CN104036946A - Method for using magnetic steel of waste permanent magnet motor to prepare high-performance high-coercivity regenerated sintered neodymium iron boron (NdFeB) magnet - Google Patents
Method for using magnetic steel of waste permanent magnet motor to prepare high-performance high-coercivity regenerated sintered neodymium iron boron (NdFeB) magnet Download PDFInfo
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Abstract
The invention relates to a method for using magnetic steel of a waste permanent magnet motor to prepare a high-performance high-coercivity regenerated sintered neodymium iron boron (NdFeB) magnet and belongs to the technical field of magnetic materials. The rare earth praseodymium hydride nano powder doping technology is used to regenerate the magnetic steel of the waste rare earth permanent magnet motor so as to prepare the high-performance regenerated sintered NdFeB permanent magnet. The method includes: using hydrogen explosion and air flow milling to prepare NdFeB powder; using the physical gas phase deposition technology to prepare praseodymium hydride nano powder; mixing the two kinds of powder, and performing magnetic field orientation and compression moulding; performing dehydrogenation, sintering and thermal treatment on the compressed base at different temperatures to obtain the sintered magnet. The method has the advantages that various magnetic performances of the regenerated magnet prepared by the method can restore to the level of the original magnetic steel, and the coercivity of the regenerated magnet is higher than that of the original magnetic steel, and the method is short in process flow, low in cost and energy consumption and resource saving.
Description
Technical field
The present invention relates to a kind ofly take that to disassemble waste and old magneto magnet be primary raw material, utilize the nano-particle doped sintered method of praseodymium hydride to prepare the new technology of high-performance high-coercive force regeneration Sintered NdFeB magnet, the present invention can realize the high-valued recycling of waste and old rare-earth permanent-magnet electric machine Nd-Fe-B magnet steel, belongs to technical field of magnetic materials.
Background technology
Recent two decades comes, and along with the fast development of China's economy, rare earth resources reduces increasingly, environmental pollution is on the rise etc., and problem becomes increasingly conspicuous.China's rare earth secondary resource reclaims development space and has a high potential, but less for rare earth resources recycling research work.Wherein neodymium iron boron waste material large for output, that added value is high carries out low value recycling becomes the current most important thing.According to incompletely statistics, by 2010, national waste and old neodymium iron boron yield reached 4.5 ten thousand tons of left and right, but lack advanced technology, caused the reduction greatly of regeneration neodymium iron boron value, wasted valuable rare earth resources; The separation of neodymium iron boron greasy filth caused serious environmental pollution and rare earth yield low.
The recycling of waste and old rare earth permanent magnet, has not only protected the rare earth strategic resource of China's preciousness, and has protected environment.Pollution itself that avoided waste and old rare-earth products to bring on the one hand; On the other hand, reduce rare earth mineral products resource consumption, greatly alleviated the serious environmental pressure that the adopting of rare earth mineral products, choosing, smelting are brought.As can be seen here; the high-valued recycling of waste and old rare earth permanent magnet not only profit margin is very large; equipment rate is high; there is good economic feasibility; and will greatly reduce Rare Earth Mine yield; containment exhaustive exploitation and the deterioration of the ecological environment, protected China's rare earth resources and biological environment effectively.
Rare-earth permanent-magnet electric machine is one of maximum application market of sintered Nd-Fe-B permanent magnet, a large amount of sintered NdFeB magnet steel has been on active service ten to 20 years, impact due to working temperature and external environment, there is reduction in various degree in the performance of magnet steel, therefore extremely urgent to the recovery of the Nd-Fe-B magnet steel of rare-earth permanent-magnet electric machine and high-valued recycling work.But that about the recycling work of rare-earth permanent-magnet electric machine magnet, carries out at present is less.
For sintered NdFeB leftover pieces, recycle and to have developed several different methods at present: 1. Extraction of rare earth element and other precious metals from waste and old magnet, this kind of technique exists the rate of recovery low and reclaim the problems such as product purity is low.Dissolution degree that its main cause is to reclaim waste product is low, the precipitation of reaction rare earth not exclusively and the problem such as the separation degree of rare earth elements lnon rare earth elements and multiple rare earth element is poor; Again melting, powder process, die mould, sinter neodymium iron boron magnetic body into, this kind of technological process is longer, takes time and effort; 3. after the explosion of waste and old magnet hydrogen is broken, this kind of technique after the Nd-Fe-B powder identical with appropriate composition mixes, airflow milling refinement, die mould, sinters Nd-Fe-B permanent magnet into, although can reach the object of recovery, but the neodymium iron boron performance of making after mixed powder can reduce, and product price reduces.
On the one hand, said method is not still reaching good effect to the recycling of sintered NdFeB leftover pieces; On the one hand, due to the impact of operating time and environment, the recycling of rare-earth permanent-magnet electric machine magnet steel is more complicated comparatively speaking in addition.Therefore be necessary to go out effective regeneration techniques for rare-earth permanent-magnet electric machine developing magnet.
Directly adopt that hydrogen explosion is broken, ball milling, orientation is compressing, prepared by sintering technology regeneration magnet, it is a kind of regeneration technology of short flow process, but magnet magnetic energy product prepared by this technique has declined 15% than original magnet magnetic energy product, remanent magnetism and coercive force have declined respectively 10% and 20%.In the recycling process of the waste and old magnet of sintered NdFeB, rare earth element can run off, and causes the particularly coercitive significantly reduction of regeneration magnet magnetic property.For the problems referred to above, the performance that how to improve regeneration magnet becomes the key of dealing with problems.At waste and old Sintered NdFeB magnet, adopt the quick-fried method of hydrogen to be broken into after magnetic, by the effectively loss of compensation regeneration Rare Earth Elements in Process of rare earth doped powder.But the quantity of rare earth powder and granularity have vital impact to the magnetic property of regeneration magnet.The quantity of rare earth powder is more, means and generates more rich neodymium phase, and then can obtain larger coercive force; But the increase of non-hard magnetic phase in magnet simultaneously, the remanent magnetism of magnet and maximum magnetic energy product reduce, and can not effectively be replied.The condition of preparing the magnet of high remanent magnetism and high-coercive force is that rich neodymium phase volume fraction is few as much as possible, but main phase grain is by the layer separation completely mutually of thin rich neodymium.Therefore reduce the size of rare earth powder particle, make it in mixed powder process, be coated on main phase grain surface, in sintering process subsequently, realize effective magnetic of main phase grain isolated.Reaching under the isolated precondition of to main phase grain effective magnetic, if rare earth powder particle is oversize, can cause in magnet rich neodymium phase volume fraction excessive, magnet remanent magnetism and maximum magnetic energy product reduce; If rare earth powder particle is undersized, there will be agglomeration, can cause adverse effect to magnet performance equally.Therefore studying rare earth powder particle size and content is the basis that obtains high-performance regeneration magnet on the impact of regeneration magnet performance.In addition, due to reducing of rare earth doped powder particle size, sintering and the heat treatment optimum temperature of regeneration magnet also can decrease, and what bring is that magnet crystallite dimension reduces thereupon, and then the coercive force of magnet can corresponding raising.
Summary of the invention
A kind of praseodymium hydride nano-powder particles doping that the present invention be directed to the above-mentioned state of the art and propose is reclaimed and prepare the regenerate method of Sintered NdFeB magnet of high-performance high-coercive force, reaches that operation is short, energy consumption is low, the object of high efficiente callback.
The present invention for raw material be waste and old rare-earth permanent-magnet electric machine magnet steel, it is characterized in that, comprise the following steps:
(1) the waste and old rare-earth permanent-magnet electric machine magnet steel of removing coating cleared up and prepared the quick-fried powder of neodymium iron boron hydrogen;
Preferably the waste and old rare-earth permanent-magnet electric machine magnet steel of removing coating is placed in to 5% nitric acid alcohol and at alcoholic solution, cleans after 10 seconds, dry up; Be placed at and in vacuum tube furnace, carry out inhaling hydrogen 3 hours, 600 ℃, 1 * 10 under 150 ℃, 0.1MPa hydrogen pressure
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen;
(2) adopt airflow milling technique that the quick-fried powder of neodymium iron boron hydrogen is crushed to single crystal grain, obtain NdFeB material powder;
(3) adopt physical gas phase deposition technology to prepare praseodymium hydride powder, its particle diameter is 100-500 nanometer;
(4) the praseodymium hydride nanometer powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is the 2-4% of NdFeB material powder weight, and two kinds of powder are mixed.
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, at 1000-1050 ℃ of sintering 5-7 hour, then carry out secondary heat treatment: first order heat treatment temperature 800-900 ℃ wherein, insulation 4-5 hour; Second level heat treatment temperature 450-500 ℃, insulation 4-5 hour; The final sintered magnet that obtains.
The feature of this method is:
1. the average grain diameter of the praseodymium hydride particle of the present invention's doping is 100-500 nanometer.Compare with the praseodymium hydride that is less than 100 nanometers is particle doped, in mixed powder process, the distribution meeting of praseodymium hydride powder particle is more even, and mixed powder effect can be better, finally in sintering process, can make rich neodymium distribute mutually more even, and effectively repair boundary defect, thereby recover the coercive force of magnet; Compare with the praseodymium hydride that is greater than 500 nanometers is particle doped, because praseodymium hydride particle diameter of the present invention is little, reaching on same coercitive basis, required praseodymium hydride content is few, so the remanent magnetism of magnet, magnetic energy product can well be replied simultaneously.
2. compare with conventional sintering technique, sintering temperature and the heat treatment temperature of regeneration sintered magnet are low, therefore can obtain higher coercive force.
3. every magnetic property of the regeneration magnet that prepared by employing the present invention can reach original magnet level, and wherein coercive force, higher than original magnet, can be realized high-valued recycling thus.
4. adopt the inventive method technological process short, cost energy consumption is low, economizes on resources.
Embodiment
Below in conjunction with each embodiment, the present invention will be further described.Right convenient contrast, the magnetic property of original magnetic steel of motor also provides in the lump
Embodiment 1
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
22.5dy
0.8pr
7.1fe
67.8co
0.7cu
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopt physical gas phase deposition technology to prepare the praseodymium hydride nanometer powder that average grain diameter is 100 nanometers.
(4) the praseodymium hydride nano metal powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is 2% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1000 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 900 ℃, be incubated 5 hours; 450 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Comparative example 1-1
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
22.5dy
0.8pr
7.1fe
67.8co
0.7cu
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopt physical gas phase deposition technology to prepare the praseodymium hydride nanometer powder that average grain diameter is 10 nanometers.
(4) the praseodymium hydride nano metal powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is 2% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1000 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 900 ℃, be incubated 5 hours; 450 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Comparative example 1-2
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
22.5dy
0.8pr
7.1fe
67.8co
0.7cu
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopting the quick-fried and ball-milling technology of hydrogen to prepare average grain diameter is the praseodymium hydride powder of 3 microns.
(4) the praseodymium hydride metal micron powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is 4% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1080 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 920 ℃, be incubated 5 hours; 550 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Comparative example 1-3
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
22.5dy
0.8pr
7.1fe
67.8co
0.7cu
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) neodymium iron boron powder is orientated in 3T magnetic field and compressing;
(4) pressed compact is inserted in vacuum sintering furnace, 1080 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 920 ℃, be incubated 5 hours; 550 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Table 1. adopts the particle doped preparation regeneration sintered magnet magnetic property of different grain size praseodymium hydride and density contrast
| ? | Remanent magnetism (kGs) | Coercive force (kOe) | Magnetic energy product (MGOe) | Density (g/cm 3) |
| Original magnet 1 | 13.8 | 16.8 | 45.1 | 7.52 |
| Embodiment 1 | 13.7 | 17.5 | 45.0 | 7.53 |
| Comparative example 1-1 | 13.1 | 16.2 | 42.0 | 7.49 |
| Comparative example 1-2 | 12.7 | 15.6 | 39.2 | 7.46 |
| Comparative example 1-3 | 12.4 | 13.2 | 37.2 | 7.35 |
Embodiment 2
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopt physical gas phase deposition technology to prepare the praseodymium hydride nanometer powder that average grain diameter is 500 nanometers.
(4) the praseodymium hydride nano metal powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is 4% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1050 ℃ of sintering 5 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 800 ℃, be incubated 4 hours; 500 ℃ of second level heat treatment temperatures, are incubated 5 hours; The final sintered magnet that obtains.
Comparative example 2-1
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopt physical gas phase deposition technology to prepare the praseodymium hydride nanometer powder that average grain diameter is 50 nanometers.
(4) the praseodymium hydride nano metal powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is 4% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1050 ℃ of sintering 5 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 800 ℃, be incubated 4 hours; 500 ℃ of second level heat treatment temperatures, are incubated 5 hours; The final sintered magnet that obtains.
Comparative example 2-2
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopting the quick-fried and ball-milling technology of hydrogen to prepare average grain diameter is the praseodymium hydride powder of 4 microns.
(4) the praseodymium hydride metal micron powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride micron powder is 6% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1080 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 920 ℃, be incubated 5 hours; 550 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Comparative example 2-3
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) neodymium iron boron powder is orientated in 3T magnetic field and compressing;
(4) pressed compact is inserted in vacuum sintering furnace, 1080 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 920 ℃, be incubated 5 hours; 550 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Table 2. adopts the particle doped preparation regeneration sintered magnet magnetic property of different grain size praseodymium hydride and density contrast
| ? | Remanent magnetism (kGs) | Coercive force (kOe) | Magnetic energy product (MGOe) | Density (g/cm 3) |
| Original magnet 2 | 13.0 | 20.8 | 40.8 | 7.55 |
| Embodiment 2 | 12.8 | 21.6 | 40.1 | 7.54 |
| Comparative example 2-1 | 12.1 | 20.0 | 35.5 | 7.47 |
| Comparative example 2-2 | 11.5 | 19.7 | 33.6 | 7.41 |
| Comparative example 2-3 | 11.4 | 15.6 | 32.6 | 7.36 |
Embodiment 3
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopt physical gas phase deposition technology to prepare the praseodymium hydride nanometer powder that average grain diameter is 300 nanometers.
(4) the praseodymium hydride nano metal powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is 3% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1030 ℃ of sintering 6 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 850 ℃, be incubated 4.5 hours; 480 ℃ of second level heat treatment temperatures, are incubated 4.5 hours; The final sintered magnet that obtains.
Comparative example 3-1
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopt physical gas phase deposition technology to prepare the praseodymium hydride nanometer powder that average grain diameter is 30 nanometers.
(4) the praseodymium hydride nano metal powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is 3% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1030 ℃ of sintering 6 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 850 ℃, be incubated 4.5 hours; 480 ℃ of second level heat treatment temperatures, are incubated 4.5 hours; The final sintered magnet that obtains.
Comparative example 3-2
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) adopting the quick-fried and ball-milling technology of hydrogen to prepare average grain diameter is the praseodymium hydride powder of 4 microns.
(4) the praseodymium hydride metal micron powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride micron powder is 6% of NdFeB material powder weight, and two kinds of powder are mixed;
(5) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(6) pressed compact is inserted in vacuum sintering furnace, 1080 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 920 ℃, be incubated 5 hours; 550 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Comparative example 3-3
(1) waste and old rare-earth permanent-magnet electric machine magnet steel composition is Nd
25.4dy
5fe
67.2co
1.1cu
0.2al
0.1b
1.The waste and old magnet steel of neodymium iron boron of removing coating is placed in to 5% nitric acid alcohol and after 10 seconds, at alcoholic solution, cleans, dry up.Useless magnet steel is placed in vacuum tube furnace, carries out 150 ℃, 0.1MPa hydrogen pressure and inhale hydrogen 3 hours, 600 ℃, 1 * 10
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
(2) adopt airflow milling technique that NdFeB magnetic powder is crushed to 3 microns.
(3) neodymium iron boron powder is orientated in 3T magnetic field and compressing;
(4) pressed compact is inserted in vacuum sintering furnace, 1080 ℃ of sintering 7 hours, then carry out secondary heat treatment: wherein first order heat treatment temperature is 920 ℃, be incubated 5 hours; 550 ℃ of second level heat treatment temperatures, are incubated 4 hours; The final sintered magnet that obtains.
Table 3. adopts the particle doped preparation regeneration sintered magnet magnetic property of different grain size praseodymium hydride and density contrast
| ? | Remanent magnetism (kGs) | Coercive force (kOe) | Magnetic energy product (MGOe) | Density (g/cm 3) |
| Original magnet 3 | 13.0 | 20.8 | 40.8 | 7.55 |
| Embodiment 3 | 12.9 | 21.3 | 40.5 | 7.55 |
| Comparative example 3-1 | 12.3 | 19.8 | 36.8 | 7.48 |
| Comparative example 3-2 | 11.5 | 19.7 | 33.6 | 7.41 |
| Comparative example 3-3 | 11.4 | 15.6 | 32.6 | 7.36 |
In sum, adopt every magnetic property of regeneration magnet prepared by method of the present invention can be returned to original magnet level.Compare with granule praseodymium hydride particle (being less than 100 nanometers) doping, there is higher remanent magnetism, coercive force and magnetic energy product; Compare with bulky grain praseodymium hydride particle (being greater than 500 nanometers) doping, reaching on same coercitive basis, required praseodymium hydride content is few, so the remanent magnetism of magnet, magnetic energy product can well be replied simultaneously.Compare with conventional sintering technique, sintering temperature and the heat treatment temperature of regeneration sintered magnet are low, therefore can obtain higher coercive force.In addition, adopt the inventive method can make full use of existing equipment, technological process is short, and cost energy consumption is low, economizes on resources.
Claims (3)
1. utilize waste and old magnetic steel of magnetoelectric machine to prepare a method for high-performance high-coercive force regeneration Sintered NdFeB magnet, it is characterized in that, comprise the following steps:
(1) the waste and old rare-earth permanent-magnet electric machine magnet steel of removing coating cleared up and prepared the quick-fried powder of neodymium iron boron hydrogen;
(2) adopt airflow milling technique that the quick-fried powder of neodymium iron boron hydrogen is crushed to single crystal grain, obtain NdFeB material powder;
(3) adopt physical gas phase deposition technology to prepare praseodymium hydride powder, its particle diameter is 100-500 nanometer;
(4) the praseodymium hydride nanometer powder of step (3) gained is joined in the NdFeB material powder of step (2), the adding proportion of praseodymium hydride nanometer powder is the 2-4% of NdFeB material powder weight, and two kinds of powder are mixed.
(4) will in 3T magnetic field, be orientated through even mixed powder and compressing;
(5) pressed compact is inserted in vacuum sintering furnace, at 1000-1050 ℃ of sintering 5-7 hour, then carry out secondary heat treatment: first order heat treatment temperature 800-900 ℃ wherein, insulation 4-5 hour; Second level heat treatment temperature 450-500 ℃, insulation 4-5 hour; The final sintered magnet that obtains.
2. according to the method for claim 1, it is characterized in that, step (1) is placed in 5% nitric acid alcohol by the waste and old rare-earth permanent-magnet electric machine magnet steel of removing coating and at alcoholic solution, cleans after 10 seconds, dries up; Be placed at and in vacuum tube furnace, carry out inhaling hydrogen 3 hours, 600 ℃, 1 * 10 under 150 ℃, 0.1MPa hydrogen pressure
-3pa dehydrogenation 10 hours, obtains the quick-fried powder of neodymium iron boron hydrogen.
3. the regeneration Sintered NdFeB magnet preparing according to the method for claim 1 or 2.
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