CN112899669A - Nano passivation coating galvanized sheet and production process thereof - Google Patents
Nano passivation coating galvanized sheet and production process thereof Download PDFInfo
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- CN112899669A CN112899669A CN202110074103.2A CN202110074103A CN112899669A CN 112899669 A CN112899669 A CN 112899669A CN 202110074103 A CN202110074103 A CN 202110074103A CN 112899669 A CN112899669 A CN 112899669A
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- nano
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- passivation
- galvanized sheet
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- 238000002161 passivation Methods 0.000 title claims abstract description 109
- 239000011248 coating agent Substances 0.000 title claims abstract description 93
- 238000000576 coating method Methods 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005246 galvanizing Methods 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 229910001868 water Inorganic materials 0.000 claims description 39
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 229920001225 polyester resin Polymers 0.000 claims description 21
- 239000004645 polyester resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229920003180 amino resin Polymers 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000003021 water soluble solvent Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000007761 roller coating Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 238000009500 colour coating Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- 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
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- 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
- C23C22/20—Orthophosphates containing aluminium cations
-
- 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
- C23C22/68—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 solutions with pH between 6 and 8
-
- 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
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention discloses a nano passivation coating galvanized sheet and a production process thereof, belonging to the technical field of galvanized sheet protection. The production process comprises forming a zinc coating on the surface of a metal substrate by electrogalvanizing or hot galvanizing; then passivating the surface of the galvanized sheet by using a chromium-free passivation solution at a low temperature to form a colorless transparent passivation layer; finally, coating a nano passivation coating containing nano fillers with lamellar and granular structures on the passivation layer in a roller coating mode to obtain a nano passivation coating galvanized plate; the galvanized sheet produced by the production process comprises a metal substrate, a colorless transparent passivation layer coated on the surface of the metal substrate and a nano passivation coating coated on the surface of the colorless transparent passivation layer. The production process is simple and convenient to operate, the production energy consumption is low, and the produced galvanized sheet has good corrosion resistance and good wear resistance.
Description
Technical Field
The invention relates to a galvanized sheet and a production process thereof, in particular to a nano passivation coating galvanized sheet and a production process thereof, belonging to the technical field of galvanized sheet protection.
Background
Galvanized metal sheets are widely used in the fields of automobiles, building materials, household electrical appliances, containers, and the like because of their excellent corrosion resistance and low price. However, the galvanized metal sheet is easily corroded in a humid environment, and white corrosion products are formed or the galvanized metal sheet is changed into a dark color on the surface, thereby affecting the appearance quality of the galvanized metal sheet and the corrosion resistance of the coating. In the prior art, in order to solve the technical problems, passivation solution is adopted to passivate the surface of a galvanized plate or color coating is carried out on the surface of the galvanized plate, but the problems of poor corrosion resistance, especially poor acid liquid resistance and alkali liquid resistance still exist.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nano passivation coating galvanized sheet and a production process thereof.
The technical scheme of the invention is as follows:
the production process of the nano passivation coating galvanized plate mainly comprises the following steps:
s1, forming a zinc coating on the surface of the metal substrate by adopting electrogalvanizing or hot galvanizing;
s2, degreasing the galvanized sheet obtained in the step S1 with alkali liquor, cleaning with clear water, drying with hot air, and passivating the surface of the galvanized sheet with a chromium-free passivation solution to form a colorless transparent passivation layer;
s3, coating a nano passivation coating with the thickness of 8-20 μm on the colorless transparent passivation layer of the galvanized sheet obtained through the treatment of the step S2 in a roll coating mode, and drying the nano passivation coating at the temperature of 150-250 ℃ until the nano passivation coating is dried to obtain a nano passivation coating galvanized sheet;
the chromium-free passivation solution in the step S2 is mainly prepared from a mixture of water-soluble resin, a water-soluble solvent, metal phosphate, phosphoric acid and water, wherein the amount of the metal phosphate accounts for 3-8g/100ml of the total amount of the chromium-free passivation solution, and the amount of the phosphoric acid accounts for 2-3g/100ml of the total amount of the chromium-free passivation solution;
the nano passivation coating in the step S3 is mainly prepared from water-based polyester resin, water-based amino resin, aliphatic dibasic acid ester, nano filler, colored pigment, a silane coupling agent, a processing aid and water, wherein the nano filler is formed by mixing nano graphene powder and nano silicon dioxide powder according to a mass ratio of 1 (4-5), and the nano filler accounts for 3-8 wt% of the total mass of the coating.
The further technical scheme is as follows:
the metal phosphate in the chromium-free passivation solution in the step S2 is at least one of zinc phosphate and aluminum phosphate.
The further technical scheme is as follows:
the passivation method in the step S2 is that the chromium-free passivation solution is coated on the surface of the galvanized sheet by adopting a roll coating mode and is dried for 30-60S at the temperature of 60-80 ℃ to form a colorless transparent passivation layer, and the coating amount of the chromium-free passivation solution is 20-50g/m2。
The further technical scheme is as follows:
in the step S3, the particle size of the nano graphene powder is 80-150nm, and the particle size of the nano silicon dioxide powder is 50-80 nm.
The further technical scheme is as follows:
the coating for the nanometer passivation coating in the step S3 mainly comprises the following components in percentage by mass: 35-45 wt.% of water-based polyester resin, 5-10 wt.% of water-based amino resin, 3-8 wt.% of aliphatic dibasic acid ester, 3-8 wt.% of nano filler, 5-8 wt.% of colored pigment, 2-3 wt.% of silane coupling agent, 1-3 wt.% of processing aid and the balance of water.
The further technical scheme is as follows:
the solid hydroxyl value of the waterborne polyester resin is 50-150mgKOH/g, the weight average molecular weight is 2000-8000, the Tg is 50-80 ℃, and the waterborne polyester resin is at least one of acrylic acid modified polyester resin and unsaturated anhydride modified polyester resin; and the aqueous amino resin is at least one of melamine formaldehyde aqueous resin, methylated aqueous amino resin and butylated amino aqueous resin.
The further technical scheme is as follows:
the aliphatic dibasic acid ester is at least two of dimethyl glutarate, dimethyl succinate and dimethyl adipate.
The further technical scheme is as follows:
the processing aid comprises an antifoaming agent, a leveling agent and wax slurry.
The invention also discloses a nano passivation coating galvanized sheet which is produced by adopting the production process and comprises a metal substrate, a colorless transparent passivation layer coated on the surface of the metal substrate and a nano passivation coating coated on the surface of the colorless transparent passivation layer.
The further technical scheme is as follows:
the metal substrate is one of a stainless steel coil plate, an aluminum coil plate and a copper coil plate.
The beneficial technical effects of the invention are as follows:
1. the processing technology adopts a mode of firstly passivating the galvanized plate and then coating the nano passivation coating, firstly forms a colorless transparent passivation layer on the galvanized plate, then forms a colored nano passivation coating, and protects the surface of the galvanized plate by utilizing the passivation layer and the nano passivation coating, so that the galvanized plate has excellent corrosion resistance and wear resistance;
2. the passivation solution adopted by the processing technology adopts the coordination of metal phosphate and phosphoric acid as corrosion-resistant components, and uses water-soluble resin to form a film, so that a colorless transparent passivation layer can be formed on the surface of a galvanized sheet at low temperature, and the color matching is conveniently carried out by using a colored nano passivation coating in the later period;
3. the graphene powder used in the nano coating for the passivation coating adopted by the processing technology has a layered structure and can be paved on the surface of a material; the used nano silicon dioxide powder has a spherical structure and can be filled in gaps among graphene sheet laminated structures, so that the sheet laminated structures and the spherical structures are filled on the surface of a protected material, and the corrosion resistance of the galvanized sheet can be enhanced;
4. the processing technology of the invention uses resin with close performance in the passivation solution and the nano passivation coating, and can enhance the binding force between the passivation layer formed after curing and the nano passivation coating, thereby avoiding the interlayer stripping and enhancing the corrosion resistance of the galvanized sheet.
Detailed Description
In order to clearly understand the technical means of the present invention and to implement the technical means according to the content of the specification, the following embodiments are further described in detail in the following with reference to the specific examples, which are used for illustrating the present invention and are not intended to limit the scope of the present invention.
The chromium-free passivation solution is mainly prepared from a mixture of water-soluble resin, a water-soluble solvent, metal phosphate, phosphoric acid and water. The water-soluble resin is mainly water-soluble acrylic resin, water-soluble polyurethane resin, water-soluble alkyd resin, water-soluble polyester resin and the like, and the water-soluble acrylic resin is preferably selected in the specific embodiment; in addition, the water-soluble resin can also be selected from emulsions of the above resins, or emulsions which are convenient for film formation, such as epoxy emulsion, styrene emulsion and the like, and when the emulsion is selected, the epoxy emulsion is preferred; the amount of the above water-soluble resin or emulsion is 8-15 wt.%. Wherein the water-soluble solvent is a solvent capable of being dissolved in water, and mainly plays a role of a cosolvent, such as an alcohol solvent, an ether solvent, an alcohol ether solvent and the like, and the alcohol ether solvent is preferably selected in the specific embodiment; and the amount of the water-soluble solvent is 6-8 wt.%. Wherein the metal phosphate is at least one of zinc phosphate and aluminum phosphate, the dosage of the metal phosphate accounts for 3-8g/100ml of the total amount of the chromium-free passivation solution, and the dosage of the phosphoric acid accounts for 2-3g/100ml of the total amount of the chromium-free passivation solution; the metal phosphates and phosphoric acid described above function mainly to form a passivation component. In addition, the chromium-free passivation solution can also comprise processing aids such as a defoaming agent, a leveling agent and the like which are convenient for film formation, and the dosage of the processing aids is generally 1-2 wt.%. The rest of the chromium-free passivation solution is water. The water-soluble resin, the water-soluble solvent and the processing aid in the chromium-free passivation solution are conventional technical schemes in the field, and are not described in detail in the application.
The coating for the nano passivation coating mainly comprises the following components in percentage by mass: 35-45 wt.% of water-based polyester resin, 5-10 wt.% of water-based amino resin, 3-8 wt.% of aliphatic dibasic acid ester, 3-8 wt.% of nano filler, 5-8 wt.% of colored pigment, 2-3 wt.% of silane coupling agent, 1-3 wt.% of processing aid and the balance of water. Wherein the solid hydroxyl value of the water-based polyester resin is 50-150mgKOH/g, the weight average molecular weight is 2000-8000, the Tg is 50-80 ℃, and the water-based polyester resin is at least one of acrylic acid modified polyester resin and unsaturated anhydride modified polyester resin. Wherein the aqueous amino resin is at least one of melamine formaldehyde aqueous resin, methylated amino aqueous resin and butylated amino aqueous resin. Wherein the aliphatic dibasic acid ester is at least two of dimethyl glutarate, dimethyl succinate and dimethyl adipate. The nano-filler is formed by mixing nano-graphene powder and nano-silicon dioxide powder according to a mass ratio of 1 (4-5), and the nano-filler accounts for 3-8 wt% of the total mass of the coating; wherein the grain diameter of the nano graphene powder is 80-150nm, and the grain diameter of the nano silicon dioxide powder is 50-80 nm. The color pigment can be high temperature resistant pigment such as carbon black. The silane coupling agent is a conventional silane coupling agent used in the art and will not be described in detail herein. The processing aid comprises a defoaming agent, a leveling agent and wax slurry.
The production of the nano-passivation coating galvanized sheet is carried out according to the production process described in the following specific example.
Detailed description of the preferred embodiment 1
And S1, forming a zinc coating on the surface of the metal substrate by electrogalvanizing or hot galvanizing.
S2, degreasing the galvanized sheet obtained in the step S1 by using a sodium hydroxide solution with the concentration of 10g/L, cleaning the galvanized sheet by using clean water, drying the galvanized sheet by using hot air, and then rolling and coating the galvanized sheet by using a chromium-free passivation solution with the concentration of 30g/m2The coating amount of (a) is coated on the surface of a galvanized sheet, and a colorless transparent passivation layer is formed after the galvanized sheet is dried for 40s at 75 ℃;
the colorless transparent passivation solution comprises the following components: acrylic resin emulsion with 35 wt.% of solid content, ethylene glycol 8 wt.%, zinc phosphate 6g/100ml, phosphoric acid 2g/100ml, processing aid 1 wt.% and water in balance; wherein the dosage of the leveling agent in the processing aid is 0.5 wt.%, and the dosage of the defoaming agent is 0.5 wt.%.
S3, coating a nano passivation coating with the thickness of 10 microns on the colorless transparent passivation layer of the galvanized plate obtained through the treatment of the step S2 in a roller coating mode at the linear speed of 100m/min, and drying the nano passivation coating at 220 ℃ until the nano passivation coating is dried to obtain a nano passivation coating galvanized plate;
the nano-passivation coating comprises the following components: 40 wt.% of water-based acrylic modified polyester resin, 8 wt.% of melamine formaldehyde water-based resin, 1 wt.% of dimethyl glutarate, 2 wt.% of dimethyl adipate, 1 wt.% of 100nm nano graphene powder, 4 wt.% of 60nm nano silicon dioxide powder, 5 wt.% of carbon black, 3 wt.% of silane coupling agent, 2 wt.% of processing aid and the balance of water; wherein the dosage of the leveling agent in the processing aid is 0.5 wt.%, the dosage of the defoaming agent is 0.5 wt.%, and the dosage of the wax slurry is 1.0 wt.%.
Specific example 2
And S1, forming a zinc coating on the surface of the metal substrate by electrogalvanizing or hot galvanizing.
S2, degreasing the galvanized sheet obtained in the step S1 by using a sodium hydroxide solution with the concentration of 10g/L, cleaning the galvanized sheet by using clean water, drying the galvanized sheet by using hot air, and then rolling the galvanized sheet by using a roller coating mode to form a chromium-free passivation solution with the concentration of 40g/m2The coating amount of (a) is coated on the surface of a galvanized sheet, and a colorless transparent passivation layer is formed after the galvanized sheet is dried for 40s at 80 ℃;
the colorless transparent passivation solution comprises the following components: 8 wt.% of water-soluble acrylic resin, 8 wt.% of mixed solvent formed by mixing ethylene glycol and glycerol according to a mass ratio of 2:1, 8g/100ml of metal phosphate formed by mixing zinc phosphate and aluminum phosphate according to a mass ratio of 3:1, 2g/100ml of phosphoric acid, 1 wt.% of processing aid and the balance of water; wherein the dosage of the leveling agent in the processing aid is 0.5 wt.%, and the dosage of the defoaming agent is 0.5 wt.%.
S3, coating a nano passivation coating with the thickness of 8 microns on the colorless transparent passivation layer of the galvanized plate obtained through the treatment of the step S2 in a roll coating mode at the linear speed of 110m/min, and drying at 200 ℃ until the nano passivation coating is dried to obtain a nano passivation coating galvanized plate;
the nano-passivation coating comprises the following components: 45 wt.% of maleic anhydride modified polyester resin, 10 wt.% of melamine formaldehyde water-based resin, 4 wt.% of dimethyl succinate, 2 wt.% of 90nm nano graphene powder, 3 wt.% of 50nm nano silicon dioxide powder, 8 wt.% of carbon black, 3 wt.% of silane coupling agent, 2 wt.% of processing aid and the balance of water; wherein the dosage of the leveling agent in the processing aid is 0.5 wt.%, the dosage of the defoaming agent is 0.5 wt.%, and the dosage of the wax slurry is 1.0 wt.%.
Specific example 3
And S1, forming a zinc coating on the surface of the metal substrate by electrogalvanizing or hot galvanizing.
S2, degreasing the galvanized sheet obtained in the step S1 by using a sodium hydroxide solution with the concentration of 10g/L, cleaning the galvanized sheet by using clean water, drying the galvanized sheet by using hot air, and then rolling and coating the galvanized sheet by using a chromium-free passivation solution with the concentration of 45g/m2The coating amount of (a) is coated on the surface of a galvanized sheet, and a colorless transparent passivation layer is formed after the galvanized sheet is dried for 60s at 80 ℃;
the colorless transparent passivation solution comprises the following components: 10 wt.% of water-based acrylic resin, 6 wt.% of mixed solvent formed by glycol and glycerol according to the mass ratio of 2:1, 5g/100ml of aluminum phosphate, 3g/100ml of phosphoric acid, 1 wt.% of processing aid and the balance of water; wherein the dosage of the leveling agent in the processing aid is 0.5 wt.%, and the dosage of the defoaming agent is 0.5 wt.%.
S3, coating a nano passivation coating with the thickness of 20 microns on the colorless transparent passivation layer of the galvanized plate obtained through the treatment of the step S2 in a roll coating mode at the linear speed of 120m/min, and drying at 240 ℃ until the nano passivation coating is dried to obtain a nano passivation coating galvanized plate;
the nano-passivation coating comprises the following components: 40 wt.% of acrylic acid modified polyester resin, 8 wt.% of melamine formaldehyde water-based resin, 6 wt.% of dimethyl adipate, 3 wt.% of 100nm nano graphene powder, 3 wt.% of 80nm nano silicon dioxide powder, 6 wt.% of carbon black, 3 wt.% of silane coupling agent, 2 wt.% of processing aid and the balance of water; wherein the dosage of the leveling agent in the processing aid is 0.5 wt.%, the dosage of the defoaming agent is 0.5 wt.%, and the dosage of the wax slurry is 1.0 wt.%.
The results of comparing the performance of the galvanized sheet prepared in the above embodiment with that of a commercially available conventional galvanized sheet are shown in the following table 1, and the testing method is as follows:
the color and appearance, adhesion (cross hatch, grade), gloss (60 °), T-bend (T), cupping (mm), MEK rub resistance, impact strength (J), pencil hardness, salt spray resistance (96h) were all tested as described in GB/T13448-2006. The alkali-resistant liquid is characterized in that 5% sodium hydroxide solution is adopted for soaking at normal temperature; the acid-resistant liquid is soaked in 5% hydrochloric acid at normal temperature; the water resistance is that tap water is soaked at normal temperature; the oil resistance is achieved by soaking in machine butter at room temperature.
TABLE 1 results of testing the properties of the examples and the commercially available panels
As can be seen from table 1, the nano-passivation coating galvanized sheet prepared by performing passivation and then coating with the nano-passivation coating by using the process described herein has excellent corrosion resistance, coating adhesion and wear resistance compared with the commercially available products in the prior art.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The production process of the nano passivation coating galvanized plate is characterized by mainly comprising the following steps of:
s1, forming a zinc coating on the surface of the metal substrate by adopting electrogalvanizing or hot galvanizing;
s2, degreasing the galvanized sheet obtained in the step S1 with alkali liquor, cleaning with clear water, drying with hot air, and passivating the surface of the galvanized sheet with a chromium-free passivation solution to form a colorless transparent passivation layer;
s3, coating a nano passivation coating with the thickness of 8-20 μm on the colorless transparent passivation layer of the galvanized sheet obtained through the treatment of the step S2 in a roll coating mode, and drying the nano passivation coating at the temperature of 150-250 ℃ until the nano passivation coating is dried to obtain a nano passivation coating galvanized sheet;
the chromium-free passivation solution in the step S2 is mainly prepared from a mixture of water-soluble resin, a water-soluble solvent, metal phosphate, phosphoric acid and water, wherein the amount of the metal phosphate accounts for 3-8g/100ml of the total amount of the chromium-free passivation solution, and the amount of the phosphoric acid accounts for 2-3g/100ml of the total amount of the chromium-free passivation solution;
the nano passivation coating in the step S3 is mainly prepared from water-based polyester resin, water-based amino resin, aliphatic dibasic acid ester, nano filler, colored pigment, a silane coupling agent, a processing aid and water, wherein the nano filler is formed by mixing nano graphene powder and nano silicon dioxide powder according to a mass ratio of 1 (4-5), and the nano filler accounts for 3-8 wt% of the total mass of the coating.
2. The process for producing a nano-passivated coating galvanized sheet according to claim 1, characterized in that: the metal phosphate in the chromium-free passivation solution in the step S2 is at least one of zinc phosphate and aluminum phosphate.
3. The process for producing a nano-passivated coating galvanized sheet according to claim 2, characterized in that: the passivation method in the step S2 is that the chromium-free passivation solution is applied to a rollerThe coating mode is coated on the surface of the galvanized sheet and forms a colorless transparent passivation layer after being dried for 30-60s at the temperature of 60-80 ℃, and the coating amount of the chromium-free passivation solution is 20-50g/m2。
4. The process for producing a nano-passivated coating galvanized sheet according to claim 1, characterized in that: in the step S3, the particle size of the nano graphene powder is 80-150nm, and the particle size of the nano silicon dioxide powder is 50-80 nm.
5. The process for producing a nano-passivated coating galvanized sheet according to claim 4, characterized in that: the coating for the nanometer passivation coating in the step S3 mainly comprises the following components in percentage by mass: 35-45 wt.% of water-based polyester resin, 5-10 wt.% of water-based amino resin, 3-8 wt.% of aliphatic dibasic acid ester, 3-8 wt.% of nano filler, 5-8 wt.% of colored pigment, 2-3 wt.% of silane coupling agent, 1-3 wt.% of processing aid and the balance of water.
6. The process for producing a nano-passivated coating galvanized sheet according to claim 5, characterized in that: the solid hydroxyl value of the waterborne polyester resin is 50-150mgKOH/g, the weight average molecular weight is 2000-8000, the Tg is 50-80 ℃, and the waterborne polyester resin is at least one of acrylic acid modified polyester resin and unsaturated anhydride modified polyester resin; and the aqueous amino resin is at least one of melamine formaldehyde aqueous resin, methylated amino aqueous resin and butylated amino aqueous resin.
7. The process for producing a nano-passivated coating galvanized sheet according to claim 5, characterized in that: the aliphatic dibasic acid ester is at least two of dimethyl glutarate, dimethyl succinate and dimethyl adipate.
8. The process for producing a nano-passivated coating galvanized sheet according to claim 5, characterized in that: the processing aid comprises an antifoaming agent, a leveling agent and wax slurry.
9. A nanometer passivation coating galvanized sheet is characterized in that: the nano-passivation coating galvanized sheet produced by the production process of any one of the above claims 1 to 8 comprises a metal substrate, a colorless transparent passivation layer coated on the surface of the metal substrate and a nano-passivation coating coated on the surface of the colorless transparent passivation layer.
10. The nano-passivated coated galvanized sheet according to claim 9, characterized in that: the metal substrate is one of a stainless steel coil plate, an aluminum coil plate and a copper coil plate.
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