CN101728043A - 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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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 present invention relates to field of chemical processing of material, especially relate to the nano-spray technology of Nd-Fe-Bo permanent magnet material, specifically, the present invention relates to a kind of surface treatment method that utilizes the nano-spray technology to permanent magnetic material.
Background technology
Application of neodymium iron boron (NdFeB) permanent magnetic material in recent years and development are very rapid, and the protection success or not of Nd-Fe-Bo permanent magnet material is related to one of key technology that can material apply.This material mainly is to be prepared from by powder metallurgical technique by elements such as rare earth metal neodymium Nd, iron and boron.As the strongest present magnetic material, be widely used in all fields such as electroplating device, machinery, medical treatment, automobile, application prospect is very wide.
The prerequisite that Nd-Fe-Bo permanent magnet material is used is at first to resolve the anticorrosion problem of Nd-Fe-Bo permanent magnet material.As the porous material that a kind of powder metallurgical technique is prepared from, because of rich neodymium phase wherein, neodymium iron boron principal phase and borderline phase are easy to form intercrystalline corrosion.Rear earth element nd in the neodymium iron boron powder alloy, character is active, make the corrosion resisting property of whole Nd Fe B alloys become very poor, very easily corrosion in damp and hot environment, cause the decline or the damage of magnetic property because of corrosion failure, have a strong impact on the useful life of Nd-Fe-B permanent magnet, reduced the stability and the reliability of product.The magnetic property of Nd-Fe-Bo permanent magnet material and its institutional framework have very big relation.The principal phase of Nd-Fe-B permanent magnet is the main source of magnet magnetic property.To coercive force contribution maximum is rich neodymium phase.Huge variation will take place in the magnetic property of material after corrosion takes place Nd-Fe-Bo permanent magnet material.Therefore, the anticorrosion problem of Nd-Fe-Bo permanent magnet material is the subject matter that Nd-Fe-Bo permanent magnet material need solve always.
The anti-corrosion method of Nd-Fe-Bo permanent magnet material has much at present.Electronickelling, electrogalvanizing (CN1421547A, CN1056133A) are wherein arranged, electroplate MULTI-LAYER NICKEL, copper facing (CN1514889A), several different methods such as phosphatization, electrophoretic paint.
Summary of the invention
Purpose of the present invention uses novel nano-spray technology to improve the surface anticorrosion performance of Nd-Fe-Bo permanent magnet material just.
According to an aspect of the present invention, the invention provides a kind of permanent magnet that has corrosion-inhibiting coating, described permanent magnet comprises permanent magnetic material matrix 1, organic substance bottom 2, organic substance transition zone 3, organic substance outermost layer 4.
Wherein, described organic substance bottom 2 is the bottom of Hydroxylated acrylic resin or epoxy resin, and its thickness is at 0.5～2 micron.
Wherein, described organic substance transition zone 3 is the transition zone of stanniferous and palladium element, and its thickness is at 0.1～0.3 micron.
Wherein, described organic substance outermost layer 4 is the nano coating of containing metal silver, and its thickness is at 0.1～1 micron.
Wherein, the transition zone of described stanniferous and palladium element is formed by the spraying of surface sensitizing activating solution, and wherein, described surface sensitizing activating solution comprises inferior tin of hydroxyalkylated sulfonic acid and palladium bichloride.
Wherein, the nano coating of described argent sprays the A agent that contains silver ion simultaneously by the transition zone to stanniferous and palladium element and the B agent that contains reducing agent forms, and described A agent: the volume ratio of B agent is 1: 1～1.5.
Wherein, described A agent is a silver ammino solution, and this silver ammino solution comprises liquor argenti nitratis ophthalmicus, ammonia spirit and sodium hydroxide solution.
Wherein, the volume ratio of described ammonia spirit and sodium hydroxide solution is 1: 1, and the silver ion concentration expressed in percentage by weight accounts for 0.5～1.5% in silver ammino solution.
Wherein, described B agent is that sodium borohydride, potassium borohydride or sulfuric acid are to the methylamino phenol solution.
Wherein, the grain size of the nano coating of described containing metal silver is in 5～100 nanometers.
Wherein, described permanent magnetic material is sintered Nd-Fe-B permanent magnetic material or Agglutinate neodymium-iron-boron material.
According to a further aspect in the invention, the present invention also provides a kind of described powder nanometer spraying method that has the permanent magnet of corrosion-inhibiting coating that is used for, and described powder nanometer spraying method comprises the steps:
(1) chamfering polishing: adopt mechanical vibration, barreling chamfering method that permanent magnetic material is polished; Wherein, described permanent magnetic material is sintered Nd-Fe-B permanent magnetic material or Agglutinate neodymium-iron-boron material;
(2) degreasing degreasing: add sodium phosphate, sodium carbonate or NaOH and carry out degreasing degreasing;
(3) derusting by sandblasting: permanent magnetic material surface is imposed blasting treatment;
(4) spraying bottom: on permanent magnet surfaces, spray the Hydroxylated acrylic resin or the epoxy resin of 0.5～2 micron thickness, to form organic substance bottom, drying with spray gun;
(5) sensitization, activation processing: spray the surface sensitizing activating solution with sprayer to the organic substance bottom surface of permanent magnet, till permanent magnet surfaces is all moistening, wash permanent magnet with pure water solution then, to form the organic substance transition zone; Wherein, described surface sensitizing activating solution comprises inferior tin of hydroxyalkylated sulfonic acid and palladium bichloride; Preferably, wherein, described surface sensitizing activating solution comprises inferior tin 15～25 grams per liters of hydroxyalkylated sulfonic acid and palladium bichloride 5～15 grams per liters;
(6) spray gun spraying reduction reaction: spray A agent and B agent with double head spray gun simultaneously to the organic substance transition zone surface of permanent magnet, to form the nano coating of containing metal silver; Wherein, described A agent is a silver ammino solution, and this silver ammino solution comprises liquor argenti nitratis ophthalmicus, ammonia spirit and sodium hydroxide solution, wherein, the volume ratio of described ammonia spirit and sodium hydroxide solution is 1: 1, and the silver ion concentration expressed in percentage by weight accounts for 0.5～1.5% in silver ammino solution; Described B agent is that sodium borohydride, potassium borohydride or sulfuric acid are to the methylamino phenol solution; Described A agent: the volume ratio of B agent is 1: 1～1.5; The mixing point of described A agent, B agent sprays the distance of permanent magnet between 15～25cm from quilt;
(7) setting is developed: with the argent coating surface spraying anhydrous sodium sulfite solution of spray gun to permanent magnet;
(8) dry up: blow to the silver mirror surface with air blowing rifle, dry up the ponding on silver mirror surface;
(9) drying: drying is 30～40 minutes in 55～65 ℃ drying oven.
The present invention adopts a kind of novel nano-spray technology to the neodymium iron boron surface treatment, and this surface treatment mode has effectively been filled up domestic neodymium iron boron surface-treated blank.Nano-spray is a kind of novel high-tech product, has not contain heavy metal, does not have three waste discharge, and a series of problem of environmental pollutions of having avoided the traditional electrical depositing process to cause are relay platings, a technological innovation after the vacuum plating.Nano-spray has multiple advantages: (1) environmental protection, (2) handling safety, simple, efficient, superior, the suitable automation of (3) physical property, mass production needs.The present invention since the corrosive medium in the external world that metallic matrix is in contact with it by inside and outside alloy-layer isolate, metallic matrix is difficult for being corroded and having excellent wet-hot aging performance, can prolong the useful life of permanent magnetic material, and its coating is thin, to the influence of magnet is little the magnetic cup wall do not arranged, reduce the production cost of investment, guarantee safe production.
Description of drawings
Fig. 1 represents the structure chart that has the permanent magnet of corrosion-inhibiting coating of the present invention.
Wherein, permanent magnetic material matrix 1, organic substance bottom 2, organic substance transition zone 3, organic substance outermost layer 4.
Embodiment
The present invention will be further described below with reference to embodiment, and embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting the present invention.
Embodiment 1
Select the material of 70*25*10 for use, chamfering polishing: adopt mechanical vibration, barreling chamfering method that sintered Nd-Fe-B permanent magnetic material is polished; Degreasing degreasing: add sodium phosphate, sodium carbonate or NaOH and carry out degreasing degreasing; Derusting by sandblasting; Spraying prime coat: on permanent magnet surfaces, spray a kind of Hydroxylated acrylic resin bottom of 0.5 micron thickness with spray gun.Sensitization, activation processing: spraying the surface sensitizing activating solution with the article surface of spraying prime coat with sprayer, till article surface is all moistening, washing article with pure water solution then; Contain inferior tin 15 grams per liters of hydroxyalkylated sulfonic acid in the described surface sensitizing activating solution, contain palladium bichloride 15 grams per liters, 0.1 micron of transition region thickness.Spray gun spraying outermost layer: spray A agent and B agent with double head spray gun simultaneously to the article surface of sensitization and activation, form the argent coating, this argent coating layer thickness is at 0.1 micron; Described A agent: the volume ratio of B agent is 1: 1, and the mixing point of described A agent, B agent sprays the distance of article between 15cm from quilt; Described A agent is a silver ammino solution, and this silver ammino solution is to be mixed by liquor argenti nitratis ophthalmicus, ammonia spirit and sodium hydroxide solution, and wherein the volume ratio of ammonia spirit and sodium hydroxide solution is 1: 1, and the silver ion concentration expressed in percentage by weight accounts for 0.5% in silver ammino solution; Described B agent is a sodium borohydride; Setting is developed: with the metal coating surface ejection anhydrous sodium sulfite solution of spray gun to article, with the stable metal coating, strengthen the antioxygenic property of protection metal coating; Dry up: blow to the silver mirror surface with air blowing rifle, dry up the ponding on silver mirror surface; Dry: drying is 30 minutes in 65 ℃ drying oven, strengthens the adhesive force of silver mirror coating layer.The grain size of coating is in 100 nanometers.Referring to table 1.
Select the material of 70*25*10 for use, chamfering polishing: adopt mechanical vibration, barreling chamfering method that binding Nd-Fe-B permanent magnetic material is polished; Degreasing degreasing: add sodium phosphate, sodium carbonate or NaOH and carry out degreasing degreasing; Derusting by sandblasting; Spraying prime coat: on permanent magnet surfaces, spray a kind of epoxy resin bottom of 2 micron thickness with spray gun.Sensitization, activation processing: spraying the surface sensitizing activating solution with the article surface of spraying prime coat with sprayer, till article surface is all moistening, washing article with pure water solution then; Contain inferior tin 25 grams per liters of hydroxyalkylated sulfonic acid in the described surface sensitizing activating solution, contain palladium bichloride 5 grams per liters, 0.3 micron of transition region thickness.Spray gun spraying outermost layer: spray A agent and B agent with double head spray gun simultaneously to the article surface of sensitization and activation, form the argent coating, this argent coating layer thickness is at 1 micron; Described A agent: the volume ratio of B agent is 1: 1.5, and the mixing point of described A agent, B agent sprays the distance of article between 25cm from quilt; Described A agent is a silver ammino solution, and this silver ammino solution is to be mixed by liquor argenti nitratis ophthalmicus, ammonia spirit and sodium hydroxide solution, and wherein the volume ratio of ammonia spirit and sodium hydroxide solution is 1: 1, and the silver ion concentration expressed in percentage by weight accounts for 1.5% in silver ammino solution; Described B agent is a potassium borohydride; Setting is developed: with the metal coating surface ejection anhydrous sodium sulfite solution of spray gun to article, with the stable metal coating, strengthen the antioxygenic property of protection metal coating; Dry up: blow to the silver mirror surface with air blowing rifle, dry up the ponding on silver mirror surface; Dry: drying is 40 minutes in 55 ℃ drying oven, strengthens the adhesive force of silver mirror coating layer.The grain size of coating is in 5 nanometers.Referring to table 1.
Select the material of 70*25*10 for use, chamfering polishing: adopt mechanical vibration, barreling chamfering method that sintered Nd-Fe-B permanent magnetic material is polished; Degreasing degreasing: add sodium phosphate, sodium carbonate or NaOH and carry out degreasing degreasing; Derusting by sandblasting; Spraying prime coat: on permanent magnet surfaces, spray a kind of Hydroxylated acrylic resin bottom of 1 micron thickness with spray gun.Sensitization, activation processing: spraying the surface sensitizing activating solution with the article surface of spraying prime coat with sprayer, till article surface is all moistening, washing article with pure water solution then; Contain inferior tin 20 grams per liters of hydroxyalkylated sulfonic acid in the described surface sensitizing activating solution, contain palladium bichloride 10 grams per liters, 0.2 micron of transition region thickness.Spray gun spraying outermost layer: spray A agent and B agent with double head spray gun simultaneously to the article surface of sensitization and activation, form the argent coating, this argent coating layer thickness is at 0.6 micron; Described A agent: the volume ratio of B agent is 1: 1.2, and the mixing point of described A agent, B agent sprays the distance of article between 20cm from quilt; Described A agent is a silver ammino solution, and this silver ammino solution is to be mixed by liquor argenti nitratis ophthalmicus, ammonia spirit and sodium hydroxide solution, and wherein the volume ratio of ammonia spirit and sodium hydroxide solution is 1: 1, and the silver ion concentration expressed in percentage by weight accounts for 1.0% in silver ammino solution; Described B agent is that sulfuric acid is to the methylamino phenol solution; Setting is developed: with the metal coating surface ejection anhydrous sodium sulfite solution of spray gun to article, with the stable metal coating, strengthen the antioxygenic property of protection metal coating; Dry up: blow to the silver mirror surface with air blowing rifle, dry up the ponding on silver mirror surface; Dry: drying is 30 minutes in 60 ℃ drying oven, strengthens the adhesive force of silver mirror coating layer.The grain size of coating is in 50 nanometers.Referring to table 1.
The comparative example 1
Select the material of 70*25*10 for use, chamfering polishing: adopt mechanical vibration, barreling chamfering method that sintered Nd-Fe-B permanent magnetic material is polished; Degreasing degreasing: add sodium phosphate, sodium carbonate or NaOH and carry out degreasing degreasing; Derusting by sandblasting, activation back electro-coppering nickel.Referring to table 1.
Table 1
| Embodiment number | Salt fog (hour) | Humid heat test (hour) | Thickness (micron) | Cost (unit) |
| Embodiment 1 | ??96 | ??500 | ??0.7 | ??0.4 |
| |
??96 | ??500 | ??3.3 | ??1.0 |
| |
??96 | ??500 | ??1.8 | ??0.8 |
| The comparative example 1 | ??48 | ??96 | ??25 | ??1.40 |
As can be seen from Table 1, salt fog was 96 hours when coating layer thickness of the present invention only was 0.7～3.3 micron, and humid heat test is 500 hours; And cost also is controlled at 0.4～0.8 yuan.And the comparative example's 1 of prior art coating layer thickness when being 25 microns salt fog be 48 hours, and humid heat test is 96 hours; And cost is 1.40 yuan.
Therefore, the present invention has the following advantages: 1, the minute surface spraying has outstanding corrosion resisting property; 2, minute surface spraying cost is low; 3, coating is thin, to the influence of magnet is little the magnetic cup wall is not arranged; 4, has excellent wet-hot aging performance.
Need to prove that foregoing invention content and embodiment are intended to prove the practical application of technical scheme provided by the present invention, should not be construed as qualification protection range of the present invention.Those skilled in the art are in spirit of the present invention and principle, when doing various modifications, being equal to and replacing or improve.Protection scope of the present invention is as the criterion with appended claims.
Claims (10)
1. permanent magnet that has corrosion-inhibiting coating, described permanent magnet comprises permanent magnetic material matrix (1), organic substance bottom (2), organic substance transition zone (3), organic substance outermost layer (4).
2. permanent magnet as claimed in claim 1, wherein, described organic substance bottom (2) is the bottom of Hydroxylated acrylic resin or epoxy resin, its thickness is at 0.5～2 micron; Described organic substance transition zone (3) is the transition zone of stanniferous and palladium element, and its thickness is at 0.1～0.3 micron; Described organic substance outermost layer (4) is the nano coating of containing metal silver, and its thickness is at 0.1～1 micron.
3. permanent magnet as claimed in claim 2, wherein, the transition zone of described stanniferous and palladium element is formed by the spraying of surface sensitizing activating solution, and described surface sensitizing activating solution comprises inferior tin of hydroxyalkylated sulfonic acid and palladium bichloride.
4. permanent magnet as claimed in claim 2, wherein, the nano coating of described containing metal silver sprays the A agent that contains silver ion simultaneously by the transition zone to stanniferous and palladium element and the B agent that contains reducing agent forms; Described A agent is a silver ammino solution, and this silver ammino solution comprises liquor argenti nitratis ophthalmicus, ammonia spirit and sodium hydroxide solution, and described B agent is that sodium borohydride, potassium borohydride or sulfuric acid are to the methylamino phenol solution; The A agent: the volume ratio of B agent is 1: 1～1.5.
5. permanent magnet as claimed in claim 4, wherein, the volume ratio of described ammonia spirit and sodium hydroxide solution is 1: 1, the silver ion concentration expressed in percentage by weight accounts for 0.5～1.5% in silver ammino solution.
6. permanent magnet as claimed in claim 4, wherein, the grain size of the nano coating of described containing metal silver is in 5～100 nanometers; Wherein, described permanent magnetic material is sintered Nd-Fe-B permanent magnetic material or Agglutinate neodymium-iron-boron material.
7. one kind is used for the described powder nanometer spraying method that has the permanent magnet of corrosion-inhibiting coating of claim 1～6, and described powder nanometer spraying method comprises the steps:
(1) chamfering polishing: adopt mechanical vibration, barreling chamfering method that permanent magnetic material is polished;
(2) degreasing degreasing: add sodium phosphate, sodium carbonate or NaOH and carry out degreasing degreasing;
(3) derusting by sandblasting: permanent magnetic material surface is imposed blasting treatment;
(4) spraying bottom: on permanent magnet surfaces, spray the Hydroxylated acrylic resin or the epoxy resin of 0.5～2 micron thickness, to form organic substance bottom, drying with spray gun;
(5) sensitization, activation processing: spray the surface sensitizing activating solution with sprayer to the organic substance bottom surface of permanent magnet, till permanent magnet surfaces is all moistening, wash permanent magnet with pure water solution then, to form the organic substance transition zone; Wherein, described surface sensitizing activating solution comprises inferior tin of hydroxyalkylated sulfonic acid and palladium bichloride;
(6) spray gun spraying reduction reaction: spray A agent and B agent with double head spray gun simultaneously to the organic substance transition zone surface of permanent magnet, to form the nano coating of containing metal silver; Wherein, described A agent is a silver ammino solution, and this silver ammino solution comprises liquor argenti nitratis ophthalmicus, ammonia spirit and sodium hydroxide solution, and described B agent is that sodium borohydride, potassium borohydride or sulfuric acid are to the methylamino phenol solution; Described A agent: the volume ratio of B agent is 1: 1～1.5;
(7) setting is developed: with the argent coating surface spraying anhydrous sodium sulfite solution of spray gun to permanent magnet;
(8) dry up: blow to the silver mirror surface with air blowing rifle, dry up the ponding on silver mirror surface;
(9) drying: drying is 30～40 minutes in 55～65 ℃ drying oven.
8. powder nanometer spraying method as claimed in claim 7, wherein, described surface sensitizing activating solution comprises inferior tin 15～25 grams per liters of hydroxyalkylated sulfonic acid and palladium bichloride 5～15 grams per liters.
9. powder nanometer spraying method as claimed in claim 7, wherein, the volume ratio of described ammonia spirit and sodium hydroxide solution is 1: 1, the silver ion concentration expressed in percentage by weight accounts for 0.5～1.5% in silver ammino solution.
10. powder nanometer spraying method as claimed in claim 7, wherein, the mixing point of described A agent, B agent sprays the distance of permanent magnet between 15～25cm from quilt.
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| 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 |
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