CN102610355B - A kind of rare-earth permanent magnet and preparation method thereof - Google Patents
A kind of rare-earth permanent magnet and preparation method thereof Download PDFInfo
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- CN102610355B CN102610355B CN201110024823.4A CN201110024823A CN102610355B CN 102610355 B CN102610355 B CN 102610355B CN 201110024823 A CN201110024823 A CN 201110024823A CN 102610355 B CN102610355 B CN 102610355B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 34
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000843 powder Substances 0.000 claims abstract description 121
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000011248 coating agent Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000007747 plating Methods 0.000 claims abstract description 31
- 238000009792 diffusion process Methods 0.000 claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 27
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 84
- 229910052771 Terbium Inorganic materials 0.000 claims description 83
- 238000011282 treatment Methods 0.000 claims description 65
- 239000002245 particle Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 52
- 229910052689 Holmium Inorganic materials 0.000 claims description 43
- 229910052691 Erbium Inorganic materials 0.000 claims description 37
- 238000005488 sandblasting Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 25
- 230000032683 aging Effects 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 21
- 239000010452 phosphate Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052789 astatine Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 229910017061 Fe Co Inorganic materials 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 30
- 230000005389 magnetism Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 239000000956 alloy Substances 0.000 description 29
- 229910045601 alloy Inorganic materials 0.000 description 29
- 229910052779 Neodymium Inorganic materials 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 238000005422 blasting Methods 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052759 nickel Inorganic materials 0.000 description 19
- 239000000523 sample Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 238000003801 milling Methods 0.000 description 17
- 239000011812 mixed powder Substances 0.000 description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
- 229910052777 Praseodymium Inorganic materials 0.000 description 13
- 238000007796 conventional method Methods 0.000 description 13
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 238000005554 pickling Methods 0.000 description 11
- 238000005266 casting Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052706 scandium Inorganic materials 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000013021 overheating Methods 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019580 granularity Nutrition 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 229910016468 DyF3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
A kind of coercivity that can improve magnet on the basis of not reducing magnet remanent magnetism and magnetic energy product, matrix and coating or the rare-earth permanent magnet of the bond strength of coating and prepare the method for this magnet and be after can also be without reducing plating or coating: first the phosphatic powder of the fluoride containing R2, the nitrate of R3 and R4 is dissolved in water or alcohol and is prepared as solution simultaneously；Above-mentioned solution is evenly arranged pending magnet surface；Then pending magnet is dehydrated or alcohol processes；Finally it is diffused pending magnet being thermally treated resulting in magnet after process.Using method used in the present invention can improve the powder uniformity in magnet surface, after reducing thermal diffusion, powder remains in magnet surface, improves the coercivity of magnet, does not reduce matrix and coating or the bond strength of coating after plating or coating.
Description
Technical field
The present invention relates to a kind of rare-earth permanent magnet and the method preparing this magnet.Especially at the coercivity base improving magnet
On plinth, improve the most again coating or coating and the rare-earth permanent magnet of substrate combinating strength and the method preparing this magnet.
Background technology
Rare-earth permanent magnet has the magnetic property of excellence, starts to be widely used in air conditioner motor, hybrid vehicle in recent years
And field of wind power generation, magnet use in these fields is all had to face high temperature and moistening environment, the most also may be used
Can apply in the dampness containing salinity.Thus, do not require nothing more than magnet and there is high magnetic property, and it is higher resistance to require that it has
Erosion property.
Industry has done substantial amounts of work for the magnetic property improving magnet, does how improving magnet coercivity in recent years
Further investigate, and open reporting provides Dy and Tb to improve magnet to the grain boundaries of magnet surface and near surface in various manners
Coercitive method.As disclosed in Chinese patent application Publication No. CN1898757 by the fluoride of rare earth, oxide and fluorine
Oxide provides magnet surface and uses heat-treating methods to make rare earth and the fluorine etc. on surface to magnet diffusion inside, and result obtains
To higher coercivity, and the remanent magnetism of magnet and magnetic energy product are basically unchanged.
But the method use the fluoride of rare earth, oxide and oxyfluoride have not after magnet surface thermal diffusion
Uniform residual, though the later stage has the acid/base carrying out surface to process or sandblasting or processed are removed, but is because diffusion depth and has
Limit (more than diffusion depth about 20 μm disclosed in Chinese patent application Publication No. CN1838342), if removing epidermis
Too much, then coercivity raising degree is the least or does not has；If it is few to remove epidermis, surface or the uneven residue of near surface
The especially residual of fluorine has considerable influence to the corrosion resistance of magnet, and general employing coating or coating carry out surfacecti proteon to magnet,
But after the magnet plating obtained in the way of diffusing to the surface rare earth β-diketone complex, Tb or coating, matrix and coating or painting often occur
The problem that layer bond strength is deteriorated, thus affect the corrosion resistance after magnet plating or coating.And CN1898757 patent application is to magnetic
The not relevant statement of the corrosion resistance of body.
Method as described in CN1898757 prepare magnet plating or coating after matrix strong with the combination of coating or coating
It is poor to spend, its reason it is important that to magnet surface arrange powder time, powder dissolubility in water or organic solvent
Very poor, and then it is not uniformly distributed in magnet surface, after thermal diffusion, magnet surface remains the molten of the powder of uneven distribution
Melt thing.Therefore the present invention is from improving the powder uniformity in magnet surface, prepares magnet, and do coating surface or
Carry out specific blasting treatment before coating, comprehensively make matrix be improved with the bond strength of coating or coating.
Summary of the invention
It is an object of the invention to provide and a kind of can improve magnet on the basis of not reducing magnet remanent magnetism and magnetic energy product
Coercivity, can also be without reducing rare-earth permanent magnet and the system of the bond strength of matrix and coating or coating after plating or coating simultaneously
The method of this magnet standby.
The preparation method of a kind of rare-earth permanent magnet of the present invention is: first by the fluoride containing R2, the nitric acid of R3
The phosphatic powder of salt and R4 is dissolved in water or alcohol and is prepared as solution；Above-mentioned solution is evenly arranged pending magnet table
Face；Then pending magnet is dehydrated or alcohol processes；After finally being diffused being thermally treated resulting in process to pending magnet
Magnet.
Preferably, described R2 is at least one in the rare earth element including Y and Sc, R3 and R4 is Tb, Dy, Ho
Or one or more in Er.
Preferably, described R2 is one or more in Tb, Dy, Ho or Er.
Preferably, described R2, R3 and R4 is at least one in Tb or Dy.
Preferably, in described powder, the content of fluoride of R2 is at least mass ratio 20%, and the nitrate content of R3 is at least
For mass ratio 10%, the phosphate content of R4 is at least mass ratio 10%；Dy, Tb total content in the powder is at least atomic ratio
15%.
Preferably, the fluoride powder size of described R2 is not more than 100 μm, the nitrate powder of R3 and the phosphate of R4
Powder size is not more than 500 μm.
Preferably, described solution carries out proportioning according to powder and water or alcohol by the mass ratio of 1: 0.5～1: 50.
Preferably, described diffusion heat treatments is 10-5Under the vacuum condition of Pa～10Pa or 10-3Pa～105Pa dividing potential drop lazy
Property gas condition under carry out, the preferred argon of noble gas, heat treatment temperature be higher than 500 DEG C, less than the sintering temperature of pending magnet
Degree, heat treatment temperature retention time is 10 minutes to 20 hours.
Preferably, described preparation method is treated before being additionally included in and above-mentioned solution being evenly arranged pending magnet surface
Process magnet acid or alkali liquor is carried out；It is 400～700 DEG C to magnet after processing in heating-up temperature, 10 minutes heat time heating times
To 20 hours, vacuum condition was 10-5Ageing Treatment is carried out under the conditions of Pa～100Pa；Magnet after Ageing Treatment is carried out acid, alkali liquor
Wash, or be ground or sand blasted surface process；After processing surface, magnet is carried out and plating or coating.
Preferably, during described sand blasted surface processes, sand-blasting abrasive selects Mohs' hardness to be at least the hard particles of 5.0, preferably
Spheroidal particle, average particle size is in 40～4000 μm, and injection gas pressure is 0.1～1.0MPa.
Preferably, described pending magnet is that cleaved or grinding one-tenth the minimum edge of blank magnet is not more than 20mm
Magnet.
The rare-earth permanent magnet using said method to prepare comprises composition R-T-B, and has R2T14The principal phase structure of B1, and
Surround the Nd-rich phase crystal boundary of principal phase structure, the one during wherein R is the rare earth element including Y and Sc, and R at least to contain
Nd；T is Fe or at least one in the element such as Fe and Co, Al, Cu, Nb, Ga, Mo, V.
Use method used in the present invention can improve the powder uniformity in magnet surface, reduce powder after thermal diffusion
Remain in magnet surface, improve the coercivity of magnet, do not reduce matrix and coating or the bond strength of coating after plating or coating.
Accompanying drawing explanation
Fig. 1 is the demagnetizing curve figure of the embodiment of the present invention 1 and 2 and comparative example；
Fig. 2 a be use comparative example method magnet surface condition diagram after Overheating Treatment.
Fig. 2 b is the method magnet surface condition diagram after Overheating Treatment using the present invention.
Fig. 2 c is to use after the inventive method heat treatment magnet surface condition diagram after blasting treatment again.
Detailed description of the invention
Initially with well-known ingot casting or the method molten alloy that gets rid of band, obtain the alloy pig that composition contains R1, T, B
Or get rid of band thin slice.R1 is at least one in the rare earth element including Y and Sc, and R1 at least contain Nd, T be Fe or Fe and
At least one in the elements such as Co, Al, Cu, Nb, Ga, Mo, V.By above-mentioned alloy of ingot or get rid of band thin slice and carry out according to a conventional method
Coarse crushing, hydrogen are broken, airflow milling makes fine powder, remix uniformly, and after through magnetic field orientating compressing, through isostatic pressed, enter
Row normal sintering, passes through or obtains blank magnet without Ageing Treatment, and blank magnet has R12T14B principal phase structure, and have
Surround the rich R1 rare-earth phase of principal phase structure.Blank magnet is processed to the pending magnet having minimum edge less than or equal to 20mm.
Pending magnet surface or with acid or alkali liquor be carried out.
The phosphate powder of the fluoride of R2, the nitrate of R3 and R4 is mixed to join in water or alcohol and makes solution.Dilute
Soil fluoride and oxyfluoride is water insoluble and alcohols, oxide is dissolved in alcohol but water insoluble；And the nitrate of rare earth and phosphorus
Hydrochlorate can be dissolved in water can be dissolved in again alcohol.Therefore addition is mixed with nitrate and phosphatic powder solubility is improved, from
And be that solute is more uniformly attached to pending magnet surface offer condition.
Wherein, R2 is at least one in the rare earth element including Y and Sc, R3 and R4 is in Tb, Dy, Ho or Er
One or more；Preferably, one or more during R2 is Tb, Dy, Ho or Er；It is highly preferred that R2, R3 and R4 are in Tb or Dy
At least one.The content of fluoride (mass ratio) of R2 at least 20% in powder, the nitrate content (mass ratio) of R3 is at least
Being 10%, the nitrate content (mass ratio) of R4 at least 10%, Dy, Tb total content (atomic ratio) in the powder is at least
15%.
Wherein, the fluoride powder size of R2 is not more than 100 μm, and the nitrate powder of R3 and the phosphate powder of R4 are little
In 500 μm.Powder particle is too thick, affects powder dissolubility in a solvent, thus has influence on solute and be attached to pending magnet
The uniformity on surface.
In solution, powder and water or alcohol carry out proportioning by (mass ratio) 1: 0.5～1: 50 and form solution.Described alcohol is preferred
Ethanol.Solution concentration is the lowest, and adhesion amount is inadequate, affects diffusing capacity thus affects coercivity and improve；Solution concentration is the highest, affects molten
Matter is attached to the uniformity of pending magnet surface.
Solution is evenly arranged above-mentioned processing, clean after pending magnet surface, can use dipping or brush or
The modes such as spraying, preferably impregnation method.Then dehydration/the alcohol carrying out routine processes, and makes moisture and the alcohol of pending magnet surface
Evaporate.
Then 10-5Pa～10Pa vacuum condition or 10-3Pa～105Under the inert gas conditions of Pa dividing potential drop, indifferent gas
The preferred argon of body, is diffused heat treatment to pending magnet, and heat treatment temperature is higher than 500 DEG C, less than the sintering temperature of magnet.
Heat treatment temperature retention time was at 10 minutes to 20 hours.Use vacuum or inert gas conditions be in order to prevent pending magnet and
Surface at high temperature with the antivacuum and gas reaction of noble gas, make magnet deteriorate；Heat treatment temperature is the lowest or the time is the shortest,
R2, R3 or R4 of magnet surface is little to pending magnet diffusion inside, affects coercivity and improves effect, and heat treatment temperature is the highest
Or the time is oversize, R2, R3 or R4 are diffused into while pending magnet inside by crystal boundary inside main phase grain by magnet surface
Diffusion, can cause the reduction of remanent magnetism, and can cause the waste of the energy.Heat treatment makes R2, R3 and R4 at least a kind of by magnet
Surface is to pending magnet diffusion inside.And make R2, R3 or R4 element from surface to center distribution gradient.
After heat treatment, magnet is carried out Ageing Treatment.Condition is heating-up temperature 400～700 DEG C, 10 minutes heat time heating times
To 20 hours, vacuum condition was 10-5Pa～100Pa.
The magnet composition now obtained contains R, T, B, has R2T14While B principal phase structure, also have and surround principal phase knot
The Nd-rich phase of structure.R is at least one in the rare earth element including Y and Sc, and R at least contain Nd, T be Fe or Fe and
At least one in the elements such as Co, Al, Cu, Nb, Ga, Mo, V.
Magnet acid after Ageing Treatment, alkali liquor are washed, or is ground or blasting treatment, preferably carries out blasting treatment and go
Except the modification layer on surface, and make the magnet surface after this surface processes have certain roughness, and then strengthen plating or painting
Cover rear matrix and coating or the combination of coating.
Wherein sand-blasting abrasive selects Mohs' hardness to be at least the hard particles of 5.0, and preferably spheroidal particle, average particle size exists
40～4000 μm, injection gas pressure is 0.1～1.0MPa.Abrasive hardness is the lowest, and granularity is too thin or sprays gas pressure
Under the lowest then efficiency, and the effect removing modification layer with increase surface roughness cannot be played；Abrasive hardness is the highest, granule
Degree is too big or injection gas pressure too Gao Zehui makes surface the most coarse, or removal surface affects coercivity too much and improves.
Magnet, after above-mentioned surface processes, is carried out and plating or coating.
Embodiment 1-2
Molten alloy, obtains (Nd, Pr)aDybFe(1-a-b-c)Bc(a=14.5, b=0.6, c=5.8, a, b, c are atom hundred
Proportion by subtraction) ingot casting, alloy of ingot is carried out according to a conventional method coarse crushing, hydrogen broken after, airflow milling makes fine powder, remixes all
Even, and after through 2.0T magnetic field orientating compressing, through 180MPa isostatic pressed, green compact sinter 3h through 1070 DEG C, obtain blank magnetic
Body, cuts into the little square piece of 12mm × 12mm × 2mm as pending magnet using the blank magnet after sintering.It is divided into A (original sample
Product), B (comparative example), C (embodiment 1), D (embodiment 2) four groups each 100.Two groups of samples of A, B are control sample, wherein
A group sample does not deals with, and B group sample is that 3% aqueous solution of nitric acid carries out pickling through mass ratio, then arranges at specimen surface
DyF3, Dy2O3With DyOF powder (each powder quality percent is respectively 80%, 10%, 10%, particle mean size is respectively 100 μm,
300 μm and 200 μm), by mixed-powder with water quality than 1: 10 configuration solution, magnet impregnates 0.5 minute in the solution, then takes
Go out drying and dehydrating in atmosphere, then 10-3Carrying out 750 DEG C in Pa vacuum, the heat diffusion treatment of 4 hours, subsequently 10-2Pa
Vacuum carries out 600 DEG C, the Ageing Treatment (calling control methods in the following text) of 5 hours；C group sample is that 3% nitric acid is water-soluble through mass ratio
Liquid carries out conventional pickling, then arranges DyF at specimen surface3, Dy (NO3)3And DyPO4Powder, three kinds of powder quality percents divide
Not ratio for 80%, 10%, 10%, particle mean size is respectively 100 μm, 300 μm and 200 μm, by mixed-powder and water quality ratio 1:
10 configuration solution, magnet impregnates 0.5 minute in the solution, then takes out drying and dehydrating in atmosphere, thermal diffusion then and time
The effect same control methods of processing mode；D group sample pretreating mode with C group sample and follow-up plus sandblasting operation, sandblasting uses hard
Degree is the spherical hard particles of 5.0, and average particle size is 400 μm, sprays gas pressure position 0.5MPa.A, B, C, D respectively separate 50
Sheet carries out electronickelling process.Then do not carry out in A, B, C, D group that the sample electroplated respectively takes out 5 and carry out magnetism testing；A,
B, C, D group carries out respectively taking out 5 in the sample electroplated and carries out nickel coating and substrate combinating strength extension test.Sample magnetism testing
The results are shown in Table 1, after sample electronickelling, between matrix and coating, bond strength test results is shown in Table 2
Table 1 sample magnetic property result
Found out by table 1 magnetic property result, use the present invention method as control methods can not reduce surplus
On the premise of magnetic and magnetic energy product, improving coercivity, the demagnetizing curve figure of A01, B01, C01, D01 sample is shown in Fig. 1.
Fig. 2 is to use oxide, fluoride and the oxyfluoride of rare earth are made the control methods of solution and use this
Bright method is the comparison diagram of magnet surface situation after Overheating Treatment.White dot in accompanying drawing 2a is powder melts residue,
The magnet surface of Fig. 2 b is hardly visible uneven white dot, and Fig. 2 c is for using the present invention through Overheating Treatment and through sandblasting
Magnet surface after process, more uniform without blasting treatment of the surface ratio present invention.
Matrix and plating interfacial bonding strength drafting results after table 2 sample electronickelling
| Process | Sample number | Coating separates (kgf/cm with matrix2) |
| Primary sample | A01 | 268 |
| Primary sample | A02 | 256 |
| Primary sample | A03 | 266 |
| Primary sample | A04 | 264 |
| Primary sample | A05 | 258 |
| Comparative example | B01 | 220 |
| Comparative example | B02 | 205 |
| Comparative example | B03 | 198 |
| Comparative example | B04 | 202 |
| Comparative example | B05 | 218 |
| Embodiment 1 | C01 | 250 |
| Embodiment 1 | C02 | 253 |
| Embodiment 1 | C03 | 254 |
| Embodiment 1 | C04 | 245 |
| Embodiment 1 | C05 | 238 |
| Embodiment 2 | D01 | 260 |
| Embodiment 2 | D02 | 263 |
| Embodiment 2 | D03 | 272 |
| Embodiment 2 | D04 | 268 |
| Embodiment 2 | D05 | 275 |
Found out by table 2 matrix coating bond strength drafting results, use the present invention without the method for sandblasting and control methods
Relatively, the bond strength between coating and matrix is close to the bond strength level after untreated samples plating, and the present invention is through spray
The method of sand, coating and substrate combinating strength can reach the bond strength level after untreated samples plating.This shows to use this
Inventive method can improve the bond strength of magnet surface and coating.
Embodiment 3
By getting rid of band technology molten alloy, obtain (Nd, Pr, Sc)aDybCodFe(1-a-b-c-d)Bc(a=15, b=0.6, c=
5.8, d=1.0, a, b, c, d are atomic percent) get rid of band thin slice, band thin slice will be got rid of and carry out that hydrogen is broken, air-flow according to a conventional method
Be milled into fine powder, remix uniformly, and after through 2.0T magnetic field orientating compressing, through 180MPa isostatic pressed, green compact are through 1060
DEG C sintering 3h, obtains blank magnet, the blank magnet after sintering cuts into the little square piece of 12mm × 12mm × 2mm as at band
Reason magnet.Pending magnet carries out conventional pickling through the aqueous solution of nitric acid of 4% mass ratio, then arranges the fluorine of R2 on its surface
Compound powder, the nitrate powder of R3 and the phosphate powder of R4, R2 is Dy and Y (Dy, Y mass ratio is 3: 1), and R3 is Tb, R4
For Tb, three kinds of powder quality percents are respectively 73%, and 12%, 15%, particle mean size is respectively 80 μm, 500 μm, 500 μm, presses
Mixed-powder configures solution with ethanol mass ratio 1: 0.5, and magnet impregnates 1 second in the solution, then takes out dry de-in atmosphere
Ethanol；Afterwards 10-5Carrying out 500 DEG C in Pa vacuum, the heat diffusion treatment of 20 hours, subsequently 10-5Pa vacuum carries out 400
DEG C, the Ageing Treatment of 4 hours；The magnet obtained carries out blasting treatment again, the spherical hard particles that sandblasting uses hardness to be 5.0,
Average particle size is 4000 μm, and injection gas pressure is 0.6MPa.Test obtains the magnetic property of magnet；The magnet part obtained is entered
Row electronickelling processes, and matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 4
By getting rid of band technology molten alloy, obtain NdaDybFe(1-a-b-c-d)AldBc(a=15, b=0.3, c=6.0, d=
0.3, a, b, c, d are atomic percent) get rid of band thin slice, band thin slice will be got rid of and carry out that hydrogen is broken, airflow milling is made according to a conventional method
Fine powder, remixes uniformly, and after through 2.0T magnetic field orientating compressing, through 180MPa isostatic pressed, green compact are through 1060 DEG C of sintering
3.5h, then through 450 DEG C of Ageing Treatment 3.5h, obtains blank magnet, the blank after timeliness is cut into 12mm × 12mm ×
The little square piece of 3mm is as pending magnet.Pending magnet carries out conventional alkali cleaning through the sodium silicate aqueous solution of 2% mass ratio,
Then its surface arrange R2 fluoride powder, the nitrate powder of R3 and the phosphate powder of R4, R2 be Tb and Sc (Tb with
Sc mass ratio is 4: 1), R3 is Dy and Ho (Dy Yu Ho mass ratio is 4: 1), and R4 is Dy and Er (Dy Yu Er mass ratio is 4: 1), three
Plant powder quality percent and be respectively 70%, 15%, 15%, particle mean size is respectively 70 μm, 400 μm, and 300 μm, by mixed powder
End configures solution with ethanol mass ratio 1: 50, and magnet impregnates 0.5 minute in the solution, then takes out and is dried de-second in atmosphere
Alcohol；Then 10-4Carrying out 550 DEG C in Pa vacuum, the heat diffusion treatment of 10 hours, subsequently 10-4Pa vacuum carries out 500 DEG C,
The Ageing Treatment of 10 minutes；The magnet obtained carries out blasting treatment again, the spherical hard particles that sandblasting uses hardness to be 6.0, flat
All granularities are 500 μm, and injection gas pressure is 0.5MPa.Test obtains the magnetic property of magnet；The magnet part obtained is carried out
Electronickelling processes, and matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 5
Molten alloy, obtains ingot casting A:(Nd, Pr, Y)15.5B5.8Febal(atomic percent), ingot casting B:(Nd, Pr)9(Dy,
Tb)6Al4Cu2B6FebalTwo kinds of ingot castings are the most conventionally carried out coarse crushing, hydrogen crushes, then by (atomic percent)
In mass ratio 4: 1 slightly mix, and carry out airflow milling subsequently and make fine powder, remix uniformly, and after through 2.0T magnetic field orientating and press
Making type, through 180MPa isostatic pressed, green compact sinter 3h through 1080 DEG C, obtain composition for (Nd, Pr, Y)14.2(Dy, Tb)1.2Al0.8Cu0.4B5.84FebalThe blank magnet of (atomic percent)；The sintering blank magnet obtained is cut into 12mm × 12mm
The little square piece of × 3mm is as pending magnet.Pending magnet carries out conventional alkaline through the sodium pyrophosphate aqueous solution of 1% mass ratio
Washing, then arrange the fluoride powder of R2 on its surface, the nitrate powder of R3 and the phosphate powder of R4, R2 is that Tb, R3 are
Dy and Er (Dy and Er mass ratio is 3: 1), R4 are Dy and Ho (Dy and Ho mass ratio is 3: 1), and three kinds of powder quality percents divide
Not being 60%, 20%, 20%, particle mean size is respectively 60 μm, 200 μm, and 400 μm, by mixed-powder and ethanol mass ratio 1: 10
Configuration solution, magnet impregnates 0.5 minute in the solution, then takes out and is dried de-ethanol in atmosphere；It is then 10 in dividing potential drop-3Pa
Vacuum in carry out 600 DEG C, the heat diffusion treatment of 5 hours, subsequently 10-3Pa vacuum carries out 600 DEG C, at the timeliness of 20 hours
Reason；The magnet obtained carries out blasting treatment again, the spherical hard particles that sandblasting uses hardness to be 8.0, and average particle size is 40 μm,
Injection gas pressure is 0.1MPa.Test obtains the magnetic property of magnet；The magnet part obtained carries out electronickelling process, test electricity
Matrix and nickel coating bond strength after plating, test result is shown in Table 3.
Embodiment 6
By getting rid of band technology molten alloy, obtain two kinds and get rid of band thin slice A:(Nd, Pr, La)16B5.8Febal(atomic percent
Than), B:(Nd, Pr)9(Dy, Tb)7Co5B6Febal(atomic percent), gets rid of band thin slice by two kinds and the most conventionally carries out
Hydrogen crushes, and the most in mass ratio 9: 1 slightly mix, and carry out airflow milling subsequently and make fine powder, remixes uniformly, and after through 2.0T magnetic
Field orientation is the most compressing, and through 180MPa isostatic pressed, green compact sinter 4h through 1060 DEG C, and obtaining composition through 560 DEG C of timeliness 5h is
(Nd, Pr, La)15.3(Dy, Tb)0.7Co0.5B5.82FebalThe blank magnet of (atomic percent)；The magnet obtained after timeliness is cut
It is slit into the little square piece of 12mm × 12mm × 4mm as pending magnet.Pending magnet is through the sodium hydroxide of 0.5% mass ratio
Aqueous solution carries out conventional alkali cleaning, then arranges the fluoride powder of R2, the nitrate powder of R3 and the phosphate of R4 on its surface
Powder, R2 is Dy and Tb (Dy and Tb mass ratio is 5: 1), and R3 is Dy and Tb (Dy and Tb mass ratio is 9: 1), and R4 is Tb and Ho
(Tb and Ho mass ratio is 9: 1), three kinds of powder quality percents are respectively 50%, and 25%, 25%, particle mean size is respectively 50 μ
M, 100 μm, 100 μm, by mixed-powder with water quality than 1: 0.5 configuration solution, magnet impregnates 0.5 minute in the solution, then
Take out drying and dehydrating in atmosphere；It is then 10 in dividing potential drop-2The vacuum of Pa carries out 650 DEG C, the heat diffusion treatment of 4 hours, with
After 10-2Pa vacuum carries out 700 DEG C, the Ageing Treatment of 10 hours；The magnet obtained carries out blasting treatment again, and sandblasting uses hard
Degree is the spherical hard particles of 7.0, and average particle size is 1000 μm, and injection gas pressure is 0.4MPa.Test obtains magnet
Magnetic property；The magnet part obtained carries out electronickelling process, and matrix and nickel coating bond strength after test plating, test result is shown in
Table 3.
Embodiment 7
With casting ingot method melting ingot casting A:(Nd, Pr, Ce)19B5.8Febal(atomic percent), uses and gets rid of band technology melting conjunction
Gold, obtains getting rid of band thin slice B:(Nd, Pr)8(Dy, Tb)7Cu6Ga3B6.1Febal(atomic percent), slightly breaks alloy of ingot
Broken, hydrogen crushes, and gets rid of band thin slice and carries out hydrogen and crush, is then slightly mixed by two kinds of powder in mass ratio 7: 3, carry out airflow milling subsequently
Make fine powder, remix uniformly, and after through 1.8T magnetic field orientating compressing, through 200MPa isostatic pressed, green compact are through 1090 DEG C
Sintering 2.5h, obtains composition for (Nd, Pr, Ce)12.9(Dy, Tb)2.1Cu1.8Ga0.9B5.89FebalThe blank magnetic of (atomic percent)
Body；The sintering blank magnet obtained is cut into the little square piece of 12mm × 12mm × 4mm as pending magnet.Pending magnet
Aqueous solution of nitric acid through 2% mass ratio carries out conventional pickling, then arranges the fluoride powder of R2, the nitric acid of R3 on its surface
Salt powder and the phosphate powder of R4, R2 is Dy and Ho (Dy and Ho mass ratio is 100: 1), and R3 is Tb and Ho (Tb and Ho mass
Ratio is 100: 1), R4 is Tb, and three kinds of powder quality percents are respectively 40%, 30%, 30%, particle mean size is respectively 40 μm,
50 μm, 200 μm, by mixed-powder with water quality than 1: 50 configuration solution, magnet impregnates 0.5 minute in the solution, then takes out
Drying and dehydrating in atmosphere；It is then 10 in dividing potential drop-1The vacuum of Pa carries out 700 DEG C, the heat diffusion treatment of 4 hours, exist subsequently
10-1Pa vacuum carries out 450 DEG C, the Ageing Treatment of 6 hours；The magnet obtained carries out blasting treatment again, and sandblasting employing hardness is
The spherical hard particles of 5.0, average particle size is 80 μm, and injection gas pressure is 0.1MPa.Test obtains the magnetic property of magnet；
The magnet part obtained carries out electronickelling process, and matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 8
By getting rid of band technology molten alloy, obtain (Nd, Pm)a(Dy, Tb)bAldVeFe(1-a-b-c-d-e)Bc(a=12, b=
1.5, c=5.9, d=1.0, e=0.5a, b, c, d, e are atomic percent) get rid of band thin slice, band thin slice will be got rid of according to a conventional method
Carry out that hydrogen is broken, airflow milling makes fine powder, remix uniformly, and after through 1.8T magnetic field orientating compressing, through 150MPa etc.
Static pressure, green compact sinter 3.5h through 1070 DEG C, then through 600 DEG C of timeliness 5h, obtain blank magnet.Blank magnet after timeliness is cut
Become the blockage of 12mm × 12mm × 5mm as pending magnet.Pending magnet is through the aqueous sodium carbonate of 2% mass ratio
Carry out conventional alkali cleaning, then be that 2.5% aqueous solution of nitric acid carries out conventional pickling through mass ratio, then arrange the fluorine of R2 on its surface
Compound powder, the nitrate powder of R3 and the phosphate powder of R4, R2 is Tb and Er (Tb and Er mass ratio is 100: 1), and R3 is
Tb and Er (Tb and Er mass ratio is 50: 1), R4 are Tb and Dy (Tb and Dy mass ratio is 4: 1), and three kinds of powder quality percents divide
Not being 30%, 25%, 45%, particle mean size is respectively 30 μm, 150 μm, 50 μm, joins by mixed-powder and ethanol mass ratio 1: 1
Putting solution, magnet impregnates 1 minute in the solution, then takes out and is dried de-ethanol in atmosphere；Then carry out in 1Pa vacuum
750 DEG C, the heat diffusion treatment of 4 hours, in 1Pa vacuum, carry out 550 DEG C subsequently, the Ageing Treatment of 15 hours；The magnet obtained
Carrying out blasting treatment again, the spherical hard particles that sandblasting uses hardness to be 10.0, average particle size is 100 μm, sprays gas pressure
Power is 0.2MPa.Test obtains the magnetic property of magnet；The magnet part obtained carries out electronickelling process, after test plating matrix with
Nickel coating bond strength, test result is shown in Table 3.
Embodiment 9
Molten alloy, obtains composition for (Nd, Sm)a(Dy, Tb)bCudMoeCofFe(1-a-b-c-d-e-f)Bc(a=13, b=
1.0, c=5.8, d=1.0, e=0.5, f=1.0, a, b, c, d, e, f are atomic percent) alloy of ingot, by alloy of ingot
Carry out that coarse crushing, hydrogen is broken, airflow milling makes fine powder according to a conventional method, remix uniformly, and after through 2.0T magnetic field orientating and press
Making type, through 180MPa isostatic pressed, green compact sinter 3h through 1095 DEG C, obtain blank magnet.The blank magnet that will obtain after sintering
Cut into the blockage of 12mm × 12mm × 5mm as pending magnet.Pending magnet is through the sodium carbonate of 3% mass ratio
Solution carries out conventional alkali cleaning, then is that 3.5% aqueous solution of nitric acid carries out conventional pickling through mass ratio, then arranges R2 on its surface
Fluoride powder, the nitrate powder of R3 and the phosphate powder of R4, R2 is Dy and Pr (Dy and Pr mass ratio is 50: 1), R3
For Dy, Tb and Ho (Dy, Tb and Ho mass ratio is 18: 1: 1), R4 is Dy, Tb and Er (Dy, Tb and E r mass ratio is 18: 1: 1),
Three kinds of powder quality percents are respectively 20%, and 10%, 70%, particle mean size is respectively 20 μm, 250 μm, and 250 μm, by mixing
Powder configures solution with ethanol mass ratio 1: 2, and magnet impregnates 1 minute in the solution, then takes out and is dried de-ethanol in atmosphere；
Then in 10Pa vacuum, carry out 800 DEG C, the heat diffusion treatment of 3.5 hours, in 10Pa vacuum, carry out 650 DEG C subsequently, 7 hours
Ageing Treatment；The magnet obtained carries out blasting treatment again, the spherical hard particles that sandblasting uses hardness to be 9.0, average grain
Degree is 200 μm, and injection gas pressure is 0.3MPa.Test obtains the magnetic property of magnet；The magnet part obtained carries out electronickelling
Processing, matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 10
Molten alloy, obtains composition for (Nd, Eu)a(Dy, Tb)bAldNbeFe(1-a-b-c-d-e-f)Bc(a=10, b=2.6, c
=6.0, d=1.5, e=0.5, a, b, c, d, e are atomic percent) alloy of ingot, alloy of ingot is carried out according to a conventional method
Coarse crushing, hydrogen are broken, airflow milling makes fine powder, remix uniformly, and after through 2.2T magnetic field orientating compressing, through 150MPa
Isostatic pressed, green compact sinter 5h through 1085 DEG C, through 620 DEG C of timeliness 3h, obtain blank magnet.The magnet obtained after timeliness is cut into
The blockage of 12mm × 12mm × 8mm is as pending magnet.Pending magnet is through the sodium silicate aqueous solution of 0.5% mass ratio
Carry out conventional alkali cleaning, then be that 2.5% aqueous solution of nitric acid carries out conventional pickling through mass ratio, then arrange the fluorine of R2 on its surface
Compound powder, the nitrate powder of R3 and the phosphate powder of R4, R2 is Tb and Pm (Tb and Pm mass ratio is 40: 1), and R3 is
Dy, Tb and E r (Dy, Tb and Er mass ratio is 20: 9: 1), R4 are Dy, Tb and Ho (Dy, Tb and Ho mass ratio is 20: 9: 1), three
Plant powder quality percent and be respectively 25%, 20%, 55%, particle mean size is respectively 10 μm, 350 μm, and 150 μm, by mixed powder
End configures solution with ethanol mass ratio 1: 5, and magnet impregnates 1 minute in the solution, then takes out and is dried de-ethanol in atmosphere；And
After 10-3Pa argon carries out 850 DEG C, the heat diffusion treatment of 3 hours, in 100Pa vacuum, carry out 480 DEG C subsequently, 13 hours
Ageing Treatment；The magnet obtained carries out blasting treatment again, the spherical hard particles that sandblasting uses hardness to be 8.0, average grain
Degree is 500 μm, and injection gas pressure is 0.5MPa.Test obtains the magnetic property of magnet；The magnet part obtained carries out electronickelling
Processing, matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 11
By getting rid of band technology molten alloy, obtain (Nd, Gd)a(Dy, Tb)bAldCueNbfCogFe(1-a-b-c-d-e-f-g)Bc(a
=14, b=0.5, c=5.8, d=1.0, e=0.5, f=0.5, g=1.2, a, b, c, d, e, f, g are atomic percent) get rid of
Band thin slice, will get rid of band thin slice and carry out that hydrogen is broken, airflow milling makes fine powder according to a conventional method, remix uniformly, and after through 1.8T magnetic
Field orientation is the most compressing, and through 170MPa isostatic pressed, green compact sinter 4h through 1065 DEG C, obtain blank magnet.Obtain after sintering
Blank magnet cut into the blockage of 12mm × 12mm × 8mm as pending magnet.Pending magnet through mass ratio is
3.5% aqueous solution of nitric acid carries out conventional pickling, then arranges the fluoride powder of R2, the nitrate powder of R3 and R4 on its surface
Phosphate powder, R2 is Dy and Sm (Dy and Sm mass ratio is 30: 1), R3 be Dy, R4 be that (Tb and Er mass ratio is 9 to Tb and Er
: 1), three kinds of powder quality percents are respectively 35%, and 15%, 50%, particle mean size is respectively 15 μm, 450 μm, 350 μm, presses
Mixed-powder configures solution with ethanol mass ratio 1: 20, and magnet impregnates 1 minute in the solution, then takes out dry de-in atmosphere
Ethanol；Then 10-2Pa argon carries out 900 DEG C, the heat diffusion treatment of 2 hours, in 50Pa vacuum, carry out 530 DEG C subsequently, 4
Hour Ageing Treatment；The magnet obtained carries out blasting treatment again, the spherical hard particles that sandblasting uses hardness to be 7.0, averagely
Granularity is 1000 μm, and injection gas pressure is 0.6MPa.Test obtains the magnetic property of magnet；The magnet part obtained carries out electricity
Nickel Plating Treatment, matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 12
By getting rid of band technology molten alloy, obtain (Nd, Pr, Y, Sc)aAlcCudVeFe(1-a-b-c-d-e)Bb(a=14.5, b=
5.8, c=1.2, d=2.0, e=0.2, a, b, c, d, e are atomic percent) get rid of band thin slice, will get rid of band thin slice routinely side
Method carries out that hydrogen is broken, airflow milling makes fine powder, remixes uniformly, and after through 1.9T magnetic field orientating compressing, through 200MPa
Isostatic pressed, green compact sinter 5h through 1075 DEG C, and through 620 DEG C of timeliness 4h, obtain blank magnet.The blank magnetic that will obtain after timeliness
Body cuts into the blockage of 12mm × 12mm × 10mm as pending magnet.Pending magnet is through the silicon of 2.5% mass ratio
Acid sodium aqueous solution carries out conventional alkali cleaning, then is that 3.5% aqueous solution of nitric acid carries out conventional pickling, then on its surface through mass ratio
Arrange R2 fluoride powder, the nitrate powder of R3 and the phosphate powder of R4, R2 be Dy and Eu (Dy and Eu mass ratio is 9:
1), R3 be Tb, R4 be Dy, three kinds of powder quality percents are respectively 45%, 15%, 40%, particle mean size is respectively 25 μm,
200 μm, 450 μm, configure solution by mixed-powder with ethanol mass ratio 1: 30, magnet impregnates in the solution 2 minutes, then takes out
It is dried de-ethanol in atmosphere；Then 10-1Pa argon carries out 950 DEG C, the heat diffusion treatment of 1 hour is true at 80Pa subsequently
Carry out 580 DEG C in the air, the Ageing Treatment of 7 hours；The magnet obtained carries out blasting treatment again, and sandblasting uses hardness to be the ball of 6.0
Shape hard particles, average particle size is 2000 μm, and injection gas pressure is 0.7MPa.Test obtains the magnetic property of magnet；Obtain
Magnet part carry out electronickelling process, matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 13
Molten alloy, obtains ingot casting A:(Nd, Pr)15Dy2B5.8Febal(atomic percent), ingot casting B:(Nd, Pr, Eu,
Pm)9(Dy, Tb)7Cu6Mo2Ga2Co4B5.9FebalTwo kinds of ingot castings are the most slightly broken by (atomic percent)
Broken, hydrogen crushes, and the most in mass ratio 4: 1 slightly mix, and carry out airflow milling subsequently and make fine powder, then it is even to be carefully mixed, by 2.0T
Magnetic field orientating is the most compressing, and through 180MPa isostatic pressed, green compact sinter 4h through 1060 DEG C, obtain composition for (Nd, Pr, Eu,
Pm)13.8(Dy, Tb)3Cu1.2Mo0.4Ga0.4Co0.8B5.82FebalThe blank magnet of (atomic percent)；The sintering blank that will obtain
Magnet cuts into the blockage of 12mm × 12mm × 12mm as pending magnet.Pending magnet is through 2.0% mass ratio
Sodium silicate aqueous solution carries out conventional alkali cleaning, then arranges the fluoride powder of R2 on its surface, the nitrate powder of R3 and R4's
Phosphate powder, R2 is Tb, Gd and Ho (Tb, Gd and Ho mass ratio is 18: 1: 1), R3 be Dy, Tb, Ho and Er (Dy, Tb, Ho and
Er mass ratio is 6: 2: 1: 1), R4 is Dy, and three kinds of powder quality percents are respectively 55%, 10%, 35%, particle mean size is respectively
It is 35 μm, 200 μm, 200 μm, configure solution by mixed-powder with ethanol mass ratio 1: 40, magnet impregnates 2 minutes in the solution,
Then take out and be dried de-ethanol in atmosphere；Then in 1Pa argon, carry out 1000 DEG C, the heat diffusion treatment of 30 minutes, subsequently
630 DEG C are carried out, the Ageing Treatment of 5 hours in 20Pa vacuum；The magnet obtained carries out blasting treatment again, and sandblasting employing hardness is
The spherical hard particles of 5.0, average particle size is 3000 μm, and injection gas pressure is 0.8MPa.Test obtains the magnetic of magnet
Energy；The magnet part obtained carries out electronickelling process, and matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 14
Molten alloy, obtains composition for (Nd, Pr, Ce, Sm)a(Dy, Tb)bAldCueGafFe(1-a-b-c-d-e-f)Bc(a=
14.5, b=0.1, c=5.8, d=2.0, e=1.0, f=0.5, a, b, c, d, e, f are atomic percent) alloy of ingot, will
Alloy of ingot carries out that coarse crushing, hydrogen is broken, airflow milling makes fine powder according to a conventional method, remixes uniformly, and after through 2.0T magnetic field
Orientation is the most compressing, and through 180MPa isostatic pressed, green compact sinter 3h through 1095 DEG C, through 520 DEG C of timeliness 5h, obtain blank magnet.
The blank magnet obtained after timeliness is cut into the blockage of 12mm × 12mm × 12mm as pending magnet.Pending magnet
Sodium silicate aqueous solution through 4.0% mass ratio carries out conventional alkali cleaning, then arranges the fluoride powder of R2 on its surface, R3's
Nitrate powder and the phosphate powder of R4, R2 is Dy, Er and Tm (Dy, E r and Tm mass ratio is 18: 1: 1), and R3 is Tb, R4
For Tb, Dy, Ho and Er (Dy, Tb, Ho and Er mass ratio is 7: 1: 1: 1), three kinds of powder quality percents are respectively 65%,
10%, 25%, particle mean size is respectively 75 μm, 300 μm, and 200 μm, by mixed-powder with water quality than 1: 1 configuration solution, magnet
Dipping 5 minutes, then take out drying and dehydrating in atmosphere in the solution；Then in 10Pa argon, carry out 1050 DEG C, 10 minutes
Heat diffusion treatment, subsequently 10-2Pa vacuum carries out 680 DEG C, the Ageing Treatment of 3 hours；The magnet obtained carries out sandblasting again
Processing, the spherical hard particles that sandblasting uses hardness to be 5.0, average particle size is 800 μm, and injection gas pressure is 0.9MPa.
Test obtains the magnetic property of magnet；The magnet part obtained carries out electronickelling process, and after test plating, matrix is combined with nickel coating
Intensity, test result is shown in Table 3.
Embodiment 15
By getting rid of band technology molten alloy, obtain (Nd, Pr, Gd, Tm)aDybFe(1-a-b-c)Bc(a=15.5, b=0.2, c
=5.8, a, b, c are atomic percent) get rid of band thin slice, band thin slice will be got rid of and carry out that hydrogen is broken, airflow milling is made according to a conventional method
Fine powder, remixes uniformly, and after through 2.0T magnetic field orientating compressing, through 180MPa isostatic pressed, green compact are through 1055 DEG C of sintering
5h, obtains blank magnet.The magnet obtained after sintering is cut into the cylinder of Φ 15mm × 15mm as pending magnet.Wait to locate
Reason magnet carries out conventional alkali cleaning through the sodium pyrophosphate aqueous solution of 4.5% mass ratio, then arranges the fluoride of R2 on its surface
Powder, the nitrate powder of R3 and the phosphate powder of R4, R2 be Dy, Tb, Ho and Er (Dy, Tb, Ho and Er mass ratio is 5: 3:
1: 1), R3 is Dy, Tb, Ho and Er (Dy, Tb, Ho and Er mass ratio is 6: 2: 1: 1), and R4 is Dy, Tb, Ho and Er (Dy, Tb, Ho
It is 6: 2: 1: 1 with Er mass ratio), three kinds of powder quality percents are respectively 75%, and 15%, 10%, particle mean size is respectively 65 μ
M, 300 μm, 200 μm, by mixed-powder with water quality than 1: 5 configuration solution, magnet impregnates 10 minutes in the solution, then takes out
Drying and dehydrating in atmosphere；Then 102Carrying out 560 DEG C in Pa argon, the heat diffusion treatment of 3 hours, subsequently 10-2Pa vacuum
In carry out 430 DEG C, the Ageing Treatment of 3 hours；The magnet obtained carries out blasting treatment again, sandblasting use hardness be 6.0 spherical
Hard particles, average particle size is 1200 μm, and injection gas pressure is 1.0MPa.Test obtains the magnetic property of magnet；Obtain
Magnet part carries out electronickelling process, and matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 16
Molten alloy, obtains composition for (Nd, Pr, Yb, Lu)aTbbNddGaeCofFe(1-a-b-c-d-e-f)Bc(a=15, b=
0.5, c=5.9, d=0.5, e=0.5, f=1.5, a, b, c, d, e, f are atomic percent) alloy of ingot, by alloy of ingot
Carry out that coarse crushing, hydrogen is broken, airflow milling makes fine powder according to a conventional method, remix uniformly, and after through 2.0T magnetic field orientating and press
Making type, through 180MPa isostatic pressed, green compact sinter 3.5h through 1085 DEG C, obtain blank magnet.The blank magnetic that will obtain after sintering
Body cuts into the cylinder of Φ 18mm × 18mm as pending magnet.Pending magnet is through the sodium carbonate of 5.0% mass ratio
Solution carries out conventional alkali cleaning, then arranges the fluoride powder of R2, the nitrate powder of R3 and the phosphoric acid salt fines of R4 on its surface
End, R2 is Dy, Tb and Ho (Dy, Tb and Ho mass ratio is 18: 1: 1), and R3 is Dy and Tb (Dy and Tb mass ratio is 4: 1), and R4 is
Tb, Dy, Ho and Er (Dy, Tb, Ho and Er mass ratio is 40: 8: 1: 1), three kinds of powder quality percents are respectively 20%, and 15%,
65%, particle mean size is respectively 45 μm, 100 μm, 300 μm, and by mixed-powder with water quality than 1: 20 configuration solution, magnet is molten
Liquid impregnates 5 minutes, then takes out drying and dehydrating in atmosphere；Then 103Pa argon carries out 680 DEG C, the heat of 12 hours
DIFFUSION TREATMENT, subsequently 10-3Pa vacuum carries out 400 DEG C, the Ageing Treatment of 18 hours；The magnet obtained is carried out at sandblasting again
Reason, the spherical hard particles that sandblasting uses hardness to be 7.0, average particle size is 1500 μm, and injection gas pressure is 0.5MPa.Survey
Examination obtains the magnetic property of magnet；The magnet part obtained carries out electronickelling process, and after test plating, matrix is combined by force with nickel coating
Degree, test result is shown in Table 3.
Embodiment 17
By getting rid of band technology molten alloy, obtain (Nd, Pr, Ho, Er, Gd, Eu, Pm)aAlcCudFe(1-a-b-c-d)Bb(a=
16.5, b=5.8, c=1.2, d=0.8, a, b, c, d are atomic percent) get rid of band thin slice, band thin slice will be got rid of according to a conventional method
Carry out that hydrogen is broken, airflow milling makes fine powder, remix uniformly, and after through 2.1T magnetic field orientating compressing, through 170MPa etc.
Static pressure, green compact sinter 4h through 1062 DEG C, obtain blank magnet.The magnet obtained after sintering is cut into the circle of Φ 20mm × 25mm
Post is as pending magnet.Pending magnet carries out conventional pickling, then at its table through the aqueous solution of nitric acid of 5.0% mass ratio
The fluoride powder of R2 is arranged in face, and the nitrate powder of R3 and the phosphate powder of R4, R2 is Dy, Tb and Er (Dy, Tb, Er matter
Amount ratio is 30: 9: 1), R3 is Dy, Tb, Ho and Er (Dy, Tb, Ho and Er mass ratio is 40: 8: 1: 1), and R4 is Dy, Tb (Dy, Tb
Mass ratio is 3: 2), three kinds of powder quality percents are respectively 20%, and 20%, 60%, particle mean size is respectively 55 μm, 150 μm,
300 μm, by mixed-powder with water quality than 1: 30 configuration solution, magnet impregnates 40 seconds in the solution, then takes out in atmosphere
Drying and dehydrating；Then 10-2Carrying out 780 DEG C in Pa vacuum, the heat diffusion treatment of 15 hours, subsequently 10-4Pa vacuum is carried out
500 DEG C, the Ageing Treatment of 30 minutes；The magnet obtained carries out blasting treatment again, the spherical hard that sandblasting uses hardness to be 8.0
Grain, average particle size is 2500 μm, and injection gas pressure is 0.6MPa.Test obtains the magnetic property of magnet；The magnet portion obtained
Dividing and carry out electronickelling process, matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Embodiment 18
By getting rid of band technology molten alloy, obtain NdaAlcCudGaeNbfVgMohCoiFe(1-a-b-c-d-e-f-g-h-i)Bb(a=
15.5, b=5.9, c=1.0, d=0.5, e=0.3, f=0.3, g=0.2, h=0.2, i=1.0, a, b, c, d, e, f, g, h,
I is atomic percent) get rid of band thin slice, band thin slice will be got rid of and carry out that hydrogen is broken, airflow milling makes fine powder according to a conventional method, remix
Uniformly, and after through 2.0T magnetic field orientating compressing, through 180MPa isostatic pressed, green compact sinter 6h through 1055 DEG C, obtain blank
Magnet.The magnet obtained after sintering is cut into the cylinder of 25mm × 25mm × 20mm as pending magnet.Pending magnet
Aqueous solution of nitric acid through 4.0% mass ratio carries out conventional pickling, then arranges the fluoride powder of R2, the nitre of R3 on its surface
Hydrochlorate powder and the phosphate powder of R4, R2 be Dy, Tb, Ho, Er and Ce (Dy, Tb, Ho, Er and Ce mass ratio is 40: 7: 1: 1:
1), R3 is Dy, Tb, Ho and Er (Dy, Tb, Ho and Er mass ratio is 30: 8: 1: 1), and R4 is Dy, Tb and Ho (Dy, Tb and Ho mass
Ratio is 15: 4: 1), three kinds of powder quality percents are respectively 30%, and 15%, 55%, particle mean size is respectively 85 μm, 50 μm,
100 μm, by mixed-powder with water quality than 1: 40 configuration solution, magnet impregnates 50 seconds in the solution, then takes out in atmosphere
Drying and dehydrating；Then 10-3Pa vacuum carries out 880 DEG C, the heat diffusion treatment of 18 hours, carry out in 10Pa vacuum subsequently
600 DEG C, the Ageing Treatment of 2 hours；The magnet obtained carries out blasting treatment again, the spherical hard that sandblasting uses hardness to be 10.0
Grain, average particle size is 3500 μm, and injection gas pressure is 0.7MPa.Test obtains the magnetic property of magnet；The magnet portion obtained
Dividing and carry out electronickelling process, matrix and nickel coating bond strength after test plating, test result is shown in Table 3.
Table 3 magnet is through different disposal magnetic property, bond strength (matrix and nickel coating) result table
It is to be understood that, foregoing invention content and detailed description of the invention are intended to prove technical scheme provided by the present invention
Actual application, should not be construed as limiting the scope of the present invention.Those skilled in the art are in spirit and principles of the present invention
In, when can various modifications may be made, equivalent or improvement.Protection scope of the present invention is as the criterion with appended claims.
Claims (10)
1. the preparation method of a rare-earth permanent magnet, it is characterised in that:
First the phosphatic powder of the fluoride containing R2, the nitrate of R3 and R4 is dissolved in water or alcohol and is prepared as solution；
Above-mentioned solution is evenly arranged pending magnet surface；
Then pending magnet is dehydrated or alcohol processes；
Finally it is diffused pending magnet being thermally treated resulting in magnet after process,
Described R2 is at least one in rare earth element, R3 and R4 is one or more in Tb, Dy, Ho or Er,
Described R2, R3 and R4 is at least one in Tb or Dy.
2. the preparation method of rare-earth permanent magnet as claimed in claim 1, it is characterised in that: described R2 is Tb, Dy, Ho or Er
In one or more.
3. the preparation method of rare-earth permanent magnet as claimed in claim 1, it is characterised in that: the fluoride of R2 in described powder
Content is at least mass ratio 20%, and the nitrate content of R3 is at least mass ratio 10%, and the phosphate content of R4 is at least quality
Ratio 10%；Dy, Tb total content in the powder is at least atomic ratio 15%.
4. the preparation method of rare-earth permanent magnet as claimed in claim 1, it is characterised in that: the fluoride powder grain of described R2
Degree is not more than 100 μm, and the nitrate powder of R3 and the phosphate powder granularity of R4 are not more than 500 μm.
5. the preparation method of rare-earth permanent magnet as claimed in claim 1, it is characterised in that: described solution according to powder and water or
Alcohol carries out proportioning by the mass ratio of 1: 0.5～1: 50.
6. the preparation method of rare-earth permanent magnet as claimed in claim 1, it is characterised in that: described diffusion heat treatments is 10-5Pa
～under the vacuum condition of 10Pa or 10-3Pa～105Carrying out under the inert gas conditions of Pa dividing potential drop, noble gas is argon, at heat
Reason temperature is higher than 500 DEG C, and less than the sintering temperature of pending magnet, heat treatment temperature retention time is 10 minutes to 20 hours.
7. the preparation method of rare-earth permanent magnet as claimed in claim 1, it is characterised in that: described preparation method be additionally included in by
The acid of pending magnet or alkali liquor are carried out before being evenly arranged pending magnet surface by above-mentioned solution；To magnetic after processing
Body is 400～700 DEG C in heating-up temperature, and 10 minutes to 20 hours heat time heating time, vacuum condition is 10-5Under the conditions of Pa～100Pa
Carry out Ageing Treatment；Magnet after Ageing Treatment is carried out acid, alkali liquor is washed, or is ground or sand blasted surface process；To surface
After reason, magnet is carried out and plating or coating.
8. the preparation method of rare-earth permanent magnet as claimed in claim 7, it is characterised in that: sand-blasting abrasive in sand blasted surface process
Selecting Mohs' hardness to be at least the hard particles of 5.0, described hard particles is spheroidal particle, and average particle size is at 40～4000 μ
M, injection gas pressure is 0.1～1.0MPa.
9. the preparation method of the rare-earth permanent magnet as according to any one of claim 1-8, it is characterised in that: described is pending
Magnet is the magnet that cleaved or grinding one-tenth the minimum edge of blank magnet is not more than 20mm.
10. the rare-earth permanent magnet that prepared by a method as according to any one of claim 1-9, it is characterised in that: described rare earth
Permanent magnet comprises composition R-T-B, and has R2T14B1Principal phase structure, and surround principal phase structure Nd-rich phase crystal boundary, its
Middle R is the one in rare earth element, and R at least contains Nd；T is Fe, or T also comprise in addition to comprising Fe Co, Al, Cu, Nb, Ga,
At least one in Mo, V element.
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| CN201110024823.4A CN102610355B (en) | 2011-01-24 | A kind of rare-earth permanent magnet and preparation method thereof |
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|---|---|---|---|---|
| EP0924715A2 (en) * | 1997-12-19 | 1999-06-23 | Shin-Etsu Chemical Co., Ltd. | Rare earth-based permanent magnet of high corrosion resistance |
| CN1898757A (en) * | 2004-10-19 | 2007-01-17 | 信越化学工业株式会社 | Method for producing rare earth permanent magnet material |
| CN101276666A (en) * | 2007-03-29 | 2008-10-01 | 日立化成工业株式会社 | Treating solution for forming fluoride coating film and method for forming fluoride coating film |
| CN101640087A (en) * | 2008-07-04 | 2010-02-03 | 大同特殊钢株式会社 | Rare earth magnet and production process thereof |
| CN101178964B (en) * | 2006-09-29 | 2011-01-05 | 日立化成工业株式会社 | Treating agent for forming a fluoride coating film and method for forming a fluoride coating film |
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|---|---|---|---|---|
| EP0924715A2 (en) * | 1997-12-19 | 1999-06-23 | Shin-Etsu Chemical Co., Ltd. | Rare earth-based permanent magnet of high corrosion resistance |
| CN1898757A (en) * | 2004-10-19 | 2007-01-17 | 信越化学工业株式会社 | Method for producing rare earth permanent magnet material |
| CN101178964B (en) * | 2006-09-29 | 2011-01-05 | 日立化成工业株式会社 | Treating agent for forming a fluoride coating film and method for forming a fluoride coating film |
| CN101276666A (en) * | 2007-03-29 | 2008-10-01 | 日立化成工业株式会社 | Treating solution for forming fluoride coating film and method for forming fluoride coating film |
| CN101640087A (en) * | 2008-07-04 | 2010-02-03 | 大同特殊钢株式会社 | Rare earth magnet and production process thereof |
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