CN101728043B - Permanent magnet with corrosion resistant coating and powder nanometer spraying method thereof - Google Patents
Permanent magnet with corrosion resistant coating and powder nanometer spraying method thereof Download PDFInfo
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- CN101728043B CN101728043B CN 200810224281 CN200810224281A CN101728043B CN 101728043 B CN101728043 B CN 101728043B CN 200810224281 CN200810224281 CN 200810224281 CN 200810224281 A CN200810224281 A CN 200810224281A CN 101728043 B CN101728043 B CN 101728043B
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- 238000005507 spraying Methods 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 title claims abstract description 11
- 238000005260 corrosion Methods 0.000 title abstract description 11
- 230000007797 corrosion Effects 0.000 title abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 45
- 239000004332 silver Substances 0.000 claims abstract description 45
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 230000007704 transition Effects 0.000 claims abstract description 22
- 239000005416 organic matter Substances 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 40
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 27
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 239000007921 spray Substances 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 21
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 20
- 206010070834 Sensitisation Diseases 0.000 claims description 19
- 230000008313 sensitization Effects 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002103 nanocoating Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005238 degreasing Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 10
- -1 silver ions Chemical class 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 238000005488 sandblasting Methods 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OHYPPUOVSUINHM-UHFFFAOYSA-N 4-(methylamino)phenol;sulfuric acid Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1 OHYPPUOVSUINHM-UHFFFAOYSA-N 0.000 claims description 3
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 239000000696 magnetic material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000009713 electroplating Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
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- 229910052779 Neodymium Inorganic materials 0.000 description 3
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
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Abstract
The invention provides a permanent magnet with a corrosion resistant coating. The permanent magnet comprises a permanent magnetic material base body 1, an organic matter bottom layer 2, an organic matter transition layer 3 and a nanometer silver layer 4, and also comprises a powder nanometer spraying method for the permanent magnet with the corrosion resistant coating. As the metal base body is isolated from the contacted outside corrosion media through the inner and outer alloy layers, the metal base body is difficult to corrode and has good humidity and heat resistance property, and then the service life of the permanent magnet is prolonged. As the coating is thin, the influence on the magnet is small, and the magnet shielding does not exist. The product investment cost is reduced, and the safety production is ensured.
Description
Technical Field
The invention relates to the field of surface chemical treatment of materials, in particular to a nano spraying technology of a neodymium iron boron permanent magnet material, and specifically relates to a surface treatment method of the permanent magnet material by using the nano spraying technology.
Background
In recent years, the application and development of neodymium iron boron (NdFeB) permanent magnet materials are very rapid, and the success of the protection of the neodymium iron boron permanent magnet materials is related to one of the key technologies of popularization and application of the materials. The material is mainly prepared from rare earth metal elements such as Nd, iron, boron and the like by a powder metallurgy process. As the strongest magnetic material at present, the magnetic material is widely applied to the fields of electroplating devices, machinery, medical treatment, automobiles and the like, and has very wide application prospect.
The application of the neodymium iron boron permanent magnet material is premised on solving the problem of corrosion resistance of the neodymium iron boron permanent magnet material. As a porous material prepared by a powder metallurgy process, the neodymium-rich phase, the main phase and the boundary phase of the neodymium iron boron are easy to form intergranular corrosion. The rare earth element neodymium in the neodymium-iron-boron powder alloy has active property, so that the corrosion resistance of the whole neodymium-iron-boron alloy is very poor, the neodymium-iron-boron powder alloy is very easy to rust and corrode in a damp and hot environment, the magnetic property is reduced or damaged due to corrosion failure, the service life of the neodymium-iron-boron permanent magnet is seriously influenced, and the stability and the reliability of the product are reduced. The magnetic performance of the Nd-Fe-B permanent magnetic material has a great relationship with the organization structure. The main phase of the ndfeb permanent magnet is the main source of magnetic performance of the magnet. The most contributing to the coercive force is the neodymium-rich phase. When the neodymium iron boron permanent magnet material is corroded, the magnetic performance of the material is greatly changed. Therefore, the problem of corrosion prevention of the ndfeb permanent magnet material has been a major problem to be solved.
At present, the corrosion prevention methods of the neodymium iron boron permanent magnet material are many. There are various methods such as electroplating nickel, electroplating zinc (CN1421547A, CN1056133A), electroplating multi-layer nickel, copper plating (CN1514889A), phosphorization, and electrophoretic paint.
Disclosure of Invention
The invention aims to improve the surface corrosion resistance of the neodymium iron boron permanent magnet material by using a novel nano spraying technology.
According to one aspect of the invention, the invention provides a permanent magnet with an anti-corrosion coating, which comprises a permanent magnet material matrix 1, an organic bottom layer 2, an organic transition layer 3 and an organic outermost layer 4.
The organic bottom layer 2 is made of hydroxy acrylic resin or epoxy resin, and the thickness of the organic bottom layer is 0.5-2 microns.
The organic matter transition layer 3 is a transition layer containing tin and palladium elements, and the thickness of the transition layer is 0.1-0.3 micrometers.
The outermost layer 4 of the organic matter is a nano coating containing metal silver, and the thickness of the nano coating is 0.1-1 micron.
Wherein the transition layer containing tin and palladium elements is formed by spraying surface sensitization activating liquid, wherein the surface sensitization activating liquid comprises hydroxyalkyl stannous sulfonate and palladium chloride.
The nano coating of the metallic silver is formed by spraying an agent A containing silver ions and an agent B containing a reducing agent to a transition layer containing tin and palladium elements at the same time, wherein the volume ratio of the agent A to the agent B is 1: 1-1.5.
The agent A is a silver ammonia solution, and the silver ammonia solution comprises a silver nitrate solution, an ammonia water solution and a sodium hydroxide solution.
Wherein the volume ratio of the ammonia water solution to the sodium hydroxide solution is 1: 1, and the weight percentage concentration of silver ions in the silver-ammonia solution is 0.5-1.5%.
Wherein the agent B is sodium borohydride, potassium borohydride or a solution of sulfuric acid p-methylaminophenol.
Wherein the grain size of the nano coating containing the metallic silver is 5-100 nanometers.
The permanent magnet material is a sintered neodymium iron boron permanent magnet material or a bonded neodymium iron boron material.
According to another aspect of the present invention, there is also provided a powder nano-spraying method for the permanent magnet with an anticorrosive coating, the powder nano-spraying method including the steps of:
(1) chamfering and polishing: polishing the permanent magnet material by adopting a mechanical vibration grinding and tumbling chamfering method; the permanent magnet material is a sintered neodymium iron boron permanent magnet material or a bonded neodymium iron boron material;
(2) degreasing and deoiling: adding sodium phosphate, sodium carbonate or sodium hydroxide for degreasing and deoiling;
(3) sand blasting and rust removing: performing sand blasting treatment on the surface of the permanent magnet material;
(4) spraying a bottom layer: spraying hydroxyl acrylic resin or epoxy resin with the thickness of 0.5-2 microns on the surface of the permanent magnet by using a spray gun to form an organic bottom layer, and drying;
(5) sensitization and activation treatment: spraying surface sensitization activating liquid on the surface of the organic matter bottom layer of the permanent magnet by using a sprayer until the surface of the permanent magnet is completely wet, and then washing the permanent magnet by using pure water solution to form an organic matter transition layer; wherein the surface-sensitizing activating solution comprises stannous hydroxyalkyl sulfonate and palladium chloride; preferably, the surface sensitization activation liquid comprises 15-25 g/L hydroxyalkyl stannous sulfonate and 5-15 g/L palladium chloride;
(6) spray gun spraying reduction reaction: spraying the agent A and the agent B to the surface of the organic matter transition layer of the permanent magnet by using a double-head spray gun simultaneously to form a nano coating containing metal silver; the agent A is a silver-ammonia solution, and the silver-ammonia solution comprises a silver nitrate solution, an ammonia water solution and a sodium hydroxide solution, wherein the volume ratio of the ammonia water solution to the sodium hydroxide solution is 1: 1, and the weight percentage concentration of silver ions in the silver-ammonia solution is 0.5-1.5%; the agent B is sodium borohydride, potassium borohydride or a solution of sulfuric acid p-methylaminophenol; the volume ratio of the agent A to the agent B is 1: 1-1.5; the distance between the mixing point of the agent A and the agent B and the sprayed permanent magnet is 15-25 cm;
(7) and (3) setting and developing: spraying anhydrous sodium sulfite solution on the surface of the metal silver coating of the permanent magnet by using a spray gun;
(8) drying: blowing the water onto the surface of the silver mirror by using an air blowing gun to blow off the accumulated water on the surface of the silver mirror;
(9) and (3) drying: drying the mixture in a drying furnace at the temperature of 55-65 ℃ for 30-40 minutes.
The invention adopts a novel nano spraying technology to treat the surface of the neodymium iron boron, and the surface treatment mode effectively fills the blank of domestic neodymium iron boron surface treatment. The nano spraying is a novel high-tech product, does not contain heavy metal, does not discharge three wastes, avoids a series of environmental pollution problems caused by the traditional electroplating process, and is a technical innovation after electroplating and vacuum plating. Nano-spraying has several advantages: (1) green and environment-friendly, (2) safe, simple and efficient operation, and (3) excellent physical performance, and is suitable for the requirements of automation and mass production. The metal substrate is isolated from the external corrosive medium contacted with the metal substrate through the inner alloy layer and the outer alloy layer, so that the metal substrate is not easy to corrode, has excellent moisture and heat resistance, can prolong the service life of the permanent magnet material, has thin coating, has little influence on the magnet, does not have a magnetic screen wall, reduces the production investment cost, and ensures safe production.
Drawings
Fig. 1 shows a structural view of a permanent magnet with an anticorrosive coating according to the present invention.
The organic matter composite material comprises a permanent magnet material substrate 1, an organic matter bottom layer 2, an organic matter transition layer 3 and an organic matter outermost layer 4.
Detailed Description
The present invention will be further described with reference to the following examples, which are only for illustrating the technical solutions of the present invention and are not to be construed as limiting the present invention.
Example 1
Selecting 70 × 25 × 10 materials, chamfering and polishing: polishing the sintered Nd-Fe-B permanent magnet material by adopting a mechanical vibration grinding and tumbling chamfering method; degreasing and deoiling: adding sodium phosphate, sodium carbonate or sodium hydroxide for degreasing and deoiling; sand blasting and rust removing; spraying a primer layer: a0.5 micron thick layer of hydroxy acrylic resin was sprayed onto the surface of the permanent magnet using a spray gun. Sensitization and activation treatment: spraying a surface sensitization activating solution on the surface of the article sprayed with the primer layer by using a sprayer until the surface of the article is completely wet, and then washing the article by using a pure water solution; the surface sensitization activating liquid contains 15 g/L hydroxyalkyl stannous sulfonate, 15 g/L palladium chloride and 0.1 micron transition layer thickness. Spraying the outermost layer by a spray gun: spraying the agent A and the agent B to the surface of the sensitized and activated article by using a double-head spray gun to form a metallic silver coating, wherein the thickness of the metallic silver coating is 0.1 micron; the volume ratio of the agent A to the agent B is 1: 1, and the distance between the mixing point of the agent A and the agent B and the sprayed article is 15 cm; the agent A is a silver-ammonia solution, and the silver-ammonia solution is formed by mixing a silver nitrate solution, an ammonia water solution and a sodium hydroxide solution, wherein the volume ratio of the ammonia water solution to the sodium hydroxide solution is 1: 1, and the weight percentage concentration of silver ions in the silver-ammonia solution accounts for 0.5%; the agent B is sodium borohydride; and (3) setting and developing: spraying an anhydrous sodium sulfite solution to the surface of the metal coating of the article by using a spray gun to stabilize the metal coating and enhance the oxidation resistance of the protective metal coating; drying: blowing the water onto the surface of the silver mirror by using an air blowing gun to blow off the accumulated water on the surface of the silver mirror; and (3) drying: drying the silver mirror coating in a drying furnace at 65 ℃ for 30 minutes to enhance the adhesion of the silver mirror coating. The grain size of the coating was 100 nm. See table 1.
Example 2
Selecting 70 × 25 × 10 materials, chamfering and polishing: polishing the bonded neodymium iron boron permanent magnet material by adopting a mechanical vibration grinding and tumbling chamfering method; degreasing and deoiling: adding sodium phosphate, sodium carbonate or sodium hydroxide for degreasing and deoiling; sand blasting and rust removing; spraying a primer layer: on the surface of the permanent magnet, a 2 μm thick epoxy resin primer layer was sprayed with a spray gun. Sensitization and activation treatment: spraying a surface sensitization activating solution on the surface of the article sprayed with the primer layer by using a sprayer until the surface of the article is completely wet, and then washing the article by using a pure water solution; the surface sensitization activating liquid contains 25 g/L hydroxyalkyl stannous sulfonate, 5 g/L palladium chloride and 0.3 micron transition layer thickness. Spraying the outermost layer by a spray gun: spraying the agent A and the agent B to the surface of the sensitized and activated article by using a double-head spray gun to form a metallic silver coating, wherein the thickness of the metallic silver coating is 1 micron; the volume ratio of the agent A to the agent B is 1: 1.5, and the distance between the mixing point of the agent A and the agent B and the sprayed article is 25 cm; the agent A is a silver-ammonia solution, and the silver-ammonia solution is formed by mixing a silver nitrate solution, an ammonia water solution and a sodium hydroxide solution, wherein the volume ratio of the ammonia water solution to the sodium hydroxide solution is 1: 1, and the weight percentage concentration of silver ions in the silver-ammonia solution accounts for 1.5%; the agent B is potassium borohydride; and (3) setting and developing: spraying an anhydrous sodium sulfite solution to the surface of the metal coating of the article by using a spray gun to stabilize the metal coating and enhance the oxidation resistance of the protective metal coating; drying: blowing the water onto the surface of the silver mirror by using an air blowing gun to blow off the accumulated water on the surface of the silver mirror; and (3) drying: drying the silver mirror coating in a drying furnace at the temperature of 55 ℃ for 40 minutes to enhance the adhesion of the silver mirror coating. The grain size of the coating was 5 nm. See table 1.
Example 3
Selecting 70 × 25 × 10 materials, chamfering and polishing: polishing the sintered Nd-Fe-B permanent magnet material by adopting a mechanical vibration grinding and tumbling chamfering method; degreasing and deoiling: adding sodium phosphate, sodium carbonate or sodium hydroxide for degreasing and deoiling; sand blasting and rust removing; spraying a primer layer: a1 micron thick layer of hydroxy acrylic resin was sprayed onto the surface of the permanent magnet using a spray gun. Sensitization and activation treatment: spraying a surface sensitization activating solution on the surface of the article sprayed with the primer layer by using a sprayer until the surface of the article is completely wet, and then washing the article by using a pure water solution; the surface sensitization activating liquid contains 20 g/L hydroxyalkyl stannous sulfonate, 10 g/L palladium chloride and 0.2 micron transition layer thickness. Spraying the outermost layer by a spray gun: spraying the agent A and the agent B to the surface of the sensitized and activated article by using a double-head spray gun to form a metallic silver coating, wherein the thickness of the metallic silver coating is 0.6 micron; the volume ratio of the agent A to the agent B is 1: 1.2, and the distance between the mixing point of the agent A and the agent B and the sprayed article is 20 cm; the agent A is a silver-ammonia solution, and the silver-ammonia solution is formed by mixing a silver nitrate solution, an ammonia water solution and a sodium hydroxide solution, wherein the volume ratio of the ammonia water solution to the sodium hydroxide solution is 1: 1, and the weight percentage concentration of silver ions in the silver-ammonia solution accounts for 1.0%; the agent B is a p-methylaminophenol sulfate solution; and (3) setting and developing: spraying an anhydrous sodium sulfite solution to the surface of the metal coating of the article by using a spray gun to stabilize the metal coating and enhance the oxidation resistance of the protective metal coating; drying: blowing the water onto the surface of the silver mirror by using an air blowing gun to blow off the accumulated water on the surface of the silver mirror; and (3) drying: drying the silver mirror coating in a drying furnace at the temperature of 60 ℃ for 30 minutes to enhance the adhesion of the silver mirror coating. The grain size of the coating was 50 nm. See table 1.
Comparative example 1
Selecting 70 × 25 × 10 materials, chamfering and polishing: polishing the sintered Nd-Fe-B permanent magnet material by adopting a mechanical vibration grinding and tumbling chamfering method; degreasing and deoiling: adding sodium phosphate, sodium carbonate or sodium hydroxide for degreasing and deoiling; and (4) blasting sand to remove rust, and electroplating copper and nickel after activation. See table 1.
TABLE 1
| Example No. 2 | Salt fog (hours) | Damp-heat test (hours) | Thickness (micron) | Cost (Yuan) |
| Example 1 | 96 | 500 | 0.7 | 0.4 |
| Example 2 | 96 | 500 | 3.3 | 1.0 |
| Example 3 | 96 | 500 | 1.8 | 0.8 |
| Comparative example 1 | 48 | 96 | 25 | 1.40 |
As can be seen from Table 1, the salt spray is 96 hours when the coating thickness is only 0.7-3.3 micrometers, and the damp-heat test is 500 hours; and the cost is controlled to be 0.4-0.8 yuan. Whereas the coating thickness of comparative example 1 of the prior art was 25 μm for 48 hours in salt spray and 96 hours in the wet heat test; and the cost is 1.40 yuan.
Therefore, the invention has the following advantages: 1. the mirror surface spraying has excellent corrosion resistance; 2. the mirror surface spraying cost is low; 3. the coating is thin, the influence on the magnet is small, and no magnetic screen wall exists; 4. has excellent moisture and heat resistance.
It should be noted that the above summary and the detailed description are intended to demonstrate the practical application of the technical solutions provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent substitutions, or improvements may be made by those skilled in the art within the spirit and principles of the invention. The scope of the invention is to be determined by the appended claims.
Claims (7)
1. A permanent magnet with an anticorrosive coating comprises a permanent magnet material matrix (1), an organic matter bottom layer (2), an organic matter transition layer (3) and an outermost layer (4); wherein,
the permanent magnet material is a sintered neodymium iron boron permanent magnet material or a bonded neodymium iron boron material;
the organic bottom layer (2) is made of hydroxyl acrylic resin, and the thickness of the organic bottom layer is 0.5-2 microns;
the organic matter transition layer (3) is a transition layer containing tin and palladium elements, the thickness of the transition layer is 0.1-0.3 micrometers, the transition layer containing tin and palladium elements is formed by spraying surface sensitization activating liquid, and the surface sensitization activating liquid comprises hydroxyalkyl stannous sulfonate and palladium chloride;
the outermost layer (4) is a nano coating containing metal silver, the thickness of the nano coating containing metal silver is 0.1-1 micron, and the grain size of the nano coating containing metal silver is 5-100 nanometers.
2. The permanent magnet according to claim 1, wherein the nano coating layer containing metallic silver is formed by simultaneously spraying an agent a containing silver ions and an agent B containing a reducing agent to a transition layer containing tin and palladium elements; the agent A is a silver ammonia solution which comprises a silver nitrate solution, an ammonia water solution and a sodium hydroxide solution, and the agent B is sodium borohydride, potassium borohydride or a sulfuric acid p-methylaminophenol solution; the volume ratio of the agent A to the agent B is 1: 1-1.5.
3. The permanent magnet according to claim 3, wherein the volume ratio of the ammonia water solution to the sodium hydroxide solution is 1: 1, and the weight percentage concentration of silver ions in the silver ammonia solution is 0.5-1.5%.
4. A powder nano-spraying method for the permanent magnet with the anticorrosive coating according to any one of claims 1 to 3, comprising the steps of:
(1) chamfering and polishing: polishing the permanent magnet material by adopting a mechanical vibration grinding and tumbling chamfering method;
(2) degreasing and deoiling: adding sodium phosphate, sodium carbonate or sodium hydroxide for degreasing and deoiling;
(3) sand blasting and rust removing: performing sand blasting treatment on the surface of the permanent magnet material;
(4) spraying a bottom layer: spraying hydroxyl acrylic resin with the thickness of 0.5-2 microns on the surface of the permanent magnet material treated in the step (3) by using a spray gun to form an organic bottom layer, and drying;
(5) sensitization and activation treatment: spraying surface sensitization activating liquid on the surface of the organic matter bottom layer of the permanent magnet by using a sprayer until the surface of the permanent magnet is completely wet, and then washing the permanent magnet by using pure water to form an organic matter transition layer; the surface sensitization activation liquid comprises hydroxyalkyl stannous sulfonate and palladium chloride, and the thickness of an organic matter transition layer is 0.1-0.3 micrometer;
(6) spray gun spraying reduction reaction: simultaneously spraying an agent A and an agent B to the surface of the organic matter transition layer of the permanent magnet by using a double-head spray gun to form a nano coating containing metal silver, wherein the thickness of the nano coating containing metal silver is 0.1-1 micron, and the grain size of the nano coating containing metal silver is 5-100 nanometers; (ii) a The agent A is a silver-ammonia solution, the silver-ammonia solution comprises a silver nitrate solution, an ammonia water solution and a sodium hydroxide solution, and the agent B is sodium borohydride, potassium borohydride or a p-methylaminophenol sulfate solution; the volume ratio of the agent A to the agent B is 1: 1-1.5;
(7) and (3) setting and developing: spraying an anhydrous sodium sulfite solution on the surface of the metal silver-containing nano coating of the permanent magnet by using a spray gun;
(8) drying: blowing the water onto the surface of the silver mirror by using an air blowing gun to blow off the accumulated water on the surface of the silver mirror;
(9) and (3) drying: drying the mixture in a drying furnace at the temperature of 55-65 ℃ for 30-40 minutes.
5. The powder nano-spraying method according to claim 4, wherein the surface-sensitizing activating solution comprises 15 to 25 g/l of hydroxyalkyl stannous sulfonate and 5 to 15 g/l of palladium chloride.
6. The method of nano-spraying the powder as claimed in claim 4, wherein the volume ratio of the aqueous ammonia solution to the sodium hydroxide solution is 1: 1, and the weight percentage concentration of the silver ions in the silver-ammonia solution is 0.5 to 1.5%.
7. The powder nano-spraying method according to claim 4, wherein a distance between a mixing point of the agent A and the agent B and the sprayed permanent magnet is 15 to 25 cm.
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| CN102397836B (en) * | 2010-09-10 | 2015-05-20 | 北京中科三环高技术股份有限公司 | Surface treatment method for spraying organoaluminum on permanent magnet |
| CN102397835B (en) * | 2010-09-10 | 2015-05-20 | 北京中科三环高技术股份有限公司 | Method for performing surface treatment on neodymium-iron-boron permanent magnet material by using nano ceramic |
| CN102453431B (en) * | 2010-10-14 | 2016-09-28 | 北京中科三环高技术股份有限公司 | A kind of silanized surface treatment technology of permanent magnet material |
| CN102453936A (en) * | 2010-10-14 | 2012-05-16 | 北京中科三环高技术股份有限公司 | Low-concentration nickel-plating technology for permanent magnet material |
| CN102453890B (en) * | 2010-10-14 | 2015-11-25 | 北京中科三环高技术股份有限公司 | A kind of zirconate process for treating surface of permanent magnet |
| CN102464909B (en) * | 2010-11-16 | 2017-03-22 | 北京中科三环高技术股份有限公司 | Surface treatment method for chromium and zinc-free coating of neodymium-iron-boron permanent magnet material |
| CN102389871B (en) * | 2011-10-18 | 2013-12-25 | 安泰科技股份有限公司 | Method for forming aluminum coating on surface of neodymium iron boron magnet |
| CN113372811B (en) * | 2021-05-22 | 2022-03-15 | 宁波市镇海兴强磁性材料有限公司 | High-binding-force surface protection coating rare earth permanent magnet and preparation method thereof |
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| CN1944710A (en) * | 2006-10-11 | 2007-04-11 | 方宏亮 | Nano mirror spray coating |
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