CN111701830A - Metal spraying treatment process - Google Patents

Metal spraying treatment process Download PDF

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Publication number
CN111701830A
CN111701830A CN202010589346.5A CN202010589346A CN111701830A CN 111701830 A CN111701830 A CN 111701830A CN 202010589346 A CN202010589346 A CN 202010589346A CN 111701830 A CN111701830 A CN 111701830A
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CN
China
Prior art keywords
parts
deionized water
graphene oxide
metal material
solution
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CN202010589346.5A
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Chinese (zh)
Inventor
计佩蓉
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Ningbo Jishi Metal New Material Co ltd
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Ningbo Jishi Metal New Material Co ltd
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Priority to CN202010589346.5A priority Critical patent/CN111701830A/en
Publication of CN111701830A publication Critical patent/CN111701830A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0272—After-treatment with ovens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of metallic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2301/00—Inorganic additives or organic salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2320/00—Organic additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/30—Change of the surface
    • B05D2350/50—Smoothing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2502/00—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2504/00—Epoxy polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Abstract

The invention relates to the field of metal treatment, in particular to a metal spraying treatment process, which comprises the following steps: step 1, polishing: roughly polishing the metal material by using sand paper; step 2, sand blasting: carrying out sand blasting treatment and drying treatment; step 3, derusting: soaking in the rust remover solution, washing with deionized water, and drying; wherein the mass ratio of the metal material to the rust remover to the water is 3-5: 10, and the soaking temperature is 15-25 ℃; step 4, coating spraying: spraying a primer; then, spraying the finish paint on the surface of the primer, and naturally leveling at room temperature; and 5, carrying out heat treatment, and naturally cooling to room temperature. Compared with the prior art, the invention is an environment-friendly metal spraying treatment process.

Description

Metal spraying treatment process
Technical Field
The invention relates to the field of metal treatment, in particular to a metal spraying treatment process.
Background
Most metal parts require not only suitable mechanical strength but also good surface wear and corrosion resistance, and one of the main causes of electrochemical corrosion of metals is the generation of various corrosion cells due to the contact of the surface with electrolyte solutions or humid atmosphere. Therefore, the metal surface can be isolated from the corrosion environment by changing the state of the metal surface, and the occurrence of corrosion can be prevented. At present, methods such as phosphorization and chromate conversion film methods are generally adopted for surface treatment of metal materials, phosphorization technology is a method generally adopted for metal spraying treatment before coating, serious pollution is brought to the environment due to the fact that a large amount of phosphorus and nitrogen are contained in a phosphorizing agent, permanent damage can be caused to a human body due to heavy metal contained in the phosphorizing agent, and similarly, the chromate conversion film method can cause great pollution to the environment in use. Therefore, there is a need for an environmentally friendly metal spray process to replace the prior art.
Disclosure of Invention
Aiming at the problems, the invention provides a metal spraying treatment process, which comprises the following steps:
step 1, polishing:
roughly polishing the metal material by using sand paper;
step 2, sand blasting:
firstly, performing sand blasting treatment on the metal material treated in the step 1, and then cleaning the metal material by using ethanol or acetone; then drying in an oven at 60-80 ℃ for 0.5-1 h;
step 3, derusting:
firstly, mixing a rust remover with deionized water to form a rust remover solution; placing the metal material treated in the step 2 in the rust remover solution to be soaked for 5-20 min, then washing the metal material by using deionized water, and then placing the metal material in an oven at 80-100 ℃ for drying treatment;
wherein the mass ratio of the metal material to the rust remover to the water is 3-5: 10, and the soaking temperature is 15-25 ℃;
step 4, coating spraying:
spraying the primer on the metal material treated in the step 3, after the primer is dried, spraying the finish on the surface of the primer, and naturally leveling for 2-10 min at room temperature;
step 5, heat treatment:
first temperature rise: putting the metal material treated in the step 4 into an oven, heating the metal material to 100-120 ℃ from room temperature, and then carrying out heat treatment for 10-20 min; and (3) second temperature rise: and continuously heating to 200-280 ℃, carrying out heat treatment for 20-30 min, and naturally cooling to room temperature.
Preferably, the grinding in step 1 is to grind the metal material by using 600#, 1500#, 2000# sandpaper in sequence.
Preferably, the sand blasting in the step 2 is to treat with 80-100 mesh sand grains and then treat with 300-350 mesh sand grains.
Preferably, in the sand blasting process in the step 2, a nozzle of the spray gun is arranged perpendicular to the metal material, and the distance is kept between 2 cm and 5 cm; the time of the sand blasting treatment is 10-15 s in total.
Preferably, the rust remover in the step 3 comprises the following components in parts by weight:
5-15 parts of citric acid, 2-5 parts of chelating agent, 2-4 parts of corrosion inhibitor, 0.5-2 parts of penetrating agent and 60-80 parts of deionized water.
Preferably, in the rust remover solution in the step 3, the rust remover and deionized water are mixed in a volume ratio of 1: 5-10.
Preferably, the spraying method in the step 4 is one of air spraying, electrophoretic spraying and electrostatic spraying.
Preferably, in the step 5, the first temperature rise rate is 1-3 ℃/min; the rate of the second temperature rise is 3-5 ℃/min.
Preferably, the primer in the step 4 is composed of the following components in parts by weight:
40-60 parts of alkyd resin; 10-20 parts of methylated amino resin; 10-18 parts of titanium dioxide; 15-20 parts of modified graphene oxide; 10-15 parts of alumina powder; 2-5 parts of silicon dioxide fibers; 5-8 parts of a bactericide; 3-7 parts of a preservative; 30-50 parts of deionized water.
Preferably, the finish paint in the step 4 comprises a component A and a component B;
the component A comprises the following components in parts by weight:
40-50 parts of modified acrylic resin and 3-5 parts of silane coupling agent.
The component B comprises the following components in parts by weight:
40-60 parts of epoxy resin, 4-12 parts of polypropylene glycol diglycidyl ether, 20-25 parts of calcium carbonate, 5-8 parts of titanium dioxide, 5-15 parts of nano titanium dioxide, 1-3 parts of dispersing agent, 0.3-0.5 part of defoaming agent and 0.5-1.0 part of flatting agent;
the mass ratio of the component A to the component B is 2-3: 1.
Preferably, the chelating agent is an organic rhenium complex.
Preferably, the preparation method of the organic rhenium complex comprises the following steps:
s1, weighing ammonium perrhenate, adding the ammonium perrhenate into deionized water, heating to 40-50 ℃, and stirring until the ammonium perrhenate is completely dissolved to obtain an ammonium perrhenate solution; dropwise adding a citric acid aqueous solution with the mass concentration of 20-30% into the ammonium perrhenate solution, adjusting the pH to 3.0-4.0, then adding disodium ethylene diamine tetraacetate, and stirring uniformly to obtain a mixed solution A;
wherein the mass ratio of the ammonium perrhenate to the deionized water is 1: 15-20; the solid-to-liquid ratio of the ethylene diamine tetraacetic acid to the ammonium perrhenate solution is 1: 30-50;
s2, weighing alpha-sodium alkenyl sulfonate, adding the alpha-sodium alkenyl sulfonate into the mixed solution A, dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L, adjusting the pH value to be 6.5-7.5, stirring uniformly, pouring the mixture into a reaction kettle, sealing, reacting at 80-120 ℃ for 3-5 hours, naturally cooling to room temperature, filtering to obtain a solid, washing the solid to be neutral by using deionized water, and drying in vacuum to obtain an organic rhenium complex;
wherein the solid-to-liquid ratio of the alpha-sodium alkenyl sulfonate to the mixed solution A is 1: 20-30.
Preferably, the preparation method of the modified graphene oxide comprises the following steps:
s1, preparing graphene oxide by a Hummers strong acid oxidation method, weighing the graphene oxide, adding the graphene oxide into deionized water, and ultrasonically dispersing until the graphene oxide is uniform to obtain a graphene oxide mixed solution; weighing N, N '-dicyclohexylcarbodiimide, adding the N, N' -dicyclohexylcarbodiimide into the graphene oxide mixed solution, heating to 60-70 ℃, stirring to be uniform, adding maleimide, continuously stirring for reaction for 1-2 hours, filtering to obtain a solid, washing with acetone for three times, drying in vacuum, and grinding into powder to obtain a graphene oxide activated substance;
wherein the mass ratio of the graphene oxide to the deionized water is 1: 8-15; the mass ratio of the N, N' -dicyclohexylcarbodiimide to the maleimide to the graphene oxide is 0.1-0.3: 0.05-0.2: 1;
s2, weighing atropine sulfate, adding the atropine sulfate into deionized water, and stirring until the atropine sulfate is completely dissolved to obtain an atropine solution; adding the graphene oxide activator into the atropine solution, ultrasonically dispersing until the graphene oxide activator is uniform, pouring the mixture into a reaction kettle, sealing, reacting at the temperature of 120-150 ℃ for 8-12 h, naturally cooling to room temperature, filtering to obtain a solid, and vacuum drying to obtain modified graphene oxide;
wherein the mass ratio of atropine sulfate to deionized water is 1: 12-15; the solid-to-liquid ratio of the graphene oxide activator to the atropine solution is 1: 15-20.
Preferably, the preparation method of the modified acrylic resin comprises the following steps:
s1, weighing 2-imidazolidinone, adding the 2-imidazolidinone into deionized water, stirring until the mixture is completely dissolved, dropwise adding 1-2 mol/L HCl solution until the pH value of the liquid is 1.0-2.0, adding 35-40% by mass of formalin, stirring and reacting for 4-8 hours at 20-30 ℃, and standing for 0.5-1 hour to obtain a mixed solution B;
wherein the mass ratio of the 2-imidazolidinone to the deionized water is 1: 10-20; the volume ratio of formalin to deionized water is 1: 2-5;
s2, dropwise adding a NaOH solution with the concentration of 0.5-1 mol/L into the mixed solution B until the pH value of the liquid is 7.5-8.0, pouring the liquid into a centrifugal extraction device, adding chloroform, uniformly shaking, standing for layering, taking an organic phase, washing the organic phase for 3 times by using deionized water, distilling under reduced pressure until the organic phase is dried, and crushing the organic phase into nano particles to finally obtain a substance C;
s3, adding the substance C into acrylic acid, stirring until the substances are uniformly mixed, dropwise adding dibutyltin diacetate, and reacting for 3-5 h in a water bath at the temperature of 40-50 ℃ to obtain modified acrylate; dropwise adding azodiisobutyronitrile into the modified acrylic ester, heating to 50-60 ℃, and stirring for reacting for 4-8 hours to obtain modified acrylic resin;
wherein the mass ratio of the substance C to acrylic acid is 1: 10-15; the mass ratio of dibutyltin diacetate to the substance C is 0.01-0.2: 1; the mass ratio of the azodiisobutyronitrile to the modified acrylate is 0.01-0.05: 2.
The invention has the beneficial effects that:
1. the abrasive paper of 600#, 1500# and 2000# is used for sequentially polishing the metal material, and the surface defects of the metal material can be processed by polishing, so that the roughness of the metal surface tends to be consistent, and a foundation is laid for subsequent processing; the sand blasting uses a method of firstly using 80-100-mesh sand grains for treatment and then using 300-350-mesh sand grains for treatment, and the treatment time of a spray gun can ensure the strength and uniformity of the sand blasting and can ensure the uniformity of the coarsening degree of the metal matrix material; the rust remover replaces the traditional treatment method of phosphating or chromate conversion film, is relatively more environment-friendly and can be recycled, and in addition, the rust remover is added with a corrosion inhibitor and a penetrating agent to further play a role in degreasing; the primer and the finish paint are also prepared by mainly adopting environment-friendly materials.
2. The citric acid as organic acid has far less environmental pollution than inorganic acid such as sulfuric acid, and can be used as an environment-friendly rust remover instead of the existing inorganic acid. However, citric acid has a certain rust removing capability, but the rust removing effect is relatively slow, so the invention enhances the stripping property of the citric acid to rust by adding the chelating agent. The organic rhenium complex is prepared by carrying out complexation reaction on ammonium perrhenate and alpha-sodium alkenyl sulfonate under the action of ethylene diamine tetraacetic acid to obtain the organic rhenium complex containing sulfonic acid groups, and the compound is added into citric acid to be used as a chelating agent, so that the derusting capacity of the citric acid can be enhanced. In addition, after the rust remover is used, a layer of compact protective film is formed on the surface of the metal material, the metal material is protected from being corroded by oxygen, and the protective film contains a large number of active groups such as hydroxyl and carboxyl, so that the binding capacity of the coating and the metal can be effectively enhanced.
3. The primer is prepared by taking environment-friendly alkyd resin as a main raw material and methylated amino resin as an auxiliary raw material. The alkyd resin has the advantages of low price, small influence of coating defects on a paint film, easiness in dispersion of materials in the paint film, poor weather resistance and corrosion resistance, and the modified graphene oxide is added to improve the weather resistance of the alkyd resin and the corrosion resistance of the alkyd resin, so that a good effect is achieved. The preparation method of the modified graphene oxide comprises the steps of firstly activating graphene oxide by using N, N' -dicyclohexylcarbodiimide and maleimide, and then grafting atropine sulfate on the activated graphene oxide, so that the corrosion resistance of the finally obtained modified graphene oxide to alkyd resin is greatly improved.
4. The finish paint is prepared by mixing two components, wherein the component A is composed of modified acrylic resin and a silane coupling agent, and the component B is mainly composed of epoxy resin, polypropylene glycol diglycidyl ether and calcium carbonate. Among them, the main raw material used is acrylic resin, which has the advantages of excellent weather resistance, heat resistance and ultraviolet resistance, but it is easily and weakly adhered to the substrate, resulting in limited application thereof. According to the invention, acrylic acid is modified by using a reaction product of 2-imidazolidinone and formalin, so that the surface active groups of the obtained modified acrylic acid are increased, the binding capacity with a substrate is enhanced, and in addition, the weather resistance of the acrylic resin is further improved.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A metal spraying treatment process comprises the following steps:
step 1, polishing:
roughly polishing the metal material by using sand paper;
step 2, sand blasting:
firstly, performing sand blasting treatment on the metal material treated in the step 1, and then cleaning the metal material by using ethanol or acetone; then drying in an oven at 60-80 ℃ for 0.5-1 h;
step 3, derusting:
firstly, mixing a rust remover with deionized water to form a rust remover solution; placing the metal material treated in the step 2 in the rust remover solution to be soaked for 5-20 min, then washing the metal material by using deionized water, and then placing the metal material in an oven at 80-100 ℃ for drying treatment;
wherein the mass ratio of the metal material to the rust remover to the water is 3-5: 10, and the soaking temperature is 15-25 ℃;
step 4, coating spraying:
spraying the primer on the metal material treated in the step 3, after the primer is dried, spraying the finish on the surface of the primer, and naturally leveling for 2-10 min at room temperature;
step 5, heat treatment:
first temperature rise: putting the metal material treated in the step 4 into an oven, heating the metal material to 100-120 ℃ from room temperature, and then carrying out heat treatment for 10-20 min; and (3) second temperature rise: and continuously heating to 200-280 ℃, carrying out heat treatment for 20-30 min, and naturally cooling to room temperature.
In the step 1, the metal material is polished by using 600#, 1500#, and 2000# sandpaper in sequence.
And in the step 2, sand blasting is carried out by using 80-100 meshes of sand grains and then using 300-350 meshes of sand grains.
In the sand blasting process in the step 2, a nozzle of the spray gun is perpendicular to the metal material, and the distance is kept between 2 and 5 cm; the time of the sand blasting treatment is 10-15 s in total.
The rust remover in the step 3 comprises the following components in parts by weight:
10 parts of citric acid, 3 parts of chelating agent, 3 parts of corrosion inhibitor, 1 part of penetrating agent and 70 parts of deionized water.
And 3, mixing the rust remover and the deionized water in a volume ratio of 1: 5-10.
The spraying method in the step 4 is one of air spraying, electrophoretic spraying and electrostatic spraying.
In the step 5, the first temperature rise rate is 1-3 ℃/min; the rate of the second temperature rise is 3-5 ℃/min.
The primer in the step 4 comprises the following components in parts by weight:
50 parts of alkyd resin; 15 parts of methylated amino resin; 15 parts of titanium dioxide; 18 parts of modified graphene oxide; 12 parts of alumina powder; 3 parts of silicon dioxide fiber; 7 parts of a bactericide; 5 parts of a preservative; 40 parts of deionized water.
The finish paint in the step 4 comprises a component A and a component B;
the component A comprises the following components in parts by weight:
45 parts of modified acrylic resin and 4 parts of silane coupling agent.
The component B comprises the following components in parts by weight:
50 parts of epoxy resin, 8 parts of polypropylene glycol diglycidyl ether, 22 parts of calcium carbonate, 7 parts of titanium dioxide, 10 parts of nano titanium dioxide, 2 parts of dispersing agent, 0.4 part of defoaming agent and 0.6 part of flatting agent;
the mass ratio of the component A to the component B is 2.5: 1.
The chelating agent is an organic rhenium complex.
The preparation method of the organic rhenium complex comprises the following steps:
s1, weighing ammonium perrhenate, adding the ammonium perrhenate into deionized water, heating to 40-50 ℃, and stirring until the ammonium perrhenate is completely dissolved to obtain an ammonium perrhenate solution; dropwise adding a citric acid aqueous solution with the mass concentration of 20-30% into the ammonium perrhenate solution, adjusting the pH to 3.0-4.0, then adding disodium ethylene diamine tetraacetate, and stirring uniformly to obtain a mixed solution A;
wherein the mass ratio of the ammonium perrhenate to the deionized water is 1: 15-20; the solid-to-liquid ratio of the ethylene diamine tetraacetic acid to the ammonium perrhenate solution is 1: 30-50;
s2, weighing alpha-sodium alkenyl sulfonate, adding the alpha-sodium alkenyl sulfonate into the mixed solution A, dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L, adjusting the pH value to be 6.5-7.5, stirring uniformly, pouring the mixture into a reaction kettle, sealing, reacting at 80-120 ℃ for 3-5 hours, naturally cooling to room temperature, filtering to obtain a solid, washing the solid to be neutral by using deionized water, and drying in vacuum to obtain an organic rhenium complex;
wherein the solid-to-liquid ratio of the alpha-sodium alkenyl sulfonate to the mixed solution A is 1: 20-30.
The preparation method of the modified graphene oxide comprises the following steps:
s1, preparing graphene oxide by a Hummers strong acid oxidation method, weighing the graphene oxide, adding the graphene oxide into deionized water, and ultrasonically dispersing until the graphene oxide is uniform to obtain a graphene oxide mixed solution; weighing N, N '-dicyclohexylcarbodiimide, adding the N, N' -dicyclohexylcarbodiimide into the graphene oxide mixed solution, heating to 60-70 ℃, stirring to be uniform, adding maleimide, continuously stirring for reaction for 1-2 hours, filtering to obtain a solid, washing with acetone for three times, drying in vacuum, and grinding into powder to obtain a graphene oxide activated substance;
wherein the mass ratio of the graphene oxide to the deionized water is 1: 8-15; the mass ratio of the N, N' -dicyclohexylcarbodiimide to the maleimide to the graphene oxide is 0.1-0.3: 0.05-0.2: 1;
s2, weighing atropine sulfate, adding the atropine sulfate into deionized water, and stirring until the atropine sulfate is completely dissolved to obtain an atropine solution; adding the graphene oxide activator into the atropine solution, ultrasonically dispersing until the graphene oxide activator is uniform, pouring the mixture into a reaction kettle, sealing, reacting at the temperature of 120-150 ℃ for 8-12 h, naturally cooling to room temperature, filtering to obtain a solid, and vacuum drying to obtain modified graphene oxide;
wherein the mass ratio of atropine sulfate to deionized water is 1: 12-15; the solid-to-liquid ratio of the graphene oxide activator to the atropine solution is 1: 15-20.
The preparation method of the modified acrylic resin comprises the following steps:
s1, weighing 2-imidazolidinone, adding the 2-imidazolidinone into deionized water, stirring until the mixture is completely dissolved, dropwise adding 1-2 mol/L HCl solution until the pH value of the liquid is 1.0-2.0, adding 35-40% by mass of formalin, stirring and reacting for 4-8 hours at 20-30 ℃, and standing for 0.5-1 hour to obtain a mixed solution B;
wherein the mass ratio of the 2-imidazolidinone to the deionized water is 1: 10-20; the volume ratio of formalin to deionized water is 1: 2-5;
s2, dropwise adding a NaOH solution with the concentration of 0.5-1 mol/L into the mixed solution B until the pH value of the liquid is 7.5-8.0, pouring the liquid into a centrifugal extraction device, adding chloroform, uniformly shaking, standing for layering, taking an organic phase, washing the organic phase for 3 times by using deionized water, distilling under reduced pressure until the organic phase is dried, and crushing the organic phase into nano particles to finally obtain a substance C;
s3, adding the substance C into acrylic acid, stirring until the substances are uniformly mixed, dropwise adding dibutyltin diacetate, and reacting for 3-5 h in a water bath at the temperature of 40-50 ℃ to obtain modified acrylate; dropwise adding azodiisobutyronitrile into the modified acrylic ester, heating to 50-60 ℃, and stirring for reacting for 4-8 hours to obtain modified acrylic resin;
wherein the mass ratio of the substance C to acrylic acid is 1: 10-15; the mass ratio of dibutyltin diacetate to the substance C is 0.01-0.2: 1; the mass ratio of the azodiisobutyronitrile to the modified acrylate is 0.01-0.05: 2.
Example 2
A metal spraying treatment process comprises the following steps:
step 1, polishing:
roughly polishing the metal material by using sand paper;
step 2, sand blasting:
firstly, performing sand blasting treatment on the metal material treated in the step 1, and then cleaning the metal material by using ethanol or acetone; then drying in an oven at 60-80 ℃ for 0.5-1 h;
step 3, derusting:
firstly, mixing a rust remover with deionized water to form a rust remover solution; placing the metal material treated in the step 2 in the rust remover solution to be soaked for 5-20 min, then washing the metal material by using deionized water, and then placing the metal material in an oven at 80-100 ℃ for drying treatment;
wherein the mass ratio of the metal material to the rust remover to the water is 3-5: 10, and the soaking temperature is 15-25 ℃;
step 4, coating spraying:
spraying the primer on the metal material treated in the step 3, after the primer is dried, spraying the finish on the surface of the primer, and naturally leveling for 2-10 min at room temperature;
step 5, heat treatment:
first temperature rise: putting the metal material treated in the step 4 into an oven, heating the metal material to 100-120 ℃ from room temperature, and then carrying out heat treatment for 10-20 min; and (3) second temperature rise: and continuously heating to 200-280 ℃, carrying out heat treatment for 20-30 min, and naturally cooling to room temperature.
In the step 1, the metal material is polished by using 600#, 1500#, and 2000# sandpaper in sequence.
And in the step 2, sand blasting is carried out by using 80-100 meshes of sand grains and then using 300-350 meshes of sand grains.
In the sand blasting process in the step 2, a nozzle of the spray gun is perpendicular to the metal material, and the distance is kept between 2 and 5 cm; the time of the sand blasting treatment is 10-15 s in total.
The rust remover in the step 3 comprises the following components in parts by weight:
5 parts of citric acid, 2 parts of chelating agent, 2 parts of corrosion inhibitor, 0.5 part of penetrating agent and 60 parts of deionized water.
And 3, mixing the rust remover and the deionized water in a volume ratio of 1: 5-10.
The spraying method in the step 4 is one of air spraying, electrophoretic spraying and electrostatic spraying.
In the step 5, the first temperature rise rate is 1-3 ℃/min; the rate of the second temperature rise is 3-5 ℃/min.
The primer in the step 4 comprises the following components in parts by weight:
40 parts of alkyd resin; 10 parts of methylated amino resin; 10 parts of titanium dioxide; 15 parts of modified graphene oxide; 10 parts of alumina powder; 2 parts of silicon dioxide fiber; 5 parts of a bactericide; 3 parts of a preservative; 30 parts of deionized water.
The finish paint in the step 4 comprises a component A and a component B;
the component A comprises the following components in parts by weight:
40 parts of modified acrylic resin and 3 parts of silane coupling agent.
The component B comprises the following components in parts by weight:
40 parts of epoxy resin, 4 parts of polypropylene glycol diglycidyl ether, 20 parts of calcium carbonate, 5 parts of titanium dioxide, 5 parts of nano titanium dioxide, 1 part of dispersing agent, 0.3 part of defoaming agent and 0.5 part of flatting agent;
the mass ratio of the component A to the component B is 2: 1.
The chelating agent is an organic rhenium complex.
The preparation method of the organic rhenium complex comprises the following steps:
s1, weighing ammonium perrhenate, adding the ammonium perrhenate into deionized water, heating to 40-50 ℃, and stirring until the ammonium perrhenate is completely dissolved to obtain an ammonium perrhenate solution; dropwise adding a citric acid aqueous solution with the mass concentration of 20-30% into the ammonium perrhenate solution, adjusting the pH to 3.0-4.0, then adding disodium ethylene diamine tetraacetate, and stirring uniformly to obtain a mixed solution A;
wherein the mass ratio of the ammonium perrhenate to the deionized water is 1: 15-20; the solid-to-liquid ratio of the ethylene diamine tetraacetic acid to the ammonium perrhenate solution is 1: 30-50;
s2, weighing alpha-sodium alkenyl sulfonate, adding the alpha-sodium alkenyl sulfonate into the mixed solution A, dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L, adjusting the pH value to be 6.5-7.5, stirring uniformly, pouring the mixture into a reaction kettle, sealing, reacting at 80-120 ℃ for 3-5 hours, naturally cooling to room temperature, filtering to obtain a solid, washing the solid to be neutral by using deionized water, and drying in vacuum to obtain an organic rhenium complex;
wherein the solid-to-liquid ratio of the alpha-sodium alkenyl sulfonate to the mixed solution A is 1: 20-30.
The preparation method of the modified graphene oxide comprises the following steps:
s1, preparing graphene oxide by a Hummers strong acid oxidation method, weighing the graphene oxide, adding the graphene oxide into deionized water, and ultrasonically dispersing until the graphene oxide is uniform to obtain a graphene oxide mixed solution; weighing N, N '-dicyclohexylcarbodiimide, adding the N, N' -dicyclohexylcarbodiimide into the graphene oxide mixed solution, heating to 60-70 ℃, stirring to be uniform, adding maleimide, continuously stirring for reaction for 1-2 hours, filtering to obtain a solid, washing with acetone for three times, drying in vacuum, and grinding into powder to obtain a graphene oxide activated substance;
wherein the mass ratio of the graphene oxide to the deionized water is 1: 8-15; the mass ratio of the N, N' -dicyclohexylcarbodiimide to the maleimide to the graphene oxide is 0.1-0.3: 0.05-0.2: 1;
s2, weighing atropine sulfate, adding the atropine sulfate into deionized water, and stirring until the atropine sulfate is completely dissolved to obtain an atropine solution; adding the graphene oxide activator into the atropine solution, ultrasonically dispersing until the graphene oxide activator is uniform, pouring the mixture into a reaction kettle, sealing, reacting at the temperature of 120-150 ℃ for 8-12 h, naturally cooling to room temperature, filtering to obtain a solid, and vacuum drying to obtain modified graphene oxide;
wherein the mass ratio of atropine sulfate to deionized water is 1: 12-15; the solid-to-liquid ratio of the graphene oxide activator to the atropine solution is 1: 15-20.
The preparation method of the modified acrylic resin comprises the following steps:
s1, weighing 2-imidazolidinone, adding the 2-imidazolidinone into deionized water, stirring until the mixture is completely dissolved, dropwise adding 1-2 mol/L HCl solution until the pH value of the liquid is 1.0-2.0, adding 35-40% by mass of formalin, stirring and reacting for 4-8 hours at 20-30 ℃, and standing for 0.5-1 hour to obtain a mixed solution B;
wherein the mass ratio of the 2-imidazolidinone to the deionized water is 1: 10-20; the volume ratio of formalin to deionized water is 1: 2-5;
s2, dropwise adding a NaOH solution with the concentration of 0.5-1 mol/L into the mixed solution B until the pH value of the liquid is 7.5-8.0, pouring the liquid into a centrifugal extraction device, adding chloroform, uniformly shaking, standing for layering, taking an organic phase, washing the organic phase for 3 times by using deionized water, distilling under reduced pressure until the organic phase is dried, and crushing the organic phase into nano particles to finally obtain a substance C;
s3, adding the substance C into acrylic acid, stirring until the substances are uniformly mixed, dropwise adding dibutyltin diacetate, and reacting for 3-5 h in a water bath at the temperature of 40-50 ℃ to obtain modified acrylate; dropwise adding azodiisobutyronitrile into the modified acrylic ester, heating to 50-60 ℃, and stirring for reacting for 4-8 hours to obtain modified acrylic resin;
wherein the mass ratio of the substance C to acrylic acid is 1: 10-15; the mass ratio of dibutyltin diacetate to the substance C is 0.01-0.2: 1; the mass ratio of the azodiisobutyronitrile to the modified acrylate is 0.01-0.05: 2.
Example 3
A metal spraying treatment process comprises the following steps:
step 1, polishing:
roughly polishing the metal material by using sand paper;
step 2, sand blasting:
firstly, performing sand blasting treatment on the metal material treated in the step 1, and then cleaning the metal material by using ethanol or acetone; then drying in an oven at 60-80 ℃ for 0.5-1 h;
step 3, derusting:
firstly, mixing a rust remover with deionized water to form a rust remover solution; placing the metal material treated in the step 2 in the rust remover solution to be soaked for 5-20 min, then washing the metal material by using deionized water, and then placing the metal material in an oven at 80-100 ℃ for drying treatment;
wherein the mass ratio of the metal material to the rust remover to the water is 3-5: 10, and the soaking temperature is 15-25 ℃;
step 4, coating spraying:
spraying the primer on the metal material treated in the step 3, after the primer is dried, spraying the finish on the surface of the primer, and naturally leveling for 2-10 min at room temperature;
step 5, heat treatment:
first temperature rise: putting the metal material treated in the step 4 into an oven, heating the metal material to 100-120 ℃ from room temperature, and then carrying out heat treatment for 10-20 min; and (3) second temperature rise: and continuously heating to 200-280 ℃, carrying out heat treatment for 20-30 min, and naturally cooling to room temperature.
In the step 1, the metal material is polished by using 600#, 1500#, and 2000# sandpaper in sequence.
And in the step 2, sand blasting is carried out by using 80-100 meshes of sand grains and then using 300-350 meshes of sand grains.
In the sand blasting process in the step 2, a nozzle of the spray gun is perpendicular to the metal material, and the distance is kept between 2 and 5 cm; the time of the sand blasting treatment is 10-15 s in total.
The rust remover in the step 3 comprises the following components in parts by weight:
15 parts of citric acid, 5 parts of chelating agent, 4 parts of corrosion inhibitor, 2 parts of penetrating agent and 80 parts of deionized water.
And 3, mixing the rust remover and the deionized water in a volume ratio of 1: 5-10.
The spraying method in the step 4 is one of air spraying, electrophoretic spraying and electrostatic spraying.
In the step 5, the first temperature rise rate is 1-3 ℃/min; the rate of the second temperature rise is 3-5 ℃/min.
The primer in the step 4 comprises the following components in parts by weight:
60 parts of alkyd resin; 20 parts of methylated amino resin; 18 parts of titanium dioxide; 20 parts of modified graphene oxide; 15 parts of alumina powder; 5 parts of silicon dioxide fiber; 8 parts of a bactericide; 7 parts of a preservative; 50 parts of deionized water.
The finish paint in the step 4 comprises a component A and a component B;
the component A comprises the following components in parts by weight:
50 parts of modified acrylic resin and 5 parts of silane coupling agent.
The component B comprises the following components in parts by weight:
60 parts of epoxy resin, 12 parts of polypropylene glycol diglycidyl ether, 25 parts of calcium carbonate, 8 parts of titanium dioxide, 15 parts of nano titanium dioxide, 3 parts of a dispersing agent, 0.5 part of a defoaming agent and 1.0 part of a flatting agent;
the mass ratio of the component A to the component B is 3: 1.
The chelating agent is an organic rhenium complex.
The preparation method of the organic rhenium complex comprises the following steps:
s1, weighing ammonium perrhenate, adding the ammonium perrhenate into deionized water, heating to 40-50 ℃, and stirring until the ammonium perrhenate is completely dissolved to obtain an ammonium perrhenate solution; dropwise adding a citric acid aqueous solution with the mass concentration of 20-30% into the ammonium perrhenate solution, adjusting the pH to 3.0-4.0, then adding disodium ethylene diamine tetraacetate, and stirring uniformly to obtain a mixed solution A;
wherein the mass ratio of the ammonium perrhenate to the deionized water is 1: 15-20; the solid-to-liquid ratio of the ethylene diamine tetraacetic acid to the ammonium perrhenate solution is 1: 30-50;
s2, weighing alpha-sodium alkenyl sulfonate, adding the alpha-sodium alkenyl sulfonate into the mixed solution A, dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L, adjusting the pH value to be 6.5-7.5, stirring uniformly, pouring the mixture into a reaction kettle, sealing, reacting at 80-120 ℃ for 3-5 hours, naturally cooling to room temperature, filtering to obtain a solid, washing the solid to be neutral by using deionized water, and drying in vacuum to obtain an organic rhenium complex;
wherein the solid-to-liquid ratio of the alpha-sodium alkenyl sulfonate to the mixed solution A is 1: 20-30.
The preparation method of the modified graphene oxide comprises the following steps:
s1, preparing graphene oxide by a Hummers strong acid oxidation method, weighing the graphene oxide, adding the graphene oxide into deionized water, and ultrasonically dispersing until the graphene oxide is uniform to obtain a graphene oxide mixed solution; weighing N, N '-dicyclohexylcarbodiimide, adding the N, N' -dicyclohexylcarbodiimide into the graphene oxide mixed solution, heating to 60-70 ℃, stirring to be uniform, adding maleimide, continuously stirring for reaction for 1-2 hours, filtering to obtain a solid, washing with acetone for three times, drying in vacuum, and grinding into powder to obtain a graphene oxide activated substance;
wherein the mass ratio of the graphene oxide to the deionized water is 1: 8-15; the mass ratio of the N, N' -dicyclohexylcarbodiimide to the maleimide to the graphene oxide is 0.1-0.3: 0.05-0.2: 1;
s2, weighing atropine sulfate, adding the atropine sulfate into deionized water, and stirring until the atropine sulfate is completely dissolved to obtain an atropine solution; adding the graphene oxide activator into the atropine solution, ultrasonically dispersing until the graphene oxide activator is uniform, pouring the mixture into a reaction kettle, sealing, reacting at the temperature of 120-150 ℃ for 8-12 h, naturally cooling to room temperature, filtering to obtain a solid, and vacuum drying to obtain modified graphene oxide;
wherein the mass ratio of atropine sulfate to deionized water is 1: 12-15; the solid-to-liquid ratio of the graphene oxide activator to the atropine solution is 1: 15-20.
The preparation method of the modified acrylic resin comprises the following steps:
s1, weighing 2-imidazolidinone, adding the 2-imidazolidinone into deionized water, stirring until the mixture is completely dissolved, dropwise adding 1-2 mol/L HCl solution until the pH value of the liquid is 1.0-2.0, adding 35-40% by mass of formalin, stirring and reacting for 4-8 hours at 20-30 ℃, and standing for 0.5-1 hour to obtain a mixed solution B;
wherein the mass ratio of the 2-imidazolidinone to the deionized water is 1: 10-20; the volume ratio of formalin to deionized water is 1: 2-5;
s2, dropwise adding a NaOH solution with the concentration of 0.5-1 mol/L into the mixed solution B until the pH value of the liquid is 7.5-8.0, pouring the liquid into a centrifugal extraction device, adding chloroform, uniformly shaking, standing for layering, taking an organic phase, washing the organic phase for 3 times by using deionized water, distilling under reduced pressure until the organic phase is dried, and crushing the organic phase into nano particles to finally obtain a substance C;
s3, adding the substance C into acrylic acid, stirring until the substances are uniformly mixed, dropwise adding dibutyltin diacetate, and reacting for 3-5 h in a water bath at the temperature of 40-50 ℃ to obtain modified acrylate; dropwise adding azodiisobutyronitrile into the modified acrylic ester, heating to 50-60 ℃, and stirring for reacting for 4-8 hours to obtain modified acrylic resin;
wherein the mass ratio of the substance C to acrylic acid is 1: 10-15; the mass ratio of dibutyltin diacetate to the substance C is 0.01-0.2: 1; the mass ratio of the azodiisobutyronitrile to the modified acrylate is 0.01-0.05: 2.
Comparative example
A metal spraying treatment process comprises the following steps:
step 1, polishing:
roughly polishing the metal material by using sand paper;
step 2, sand blasting:
firstly, performing sand blasting treatment on the metal material treated in the step 1, and then cleaning the metal material by using ethanol or acetone; then drying in an oven at 60-80 ℃ for 0.5-1 h;
step 3, derusting:
firstly, mixing a rust remover with deionized water to form a rust remover solution; placing the metal material treated in the step 2 in the rust remover solution to be soaked for 5-20 min, then washing the metal material by using deionized water, and then placing the metal material in an oven at 80-100 ℃ for drying treatment;
wherein the mass ratio of the metal material to the rust remover to the water is 3-5: 10, and the soaking temperature is 15-25 ℃;
step 4, coating spraying:
spraying the primer on the metal material treated in the step 3, after the primer is dried, spraying the finish on the surface of the primer, and naturally leveling for 2-10 min at room temperature;
step 5, heat treatment:
first temperature rise: putting the metal material treated in the step 4 into an oven, heating the metal material to 100-120 ℃ from room temperature, and then carrying out heat treatment for 10-20 min; and (3) second temperature rise: and continuously heating to 200-280 ℃, carrying out heat treatment for 20-30 min, and naturally cooling to room temperature.
In the step 1, the metal material is polished by using 600#, 1500#, and 2000# sandpaper in sequence.
And in the step 2, sand blasting is carried out by using 80-100 meshes of sand grains and then using 300-350 meshes of sand grains.
In the sand blasting process in the step 2, a nozzle of the spray gun is perpendicular to the metal material, and the distance is kept between 2 and 5 cm; the time of the sand blasting treatment is 10-15 s in total.
The rust remover in the step 3 comprises the following components in parts by weight:
10 parts of citric acid, 3 parts of chelating agent, 3 parts of corrosion inhibitor, 1 part of penetrating agent and 70 parts of deionized water.
And 3, mixing the rust remover and the deionized water in a volume ratio of 1: 5-10.
The spraying method in the step 4 is one of air spraying, electrophoretic spraying and electrostatic spraying.
In the step 5, the first temperature rise rate is 1-3 ℃/min; the rate of the second temperature rise is 3-5 ℃/min.
The primer in the step 4 comprises the following components in parts by weight:
50 parts of alkyd resin; 15 parts of methylated amino resin; 15 parts of titanium dioxide; 18 parts of graphene oxide; 12 parts of alumina powder; 3 parts of silicon dioxide fiber; 7 parts of a bactericide; 5 parts of a preservative; 40 parts of deionized water.
The finish paint in the step 4 comprises a component A and a component B;
the component A comprises the following components in parts by weight:
45 parts of acrylic resin and 4 parts of silane coupling agent.
The component B comprises the following components in parts by weight:
50 parts of epoxy resin, 8 parts of polypropylene glycol diglycidyl ether, 22 parts of calcium carbonate, 7 parts of titanium dioxide, 10 parts of nano titanium dioxide, 2 parts of dispersing agent, 0.4 part of defoaming agent and 0.6 part of flatting agent;
the mass ratio of the component A to the component B is 2.5: 1.
For a more clear description of the invention, the results of the tests performed on the metals treated in examples 1 to 3 of the invention and comparative examples are shown in Table 1:
TABLE 1 detection of metals treated by different methods
Figure BDA0002555796650000141
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The metal spraying treatment process is characterized by comprising the following steps of:
step 1, polishing:
roughly polishing the metal material by using sand paper;
step 2, sand blasting:
firstly, performing sand blasting treatment on the metal material treated in the step 1, and then cleaning the metal material by using ethanol or acetone; then drying in an oven at 60-80 ℃ for 0.5-1 h;
step 3, derusting:
firstly, mixing a rust remover with deionized water to form a rust remover solution; placing the metal material treated in the step 2 in the rust remover solution to be soaked for 5-20 min, then washing the metal material by using deionized water, and then placing the metal material in an oven at 80-100 ℃ for drying treatment;
wherein the mass ratio of the metal material to the rust remover to the water is 3-5: 10, and the soaking temperature is 15-25 ℃;
step 4, coating spraying:
spraying the primer on the metal material treated in the step 3, after the primer is dried, spraying the finish on the surface of the primer, and naturally leveling for 2-10 min at room temperature;
step 5, heat treatment:
first temperature rise: putting the metal material treated in the step 4 into an oven, heating the metal material to 100-120 ℃ from room temperature, and then carrying out heat treatment for 10-20 min; and (3) second temperature rise: and continuously heating to 200-280 ℃, carrying out heat treatment for 20-30 min, and naturally cooling to room temperature.
2. The metal spraying treatment process according to claim 1, wherein the grinding in step 1 is sequentially grinding metal materials by using 600#, 1500#, 2000# sandpaper.
3. The metal spraying treatment process according to claim 1, wherein the sand blasting in the step 2 is carried out by using 80-100 meshes of sand grains and then using 300-350 meshes of sand grains;
in the sand blasting process in the step 2, a nozzle of the spray gun is perpendicular to the metal material, and the distance is kept between 2 and 5 cm; the time of the sand blasting treatment is 10-15 s in total.
4. The metal spraying treatment process as claimed in claim 1, wherein the rust remover in the step 3 comprises the following components in parts by weight:
5-15 parts of citric acid, 2-5 parts of chelating agent, 2-4 parts of corrosion inhibitor, 0.5-2 parts of penetrating agent and 60-80 parts of deionized water.
5. The metal spraying treatment process according to claim 1, wherein the spraying method in the step 4 is one of air spraying, electrophoretic spraying and electrostatic spraying; in the step 5, the first temperature rise rate is 1-3 ℃/min; the rate of the second temperature rise is 3-5 ℃/min.
6. The metal spraying treatment process according to claim 1, wherein the primer in the step 4 comprises the following components in parts by weight:
40-60 parts of alkyd resin; 10-20 parts of methylated amino resin; 10-18 parts of titanium dioxide; 15-20 parts of modified graphene oxide; 10-15 parts of alumina powder; 2-5 parts of silicon dioxide fibers; 5-8 parts of a bactericide; 3-7 parts of a preservative; 30-50 parts of deionized water.
7. The metal spraying treatment process according to claim 1, wherein the finish paint in the step 4 comprises a component A and a component B;
the component A comprises the following components in parts by weight:
40-50 parts of modified acrylic resin and 3-5 parts of silane coupling agent.
The component B comprises the following components in parts by weight:
40-60 parts of epoxy resin, 4-12 parts of polypropylene glycol diglycidyl ether, 20-25 parts of calcium carbonate, 5-8 parts of titanium dioxide, 5-15 parts of nano titanium dioxide, 1-3 parts of dispersing agent, 0.3-0.5 part of defoaming agent and 0.5-1.0 part of flatting agent;
the mass ratio of the component A to the component B is 2-3: 1.
8. The metal spraying treatment process according to claim 4, wherein the chelating agent is an organic rhenium complex;
the preparation method of the organic rhenium complex comprises the following steps:
s1, weighing ammonium perrhenate, adding the ammonium perrhenate into deionized water, heating to 40-50 ℃, and stirring until the ammonium perrhenate is completely dissolved to obtain an ammonium perrhenate solution; dropwise adding a citric acid aqueous solution with the mass concentration of 20-30% into the ammonium perrhenate solution, adjusting the pH to 3.0-4.0, then adding disodium ethylene diamine tetraacetate, and stirring uniformly to obtain a mixed solution A;
wherein the mass ratio of the ammonium perrhenate to the deionized water is 1: 15-20; the solid-to-liquid ratio of the ethylene diamine tetraacetic acid to the ammonium perrhenate solution is 1: 30-50;
s2, weighing alpha-sodium alkenyl sulfonate, adding the alpha-sodium alkenyl sulfonate into the mixed solution A, dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L, adjusting the pH value to be 6.5-7.5, stirring uniformly, pouring the mixture into a reaction kettle, sealing, reacting at 80-120 ℃ for 3-5 hours, naturally cooling to room temperature, filtering to obtain a solid, washing the solid to be neutral by using deionized water, and drying in vacuum to obtain an organic rhenium complex;
wherein the solid-to-liquid ratio of the alpha-sodium alkenyl sulfonate to the mixed solution A is 1: 20-30.
9. The metal spraying treatment process according to claim 6, wherein the preparation method of the modified graphene oxide comprises the following steps:
s1, preparing graphene oxide by a Hummers strong acid oxidation method, weighing the graphene oxide, adding the graphene oxide into deionized water, and ultrasonically dispersing until the graphene oxide is uniform to obtain a graphene oxide mixed solution; weighing N, N '-dicyclohexylcarbodiimide, adding the N, N' -dicyclohexylcarbodiimide into the graphene oxide mixed solution, heating to 60-70 ℃, stirring to be uniform, adding maleimide, continuously stirring for reaction for 1-2 hours, filtering to obtain a solid, washing with acetone for three times, drying in vacuum, and grinding into powder to obtain a graphene oxide activated substance;
wherein the mass ratio of the graphene oxide to the deionized water is 1: 8-15; the mass ratio of the N, N' -dicyclohexylcarbodiimide to the maleimide to the graphene oxide is 0.1-0.3: 0.05-0.2: 1;
s2, weighing atropine sulfate, adding the atropine sulfate into deionized water, and stirring until the atropine sulfate is completely dissolved to obtain an atropine solution; adding the graphene oxide activator into the atropine solution, ultrasonically dispersing until the graphene oxide activator is uniform, pouring the mixture into a reaction kettle, sealing, reacting at the temperature of 120-150 ℃ for 8-12 h, naturally cooling to room temperature, filtering to obtain a solid, and vacuum drying to obtain modified graphene oxide;
wherein the mass ratio of atropine sulfate to deionized water is 1: 12-15; the solid-to-liquid ratio of the graphene oxide activator to the atropine solution is 1: 15-20.
10. The metal spraying treatment process according to claim 7, wherein the preparation method of the modified acrylic resin comprises the following steps:
s1, weighing 2-imidazolidinone, adding the 2-imidazolidinone into deionized water, stirring until the mixture is completely dissolved, dropwise adding 1-2 mol/L HCl solution until the pH value of the liquid is 1.0-2.0, adding 35-40% by mass of formalin, stirring and reacting for 4-8 hours at 20-30 ℃, and standing for 0.5-1 hour to obtain a mixed solution B;
wherein the mass ratio of the 2-imidazolidinone to the deionized water is 1: 10-20; the volume ratio of formalin to deionized water is 1: 2-5;
s2, dropwise adding a NaOH solution with the concentration of 0.5-1 mol/L into the mixed solution B until the pH value of the liquid is 7.5-8.0, pouring the liquid into a centrifugal extraction device, adding chloroform, uniformly shaking, standing for layering, taking an organic phase, washing the organic phase for 3 times by using deionized water, distilling under reduced pressure until the organic phase is dried, and crushing the organic phase into nano particles to finally obtain a substance C;
s3, adding the substance C into acrylic acid, stirring until the substances are uniformly mixed, dropwise adding dibutyltin diacetate, and reacting for 3-5 h in a water bath at the temperature of 40-50 ℃ to obtain modified acrylate; dropwise adding azodiisobutyronitrile into the modified acrylic ester, heating to 50-60 ℃, and stirring for reacting for 4-8 hours to obtain modified acrylic resin;
wherein the mass ratio of the substance C to acrylic acid is 1: 10-15; the mass ratio of dibutyltin diacetate to the substance C is 0.01-0.2: 1; the mass ratio of the azodiisobutyronitrile to the modified acrylate is 0.01-0.05: 2.
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