CN112191482A - Composite coating and preparation method and application thereof - Google Patents
Composite coating and preparation method and application thereof Download PDFInfo
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- CN112191482A CN112191482A CN202011133050.9A CN202011133050A CN112191482A CN 112191482 A CN112191482 A CN 112191482A CN 202011133050 A CN202011133050 A CN 202011133050A CN 112191482 A CN112191482 A CN 112191482A
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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
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- 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
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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
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
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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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/02—Condensation polymers of aldehydes or ketones only
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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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
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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
- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05D2503/00—Polyurethanes
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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
- B05D2504/00—Epoxy polymers
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Abstract
The invention provides a composite coating, a preparation method and application thereof, wherein the composite coating at least comprises the following components: a metal base layer; the first coating layer is positioned on the metal base layer; the second coating layer is positioned on the first coating layer; wherein the metal base layer comprises one or more of zinc, aluminum and nickel; the composite coating can greatly improve the neutral salt spray resistance of metal products.
Description
Technical Field
The invention relates to the field of surface corrosion prevention of metal products, in particular to a composite coating and a preparation method and application thereof.
Background
The corrosion resistance of metal products is always a key factor for restricting the performances of the metal products in all aspects such as service life and the like. Since 1983, neodymium iron boron rare earth permanent magnet material (NdFeB) has the characteristics of light weight, small volume, excellent performance and the like, so that the miniaturization, light weight and thinning of instruments, notebook computers, automobile motors and other equipment become reality, and the progress of the whole industry is promoted. However, NdFeB has a porous and multi-phase structure, and is very easy to corrode in a natural environment, so that magnetic properties are degraded or even disappear. In addition, because the application field of the bonded NdFeB is continuously expanded, the working environment of some fields is very poor, a single coating can not meet the requirement, and a composite coating formed by combining a plurality of protection methods and the coating is required to meet the corrosion resistance in the poor environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite coating, a preparation method and application thereof.
In order to achieve the above objects and other objects, the present invention includes the following technical solutions: the invention firstly provides a composite coating, which at least comprises: a metal base layer; the first coating layer is positioned on the metal base layer; the second coating layer is positioned on the first coating layer; wherein the metal base layer comprises one or more of zinc, aluminum and nickel; the first coating layer comprises a substance composed of nano particles, epoxy resin and amino resin, and the second coating layer comprises a substance composed of one or more of epoxy resin, polyurethane resin, linear phenolic resin or aldehyde ketone resin.
In one embodiment, the thickness of the metal base layer is 10 μm to 35 μm, the thickness of the first paint layer is 10 μm to 35 μm, and the thickness of the second paint layer is 10 μm to 35 μm.
In one embodiment, the thickness of the composite coating is 30 μm to 60 μm.
In one embodiment, the nanoparticles comprise any one or more of silicon dioxide, cerium dioxide, titanium dioxide and graphite, and the particle size of the nanoparticles is 30-300 nm.
In one embodiment, the weight ratio of the nanoparticles, the epoxy resin and the amino resin is (1-5): (50-60): (10-15).
The invention also provides a preparation method of the composite coating, which comprises the following steps: providing a substrate; forming a metal base layer on the substrate; forming a first coating layer on the metal base layer; forming a second coating layer on the first coating layer to obtain the composite coating; wherein the metal base layer comprises one or more of zinc, aluminum and nickel; the first coating layer comprises a substance composed of nano particles, epoxy resin and amino resin, and the second coating layer comprises a substance composed of one or more of epoxy resin, polyurethane resin, linear phenolic resin or aldehyde ketone resin.
In one embodiment, the forming method includes drying, and the drying temperature is 120-250 ℃.
In one embodiment, forming a first coating layer on the metal base layer includes: adding a diluent into a first coating layer slurry, and spraying the first coating layer slurry onto the metal base layer, wherein the first coating layer slurry comprises the following raw materials in parts by weight: 50-60% of epoxy resin, 10-15% of amino resin, 5-10% of xylene, 1-5% of isobutanol, 1-5% of methyl isobutanol, 1-5% of silicon dioxide and 1-5% of carbon black.
In one embodiment, the diluent comprises the following raw materials in parts by weight: 25-35% of methyl isobutyl ketone, 10-20% of xylene, 30-40% of propylene glycol methyl ether acetate and 5-15% of 2-methyl propanol acetate, wherein the weight ratio of the first coating layer slurry to the diluent is 1: (1.8-2).
In one embodiment, the viscosity of the diluted first coating layer slurry is 7-20 s.
In one embodiment, forming a second coating layer on the first coating layer to obtain the composite coating comprises: spraying a second coating layer slurry onto the first coating layer.
In one embodiment, the viscosity of the second coating layer slurry is 7.8-15 s.
In one embodiment, the substrate is a bonded neodymium iron boron magnet.
In one embodiment, the bonded ndfeb magnet includes any one or more of the following features:
outer diameter: phi 21.990 mm-phi 22.050 mm; inner diameter: phi 19.700 mm-phi 19.760 mm; height: 12.25 mm-12.3 mm; the pressed density of the magnet is more than or equal to 6.0g/cm 3; the roundness is less than or equal to 0.03 mm; the concentricity is less than or equal to 0.03 mm; the full-size CPK is more than or equal to 1.33.
In a further aspect of the invention there is provided a metal article comprising a composite coating as described above.
As described above, the present invention provides a composite coating, a method for preparing the same, and a use thereof, having the following advantageous effects: the composite coating provided by the invention can greatly improve the neutral salt spray resistance of the metal product, so that the metal product can be applied to the body climate with a severe body environment. When the thickness of the coating is 30-60 mu m, the invention can ensure that the interface of the coating is smooth and has no fracture, and the neutral salt spray resistance time of the bonded neodymium iron boron magnet can reach 1500h on the premise that the magnetic property is not influenced, thereby having better corrosion resistance.
Drawings
Fig. 1 shows a schematic structural diagram of the composite coating according to the present invention.
FIG. 2 is a schematic flow chart of the preparation method of the present invention.
FIG. 3 shows a scanning electron microscope image of the composite coating according to the invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 3. The present invention firstly provides a composite coating 200, the composite coating 200 may be a metal/organic composite coating 200, the composite coating 200 may firstly include a metal base layer 201, the metal base layer 201 may be attached on a substrate 100 to be protected, the substrate 100 may be a metal substrate, the metal type of the metal base layer 201 may not be limited as long as it satisfies that the corrosion activity is stronger than that of the metal substrate to be protected, such as one or more combinations of zinc, aluminum, and nickel, and further may be a combination of zinc and aluminum, as can be seen from fig. 3, the metal base layer 201 may have a layered structure inside, the layered structure may prevent the formation of corrosion channels, in an embodiment, the metal substrate 100 may be a neodymium iron boron rare earth permanent magnet material, such as a bonded neodymium iron boron magnet, in an embodiment, the magnetic ring can be a bonded neodymium iron boron magnetic ring, the outer diameter of the bonded neodymium iron boron magnetic ring can be 21.990-22.050 mm, the inner diameter can be 19.700-19.760 mm, the height can be 12.25-12.3 mm, the pressing density of the magnetic ring can be more than or equal to 6.0g/cm3, the roundness can be less than or equal to 0.03mm, the concentricity can be less than or equal to 0.03mm, and the full-size CPK can be more than or equal to 1.33. In one embodiment, the thickness of the metal base layer 201 may be 10 μm to 35 μm, for example, 20 μm. The metal base layer 201 may ensure the hardness of the composite coating 200 as a whole.
The composite coating 200 may further include a first coating layer 202, the first coating layer 202 may be disposed on the metal base layer 201, and the thickness of the first coating layer 202 may be 10 μm to 35 μm, for example, 20 μm. The first coating layer 202 may be formed by diluting a certain first coating layer slurry and spraying the diluted first coating layer slurry onto the metal base layer 201, where the first coating layer slurry may include a substance composed of nanoparticles, epoxy resin, and amino resin, the nanoparticles may include any one or more of silica, ceria, titania, and graphite, the nanoparticles may have a particle size of 30-300nm, and in one embodiment, the weight ratio of the nanoparticles, epoxy resin, and amino resin may be (1-5): (50-60): (10-15).
In an embodiment, the first coating layer slurry may further include a solvent and an auxiliary agent, the solvent may be any one or more of xylene, isobutanol and methyl isobutanol, in an embodiment, the solvent may be xylene, isobutanol and methyl isobutanol according to a weight ratio of (5-10): (1-5): 1-5, and the auxiliary agent may include carbon black.
The composite coating 200 may further include a second coating layer 203, the second coating layer 203 may be located on the first coating layer 202, the thickness of the second coating layer 203 may be 10 μm to 35 μm, for example, 20 μm, the second coating layer 203 may also be formed by spraying a certain second coating layer slurry onto the first coating layer 202, the second coating layer slurry may include any one or more of epoxy resin, polyurethane, phenol novolac resin, or aldehyde ketone resin, the thickness of the second coating layer 203 may be 10 μm to 35 μm, for example, 20 μm, the viscosity of the second coating layer slurry may be 7.8 to 15s, and controlling the viscosity within the above range may enable the coating to be uniform without sagging, orange peel, and the like.
The total thickness of the composite coating 200 of the present invention may be 30 to 60 μm, for example, 40 μm or 59 μm, and limiting the thickness of the composite coating 200 within the above disclosed range may allow the metal substrate 100 to have better corrosion resistance.
Please refer to fig. 1 to 3. The present invention also provides a method for preparing the composite coating as described above, the method at least comprising the steps of S1-S4:
s1: providing a substrate;
s2: forming a metal base layer on the substrate;
s3: forming a first coating layer on the metal base layer;
s4: forming a second coating layer on the first coating layer to obtain the composite coating;
wherein the metal base layer comprises one or more of zinc, aluminum and nickel; the first coating layer comprises a substance composed of nano particles, epoxy resin and amino resin, and the second coating layer comprises a substance composed of one or more of epoxy resin, polyurethane resin, linear phenolic resin or aldehyde ketone resin.
In step S1, the substrate 100 may be a metal product such as a neodymium-iron-boron magnet, and the substrate 100 may further be pretreated before forming the composite coating 200, the pretreatment may cause a protective film to be formed on the substrate 100 to block the holes on the metal substrate 100, and the pretreatment may include, but is not limited to, polishing, cleaning, and phosphating, passivation, etc. In one embodiment, the polishing may be a surface polishing treatment of the substrate 100, the polishing may include mechanical vibration polishing, tumbling a chamfer, and the like, and the cleaning may be ultrasonic cleaning, for example, the chamfered substrate 100 may be cleaned in an ultrasonic cleaning machine. The surface phosphating can be carried out by putting the cleaned substrate 100 into phosphating solution for surface phosphating treatment, wherein the phosphating can be carried out by adopting medium-temperature phosphating, the phosphating temperature can be 50-75 ℃, the phosphating time can be 5-30 min, the passivation can be carried out by using 3901 passivation solution and water according to the proportion 1 (1.2-2.2) for 10min, and the phosphating solution can be any one or more of zinc, zinc-calcium, zinc-manganese, iron and amorphous iron.
In step S2, the metal base layer 201 may be a metal base layer 201 composed of zinc and aluminum, and the zinc and the aluminum may be disposed in a weight ratio of (1-5): 1.
In step S3, the first coating layer 202 may be formed by spraying the first coating layer slurry onto the metal base layer 201 after adding a diluent, wherein the dilution may be to dilute the first coating layer slurry to a viscosity of 7 to 20S, for example, 14.5S, 14.9S. In one embodiment, the first coating layer slurry comprises the following raw materials in parts by weight: 50-60% of epoxy resin, 10-15% of amino resin, 5-10% of xylene, 1-5% of isobutanol, 1-5% of methyl isobutanol, 1-5% of silicon dioxide and 1-5% of carbon black. In one embodiment, the diluent may include the following raw materials and parts by weight: 25-35% of methyl isobutyl ketone, 10-20% of xylene, 30-40% of propylene glycol methyl ether acetate and 5-15% of 2-methyl propanol acetate, wherein the weight ratio of the first coating layer slurry to the diluent can be 1: (1.8-2).
In steps S2 to S4, the forming method may include spraying and drying, the spraying may include front-side spraying and back-side spraying of the substrate 100, the spraying may be achieved by multiple spraying with a sprayer, the substrate may be dried after each spraying, the spraying amount of the spraying may be 20g to 30g/30S, for example, 26g/30S, the atomization pressure may be 0.3 to 0.5Mpa, the drying temperature may be 120 to 250 ℃, for example, 150 ℃, 160 ℃, 200 ℃, 220 ℃, and the drying time may be 2 to 60min, for example, 15min, 30min, 45 min. In one embodiment, the drying temperature of the metal base layer 201 may be 180 to 250 ℃, and further may be 180 to 200 ℃. This application prescribes a limit to stoving temperature in above scope, can be so that composite coating 200 compactness is good, can prevent effectively that metal substrate 100 temperature is too high when drying from appearing the hole, causes the magnetic powder oxidation to reduce metal substrate 100's magnetic flux.
In step S4, after the composite coating 200 is formed, the composite coating 200 may be integrally cured and dried, where the curing and drying temperature may be 160 to 200 ℃, and the curing and drying time may be 30 to 60 min.
The invention also provides an application of the composite coating 200, for example, the composite coating can be used in the field of corrosion prevention of metal products, in one embodiment, the composite coating can be used in corrosion prevention of bonded NdFeB magnets, and metal products prepared by the composite coating 200 can be used in the field of automobile motors and the like, and have good corrosion prevention performance.
Note that "%" and "part(s)" shown herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
Hereinafter, the present invention will be more specifically explained by referring to examples, which should not be construed as limiting. Appropriate modifications may be made within the scope consistent with the gist of the present invention, and all of them fall within the technical scope of the present invention. In the following examples, the first coating layer slurry was made of Shanghai Dabao SEPD7000, the diluent used in the first coating layer slurry was made of Shanghai Dabao SNO.20, and the second coating layer slurry was made of F-1 coating.
Example 1
(I) chamfer polishing: adopting mechanical vibration grinding and barreling chamfer to carry out surface polishing treatment on the bonded neodymium iron boron magnet, and finally obtaining the size of the magnet: 22mm outside diameter, 19.7mm inside diameter, 12.3mm thickness.
(II) ultrasonic cleaning: and putting the magnet after chamfering and polishing into an ultrasonic cleaning machine for cleaning.
(III) surface phosphorization: and (3) putting the cleaned magnet into a phosphating solution for surface phosphating, wherein medium-temperature phosphating is adopted for phosphating at the temperature of 50-75 ℃ for 5-30 min.
(IV) a metal base layer: preparing a ZnAl metal base layer on the surface of the treated magnet by adopting a spraying process, which comprises the following specific steps: firstly, spraying the front surface of the magnet with the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa, and drying after spraying, wherein the drying temperature is 120 ℃ and the time is 15 min. And after the cooled product is turned over, spraying the other surface by using the same coating and process, wherein the drying temperature is 230 ℃, the drying time is 45min, and the thickness of the ZnAl metal base layer is 20 mu m.
(V) first dope layer: the first dope layer thick liquids after the metal substrate surface coating is diluted are in order to form first dope layer, and the concrete process is: the front surface of the magnet is firstly sprayed with the first coating slurry twice and then dried, the spraying amount is 26g/30s, the atomization pressure is 0.3-0.5Mpa, and the drying is carried out after spraying, the drying temperature is 120 ℃, and the time is 2 min. And continuously spraying the first coating slurry twice, and drying at 120 ℃ for 2min to obtain a first coating layer with the thickness of 16.8 mu m.
(sixth), second dope layer: coating a second coating layer slurry on the surface of the closed first coating layer to form a second coating layer, wherein the second coating layer slurry is modified polyurethane epoxy resin, and the specific process comprises the following steps: and spraying the second coating slurry on the front surface of the magnet twice, and then drying at the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa for 2min at the drying temperature of 120 ℃. And continuously spraying the second coating layer slurry twice, and drying at 150 ℃ for 15min, wherein the thickness of the second coating layer is 16.9 mu m.
And sequentially carrying out the spraying process on the reverse side of the bonded neodymium iron boron magnet, and finally curing and drying at the curing and drying temperature of 160 ℃ for 45min, wherein the thickness of the composite coating is 53.7 mu m.
Example 2
(I) chamfer polishing: carrying out surface polishing treatment on the bonded neodymium iron boron magnet by adopting a mechanical vibration grinding and tumbling chamfering method, and finally, sizing the magnet ring: the outer diameter is 18.8mm, the inner diameter is 15.8mm, and the thickness is 2.5 mm.
(II) ultrasonic cleaning: and putting the magnet after chamfering and polishing into an ultrasonic cleaning machine for cleaning.
(III) surface phosphorization: and putting the cleaned permanent magnet into a phosphating solution for surface phosphating, wherein medium-temperature phosphating is adopted for phosphating at the temperature of 50-75 ℃ for 5-30 min.
(IV) a metal base layer: preparing a ZnAl metal base layer on the surface of the treated magnet by adopting a spraying process; the specific process is as follows: firstly, spraying the front surface of the magnet with the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa, and drying after spraying, wherein the drying temperature is 120 ℃ and the time is 15 min. And after the cooled product is turned over, spraying the other surface by using the same coating and process, wherein the drying temperature is 230 ℃, the time is 45min, and the thickness of the metal base layer is 20 mu m.
(V) first dope layer: the first dope layer thick liquids after the metal substrate surface coating dilutes form first dope layer, and the concrete process is: the front surface of the magnet is firstly sprayed with the first coating slurry twice and then dried, the spraying amount is 26g/30s, the atomization pressure is 0.3-0.5Mpa, and the drying is carried out after spraying, the drying temperature is 120 ℃, and the time is 2 min. And continuously spraying the primer for two times, and drying at 120 ℃ for 2min to obtain a first coating layer with the thickness of 16.8 mu m.
(sixth), second dope layer: coating a second coating layer slurry on the surface of the closed first coating layer to form a second coating layer, wherein the second coating layer slurry is modified polyurethane epoxy resin, and the specific process comprises the following steps: firstly, spraying primer twice on the front surface of the magnet, and then drying, wherein the spraying amount is 26g/30s, the atomization pressure is 0.3-0.5Mpa, and the drying is carried out after spraying, and the drying temperature is 120 ℃ for 2 min. And continuously spraying the primer for two times, and drying at the drying temperature of 150 ℃ for 15min, wherein the thickness of the second coating layer is 16.9 mu m.
And sequentially carrying out the spraying process on the reverse side of the bonded neodymium iron boron magnet, and finally drying and curing at the curing drying temperature of 160 ℃ for 45min, wherein the thickness of the composite coating is 53.7 mu m.
Comparative example 1
(I) chamfer polishing: carrying out surface polishing treatment on the bonded neodymium iron boron magnet by adopting a mechanical vibration grinding and tumbling chamfering method, and finally, sizing the magnet ring: the outer diameter is 18.8mm, the inner diameter is 15.8mm, and the thickness is 2.5 mm.
(II) ultrasonic cleaning: and putting the magnet after chamfering and polishing into an ultrasonic cleaning machine for cleaning.
(III) surface phosphorization: and putting the cleaned permanent magnet into a phosphating solution for surface phosphating, wherein medium-temperature phosphating is adopted for phosphating at the temperature of 50-75 ℃ for 5-30 min.
(IV) a metal base layer: preparing a ZnAl metal base layer on the surface of the treated magnet by adopting a spraying process; the specific process is as follows: firstly, spraying the front surface of the magnet with the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa, and drying after spraying, wherein the drying temperature is 120 ℃ and the time is 15 min. And after the cooled product is turned over, spraying the other surface by using the same coating and process, wherein the drying temperature is 230 ℃, the time is 45min, and the thickness of the metal base layer is 9 mu m.
(V) first dope layer: the first dope layer thick liquids after the metal substrate surface coating dilutes form first dope layer, and the concrete process is: the front surface of the magnet is firstly sprayed with the first coating slurry twice and then dried, the spraying amount is 26g/30s, the atomization pressure is 0.3-0.5Mpa, and the drying is carried out after spraying, the drying temperature is 120 ℃, and the time is 2 min. And continuously spraying the primer for two times, and drying at 120 ℃ for 2min to obtain a first coating layer with the thickness of 9 mu m.
(sixth), second dope layer: coating a second coating layer slurry on the surface of the closed first coating layer to form a second coating layer, wherein the second coating layer slurry is modified polyurethane epoxy resin, and the specific process comprises the following steps: firstly, spraying primer twice on the front surface of the magnet, then drying, wherein the spraying amount is 23g/30s, the atomization pressure is 0.3-0.5Mpa, and drying is carried out after spraying, and the drying temperature is 120 ℃ for 2 min. And continuously spraying the primer for two times, and drying at the drying temperature of 150 ℃ for 15min, wherein the thickness of the second coating layer is 9 mu m.
And sequentially carrying out the spraying process on the reverse side of the bonded neodymium iron boron magnet, and finally drying and curing at the drying and curing temperature of 160 ℃ for 45min, wherein the thickness of the composite coating is 27 mu m.
Comparative example 2
(I) chamfer polishing: adopting mechanical vibration grinding and tumbling chamfering methods to carry out surface polishing treatment on the bonded neodymium iron boron magnet, and finally obtaining the size of the magnet: 22mm outside diameter, 19.7mm inside diameter, 12.3mm thickness.
(II) ultrasonic cleaning: and putting the magnet after chamfering and polishing into an ultrasonic cleaning machine for cleaning.
(III) surface passivation: passivating for 10min by using 3901 passivating solution in a proportion of 1 (1.2-2.2).
(IV) a metal base layer: preparing a ZnAl metal base layer on the surface of the treated magnet by adopting a spraying process; the specific process is as follows: firstly, spraying the front surface of the magnet with the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa, and drying after spraying, wherein the drying temperature is 120 ℃ and the time is 15 min. And after the cooled product is turned over, spraying the other surface by using the same coating and process, wherein the drying temperature is 230 ℃, the drying time is 45min, and the thickness of the ZnAl metal base layer is 20 mu m.
Comparative example 3
(I) chamfer polishing: adopting mechanical vibration grinding and tumbling chamfering methods to carry out surface polishing treatment on the bonded neodymium iron boron magnet, and finally obtaining the size of the magnet: 22mm outside diameter, 19.7mm inside diameter, 12.3mm thickness.
(II) ultrasonic cleaning: and putting the magnet after chamfering and polishing into an ultrasonic cleaning machine for cleaning.
(III) surface passivation: passivating with 3901 passivating solution at a ratio (1:1.2-2.2) for 10 min.
(IV) the first coating layer: the diluted first coating layer slurry is coated on the surface of the magnetic ring to form a first coating layer, and the specific process is as follows: the front surface of the magnet is firstly sprayed with the first coating slurry twice and then dried, the spraying amount is 26g/30s, the atomization pressure is 0.3-0.5Mpa, and the drying is carried out after spraying, the drying temperature is 120 ℃, and the time is 2 min. And continuously spraying the first coating layer slurry twice and then drying at the drying temperature of 120 ℃ for 2 min.
(V) a second coating layer: coating a second coating layer slurry on the surface of the closed first coating layer to form a second coating layer, wherein the second coating layer is modified polyurethane epoxy resin, and the specific process comprises the following steps: and spraying the second coating slurry on the front surface of the magnet twice, and then drying at the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa for 2min at the drying temperature of 120 ℃. And continuously spraying the second coating layer slurry twice, and drying at the drying temperature of 150 ℃ for 15 min.
And sequentially carrying out the spraying process on the reverse side of the bonded neodymium iron boron magnet, and finally drying and curing at the drying and curing temperature of 160 ℃ for 45 min.
Comparative example 4
(I) chamfer polishing: carrying out surface polishing treatment on the bonded neodymium iron boron magnet by adopting a mechanical vibration grinding and tumbling chamfering method, and finally, sizing the magnet ring: 22mm outside diameter, 19.7mm inside diameter, 12.3mm thickness.
(II) ultrasonic cleaning: and putting the magnet after chamfering and polishing into an ultrasonic cleaning machine for cleaning.
(III) surface passivation: passivating with 3901 passivating solution at a ratio (1:1.2-2.2) for 10 min.
(IV) a metal base layer: preparing a ZnAl metal base layer on the surface of the treated magnet by adopting a spraying process, which comprises the following specific steps: firstly, spraying the front surface of the magnet with the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa, and drying after spraying, wherein the drying temperature is 120 ℃ and the time is 15 min. And after the cooled product is turned over, spraying the other surface by using the same coating and process, wherein the drying temperature is 230 ℃, the drying time is 45min, and the thickness of the ZnAl metal base layer is 20 mu m.
(V) a second coating layer: coating a second coating layer slurry on the surface of the ZnAl metal base layer to form a second coating layer, wherein the second coating layer slurry is modified polyurethane epoxy resin, and the specific process comprises the following steps: and spraying the second coating slurry on the front surface of the magnet twice, and then drying at the spraying amount of 26g/30s and the atomizing pressure of 0.3-0.5Mpa for 2min at the drying temperature of 120 ℃. And continuously spraying the primer for two times, and drying at the drying temperature of 150 ℃ for 15 min.
And sequentially carrying out the spraying process on the reverse side of the bonded neodymium iron boron magnet, and finally drying and curing at the drying and curing temperature of 160 ℃ for 45 min.
The results of the neutral salt spray test performed on the samples obtained in the above examples are shown in table 2 below. The test conditions of the neutral salt spray test of the invention are shown in table 1.
Table 1 neutral salt spray test conditions
TABLE 2 neutral salt spray test Performance test Table
| Sample name | Neutral salt spray test |
| Example 1 | 1500h non-rust spot |
| Example 2 | 1500h non-rust spot |
| Comparative example 1 | Rust spot appears in 456h |
| Comparative example 2 | Rust spot appears in 120h |
| Comparative example 3 | Rust spot appears after 600h |
| Comparative example 4 | Rust points appear in 360h |
Magnetic flux before and after spraying of the bonded ndfeb magnet with the composite coating (each expressed as Φ) was tested using a fluxmeter by performing a magnetic flux test on example 1 as follows1Phi of2) Then, the magnetic flux change rate is calculated: the magnetic flux change rate was calculated using the following formula i, and the results are shown in table 3. As can be seen from table 3, the magnetic flux of the bonded ndfeb magnet after the composite coating is coated in example 1 is reduced by only 0.15%, which indicates that the coating and the preparation process thereof have almost no influence on the magnetic performance of the magnet.
△Ф＝(Ф1-Ф2)/Ф1·100％ (Ι)
TABLE 3 magnetic flux variability Performance test Table
| Sample name | Ф1/mWb | Ф2/mWb | △Ф/％ |
| Example 1 | 4.710 | 4.703 | 0.15 |
FIG. 3 is a scanning electron microscope image of the sample in example 1, and it can be seen that the composite coating forms an obvious three-layer structure, the coating is uniform and flat, and has good corrosion resistance.
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value. The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. Composite coating, characterized in that it comprises at least:
a metal base layer;
the first coating layer is positioned on the metal base layer;
the second coating layer is positioned on the first coating layer;
wherein the metal base layer comprises one or more of zinc, aluminum and nickel;
the first coating layer comprises a substance composed of nano particles, epoxy resin and amino resin, and the second coating layer comprises a substance composed of one or more of epoxy resin, polyurethane resin, linear phenolic resin or aldehyde ketone resin.
2. A composite coating according to claim 1, wherein: the thickness of the metal base layer is 10-35 mu m, the thickness of the first coating layer is 10-35 mu m, and the thickness of the second coating layer is 10-35 mu m.
3. A composite coating according to claim 1, wherein: the thickness of the composite coating is 30-60 mu m.
4. A composite coating according to claim 1, wherein: the nano-particles comprise any one or more of silicon dioxide, cerium dioxide, titanium dioxide and graphite, and the particle size of the nano-particles is 30-300 nm.
5. A composite coating according to claim 1, wherein: the weight ratio of the nano particles to the epoxy resin to the amino resin is (1-5): (50-60): (10-15).
6. The preparation method of the composite coating is characterized by comprising the following steps:
providing a substrate;
forming a metal base layer on the substrate;
forming a first coating layer on the metal base layer;
forming a second coating layer on the first coating layer to obtain the composite coating;
wherein the metal base layer comprises one or more of zinc, aluminum and nickel;
the first coating layer comprises a substance composed of nano particles, epoxy resin and amino resin, and the second coating layer comprises a substance composed of one or more of epoxy resin, polyurethane resin, linear phenolic resin or aldehyde ketone resin.
7. The method of claim 6, wherein: the forming mode comprises drying, and the drying temperature is 120-250 ℃.
8. The method of claim 6, wherein: forming a first coating layer on the metal base layer, comprising:
adding a diluent into a first coating layer slurry, and spraying the first coating layer slurry onto the metal base layer, wherein the first coating layer slurry comprises the following raw materials in parts by weight: 50-60% of epoxy resin, 10-15% of amino resin, 5-10% of xylene, 1-5% of isobutanol, 1-5% of methyl isobutanol, 1-5% of silicon dioxide and 1-5% of carbon black.
9. The method of claim 8, wherein: the diluent comprises the following raw materials in parts by weight: 25-35% of methyl isobutyl ketone, 10-20% of xylene, 30-40% of propylene glycol methyl ether acetate and 5-15% of 2-methyl propanol acetate, wherein the weight ratio of the first coating layer slurry to the diluent is 1: (1.8-2).
10. A metal article, characterized by: comprising a composite coating according to any of claims 1 to 5.
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