CN1258757A - Fast melt-quenching process to synthesize cubic laves phase giant magnetostrictive material with high Pr content - Google Patents
Fast melt-quenching process to synthesize cubic laves phase giant magnetostrictive material with high Pr content Download PDFInfo
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- CN1258757A CN1258757A CN99120674.6A CN99120674A CN1258757A CN 1258757 A CN1258757 A CN 1258757A CN 99120674 A CN99120674 A CN 99120674A CN 1258757 A CN1258757 A CN 1258757A
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- giant magnetostrictive
- alloy
- rare
- annealing
- fast quenching
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- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 11
- 229910001068 laves phase Inorganic materials 0.000 title abstract description 8
- 238000007578 melt-quenching technique Methods 0.000 title description 2
- 238000010791 quenching Methods 0.000 claims abstract description 25
- 230000000171 quenching effect Effects 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001154 Pr alloy Inorganic materials 0.000 description 1
- 229910001329 Terfenol-D Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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Abstract
One kind of high-Pr giant magnetostrictive material is Pr1-xTbx(Fe1-yCoy)2 alloy where 0 is less than or equal x is less than or equal 0.4 and 0.2 is less than or equal y is less than or equal 0.5. It is manufactured through smelting to obtain homogeneous cast ingot in high-purity argon atmosphere inside a magnetically controlled arc furnace, fast quenching inside a fast quenching furnace and annealing to obtain cubic (Pr, Tb)(Fe,Co)2 Laves phase. The smelted alloy is sprayed through 0.5-1 mm holes to obtain alloy strip.
Description
The present invention relates to a kind of composition and manufacture method of Rare-Earth Giant Magnetostrictive Materials, relate in particular to the composition and the manufacture method of high Pr Rare-Earth Giant Magnetostrictive Materials.
Rare-Earth Giant Magnetostrictive Materials is meant the material that produces huge dilatation under the action of a magnetic field adding.This material has very high effciency of energy transfer, can produce very big mechanical force, response speed is fast, can be widely used in underwater acoustic transducer, the controller valve, stopper, sensor field etc., estimate that external rare earth giant magnetostrictive material and device annual value of production are more than 1,000,000,000 dollars (wherein be used for oil press and robot aspect, only American market just is about 600,000,000 dollars).The rare-earth-iron alloy has very high magnetostriction coefficient, but its magnetocrystalline anisotropy is big, needs high externally-applied magnetic field could obtain big coefficient of dilatation, is unfavorable for practical application.For reducing its magnetocrystalline anisotropy, can be by adjusting rare earth composition.As the commercial trade mark is the Tb of Terfenol-D
0.3Dy
0.7Fe
2Alloy (, having lower magnetocrystalline anisotropy) because of Tb and the just in time compensation mutually of Dy ionic local anisotropy.Yet,, limited its production and application worldwide because the Tefenol-D sample costs an arm and a leg.Thereby develop a kind of cheaply, the rare earth giant magnetostrictive material that magnetostriction coefficient is big is very important to enlarging its application in practice.
According to Stevens calculation result, Pr ion ratio Tb ion has bigger magnetocrystalline anisotropy and magnetostriction coefficient.PrFe in addition
2With TbFe
2Opposite anisotropy constant symbol is arranged, Tb
1-xPr
xFe
2Pseudo-binary system resembles Tb
1-xDy
xFe
2Also be that the acceptable anisotropy remedies system.And low price.Adopt high pressure synthetic PrFe
2Compound, when having that pure phase does not exist in a large number, the room temperature magnetostriction is still up to 1060 * 10
-6, can estimate monophasic PrFe
2Compound has very big magnetostriction coefficient.But PrFe
2The compound normal pressure can not synthesize, even under high pressure also be difficult to synthetic monophasic PrFe
2Compound.In recent years, researcher has carried out the magnetostriction performance that the Laves phase compound that contains Pr has been studied in a lot of effort, mainly be by substituting Pr with rare earth Tb, Dy and Ce, come the stable Laves phase compound that contains Pr, surpass half even could obtain single-phase preferably at 80% o'clock but these results show that the amount of Pr is replaced.Recently, there are some researches show that substituting part Fe with Co helps the synthetic PrLaves phase compound that contains.Find when the alternative amount of Co is lower than 60%, can not synthesize Pr (Fe, Co)
2Laves phase compound, when Co alternative measures 60%, Pr (Fe
0.4Co
0.6)
1.9Alloy melting annealing back principal phase be Pr (Fe, Co)
2Laves phase compound, contain simultaneously 20% the Pr of having an appointment (Fe, Co)
3Pure phase not.Though high to contain the Co amount unfavorable with a large amount of impure relative magnetostriction performances, this alloy has still showed big magnetostriction performance (λ under the foreign field of room temperature, 10kOe
11-λ
⊥=800 * 10
-6).
The objective of the invention is: provide a kind of can the acquisition to contain the single-phase compound of cube Laves that Co measures lower and high Pr content, further improve the magnetostriction performance, thereby develop low-cost Pr series giant magnetostriction material.The method that the present invention also aims to provide a kind of melt-spun and make the Pr series giant magnetostriction material with after annealing.
The object of the present invention is achieved like this: utilize the melt-spun method to obtain amorphous or non-product and nanocrystalline mixture band, obtain the single-phase compound of cube Laves more than 1 minute in low temperature (300 ℃～650 ℃) annealing then.
A kind of high Pr Rare-Earth Giant Magnetostrictive Materials is characterized in that having the alloy Pr of following composition
1-xTb
x(Fe
1-yCo
y)
2(0≤x≤0.4,0.2≤y≤0.5).
A kind of method for making of high Pr Rare-Earth Giant Magnetostrictive Materials is characterized in that the alloy Pr of following composition
1-xTb
x(Fe
1-yCo
y)
2(0≤x≤0.4,0.2≤y≤0.5) is the uniform ingot casting of twice acquisition of melting in magnetic control arc stove high-purity argon atmosphere.Fast quenching carries out in the ratio-frequency heating single roller rapid quenching stove under argon shield, and the wheel surface linear velocity is adjustable in the scope of 20～45m/s.Molten alloy is put into silica tube, and the fusing back is the aperture ejection of 0.5mm～1mm by diameter, obtains fast quenching thin strap.(300 ℃～650 ℃) annealing obtains the single-phase compound of cube Laves under cold condition then.
Characteristics of the present invention are: utilize melt-spun and subsequently the annealed method synthesized ordinary method (as: melting and with after annealing) be difficult to the synthetic high Pr content (Pr, Tb) (Fe, Co)
2Cube Laves is single-phase.
Analyze phase structure and measure intrinsic magnetostriction coefficient λ with X-ray diffractometer
111Adopt vibrating sample magnetometer to measure magnetic performance.Magnetostriction coefficient adopts static strain instrumentation amount.As an example, Pr
0.8Tb
0.2(Fe
0.6Co
0.4)
2The alloy measuring result as shown in the figure.
Fig. 1 is Pr
0.8Tb
0.2(Fe
0.6Co
0.4)
2The X-ray diffraction spectrum of alloy
(a) 40m/s fast quenching (b) was annealed 30 minutes at 550 ℃ behind the 40m/s fast quenching.
Fig. 2 is Pr
0.8Tb
0.2(Fe
0.6Co
0.4)
2Alloy is 30 minutes stepping x of 450 ℃ of annealing behind the 40m/s fast quenching
Ray slow sweep diffraction spectra can be calculated λ from the division of spectral line
111Should be greater than 2000 * 10
-6
Fig. 3 Pr
0.8Tb
0.2(Fe
0.6Co
0.4)
2Demagnetizing curve (a) 40m/s quenched state after the annealing of alloy fast quenching: (b)
Behind the 40m/s fast quenching 450 ℃ annealing 30min; (c) behind the 40m/s fast quenching 550 ℃ annealing 30min.
Fig. 4 Pr
0.8Tb
0.2(Fe
0.6Co
0.4)
2The powder that alloy strip is ground into is with after about 3% epoxy resin glue mixes,
Room temperature pressurization and the thin slice sample that obtains 140 ℃ of curing, magnetostriction coefficient under the room temperature and magnetic field concern song
Line.
(a) behind the 40m/s fast quenching 450 ℃ annealing 30min;
(b) behind the 40m/s fast quenching 550 ℃ annealing 30min.
The invention will be further described by the following examples:
High Pr alloy Pr
1-xTb
x(Fe
1-yCo
y)
2(0≤x≤0.4,0.2≤y≤0.5) prescription has a certain limit, with following method manufacturing: the uniform ingot casting of twice acquisition of melting in magnetic control arc stove high-purity argon atmosphere earlier.Fast quenching carries out in the ratio-frequency heating single roller rapid quenching stove under argon shield then, and the wheel surface linear velocity is adjustable in the scope of 20～45m/s, fast quenching speed by control wheel surface linear velocity 20,30, the not obviously difference of scope of 45m/s.Molten alloy is put into silica tube, and the fusing back is the aperture ejection of 0.5mm～1mm by diameter, obtains fast quenching thin strap, with after annealing.Embodiment among the figure, with behind the 40m/s fast quenching at 450 ℃ of annealing 30min; In fact annealed time and temperature are extremely wide, as long as can keep all having into more than several minutes phase effect in 300-650 ℃ of temperature range.
(1) be combined to: high Pr content Pr has been synthesized in melt-spun and annealing subsequently
1-xTb
x(Fe
1-yCo
y)
2Cube Laves is single-phase, x=0～0.4, y=0.2～0.5.Control fast quenching speed, annealing temperature and annealing time are in above-mentioned scope, molten alloy is put into silica tube, fusing back is the aperture ejection of 0.5mm～1mm by diameter, obtains fast quenching thin strap and can control the grain-size size of Laves phase (I obtain the nanometer crystal microstructure of about 20nm uniformly).
(2) magnetic:
(i) the intrinsic magnetostriction coefficient λ under the room temperature
111
(a) x=0 does not observe the division of (440) crystal face diffraction peak, shows λ
111Less.
(b)0.1≤x＜0.2，0.3≤y≤0.5?λ
111≥1500×1000
-6
(c)0.2≤x≤0.4，0.2≤y≤0.5?λ
111≥2000×1000
-6
(d) to (Pr
1-xTb
x) (Fe
0.6Co
0.4)
2Alloy series, anisotropy remedy composition about the x=0.1 place.
(ii) the nanocrystalline material of fast quenching acquisition at room temperature has big coercive force (about 4～5kOe).After the annealing, crystal grain
Grow up, coercive force reduces.
(iii) after the powder mixes that low amounts of resin glue and nanocrystalline band are ground into, surely pressurize and 140 ℃ of curing in the chamber
The thin slice sample that obtains (for example: to the sample of x=0.2 at room temperature has big magnetostriction coefficient
When outside magnetic field is 8kOe, λ
11-λ
⊥Can reach 350 * 10
-6) hard magnetic property of becoming reconciled.
Claims (4)
1. one kind high Pr Rare-Earth Giant Magnetostrictive Materials is characterized in that having the alloy Pr of following composition
1-xTb
x(Fe
1-yCo
y)
2(0≤x≤0.4,0.2≤y≤0.5).
2. the method for making of a high Pr Rare-Earth Giant Magnetostrictive Materials: the alloy Pr that it is characterized in that following composition
1-xTb
x(Fe
1-yCo
y)
2(0≤x≤0.4,0.2≤y≤0.5) melting in magnetic control arc stove high-purity argon atmosphere obtains uniform ingot casting, and fast quenching carries out in quick quenching furnace, molten alloy fusing back is the aperture ejection of 0.5mm～1mm by diameter, obtains quick quenching band, and the quick quenching band of annealing then obtains (Pr, Tb) (Fe, Co)
2Cube Laves is single-phase.
3. the method for making of a high Pr Rare-Earth Giant Magnetostrictive Materials: it is characterized in that annealing under 300 ℃～650 ℃ cold condition.
4. by the described high Pr Rare-Earth Giant Magnetostrictive Materials of claim 1, it is characterized in that 0.1≤x＜0.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99120674A CN1090682C (en) | 1999-12-30 | 1999-12-30 | Fast melt-quenching process to synthesize cubic laves phase giant magnetostrictive material with high Pr content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99120674A CN1090682C (en) | 1999-12-30 | 1999-12-30 | Fast melt-quenching process to synthesize cubic laves phase giant magnetostrictive material with high Pr content |
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| Publication Number | Publication Date |
|---|---|
| CN1258757A true CN1258757A (en) | 2000-07-05 |
| CN1090682C CN1090682C (en) | 2002-09-11 |
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ID=5281638
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352961C (en) * | 2005-04-21 | 2007-12-05 | 南京大学 | Pr series rare earth super magnetostric tive material and its preparing method |
| CN102866172A (en) * | 2012-08-31 | 2013-01-09 | 广东电网公司电力科学研究院 | Measuring method of Laves phase content of T/P 92 steel |
| CN105575574A (en) * | 2014-10-16 | 2016-05-11 | 桂林电子科技大学 | PrFeNi alloy magnetic microwave absorbing material and preparation method thereof |
| CN111057959A (en) * | 2019-12-05 | 2020-04-24 | 南京信息职业技术学院 | Magnetostrictive material and preparation process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK52393D0 (en) * | 1993-05-05 | 1993-05-05 | Novo Nordisk As |
-
1999
- 1999-12-30 CN CN99120674A patent/CN1090682C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352961C (en) * | 2005-04-21 | 2007-12-05 | 南京大学 | Pr series rare earth super magnetostric tive material and its preparing method |
| CN102866172A (en) * | 2012-08-31 | 2013-01-09 | 广东电网公司电力科学研究院 | Measuring method of Laves phase content of T/P 92 steel |
| CN105575574A (en) * | 2014-10-16 | 2016-05-11 | 桂林电子科技大学 | PrFeNi alloy magnetic microwave absorbing material and preparation method thereof |
| CN111057959A (en) * | 2019-12-05 | 2020-04-24 | 南京信息职业技术学院 | Magnetostrictive material and preparation process thereof |
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| Publication number | Publication date |
|---|---|
| CN1090682C (en) | 2002-09-11 |
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