CN104036897B - A kind of permanent-magnet material and its manufacture method - Google Patents

A kind of permanent-magnet material and its manufacture method Download PDF

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CN104036897B
CN104036897B CN201310073159.1A CN201310073159A CN104036897B CN 104036897 B CN104036897 B CN 104036897B CN 201310073159 A CN201310073159 A CN 201310073159A CN 104036897 B CN104036897 B CN 104036897B
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magnet
magnet material
permanent
blank
temperature
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CN104036897A (en
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王浩颉
赵玉刚
张瑾
孙立柏
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SANVAC (BEIJING) MAGNETICS CO Ltd
Beijing Zhong Ke San Huan High Tech Co Ltd
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SANVAC (BEIJING) MAGNETICS CO Ltd
Beijing Zhong Ke San Huan High Tech Co Ltd
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Abstract

A kind of permanent-magnet material, its composition are RXMYBZFe100‑X‑Y‑Z, wherein:R is Pr, Nd, Dy, two kinds in Tb, Ho or two or more;M is Co, Cu, Al, Ga, Zr, two or more in Nb;X, Y, Z be each element percentage by weight, 29.5wt%≤X≤33wt%, 1wt%≤Y≤3.5wt%, 0.97wt%≤Z≤1.20wt%.Its manufacture method is to carry out second level tempering process to it again after the blank magnet come out of the stove is worked into required size.The permanent-magnet material and manufacture method of the present invention can be such that the magnet surface richness neodymium of machining damage is mutually repaired, so that the uniformity for the sheet magnet product magnetic property produced in enormous quantities, uniformity is improved, and corrosion resistance is improved.

Description

A kind of permanent-magnet material and its manufacture method
Technical field
The present invention relates to a kind of permanent-magnet material and its manufacture method, more particularly to a kind of sheet agglomeration permanent magnetic material and Its manufacture method.
Background technology
Sintered NdFeB magnet is due to high remanent magnetism and high-coercive force magnetic property, having become in modern industrial production not The material that can or lack, its application field are very extensive.Although sintered neodymium iron boron material has a very high magnetic property, but with other permanent magnetism Material such as Sm-Co magnets are compared, and its corrosion resistance is poor, limit its application.The corrosion of Sintered NdFeB magnet mainly from The rich neodymium of magnet surface mutually starts, and is constantly spread along the opposite material internal of crystal boundary, the final efflorescence and oxidation for producing surface, leads Magnet loss of excitation is caused to occur.Therefore say the surface state of magnet, partly determine product magnetic property and corrosion resistance it is excellent. Some sintered NdFeB application high-tech areas, as used in green home appliance class Sintered NdFeB magnet used for air compressor and automobile EPS Sintered NdFeB magnet, its specification shape are all flakes.Its feature is exactly that the magnetizing direction of magnet is smaller, generally 1~ 3.5mm, other both directions will be far longer than magnetizing direction, generally 15~65mm.Due to the particularity of its shape, product Specific surface area is larger, and relative to bulk magnet, sheet magnet is more sensitive to surface state.Its surface of sintered NdFeB magnet The enrichment of rich neodymium phase is had, for sheet magnet, need to typically pass through the manufacturing procedure from blank to finished product.In processing work Sequence, is either cut or grinding technique to blank, is all the damage to blank surface, so as to reduce product Performance.Simultaneously because the damage of superficial layer, matrix is easier to corrode with the external world, so as to influence decay resistance.It is in addition, right In sheet type product magnet, typically there is the low requirement of high temperature flux loss.It is therefore desirable to sheet magnet coercivity is high and high Warm magnetic energy curvilinear squares degree is good.The method of generally compacting sheet magnet is progress thin slice processing after compacting bulk blank, When having difference for the coercivity of its magnet of bulk blank inside diverse location, therefore producing in enormous quantities, sheet magnet Magnetic property uniformity and uniformity can be affected.
It is that corrosion resistant diaphragm is formed on surface for current solution Sintered NdFeB magnet anti-corrosion method, such as electroplates Ni or Pization layer.For sheet magnet, the general method for using Pization layer.But if only by diaphragm, can not be complete Complete solution is determined etching problem, if the corrosion resistance of magnet itself improves, it will greatly improve the corrosion resistance of product, while its magnetic Can also it be guaranteed.
Patent ZL200710114562.9 discloses one kind by using anaerobic technique, controls oxygen, nitrogen, hydrogen in magnet to contain Amount, finally give the magnet of excellent corrosion resistance.ZL200610038444.X patents disclose one kind and added by dual alloy mode Nd Kiev alloy with amorphous formation ability obtains the magnet of fine corrosion resistance as intergranular phase.This two patent skills Although art can obtain the blank magnet of excellent corrosion resistance, for the sheet type product after processing, its surface richness neodymium phase After manufacturing procedure is by partial destruction, then the magnetic property of product and corrosion resistance influence all to reduce.
ZL200910235436.8 provides a kind of new sintering aging technique for semi-finished product, but the technique pair of its offer Larger cracking risk is had in sheet type product.Because sheet type product is relatively thin along differently- oriented directivity, and sintered neodymium iron boron material Its anisotropy is strong in the orientation direction, is easily broken along differently- oriented directivity.Therefore, relatively thin product is when high-temperature aging is handled Cooling procedure easily cracks, and influences the ultimate yield rate of product.
The content of the invention
Present invention aims at for sheet permanent-magnet material, particularly sheet Sintered NdFeB magnet process institute The defects of corrosion resistance, homogeneity of product and uniformity and magnetic property reduction brought, there is provided a kind of product corrosion resistance, consistent The permanent magnet and its manufacture method that uniformity and magnetic property are significantly improved.
A kind of permanent-magnet material, its composition include rare-earth element R, iron Fe, boron and addition element M, it is characterised in that:It is described The composition of permanent-magnet material is RXMYBZFe100-X-Y-Z, wherein:
R is Pr, Nd, Dy, two kinds or two or more element combinations in Tb, Ho;
M is Co, Cu, Al, Ga, Zr, two or more element in Nb
X, Y, Z be each element percentage by weight, 29.5wt%≤X≤33wt%, 1wt%≤Y≤3.5wt%, 0.97wt%≤ Z≤1.20wt%。
Preferably, the permanent-magnet material also includes 500~3500ppm oxygen.
A kind of method of permanent-magnet material described in manufacturing claims 1, including dispensing-molten alloy-crush-are pressed into Type-sintering-first order tempering process, it is characterised in that:After first order tempering process, the blank magnet come out of the stove is worked into Second level tempering process is carried out to it again after required size.
Preferably, described second level tempering process is that vacuum sintering furnace is evacuated into 10-3Is warming up to after below Pa 470~520 DEG C of second annealing temperature, 4~6 hours are incubated at this temperature, then rapid applying argon gas are cooled to room temperature and come out of the stove.
Preferably, the blank magnet surface after processing is cleaned before described second level tempering process.
Preferably, the blank magnet after processing is piled up in closed magazine before described second level tempering process.
Preferably, described closed magazine still at least retains 1/10 space after the blank magnet after piling up processing and not put Material.
Preferably, described molten alloy is molten alloy ingot or gets rid of band using rapid hardening slice technique melting rapid hardening alloy Piece.
Preferably, it is described to be broken for that molten alloy is broken into middle powder using HD process, then with airflow milling will in Fine powder is made in powder.
Preferably, described powder particle size is 3.7~4.0 μm.
Preferably, it is described compressing for fine powder is pressed into after bulk blank again with isostatic pressing machine pressure with vertical press System.
Preferably, the described temperature that is sintered to is 1040~1065 DEG C, and the time is 3~6 hours.
Preferably, described first order tempering process is to be incubated 2~2.5 hours at a temperature of 900~950 DEG C.
Preferably, the material of described closed magazine is graphite or metal magazine, such as tinplate.
Preferably, after first order tempering process, the blank magnet come out of the stove is processed into the thin slice magnetic that thickness is 2~5mm Body.
Preferably, the thickness direction of the thin slice magnet is differently- oriented directivity.
Present invention is specifically directed to the characteristics of thin slice Sintered NdFeB magnet, the second level lonneal of aging technique is placed Carry out after machining, the magnet surface richness neodymium of machining damage is mutually repaired, so that the sheet produced in enormous quantities The uniformity of magnet product magnetic property, uniformity is improved, and corrosion resistance is improved.Meanwhile in processing procedure The magazine of high vacuum environment and good airproof performance, it ensure that the sheet product surface color after processing will not produce change.So as to this Sheet product after sample processing can be used as semi-finished product to carry out next step surface treatment procedure or direct without being surface-treated Used as finished product.
Embodiment
Sintered NdFeB magnet described in the method for the present invention, consisting of RXMYBZFe100-X-Y-Z, wherein:
R is Pr, Nd, Dy, two kinds or two or more element combinations in Tb, Ho;
M is Co, Cu, Al, Ga, Zr, two or more element in Nb;
X, Y, Z be each element percentage by weight, 29.5wt%≤X≤33wt%, 1wt%≤Y≤3.5wt%, 0.97wt%≤ Z≤1.20wt%.Also include 500~3500ppm oxygen in magnet.
According to this proportioning melting steel ingot, alloy breaks down and powder processed are carried out with airflow milling powder equipment using hydrogen is broken, through pressure Machine slug press bulk, is sintered in vacuum sintering furnace, the bulk blank after sintering, at first order tempering process Reason, its temperature are 900~950 DEG C, are incubated 2~2.5h(Hour)Afterwards, room temperature is rapidly cooled to come out of the stove.Machine is carried out to this blank to add After work process, after being worked into sheet type product size, product code is placed on to clean graphite grazing magazine or metal sealing magazine, Certain space is left in magazine.Then vacuumized in vacuum sintering furnace, vacuum enters 10-3Started to warm up after below Pa To 470~520 DEG C of second level temperature, 4~6h is incubated under high vacuum environment, then rapid applying argon gas are cooled to room temperature and gone out Stove.
According to this inventive method, sheet Sintered NdFeB magnet product after treatment, its decay resistance obtains Improve, it is low that the high temperature of the large quantities of products subtracts magnetic, and uniformity is good.
Certain specific embodiments of the invention are given below.
Embodiment 1:According to percentage by weight Nd19.5Pr6.5Dy4.1Tb0.4B1.1Cu0.8Co1Ga0.1Nb0.1Zr0.1FebalComposition Dispensing, FebalExpression surplus is iron, then molten alloy ingot, melted alloy pig is broken into middle powder with HD process, so Powder in this is worn into fine powder with airflow milling afterwards, the powder size of the fine powder is controlled at 3.8 μm, and fine powder is pressed into vertical press Bulk blank, blank specification are 33mmx51mmx32mm(32 directions are differently- oriented directivity), then by isostatic pressed raising green density Afterwards, blank is piled up in magazine, is sent into vacuum sintering furnace and is sintered, 1050 DEG C of sintering temperature, be incubated 4 hours, cooling First order tempering process, 920 DEG C of temperature, soaking time 2 hours, tempering rapid argon filling air-blowing after terminating are carried out after to room temperature Come out of the stove to room temperature.Blank after processing is processed into 33mmx12.5mmx3mm thin slice by slicing process, 3mm is differently- oriented directivity. The processing liquid that sheet surface remains is cleaned up, after drying surface, thin slice magnet is piled up in sealed graphite magazine, 1/10 space not blowing is at least left in magazine.The magazine piled up is put into vacuum sintering furnace and vacuumized, vacuum Reach 10-3Started to warm up after below Pa to 480 DEG C of second level temperature, be incubated 5 hours under high vacuum environment, then rapidly Applying argon gas are cooled to room temperature and come out of the stove into final products.Oxygen content is 1200ppm in product.
Comparative example 1:Using the technical process of formula the same manner as in Example 1 as, but the first order is tempered and second Level drawing process is carried out continuously, and centre is not come out of the stove and blank is processed.After the completion for the treatment of second level tempering, magnet is cut into slices It is processed into 33mmx12.5mmx3mm final products.
The final products of 32 embodiments 1 and comparative example 1 are taken to be contrasted after magnetizing respectively.Measure 20 DEG C of temperature respectively first Normal temperature flux value under degree, is then placed into putting baking oven on aluminium sheet into, is warming up to 150 DEG C, and insulation takes out cooling after 2 hours, point Not Ce Liang sample 20 DEG C of high temperature flux value is cooled to after high-temperature baking, calculate magnetic flux demagnetizing factor.
Magnetic flux demagnetizing factor=(Normal temperature flux value-high temperature flux value)/ normal temperature flux value * 100%
Maximum magnetic flux demagnetizing factor is the maximum of magnetic flux demagnetizing factor in 32 samples, and minimum magnetic flux demagnetizing factor is 32 samples The minimum value of middle magnetic flux demagnetizing factor.Average demagnetizing factor is all 32 demagnetizing factor average values.
Taking the final products of 5 embodiments 1 and comparative example 1 to carry out corrosion resistance respectively accelerates weightless contrast experiment to measure production The weightlessness of product, experiment condition are to be placed 96 hours under 121 DEG C, 2 atmospheric pressure, 100% relative humidity.Weightless definition is:Lose Weight(mg/cm2)=(W1-W0)/S0.Wherein:W0For the weight before sample test, W1After room temperature being cooled to for sample afterwards after tested Weight, S0For the surface area before sample test.The embodiment 1 measured and the weightless value of the sample of comparative example 1 are subjected to arithmetic average After obtain average weightless value.
Experimental result is shown in Table 1.
Embodiment 2:According to percentage by weight Nd19.0Pr7.0Dy1.0Tb2.5B0.97Cu0.8Co1.2Ga0.1Nb0.3Zr0.3FebalMatch somebody with somebody Material, then carry out getting rid of band melting using rapid hardening slice technique, the alloy sheet thrown away is broken into middle powder with HD process, then Powder in this is worn into fine powder with airflow milling, the powder size of the fine powder is controlled at 3.7 μm, and fine powder is suppressed into bulk with vertical press Blank, blank specification 33mmx51mmx32mm(32 directions are differently- oriented directivity), then after isostatic pressed improves green density, by hair Base is piled up in magazine, into vacuum sintering furnace in be sintered, 1040 DEG C of sintering temperature, be incubated 3h(Hour), it is cooled to room First order tempering process, 930 DEG C, soaking time 2.5h of temperature are carried out after temperature, tempering terminates rear rapid applying argon gas and is blown to room Temperature is come out of the stove.Blank after processing is processed into 33mmx12.5mmx3mm thin slice by slicing process, 3mm is differently- oriented directivity,.Will The processing liquid of sheet surface residual cleans up, and after drying surface, thin slice magnet is piled up in sealed graphite magazine, expected 1/10 space not blowing is at least left in box.The magazine piled up is put into vacuum sintering furnace and vacuumized, vacuum reaches To 10-3Started to warm up after below Pa to 470 DEG C of second level temperature, 6h is incubated under high vacuum environment, then rapid argon filling Air cooling to room temperature comes out of the stove into final products.Oxygen content is 500ppm in product.
Comparative example 2:Using the technical process of formula the same manner as in Example 2 as, but the first order is tempered and second Level drawing process is carried out continuously, and centre is not come out of the stove and blank is processed.After the completion for the treatment of second level tempering, carry out section and add Product thin slice of the work into 33mmx12.5mmx3mm.
Take the final products of 32 embodiments 2 and comparative example 2 to measure magnetic flux demagnetizing factor after magnetizing respectively to be contrasted.Respectively The final products of 5 embodiments 2 and comparative example 2 are taken to carry out the weightlessness that corrosion resistance accelerates weightless contrast experiment to measure product, meter Calculate average weightlessness.Experimental method and experiment condition are identical with embodiment 1 and comparative example 1.
Experimental result is shown in Table 1.
Embodiment 3:According to percentage by weight Nd20.0Pr7Dy4.0Tb2.0B1.1Cu0.2Co0.8FebalDispensing, then molten alloy Ingot, melted alloy pig is broken into middle powder with HD process, powder in this is then worn into fine powder with airflow milling, the fine powder Powder size is controlled at 4.0 μm, and fine powder is suppressed into bulk blank, blank specification 33mmx51mmx32mm with vertical press(32 sides To for differently- oriented directivity), then after isostatic pressed improves green density, blank is piled up in magazine, into vacuum sintering furnace It is sintered, 1065 DEG C of sintering temperature, is incubated 4.5h, first order tempering process, temperature 920 is carried out after being cooled to room temperature DEG C, soaking time 2h, tempering after terminating rapid applying argon gas be blown to room temperature and come out of the stove.Blank after processing is processed by slicing process Into 33mmx12.5mmx2mm thin slice, 2mm is differently- oriented directivity.The processing liquid that sheet surface remains is cleaned up, dries table Behind face, thin slice magnet is piled up in tinplate material magazine is sealed, 1/10 space not blowing is at least left in magazine.By code The magazine put well, which is put into vacuum sintering furnace, to be vacuumized, and vacuum reaches 10-3Start to warm up to the second level and return after below Pa Fiery 490 DEG C of temperature, is incubated 4.5h, then rapid applying argon gas are cooled to room temperature and come out of the stove into final products under high vacuum environment.Production Oxygen content is 2000ppm in product.
Comparative example 3:Using the technical process of formula the same manner as in Example 3 as, but the first order is tempered and second Level drawing process is carried out continuously, and centre is not come out of the stove and blank is processed.After the completion for the treatment of second level tempering, carry out section and add Product thin slice of the work into 33mmx12.5mmx2mm.
Take the final products of 32 embodiments 3 and comparative example 3 to measure magnetic flux demagnetizing factor after magnetizing respectively to be contrasted.Respectively The final products of 5 embodiments 3 and comparative example 3 are taken to carry out the weightlessness that corrosion resistance accelerates weightless contrast experiment to measure product, meter Calculate average weightlessness.Experimental method and experiment condition are identical with embodiment 1 and comparative example 1.
Experimental result is shown in Table 1.
Embodiment 4:According to percentage by weight Nd19.0Pr8Dy4.0Tb0.2B1.2Cu0.8Co1.0Ga0.1Nb0.2Zr0.2FebalDispensing Carry out getting rid of band melting using rapid hardening slice technique afterwards, the alloy sheet thrown away is broken into middle powder with HD process, then by this Middle powder wears into fine powder with airflow milling, and the fine powder powder size is controlled at 3.8 μm, and fine powder is suppressed into bulk blank with vertical press, Blank specification 33mmx51mmx32mm(32 directions are differently- oriented directivity), then after isostatic pressed improves green density, by blank code Base is bled off pressure in magazine, into vacuum sintering furnace in be sintered, 1060 DEG C of sintering temperature, be incubated 5h, it is laggard to be cooled to room temperature Row first order tempering process, 950 DEG C, soaking time 2h of temperature, tempering after terminating rapid applying argon gas be blown to room temperature and come out of the stove.Will Blank is processed into 33mmx12.5mmx5mm product thin slice by slicing process after processing, and 5mm is differently- oriented directivity.By thin slice table The processing liquid of face residual cleans up, and after drying surface, thin slice magnet is piled up in tinplate material magazine is sealed, expected 1/10 space not blowing is at least left in box.The magazine piled up is put into vacuum sintering furnace and vacuumized, vacuum reaches To 10-3Started to warm up after below Pa to 520 DEG C of second level temperature, 4.5h is incubated under high vacuum environment, is then filled rapidly Argon gas is cooled to room temperature and comes out of the stove into final products.Oxygen content is 3500ppm in product.
Comparative example 4:Using the technical process of formula the same manner as in Example 3 as, but the first order is tempered and second Level drawing process is carried out continuously, and centre is not come out of the stove and blank is processed.After the completion for the treatment of second level tempering, carry out section and add Product thin slice of the work into 33mmx12.5mmx5mm.
Take the final products of 32 embodiments 4 and comparative example 4 to measure magnetic flux demagnetizing factor after magnetizing respectively to be contrasted.Respectively The final products of 5 embodiments 4 and comparative example 4 are taken to carry out the weightlessness that corrosion resistance accelerates weightless contrast experiment to measure product, meter Calculate average weightlessness.Experimental method and experiment condition are identical with embodiment 1 and comparative example 1.
Experimental result is shown in Table 1.
The embodiment of table 1 and comparative example assay
In terms of the result of table 1, embodiment sheet product its high temperature demagnetizing factor handled by this invented technology is less than comparative example High temperature demagnetizing factor, and uniformity is good.The decay resistance of embodiment thin slice magnet is better than comparative example.
Comparative example 5:Using technical process of the formula the same manner as in Example 3 with as, it is its 920 DEG C of first order height Warm drawing process is placed on to being carried out after blank slice processing process.Use and the identical work of patent 200910235436.8 Skill, bulk blank is processed into flakiness magnet after the completion of sintering circuit, then carrying out the continuous first order to thin slice magnet returns Fire and second level drawing process.
100 flake products are respectively chosen from the final products of embodiment 3 and comparative example 5 and carry out appearance test, wherein discovery table What there was a micro-crack in face is all included in defective work, and the defective work ratio of statistical result showed embodiment 3 is 1%, and comparative example 5 does not conform to Lattice product ratio is 20%.As a result show, the product appearance qualification rate of embodiment 3 is obviously improved.

Claims (14)

1. a kind of method for manufacturing permanent-magnet material,
The composition of the permanent-magnet material includes rare-earth element R, iron Fe, boron and addition element M, the composition of the permanent-magnet material RXMYBZFe100-X-Y-Z, wherein:
R is Pr, Nd, Dy, two kinds or two or more element combinations in Tb, Ho;
M is Co, Cu, Al, Ga, Zr, two or more element in Nb;
X, Y, Z be each element percentage by weight, 29.5wt%≤X≤33wt%, 1wt%≤Y≤3.5wt%, 0.97wt% ≤ Z≤1.20wt%,
Methods described includes dispensing-molten alloy-broken-compressing-sintering-first order tempering process, it is characterised in that: After first order tempering process, second is carried out to it again after the blank magnet come out of the stove is worked into the thin slice magnet that thickness is 2~5mm Level tempering process.
2. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:Described second level tempering process is will Vacuum sintering furnace is evacuated to 10-3470~520 DEG C of second level temperature is warming up to after below Pa, at this temperature be incubated 4~ 6 hours, then rapid applying argon gas be cooled to room temperature and come out of the stove.
3. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:The described second level is the same as right before firer's sequence Blank magnet surface after processing is cleaned.
4. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:Will before described second level tempering process Blank magnet after processing is piled up in closed magazine.
5. the method for manufacture permanent-magnet material as claimed in claim 4, it is characterised in that:Described closed magazine is piling up processing Still at least retain 1/10 space not blowing after blank magnet afterwards.
6. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:Described molten alloy is molten alloy Ingot gets rid of strap using rapid hardening slice technique melting rapid hardening alloy.
7. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:It is described to be broken for using HD process Molten alloy is broken into middle powder, fine powder then is made in middle powder with airflow milling.
8. the method for manufacture permanent-magnet material as claimed in claim 7, it is characterised in that:Described powder particle size is 3.7~4.0 μm。
9. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:Described is compressing for the vertical pressure of use Fine powder is pressed into after bulk blank and suppressed again with isostatic pressing machine by machine.
10. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:Described is sintered to temperature as 1040 ~1065 DEG C, the time is 3~6 hours.
11. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:Described first order tempering process is 2~2.5 hours are incubated at a temperature of 900~950 DEG C.
12. the method for the manufacture permanent-magnet material as described in claim 4 or 5, it is characterised in that:The material of described closed magazine For graphite or metal magazine.
13. the method for manufacture permanent-magnet material as claimed in claim 12, it is characterised in that:The material of described closed magazine is Tinplate.
14. the method for manufacture permanent-magnet material as claimed in claim 1, it is characterised in that:The thickness direction of the thin slice magnet For differently- oriented directivity.
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CN107731437B (en) * 2017-10-30 2019-10-15 北京工业大学 A method of reducing sintered NdFeB thin slice magnet irreversible loss
CN108831650B (en) * 2018-06-21 2020-10-23 宁波可可磁业股份有限公司 Neodymium-iron-boron magnet and preparation method thereof
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