CN1068953C - Method of preparing rare-earth ferrronitrides permanent megnet material - Google Patents
Method of preparing rare-earth ferrronitrides permanent megnet material Download PDFInfo
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- CN1068953C CN1068953C CN98102207A CN98102207A CN1068953C CN 1068953 C CN1068953 C CN 1068953C CN 98102207 A CN98102207 A CN 98102207A CN 98102207 A CN98102207 A CN 98102207A CN 1068953 C CN1068953 C CN 1068953C
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- earth
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- mechanical alloying
- ferrronitrides
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- 239000000463 material Substances 0.000 title claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 title claims description 12
- 238000000034 method Methods 0.000 title abstract description 12
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 229910000859 α-Fe Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005121 nitriding Methods 0.000 claims description 7
- 229910001337 iron nitride Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000696 magnetic material Substances 0.000 abstract description 3
- -1 rare-earth ferrum nitrides Chemical class 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000011858 nanopowder Substances 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- Hard Magnetic Materials (AREA)
Abstract
The present invention relates to a method of preparing a permanent magnet material of rare-earth ferrum nitrides, which belongs to the technical field of magnetic material manufacture. The method has the following steps: rare-earth elements R, Fe, at least one of which is nano powder are mixed with M according to a certain proportion; mechanical alloying is from 1 to 16 hours; after crystallizing treatment is carried out for 15 to 30 minutes under the temperature from 600 to 900DEG C, 1: 12 type compound R (Fe, M) 12 is formed; after nitridation is carried out for 1 to 5 hours in nitrogen gas with one atmospheric pressure under the temperature from 350 to 550DEG C, 1: 12 type rare-earth ferrum nitrides R (Fe, M) 12Nx are obtained. The method has the advantages of simple manufacturing process, small crystal grains of the prepared R (Fe, M) 12Nx permanent magnet materials, high purity and favorable performance. The present invention can be widely applied to electric appliances, electric machines and electronic instruments.
Description
A kind of preparation method of rare-earth ferrronitrides permanent megnet material belongs to magnetic material manufacturing technology field.
Prepared in the past 1: 12 type rare-earth-iron nitride R (Fe, M)
12N
xThe technology of permanent magnetic material all adopt vacuum melting, homogenizing handle, broken, inhale the method for nitrogen at last, its shortcoming is that the crystal grain after the heat treatment of alloy cast ingot homogenizing is thicker, dephasign content height, the poor performance of the rare-earth ferrronitrides permanent megnet material of gained.Afterwards, open flat 5-234731, name 1992.2.21 application, the disclosed spy of 1993.9.10 and be called " permanet magnet powder and manufacture method thereof " and open flat 6-69010, name 1992.8.19 application, the disclosed spy of 1994.3.11 and be called in " manufacture method that R-T-M-N is sintered magnet " these two parts Japanese application for a patent for invention cases and disclose a kind of method that adopts mechanical alloying prepared rare-earth-iron nitride powder, described in the method iron-nitride is RT
12-XM
x(X=1～2) type, wherein, R is rare earth element Pr or/and Nd, and T is that Fe or Fe add Co, and M gets a kind ofly in Cr, V, Mo at least, also can mix a part of Ti, and they all are micron powders.Its preparation method is: earlier proportioning is mixed in accordance with regulations, vacuumize again, or in Ar gas, carry out mechanical alloying and handle, again above-mentioned alloy powder in vacuum or Ar gas, handled 10 minutes～12 hours 600～850 ℃ of following crystallization, form and have ThMn
12The type crystal structure, with RT
12-XM
x(X=1～2) for average crystallite particle diameter principal phase, the fine crystal tissue be 0.05～0.5 μ m, particle mean size is the powder of 0.5～500 μ m, the nitrogenize 10 minutes～12 hours in 420～650 ℃, 0.5～50 atmospheric nitrogen of this powder, can obtain at last with RT
12-XM
x(X=1～2) are the rare-earth-iron nitride permanent-magnet powder of principal phase.But in the embodiment of documents, employing be micron powder, thereby the parameter of its mechanical alloying and nitriding process is inapplicable for nanometer grade powder of the present invention.
The objective of the invention is to overcome the defective that exists in the above-mentioned prior art, adopt nanometer grade powder, a kind of preparation method with small grains, purity height, function admirable and the simple rare-earth ferrronitrides permanent megnet material of technology is provided.
The preparation method of the rare-earth ferrronitrides permanent megnet material that the present invention proposes may further comprise the steps: (1) mechanical alloying
After rare-earth element R, Fe and the M of material powder mixed by a certain percentage, vacuumize, feed inert gas shielding: (2) crystallization
With above-mentioned alloy powder under vacuum condition or inert gas shielding, 600～900 ℃ form down 1: 12 type compound R (Fe, M)
12(3) nitrogenize
In 350～550 ℃ atmospheric pressure nitrogen, carry out nitrogen treatment, obtain 1: 12 type structure rare-earth-iron nitride R (Fe, M)
12N
x
It is characterized in that: the mechanical alloying material powder is selected a kind of nano level powder that is at least for use in above-mentioned (1), mixing the back ratio of grinding media to material is 5: 1～20: 1, mechanical alloying 1～16 hour finally obtains the alloy powder by amorphous and nanocrystalline α-Fe two phase compositions; The crystallization processing time is 15～30 minutes in above-mentioned (2), and nitridation time is 1～5 hour in above-mentioned (3).
In this method, R=Nd or Pr, M=Mo, V, Ti, Mn, W, Al, Si, Ga, Co, B, x ≈ 1.
In above-mentioned preparation method, the optimal mechanical alloying time is 6～12 hours, and optimum crystallization temperature is 700～800 ℃, and best nitriding temperature is 400～500 ℃.
With R=Nd, M=Mo is that example is carried out drawing explanation (wherein, Nd, Fe, Mo atomic ratio are 1.25: 10.5: 1.5) to accompanying drawing below:
Fig. 1: the X-ray diffractogram of different mechanical alloying times; Wherein, (a) be mechanical alloying 12 hour for mechanical alloying 6 hours (d) for mechanical alloying 9 hours (e) for mechanical alloying 3 hours (c) for mechanical alloying 1 hour (b)
Fig. 2: the alloy powder after the mechanical alloying is through the X-ray diffractogram of different temperatures crystallization after 30 minutes; Wherein, (a) be that crystallization temperature 700 ℃ (b) is 800 ℃ of crystallization temperatures for crystallization temperature 750 ℃ (c)
Fig. 3: Nd (Fe, Mo)
12N
xTypical magnetic hysteresis loop.Wherein, mechanical alloy turns to 6 hours, and 800 ℃ of crystallization were handled 30 minutes, 450 ℃ of nitrogenize 2 hours.
After table 1 is the different mechanical alloying times, the average grain size of nanocrystalline α-Fe in the alloy powder that calculates by the Scherrer formula.As can be seen from Table 1, along with the prolongation of mechanical alloying time, the average grain size of nanocrystalline α-Fe reduces gradually, and in initial 6 hours of mechanical alloying, it is very fast that average crystal grain reduces speed.Show on the X-ray diffractogram shown in Figure 1, α-Fe diffraction maximum broadens gradually, and do not see other diffraction maximum, this explanation is made up of amorphous and nanocrystalline α-Fe by the alloy powder that mechanical alloying obtains, and can control the average grain size of content of amorphous and nanocrystalline α-Fe at an easy rate, thereby the alloy that obtains having small grains by controlling mechanical alloying time.
As can be seen from Figure 2, along with the rising of crystallization temperature, amorphous and nanocrystalline α-Fe by solid-state reaction generate 1: 12 type Nd (Fe, Mo)
12React complete more.700 ℃ of crystallization are handled in the X-ray diffractogram of the alloy powder that obtained in 30 minutes and are contained a certain amount of α-Fe; 750 ℃ of crystallization were handled 30 minutes, and the X-ray diffraction peak of α-Fe disappears; When crystallization temperature is 800 ℃, almost obtain single 1: 12 type Nd (Fe, Mo)
12Compound is not seen other dephasign.This explanation can be controlled the single phase property of 1: 12 type alloy at an easy rate by controlling crystallization temperature, obtains to contain hardly 1: 12 type alloy of dephasign.
In addition, the present invention adopts the element nanometer powder to carry out the rare-earth ferrronitrides permanent megnet material of prepared by mechanical alloy, its manufacturing process is not only simple, technologies such as vacuum melting, homogenizing heat treatment, fragmentation have been saved, and easy control of process conditions, can obtain tiny 1: 12 type rare-earth ferrronitrides permanent megnet material of crystal grain.
Embodiment:
Nanometer powder Nd, Fe, Mo are pressed atomic ratio mix at 1.25: 10.5: 1.5, ratio of grinding media to material is 10: 1, in the ball grinder of packing into, is evacuated to 10
-3Pa charges into 1 atmospheric pressure argon shield, and mechanical alloying time was selected in sealing between 1～16 hour, and voltage is 150V, and electric current is 1.0A, then 10
-3Under the Pa vacuum condition, select crystallization temperature between 600～900 ℃, crystallization was handled 30 minutes, selected nitriding temperature at last between 350～550 ℃, and nitrogenize 2 hours in 1 atmospheric pressure nitrogen, obtain 1: 12 type structure Nd (Fe, Mo)
12N
x
Optimum implementation is as follows: example 1: nanometer powder Nd, Fe, Mo are pressed atomic ratio mix at 1.25: 10.5: 1.5, ratio of grinding media to material is 10: 1, in the ball grinder of packing into, is evacuated to 10
-3Pa charges into 1 atmospheric pressure argon shield, sealing, and mechanical alloying 6 hours, voltage is 150V, electric current is 1.0A, then 10
-3Under the Pa vacuum condition, 700 ℃ of crystallization were handled 30 minutes, nitrogenize 2 hours in 450 ℃, 1 atmospheric pressure nitrogen at last, obtain 1: 12 type structure Nd (Fe, Mo)
12N
xThe squareness S.R. of the remanent magnetism Br when adopting vibrating specimen magnetometer to measure its room temperature, coercivity H, saturation magnetization Ms, curve, it the results are shown in Table 2.Example 2: other condition and preparation process are with example 1, and crystallization temperature is 750 ℃, and the Nd that obtains (Fe, Mo)
12N
xMagnetic property during room temperature sees Table 2.Example 3: other condition and preparation process are with example 1, and crystallization temperature is 800 ℃, and the Nd that obtains (Fe, Mo)
12N
xMagnetic property during room temperature sees Table 2.Example 4: other condition and preparation process be with example 1, mechanical alloying 12 hours, and crystallization temperature is 700 ℃, the Nd that obtains (Fe, Mo)
12N
xMagnetic property during room temperature sees Table 2.Example 5: other condition and preparation process are with example 4, and crystallization temperature is 750 ℃, and the Nd that obtains (Fe, Mo)
12N
xMagnetic property during room temperature sees Table 2.Example 6: other condition and preparation process are with example 4, and crystallization temperature is 800 ℃, and the Nd that obtains (Fe, Mo)
12N
xMagnetic property during room temperature sees Table 2.Example 7: nanometer powder Nd, Fe, Mo are pressed atomic ratio mix at 1.25: 10.5: 1.5, ratio of grinding media to material is 10: 1, in the ball grinder of packing into, is evacuated to 10
-3Pa charges into 1 atmospheric pressure argon shield, sealing, and mechanical alloying 9 hours, voltage is 100V, electric current is 0.8A, then 10
-3Under the Pa vacuum condition, 750 ℃ of crystallization were handled 30 minutes, nitrogenize 2 hours in 400 ℃, 1 atmospheric pressure nitrogen at last, obtain 1: 12 type structure Nd (Fe, Mo)
12N
x, its magnetic property sees Table 3 during room temperature.Example 8: other condition and preparation process are with example 7, and nitriding temperature is 450 ℃, and the Nd that obtains (Fe, Mo)
12N
xMagnetic property during room temperature sees Table 3.Example 9: other condition and preparation process are with example 7, and nitriding temperature is 500 ℃, and the Nd that obtains (Fe, Mo)
12N
xMagnetic property during room temperature sees Table 3.
Table 1
| The mechanical alloying time (h) | Average grain size (nm) |
| 1 | 16.6 |
| 3 | 10.0 |
| 6 | 5.0 |
| 9 | 4.2 |
| 12 | 3.7 |
Table 2
| The mechanical alloying time (h) | Crystallization temperature (℃) | Br(Gs) | Hc(Oe) | Ms(emμ/g) | S.R. |
| 6 | 700 | 8991 | 7438 | 137.8 | 0.6659 |
| 750 | 8515 | 8997 | 123.4 | 0.7038 | |
| 800 | 9084 | 9073 | 124.7 | 0.7433 | |
| 12 | 700 | 9165 | 7044 | 142.0 | 0.6583 |
| 750 | 8913 | 8238 | 132.1 | 0.6884 | |
| 800 | 9831 | 8506 | 143.2 | 0.7005 |
Table 3
| Nitriding temperature (℃) | Br(Gs) | Hc(Oe) | Ms(emμ/g) | S.R. |
| 400 | 6.363 | 4528 | 108.9 | 0.5963 |
| 450 | 8982 | 8844 | 126.4 | 0.7251 |
| 500 | 9063 | 7829 | 135.1 | 0.7829 |
Claims (4)
1. the preparation method of a rare-earth ferrronitrides permanent megnet material may further comprise the steps:
(1) mechanical alloying
After rare-earth element R, Fe and the M of material powder mixed by a certain percentage, vacuumize, feed inert gas shielding;
(2) crystallization
With above-mentioned alloy powder under vacuum condition or inert gas shielding, 600～900 ℃ form down 1: 12 type compound R (Fe, M)
12
(3) nitrogenize
In 350～550 ℃ atmospheric pressure nitrogen, carry out nitrogen treatment, obtain 1: 12 type structure rare-earth-iron nitride R (Fe, M)
12N
x
It is characterized in that: the mechanical alloying material powder is selected a kind of nano level powder that is at least for use in above-mentioned (1), mixing the back ratio of grinding media to material is 5: 1～20: 1, mechanical alloying 1～16 hour finally obtains the alloy powder by amorphous and nanocrystalline α-Fe two phase compositions; The crystallization processing time is 15～30 minutes in above-mentioned (2), and nitridation time is 1～5 hour in above-mentioned (3).
2. the preparation method of rare-earth ferrronitrides permanent megnet material according to claim 1, it is characterized in that: the optimal mechanical alloying time is 6～12 hours.
3. the preparation method of rare-earth ferrronitrides permanent megnet material according to claim 1, it is characterized in that: optimum crystallization temperature is 700～800 ℃.
4. the preparation method of rare-earth ferrronitrides permanent megnet material according to claim 1, it is characterized in that: best nitriding temperature is 400～500 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102207A CN1068953C (en) | 1998-06-03 | 1998-06-03 | Method of preparing rare-earth ferrronitrides permanent megnet material |
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|---|---|---|---|
| CN98102207A CN1068953C (en) | 1998-06-03 | 1998-06-03 | Method of preparing rare-earth ferrronitrides permanent megnet material |
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|---|---|
| CN1205525A CN1205525A (en) | 1999-01-20 |
| CN1068953C true CN1068953C (en) | 2001-07-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6049010A (en) * | 1983-08-29 | 1985-03-18 | Toyo Soda Mfg Co Ltd | Vapor-phase polymerization of vinyl chloride |
| JPH05234731A (en) * | 1992-02-21 | 1993-09-10 | Sumitomo Special Metals Co Ltd | Permanent magnet powder and manufacture thereof |
-
1998
- 1998-06-03 CN CN98102207A patent/CN1068953C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6049010A (en) * | 1983-08-29 | 1985-03-18 | Toyo Soda Mfg Co Ltd | Vapor-phase polymerization of vinyl chloride |
| JPH05234731A (en) * | 1992-02-21 | 1993-09-10 | Sumitomo Special Metals Co Ltd | Permanent magnet powder and manufacture thereof |
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| Publication number | Publication date |
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| CN1205525A (en) | 1999-01-20 |
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