CN112877737A - Method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel and protective coating - Google Patents
Method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel and protective coating Download PDFInfo
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- CN112877737A CN112877737A CN202110039835.8A CN202110039835A CN112877737A CN 112877737 A CN112877737 A CN 112877737A CN 202110039835 A CN202110039835 A CN 202110039835A CN 112877737 A CN112877737 A CN 112877737A
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 143
- 239000010935 stainless steel Substances 0.000 title claims abstract description 142
- 238000000576 coating method Methods 0.000 title claims abstract description 132
- 239000011248 coating agent Substances 0.000 title claims abstract description 131
- -1 hydroxyl graphene Chemical compound 0.000 title claims abstract description 108
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- 239000003973 paint Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000011253 protective coating Substances 0.000 title claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 91
- 239000011651 chromium Substances 0.000 claims abstract description 91
- 238000007747 plating Methods 0.000 claims abstract description 47
- 238000009713 electroplating Methods 0.000 claims abstract description 37
- 230000004913 activation Effects 0.000 claims abstract description 21
- 238000005491 wire drawing Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- 239000000945 filler Substances 0.000 claims description 23
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- 239000004814 polyurethane Substances 0.000 claims description 19
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 229920002635 polyurethane Polymers 0.000 claims description 17
- 229910000077 silane Inorganic materials 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 229920003180 amino resin Polymers 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- KZQSXALQTHVPDQ-UHFFFAOYSA-M sodium;butanedioate;hydron Chemical compound [Na+].OC(=O)CCC([O-])=O KZQSXALQTHVPDQ-UHFFFAOYSA-M 0.000 claims description 7
- LXWZLYDXYCQRJT-UHFFFAOYSA-M sodium;hydron;propanedioate Chemical group [H+].[Na+].[O-]C(=O)CC([O-])=O LXWZLYDXYCQRJT-UHFFFAOYSA-M 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000006179 pH buffering agent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 22
- 238000001994 activation Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000005238 degreasing Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4461—Polyamides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
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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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to the technical field of metal electroplating and coating, in particular to a method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel and a protective coating. The method provided by the invention comprises the following steps: carrying out wire drawing on the nickel-free stainless steel, and carrying out cathode electrolytic activation on the surface of the nickel-free stainless steel after wire drawing to obtain pretreated nickel-free stainless steel; electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating; and coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating by adopting a cathode electrophoretic coating mode. The trivalent chromium plating layer improves the binding force between the coating and the nickel-free stainless steel substrate, simultaneously improves the corrosion resistance of the nickel-free stainless steel, and overcomes the technical defect of low corrosion resistance of the nickel-free stainless steel; meanwhile, the electrophoretic paint coating modified by the hydroxyl graphene has good lubricity, wear resistance and corrosion resistance.
Description
Technical Field
The invention relates to the technical field of metal electroplating and coating, in particular to a method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel and a protective coating.
Background
It is well known that nickel has a harmful effect on the human body and even a part of human skin has a significant allergic reaction to nickel. Nickel-free stainless steels, such as 0Cr13 and 1Cr13, are susceptible to discoloration and even rust in the natural environment. Therefore, such materials have not been commonly used. With the increasing awareness of environmental protection, more and more countries have restrictions on the use of nickel-containing steel, particularly nickel-containing stainless steel parts that come into contact with the human body. Therefore, the manufacturing industry has to use a nickel-free stainless steel material instead of a nickel-containing stainless steel. However, when parts and products are made of nickel-free stainless steel, the corrosion resistance is difficult to satisfy the use requirements without performing an anti-corrosion treatment.
In the prior art, the corrosion resistance of the nickel-free stainless steel is generally improved by adopting an electroplating technology. The surface of the stainless steel is provided with a layer of compact oxide film, and the problem of poor bonding force exists when a protective and decorative coating is directly electroplated on the surface of the stainless steel, so that the common electroplating process is generally not feasible. Therefore, it is necessary to plate a layer of strike nickel on the surface of stainless steel, followed by other protective and decorative coatings. It has not been able to fully achieve the nickel-free goal.
Therefore, no report is found on how to improve the corrosion resistance of the nickel-free stainless steel while achieving the purpose of nickel-free by the machining process and the surface treatment process of the nickel-free stainless steel.
Disclosure of Invention
The invention aims to provide a method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel and a protective coating, and the method can realize the purpose of nickel-free and improve the corrosion resistance of the nickel-free stainless steel.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel, which comprises the following steps:
carrying out wire drawing on the nickel-free stainless steel, and carrying out cathode electrolytic activation on the surface of the nickel-free stainless steel after wire drawing to obtain pretreated nickel-free stainless steel;
electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating;
coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating in a cathode electrophoretic coating mode;
the conditions of the cathode electrolysis activation are as follows: the anode is a graphite rod; the cathode is the nickel-free stainless steel after wire drawing; the electrolyte comprises 100-200 g/L of sulfuric acid, 10-30 g/L of acrylic acid and 0.1-0.5 g/L of trimercapto-s-triazine; the current density of the cathode is 0.5-3.0A/dm2The electrolysis time is 1-3 min;
the conditions of the cathode electrophoretic coating are as follows: the anode is a 0Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with a trivalent chromium coating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 300-350 g/L of electrophoretic paint and 150-200 g/L of hydroxyl graphene filler; the pH value of the coating is 4-5; the cathode electrophoretic coating temperature is 25-30 ℃, and the bath voltage is 30-100V;
the hydroxyl graphene filler comprises hydroxyl graphene, waterborne polyurethane and a waterborne silane polymer.
Preferably, the mass ratio of the hydroxyl graphene to the aqueous polyurethane to the aqueous silane polymer is (0.8-3.5): 50-150).
Preferably, the preparation process of the hydroxy graphene filler comprises the following steps:
uniformly mixing 80-350 g of 1% by mass of hydroxyl graphene colloid, waterborne polyurethane, a waterborne silane polymer and 300g of water, adding 1000mL of water, and reacting at normal temperature for 7 days to obtain the hydroxyl graphene filler;
the pH value of the hydroxyl graphene colloid is 7-8, and the hydroxyl graphene in the hydroxyl graphene colloid is nano-grade hydroxyl graphene.
Preferably, the electrophoretic paint comprises the following preparation raw materials in parts by weight: 4-8 parts of epoxy polyamide modified resin, 4-8 parts of amino resin, 3-6 parts of closed polyisocyanate resin, 4-8 parts of pH buffering agent, 10-16 parts of 1-methoxy-2-propanol and 15-25 parts of water.
Preferably, the pH buffer is sodium hydrogen malonate and/or sodium hydrogen succinate.
Preferably, the thickness of the hydroxyl graphene modified electrophoretic paint coating is 5-15 μm.
Preferably, the method for electroplating the trivalent chromium plating layer on the pretreated nickel-free stainless steel surface is sulfate trivalent chromium plating or chloride trivalent chromium plating.
Preferably, the thickness of the trivalent chromium plating layer is 0.05-0.25 μm.
Preferably, the wire drawing is performed by a felt wheel wire drawing machine.
The invention also provides a protective coating of the nickel-free stainless steel prepared by the method in the technical scheme, which comprises a trivalent chromium plating layer and a hydroxyl graphene modified electrophoretic paint coating which are sequentially arranged on the surface of the nickel-free stainless steel.
The invention provides a method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel, which is characterized by comprising the following steps of: drawing the nickel-free stainless steel, and performing cathode electrolytic activation on the surface of the drawn nickel-free stainless steel to obtain the pretreated nickel-free stainless steelStainless steel; electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating; coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating in a cathode electrophoretic coating mode; the conditions of the cathode electrolysis activation are as follows: the anode is a graphite rod; the cathode is the nickel-free stainless steel after wire drawing; the electrolyte comprises 100-200 g/L of sulfuric acid, 10-30 g/L of acrylic acid and 0.1-0.5 g/L of trimercapto-s-triazine; the current density of the cathode is 0.5-3.0A/dm2The electrolysis time is 1-3 min; the conditions of the cathode electrophoretic coating are as follows: the anode is a 0Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with a trivalent chromium coating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 300-350 g/L of electrophoretic paint and 150-200 g/L of hydroxyl graphene filler; the pH value of the coating is 4-5; the cathode electrophoretic coating temperature is 25-30 ℃, and the bath voltage is 30-100V; the hydroxyl graphene filler comprises hydroxyl graphene, waterborne polyurethane and a waterborne silane polymer.
Compared with the prior art, the invention has the following beneficial effects:
1) hydroxyl, epoxy and carbonyl on the surface of the hydroxyl graphene in the hydroxyl graphene filler can react with active groups in molecules of the waterborne polyurethane and the waterborne silane polymer, so that the hydroxyl graphene is combined with the molecules of the waterborne polyurethane and the waterborne silane polymer, the chemical stability and solubility of the hydroxyl graphene in the electrophoretic paint are improved, and the aggregation and precipitation of the hydroxyl graphene in the electrophoresis process are avoided;
2) according to the invention, the oxide film on the surface of the nickel-free stainless steel can be removed in the cathode electrolytic activation process, the chromium sesquioxide on the surface of the nickel-free stainless steel is reduced into metal chromium in the electrolytic process, and the electrolyzed acrylic acid and the trimercapto-s-triazine are adsorbed on the surface of the nickel-free stainless steel, so that the oxide film is inhibited from being regenerated on the surface of the nickel-free stainless steel, and the surface of the nickel-free stainless steel is ensured to be in a better activation state;
3) according to the invention, the trivalent chromium is plated on the surface of the nickel-free stainless steel, and the trivalent chromium plating layer can form good binding force with the nickel-free stainless steel substrate, so that the technical problem that the traditional method can only plate impact nickel on the surface of the stainless steel is solved, meanwhile, the corrosion resistance of the nickel-free stainless steel is also improved, and the technical defect of low corrosion resistance of the nickel-free stainless steel is overcome;
4) the hydroxyl graphene modified electrophoretic paint coating is modified by the hydroxyl graphene, so that the prepared electrophoretic paint coating has good lubricity, wear resistance and corrosion resistance;
5) the hydroxyl graphene modified electrophoretic paint coating is colorless and transparent, has elegant and beautiful appearance and has good anti-tarnishing capability.
Drawings
FIG. 1 is a schematic structural view of a protective coating on a nickel-free stainless steel surface according to the present invention;
wherein, the coating comprises 1-nickel-free stainless steel, a 2-trivalent chromium coating and a 3-hydroxy graphene modified electrophoretic paint coating.
Detailed Description
The invention provides a method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel, which comprises the following steps:
carrying out wire drawing on the nickel-free stainless steel, and carrying out cathode electrolytic activation on the surface of the nickel-free stainless steel after wire drawing to obtain pretreated nickel-free stainless steel;
electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating;
coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating in a cathode electrophoretic coating mode;
the conditions of the cathode electrolysis activation are as follows: the anode is a graphite rod; the cathode is the nickel-free stainless steel after wire drawing; the electrolyte comprises 100-200 g/L of sulfuric acid, 10-30 g/L of acrylic acid and 0.1-0.5 g/L of trimercapto-s-triazine; the current density of the cathode is 0.5-3.0A/dm2The electrolysis time is 1-3 min;
the conditions of the cathode electrophoretic coating are as follows: the anode is a 0Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with a trivalent chromium coating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 300-350 g/L of electrophoretic paint and 150-200 g/L of hydroxyl graphene filler; the pH value of the coating is 4-5; the cathode electrophoretic coating temperature is 25-30 ℃, and the bath voltage is 30-100V;
the hydroxyl graphene filler comprises hydroxyl graphene, waterborne polyurethane and a waterborne silane polymer.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The method comprises the steps of drawing the nickel-free stainless steel, and then performing cathode electrolytic activation on the surface of the drawn nickel-free stainless steel to obtain the pretreated nickel-free stainless steel. In the invention, the drawing is preferably performed by a felt wheel drawing machine. The process of drawing is not particularly limited, and may be performed by a process known to those skilled in the art.
After the wire drawing is finished, the invention also preferably comprises the steps of sequentially carrying out alkaline chemical degreasing, water washing, alkaline cathode electrolytic degreasing, water washing, alkaline anode electrolytic degreasing and water washing on the surface of the nickel-free stainless steel after wire drawing; the present invention does not have any particular limitation to the above-mentioned processes, and can be carried out by processes well known to those skilled in the art.
In the invention, in the cathode electrolysis activation, the electrolyte comprises 100-200 g/L of sulfuric acid, preferably 120-180 g/L, and more preferably 140-160 g/L; the electrolyte also comprises 10-30 g/L of acrylic acid, preferably 15-25 g/L, and more preferably 18-22 g/L; the electrolyte also comprises 0.1-0.5 g/L trimercapto-s-triazine, preferably 0.2-0.4 g/L, and more preferably 0.25-0.35 g/L. The current density of the cathode is 0.5-3.0A/dm2Preferably 1.0 to 2.5A/dm2More preferably 1.5 to 2.0A/dm2. The electrolysis time is 1-3 min, preferably 1.5-2.5 min. The graphite rod is not limited in any way, and a graphite rod specially used for electroplating, which is well known to those skilled in the art, can be adopted. In the present invention, the temperature of the cathodic electrolytic activation is preferably room temperature.
In the invention, the cathode electrolysis activation process can remove the oxide film on the surface of the nickel-free stainless steel, the chromium sesquioxide on the surface of the nickel-free stainless steel is reduced into metal chromium in the electrolysis process, and the acrylic acid and the trimercapto-s-triazine are adsorbed on the surface of the nickel-free stainless steel after electrolysis, so that the oxide film is inhibited from being regenerated on the surface of the nickel-free stainless steel, and the surface of the nickel-free stainless steel is ensured to be in a better activation state.
After the cathodic electrolytic activation is completed, the method also preferably comprises water washing; the process of the water washing is not limited in any way, and can be carried out by a process known to those skilled in the art.
After the pretreated nickel-free stainless steel is obtained, the invention electroplates a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain the nickel-free stainless steel with the trivalent chromium coating. In the invention, the method for electroplating the trivalent chromium plating layer on the pretreated nickel-free stainless steel surface is sulfate trivalent chromium plating or chloride trivalent chromium plating. More preferably, the chromium plating is the chromium plating by the Trich-9551 sulfate trivalent chromium developed by the ultra-high chemical industry, the chromium plating by the Trich-7677 sulfate trivalent chromium developed by the ultra-high chemical industry or the chromium plating by the Trich-6561 chloride trivalent chromium developed by the ultra-high chemical industry.
In the invention, the chromium plating conditions of the Trich-9551 sulfate trivalent chromium developed by the ultra-high chemical industry are as follows: taking pretreated nickel-free stainless steel as a cathode; the electroplating solution comprises 8-12 mL/L of a Trich-9551M cylinder opener, 260-300 mL/L of a Trich-9551B replenisher, 260-300 g/L of a Trich-9551CS conductive salt and 0.5-2.0 mL/L of a Trich-9551 WA wetting agent; the pH value of the electroplating solution is preferably 3.4-3.8. The temperature of the plating tank is preferably 48-55 ℃, and more preferably 50-52 ℃; the preferred cathode ionization density is 8-15A/dm2More preferably 10 to 12A/dm2(ii) a The electroplating time is preferably 1-2 min; the plating is preferably carried out by moving the cathode or by air stirring.
In the invention, the chromium plating conditions of the Trich-7677 sulfate trivalent chromium developed by the ultra-high chemical industry are specifically as follows: taking pretreated nickel-free stainless steel as a cathode; the electroplating solution comprises 280mL/L of Trich-7677M cylinder opening agent, 10mL/L of Trich-7677S initiator, 300g/L of Trich-7677CS conductive salt and 3-4 mL/L of Trich-7677C blackening agent, 0-4 mL/L of Trich-7677D toner and 1mL/L of Trich-7677 WA wetting agent; the pH value of the plating solution is preferably 3.2-3.6; the temperature of the plating tank is preferably 25-40 ℃, and more preferably 30-35 ℃; the preferred cathode ionization density is 8-15A/dm2More preferably 10 to 12A/dm2(ii) a The electroplating time is preferably 1-2 min; the plating is preferably carried out by moving the cathode or by air stirring.
In the invention, the chromium plating conditions of the Trich-6561 chloride trivalent chromium developed by the ultra-nation chemical industry are as follows: taking pretreated nickel-free stainless steel as a cathode; the electroplating solution comprises 410g/L of Trich-6561 vat salt, 75mL/L of Trich-6561 complexing agent and 2mL/L of Trich-6561 wetting agent; the pH value of the electroplating solution is preferably 2.5-3.0, and more preferably 2.6-2.8. The temperature of the plating tank is preferably 28-34 ℃, and more preferably 30-32 ℃; the preferred cathode ionization density is 8-16A/dm2More preferably 11 to 13A/dm2(ii) a The electroplating time is preferably 1-2 min; the plating is preferably carried out by moving the cathode or by air stirring.
In the invention, the trivalent chromium plating layer is preferably a trivalent chromium white chromium plating layer or a trivalent chromium black chromium plating layer. The thickness of the trivalent chromium plating layer is preferably 0.05-0.25 μm, and more preferably 0.1-0.2 μm.
After the nickel-free stainless steel with the trivalent chromium coating is obtained, the surface of the nickel-free stainless steel with the trivalent chromium coating is coated with the hydroxyl graphene modified electrophoretic paint coating in a cathode electrophoretic coating mode.
In the invention, the conditions of the cathodic electrocoating are as follows: the anode is a 0Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with a trivalent chromium coating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 300-350 g/L electrophoretic paint, preferably 310-340 g/L, and more preferably 320-330 g/L; the hydroxyl graphite modified electrophoretic paint also comprises 150-200 g/L of hydroxyl graphene filler, and preferably 160-180 g/L. In the invention, the pH value of the coating is 4-5, preferably 4.3-4.6.
In the invention, the hydroxyl graphene filler comprises hydroxyl graphene, aqueous polyurethane and aqueous silane polymer; the type of the waterborne polyurethane is preferably AH-1720A; the type of the aqueous silane polymer is preferably PU 113. In the invention, the mass ratio of the hydroxyl graphene to the aqueous polyurethane to the aqueous silane polymer is preferably (0.8-3.5): 50-150, and more preferably (2.8-3.2): 90-110.
In the present invention, the preparation process of the hydroxy graphene filler preferably includes the following steps:
uniformly mixing 80-350 g of 1% by mass of hydroxyl graphene colloid, waterborne polyurethane, a waterborne silane polymer and 300g of water, adding 1000mL of water, and reacting at normal temperature for 7 days to obtain the hydroxyl graphene filler;
the pH value of the hydroxyl graphene colloid is preferably 7-8, and the hydroxyl graphene in the hydroxyl graphene colloid is preferably nano-grade hydroxyl graphene; the particle size of the nano-grade hydroxyl graphene is preferably 5-80 nm, and more preferably 10-30 nm.
In the present invention, the electrophoretic paint preferably comprises the following preparation raw materials in parts by mass: 4-8 parts of epoxy polyamide modified resin, 4-8 parts of amino resin, 3-6 parts of closed polyisocyanate resin, 4-8 parts of pH buffering agent, 10-16 parts of 1-methoxy-2-propanol and 15-25 parts of water; the pH buffer is preferably sodium hydrogen malonate and/or sodium hydrogen succinate. The electrophoretic paint more preferably comprises 8 parts of epoxy polyamide modified resin, 4 parts of amino resin, 4 parts of blocked polyisocyanate resin, 6 parts of sodium hydrogen malonate, 15 parts of 1-methoxy-2-propanol and 20 parts of water; or 6 parts of epoxy polyamide modified resin, 6 parts of amino resin, 5 parts of closed polyisocyanate resin, 6 parts of sodium hydrogen succinate, 12 parts of 1-methoxy-2-propanol and 20 parts of water; or 7 parts of epoxy polyamide modified resin, 7 parts of amino resin, 6 parts of closed polyisocyanate resin, 2 parts of sodium hydrogen malonate, 4 parts of sodium hydrogen succinate, 16 parts of 1-methoxy-2-propanol and 20 parts of water; the water is preferably deionized water.
In the invention, the cathode electrophoretic coating temperature is preferably 25-30 ℃, and more preferably 26-28 ℃; the cell voltage is preferably 30 to 100V, and more preferably 30 to 60V.
In the invention, the thickness of the hydroxyl graphene modified electrophoretic paint coating is preferably 5-15 μm, and more preferably 8-13 μm.
After the cathode electrophoretic coating is finished, the invention also preferably comprises the steps of washing and drying which are sequentially carried out; the process of the water washing is not limited in any way, and the process known by the person skilled in the art can be adopted; the drying is preferably drying, the drying temperature is preferably 140 ℃, the drying time is preferably 40-70 min, and more preferably 50-60 min.
The invention also provides a protective coating of the nickel-free stainless steel prepared by the method in the technical scheme, which comprises a trivalent chromium plating layer and a hydroxyl graphene modified electrophoretic paint coating (as shown in figure 1) which are sequentially arranged on the surface of the nickel-free stainless steel. In the invention, the trivalent chromium plating layer is preferably a trivalent chromium white chromium plating layer or a trivalent chromium black chromium plating layer. The thickness of the trivalent chromium plating layer is preferably 0.05-0.25 μm, and more preferably 0.1-0.2 μm. In the invention, the thickness of the hydroxyl graphene modified electrophoretic paint coating is preferably 5-15 μm, and more preferably 8-13 μm.
The method for coating nickel-free stainless steel with hydroxyl graphene modified electrophoretic paint and the protective coating provided by the invention are described in detail below with reference to the following examples, but they should not be construed as limiting the scope of the invention.
Example 1
As shown in fig. 1, the coating sequentially comprises a 0Cr13 stainless steel substrate, a trivalent chromium white chromium plating layer of 0.1 μm and a hydroxyl graphene modified electrophoretic paint coating of 8 μm from bottom to top;
the method for coating the hydroxyl graphene modified electrophoretic paint on the nickel-free stainless steel comprises the following steps:
after drawing the surface of a 0Cr13 stainless steel matrix by using a felt wheel drawing machine, sequentially carrying out alkaline chemical degreasing, washing, alkaline cathode electrolytic degreasing, washing, alkaline anode electrolytic degreasing, washing, cathode electrolytic activation and washing on the surface of the drawn nickel-free stainless steel to obtain pretreated nickel-free stainless steel; in the cathode electrolysis activation, the nickel-free stainless steel after wire drawing is taken as a cathode, and a graphite rod is taken as an anode; the electrolyte is 100g/L of sulfuric acid,20g/L of acrylic acid, 0.1g/L of trimercapto-s-triazine; the current density of the cathode was 1.0A/dm2(ii) a The electrolysis time is 2min, and the temperature is room temperature.
Electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating; the electroplating is carried out by adopting Trich-9551 sulfate trivalent chromium developed by the nation chemical industry for chromium plating, and the conditions are as follows: taking pretreated nickel-free stainless steel as a cathode; the electroplating solution comprises 10mL/L of a Trich-9551M cylinder opening agent, 280mL/L of a Trich-9551B supplement, 280g/L of a Trich-9551CS conductive salt and 1mL/L of a Trich-9551 WA wetting agent; the pH of the plating solution is preferably 3.6. The temperature of the plating bath is 52 ℃; the cathode ionization density is 12A/dm2(ii) a The electroplating time is 2 min; moving the cathode or stirring the cathode with air in the electroplating process.
Uniformly mixing 200g of a 1% hydroxyl graphene colloid (with the pH being 8 and the particle size of the hydroxyl graphene being 20nm), 100g of waterborne polyurethane (AH-1720A), 100g of waterborne silane polymer (PU 113) and 300g of deionized water, adding water to 1000mL, and reacting at normal temperature for 7 days to obtain the hydroxyl graphene filler;
and coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating by adopting a cathode electrophoretic coating mode, and then sequentially washing and drying for 50min at 140 ℃. The conditions of the cathode electrophoretic coating are as follows: the anode is a 0Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with a trivalent chromium coating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 320g/L electrophoretic paint and 160g/L hydroxyl graphene filler; the pH of the coating was 4.5. The electrophoretic paint comprises 8 parts of epoxy polyamide modified resin, 4 parts of amino resin, 4 parts of closed polyisocyanate resin, 6 parts of sodium hydrogen malonate, 15 parts of 1-methoxy-2-propanol and 20 parts of deionized water by mass; the temperature of the cathode electrophoretic coating is 28 ℃; the cell voltage was 40V.
Example 2
As shown in fig. 1, the coating sequentially comprises a 1Cr13 stainless steel substrate, a trivalent chromium white chromium plating layer of 0.15 μm and a hydroxyl graphene modified electrophoretic paint coating of 10 μm from bottom to top;
the method for coating the hydroxyl graphene modified electrophoretic paint on the nickel-free stainless steel comprises the following steps:
after drawing the surface of a 1Cr13 stainless steel matrix by using a felt wheel drawing machine, sequentially carrying out alkaline chemical degreasing, washing, alkaline cathode electrolytic degreasing, washing, alkaline anode electrolytic degreasing, washing, cathode electrolytic activation and washing on the surface of the drawn nickel-free stainless steel to obtain pretreated nickel-free stainless steel; in the cathode electrolysis activation, the nickel-free stainless steel after wire drawing is taken as a cathode, and a graphite rod is taken as an anode; the electrolyte is 180g/L of sulfuric acid, 30g/L of acrylic acid and 0.2g/L of trimercapto-s-triazine; the current density of the cathode was 1.5A/dm2(ii) a The electrolysis time is 1.5min, and the temperature is room temperature.
Electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating; the electroplating is carried out by adopting Trich-6561 chloride trivalent chromium chrome plating developed by the nation chemical industry, and the conditions are as follows: taking pretreated nickel-free stainless steel as a cathode; the electroplating solution comprises 410g/L of Trich-6561 vat salt, 75mL/L of Trich-6561 complexing agent and 2mL/L of Trich-6561 wetting agent; the pH value of the electroplating solution is preferably 2.8; the temperature of the plating bath is 30 ℃; the cathode ionization density is 12A/dm2(ii) a The electroplating time is 1.5 min; moving the cathode or stirring the cathode with air in the electroplating process.
Uniformly mixing 80g of 1% hydroxyl graphene colloid (pH is 7, the particle size of the hydroxyl graphene is 45nm), 120g of waterborne polyurethane, 80g of waterborne silane polymer and 300g of deionized water, adding water to 1000mL, and reacting at normal temperature for 7 days to obtain the hydroxyl graphene filler;
and coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating by adopting a cathode electrophoretic coating mode, and then sequentially washing and drying for 60min at 140 ℃. The conditions of the cathode electrophoretic coating are as follows: the anode is a 1Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with a trivalent chromium coating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 320g/L electrophoretic paint and 180g/L hydroxyl graphene filler; the pH of the coating was 5. The electrophoretic paint comprises 6 parts of epoxy polyamide modified resin, 6 parts of amino resin, 5 parts of closed polyisocyanate resin, 6 parts of sodium hydrogen succinate, 12 parts of 1-methoxy-2-propanol and 20 parts of deionized water by mass; the temperature of the cathode electrophoretic coating is 30 ℃; the cell voltage was 50V.
Example 3
As shown in fig. 1, the coating sequentially comprises a 2Cr13 stainless steel substrate, a trivalent chromium black chromium plating layer of 0.07 mu m and a hydroxyl graphene modified electrophoretic paint coating of 15 mu m from bottom to top;
the method for coating the hydroxyl graphene modified electrophoretic paint on the nickel-free stainless steel comprises the following steps:
after drawing the surface of a 2Cr13 stainless steel matrix by using a felt wheel drawing machine, sequentially carrying out alkaline chemical degreasing, washing, alkaline cathode electrolytic degreasing, washing, alkaline anode electrolytic degreasing, washing, cathode electrolytic activation and washing on the surface of the drawn nickel-free stainless steel to obtain pretreated nickel-free stainless steel; in the cathode electrolysis activation, the nickel-free stainless steel after wire drawing is taken as a cathode, and a graphite rod is taken as an anode; the electrolyte is 150g/L of sulfuric acid, 25g/L of acrylic acid and 0.15g/L of trimercapto-s-triazine; the current density of the cathode was 2.0A/dm2(ii) a The electrolysis time is 3min, and the temperature is room temperature.
Electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating; the electroplating is carried out by adopting Trich-7677 sulfate trivalent chromium developed by the nation chemical industry, and the conditions are as follows: taking pretreated nickel-free stainless steel as a cathode; the electroplating solution comprises 280mL/L of a Trich-7677M cylinder opening agent, 10mL/L of a Trich-7677S initiator, 300g/L of Trich-7677CS conductive salt, 3mL/L of a Trich-7677C blackening agent, 2mL/L of a Trich-7677D conditioner and 1mL/L of a Trich-7677 WA wetting agent; the pH value of the electroplating solution is preferably 3.4; the temperature of the plating bath is 35 ℃; the cathode ionization density is 10A/dm2(ii) a The electroplating time is 2 min; moving the cathode or stirring the cathode with air in the electroplating process.
Uniformly mixing 200g of 1% hydroxyl graphene colloid (pH is 7.5, the particle size of the hydroxyl graphene is 15), 100g of waterborne polyurethane, 100g of waterborne silane polymer and 300g of deionized water, adding water to 1000mL, and reacting at normal temperature for 7 days to obtain the hydroxyl graphene filler;
and coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating by adopting a cathode electrophoretic coating mode, and then sequentially washing and drying for 70min at 140 ℃. The conditions of the cathode electrophoretic coating are as follows: the anode is 2Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with trivalent chromium plating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 350g/L electrophoretic paint and 200g/L hydroxyl graphene filler; the pH of the coating was 4. The electrophoretic paint comprises 7 parts of epoxy polyamide modified resin, 7 parts of amino resin, 6 parts of closed polyisocyanate resin, 2 parts of sodium hydrogen malonate, 4 parts of sodium hydrogen succinate, 16 parts of 1-methoxy-2-propanol and 20 parts of deionized water by mass; the cathode electrophoretic coating temperature is 25 ℃; the cell voltage was 30V.
Test example
According to JB 2111-1977, namely the test method for the bonding strength of the metal covering layer, the bonding force between the protective layer prepared in the examples 1 to 3 and the nickel-free stainless steel substrate is measured by a thermal shock test method. Heating the plated part in a heating furnace to 190 ℃, taking out the plated part after 30min, placing the plated part in water at room temperature, and cooling the plated part suddenly without foaming and falling off of a protective layer;
the protective layer prepared in the embodiment 1-3 is subjected to a neutral salt spray test for 1000h according to GB/T10125-2012 salt spray test for artificial atmosphere corrosion test, and no corrosive substances are generated on the surface of the protective layer.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for coating hydroxyl graphene modified electrophoretic paint on nickel-free stainless steel is characterized by comprising the following steps:
carrying out wire drawing on the nickel-free stainless steel, and carrying out cathode electrolytic activation on the surface of the nickel-free stainless steel after wire drawing to obtain pretreated nickel-free stainless steel;
electroplating a trivalent chromium coating on the surface of the pretreated nickel-free stainless steel to obtain nickel-free stainless steel with the trivalent chromium coating;
coating a hydroxyl graphene modified electrophoretic paint coating on the surface of the nickel-free stainless steel with the trivalent chromium coating in a cathode electrophoretic coating mode;
the conditions of the cathode electrolysis activation are as follows: the anode is a graphite rod; the cathode is the nickel-free stainless steel after wire drawing; the electrolyte comprises 100-200 g/L of sulfuric acid, 10-30 g/L of acrylic acid and 0.1-0.5 g/L of trimercapto-s-triazine; the current density of the cathode is 0.5-3.0A/dm2The electrolysis time is 1-3 min;
the conditions of the cathode electrophoretic coating are as follows: the anode is a 0Cr13 stainless steel plate, and the cathode is nickel-free stainless steel with a trivalent chromium coating; the coating is hydroxyl graphite modified electrophoretic paint; the hydroxyl graphite modified electrophoretic paint comprises 300-350 g/L of electrophoretic paint and 150-200 g/L of hydroxyl graphene filler; the pH value of the coating is 4-5; the cathode electrophoretic coating temperature is 25-30 ℃, and the bath voltage is 30-100V;
the hydroxyl graphene filler comprises hydroxyl graphene, waterborne polyurethane and a waterborne silane polymer.
2. The method of claim 1, wherein the mass ratio of the graphene oxide, the aqueous polyurethane and the aqueous silane polymer is (0.8-3.5): 50-150.
3. The method of claim 2, wherein the preparation process of the hydroxy graphene filler comprises the following steps:
uniformly mixing 80-350 g of 1% by mass of hydroxyl graphene colloid, waterborne polyurethane, a waterborne silane polymer and 300g of water, adding 1000mL of water, and reacting at normal temperature for 7 days to obtain the hydroxyl graphene filler;
the pH value of the hydroxyl graphene colloid is 7-8, and the hydroxyl graphene in the hydroxyl graphene colloid is nano-grade hydroxyl graphene.
4. The method according to claim 1, wherein the electrophoretic paint comprises the following preparation raw materials in parts by weight: 4-8 parts of epoxy polyamide modified resin, 4-8 parts of amino resin, 3-6 parts of closed polyisocyanate resin, 4-8 parts of pH buffering agent, 10-16 parts of 1-methoxy-2-propanol and 15-25 parts of water.
5. The method of claim 4, wherein the pH buffering agent is sodium hydrogen malonate and/or sodium hydrogen succinate.
6. The method according to any one of claims 1 to 5, wherein the thickness of the hydroxygraphene-modified electrophoretic paint coating is 5 to 15 μm.
7. The method of claim 1, wherein the plating of trivalent chromium on the pretreated nickel-free stainless steel surface is performed by sulfate trivalent chromium plating or chloride trivalent chromium plating.
8. The method of claim 1 or 7, wherein the trivalent chromium coating has a thickness of 0.05 to 0.25 μm.
9. The method of claim 1, wherein the drawing is performed using a felt wheel drawing machine.
10. The protective coating of the nickel-free stainless steel prepared by the method of any one of claims 1 to 9 comprises a trivalent chromium plating layer and a hydroxyl graphene modified electrophoretic paint coating which are sequentially arranged on the surface of the nickel-free stainless steel.
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