CN114381779A - Tin plate with good corrosion resistance and extremely low tin content and preparation method thereof - Google Patents
Tin plate with good corrosion resistance and extremely low tin content and preparation method thereof Download PDFInfo
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- CN114381779A CN114381779A CN202111513556.7A CN202111513556A CN114381779A CN 114381779 A CN114381779 A CN 114381779A CN 202111513556 A CN202111513556 A CN 202111513556A CN 114381779 A CN114381779 A CN 114381779A
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- phosphating
- tin
- passivation
- corrosion resistance
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- 239000005028 tinplate Substances 0.000 title claims abstract description 105
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000005260 corrosion Methods 0.000 title claims abstract description 50
- 230000007797 corrosion Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000002161 passivation Methods 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 37
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims description 22
- 229910019142 PO4 Inorganic materials 0.000 claims description 21
- 239000010452 phosphate Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000001978 electrochemical passivation Methods 0.000 claims description 20
- -1 aluminum ions Chemical class 0.000 claims description 12
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 238000006388 chemical passivation reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 229910001432 tin ion Inorganic materials 0.000 claims description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000002411 adverse Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 4
- 235000019801 trisodium phosphate Nutrition 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 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
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- VQYKQHDWCVUGBB-UHFFFAOYSA-N phosphanylidynezirconium Chemical compound [Zr]#P VQYKQHDWCVUGBB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
-
- 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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention particularly relates to a tin plate with good corrosion resistance and extremely low tin content and a preparation method thereof, belonging to the technical field of tin plate passivation, and the method comprises the following steps: carrying out phosphating treatment on the tin plate body in phosphating solution to obtain a tin plate with a phosphating film; said platingThe tin content of the tin plate body is less than or equal to 1.1g/m2(ii) a Passivating the tin plate with the phosphating film in a chromate passivating solution to obtain a tin plate with extremely low tin content and good corrosion resistance; the corrosion resistance of the tin plate with extremely low tin content is effectively improved.
Description
Technical Field
The invention belongs to the technical field of tin plate passivation, and particularly relates to a tin plate with good corrosion resistance and extremely low tin content and a preparation method thereof.
Background
The tin plate is also called tin plate and is widely applied in the field of food packaging. The passivation film on the surface of the tin plate is a conversion film formed on the surface of the tin plate by a chemical or electrochemical method, and for the tin plate, the passivation film plays the roles of a barrier layer and a connecting layer, so that on one hand, the passivation film can prevent oxygen from diffusing into the tin plate and prevent corrosive media such as chloride ions and sulfur ions from permeating, and the oxidation resistance and the corrosion resistance of the tin plate are improved; on the other hand, the coating can play a role in connecting the tin plate with the coating or paint film, and the adhesive force of the paint film on the surface of the tin plate is improved.
Because the tin amount of the tin plate with the extremely low tin amount is less, the tin layer is below 160nm, iron leakage parts can appear on the tin plate, and a tin phase, an iron phase and a tin-iron alloy phase exist on the surface of the tin plate.
Only the corrosion resistance of the tin plate with extremely low tin content can the tin plate with extremely low tin content be applied in the market, so the passivation process for improving the corrosion resistance of the tin plate with extremely low tin content has urgent requirements.
The current solutions are: chinese patent application CN103108990B steel sheet for containers, which discloses a passivation process on an island-like tin matrix. The passivation solution is zirconium phosphorus passivation solution and contains zirconium ions, phosphate radicals, fluorine ions, phenolic resin and the like. The Chinese patent application CN101358342A discloses a tinning plate phosphating process, wherein phosphating solution contains trisodium phosphate, cobalt sulfate, sodium molybdate, phosphoric acid and other substances, the pH value is 3-5, a phosphating film is formed on the surface of a tinning plate, and certain corrosion resistance and paint film bonding performance can be provided. The above patent can improve certain corrosion resistance of low tin content tin plate, but the overall effect is different from that of traditional chromate passivation process.
Disclosure of Invention
The applicant finds in the course of the invention that: the tin plate with extremely low tin content has a thin tin layer of 1.1g/m because of less tin plating2The tin layer thickness of the tin-plated plate is only 160 nm. Because of the surface roughness of the steel plate, an iron leakage area exists on the tin plate, which can lead to the reduction of the corrosion resistance of the tin plate, and because of the different properties of the hydrogen evolution overpotential of iron and tin, the passivation film of chromate on the tin plate with extremely low tin content is not uniform, so that the corrosion resistance of the tin plate with extremely low tin content can not be effectively improved by the chromate passivation.
The application aims to provide a tin plate with a very low tin content and good corrosion resistance and a preparation method thereof, so as to solve the problem of low corrosion resistance caused by uneven surface passivation film of the existing tin plate with a very low tin content.
The embodiment of the invention provides a preparation method of a tin plate with a very low tin content and good corrosion resistance, which comprises the following steps:
carrying out phosphating treatment on the tin plate body in phosphating solution to obtain a tin plate with a phosphating film; the tin content of the tin plate body is less than or equal to 1.1g/m2；
And passivating the tin plate with the phosphating film in a chromate passivating solution to obtain the tin plate with extremely low tin content and good corrosion resistance.
Optionally, the phosphating treatment comprises chemical phosphating treatment, wherein phosphating solution of the chemical phosphating treatment comprises phosphate radical, and the molar concentration of the phosphate radical is 0.08-0.50 mol/L; the pH value of the phosphating solution for chemical phosphating is 1.5-3.5.
Optionally, the phosphating solution for chemical phosphating also comprises a surfactant, and the surfactant comprises at least one of OP-10, PEG2000 and X-100.
Optionally, the phosphating temperature of the chemical phosphating treatment is 30-70 ℃, and the phosphating time of the chemical phosphating treatment is 30-1200 s.
Optionally, the phosphating treatment comprises electrochemical phosphating treatment, wherein a phosphating solution of the electrochemical phosphating treatment comprises phosphate radical, zinc ions, aluminum ions, tin ions and an accelerator, the molar concentration of the phosphate radical is 0.08-0.50 mol/L, the molar concentration of the zinc ions is 0.01-0.2 mol/L, the molar concentration of the aluminum ions is 0.01-0.2 mol/L, the molar concentration of the tin ions is 0.01-0.2 mol/L, and the molar concentration of the accelerator is 0.01-0.06 mol/L; the pH value of the phosphating solution for electrochemical phosphating is 2-4.
Optionally, the promoter comprises at least one of sodium nitrate and sodium nitrite.
Optionally, the phosphating current of the electrochemical phosphating treatment is 1A/dm2-10A/dm2The phosphating temperature of the electrochemical phosphating treatment is 30-70 ℃, and the phosphating time of the electrochemical phosphating treatment is 1-180 s.
Optionally, the method further includes:
and drying the tin plate with the phosphating film.
Optionally, the drying temperature is 30-60 ℃, and the drying time is 10-300 s.
Optionally, the passivation treatment comprises a chemical passivation treatment and an electrochemical passivation treatment; the components of the passivation solution comprise at least one of sodium dichromate and chromic anhydride, the molar content of hexavalent chromium in the passivation solution is 0.06-0.5 mol/L, and the pH value of the passivation solution is 3.5-5.5.
Optionally, the passivation temperature of the chemical passivation treatment is 30-60 ℃, and the passivation time of the chemical passivation treatment is 1-60 s; the passivation current of the electrochemical passivation treatment is 1A/dm2-3A/dm2The passivation temperature of the electrochemical passivation treatment is 30-60 ℃, and the passivation time of the electrochemical passivation treatment is 1-60 s.
Based on the same invention concept, the embodiment of the invention also provides the extremely low tin content tin plate with good corrosion resistance, and the extremely low tin content tin plate with good corrosion resistance is prepared by adopting the preparation method of the extremely low tin content tin plate with good corrosion resistance.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the preparation method of the tin plate with the extremely low tin content and good corrosion resistance, provided by the embodiment of the invention, comprises the following steps: carrying out phosphating treatment on the tin plate body in phosphating solution to obtain a tin plate with a phosphating film; the tin content of the tin plate body is less than or equal to
1.1g/m2(ii) a Passivating the tin plate with the phosphating film in a chromate passivating solution to obtain a tin plate with extremely low tin content and good corrosion resistance; the corrosion resistance of the tin plate with extremely low tin content is effectively improved.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a flow chart of a method provided by an embodiment of the invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
the applicant finds in the course of the invention that: the tin plate with extremely low tin content has a thin tin layer of 1.1g/m because of less tin plating2The tin layer thickness of the tin-plated plate is only 160 nm. Because of the surface roughness of the steel plate, an iron leakage area exists on the tin plate, which can lead to the reduction of the corrosion resistance of the tin plate, and because of the different properties of the hydrogen evolution overpotential of iron and tin, the passivation film of chromate on the tin plate with extremely low tin content is not uniform, so that the corrosion resistance of the tin plate with extremely low tin content can not be effectively improved by the chromate passivation.
The applicant finds that chromate is easy to form a film on tin, phosphate is easy to form a film on iron, and in order to solve the problem that chromate cannot uniformly form a film on a tin plate with extremely low tin content, the method determines that the tin plate with extremely low tin content is firstly subjected to phosphating treatment, a phosphating film can be formed at an iron leakage position, then chromate passivation treatment is carried out, and a passivation film is formed on the tin plate, so that a chemical film with better corrosion resistance can be formed on the tin plate with extremely low tin content, and the corrosion resistance of the tin plate with extremely low tin content is effectively improved.
According to an exemplary embodiment of the present invention, there is provided a method for manufacturing a very low tin plated sheet having good corrosion resistance, the method including:
s1, carrying out phosphating treatment on a tinned plate body in phosphating solution to obtain a tinned plate with a phosphating film; the tin content of the tin plate body is less than or equal to 1.1g/m2；
As an alternative embodiment, the phosphating treatment can adopt a chemical phosphating treatment, wherein a phosphating solution of the chemical phosphating treatment comprises phosphate radical, and the molar concentration of the phosphate radical is 0.08mol/L-0.50 mol/L; the pH value of the phosphating solution for chemical phosphating is 1.5-3.5.
The reason for controlling the molar concentration of the phosphate radical to be 0.08mol/L-0.50mol/L is that a phosphating film with better resistance can be obtained in the range, the adverse effect of overlarge concentration value is that the formed phosphating film is not compact enough and has poorer corrosion resistance, and the adverse effect of undersize is that the phosphating film is not easy to form and has poorer corrosion resistance.
The reason for controlling the pH value of the phosphating solution to be 1.5-3.5 is that a phosphating film with better resistance can be obtained in the range, the over-large pH value has the adverse effect that the phosphating film is formed slowly, the phosphating solution is unstable, and the over-small pH value has the adverse effect that more hydrogen is generated, so that the phosphating film is rough and has poorer corrosion resistance.
More preferably, the phosphating solution for chemical phosphating also comprises a surfactant, wherein the surfactant comprises at least one of OP-10, PEG2000 and X-100, and the addition amount of the surfactant is as follows: 0.00006 mol/L-0.006 mol/L.
In the specific operation, the phosphating temperature of the chemical phosphating treatment is 30-70 ℃, and the phosphating time of the chemical phosphating treatment is 30-1200 s.
As an alternative embodiment, the phosphating treatment can be an electrochemical phosphating treatment, wherein the components of a phosphating solution of the electrochemical phosphating treatment comprise phosphate radical, zinc ions, aluminum ions, tin ions and an accelerator, the molar concentration of the phosphate radical is 0.08mol/L-0.50mol/L, the molar concentration of the zinc ions is 0.01mol/L-0.2mol/L, the molar concentration of the aluminum ions is 0.01mol/L-0.2mol/L, the molar concentration of the tin ions is 0.01mol/L-0.2mol/L, and the molar concentration of the accelerator is 0.01mol/L-0.06 mol/L; the pH value of the phosphating solution for electrochemical phosphating is 2-4; the accelerator includes at least one of sodium nitrate and sodium nitrite.
The reason for controlling the molar concentration of the phosphate radical to be 0.08mol/L-0.50mol/L is that a phosphate film with better resistance can be obtained in the range, the adverse effect of overlarge concentration is that the formed phosphate film is loose and porous, the corrosion resistance is poorer, and the adverse effect of undersize is that the phosphate film is not easy to form.
The reason for controlling the molar concentration of zinc ions to 0.01mol/L to 0.2mol/L, the molar concentration of aluminum ions to 0.01mol/L to 0.2mol/L and the molar concentration of tin ions to 0.01mol/L to 0.2mol/L is that a phosphate film having good resistance can be obtained in this range, and the adverse effect of excessively large concentration is that the adverse effect of excessively small decrease in corrosion resistance is that the formation of a phosphate film is not easily caused.
The molar concentration of the accelerator is controlled to be 0.01-0.06 mol/L, the accelerator can generate nitrogen oxide, the concentration is too high to be beneficial to safety, and the concentration is lower to be beneficial to the formation of a phosphating film.
The reason for controlling the pH value of the phosphating solution of the electrochemical phosphating treatment to be 2-4 is that a phosphating film with better resistance can be obtained in the range, the over-large pH value has the adverse effect that the phosphating solution is unstable and the speed of forming the phosphating film is slower, the over-small adverse effect is that the generated hydrogen is more violent, and the formed phosphating film is rougher.
In specific operation, the phosphating current of electrochemical phosphating treatment is 1A/dm2-10A/dm2The phosphating temperature of the electrochemical phosphating treatment is 30-70 ℃, and the phosphating time of the electrochemical phosphating treatment is 1-180 s.
And after phosphating, the tin plate with the extremely low tin content is washed clean by deionized water, is dried and is passivated.
S2, passivating the tin plate with the phosphating film in a chromate passivating solution to obtain the tin plate with extremely low tin content and good corrosion resistance.
As an alternative embodiment, the passivation treatment can be chemical passivation treatment or electrochemical passivation treatment, the components of the passivation solution comprise at least one of sodium dichromate and chromic anhydride, the molar content of hexavalent chromium in the passivation solution is 0.06mol/L-0.5mol/L, and the pH value of the passivation solution is 3.5-5.5.
During the specific operation, the passivation temperature of the chemical passivation treatment is 30-60 ℃, and the passivation time of the chemical passivation treatment is 1-60 s.
In specific operation, the passivation current of electrochemical passivation treatment is 1A/dm2-3A/dm2The passivation temperature of the electrochemical passivation treatment is 30-60 ℃, and the passivation time of the electrochemical passivation treatment is 1-60 s.
As an optional implementation mode, after phosphating the tin-plated plate with the extremely low tin content, drying treatment can be carried out to promote the formation of a phosphating film; the drying temperature is 30-60 ℃, the drying time is 10-300 s, and the drying treatment can be omitted.
In actual operation, the whole preparation process is as follows:
1) firstly, phosphating the tin plate in phosphating solution, which can be chemical phosphating or electrochemical phosphating, using deionized water to clean and blow the tin plate after phosphating, and drying the tin plate for 50s at 30-70 ℃.
2) Carrying out cathodic electrolytic passivation on the phosphated extremely-low-tin-content tin-plated plate in a chromate passivation solution, wherein the passivation current is 1-3A/dm2The passivation temperature is 40-60 ℃, and the passivation time is 1-30 s.
3) And drying the dried tin plate at 60 ℃ for 10-60 min to completely dry the tin plate.
The extremely low tin plated sheet excellent in corrosion resistance and the method for producing the same according to the present invention will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
Using 10ml/L phosphoric acid solution, pH1.5, first plating the surface of the plate with very low tin contentAnd (4) performing roller coating, and drying the extremely-low-tin-content tin-plated plate subjected to roller coating at 50 ℃ for 2 min. The phosphated tin plate with extremely low tin content is subjected to cathodic electrolytic passivation in sodium dichromate passivation solution with the concentration of 25g/L, pH being 4.2, and the passivation current is 1A/dm2The passivation time is 3s, and the passivation temperature is 40 ℃. And cleaning the passivated tin plate with extremely low tin content by using deionized water and drying.
Comparative example 1
The tin-plated sheet of the same process as that of example 1 was subjected only to the passivation process described in example 1.
Example 2
The tin plate with the extremely low tin content is soaked in 10ml/L phosphoric acid solution with the pH value of 1.5 for 3s, and then is baked for 3min at the temperature of 80 ℃, and a phosphating film is formed on the surface of the tin plate with the extremely low tin content. The phosphated tin plate with extremely low tin content is subjected to cathodic electrolytic passivation in sodium dichromate passivation solution with the concentration of 25g/L, pH being 4.2, and the passivation current is 1A/dm2The passivation time is 3s, and the passivation temperature is 40 ℃. And cleaning the passivated tin plate with extremely low tin content by using deionized water and drying.
Comparative example 2
The tin-plated sheet of the same process as that of example 2 was subjected to only the passivation process described in example 2.
Example 3
Firstly, carrying out anode phosphorization in phosphorization liquid, wherein the phosphorization liquid comprises 10ml/L phosphoric acid and 30g/L trisodium phosphate, the pH value of the phosphorization liquid is 2.5, and the process condition of the anode phosphorization is 1A/dm2The phosphating temperature is 25 ℃ and the phosphating time is 60 s. And cleaning the phosphatized tin plate with deionized water and drying the phosphatized tin plate by blowing, and then performing cathode electrolytic passivation on the phosphatized tin plate in a chromate passivation solution, wherein the chromate passivation solution consists of 25g/L sodium dichromate, the pH value is 4.2, the passivation current density is 1A/dm, the passivation temperature is 40 ℃, and the passivation time is 3 s.
Comparative example 3
The tin-plated sheet of the same process as that of example 3 was subjected only to the passivation process described in example 3.
Example 4
Firstly, carrying out anode phosphorization in phosphorization liquid, wherein the composition of the phosphorization liquid is 30g/L trisodium phosphate,the pH value of the phosphating solution is 12, and the anode phosphating process condition is 1A/dm2The phosphating temperature is 25 ℃ and the phosphating time is 60 s. And cleaning the phosphatized tin plate with deionized water and drying the phosphatized tin plate by blowing, and then performing cathode electrolytic passivation on the phosphatized tin plate in a chromate passivation solution, wherein the chromate passivation solution consists of 25g/L sodium dichromate, the pH value is 4.2, the passivation current density is 1A/dm, the passivation temperature is 40 ℃, and the passivation time is 3 s.
Comparative example 4
The tin-plated sheet of the same process as that of example 4 was subjected only to the passivation process described in example 4.
Example 5
Firstly, carrying out anode phosphorization in phosphorization liquid, wherein the composition of the phosphorization liquid is 30g/L trisodium phosphate, the pH value of the phosphorization liquid is 12, and the process condition of the anode phosphorization is 2A/dm2The phosphating temperature is 25 ℃ and the phosphating time is 60 s. And cleaning the phosphatized tin plate with deionized water and drying the phosphatized tin plate by blowing, and then performing cathode electrolytic passivation on the phosphatized tin plate in a chromate passivation solution, wherein the chromate passivation solution consists of 25g/L sodium dichromate, the pH value is 4.2, the passivation current density is 1A/dm, the passivation temperature is 40 ℃, and the passivation time is 3 s.
Comparative example 5
The tin-plated sheet of the same process as that of example 5 was subjected only to the passivation process described in example 5.
Example 6
Firstly, carrying out cathodic electrolysis and electrode phosphating in phosphating solution, wherein the phosphating solution comprises the following components: 5g/L of zinc oxide, 12ml/L of phosphoric acid, 1.8g/L of sodium nitrite, 2.4 of pH value and 1A/dm of current density2Phosphating time 30s, phosphating temperature 25 ℃ and p. And cleaning the phosphatized tin plate with deionized water and drying the phosphatized tin plate by blowing, and then performing cathode electrolytic passivation on the phosphatized tin plate in a chromate passivation solution, wherein the chromate passivation solution consists of 25g/L sodium dichromate, the pH value is 4.2, the passivation current density is 1A/dm, the passivation temperature is 40 ℃, and the passivation time is 3 s.
Comparative example 6
The tin-plated sheet of the same process as that of example 6 was subjected only to the passivation process described in example 6.
Example 7
Firstly, carrying out cathodic electrolysis and electrode phosphating in phosphating solution, wherein the phosphating solution comprises the following components: 5g/L of zinc oxide, 12ml/L of phosphoric acid, 1.8g/L of sodium nitrite, 2.4 of pH value and 2A/dm of current density2Phosphating time 15s, phosphating temperature 25 ℃ and p. And cleaning the phosphatized tin plate with deionized water and drying the phosphatized tin plate by blowing, and then performing cathode electrolytic passivation on the phosphatized tin plate in a chromate passivation solution, wherein the chromate passivation solution consists of 25g/L sodium dichromate, the pH value is 4.2, the passivation current density is 1A/dm, the passivation temperature is 40 ℃, and the passivation time is 3 s.
Comparative example 7
The tin-plated sheet of the same process as that of example 7 was subjected only to the passivation process described in example 7.
Examples of the experiments
The very low tin content tin-plated sheets obtained in examples 1 to 7 and comparative examples 1 to 7 were subjected to the property test, and the test results are shown in the following table:
| salt spray rating | |
| Example 1 | 4 |
| Example 2 | 4 |
| Example 3 | 3 |
| Example 4 | 4 |
| Example 5 | 4 |
| Example 6 | 4 |
| Example 7 | 6 |
| Comparative example 1 | 3 |
| Comparative example 2 | 2 |
| Comparative example 3 | 2 |
| Comparative example 4 | 3 |
| Comparative example 5 | 3 |
| Comparative example 6 | 2 |
| Comparative example 7 | 3 |
From the above table, the corrosion resistance of the tin plate with extremely low tin content, which is passivated after phosphating, by adopting the method provided by the embodiment of the invention is obviously better than that of the tin plate passivated only by chromate.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
according to the method provided by the embodiment of the invention, the extremely low tin content tin plate is firstly subjected to phosphating treatment, a phosphating film can be formed at the iron leakage position, and then chromate passivation treatment is carried out, so that a passivation film is formed on the tin plate, a chemical film with better corrosion resistance can be formed on the extremely low tin content tin plate, and the corrosion resistance of the extremely low tin content tin plate is effectively improved.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A method for preparing a tin plate with extremely low tin content and good corrosion resistance is characterized by comprising the following steps:
carrying out phosphating treatment on the tin plate body in phosphating solution to obtain a tin plate with a phosphating film; the tin content of the tin plate body is less than or equal to 1.1g/m2；
And passivating the tin plate with the phosphating film in a chromate passivating solution to obtain the tin plate with extremely low tin content and good corrosion resistance.
2. The method for producing a very low tin-plated plate excellent in corrosion resistance according to claim 1, wherein said phosphating treatment comprises a chemical phosphating treatment, a component of a phosphating solution of said chemical phosphating treatment comprises phosphate, and a molar concentration of said phosphate is 0.08mol/L to 0.50 mol/L; the pH value of the phosphating solution for chemical phosphating is 1.5-3.5.
3. The method of claim 2, wherein the phosphating solution further comprises a surfactant, and the surfactant comprises at least one of OP-10, PEG2000 and X-100.
4. The method for producing a very low tin content tin-plated sheet having good corrosion resistance according to claim 2, wherein the phosphating temperature of the chemical phosphating is 30 ℃ to 70 ℃ and the phosphating time of the chemical phosphating is 30s to 1200 s.
5. The method for producing a very low tin-plated plate excellent in corrosion resistance according to claim 1, wherein the phosphating treatment comprises an electrochemical phosphating treatment, and the components of a phosphating solution of the electrochemical phosphating treatment comprise phosphate, zinc ions, aluminum ions, tin ions and an accelerator, wherein the molar concentration of the phosphate is 0.08mol/L to 0.50mol/L, the molar concentration of the zinc ions is 0.01mol/L to 0.2mol/L, the molar concentration of the aluminum ions is 0.01mol/L to 0.2mol/L, the molar concentration of the tin ions is 0.01mol/L to 0.2mol/L, and the molar concentration of the accelerator is 0.01mol/L to 0.06 mol/L; the pH value of the phosphating solution for electrochemical phosphating is 2-4; the accelerator includes at least one of sodium nitrate and sodium nitrite.
6. The method for producing a very low tin-plated sheet excellent in corrosion resistance according to claim 5, wherein said electrochemical phosphating treatment is carried out at a phosphating current of 1A/dm2-10A/dm2The phosphating temperature of the electrochemical phosphating treatment is 30-70 ℃, and the phosphating time of the electrochemical phosphating treatment is 1-180 s.
7. The method for producing a very low tin-plated sheet having good corrosion resistance according to claim 1, wherein the passivation treatment comprises a chemical passivation treatment and an electrochemical passivation treatment; the components of the passivation solution comprise at least one of sodium dichromate and chromic anhydride, the molar content of hexavalent chromium in the passivation solution is 0.06-0.5 mol/L, and the pH value of the passivation solution is 3.5-5.5.
8. The method for preparing a very low tin-plated plate with good corrosion resistance according to claim 7, wherein the passivation temperature of the chemical passivation treatment is 30-60 ℃, and the passivation time of the chemical passivation treatment is 1-60 s; the passivation current of the electrochemical passivation treatment is 1A/dm2-3A/dm2The passivation temperature of the electrochemical passivation treatment is 30-60 ℃, and the passivation time of the electrochemical passivation treatment is 1-60 s.
9. The method for producing a very low tin-plated sheet having good corrosion resistance according to claim 1, further comprising:
drying the tin plate with the phosphating film; the drying temperature is 30-60 ℃, and the drying time is 10-300 s.
10. An extremely low tin-plated plate with good corrosion resistance, characterized in that the extremely low tin-plated plate with good corrosion resistance is produced by the method for producing an extremely low tin-plated plate with good corrosion resistance according to any one of claims 1 to 9.
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| GB8824016D0 (en) * | 1987-10-13 | 1988-11-23 | Nihon Parkerizing | Compositions & processes for forming phosphate coatings on metals |
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| CN109023445A (en) * | 2018-08-06 | 2018-12-18 | 首钢集团有限公司 | A kind of preparation method and applications of extremely low tin amount tin plate |
| CN110284131A (en) * | 2019-06-17 | 2019-09-27 | 首钢集团有限公司 | A kind of low tinplating steel sheet passivation technology |
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2021
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| GB8824016D0 (en) * | 1987-10-13 | 1988-11-23 | Nihon Parkerizing | Compositions & processes for forming phosphate coatings on metals |
| CN107488845A (en) * | 2016-06-11 | 2017-12-19 | 上海梅山钢铁股份有限公司 | A kind of chromium-free passivation liquid and its application method for tin plate |
| CN109023445A (en) * | 2018-08-06 | 2018-12-18 | 首钢集团有限公司 | A kind of preparation method and applications of extremely low tin amount tin plate |
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