABSTRACT An electroplated steel plate product with a zinc-rich deposit on the steel surface, said deposit comprising an oxide of molybdenum and tungsten (including hydrated oxides), and/or the total amount in the oxide being about 0.05 to about 2 weight percent of the deposit. In addition, the deposit may further include at least one additional material selected from the group consisting of iron, nickel, cobalt, tin and lead, and compound of said metal, the total metal content of the said additional material being about 0.5 to about 15 weight percent of the deposit.
2 Claims, No Drawings ELECTROPLATED STEEL SHEET BACKGROUND OF THE INVENTION The present invention relates to electroplated steel products and a method of producing an electroplated steel plate or sheet having excellent corrosion resistance and formability suitable for coating paint or synthetic resin enamel on the surface thereof.
OBJECT OF THE INVENTION Thus, it is an object of the present invention to provide a steel sheet or plate which, when coated with a paint, has excellent paint adhesion properties, as well as excellent corrosion resistance and formability when paints made of resins such as melamine, acrylic, epoxy, vinyl or others are applied onto the steel sheet.
BRIEF DISCUSSION OF THE PRIOR ART Zinc is electrochemically so active that the phenomenon of white rust or self dissolution of zinc coating easily occurs, especially in corrosive circumstances, such as wet, salty or acidic atmospheres. Though its corrosion resistance can be improved by applying some organic coatings, in many cases its paint adhesion property is not satisfactory.
Therefore, many attempts have been made to improve the above-mentioned defects of zinc coated steel surfaces. One of them is chemical or electrolytical posttreatment, and another is the galvannealing process.
Conventional, well-known methods of posttreatment generally comprise:
l. Dipping of zinc coated steel in a chromic acid base or phosphoric acid base solution.
2. Coating a zinc coated surface with a solution of chromic acid base or phosphoric acid base.
3. Treating the zinc or zinc alloy surface in a solution which has a high pH value on the alkaline side (more than 11) and contains at least one metal ion selected from the group consisting of silver, magnesium, cadmium, molybdenum, aluminum, titanium, chromium and others, and further containing enough complexing agent to dissolve the metal ions (Japanese Patent No. 531221).
These treatments will prevent white rust and enhance paint adhesion, but the treatments are effective for only a short period of time. The reason is that the paint adhesion quickly deteriorates because the corrosion of the zinc coating is accelerated by mechanical damage or chemical self-deterioration of the treated film. So it is conventional to overcoat the surface with organic finishes.
On the other hand, the galvannealed steel sheet, (the surface layer of which consists of a zinc-iron alloy) has better paint adhesion and corrosion resistance than a conventional electrogalvanized steel sheet, but a zinciron alloy layer has rather poor formability, and therefore, after forming, the paint adhesion deteriorates because of the fractures of the zinc-iron alloy layer.
The present invention is based upon the technological discovery that the passive properties of a zinc-rich deposit with at least one oxide of molybdenum and/or tungsten is effective to restrain the dissolution of zinc under corrosive conditions so that excellent corrosion resistance and paint adhesion can be obtained.
SUMMARY OF THE INVENTION Generally speaking, the present invention contemplates providing an electroplated steel product with a zinc-rich deposit on the steel surface, the deposit comprising (1) an oxide (and as used herein, this term includes hydrated oxides) of molybdenum and tungsten, and/or (2) in addition, the deposit may also include at least one of the metals or metal compounds selected from the group consisting of iron, nickel, cobalt, tin and lead, so as to give to the finished product excellent corrosion resistance and formability. As the base metal employed in the present invention, the plate, cut sheet,
. or strip of steel or iron is most convenient, and the term base metal, as used herein, refers to such a plate, cut sheet, or strip of steel or iron, which hereinafter for convenience, is referred to as a sheet.
The electroplated steel sheet contemplated herein is produced by cathodically electroplating thesteel sheet in an aqueous solution which comprises mainly water soluble, or bath soluble zinc compounds, and at least one compound of molybdenum or tungsten. Or, another method of producing the electroplated steel sheet is by cathodically electroplating the steel sheet in an aqueous solution which comprises mainly a water soluble, or bath soluble zinc compound, and at least one compound of molybdenum or tungsten, and further includes at least one water soluble or bath soluble metal compound of iron, nickel, cobalt, tin or lead.
DETAILED DESCRIPTION The composition of the deposit of the present invention is classified into two main groups, namely, (1) the deposit which comprises at least one of the oxides of molybdenum and tungsten, the total metal amount in said oxides being about 0.05 to about 2 weight percent of the deposit, and the balance zinc, and (2) the deposit which comprises at least one of the oxides of molybdenum and tungsten, the total metal amount in said oxides being about 0.05 to about 2 weight percent of the deposit, and further includes at least one metal or metal compound of the group consisting of iron, nickel, cobalt, tin and lead, the total metal amount of the additional metal or metal compound being about 0.5 to about 15 weight percent of the deposit, and the balance zinc.
The electroplated steel sheet produced according to the present invention can be surface coated with conventional coating materials, such as paint, varnish, lac quer and other organic finishes, among which are acryl based paint, melamine based paint, epoxy based paint, vinyl based paint, vinyl chloride based paint, oil based paint and other paints.
As to the methods of applying these coating materials to the electroplated steel sheet of the present invention, there can be utilized roller coating, spray coating, knife coating, laminating, injection coating, electrostatic coating, and others.
The electroplated steel sheet according to the present invention is produced by the following method.
The steel sheet is subjected to a conventional pretreatment such as pickling with acids after degreasing with alkalis, or pickling with acids only, or degreasing with alkalis only, and rinsing with water. Then, the steel sheet is put into an electrolytic bath and cathodically plated. The composition of the bath is mainly water soluble or bath soluble zinc compounds, (for example,
zinc sulfate, zinc chloride, zinc acetate, zinc fluoborate) and at least one water soluble or bath soluble compound of molybdenum and tungsten. (For exam ple, ammonium molybdate, sodium molybdate, potassium molybdate, ammonium tungstate, sodium tungstate, potassium tungstate).
Also, another bath composition for the present invention is mainly water soluble or bath soluble zinc compounds, at least one water soluble or bath soluble 'compound of molybdenum and tungsten, and further,
at least one water soluble or bath soluble compound of iron, nickeLcobalt, tinor lead, (for example, iron sulfate, nickel sulfate, cobalt sulfate, stannous sulfate, iron nitrate, nickel nitrate, cobalt nitrate, lead nitrate, iron chloride, nickel chloride, cobalt chloride, tin chloride, cobalt acetate, lead acetate).
However, as the composition of the deposit changes owing to current density, bath temperature, bath concentration, degree of agitation and other factors, the electrolysis operation should be controlled so that the composition of deposit is within the range of the composition of deposit of the present invention. The appearance of the treated surface with regard to the deposit formed changes with the kind or amount of the additional element. The color of the deposit changes depending upon the conditions of electrolysis, for example, blue, gray, brown or black. The deeper the degree of tint, the better the corrosion resistance, the formability and paint adhesion. However, if the composition of the deposit is not within the range of the composition of the present invention, the formability becomes poor, as hereinafter described.
For the purpose of giving those skilled in the art a better understanding of the invention, the following illustrative examples are given.
EXAMPLE 1 A 0.45 mm thick low carbon steel sheet was cathodically cleaned for 15 seconds at a current density of 3 A/sq.dm at 70C in a sodium hydroxide (70 g/liter) solution, and rinsed with water, then pickled for 5 seconds at room temperature in a sulfuric acid (70 g/liter) solution, and again rinsed with water. Then the steel sheet was put in an electrolytic bath and direct current was applied, wherein the steel sheet acted as the cathode and zinc acted as the anode. The composition of the bath was: zinc sulfate 250 g/liter, aluminum sulfate 20 g/liter, ammonium molybdate 4 g/liter and sodium sulfate 30 g/liter. The temperature was 45C, current density was 20 A/sq.dm and treating time was 16 seconds. The amount of the deposit formed was g/sq.m. The color of the deposit formed was blue-gray. As a result of the electrondiffraction analysis, it was established that the deposit formed was composed of Zn, Zn (OH) ZnO, M00 M0 0 and minor amounts of constituents. According to the quantitative analysis, the total molybdenum metal amount in the molybdenum oxides was'0.5 weight percent of the deposit. The properties of the sample are indicated as No. 5 in the Table given hereinafter.
EXAMPLE 2 The same low carbon steel sheet as described in Example l was subjected to the same pre-treatment, as described in Example 1. After that, the steel sheet was cathodically treated for seconds at 45C at a current density of A/sq.dm in an electrolyte containing 250 g/liter zinc sulfate, 0.5 g/liter ammonium molybdate and 30 g/liter cobalt sulfate. The amount of the deposit formed was 10 g/sq.m. From the result of the electrondiffraction analysis, it was found that the deposit formed was composed of Zn, Zn (OH) ZnO, M00 M0 0 Co(OH) C00, and other minor constituents, and the total molybdenum metal amount in the molybdenum oxides and total cobalt metal amount was 0.5 and 3.0 weight percent of the deposit, respectively.
The salt spray test provided by 118 (Japanese lndustrial Standard) Z 2371 was applied (first) to the electroplated steel sheet produced according to the present invention; (second) to a conventional zinc-cobalt alloy plated steel sheet (coating weight 10 g/sq.m) containing 2 weight percent of cobalt; and, (third) to a conventional electrogalvanized steel sheet (coating weight 10 g/sq.m). The (first) electroplated steel sheet according to the present invention showed no red, rusty spots after 12 hours; in the case of the (third) conventional electrogalvanized steel sheet, to percent of the total surface was covered with red, rusty spots. The (second) conventional zinc-cobalt alloy plated steel sheet showed rusty spots which covered 50 percent of the total surface. From the results of successive tests, the electroplated steel sheet according to the present invention was proved to withstand about 4 times longer in corrosion resistance tests in comparison with conventional electrogalvanized steel sheets.
The conventional electrogalvanized steel sheet was then treated in a phosphate based solution and rinsed with water, then treated in the chromate based solution. The conventional electrogalvanized steel sheet, which has 20 mg/sq.dm of phosphate film on the surface by the conventional phosphating treatment and 0.2 mg/sq.dm of elemental chromium in chromate film overlaid by the conventional chromating treatment, revealed as many blisters as those of the zinc-cobalt alloy plated steel sheet after 500 hours of paint adhesion test described in (c) in Note: 3 of the Table, whereas the electroplated steel sheet according to the present invention showed no evidence of blisters.
These same samples were coated with 250 mg/sq.dm of a melamine based paint and cross hatched on the paint film baked, then immersed in running water for half a year, after that period, a piece of adhesive tape was applied firmly on the surface thereof and then pulled off quickly. whereupon the conventional electrogalvanized steel sheet showed many blisters and adhesion loss of paint film was 20 percent. In case of the zinc-cobalt alloy plated steel sheet there were many blisters and adhesion loss of paint film was 15 percent. On the other hand, the electroplated steel sheet according to the present invention could withstand the running water exposure test for more than one and a half year, without any signs of blisters and adhesion loss of paint film did not occur.
Furthermore, it was found that the electroplated steel sheet according to the present invention, which is coated with 70 mg/sq.dm of acryl based adhesive agent and then with 0.2 mm thick polyvinyl chloride thereon, had much higher resistance to the degradation of film adhesion in the said running water exposure test than the conventional electrogalvanized steel sheet. The properties of this sample are indicated as No. l l in the Table.
EXAMPLE 3 Low carbon steel sheet, as described in Example, 1
was subjected to the same pre-treatment as described in Example 1. Then, the steel sheet was cathodically ample 1 was subjected to the same pre-treatment as described in Example I. Then the steel was cathodically treated for 16 seconds at 45C at a current density of 20 A/sq.dm in the electrolyte containing 60 g/liter of treated for 16 seconds at 45C at a current density of 5 zinc f 150 gmter of Zinc q glut of 20 A/sq.dm in an electrolyte containing 250 g/liter of ifz fig z 60 Elmer of i: zinc sulfate, 0.5 g/liter of ammonium molybdate and e co or 0 e eposit 0mm a 05 glut of Sodium tungstaw The amount of the of the electron-diffraction analysis, it was found that posit formed was g/sq.m. The color of the deposit gs s g g g g -"gg ig 9 3" 95 3 formed was blue-gray. As a result of electon-diffraction l0 and a, g yz g filgg iz t 2; g: 2 ?gg ggg a gg j gg molybdenum oxides and total metal amount of lead was 5v 0 and other minor constituents a rid the trital m and 5 w-eight pefcem of the dpo-sil' respectively yg gfi and tungsten metal amount in the Said m0 The properties of this sample are indicated as No. 22
. 15 in the Table.
gg i g ggsz xf s fsi i g ii g 25 22 Regarding the electroplated steel sheet according to ti 5 1 d P N Z1 th L the present invention, the relationship between the var- 1 samp e are m 6 as m e a ious compositions of the deposit and their properties EXAMPLE 4 are indicated in the Table.
The low carbon steel sheet as described in Example In the case ofgroup Ofthe combmatlonfomppsb l was subjected to the same pre-treatment as described i zg gigig zi ggig f w grj 5:3 ?:2232: in Example 1. After that, the steel sheet was cathodil bdenum Oxides i as low as 0 O4 ht ercent of cally treated for 16 seconds at 45C at a current density j de 08 (listed as No 3 in the'Tablwgthepmol of 20 A/sq.dm in the electrolyte containing 250 g/liter h d ff d y of zinc sulfate, 0.5 g/liter of ammonium molybdate and 25 g 1 i the pzfpemeshwere poor 50 g/liter of nickel sulfate. The amount of the deposit i a accorHmg to t 6 s formedwas l0 g/sqm. The color of the deposit formed nona g g processf' rg t e was gray. As a result of the electron-diffraction analy- 22 33 .3 l jz z j fi 3 gj z fi g s g; thazt ii g fa g iff coglpoied ing to the present invention resulted in excellent corroz s ki 2 tztal 2 i' i s; sion resistance and good resistance to the degradation of paint adhesion. However, in case of more than 2 amontmthe dmlbd m th t a t t of the deposit respectively. The properties of this sam- 35 2 3 25 as O m e a e) revea 6 poor orm ple are mdlcated as 21 m the Table In the case of group (2) of the combination of com- E AM E 5 position of deposit according to the present invention,
th t t l 1 bd l t' th The same low carbon steel sheet as described in Ex- $232 g g i if gf j 2 23:; S
2F 2; n g ifi iz fflfigggig:gizg gz ggfzgx ii' 40 posit, and further, the total iron metal amounted to 15 cally treated for l 6 seconds at C at a current density K a g g iz g i g f fi s 'g' iste as o. 0. ,an o. mte a e,ac-
g; g /l z 2?:giiggfifiiigfiyiigg 2 :5 cording to the present invention, an excellent effect for improving the properties of deposits was found.
: g g f g g i g g fgff fig 5 Namely, the existence of the molybdenum oxides and 9" a S F re u h e S metal or compounds of iron resulted in excellent resisg if i g gg 5 11 555 p 2 5 ztnf) mg" tance against the degradation of paint adhesion in comparlson with Sample No. 4 or No. 2 1n the Table acxgfgii ii z g g g g gaz ig ig zg sgfiygf g rzl cording to the conventional zinc iron alloy plating prooxides and the total metal amount of iron was 0.7 and 50 2 2: 23: 1:32 s zfis zgzfi t i zi ig g g 3 :f Fj i the ifg g gs gg E 3 weight percent of the deposit, if the total iron metal er 0 18 p e are l amount exceeded 15 weight percent of the deposits, as E 6 shown in No. 18 in the Table, the effect for the resis- EXA L 55 tance against the degradation of paint adhesion was sat- The same low carbon steel sheet as described in Exurated andconversely the formability became worse.
TABLE Film Composition Properties (b) Formability (c) Paint Adhesion (a) Corrosion No Metal Component Weight Percent Resistance Performance l Zn 100 C A 2 Zn-Fe -10 C C C43 3 Zn-Mo 99.96-0.04 C A C 4 Zn-Mo 99.95-005 B A B 5 Zn-Mo 9950-050 B A A 6 Zn'Mo 97 .50-2.50 A a C .A
Table;- C o rninued Film Composition Properties No Metal Component Weight Percent (a) Corrosion (b) Formability (c) Paint Adhesion Resistance Performance 7 Zn-Mo-W 99.95- 02-003 B A B-A 8 Zn-Mo-W 99.70-0 l0-0.20 B-A A B-A 9 Zn-Mo-W 99.30-0 50-010 8 A B-A l0 Zn-Mo-Co 99.45-0 -050 B-A A B-A ll Zn-Mo-Co 96.50-0.S0-3.00 B A A 12 Zn-Mo-Co 84.95-0.05-l5.00 A A A 13 Zn-Mo-Co 82.95-0.05-l7.00 A C A 14 Zn-Mo-W-Co 99.30-0.l0-O.l0-0.50 A A A 15 Zn-Mo-Fe 99.45-0.05-0.50 B A B-A l6 Zn-Mo-Fe 96.30-0.70-3.00 B A A l7 Zn-Mo-Fe 84.95-0.05-l5.00 B A A 18 v Zn-Mo-Fe 80.50-0.50-l9.00 B C A 19 Zn-MoNi 99.70-010-020 B-A A A 20 Zn-Mo-Ni 99.90-0.05-0.05 B-A A B-A 2l Zn-Mo-Ni 97.70-0.30-2.0 B A A 22 Zn-Mo-Pb 94.80-0.20-5.0 B A B-A Note: I The deposit weight of Samples No.5, No. 9, No. ll. No. 16, No. 21, and No. 22 was It] g/sq.m. The
deposit weight of the other Samples was g/sq.m.
Note: 2 Samples No. l and No. 2 in the Table were treated in the phosphate based solution. The weight of the Phosphate film was 1 g/sq.m. Note: 3 The method for testing properties in the Table:
a. Corrosion Resistance The salt spray test provided by 11S (Japanese Industrial Standard) 2 237l was practiced for those samples, and the red rust spots developed after I00 hours was observed. Test results are classified into 3 classes: A,-B, and C. A means that no area of rusty spots was found.
B means that the area of rusty spots was 20 to percent.
C means that the area of rusty spots was 80 to I00 percent.
b. Formability Samples were coated with 200 mg/sqm of alkyl based paint and deeply drawn to the cup (drawing ratio: 2.0) and a piece of adhesive tape was applied firmly on the deeply drawn part of the cup and then pulled off quickly. Test results are classified into 3 classes: A, B, and C.
A means that no adhesion lossof the coated paint was found. 8 means that adhesion loss of the coated paint was 20 to 40 percent. C means that adhesion loss of the coated paint was 80 to 100 percent.
c. The Resistance Against the Degradation of Paint Adhesion Samples were coated with 250 mglsq.rn of melamine based paint, cross hatched with a razor on the paint film and subjected to the salt spray test A, B, and C.
A means that no blisters were found on the cross hatched part.
B means that some blisters were found on the cross hatched part. .C means that many blisters were found on the cross hatched part.
One of the reasons why the electroplated steel sheet, according to the present invention, has excellent resistance against degradation of paint adhesion, has good formability, and good corrosion resistance, is because of the effect of metal oxides in the deposit formed. The behavior of the metal oxides and metal compounds which produce the excellent properties hereinbefore described is believed to be that when some corrosive substances permeate through the paint layer perpendicularly to the electroplated steel sheet, the oxides and compounds of such metals as molybdenum, tungsten, iron, nickel, cobalt, tin, and lead are effective to prevent the propagation of zinc dissolution along the horizontal directions and thus prevent the direct reaction of the steel base with corrosive substances.
We claim:
1. An electroplated steel product having a zinc-rich deposit onthe steel surface, said product is formed in for 500 hours according to HS 2 2371. Then, blisters on the cross hatched part were observed. The results are classified into 3 classes:
an acidic aqueous electrolytic bath, and said deposit comprising at least one of the oxides, of molybdenum and tungsten, the total amount of metal in said oxide being from 0.05 to 2 weight percent of the deposit.
2. An electroplated stccl product with a zinc-rich deposit on the steel surface, said deposit comprising at least one oxide material selected from the group consisting of the oxides of molybdenum and tungsten, the total amount of molybdenum and tungsten being about 0.05 to about 2 weight percent of the deposit, and further, including at least one additional material selected from the group consisting of iron, nickel, cobalt, tin and lead, and oxides and hydroxides of said metals, the total metal content of the said additional material being about 0.5 to about 15 weight percent of the deposit said product having been formed by electro-deposition in an acidic aqueous electrolytic bath.
Claims (1)
- 2. An electroplated steel product with a zinc-rich deposit on the steel surface, said deposit comprising at least one oxide material selected from the group consisting of the oxides of molybdenum and tungsten, the total amount of molybdenum and tungsten being about 0.05 to about 2 weight percent of the deposit, and further, including at least one additional material selected from the group consisting of iron, nickel, cobalt, tin and lead, and oxides and hydroxides of said metals, the total metal content of the said additional material being about 0.5 to about 15 weight percent of the deposit said product having been formed by electro-deposition in an acidic aqueous electrolytic bath.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16575171A | 1971-07-23 | 1971-07-23 |
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| Publication Number | Publication Date |
|---|---|
| US3791801A true US3791801A (en) | 1974-02-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00165751A Expired - Lifetime US3791801A (en) | 1971-07-23 | 1971-07-23 | Electroplated steel sheet |
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Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4036600A (en) * | 1975-06-05 | 1977-07-19 | Kawasaki Steel Corporation | Steel substrate electroplated with Al powder dispersed in Zn |
| US4048381A (en) * | 1975-01-22 | 1977-09-13 | Nippon Kokan Kabushiki Kaisha | Method for manufacturing an electro-galvanized steel sheet excellent in bare corrosion resistance and adaptability to chromating, and product thereof |
| FR2377460A1 (en) * | 1977-01-13 | 1978-08-11 | Oxy Metal Industries Corp | PROCESS FOR THE PRODUCTION OF MULTIPLE COATINGS CONTAINING ZINC AND NEW PRODUCTS THUS OBTAINED |
| US4216272A (en) * | 1978-06-02 | 1980-08-05 | Oxy Metal Industries Corporation | Multiple zinc-containing coatings |
| US4290860A (en) * | 1979-07-02 | 1981-09-22 | Nippon Kokan Kabushiki Kaisha | Process for manufacturing electro-galvanized steel sheet excellent in paint adherence |
| US4800134A (en) * | 1987-04-13 | 1989-01-24 | Teruaki Izaki | High corrosion resistant plated composite steel strip |
| EP0329057A1 (en) * | 1988-02-19 | 1989-08-23 | Nippon Steel Corporation | Use of a zinc- or zinc alloy-coated steel sheet having excellent spot-weldability |
| US4904545A (en) * | 1987-07-10 | 1990-02-27 | Nkk Corporation | Composite electroplated steel sheet |
| US4910095A (en) * | 1987-12-29 | 1990-03-20 | Nippon Steel Corporation | High corrosion resistant plated composite steel strip |
| US4915906A (en) * | 1988-06-17 | 1990-04-10 | Canadian Patents And Development Limited/Societie Canadienne Des Brevets Et D'exploitation Limitee | Novel zinc-based alloys, preparation and use thereof for producing thermal-sprayed coatings having improved corrosion resistance and adherence |
| US5266182A (en) * | 1988-03-16 | 1993-11-30 | Kawasaki Steel Corporation | Method for producing Zn-Ni alloy plated steel plate having superior press formability |
| US5401586A (en) * | 1993-04-05 | 1995-03-28 | The Louis Berkman Company | Architectural material coating |
| US5429882A (en) * | 1993-04-05 | 1995-07-04 | The Louis Berkman Company | Building material coating |
| US5455122A (en) * | 1993-04-05 | 1995-10-03 | The Louis Berkman Company | Environmental gasoline tank |
| US5489490A (en) * | 1993-04-05 | 1996-02-06 | The Louis Berkman Company | Coated metal strip |
| US5491036A (en) * | 1992-03-27 | 1996-02-13 | The Louis Berkman Company | Coated strip |
| US5491035A (en) * | 1992-03-27 | 1996-02-13 | The Louis Berkman Company | Coated metal strip |
| US5525431A (en) * | 1989-12-12 | 1996-06-11 | Nippon Steel Corporation | Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same |
| US5597656A (en) * | 1993-04-05 | 1997-01-28 | The Louis Berkman Company | Coated metal strip |
| WO1999036595A1 (en) * | 1998-01-13 | 1999-07-22 | Nickel Rainbow Ltd. | Articles having a colored metallic coating with special properties |
| US6080497A (en) * | 1992-03-27 | 2000-06-27 | The Louis Berkman Company | Corrosion-resistant coated copper metal and method for making the same |
| US6224463B1 (en) | 1998-11-02 | 2001-05-01 | J.C.J. Metal Processing, Incorporated | Workpiece finishing system and method of operating same |
| GB2320456B (en) * | 1996-12-18 | 2001-09-05 | Fip Holdings Ltd | Polymer processing method |
| US6416648B1 (en) * | 1999-10-30 | 2002-07-09 | Hyundai Motor Company | Method of manufacturing steel sheets coated with Zn-Fe alloy |
| US6652990B2 (en) | 1992-03-27 | 2003-11-25 | The Louis Berkman Company | Corrosion-resistant coated metal and method for making the same |
| US6677057B2 (en) | 2000-12-22 | 2004-01-13 | Posco | Zn-Co-W alloy electroplated steel sheet with excellent corrosion resistance and weldability, and electrolyte for plating same |
| US20040091385A1 (en) * | 2000-09-16 | 2004-05-13 | Klaus Leyendecker | Ternary tin zinc alloy, electroplating solutions and galvanic method for producing ternary tin zinc alloy coatings |
| US20040173293A1 (en) * | 2003-03-07 | 2004-09-09 | Sung-Man Jung | Apparatus and method of manufacturing laminated steel sheet |
| US6794060B2 (en) | 1992-03-27 | 2004-09-21 | The Louis Berkman Company | Corrosion-resistant coated metal and method for making the same |
| US20040214029A1 (en) * | 1992-03-27 | 2004-10-28 | The Louis Berkman Company, An Ohio Corporation | Corrosion-resistant coated copper and method for making the same |
| US20110045316A1 (en) * | 2003-07-29 | 2011-02-24 | Voestalpine Stahl Gmbh | Method for producing a hardened profiled structural part |
| US20110117179A1 (en) * | 2005-06-03 | 2011-05-19 | Prezacor, Inc. | Compositions comprising elemental metals and uses therefor |
| WO2011135787A1 (en) * | 2010-04-26 | 2011-11-03 | 東洋鋼鈑株式会社 | Plated steel sheet for producing pipe having corrosion resistance against fuel vapor, and pipe and oil supply pipe using the plated steel sheet |
| US10905894B2 (en) | 2013-03-15 | 2021-02-02 | Prezacor, Inc. | Therapeutic bioelectromagnetic fields, pain relief devices, and related methods |
| CZ309341B6 (en) * | 2021-04-13 | 2022-09-07 | Výzkumný a zkušební letecký ústav, a.s. | Alloy coating for protecting metal surfaces and preparing it |
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| US2900313A (en) * | 1956-03-06 | 1959-08-18 | Sylvania Electric Prod | Addition materials for improving plating speeds |
| US3317412A (en) * | 1961-07-06 | 1967-05-02 | Schering Ag | Method for obtaining a bright zinc coating by electrodeposition and the bath used therefor |
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Cited By (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048381A (en) * | 1975-01-22 | 1977-09-13 | Nippon Kokan Kabushiki Kaisha | Method for manufacturing an electro-galvanized steel sheet excellent in bare corrosion resistance and adaptability to chromating, and product thereof |
| US4036600A (en) * | 1975-06-05 | 1977-07-19 | Kawasaki Steel Corporation | Steel substrate electroplated with Al powder dispersed in Zn |
| FR2377460A1 (en) * | 1977-01-13 | 1978-08-11 | Oxy Metal Industries Corp | PROCESS FOR THE PRODUCTION OF MULTIPLE COATINGS CONTAINING ZINC AND NEW PRODUCTS THUS OBTAINED |
| US4216272A (en) * | 1978-06-02 | 1980-08-05 | Oxy Metal Industries Corporation | Multiple zinc-containing coatings |
| US4290860A (en) * | 1979-07-02 | 1981-09-22 | Nippon Kokan Kabushiki Kaisha | Process for manufacturing electro-galvanized steel sheet excellent in paint adherence |
| US4800134A (en) * | 1987-04-13 | 1989-01-24 | Teruaki Izaki | High corrosion resistant plated composite steel strip |
| US4904545A (en) * | 1987-07-10 | 1990-02-27 | Nkk Corporation | Composite electroplated steel sheet |
| US5082536A (en) * | 1987-12-29 | 1992-01-21 | Nippon Steel Corporation | Method of producing a high corrosion resistant plated composite steel strip |
| US4910095A (en) * | 1987-12-29 | 1990-03-20 | Nippon Steel Corporation | High corrosion resistant plated composite steel strip |
| EP0329057A1 (en) * | 1988-02-19 | 1989-08-23 | Nippon Steel Corporation | Use of a zinc- or zinc alloy-coated steel sheet having excellent spot-weldability |
| US5266182A (en) * | 1988-03-16 | 1993-11-30 | Kawasaki Steel Corporation | Method for producing Zn-Ni alloy plated steel plate having superior press formability |
| US4915906A (en) * | 1988-06-17 | 1990-04-10 | Canadian Patents And Development Limited/Societie Canadienne Des Brevets Et D'exploitation Limitee | Novel zinc-based alloys, preparation and use thereof for producing thermal-sprayed coatings having improved corrosion resistance and adherence |
| US5525431A (en) * | 1989-12-12 | 1996-06-11 | Nippon Steel Corporation | Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same |
| US20070104975A1 (en) * | 1992-03-27 | 2007-05-10 | The Louis Berkman Company | Corrosion-resistant coated copper and method for making the same |
| US7575647B2 (en) | 1992-03-27 | 2009-08-18 | The Louis Berkman Co. | Corrosion-resistant fuel tank |
| US20070023111A1 (en) * | 1992-03-27 | 2007-02-01 | The Louis Berkman Company, A Corporation Of Ohio | Corrosion-resistant fuel tank |
| US7045221B2 (en) | 1992-03-27 | 2006-05-16 | The Louis Berkman Company | Corrosion-resistant coated copper and method for making the same |
| US5491036A (en) * | 1992-03-27 | 1996-02-13 | The Louis Berkman Company | Coated strip |
| US5491035A (en) * | 1992-03-27 | 1996-02-13 | The Louis Berkman Company | Coated metal strip |
| US6861159B2 (en) | 1992-03-27 | 2005-03-01 | The Louis Berkman Company | Corrosion-resistant coated copper and method for making the same |
| US6652990B2 (en) | 1992-03-27 | 2003-11-25 | The Louis Berkman Company | Corrosion-resistant coated metal and method for making the same |
| US6858322B2 (en) | 1992-03-27 | 2005-02-22 | The Louis Berkman Company | Corrosion-resistant fuel tank |
| US5616424A (en) * | 1992-03-27 | 1997-04-01 | The Louis Berkman Company | Corrosion-resistant coated metal strip |
| US5667849A (en) * | 1992-03-27 | 1997-09-16 | The Louis Berkman Company | Method for coating a metal strip |
| US6811891B2 (en) | 1992-03-27 | 2004-11-02 | The Louis Berkman Company | Corrosion-resistant coated metal and method for making the same |
| US20040213916A1 (en) * | 1992-03-27 | 2004-10-28 | The Louis Berkman Company, A Corporation Of Ohio | Corrosion-resistant fuel tank |
| US6080497A (en) * | 1992-03-27 | 2000-06-27 | The Louis Berkman Company | Corrosion-resistant coated copper metal and method for making the same |
| US20040214029A1 (en) * | 1992-03-27 | 2004-10-28 | The Louis Berkman Company, An Ohio Corporation | Corrosion-resistant coated copper and method for making the same |
| US6794060B2 (en) | 1992-03-27 | 2004-09-21 | The Louis Berkman Company | Corrosion-resistant coated metal and method for making the same |
| US5429882A (en) * | 1993-04-05 | 1995-07-04 | The Louis Berkman Company | Building material coating |
| US5492772A (en) * | 1993-04-05 | 1996-02-20 | The Louis Berkman Company | Building material coating |
| US5470667A (en) * | 1993-04-05 | 1995-11-28 | The Louis Berkman Company | Coated metal strip |
| US5489490A (en) * | 1993-04-05 | 1996-02-06 | The Louis Berkman Company | Coated metal strip |
| US5401586A (en) * | 1993-04-05 | 1995-03-28 | The Louis Berkman Company | Architectural material coating |
| US5455122A (en) * | 1993-04-05 | 1995-10-03 | The Louis Berkman Company | Environmental gasoline tank |
| US5695822A (en) * | 1993-04-05 | 1997-12-09 | The Louis Berkman Company | Method for coating a metal strip |
| US5597656A (en) * | 1993-04-05 | 1997-01-28 | The Louis Berkman Company | Coated metal strip |
| GB2320456B (en) * | 1996-12-18 | 2001-09-05 | Fip Holdings Ltd | Polymer processing method |
| US6420053B1 (en) | 1998-01-13 | 2002-07-16 | Nickel Rainbow Ltd. | Articles having a colored metallic coating with special properties |
| WO1999036595A1 (en) * | 1998-01-13 | 1999-07-22 | Nickel Rainbow Ltd. | Articles having a colored metallic coating with special properties |
| US6224463B1 (en) | 1998-11-02 | 2001-05-01 | J.C.J. Metal Processing, Incorporated | Workpiece finishing system and method of operating same |
| US6416648B1 (en) * | 1999-10-30 | 2002-07-09 | Hyundai Motor Company | Method of manufacturing steel sheets coated with Zn-Fe alloy |
| US20040091385A1 (en) * | 2000-09-16 | 2004-05-13 | Klaus Leyendecker | Ternary tin zinc alloy, electroplating solutions and galvanic method for producing ternary tin zinc alloy coatings |
| US6677057B2 (en) | 2000-12-22 | 2004-01-13 | Posco | Zn-Co-W alloy electroplated steel sheet with excellent corrosion resistance and weldability, and electrolyte for plating same |
| US7066232B2 (en) * | 2003-03-07 | 2006-06-27 | Daesung Inc. | Apparatus and method of manufacturing laminated steel sheet |
| US20040173293A1 (en) * | 2003-03-07 | 2004-09-09 | Sung-Man Jung | Apparatus and method of manufacturing laminated steel sheet |
| US20110045316A1 (en) * | 2003-07-29 | 2011-02-24 | Voestalpine Stahl Gmbh | Method for producing a hardened profiled structural part |
| US7938949B2 (en) * | 2003-07-29 | 2011-05-10 | Voestalpine Stahl Gmbh | Method for producing a hardened profiled structural part |
| US20110117179A1 (en) * | 2005-06-03 | 2011-05-19 | Prezacor, Inc. | Compositions comprising elemental metals and uses therefor |
| US9173900B2 (en) * | 2005-06-03 | 2015-11-03 | Prezacor, Inc. | Compositions comprising elemental metals |
| US10195148B2 (en) | 2005-06-03 | 2019-02-05 | Prezacor, Inc. | Pain relieving compositions comprising elemental metals |
| WO2011135787A1 (en) * | 2010-04-26 | 2011-11-03 | 東洋鋼鈑株式会社 | Plated steel sheet for producing pipe having corrosion resistance against fuel vapor, and pipe and oil supply pipe using the plated steel sheet |
| US10905894B2 (en) | 2013-03-15 | 2021-02-02 | Prezacor, Inc. | Therapeutic bioelectromagnetic fields, pain relief devices, and related methods |
| US12102837B2 (en) | 2013-03-15 | 2024-10-01 | Gary A. Karpf | Therapeutic bioelectromagnetic fields, pain relief devices, and related methods |
| CZ309341B6 (en) * | 2021-04-13 | 2022-09-07 | Výzkumný a zkušební letecký ústav, a.s. | Alloy coating for protecting metal surfaces and preparing it |
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