CN1271169A - High-performance permanent-magnet RE alloy and its making process - Google Patents
High-performance permanent-magnet RE alloy and its making process Download PDFInfo
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Abstract
The high-performance permanent magnet RE alloy has a double-phase metallurgical tissue with hard magnetic Nd2Fe14B phase and soft magnetic Alpha-Fe phase as main parts. In the crystallite borders of different phases, there is very thin film of non-magnetic metal elements, which have atom radius between that of Fe and Nd atoms and are different to form solid solution with Fe and Nd. The non-magnetic metal elements are at least one of Nb, Zr, Ta and Hf. The thickness of the very thin film is 10-20 angstroms, and the crystallite size in different phase is 5-100 nm, preferably 10-40 nm.
Description
The present invention relates to high-performance permanent-magnet RE alloy and manufacture method thereof, particularly relate to used high-performance permanent-magnet RE alloy and manufacture methods thereof such as braking automobile device, motor, generator.
In recent years, the high performance of magnet and the requirement of low price being improved, is that alloy is widely used as high-performance permanent-magnet RE alloy with the Nd-Fe-B of the low Nd of price comparison in the rare earth element.
It is multiple that Nd-Fe-B is that the manufacture method of permanent-magnet alloy has.In these methods, mainly be divided into two kinds of methods:
First method is powder metallurgic method (opening clear 59-46008 communique etc. with reference to the spy).This method is, the ingot casting of casting after the melting pulverized made powder, then this powder carried out successively forming processes, sintering processes and timeliness and handles.During forming processes, Yi Bian apply magnetic field one edge forming, what obtain is anisotropic magnet.But, because the coercive force after this magnet powderization is very low, so can only can not use as bonded permanent magnet as sintered magnet.
Second method is melt-quenching method (opening clear 59-64739 communique etc. with reference to the spy).This method is that the alloy liquation is ejected on the copper roller or iron roll of high speed rotating, and the alloy liquation obtains the alloy that amorphous mixes with crystallite to cool off fast greater than 105 ℃/second speed.In this case, adopt suitable cooling rate or adopt the high speed chilling to add suitable heat treatment, can obtain the alloy of high-coercive force.This alloy that obtains is isotropic, this alloyed powder is broken into powder and promptly can be made into bonded permanent magnet with mixed with resin use.Simultaneously, this powder can access block magnet by hot pressing, can make anisotropic block materials (opening clear 60-100402 communique etc. with reference to the spy) by thermal deformation.
In the magnet that said method obtains, no matter that is a kind of, and its metal structure all is at strong magnetic phase Nd
2Fe
14Have on the border of B compound to be called the non magnetic of rich Nd phase and to separate out mutually, that is, in various magnets, the Nd of being higher than is arranged all
2Fe
14The interpolation of the Nd of B stoichiometric composition.The rich Nd existence of layer mutually becomes the main cause with high-coercive force.
But the magnetic of this magnet only depends on Nd
2Fe
14The magnetic of B compound is so will obtain being higher than Nd
2Fe
14The magnet of B phase magnetic is impossible in theory.
Be higher than Nd in order to obtain performance
2Fe
14The magnet of B phase can be realized with the soft magnetism exchange coupling mutually of high saturation and magnetic intensity mutually by the Hard Magnetic of high-coercive force.Now having developed Hard Magnetic is Nd mutually
2Fe
14B phase, soft magnetism are Fe mutually
3The biphase composite permanent magnetic alloy of B phase (claiming the exchange coupling magnet again).But, for this Nd
2Fe
14B/Fe
3B biphase composite permanent magnetic alloy, if want to obtain high-coercive force, then remanent magnetization is low, can not satisfy the requirement of high-performance magnet.
As more high performance nano combined two-phase alloys, should be by hard magnetic phase Nd
2Fe
14B mutually and have the α-Fe soft magnetism phase composition of high magnetic intensity in the simple substance element.
Such Nd
2Fe
14B/ α-Fe is the biphase composite permanent magnetic alloy, and the report of experimental work has Nd-Fe-Co-Zr-B/ α-Fe (J.Alloy ﹠amp; Compounds 230 (1995) L1～L3), Nd-Fe-Co-Al-Cr-B/ α-Fe (J.Magnetism ﹠amp; MagneticMaterials 208 (2000) 163～168) etc.And, with the Nd of rapid quench method preparation
2Fe
14B/ α-Fe be the existing Nd-Fe-B/ α-Fe of biphase composite permanent magnetic alloyed powder and the block magnet that bonds and R-Fe-Co-M-B/ α-Fe system (R: rare earth element, M: magnesium-yttrium-transition metal) (with reference to the spy open flat 8-162312, the spy opens flat 11-288807 communique etc.).
Yet above-mentioned Nd-Fe-Co-Zr-B/ α-Fe, Nd-Fe-Co-Al-Cr-B/ α-Fe alloy is that the compound with Nd mixes with α-Fe, carries out alloying by mechanical alloying method, and alloying needs tens of to hundreds of hours, is difficult to carry out large-scale production.And, after this alloy blockization, can not fully guarantee to obtain high performance magnet.
Simultaneously, the metal structure (being shown in Fig. 8) of above-mentioned Nd-Fe-B/ α-Fe, R-Nd-Fe-Co-M-B/ α-Fe alloy is in the amorphous state phase 80 island Nd to be arranged
2Fe
14B mutually 81 with α-Fe 82 three-phase contextures of separating out mutually, that is, and the Nd of high-coercive force
2Fe
14B mutually 81 and the α-Fe of high saturation and magnetic intensity 82 on distance, be in released state, consequently Nd mutually
2Fe
14B mutually 81 82 is difficult to give full play to mutual exchanging action with α-Fe mutually.
Consider above situation, the purpose of this invention is to provide metal structure mainly is Nd
2Fe
14B mutually with α-Fe high-performance permanent-magnet RE alloy and the manufacture method thereof of duplex structure mutually.
Reach purpose of the present invention---high-performance permanent-magnet RE alloy, its metal structure are provided should be Hard Magnetic phase crystal grain Nd
2Fe
14B mutually and soft magnetism phase crystal grain α-Fe be mutually exist on the grain boundary of main duplex structure, this each phase contain more atomic radius be between Fe and the Nd atomic radius and also all be difficult to form the very thin films of the nonmagnetic metal element of solid solution with Fe, Nd any.
According to above formation, metallographic structure should be the Nd of high-coercive force
2Fe
14α-Fe desirable substantially duplex structure mutually of B and high saturation and magnetic intensity, the distance of each phase is near state, and each exchange-coupling interaction between mutually can be brought into play fully, can access the high-performance permanent-magnet RE alloy of magnetic property excellence.
And above-mentioned nonmagnetic metal element is made up of at least a institute in Nb, Zr, Ta or the Hf element, and the thickness that contains the very thin films of more these nonmagnetic metal elements can be 10～20 dusts.
Simultaneously, the crystallite dimension of each above-mentioned phase is 5～100nm, is desirably 10～40nm.
The high-performance permanent-magnet RE alloy relevant with the present invention is that Hard Magnetic phase crystal grain is Nd
2Fe
14B mutually with soft magnetism mutually crystal grain be the high-performance permanent-magnet RE alloy of α-Fe, component ratio is,
Nd?6.125～11.6at％，
At least a nonmetal magnetic element of forming among Nb, Zr, Ta or the Hf, component ratio is 0.2～1.3at%,
B and C add up to 4.0～5.8at%, and simultaneously, C is 0～0.5at%,
All the other are Fe,
Above-mentioned Nd and the ratio of B (atom) are 1.75～2.25: 1.
According to above formation, the composition of alloy is to be the Nd of ternary state diagram at Nd-Fe-B
2Fe
14On two phase lines of B+ α-Fe or near it, can access the high-performance permanent-magnet RE alloy of magnetic property excellence.
Simultaneously, the crystallite dimension of above-mentioned each phase is 10～100nm, is desirably 10～40nm.
In addition, above-mentioned nonmagnetic metal element can be single Nb.
The high-performance permanent-magnet RE alloy relevant with the present invention is that Hard Magnetic phase crystal grain is Nd
2Fe
14B mutually with soft magnetism mutually crystal grain be the high-performance permanent-magnet RE alloy of α-Fe, component ratio is,
Nd?7.0～11.6at％，
Nb?0.50～1.00at％，
B??4.0～5.8at％，
All the other are Fe
Above-mentioned Nd and the ratio of B (atom) are 2: 1, and the crystallite dimension of above-mentioned each phase is 10～100nm, is desirably 10～40nm.
According to above formation, the composition of alloy is to be the Nd of ternary state diagram at Nd-Fe-B
2Fe
14On two phase lines of B+ α-Fe, very tiny of the crystal grain of each phase simultaneously can access the high-performance permanent-magnet RE alloy of magnetic property excellence.
The manufacture method of the high-performance permanent-magnet RE alloy relevant with the present invention is to be Nd by Hard Magnetic phase crystal grain
2Fe
14B mutually with soft magnetism mutually crystal grain be the manufacture method of the high-performance permanent-magnet RE alloy of α-Fe phase, component ratio is:
Nd?6.125～11.6at％，
At least a nonmetal magnetic element of forming among Nb, Zr, Ta or the Hf, component ratio is 0.2～1.3at%,
B and C add up to 4.0～5.8at%, and simultaneously, C is 0～0.5at%,
All the other are Fe.
Above-mentioned Nd and the component ratio of B (atom) are 1.75～2.25: 1 alloy, through being melted into the alloy liquation, then with this alloy liquation with speed chilling greater than 104 ℃/sec, form the quench solidification body.Then with this quench solidification body 600～750 ℃, desirable 650～740 ℃, be preferably under 660-730 ℃ the temperature, carry out more than 13 minutes, best heat treatment more than 15 minutes, form above-mentioned with Nd
2Fe
14B mutually and α-Fe be main duplex structure mutually, existence contains the very thin films of more above-mentioned nonmagnetic metal element on the grain boundary of each phase simultaneously.
According to above method, can access really with Nd
2Fe
14B mutually and α-Fe be the high-performance permanent-magnet RE alloy of the magnetic property excellence of the duplex structure that leads mutually.
Simultaneously, carry out above-mentioned heat treatment, can obtain with Nd
2Fe
14B mutually and α-Fe be that the crystallite dimension of the two-phase led, each phase is 5～100nm, is desirably the metal structure of 10～40nm mutually.
Below be with reference to the accompanying drawings to being fit to the explanation of the invention process situation:
Present inventors, having made metal structure only is that Hard Magnetic is Nd mutually
2Fe
14B is the Nd of α-Fe phase with soft magnetism mutually mutually
2Fe
14B/ α-Fe is the biphase composite permanent magnetic alloy, through repeatedly checking the result of duplicate test, thinks that only meeting Nd-Fe-B shown in Figure 2 is that the duplex structure of the composition on the AC line in the ternary state diagram is just passable.
Among Fig. 2, in Δ ABC composition range, there is nonmagnetic Nd in the interstage
2Fe
22B separates out mutually, final Nd
2Fe
22B
3Phase decomposition is Fe
3B+Nd
2Fe
14The three-phase contexture of B+ α-Fe.Simultaneously, the composition range of the Δ ACD among Fig. 2 is α-Fe+Nd
2Fe
14B+Nd
2Fe
17Three-phase contexture.
At this, ratio of components α-Fe:Nd that the P on the line AC of the two-phase structure line is ordered
2Fe
14B is line segment PC:AP, and each atomic percent useful molecules formula of forming is expressed as on the AC line:
Nd
2xFe
100-3xB
x(3.5∝x＜5.8)?----(1)
This composition can not obtain desirable Nd
2Fe
14B phase and α-Fe duplex structure mutually.For this reason, promote that exist (interpolation) of the 4th kind of element of desirable two-phaseization is necessary.
This 4th kind of element, through the result of all tests, atomic radius between Fe atom and Nd atomic radius and and Fe, Nd any nonmagnetic metal element of all being difficult to form solid solution be selected.Specifically, at least a nonmagnetic metal element of forming in Nb, Zr, Ta or the Hf element is selected.Particularly, it is effective especially to add the Nb element separately.
At least a nonmagnetic metal element of forming by elements such as Nb, Zr, Ta or Hf all is difficult to solid solution in α-Fe, follows the growth of α-Fe, and these elements are outwards got rid of.At this moment, because these nonmagnetic metal element diffusions in α-Fe are slow, the nanocrystal tissue has been stablized in the growth that has slowed down α-Fe.As shown in Figure 1, the nonmagnetic metal element with B and Fe at Nd
2Fe
14Form very thin films 3 on the crystal boundary of B phase and α-Fe two-phase alloys mutually, contained α-Fe in this very thin films 3, shown as soft magnetism, can realize exchange coupling (elastic reaction).In view of the above, by to the magnetized opposing in outside, coercive force is improved.If there is not this very thin films 3, a little less than the ability of antagonism external magnetisation, coercive force will be Nd
2Fe
14B mutually 1 with α-Fe mean value of 2 mutually.Therefore, in order to give full play to exchange-coupling interaction, wish that the thickness of very thin films 3 is thin as far as possible, concretely, thickness is 10～20 dusts, and ideal is the 15 Izod right sides.In view of the above, the addition of nonmagnetic metal element is 0.2～1.3at%, is preferably 0.5～1.0at%.
Simultaneously, for substituting that B adds, C adds the similar performance that adds with B, and magnetic property does not reduce very much, and finds that coercive force improves a little.But the interpolation of C should be the scope of 0～0.5at%.This result, according to (1) formula, the standard ratio of Nd and B is 2: 1, owing to allow the interpolation of C, actual Nd and the ratio (atom) of B they are 1.75～2.25: 1.
Further,, need to strengthen the exchange coupling of biphase composite permanent magnetic body, and need Nd with high anisotropy in order to obtain high coercive force
2Fe
14B suppresses the magnetization inversion of α-Fe phase mutually.For this reason, Nd
2Fe
14B must increase with α-Fe contact area mutually mutually, and promptly the crystallite dimension of each phase is 5～100nm, and it is effective being desirably 10～40nm.
According to the above fact, find from organizing viewpoint, high-performance permanent-magnet RE alloy of the present invention, metallographic structure is Nd
2Fe
14B 12 is the duplex structure that leads with α-Fe mutually mutually; On the grain boundary of each phase, exist at least a nonmagnetic metal element of forming contain among more Nb, Zr, Ta or the Hf etc., thickness is 10～20 dusts, ideal is the very thin films on the 15 Izod right sides; The crystallite dimension of each phase is 5～100nm, is desirably 10～40nm.
Simultaneously, find that from the viewpoint of composition high-performance permanent-magnet RE alloy of the present invention is that Hard Magnetic phase crystal grain is Nd
2Fe
14B phase 1 is α-Fe two-phase alloys of 2 mutually with soft magnetism crystal grain mutually, and component ratio is
Nd?6.125～11.6at％，
At least a nonmagnetic metal element of forming among Nb, Zr, Ta or the Hf, component ratio is 0.2～1.3at%, preferably single nonmagnetic metal element nb, component ratio is 0.2～1.3at%,
B and C add up to 4.0～5.8at%, and simultaneously, C is 0～0.5at%, is separately that B is best, be B4.0～5.8at%, all the other are Fe, and the ratio of Nd and B (atom) is 1.75～2.25: 1, be preferably 2: 1, the crystallite dimension of each phase is 5～100nm, is desirably 10～40nm.
High-performance rare-earth magnetically hard alloy of the present invention, composition are in the scope of afore mentioned rules, and metal structure is the Nd of high-coercive force basically
2Fe
14α-Fe desirable duplex structure mutually of B phase and high saturation and magnetic intensity, Nd
2Fe
14B is on distance near state with α-Fe mutually, exchange-coupling interaction can be given full play between each phase,, has both given full play to the high saturation and magnetic intensity of α-Fe phase that is, coercive force is improved fully, can obtain the high-performance permanent-magnet RE alloy of magnetic property excellence.
Simultaneously, select at least a among Nb, Zr, Ta or the Hf etc. as the 4th kind of element and when in above-mentioned scope, adding, at Nd
2Fe
14B has formed the very thin films that contains more nonmagnetic metal element mutually with on α-Fe each phase grain boundary mutually, has also further improved coercive force.
And, Nd
2Fe
14B is mutually with α-Fe crystallite dimension mutually in the scope of afore mentioned rules the time, and the contact area increase of each phase has further improved coercive force.
And then alloy of the present invention is that Nd-Fe-Nb-B is an alloy, is the alloy that does not contain Co.In contrast, special flat to open what record and narrate for 11-288807 number be that former Nd-Fe-Co-M-B is an alloy, and Co is necessary composition.The cost of raw material Co is identical substantially with Nd, is more than 10 times or 10 times of Fe and Nb cost of material, and therefore the Nd-Fe-Co-M-B before is that alloy is a high price.Alloy of the present invention does not contain Co, is alloy compared with former Nd-Fe-Co-M-B, and manufacturing cost is cheap.
Secondly, the manufacture method of high-performance permanent-magnet RE alloy of the present invention is illustrated,
At first, component ratio is,
Nd?6.125～11.6at％，
The nonmagnetic metal element of at least a composition among Nb, Zr, Ta or the Hf, component ratio (atom) is 0.2～1.3at%, preferably single nonmagnetic metal element nb, component ratio is 0.2～1.3at%, and B and C add up to 4.0～5.8at%, and, C is 0～0.5 atom %, be that B is best separately, B4.0～5.8at%, all the other are Fe, the component ratio of Nd and B (atom) is 1.75～2.25: 1, be preferably 2: 1, after the raw material weighing of each element, obtain alloy raw material.
Then,, be fused into the alloy liquation, use inert gas (for example Ar gas) that the alloy liquation is generated the alloy liquation again and drip, this alloy liquid droplet is impacted on the rotation cooling body, with greater than 10 the heating of this alloy raw material
4℃/speed of sec cools off fast, obtains banded quench solidification alloy body.
To the quick cooling alloy body carry out 640 ℃～750 ℃, better 650 ℃～740 ℃, be preferably in 660 ℃～730 ℃, more than 13 minutes, desirable heat treatment more than 15 minutes.
In view of the above, the metal structure that obtains is Nd
2Fe
14B mutually and α-Fe be that the crystallite dimension of the duplex structure that leads, each phase is 5～100nm, is desirably the alloy body of 10～40nm mutually.And having formed thickness on the grain boundary of this alloy body is 10～20 dusts, is desirably the very thin films based on the nonmagnetic metal element on the 15 Izod right sides.
The alloy body that obtains is carried out suitable pulverizing, again powder and the mixed with resin pulverized are made bonded permanent magnet.And, this powder is carried out hot pressing processing, can make block materials.And then, this powder is carried out thermal deformation can obtain anisotropic block materials.
With greater than 10
4℃/the speed rapid cooling method of sec, can be be fit to industrial rapid quench method in the past, there is no particular limitation.The alloy liquation is with greater than 10
4℃/speed of sec cools off fast, and the cooling rate by the control running roller can obtain the amorphous state of above-mentioned composition or contain the banded quench solidification body that tiny α-Fe partial crystallization goes out.Then, this banded quench solidification body is heat-treated, obtained Nd
2Fe
14B phase and α-Fe two-phase structure mutually.
The banded quench solidification body that chilling is obtained has carried out differential thermal analysis, the results are shown in Fig. 3.The longitudinal axis among Fig. 3 be differential temperature Δ T (℃), transverse axis represent heating-up temperature (℃).
According to differential thermal analysis result shown in Figure 3, the Curie point of the banded quench solidification body of above-mentioned composition is about 373 ℃, and presents crystallization at about 546 ℃; And present the phase allergy at about 693 ℃ and generated Nd
2Fe
14B and α-Fe; Can infer that thus heat treatment temperature is good about 693 ℃.
Determined about 693 ℃ heat treatment, the quench solidification body before and after the heat treatment has been carried out X-ray diffraction.Fig. 4 (a) is the X-ray diffraction spectrum of the quench solidification body of preparation attitude, Fig. 4 (b) carries out 700 ℃ * 15 minutes heat treated X-ray diffraction spectrums to the quench solidification body, the longitudinal axis in Fig. 4 (a) and (b) is intensity (cps), and transverse axis is 2 θ (θ: incidence angle, degree).
Carried out comparative analysis to the quench solidification body of preparation attitude with through the X-ray diffraction spectrum result of 700 ℃ * 15 minutes heat treated quench solidification bodies.Among Fig. 4 (a), what obtain is the diffraction spectra of broadening, is inferred as single amorphous microstructure.In contrast, among Fig. 4 (b), except that the strong diffracted ray of having observed α-Fe, also observe flat diffraction spectra, can infer it is Nd
2Fe
14B phase and α-Fe duplex structure mutually.That is,, confirmed that amorphous state changes Nd into by heat treatment in 700 ℃ * 15 minutes
2Fe
14B phase and α-Fe duplex structure mutually.
Simultaneously, that shown in Figure 5 is the transmission electron microscope observation result of the quench solidification body after this heat treatment.Viewed metal structure is Nd really
2Fe
14B and α-Fe duplex structure, and the crystal grain of each phase is the small grains that size is about 10～40nm.
The method according to this invention is controlled within the limits prescribed with the cooling rate of alloy liquation and to the temperature and time that the quench solidification body that cools off the back gained is heat-treated, and has obtained comparatively ideal Nd really
2Fe
14B mutually and α-Fe mutually duplex structure and existence is the very thin films of matrix with above-mentioned nonmagnetic metal element on the grain boundary of each phase alloy, and the crystallite dimension of each phase is about tens nanometers.
Raw material are Nd, Fe, Nb and Fe-B alloy, press Nd
9Fe
85.5Nb
1.0B
4.5The alloy composition weighing raw materials.Then, raw material are smelted in the arc furnace of pure Ar gas shiled and are cast as φ 8～12mm, grow the ingot casting of 50～200mm.
Secondly, as shown in Figure 6, ingot casting 60 is positioned over fusion gets rid of the quartz ampoule of band machine 61 (quartz ampoule external diameter 12mm is in the most advanced and sophisticated nozzle bore 0.3～0.6mm) 62.The nozzle tip of quartz ampoule 62 is placed in the hole of carbon plate 64.And, in the bottom of quartz ampoule 62, be provided with the high frequency electric source induction coil 63 that surrounds quartz ampoule and carbon plate.
Afterwards, the ingot casting 60 in high-frequency induction coil 63 heated quarty tube 62, heating-up temperature is about 1400 ℃, after ingot casting 60 fusings, with pressure 1.2～2.0 * 10
5The Ar gas 65 of Pa with the tip ejection of alloy liquation by quartz ampoule 62, generates the drop of alloy liquation.This drop is under Ar gas atmosphere, and spraying to external diameter is the surface of 250mm, linear velocity 15m/s copper roller rotating 66, rapid solidification.Like this, just, obtained the banded quench solidification body that thickness is about 30 μ m.
Secondly, it is 5.0 * 10 that this banded quench solidification body is placed pressure
-3～1.0 * 10
-4In the vacuum furnace of Pa, fixed temperature be respectively 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, be incubated after 15 minutes, be cooled fast to room temperature, make sample 1～5.
Once more, the magnetic property of each sample detects with vibrating specimen magnetometer (VSM).The magnetic property that is detected is saturation magnetization J
s, remanent magnetism J
r, coercive force
jH
c, maximum magnetic energy product (BH)
Max, the results are shown in table 1.
As shown in table 1, saturation magnetization, remanent magnetism, coercive force and the maximum magnetic energy product of the sample 2,3,4 after 650 ℃, 700 ℃, 750 ℃ heat treatment all are preferably.
In contrast, at 600 ℃ of heat treated samples 1, maximum magnetic energy product is about 0.7 * 10
5T.A/m (9.0MGOe), magnetic property is obviously low.800 ℃ of heat treated samples 5, maximum magnetic energy product is about 0.76 * 10
5T.A/m (9.5MGOe) compares with sample 2～4, and magnetic property is not high yet.
According to the magnetic property result of sample 1～5, better during at 640 ℃～750 ℃ when heat treated temperature range, 650 ℃～740 ℃ better, and 660 ℃～730 ℃ best.It is maximum that magnetic property reaches 700 ℃ of front and back, and be lower than 640 ℃ and be higher than 750 ℃ heat treatment, and magnetic property is all lower.Table 1
Embodiment 2.
| Sample | Saturation magnetization (J s) | Remanent magnetism (J r) | Coercive force ( jH c) | Maximum magnetic energy product (BH) max | ||||
| ????T | ??kGs | ????T | ??kGs | ?×10 5A/m | ?kOe | ??×10 5T.A/m | ??MGOe | |
| ?1 | ??1.34 | ??13.4 | ??0.90 | ???9.0 | ???3.4 | ??4.3 | ?????0.70 | ???9.0 |
| ?2 | ??1.45 | ??14.5 | ??1.09 | ??10.9 | ???4.9 | ??6.1 | ?????1.07 | ??13.4 |
| ?3 | ??1.49 | ??14.9 | ??1.07 | ??10.7 | ???4.9 | ??6.1 | ?????1.21 | ??15.2 |
| ?4 | ??1.40 | ??14.0 | ??0.99 | ???9.9 | ???4.2 | ??5.3 | ?????1.00 | ??12.6 |
| ?5 | ??1.44 | ??14.4 | ??0.98 | ???9.8 | ???3.9 | ??4.9 | ?????0.76 | ???9.5 |
Raw material are Nd, Fe, Nb, Fe-B and Fe-C alloy, are Nd by alloy composition
9Fe
85.5Nb
1.0B
4.5, Nd
9Fe
85.5Nb
1.0B
4.4C
0.1, Nd
9Fe
85.5Nb
1.0B
4.0C
0.5, Nd
9Fe
85.5Nb
1.0B
3.0C
1.5, Nd
15Fe
77B
8.0, Nd
9Fe
85.5Nb
1.0B
4.0C
0.5Weighing raw materials.Then, by the method identical, make the banded quench solidification body of 6 kinds of thick about 30 μ m with embodiment 1.
Secondly, each banded quench solidification body is 5.0 * 10
-2～10
-4In 700 ℃ of maintenances 15 minutes, cool to room temperature made sample 3,6～10 then in the vacuum furnace of Pa.
Once more, the magnetic property of each sample detects with vibrating specimen magnetometer (VSM).The magnetic property index that is detected is remanent magnetism J
r, coercive force
jH
c, maximum magnetic energy product (BH)
Max, the results are shown in table 2.Table 2
| Sample | Alloying component (at%) | Remanent magnetism (J r) | Coercive force ( jH c) | Maximum magnetic energy product (BH) max | |||
| ????T | ?kGs | ×10 5?A/m | ?kOe | ??×10 5??T.A/m | ?MGOe | ||
| ?3 | ?Nd 9Fe 85.5Nb 1B 4.5 | ??1.07 | ??10.7 | ??4.9 | ??6.1 | ????1.21 | ??15.2 |
| ?6 | ?Nd 9Fe 85.5Nb 1B 4.4C 0.1 | ??1.04 | ??10.4 | ??4.0 | ??5.0 | ????1.12 | ??14.1 |
| ?7 | ?Nd 9Fe 85.5Nb 1B 4.0C 0.5 | ??1.02 | ??10.2 | ??5.3 | ??6.6 | ????1.11 | ??13.9 |
| ?8 | ?Nd 9Fe 86.0Nb 1B 3.0C 1.0 | ??0.94 | ???9.4 | ??4.9 | ??6.1 | ?????3.9 | ??11.4 |
| ?9 | ?Nd 15Fe 77B 8 | ??0.61 | ???6.1 | ??3.7 | ??4.6 | ?????3.9 | ???3.7 |
| ?10 | ?Nd 9Fe 85.5Nb 1B 4.0C 0.5 | ??0.87 | ???8.7 | ??2.1 | ??2.7 | ?????3.9 | ???4.3 |
Sample 9 is that maximum magnetic energy product is minimum in the sample 3,6～10.Sample 9 is that in the past Nd-Fe-B is an alloy, not in the composition range of the high-performance permanent-magnet RE alloy of rich Nd side of the present invention, and does not have the interpolation of the 4th kind of element.Therefore, the metal structure of sample 9 is not the α-Fe+Nd of other samples
2Fe
14The duplex structure of B, but α-Fe+Nd
2Fe
17+ Nd
2Fe
14The three-phase contexture of B.Embodiment 3.
Raw material are Nd, Fe, Nb, Fe-B and Fe-C alloy, press alloy composition Nd
9Fe
85.5Nb
1.0B
4.0C
0.5Each raw material of weighing.By with embodiment 1 identical method, make the 4 kind quench solidification bodies of thick about 30 μ ms thereafter.
Secondly, each quench solidification body is 5.0 * 10
-2～1.0 * 10
-4In 700 ℃, kept respectively 5,15,20 and 30 minutes in the vacuum furnace of Pa, cool to room temperature makes sample 11～14 then.
Once more, detect the influence of heat treatment time to the magnetic property of each sample.The magnetic property index that is detected is remanence ratio J
r/ J
s, remanent magnetism J
r, coercive force
jH
cAnd maximum magnetic energy product (BH)
Max, the results are shown in Fig. 7.
According to Fig. 7, when heat treatment time is between 5～15 minutes, increase with heat treatment time, magnetic property raises.Heat treatment time was greater than 15 minutes, and magnetic property changes little, and numerical value is more stable.According to this result, the phase transformation of duplex structure prolongs heat treatment time after finishing again, and crystal grain also not too can be grown up, and has shown that duplex structure is stable.
More than alloy of the present invention, external except being applied to the required high-performance magnetism of braking automobile device, motor or generator, need can also to be applied to the various devices and the machine of the high-performance magnet of magnetic property excellence.
According to above-described embodiment, the present invention has obtained following excellent effect: (1) metal structure is Nd2Fe
14The B phase is main desirable duplex structure with α-Fe mutually, and each is to be near state in distance, and the exchange-coupling interaction between each phase is very strong. (2) at Nd2Fe
14On the grain boundary of each phase of the metal structure that B phase and α-Fe form mutually, form the very thin films that contains more the 4th kind of element, coercivity improves more when giving full play to exchange-coupling interaction. (3) manufacturing method according to the invention, (1), (2) described high-performance permanent-magnet RE alloy above really having obtained.
The below is the simple declaration of accompanying drawing: Fig. 1. metal structure figure Fig. 2 .Nd-Fe-B of the present invention's one high-performance permanent-magnet RE alloy is ternary state diagram Fig. 3. and differential thermal analysis curve Fig. 4 of quench solidification body. the X-ray diffractogram Fig. 5 before and after the quench solidification body heat is processed. transmission electron microscope observation figure Fig. 6 of the quench solidification body after the heat treatment. liquation rotation quenching apparatus schematic diagram Fig. 7. heat treatment time affects schematic diagram Fig. 8 to magnetic property. the explanation of the metal structure schematic symbol of existing biphase built-up magnet:
1.Nd
2Fe
14The B phase
2. α-Fe phase
3. very thin films (very thin films that contains more nonmagnetic metal element)
Claims (9)
1. high-performance permanent-magnet RE alloy, it is characterized by metal structure is Hard Magnetic phase crystal grain Nd
2Fe
14B mutually and soft magnetism mutually crystal grain α-Fe be main duplex structure mutually, and on the grain boundary of each phase existence contain that more atomic radius is between Fe and the Nd atomic radius and also with Fe and Nd in any very thin films that all is difficult to form the nonmagnetic metal element of solid solution.
2. by the high-performance permanent magnet alloy described in the claim 1, it is characterized by above-mentioned nonmagnetic metal element and be made up of at least a institute among Nb, Zr, Ta or the Hf, the thickness of the above-mentioned very thin films that contains more nonmagnetic metal element is 10～20 dusts.
3. by the high-performance permanent-magnet RE alloy described in the claim 1 or 2, the crystallite dimension that it is characterized by each above-mentioned phase is 5～100nm, be desirably 10～40nm.
4. one kind by Hard Magnetic phase crystal grain Nd
2Fe
14B mutually with the soft magnetism high-performance permanent-magnet RE alloy of crystal grain α-Fe phase composition mutually, it is characterized by its component ratio is: Nd 6.125～11.6at%, the content of at least a nonmagnetic metal element of forming among Nb, Zr, Ta or the Hf is 0.7～1.3at%, B and C add up to 4.0～5.8at%, and C is 0～0.5at%, and all the other are Fe; Above-mentioned Nd and the ratio of B (atom) are 1.75～2.25: 1.
5. by the described high-performance permanent-magnet RE alloy of claim 4, the crystallite dimension that it is characterized by each phase is 5～100nm, be desirably 10～40nm.
By claim 4 and 5 described high-performance permanent-magnet RE alloys, to it is characterized by the nonmagnetic metal element only be Nb.
7. one kind by Hard Magnetic phase Nd
2Fe
14B mutually and the soft magnetism high-performance permanent-magnet RE alloy that α-the Fe phase is formed mutually is characterized by its component ratio and is: Nd 7.0～11.6at%, and Nb 0.5～1.0at%, B 4.0～5.8at%, all the other are Fe; The above-mentioned component ratio with Nd and B (atom) is 2: 1, and the crystallite dimension of each phase is that 5～100nm, ideal are 10～40nm.
8. one kind by Hard Magnetic phase Nd
2Fe
14B mutually with the soft magnetism manufacture method of α-high-performance permanent-magnet RE alloy that the Fe phase is formed mutually, the component ratio that it is characterized by alloy is: Nd 6.125～11.6at%, the content of at least a nonmagnetic metal element of forming among Nb, Zr, Ta or the Hf is 0.2～1.3at%, B and C add up to 4.0～5.8at%, and C is 0～0.5at%, and all the other are Fe; With above-mentioned Nd and the component ratio of B (atom) is 1.75～2.25: 1 alloy melting, then with this alloy liquation with greater than 10
4℃/the speed chilling of sec forms the quench solidification alloy body, then with this quench solidification alloy body in 640～750 ℃, 650～740 ℃ more fortunately, be preferably under 660～730 ℃ the temperature, carry out more than 13 minutes, best heat treatment more than 15 minutes, form above-mentioned with Nd
2Fe
14B is main duplex structure mutually with α-Fe mutually and has the very thin films that contains more nonmagnetic metal element on each phase border.
9. by the manufacture method of the described high-performance permanent-magnet RE alloy of claim 8, after it is characterized in that carrying out above-mentioned heat treatment, form with Nd
2Fe
14B mutually and α-Fe be the duplex structure that leads mutually, and the crystallite dimension of each phase is 5～100nm, is desirably 10～40nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424791C (en) * | 2005-12-19 | 2008-10-08 | 锦州东方微纳科技有限公司 | High stability and high magnetism quenched R-Fe-B base permanent magnetic alloy powder |
| CN104011811B (en) * | 2012-01-04 | 2016-11-02 | 丰田自动车株式会社 | Terres rares nano-composite magnet |
| CN107768065A (en) * | 2016-08-22 | 2018-03-06 | 福特全球技术公司 | Magnetic in composite permanent magnet is coupled |
| CN108666127A (en) * | 2018-06-04 | 2018-10-16 | 安徽天宇磁业股份有限公司 | Based on energy-saving and environment-friendly permanent magnet processing technology |
| CN116864253A (en) * | 2023-08-04 | 2023-10-10 | 朗峰新材料(菏泽)有限公司 | Nanocrystalline soft magnetic material and preparation method thereof |
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2000
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100424791C (en) * | 2005-12-19 | 2008-10-08 | 锦州东方微纳科技有限公司 | High stability and high magnetism quenched R-Fe-B base permanent magnetic alloy powder |
| CN104011811B (en) * | 2012-01-04 | 2016-11-02 | 丰田自动车株式会社 | Terres rares nano-composite magnet |
| US9818520B2 (en) | 2012-01-04 | 2017-11-14 | Toyota Jidosha Kabushiki Kaisha | Rare-earth nanocomposite magnet |
| US10090090B2 (en) | 2012-01-04 | 2018-10-02 | Toyota Jidosha Kabushiki Kaisha | Rare-earth nanocomposite magnet |
| CN107768065A (en) * | 2016-08-22 | 2018-03-06 | 福特全球技术公司 | Magnetic in composite permanent magnet is coupled |
| CN108666127A (en) * | 2018-06-04 | 2018-10-16 | 安徽天宇磁业股份有限公司 | Based on energy-saving and environment-friendly permanent magnet processing technology |
| CN116864253A (en) * | 2023-08-04 | 2023-10-10 | 朗峰新材料(菏泽)有限公司 | Nanocrystalline soft magnetic material and preparation method thereof |
| CN116864253B (en) * | 2023-08-04 | 2024-01-12 | 朗峰新材料(菏泽)有限公司 | Nanocrystalline soft magnetic material and preparation method thereof |
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