CN102397835B - Method for performing surface treatment on neodymium-iron-boron permanent magnet material by using nano ceramic - Google Patents
Method for performing surface treatment on neodymium-iron-boron permanent magnet material by using nano ceramic Download PDFInfo
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Abstract
The invention provides a method for performing surface treatment on a neodymium-iron-boron permanent magnet material by using nano ceramic. The method comprises the following steps of: (1) polishing chamfers; (2) degreasing and removing oil; (3) acid-washing and derusting; (4) treating by using the nano ceramic, namely putting the neodymium-iron-boron permanent magnet material into a nano ceramic plating solution and performing nano ceramic treatment, wherein the nano ceramic plating solution comprises a main film-forming agent, a film-forming aid, a filler and a curing agent, the main film-forming agent is epoxy resin with an amino group or an epoxy group, the film-forming aid is at least one of methyl isobutyl ketone, methyl ethyl ketone peroxide and tert-butyl peroxyacetate, the filler is nano-silicon dioxide and/or alumina, and the curing agent is triethanolamine and/or diethanolamine; and (5) washing and blow-drying to solidify a nano ceramic plated layer. By the surface treatment method, the neodymium-iron-boron permanent magnet material can obtain excellent corrosion resistance, and the high-temperature demagnetization rate of the neodymium-iron-boron permanent magnet material is greatly reduced.
Description
Technical field
The present invention relates to a kind of surface treatment method of Nd-Fe-Bo permanent magnet material, particularly a kind of nano ceramics that adopts carries out surface-treated method to Nd-Fe-Bo permanent magnet material.
Background technology
The application and development of neodymium iron boron (NdFeB) permanent-magnet material is very rapid in recent years, and the protection of Nd-Fe-Bo permanent magnet material is related to one of key technology that can Nd-Fe-Bo permanent magnet material apply.Nd-Fe-Bo permanent magnet material is mainly prepared from by powder metallurgical technique by elements such as rare earth metal neodymium (Nd), iron and boron.As magnetic material the strongest at present, Nd-Fe-Bo permanent magnet material has been widely used in the fields such as electroplating device, machinery, medical treatment, automobile, and application prospect is very wide.
The prerequisite of Nd-Fe-Bo permanent magnet material application first to resolve the Anticorrosion of Nd-Fe-Bo permanent magnet material.As a kind of porous material be prepared from by powder metallurgical technique, the rich neodymium phase in Nd-Fe-Bo permanent magnet material, neodymium iron boron principal phase and border are easy to form intercrystalline corrosion mutually.Because the character of the rear earth element nd in neodymium iron boron powder metallurgy is active, thus the corrosion resisting property of whole Nd Fe B alloys is made to become very poor, particularly very easily corrosion in damp and hot environment, and cause decline or the damage of magnetic property because of corrosion failure, have a strong impact on the service life of Nd-Fe-Bo permanent magnet material, reduce stability and the reliability of product.The magnetic property of Nd-Fe-Bo permanent magnet material and its institutional framework have very large relation.The principal phase of Nd-Fe-Bo permanent magnet material is the main source of its magnetic property, and maximum to coercivity contribution be rich neodymium phase.After Nd-Fe-Bo permanent magnet material corrodes, will there is huge change in its magnetic property.Therefore, the Anticorrosion of Nd-Fe-Bo permanent magnet material is the subject matter that Nd-Fe-Bo permanent magnet material needs to solve always.
At present, the anti-corrosion method of Nd-Fe-Bo permanent magnet material has a variety of, such as electronickelling, electrogalvanizing (CN1421547A, CN1056133A), shooting of multi-layer nickel electroplating, copper facing (CN1514889A), phosphatization, electrophoretic paint etc.Electrogalvanizing is under the effect of dc source, and metallic zinc ion is reduced into metallic zinc on negative electrode.
On the other hand, how to reduce the flux loss of Nd-Fe-Bo permanent magnet material in surface treatment process and more and more become a sharp-pointed problem.Measure the magnetic flux of the Nd-Fe-Bo permanent magnet material of film forming, after then this Nd-Fe-Bo permanent magnet material being placed 1 hour at 150 DEG C, cool to normal temperature, after so repeating 2-3 time, then measure the flux value of this Nd-Fe-Bo permanent magnet material.Flux value according to this twice measurement can calculate high temperature demagnetize.The high temperature demagnetize of the Nd-Fe-Bo permanent magnet material after surface treatment method process of the prior art is generally 2-15%.
Summary of the invention
The object of the present invention is to provide a kind of nano ceramics that adopts to carry out surface treatment method to Nd-Fe-Bo permanent magnet material, described method comprises the steps:
(1) chamfering polishing: adopt mechanical vibration or barreling chamfering method to carry out routine polishing to Nd-Fe-Bo permanent magnet material;
(2) degreasing degreasing: use sodium phosphate, sodium carbonate or NaOH to carry out conventional degreasing degreasing to described Nd-Fe-Bo permanent magnet material;
(3) acid pickling and rust removing: then use salpeter solution to carry out conventional acid pickling and rust removing, washing to described Nd-Fe-Bo permanent magnet material;
(4) nano ceramics process: described Nd-Fe-Bo permanent magnet material is put into nano ceramics plating solution and carries out nano ceramics process, described nano ceramics plating solution comprises main film forming agent, coalescents, filler and curing agent; Wherein, described main film forming agent is the epoxy resin with amino or epoxy radicals, described coalescents is selected from least one in the tertiary fourth fat of methyl iso-butyl ketone (MIBK), methyl ethyl ketone peroxide and peracetic acid, described filler is nano silicon and/or aluminium oxide, and described curing agent is triethanolamine and/or diethanol amine; With
(5) wash, dry up, with curing nano ceramic plated layer.
Preferably, described main film forming agent is E-44 epoxy resin or E-51 epoxy resin.
Preferably, the content of described main film forming agent is 15-25 gram.
Preferably, the content of described coalescents is 5-25 gram.
Preferably, the content of described filler is 50-65 gram.
Preferably, the content of described curing agent is 5-20 gram.
Preferably, described nano ceramics process is carried out at normal temperatures.
Preferably, solidification temperature is 120 DEG C, and hardening time is 1.5 hours.
Preferably, described Nd-Fe-Bo permanent magnet material is sintered Nd-Fe-B permanent magnetic material or binding Nd-Fe-B permanent magnetic material.
In surface treatment method of the present invention, first carry out surface treatment to Nd-Fe-Bo permanent magnet material, this surface treatment can adopt known method of the prior art to carry out.Such as, mechanical vibration or barreling chamfering method is first used to polish Nd-Fe-Bo permanent magnet material.Then use alkaline solution to carry out degreasing degreasing to Nd-Fe-Bo permanent magnet material, such as, Nd-Fe-Bo permanent magnet material is put into sodium carbonate that the sodium phosphate, the 10g/ that are risen by 20g/ rise and the alkaline solution that forms of NaOH that 10g/ rises carries out degreasing degreasing.Then acid pickling and rust removing is carried out to this Nd-Fe-Bo permanent magnet material, such as, use the oxide of this neodymium-iron-boron permanent magnetic material surface of salpeter solution cleaning removing of 1% (volume ratio).Final rinse water falls acid and the impurity of neodymium-iron-boron permanent magnetic material surface.
Surface treatment method provided by the present invention is that this surface treatment method does not use phosphorus, and does not produce sediment in processing procedure, therefore has the advantage of environmental protection with epoxy resin and some inorganic fillers for primary raw material carries out surface treatment to Nd-Fe-Bo permanent magnet material.Meanwhile, method of the present invention can be carried out at normal temperatures, without the need to heating, and the processing time short, control easy, can save table adjust operation, tank liquor is reusable.Compared with phosphatization surface treatment, cost can be reduced by 15 ~ 30% by surface treatment method of the present invention.
The surface treatment method of the application of the invention can make Nd-Fe-Bo permanent magnet material obtain excellent decay resistance.Meanwhile, another beneficial effect of surface treatment method of the present invention is the high temperature demagnetizing factor greatly reducing Nd-Fe-Bo permanent magnet material, and is controlled below 0.01% by high temperature demagnetizing factor.
Detailed description of the invention
In order to understand structure of the present invention, feature and other objects further, the appended preferred embodiment of existing combination is described in detail as follows, and illustrated preferred embodiment is only for illustration of technical scheme of the present invention, and non-limiting the present invention.
Embodiment 1
Will
sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations of 18mm polish 2 hours in vibrating ball-mill.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after NaOH 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, nano ceramics process.Wherein main film forming agent is E-51 epoxy resin 15 grams, methyl iso-butyl ketone (MIBK) 25 grams, nano silicon 50 grams, and triethanolamine 5 grams mixes for subsequent use.120 DEG C solidify 1.5 hours.Coating layer thickness 20 nanometer.Then carry out salt spray test, PCT test, damp heat test and high temperature demagnetize to measure, can find out that coating binding force is good, cross cut test is qualified, and Corrosion Protection is see table 1.
Embodiment 2
Will
sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations of 18mm polish 2 hours in vibrating ball-mill.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after NaOH 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, nano ceramics process.Wherein main film forming agent is E-44 epoxy resin 25 grams, methyl ethyl ketone peroxide 15 grams, nano aluminium oxide 65, and diethanol amine 20 grams mixes for subsequent use.120 DEG C solidify 1.5 hours.Coating layer thickness 20 nanometer.Coating binding force is good, and cross cut test is qualified, and Corrosion Protection is see table 1.
Embodiment 3
Will
sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations of 18mm polish 2 hours in vibrating ball-mill.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after NaOH 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, nano ceramics process.Wherein main film forming agent is E-51 epoxy resin 20 grams, methyl iso-butyl ketone (MIBK) 2 grams, methyl ethyl ketone peroxide 20 grams, nano silicon 10 grams, aluminium oxide 50, and triethanolamine 5 grams, diethanol amine 12 grams mix for subsequent use.120 DEG C solidify 1.5 hours.Coating layer thickness 23 nanometer.Then carry out salt spray test, PCT test, damp heat test and high temperature demagnetize to measure, can find out that coating binding force is good, cross cut test is qualified, and Corrosion Protection is see table 1.
Embodiment 4
Will
sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations of 18mm polish 2 hours in vibrating ball-mill.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after NaOH 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, nano ceramics process.Wherein main film forming agent is E-44 epoxy resin 18 grams, methyl iso-butyl ketone (MIBK) 5 grams, methyl ethyl ketone peroxide 10 grams, 12 grams, the tertiary fourth fat of peracetic acid, and nano silicon 50 grams, aluminium oxide 10, diethanol amine 15 grams mixes for subsequent use.120 DEG C solidify 1.5 hours.Coating layer thickness 20 nanometer.Then carry out salt spray test, PCT test, damp heat test and high temperature demagnetize to measure, can find out that coating binding force is good, cross cut test is qualified, and Corrosion Protection is see table 1.
Embodiment 5
Will
sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations of 18mm polish 2 hours in vibrating ball-mill.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after NaOH 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, nano ceramics process.Wherein main film forming agent is E-44 epoxy resin 19 grams, the tertiary fourth fat of methyl iso-butyl ketone (MIBK), methyl ethyl ketone peroxide, peracetic acid is made into 24 grams by 1: 1: 1, nano silicon and aluminium oxide are made into 60 grams by 1: 3, and triethanolamine and diethanol amine are made into 15 grams by 1: 2 and mix for subsequent use.120 DEG C solidify 1.5 hours.Coating layer thickness 20 nanometer.Then carry out salt spray test, PCT test, damp heat test and high temperature demagnetize to measure, can find out that coating binding force is good, cross cut test is qualified, and Corrosion Protection is see table 1.
Embodiment 6
Will
sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations of 18mm polish 2 hours in vibrating ball-mill.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after NaOH 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, nano ceramics process.Wherein main film forming agent is E-51 epoxy resin 15 grams, and the tertiary fourth fat of methyl iso-butyl ketone (MIBK), methyl ethyl ketone peroxide, peracetic acid is made into 25 grams by 1: 2: 2, and nano silicon and aluminium oxide are made into 58 grams by 1: 1, and diethanol amine 13 grams mixes for subsequent use.120 DEG C solidify 1.5 hours.Coating layer thickness 20 nanometer.Then carry out salt spray test, PCT test, damp heat test and high temperature demagnetize to measure, can find out that coating binding force is good, cross cut test is qualified, and Corrosion Protection is see table 1.
Comparative example 1
Will
sintered Nd-Fe-B permanent magnetic material 2.3 kilograms of elder generations of 18mm polish 2 hours in vibrating ball-mill.Through sodium phosphate 20g/ liter, sodium carbonate 10g/ liter, after NaOH 10g/ rises degreasing degreasing, pickling removing oxide on surface in 1% nitric acid, washing, table is adjusted, and uses conventional method to carry out phosphatization.Then carry out salt spray test, PCT test, damp heat test and high temperature demagnetize to measure, Corrosion Protection is see table 1.(details consult Su Jiwen etc. publication number be the patent of 200510020633X).
Below, table 1 illustrates that the coating by obtaining above-described embodiment 1 ~ 6 carries out the experimental data of physical parameter.
Table 1
As can be seen from Table 1, coating surface of the present invention is even, and corrosion resistance is high, and high temperature and pressure test and damp heat test (temperature 85 DEG C, humidity 80, relative humidity 100%) are with neutral salt spray test compared with phosphatization, and the present invention has good antiseptic effect.Also cost can be reduced by 15 ~ 30% simultaneously
It should be noted that, foregoing invention content and detailed description of the invention are intended to the practical application proving technical scheme provided by the present invention, should not be construed as limiting the scope of the present invention.Those skilled in the art in spirit of the present invention and principle, when doing various amendment, equivalent replace or improve.Protection scope of the present invention is as the criterion with appended claims.
Claims (5)
1. adopt nano ceramics to carry out a surface treatment method to Nd-Fe-Bo permanent magnet material, described method comprises the steps:
(1) chamfering polishing: adopt mechanical vibration or barreling chamfering method to carry out routine polishing to Nd-Fe-Bo permanent magnet material;
(2) degreasing degreasing: use sodium phosphate, sodium carbonate or NaOH to carry out conventional degreasing degreasing to described Nd-Fe-Bo permanent magnet material;
(3) acid pickling and rust removing: then use salpeter solution to carry out conventional acid pickling and rust removing, washing to described Nd-Fe-Bo permanent magnet material;
(4) nano ceramics process: described Nd-Fe-Bo permanent magnet material is put into nano ceramics plating solution and carries out nano ceramics process, described nano ceramics plating solution comprises main film forming agent, coalescents, filler and curing agent; Wherein, described main film forming agent is E-51 epoxy resin, and the content of described main film forming agent is 15-25 gram; Described coalescents is selected from least one in the tertiary fourth fat of methyl iso-butyl ketone (MIBK), methyl ethyl ketone peroxide and peracetic acid, and the content of described coalescents is 15-25 gram; Described filler is nano silicon and nano aluminium oxide, and the content of described filler is 50-65 gram; Described curing agent is diethanol amine, and the content of described curing agent is 5-20 gram; With
(5) wash, dry up, with curing nano ceramic plated layer.
2. surface treatment method according to claim 1, is characterized in that, described nano ceramics process is carried out at normal temperatures.
3. surface treatment method according to claim 1, is characterized in that, solidification temperature is 120 DEG C, and hardening time is 1.5 hours.
4. surface treatment method according to claim 1, is characterized in that, the thickness of described nano ceramics coating is 20 ~ 23 nanometers.
5. surface treatment method according to claim 1, is characterized in that, described Nd-Fe-Bo permanent magnet material is sintered Nd-Fe-B permanent magnetic material or binding Nd-Fe-B permanent magnetic material.
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| CN201010280089.3A CN102397835B (en) | 2010-09-10 | 2010-09-10 | Method for performing surface treatment on neodymium-iron-boron permanent magnet material by using nano ceramic |
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| CN103938241B (en) * | 2014-04-08 | 2016-06-29 | 湖北桑夏太阳能产业有限公司 | A kind of method strengthening Nd-Fe-B permanent magnet antiseptic property |
| CN107377330A (en) * | 2017-06-19 | 2017-11-24 | 苏州乔纳森新材料科技有限公司 | A kind of method that nano ceramics is surface-treated to Nd-Fe-B permanent magnet material |
| CN107151387A (en) * | 2017-06-28 | 2017-09-12 | 昆山特酷信息科技有限公司 | A kind of hard plastics display screen of tablet personal computer |
| CN107118380A (en) * | 2017-06-28 | 2017-09-01 | 昆山特酷信息科技有限公司 | A kind of preparation method of the hard plastics display screen of tablet personal computer |
| CN112007781A (en) | 2020-09-07 | 2020-12-01 | 烟台首钢磁性材料股份有限公司 | Preparation device and preparation method of neodymium iron boron permanent magnet ceramic coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924715A2 (en) * | 1997-12-19 | 1999-06-23 | Shin-Etsu Chemical Co., Ltd. | Rare earth-based permanent magnet of high corrosion resistance |
| CN1702139A (en) * | 2004-05-25 | 2005-11-30 | 上海赛科现代交通设备有限公司 | Epoxy sealing material for linear motor stator electric magnet |
| CN101029389A (en) * | 2007-04-12 | 2007-09-05 | 北京中科三环高技术股份有限公司 | Surface protection of neodymium iron boron permanent-magnet material |
| CN101728043A (en) * | 2008-10-16 | 2010-06-09 | 北京中科三环高技术股份有限公司 | Permanent magnet with corrosion resistant coating and powder nanometer spraying method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2770857B2 (en) * | 1988-03-29 | 1998-07-02 | 大同特殊鋼株式会社 | Rare earth magnet coating method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0924715A2 (en) * | 1997-12-19 | 1999-06-23 | Shin-Etsu Chemical Co., Ltd. | Rare earth-based permanent magnet of high corrosion resistance |
| CN1702139A (en) * | 2004-05-25 | 2005-11-30 | 上海赛科现代交通设备有限公司 | Epoxy sealing material for linear motor stator electric magnet |
| CN101029389A (en) * | 2007-04-12 | 2007-09-05 | 北京中科三环高技术股份有限公司 | Surface protection of neodymium iron boron permanent-magnet material |
| CN101728043A (en) * | 2008-10-16 | 2010-06-09 | 北京中科三环高技术股份有限公司 | Permanent magnet with corrosion resistant coating and powder nanometer spraying method thereof |
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