CN113145420A - Coating method for coating anti-corrosion heat dissipation graphene coating - Google Patents
Coating method for coating anti-corrosion heat dissipation graphene coating Download PDFInfo
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Abstract
The invention relates to the technical field of magnets, in particular to a coating method for coating an anticorrosive heat-dissipation graphene coating, which comprises the following steps: (1) dipping a magnet into the prepared anticorrosive heat-dissipation graphene coating; after dipping, pulling the magnet matrix upwards to suspend the magnet matrix above the anticorrosive heat dissipation graphene coating, so that a continuous adhesive film is formed on the surface of the magnet, and repeating the dipping and pulling steps to obtain the magnet with a primary coating film; (2) and curing the primary coating film of the magnet substrate to obtain the magnet coated with the anticorrosive heat-dissipation graphene coating. The coating method is simple to operate, high in production efficiency and product yield, good in coating smoothness, uniform in coating distribution and strong in binding force with the magnet; the anticorrosive heat-dissipation graphene coating is coated on the surface of the magnet, so that the corrosion resistance of the magnet can be improved, the anticorrosive heat-dissipation graphene coating has good heat dissipation performance, the service life of the magnet can be prolonged, and the application range of the anticorrosive heat-dissipation graphene coating is expanded.
Description
Technical Field
The invention relates to the technical field of magnets, in particular to a coating method for coating an anticorrosive heat-dissipation graphene coating.
Background
With the development of economy and social progress, magnets have played a very important role in industrial production and daily life. There are many kinds of magnets, such as alnico, samarium cobalt, ferrite, and neodymium iron boron. The neodymium iron boron magnet is an important magnet, has excellent magnetic performance and good machinability, and is widely applied to the industries of machinery, traffic, energy, medical treatment, IT, household appliances and the like, however, the existing neodymium iron boron has poor heat conductivity, is easy to rust and oxidize, has insufficient corrosion resistance, is usually coated with a protective coating on the surface thereof in the prior art to improve the corrosion resistance, however, the protective coating in the prior art still needs to be improved in corrosion resistance, has poor coating performance, is insufficient in heat dissipation, is difficult to conduct heat outwards, and needs to be further improved.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the coating method for coating the anti-corrosion heat-dissipation graphene coating, and the coating method is simple to operate, high in production efficiency and product yield, good in coating smoothness, uniform in coating distribution and strong in binding force with a magnet; the anticorrosive heat-dissipation graphene coating is coated on the surface of the magnet, so that the corrosion resistance of the magnet can be improved, the anticorrosive heat-dissipation graphene coating has good heat dissipation performance, the service life of the magnet can be prolonged, and the application range of the anticorrosive heat-dissipation graphene coating is expanded.
The purpose of the invention is realized by the following technical scheme: a coating method for coating an anti-corrosion heat dissipation graphene coating comprises the following steps:
(1) dipping a magnet into the prepared anticorrosive heat-dissipation graphene coating; after dipping, pulling the magnet matrix upwards to suspend the magnet matrix above the anticorrosive heat dissipation graphene coating, so that a continuous adhesive film is formed on the surface of the magnet, and repeating the dipping and pulling steps to obtain the magnet with a primary coating film;
(2) and curing the primary coating film of the magnet substrate to obtain the magnet coated with the anticorrosive heat-dissipation graphene coating.
According to the invention, by adopting a dip-coating method, an anticorrosive heat-dissipation graphene coating is formed on the surface of the magnet by a coating machine, the liquid level is ensured to be free of vibration in the lifting process, and the substrate is vertical, uniform, stable and continuous to rise, so that a continuous and uniform thin film is formed on the surface of the substrate, the conversion from a wet gel film to a dry gel film is completed, and the anticorrosive heat-dissipation graphene coating which is uniform in distribution, smooth in surface and tightly combined with the substrate is obtained by further curing the dry gel film.
Further, the anticorrosive heat-dissipation graphene coating comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 40-50 parts of epoxy resin, 6-10 parts of acrylic resin, 15-20 parts of zinc powder, 0.4-2 parts of graphene, 2-5 parts of dispersing agent, 0.5-4 parts of coupling agent, 1-3 parts of flatting agent, 6-10 parts of filler, 9-14 parts of synergistic additive and 22-30 parts of solvent, wherein the component B comprises the following raw materials in parts by weight: 1-4 parts of curing agent and 3-5 parts of diluent.
The anticorrosive heat-dissipation graphene coating comprises a component A containing raw materials such as epoxy resin and a dispersing agent and a component B containing a curing agent, wherein the component A and the component B are separately placed before use, so that the anticorrosive heat-dissipation graphene coating is convenient to transport and store, and the component A and the component B are mixed when in use; adding graphene into an epoxy resin mixture, and matching with acrylic resin, a coupling agent, zinc powder and other raw materials to prepare the anticorrosive heat-dissipation graphene coating; the anticorrosive heat dissipation graphene coating can be uniformly coated on the surface of a magnet, is tightly combined with the surface of the magnet, has strong adhesive force, can improve the corrosion resistance of the magnet, has good heat dissipation performance, can prolong the service life of the magnet, and can expand the application range of the magnet.
Further, in the step (1), the filler is at least one of mica powder, calcium carbonate and talcum powder. The particle size of the filler is 50-100 nm. Furthermore, the filler is prepared from mica powder, calcium carbonate and talcum powder in a weight ratio of 1-2: 0.8-1.2: 1. The filler is adopted, so that the production cost is reduced, and the mechanical property, the weather resistance and the corrosion resistance of the coating are improved by enhancing the effect of adopting the filler. The corrosion-resistant and heat-dissipating graphene coating has the advantages that the mechanical performance, weather resistance and corrosion resistance of the coating are improved, and the size stability and the surface smoothness of a product are improved; the adoption of the nano filler can increase the specific surface area and the surface adsorption capacity and improve the dispersion effect.
Further, in the step (1), the epoxy resin is bisphenol a type epoxy resin. By matching the epoxy resin with the graphene and other raw materials, the coating has good mechanical properties, corrosion resistance and good binding property with magnets. The bisphenol a type epoxy resin is preferably, but not limited to, bisphenol a type epoxy resin E44. The solvent consists of butanol, xylene and 1, 4-butanediol glycidyl ether according to the weight ratio of 3-5:0.8-1.4: 1. The acrylic resin is preferably, but not limited to, acrylic resin DS 8030-TB.
Further, in the step (1), the coupling agent is a silane coupling agent, and the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, vinyltriethoxysilane and vinyltris (beta-methoxyethoxy) silane. By adopting the silane coupling agent, the crosslinking density and the compactness of a paint film are improved, and the mechanical property, the storage stability and the adhesive force of the paint are improved.
Further, in the step (1), the dispersant is at least one of polyacrylate, sodium polycarboxylate and sodium carboxylate. By adopting the dispersing agent, the graphene, the filler and the like in the component A are uniformly distributed in a coating system, the graphene is not easy to gather, and the coating performance of the coating on the surface of the magnet is improved.
Further, in the step (1), the leveling agent is at least one of polydisiloxane and cellulose acetate butyrate. Furthermore, the leveling agent is composed of polydisiloxane and cellulose acetate butyrate according to the weight ratio of 0.8-2: 1. By adopting the leveling agent, the anti-corrosion heat dissipation graphene coating has excellent substrate wetting capacity and good compatibility with raw materials such as epoxy resin, the surface of the anti-corrosion heat dissipation graphene coating has a good leveling effect, the coating is not easy to generate defects such as abnormal leveling and shrinkage cavity, and the bonding force with the surface of a magnet is good.
Further, in the step (1), the preparation method of each part of the synergist comprises the following steps: adding 9-12 parts of nano aluminum oxide, 7-10 parts of PVDF resin, 5-7 parts of maleic anhydride grafted ethylene-octene copolymer and 4-7 parts of gamma-glycidyl ether oxypropyltrimethoxysilane into 20-30 parts of polyethylene glycol by weight, and stirring and mixing uniformly to obtain a mixture A; stirring the mixture A at 80-95 ℃, preserving heat for 60-90min, performing ultrasonic dispersion, then centrifugally washing, and drying to obtain the synergistic auxiliary agent. The maleic anhydride grafted ethylene-octene copolymer is preferably but not limited to Nanjing plastetamide maleic anhydride grafted ethylene-octene copolymer ST-8. The PVDF resin is preferably, but not limited to, Kynar 761. According to the invention, through matching the nano aluminum oxide, the PVDF resin, the maleic anhydride grafted ethylene-octene copolymer and the like, the synergistic auxiliary agent has good compatibility with epoxy resin, acrylic resin and the like in the raw materials, and is beneficial to improving the heat dissipation performance, corrosion resistance and weather resistance of the coating, and the coating is uniformly dispersed during coating and has good dispersibility with magnets. The thermal conductivity of the graphene is 4400-5780W/mK, and the graphene is matched with nano aluminum oxide and the like, so that the graphene is uniformly distributed in the coating, the heat dissipation performance of the coating is improved, and the performance is more stable when the magnet coated with the coating is used in occasions such as a motor rotor and the like.
Further, in the step (1), the curing agent is at least one of diethylenetriamine, triethylene tetramine, diethylaminopropylamine, and 2, 4, 6-tris (dimethylaminomethyl) phenol. The curing agent can react with epoxy resin to form a reticular three-dimensional polymer, so that the mechanical property, the corrosion resistance and the adhesive force with the surface of a magnet of the coating are improved.
Further, in the step (1), the diluent is at least one of xylene, ethanol, decanoic acid glycidyl ether and 1-4 butanediol glycidyl ether. Furthermore, the diluent consists of xylene, ethanol and decanoic acid glycidyl ether according to the weight ratio of 0.4-0.8:1.5-2: 1. By adopting the diluent, the compatibility of all raw materials can be improved, so that the anticorrosive heat-dissipation graphene coating is uniformly dispersed and has good coating property.
Further, the preparation method of the anticorrosive heat dissipation graphene coating comprises the following steps:
preparation of component A:
a1, mixing the graphene, the coupling agent and the dispersing agent in proportion, and uniformly stirring at the stirring speed of 1000-1600r/min for 10-20 min; then adding epoxy resin and acrylic resin, and stirring at the temperature of 65-70 ℃ for 20-40min to obtain resin graphene slurry;
a2, adding zinc powder, graphene, a dispersing agent, a leveling agent, a filler and a synergistic auxiliary agent into the resin graphene slurry, and stirring at the temperature of 65-70 ℃ for 20-40min at the stirring speed of 1000-1600r/min to obtain mixed slurry; grinding the mixed slurry, controlling the discharge fineness to be 10-30 mu m, and filtering to obtain the component A for later use.
Preparation of the component B:
mixing the curing agent and the diluent, and uniformly stirring at the stirring speed of 1000-1600r/min for 10-20min for later use.
The preparation method of the anticorrosive heat-dissipation graphene coating is simple in process, convenient to control, high in production efficiency, beneficial to industrial production, beneficial to preventing agglomeration of graphene, fillers and the like, good in coating performance, and capable of forming a uniform coating with strong adhesive force on the surface of a magnet.
Further, in the step (1), the dipping time is 25-35s each time, the suspension time of the magnet after each pulling is 70-90s, and the repetition times are 30-50 times.
Further, in the step (1), the speed of pulling the magnet each time is 2-3.5 cm/min.
Further, in the step (2), the curing temperature is 85-95 ℃, and the curing time is 20-30 min.
The invention can control the thickness of the coating film by strictly controlling the dip-coating parameters of the matrix through the coating process, is beneficial to forming a uniform and flat protective coating which is tightly combined with the surface of the magnet on the surface of the magnet, can improve the corrosion resistance of the magnet, has good heat dissipation performance, can prolong the service life of the magnet, and expands the application range of the magnet.
The invention has the beneficial effects that: the coating method for coating the anti-corrosion heat dissipation graphene coating is simple to operate, high in production efficiency and product yield, smooth in coating surface, good in smoothness, uniform in coating distribution and strong in binding force with a magnet; the anticorrosive heat-dissipation graphene coating is coated on the surface of the magnet, so that the corrosion resistance of the magnet can be improved, the anticorrosive heat-dissipation graphene coating has good heat dissipation performance, the service life of the magnet can be prolonged, and the application range of the anticorrosive heat-dissipation graphene coating is expanded.
Drawings
Fig. 1 is a diagram illustrating an effect of coating the anticorrosive heat dissipation graphene paint of embodiment 1 on a chromium-plated non-magnetized neodymium iron boron magnet.
Fig. 2 is a graph showing the effect of coating the anticorrosive heat dissipation graphene paint of example 1 on an un-plated and un-magnetized ndfeb magnet.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A coating method for coating an anti-corrosion heat dissipation graphene coating comprises the following steps:
(1) dipping a magnet into the prepared anticorrosive heat-dissipation graphene coating; after dipping, pulling the magnet matrix upwards to suspend the magnet matrix above the anticorrosive heat dissipation graphene coating, so that a continuous adhesive film is formed on the surface of the magnet, and repeating the dipping and pulling steps to obtain the magnet with a primary coating film;
(2) and curing the primary coating film of the magnet substrate to obtain the magnet coated with the anticorrosive heat-dissipation graphene coating.
Further, in the step (1), the dipping time is 30s each time, the magnet suspension time after each pulling is 80s, and the repetition times are 40 times.
Further, in the step (1), the speed of pulling the magnet each time is 3 cm/min.
Further, in the step (2), the curing temperature is 90 ℃ and the curing time is 25 min.
Further, the anticorrosive heat dissipation graphene coating comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 45 parts of epoxy resin, 8 parts of acrylic resin, 17 parts of zinc powder, 1 part of graphene, 3 parts of a dispersing agent, 2 parts of a coupling agent, 2 parts of a leveling agent, 7 parts of a filler, 12 parts of a synergistic assistant and 25 parts of a solvent, wherein the component B comprises the following raw materials in parts by weight: 2 parts of curing agent and 4 parts of diluent.
Further, the filler is prepared from mica powder, calcium carbonate and talcum powder according to the weight ratio of 1, 5: 1:1. The particle size of the filler is 50-100 nm. The bisphenol A type epoxy resin is bisphenol A type epoxy resin E44. The solvent consists of butanol, xylene and 1, 4-butanediol glycidyl ether according to the weight ratio of 4:1:1, and the acrylic resin is acrylic resin DS 8030-TB.
Further, the coupling agent is a silane coupling agent which is gamma-aminopropyltriethoxysilane and vinyl tri (beta-methoxyethoxy) silane in a weight ratio of 1:1.
Further, the Dispersant is sodium polycarboxylate Dispersant SN-5040 or sodium polyacrylate Dispersant Dispersant-9100. The leveling agent consists of polydisiloxane and cellulose acetate butyrate according to the weight ratio of 1.2: 1.
Further, the preparation method of each part of the synergistic auxiliary comprises the following steps: adding 11 parts by weight of nano aluminum oxide, 8 parts by weight of PVDF resin, 6 parts by weight of maleic anhydride grafted ethylene-octene copolymer and 5 parts by weight of gamma-glycidyl ether oxypropyltrimethoxysilane into 25 parts by weight of polyethylene glycol, and uniformly stirring and mixing to obtain a mixture A; and stirring the mixture A at 85 ℃, keeping the temperature for 75min, performing ultrasonic dispersion, then performing centrifugal washing, and drying to obtain the synergistic auxiliary agent. The maleic anhydride grafted ethylene-octene copolymer is Nanjing plastetamide maleic anhydride grafted ethylene-octene copolymer ST-8. The PVDF resin is Kynar 761.
Further, the curing agent is diethylenetriamine and 2, 4, 6-tris (dimethylaminomethyl) according to the weight ratio of 2: 1.
Further, the diluent consists of xylene, ethanol and decanoic acid glycidyl ether according to the weight ratio of 0.6:1.8: 1.
The preparation method of the anticorrosive heat dissipation graphene coating comprises the following steps:
preparation of component A:
a1, mixing the graphene, the coupling agent and the dispersing agent in proportion, and uniformly stirring at the stirring speed of 1400r/min for 15 min; then adding epoxy resin and acrylic resin, and stirring at 68 ℃ for 30min to obtain resin graphene slurry;
a2, adding zinc powder, graphene, a dispersing agent, a leveling agent, a filler and a synergistic auxiliary agent into the resin graphene slurry, and stirring at 68 ℃ for 30min at a stirring speed of 1400r/min to obtain a mixed slurry; grinding the mixed slurry, controlling the discharge fineness to be 10-30 mu m, and filtering to obtain the component A for later use.
Preparation of the component B:
and mixing the curing agent and the diluent, and uniformly stirring at the stirring speed of 1400r/min for 15min for later use.
Fig. 1 is a diagram illustrating an effect of the anti-corrosion heat dissipation graphene coating of the embodiment partially coated on the chromium-plated non-magnetized neodymium iron boron, and in fig. 1, the surface morphology of the coating is uniform and the distribution of graphene is uniform. Fig. 2 is a graph showing the effect of coating the anticorrosive heat dissipation graphene paint of example 1 on the non-chrome-plated non-magnetized neodymium iron boron. In FIG. 2, the surface of the coating is uniform in appearance, graphene is uniformly distributed, and the surface bonding force is strong.
Example 2
A coating method for coating an anti-corrosion heat dissipation graphene coating comprises the following steps:
(1) dipping a magnet into the prepared anticorrosive heat-dissipation graphene coating; after dipping, pulling the magnet matrix upwards to suspend the magnet matrix above the anticorrosive heat dissipation graphene coating, so that a continuous adhesive film is formed on the surface of the magnet, and repeating the dipping and pulling steps to obtain the magnet with a primary coating film;
(2) and curing the primary coating film of the magnet substrate to obtain the magnet coated with the anticorrosive heat-dissipation graphene coating. The coating method adopts a dip coating machine.
The anticorrosive heat dissipation graphene coating comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 40 parts of epoxy resin, 6 parts of acrylic resin, 15 parts of zinc powder, 0.4 part of graphene, 2 parts of a dispersing agent, 0.5 part of a coupling agent, 1 part of a leveling agent, 6 parts of a filler, 9 parts of a synergistic assistant and 22 parts of a solvent, wherein the component B comprises the following raw materials in parts by weight: 1 part of curing agent and 3 parts of diluent.
Further, the filler is prepared from mica powder, calcium carbonate and talcum powder according to the weight ratio of 1: 0.8:1. The solvent consists of butanol, xylene and 1, 4-butanediol glycidyl ether in a weight ratio of 3:0.8: 1.
Further, the coupling agent is a silane coupling agent which is composed of gamma-aminopropyl triethoxysilane and vinyl triethoxysilane according to a mass ratio of 2: 1.
Further, the Dispersant is a sodium polyacrylate Dispersant Dispersant-9100. The leveling agent consists of polydisiloxane and cellulose acetate butyrate according to the weight ratio of 0.8:1.
Further, the preparation method of each part of the synergistic auxiliary comprises the following steps: adding 9 parts by weight of nano aluminum oxide, 7 parts by weight of PVDF resin, 5 parts by weight of maleic anhydride grafted ethylene-octene copolymer and 4 parts by weight of gamma-glycidyl ether oxypropyltrimethoxysilane into 20 parts by weight of polyethylene glycol, and uniformly stirring and mixing to obtain a mixture A; and stirring the mixture A at 80 ℃, preserving heat for 90min, performing ultrasonic dispersion, then performing centrifugal washing, and drying to obtain the synergistic auxiliary agent.
Further, the curing agent is composed of diethylenetriamine and 2, 4, 6-tris (dimethylaminomethyl) phenol according to the weight ratio of 1: 1.5.
Further, the diluent consists of xylene, ethanol and decanoic acid glycidyl ether according to the weight ratio of 0.4:1.5: 1.
The preparation method of the anticorrosive heat dissipation graphene coating comprises the following steps:
preparation of component A:
a1, mixing the graphene, the coupling agent and the dispersing agent in proportion, and uniformly stirring at the stirring speed of 1000r/min for 20 min; then adding epoxy resin and acrylic resin, and stirring at 65 ℃ for 35min to obtain resin graphene slurry;
a2, adding zinc powder, graphene, a dispersing agent, a leveling agent, a filler and a synergistic auxiliary agent into the resin graphene slurry, and stirring at the temperature of 65 ℃ for 40min at the stirring speed of 1000r/min to obtain mixed slurry; grinding the mixed slurry, controlling the discharge fineness to be 10-30 mu m, and filtering to obtain the component A for later use.
Preparation of the component B:
and mixing the curing agent and the diluent, and uniformly stirring at the stirring speed of 1000r/min for 20min for later use.
Example 3
A coating method for coating an anti-corrosion heat dissipation graphene coating comprises the following steps:
(1) dipping a magnet into the prepared anticorrosive heat-dissipation graphene coating; after dipping, pulling the magnet matrix upwards to suspend the magnet matrix above the anticorrosive heat dissipation graphene coating, so that a continuous adhesive film is formed on the surface of the magnet, and repeating the dipping and pulling steps to obtain the magnet with a primary coating film;
(2) and curing the primary coating film of the magnet substrate to obtain the magnet coated with the anticorrosive heat-dissipation graphene coating.
The anticorrosive heat dissipation graphene coating comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 50 parts of epoxy resin, 10 parts of acrylic resin, 20 parts of zinc powder, 2 parts of graphene, 5 parts of a dispersing agent, 4 parts of a coupling agent, 3 parts of a leveling agent, 10 parts of a filler, 14 parts of a synergistic assistant and 30 parts of a solvent, wherein the component B comprises the following raw materials in parts by weight: 4 parts of curing agent and 5 parts of diluent.
Further, the filler is prepared from mica powder, calcium carbonate and talcum powder according to the weight ratio of 2: 1.2: 1. The solvent consists of butanol, xylene and 1, 4-butanediol glycidyl ether in a weight ratio of 5:1.4: 1.
Further, the silane coupling agent is composed of gamma-aminopropyltriethoxysilane, vinyltriethoxysilane and vinyltris (beta-methoxyethoxy) silane according to the weight ratio of 1:1: 2.
Further, the dispersant is a sodium polycarboxylate dispersant SN-5040. The leveling agent consists of polydisiloxane and cellulose acetate butyrate according to the weight ratio of 2: 1.
Further, the preparation method of each part of the synergistic auxiliary comprises the following steps: adding 12 parts by weight of nano aluminum oxide, 10 parts by weight of PVDF resin, 7 parts by weight of maleic anhydride grafted ethylene-octene copolymer and 7 parts by weight of gamma-glycidyl ether oxypropyltrimethoxysilane into 30 parts by weight of polyethylene glycol, and uniformly stirring and mixing to obtain a mixture A; and stirring the mixture A at 95 ℃, preserving heat for 60min, performing ultrasonic dispersion, then performing centrifugal washing, and drying to obtain the synergistic auxiliary agent.
Further, the curing agent is diethylaminopropylamine and 2, 4, 6-tris (dimethylaminomethyl) phenol in a weight ratio of 2: 1.
Further, the diluent consists of xylene, ethanol and decanoic acid glycidyl ether according to the weight ratio of 0.8:2: 1.
The preparation method of the anticorrosive heat dissipation graphene coating comprises the following steps:
preparation of component A:
a1, mixing the graphene, the coupling agent and the dispersing agent in proportion, and uniformly stirring at a stirring speed of 1600r/min for 10 min; then adding epoxy resin and acrylic resin, and stirring at 70 ℃ for 20min to obtain resin graphene slurry;
a2, adding zinc powder, graphene, a dispersing agent, a leveling agent, a filler and a synergistic auxiliary agent into the resin graphene slurry, and stirring at the temperature of 70 ℃ for 20min at the stirring speed of 1600r/min to obtain a mixed slurry; grinding the mixed slurry, controlling the discharge fineness to be 10-30 mu m, and filtering to obtain the component A for later use.
Preparation of the component B:
and mixing the curing agent and the diluent, and uniformly stirring at 1600r/min for 10min for later use.
Example 4
In this embodiment, the anticorrosive heat dissipation graphene coating comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 46 parts of epoxy resin, 7 parts of acrylic resin, 16 parts of zinc powder, 1.5 parts of graphene, 3 parts of a dispersing agent, 3 parts of a coupling agent, 1.5 parts of a leveling agent, 7 parts of a filler, 11 parts of a synergistic assistant and 28 parts of a solvent, wherein the component B comprises the following raw materials in parts by weight: 3 parts of curing agent and 5 parts of diluent.
Further, the filler is prepared from mica powder, calcium carbonate and talcum powder according to the weight ratio of 1.5: 1:1. Further, the solvent consists of butanol, xylene and 1, 4-butanediol glycidyl ether in a weight ratio of 3.5: 1.2: 1. The leveling agent consists of polydisiloxane and cellulose acetate butyrate according to the weight ratio of 0.8-2: 1. The Dispersant is composed of a sodium polycarboxylate Dispersant SN-5040 and a sodium polyacrylate Dispersant Dispersant-9100 according to a weight ratio of 1.5: 1.
Further, the preparation method of each part of the synergistic auxiliary comprises the following steps: adding 11 parts by weight of nano aluminum oxide, 8 parts by weight of PVDF resin, 5.5 parts by weight of maleic anhydride grafted ethylene-octene copolymer and 5 parts by weight of gamma-glycidyl ether oxypropyl trimethoxy silane into 24 parts by weight of polyethylene glycol, and uniformly stirring and mixing to obtain a mixture A; and stirring the mixture A at 85 ℃, preserving the heat for 80min, performing ultrasonic dispersion, then performing centrifugal washing and drying to obtain the synergistic auxiliary agent.
The preparation method of the anticorrosive heat dissipation graphene coating comprises the following steps:
preparation of component A:
a1, mixing the graphene, the coupling agent and the dispersing agent in proportion, and uniformly stirring at the stirring speed of 1500r/min for 15 min; then adding epoxy resin and acrylic resin, and stirring at 68 ℃ for 25min to obtain resin graphene slurry;
a2, adding zinc powder, graphene, a dispersing agent, a leveling agent, a filler and a synergistic auxiliary agent into the resin graphene slurry, and stirring at the temperature of 65 ℃ for 360min at the stirring speed of 1300r/min to obtain mixed slurry; grinding the mixed slurry, controlling the discharge fineness to be 10-30 mu m, and filtering to obtain the component A for later use.
Preparation of the component B:
and mixing the curing agent and the diluent, and uniformly stirring at the stirring speed of 1300r/min for 20min for later use.
The rest of this embodiment is similar to embodiment 1, and is not described herein again.
Example 5
In this embodiment, in the step (1), the dipping time is 25s each time, the suspension time of the magnet after each pulling is 70s, and the number of times of repetition is 50. The speed of pulling the magnet each time was 3.5 cm/min.
Further, in the step (2), the curing temperature is 85 ℃ and the curing time is 30 min.
The rest of this embodiment is similar to embodiment 1, and is not described herein again.
Example 6
In this embodiment, in the step (1), the dipping time is 35s each time, the suspension time of the magnet after each pulling is 90s, and the number of times of repetition is 30. The speed of pulling the magnet each time was 2 cm/min.
Further, in the step (2), the curing temperature is 95 ℃ and the curing time is 20 min.
The rest of this embodiment is similar to embodiment 1, and is not described herein again.
Comparative example 1
This comparative example differs from example 1 in that: the comparative example does not contain a synergist and is replaced by equal amounts of epoxy resin and acrylic resin, and the weight ratio of the epoxy resin to the acrylic resin in the comparative example is the same as that in example 1.
The anticorrosive heat dissipation graphene coating prepared in the examples 1 to 4 and the comparative example 1 is subjected to dipping, lifting and curing, the curing temperature is 90 ℃, the curing time is 25min, and the anticorrosive heat dissipation graphene coating is formed on the surface of the non-chromium-plated neodymium iron boron annular magnet. The test is carried out according to HG/T4759-2014, and the performance measurement results are as follows:
the coatings of examples 1-4 and comparative example 1 were all smooth in appearance, particle free, flash rust inhibitedThe fabricability was normal, with relatively little coating at the edge radii in comparative example 1. Water resistance/500 h: examples 1-4 and comparative example 1 did not blister, flake, rust, or crack. Moisture and heat resistance/168 h: examples 1-4 and comparative example 1 did not blister, flake, rust, or crack. Salt spray resistance/500 h: examples 1-4 were all free of blistering, flaking, rusting, and cracking; comparative example 1 foamed, slightly peeled, and rusted. Alkali resistance/240 h (50g/L, NaOH): examples 1-4 were all free of blistering, flaking, rusting, and cracking; comparative example 1 was slightly peeled off and rusted. Acid resistance/36H (50g/L, H)2SO4): examples 1-4 were all free of blistering, flaking, rusting, and cracking; comparative example 1 was foamed.
The remaining properties of examples 1-4 and comparative example 1 are as follows:
the thickness of the coating formed by the anti-corrosion heat dissipation graphene coating in the embodiments 1 to 6 is 20 to 25 μm. The impact resistance test is in an interval of 5 cm. The coating method for coating the anti-corrosion heat dissipation graphene coating is simple to operate, high in production efficiency and product yield, smooth in coating surface, good in smoothness, uniform in coating distribution and strong in binding force with a magnet; the anticorrosive heat-dissipation graphene coating is coated on the surface of the magnet, so that the corrosion resistance of the magnet can be improved, the anticorrosive heat-dissipation graphene coating has good heat dissipation performance, the service life of the magnet can be prolonged, and the application range of the anticorrosive heat-dissipation graphene coating is expanded.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
1. A coating method for coating an anti-corrosion heat dissipation graphene coating is characterized by comprising the following steps: the method comprises the following steps:
(1) dipping a magnet into the prepared anticorrosive heat-dissipation graphene coating; after dipping, pulling the magnet matrix upwards to suspend the magnet matrix above the anticorrosive heat dissipation graphene coating, so that a continuous adhesive film is formed on the surface of the magnet, and repeating the dipping and pulling steps to obtain the magnet with a primary coating film;
(2) and curing the primary coating film of the magnet substrate to obtain the magnet coated with the anticorrosive heat-dissipation graphene coating.
2. The coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 1, characterized in that: in the step (1), the anticorrosive heat-dissipation graphene coating comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 40-50 parts of epoxy resin, 6-10 parts of acrylic resin, 15-20 parts of zinc powder, 0.4-2 parts of graphene, 2-5 parts of dispersing agent, 0.5-4 parts of coupling agent, 1-3 parts of flatting agent, 6-10 parts of filler, 9-14 parts of synergistic additive and 22-30 parts of solvent, wherein the component B comprises the following raw materials in parts by weight: 1-4 parts of curing agent and 3-5 parts of diluent.
3. The coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 2, characterized in that: in the step (1), the filler is at least one of mica powder, calcium carbonate and talcum powder.
4. The coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 2, characterized in that: in the step (1), the epoxy resin is bisphenol a type epoxy resin.
5. The preparation method of the coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 2, is characterized in that: in the step (1), the coupling agent is a silane coupling agent, and the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, vinyltriethoxysilane and vinyltris (beta-methoxyethoxy) silane.
6. The preparation method of the coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 2, is characterized in that: the dispersing agent is at least one of polyacrylate, sodium polycarboxylate and sodium carboxylate.
7. The preparation method of the coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 1, is characterized in that: in the step (1), the dipping time is 25-35s each time, the suspension time of the magnet after each time of lifting is 70-90s, and the repetition times are 30-50 times.
8. The preparation method of the coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 1, is characterized in that: in the step (1), the speed of pulling the magnet each time is 2-3.5 cm/min.
9. The preparation method of the coating method for coating the anti-corrosion heat dissipation graphene coating according to claim 1, is characterized in that: in the step (2), the curing temperature is 85-95 ℃, and the curing time is 20-30 min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015329A (en) * | 2021-12-21 | 2022-02-08 | 东莞市嘉达磁电制品有限公司 | Corrosion-resistant neodymium-iron-boron magnet and preparation method thereof |
| CN114267532A (en) * | 2021-12-27 | 2022-04-01 | 东莞市嘉达磁电制品有限公司 | Processing method of high-magnetism sintered neodymium-iron-boron magnet |
| CN115863042A (en) * | 2022-12-28 | 2023-03-28 | 东莞金坤新材料股份有限公司 | Preparation method of epoxy resin graphene composite film layer made of neodymium iron boron permanent magnet material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106400012A (en) * | 2016-10-14 | 2017-02-15 | 哈尔滨工业大学 | Preparation method for metal surface corrosion resistant/radiating/electromagnetic shielding composite coating |
| CN107418382A (en) * | 2017-08-25 | 2017-12-01 | 深圳市烯世传奇科技有限公司 | A kind of heat radiation coating based on graphene and preparation method thereof |
| CN107793884A (en) * | 2017-09-30 | 2018-03-13 | 珠海聚碳复合材料有限公司 | A kind of graphene anticorrosive paint and preparation method |
| CN109468017A (en) * | 2018-10-15 | 2019-03-15 | 湖南湘贤科技有限公司 | A kind of watersoluble plumbago alkene anticorrosive paint |
| CN109749569A (en) * | 2017-11-01 | 2019-05-14 | 深圳市烯世传奇科技有限公司 | Two-component graphene anticorrosive paint and preparation method thereof |
| CN110093087A (en) * | 2018-12-06 | 2019-08-06 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of double-component aqueous graphene heavy antisepsis heat radiation coating and preparation method |
| CN110437703A (en) * | 2018-05-02 | 2019-11-12 | 深圳市烯世传奇科技有限公司 | Graphene/epoxy zinc powder anticorrosive paint and preparation method thereof |
| CN110724432A (en) * | 2018-07-16 | 2020-01-24 | 深圳市烯世传奇科技有限公司 | Graphene water-based anticorrosive paint and preparation method thereof |
-
2021
- 2021-03-16 CN CN202110281794.3A patent/CN113145420B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106400012A (en) * | 2016-10-14 | 2017-02-15 | 哈尔滨工业大学 | Preparation method for metal surface corrosion resistant/radiating/electromagnetic shielding composite coating |
| CN107418382A (en) * | 2017-08-25 | 2017-12-01 | 深圳市烯世传奇科技有限公司 | A kind of heat radiation coating based on graphene and preparation method thereof |
| CN107793884A (en) * | 2017-09-30 | 2018-03-13 | 珠海聚碳复合材料有限公司 | A kind of graphene anticorrosive paint and preparation method |
| CN109749569A (en) * | 2017-11-01 | 2019-05-14 | 深圳市烯世传奇科技有限公司 | Two-component graphene anticorrosive paint and preparation method thereof |
| CN110437703A (en) * | 2018-05-02 | 2019-11-12 | 深圳市烯世传奇科技有限公司 | Graphene/epoxy zinc powder anticorrosive paint and preparation method thereof |
| CN110724432A (en) * | 2018-07-16 | 2020-01-24 | 深圳市烯世传奇科技有限公司 | Graphene water-based anticorrosive paint and preparation method thereof |
| CN109468017A (en) * | 2018-10-15 | 2019-03-15 | 湖南湘贤科技有限公司 | A kind of watersoluble plumbago alkene anticorrosive paint |
| CN110093087A (en) * | 2018-12-06 | 2019-08-06 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of double-component aqueous graphene heavy antisepsis heat radiation coating and preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114015329A (en) * | 2021-12-21 | 2022-02-08 | 东莞市嘉达磁电制品有限公司 | Corrosion-resistant neodymium-iron-boron magnet and preparation method thereof |
| CN114267532A (en) * | 2021-12-27 | 2022-04-01 | 东莞市嘉达磁电制品有限公司 | Processing method of high-magnetism sintered neodymium-iron-boron magnet |
| CN114267532B (en) * | 2021-12-27 | 2024-04-09 | 东莞市嘉达磁电制品有限公司 | Processing method of high-magnetism sintered NdFeB magnet |
| CN115863042A (en) * | 2022-12-28 | 2023-03-28 | 东莞金坤新材料股份有限公司 | Preparation method of epoxy resin graphene composite film layer made of neodymium iron boron permanent magnet material |
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|---|---|
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