CN104575906A - High-performance low-cost rear earth permanent magnet material and preparation method thereof - Google Patents
High-performance low-cost rear earth permanent magnet material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of rear earth permanent magnets and particularly relates to a high-performance low-cost rear earth permanent magnet material and a preparation method thereof. The high-performance low-cost rear earth permanent magnet material is formed by mixing and sintering a principal phase and a grain-boundary phase alloy in a weight ratio of 1 to (0.005-0.2), wherein the principal phase is a mixture comprising any two or more than two of an R1-Fe-M-B alloy, an R2-Fe-M-B alloy, an R3-Fe-M-B alloy, an R4-Fe-M-B alloy and an R5-Fe-M-B alloy; R1 is praseodymium, R2 is neodymium, R3 is lanthanum, R4 is cerium, and R5 is yttrium; M is selected from one or more of Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu and Ga; the grain-boundary phase alloy is a rear-earth-rich alloy.
Description
Technical field
The invention belongs to rare earth permanent magnet field, particularly a kind of high-performance and low-cost rare earth permanent-magnetic material and preparation method thereof.
Background technology
Take neodymium iron boron as the rare-earth-iron-boron series permanent magnetic material of representative be the permanent magnetic material of new generation that magnetic property (energy density) is the highest, range of application is wide, the most with the fastest developing speed, be described as " magnetic king ", apply widely in various electric equipment.R-Fe-B magnet microscopic structure as shown in Figure 1, in this magnet to magnetic property contribute maximum ferromagnetic be R mutually
2fe
14b phase, this is called as principal phase mutually, as white portion.Also there is Grain-Boundary Phase in addition, in general Grain-Boundary Phase is a kind of rich R phase, as black region.The transition zone of a composition of layer between principal phase and crystal boundary is there is at the intersection of principal phase and Grain-Boundary Phase.
Wherein the important function of rich R phase is:
(1) rich R phase has low melting point, and therefore it becomes liquid phase in the sintering step of magnet generation technique, so rich R phase impels the densification of magnet, improves the magnetization thus;
(2) rich R phase eliminates R
2fe
14the defect of B phase crystal boundary, this defect causes the nucleating point of reverse magnetic domain, makes coercive force increase like this due to the minimizing of this nucleating point;
(3) because rich R phase is nonmagnetic, so this principal phase is being magnetically mutually isolated, coercive force is made to increase like this.
The main magnetic property index of R-Fe-B magnet comprises remanent magnetism and coercive force.The height of magnet remanent magnetism depends primarily on the factors such as the percent by volume of principal phase, the saturated pole intensity of principal phase and the degree of orientation.Affect the coercitive factor of magnet a lot, just current, add dysprosium, terbium is the most frequently used, the most effective coercitive method of raising magnet, because dysprosium terbium-iron-boron has the anisotropy field times over Nd-Fe-B phase mutually.But dysprosium, terbium belong to scarce resource, expensive, not easily add in a large number, so dysprosium, terbium minimizing have become the research theme of a lot of scholar.In general, magnet crystal boundary and transition zone more easily become the forming core point of reverse magnetic domain, so sclerosis crystal boundary can improve the coercive force of magnet more significantly.That is, R
2fe
14b compound has the coercive force waiting rare earth element to enter crystal boundary and transition zone to be more conducive to improving magnet compared with high anisotropy field.Thus, the crystal structure that R-Fe-B magnet is desirable should be R
2fe
14b compound has and enters Grain-Boundary Phase compared with the rare earth element of high anisotropy field.Such as CN200680003392.0, CN200810179949.7 are the technical methods of this respect.
In actual production, the common meltings of multiple rare earth element such as praseodymium, neodymium, dysprosium, terbium are normally prepared R-Fe-B alloy by people.According to R
2fe
14the intrinsic characteristic of B compound is R substantially
2fe
14the high rare earth element crystallization temperature in B compound anisotropy field is also high, as shown in Figure 2.That is, because the crystallization temperature of dysprosium terbium-iron-boron phase is high, in molten steel is from high temperature to sub-cooled, preferential crystallization generates dysprosium terbium-iron-boron phase, and makes R
2fe
14the lower rare earth element such as praseodymium, neodymium in B compound anisotropy field enters Grain-Boundary Phase, and this and desirable magnet model are on the contrary.
Summary of the invention
The invention provides a kind of high-performance and low-cost rare earth permanent-magnetic material, the principal phase of this rare earth permanent-magnetic material has the advantages that a crystal grain only has single rare earth.
The present invention also provides the preparation method of described high-performance and low-cost rare earth permanent-magnetic material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of high-performance and low-cost rare earth permanent-magnetic material, this material primarily of principal phase and crystal-boundary phase alloy by 1: 0.005-0.2 weight ratio mixed sintering form,
Described principal phase is by R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy, R
5the mixture of two or more composition any in-Fe-M-B alloy, wherein R
1praseodymium, R
2neodymium, R
3lanthanum, R
4cerium, R
5be yttrium, M is selected from one or more in Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga,
Aforesaid R
xin-Fe-M-B alloy, x gets the positive integer of 1-5,26wt%≤R
x≤ 33wt%; 0wt%≤M≤10wt%; 0.9wt%≤B≤2wt%; All the other are iron and inevitable impurity;
Described crystal-boundary phase alloy is a kind of rich rare earth alloy, the composition of this alloy is RQ, in formula, R is one or more in praseodymium, neodymium, gadolinium, promethium, europium, samarium, dysprosium, terbium, and Q is one or more in Fe, Co, Ni, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, B; In crystal-boundary phase alloy, 0≤Q≤72wt%, all the other are R and inevitable impurity.
As preferably, the particle mean size of crystal-boundary phase alloy is 0.5 ~ 5 μm.When particle mean size is greater than 5 μm, Grain-Boundary Phase skewness can be made and make part crystal boundary can not get sclerosis; If particle mean size is less than 0.5 μm, magnetic activity is very high, very easily oxidation and spontaneous combustion, thus cannot play the effect of crystal boundary sclerosis, also danger close.
A preparation method for described high-performance and low-cost rare earth permanent-magnetic material, the method comprises the steps:
1. prepare principal phase, principal phase is by R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy, R
5the mixture of two or more composition any in-Fe-M-B alloy, wherein R
1praseodymium, R
2neodymium, R
3lanthanum, R
4cerium, R
5be yttrium, M is selected from one or more in Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, (R
1-Fe-M-B alloy+R
2-Fe-M-B alloy) than (R
3-Fe-M-B alloy+R
4-Fe-M-B alloy+R
5-Fe-M-B alloy)=1: 0 ~ 1.
Aforesaid R
xin-Fe-M-B alloy, x gets the positive integer of 1-5,26wt%≤R
x≤ 35wt%; 0wt%≤M≤10wt%; 0.9wt%≤B≤2wt%; All the other are iron and inevitable impurity; Because as conventional principal phase Rare Earth Elements of Praseodymium, neodymium, lanthanum, cerium, yttrium, their crystallization temperature and anisotropy field have difference equally, also substantially meet R
2fe
14rare earth element crystallization temperature also this rule high that B compound anisotropy field is high.If by the melting together of (PrNdLaCeY)-Fe-M-B alloy, its result is exactly that preferential praseodymium neodymium enters principal phase, and R
2fe
14the lower LaCeY element in B compound anisotropy field enters Grain-Boundary Phase, and makes magnet coercive force very low.This step selects different rare earth elements obtained R-Fe-M-B system alloy respectively, and each R-Fe-M-B system alloy is mixed to get main-phase alloy by different proportion;
2. crystal-boundary phase alloy is prepared, crystal-boundary phase alloy is a kind of rich rare earth alloy, the composition of this alloy is RQ, in formula, R is one or more in praseodymium, neodymium, gadolinium, promethium, europium, samarium, dysprosium, terbium, and Q is one or more in Fe, Co, Ni, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, B;
In crystal-boundary phase alloy, 0≤Q≤72wt%, all the other are R and inevitable impurity; The rare earth element of Grain-Boundary Phase compared with the rare earth element in principal phase, R
2fe
14b compound has higher anisotropy field.In sintering and drawing process, the rare earth element in Grain-Boundary Phase also form small part R
2fe
14b compound to be dispersed in crystal boundary and transition zone thus to play sclerosis crystal boundary and improves coercitive effect.After adding rich rare earth alloy, rare earth element can harden crystal boundary, improves magnetic property;
3. principal phase and crystal-boundary phase alloy are pressed the weight ratio mixing of 1: 0.005-0.1, the alloy powder mixed is put into orientation in magnetic field and is pressed into green compact, green compact are sintered in sintering furnace and obtains rare-earth permanent magnet.Further, step 3. in, sintering process is: green compact are put into vacuum sintering furnace and sinter 1 ~ 5h at 1030 ~ 1120 DEG C of temperature, 750 ~ 950 DEG C are warming up to again after cooling, insulation 1 ~ 10h tempering, then cool, and be again warming up to 400 ~ 680 DEG C and carry out Ageing Treatment, the time is 1 ~ 10h.
In the preparation process in accordance with the present invention, the preparation of main-phase alloy, a kind of rare earth is only added in melting each time, can be used in combination by the main-phase alloy with several rare earth according to need of production, but often kind of main-phase alloy is all independent preparation.Then by R
2fe
14the rare earth element that B compound has high anisotropy field is directly prepared into Grain-Boundary Phase interpolation, and magnet obtained by this method, closer to ideal model, has the feature of high magnetic characteristics, low cost.
The invention has the beneficial effects as follows: principal phase is resolved into several R-Fe-M-B system alloys, first the R of preparation only containing single rare earth
x-Fe-M-B alloy, and then by each R
x-Fe-M-B alloy mixes, and adds crystal-boundary phase alloy and carry out magnetic field orientating, be pressed into base, thus can obtain more preferably crystal structure, makes the rare-earth permanent magnet of high magnetic characteristics, low cost.
After using this technical method, the feature that magnet has is: in magnet, a kind of rare earth of the intra-die of 80% accounts for more than 95% of total amount of rare earth; R in magnet
2fe
14the highest rare earth element in B compound anisotropy field is high at intra-die at the concentration ratio of crystal boundary.
Accompanying drawing explanation
Fig. 1 is R-Fe-B magnet microscopic structure schematic diagram;
Fig. 2 R
2fe
14the corresponding relation figure of B compound crystallization temperature and anisotropy field.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, percentage are unit of weight, and the equipment adopted and raw material etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the conventional method of this area.
Embodiment 1:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy and R
3-Fe-M-B alloy composition, R
1-Fe-M-B alloying component by the neodymium of 32wt%, the Co of the B of 1.00wt%, 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Ga of 0.10wt%, the W of the Mo of the V of 0.10wt%, 0.10wt%, 0.10wt%, the Cr of 0.10wt%, the Zr of the Ti of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
3-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy and R
3-Fe-M-B alloy adopts HD+JM powder process, R
1-Fe-M-B alloy particle mean size 3.5 μm, R
3-Fe-M-B alloy particle mean size 4.0 μm, by R
1-Fe-M-B alloy and R
3-Fe-M-B alloy is by 5: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1070 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 2:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy and R
4-Fe-M-B alloy composition, R
1-Fe-M-B alloying component is by the neodymium of 32wt%, the B of 1.00wt%, the Co of 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Ga of 0.10wt%, the Zr of the Ti of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
4-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, 0.20wt%, 0.40wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy and R
4-Fe-M-B alloy adopts HD+JM powder process, R
1-Fe-M-B alloy particle mean size 3.5 μm, R
4-Fe-M-B alloy particle mean size 4.0 μm, by R
1-Fe-M-B alloy and R
4-Fe-M-B alloy is by 4: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1070 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 3:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy and R
5-Fe-M-B alloy composition, R
1-Fe-M-B alloying component by the neodymium of 32wt%, the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, the Ga of the Nb of the Cu of 0.10wt%, 0.50wt%, 0.10wt%, the Zr of the V of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
5-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy and R
5-Fe-M-B alloy adopts HD+JM powder process, R
1-Fe-M-B alloy particle mean size 3.5 μm, R
5-Fe-M-B alloy particle mean size 4.0 μm, by R
1-Fe-M-B alloy and R
5-Fe-M-B alloy is by 3: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1060 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 4:
Main-phase alloy is by a kind of R
2-Fe-M-B alloy and R
3-Fe-M-B alloy composition, R
2-Fe-M-B alloying component is by the neodymium of 34wt%, the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, the Cu of 0.10wt%, the W of the Ga of the Nb of 0.50wt%, 0.10wt%, 0.10wt%, the Cr of 0.10wt%, the Zr of the Ti of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
3-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
2-Fe-M-B alloy and R
3-Fe-M-B alloy adopts HD+JM powder process, R
2-Fe-M-B alloy particle mean size 3.5 μm, R
3-Fe-M-B alloy particle mean size 4.0 μm, by R
2-Fe-M-B alloy and R
3-Fe-M-B alloy is by 2: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1070 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 5:
Main-phase alloy is by a kind of R
2-Fe-M-B alloy and R
4-Fe-M-B alloy composition, R
2-Fe-M-B alloying component is by the neodymium of 35wt%, the B of 1.00wt%, the Co of 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Ga of 0.10wt%, the Zr of the Ti of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
4-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, 0.20wt%, 0.40wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
2-Fe-M-B alloy and R
4-Fe-M-B alloy adopts HD+JM powder process, R
2-Fe-M-B alloy particle mean size 3.5 μm, R
4-Fe-M-B alloy particle mean size 4.0 μm, by R
2-Fe-M-B alloy and R
4-Fe-M-B alloy is by 1: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1070 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 6:
Main-phase alloy is by a kind of R
2-Fe-M-B alloy and R
5-Fe-M-B alloy composition, R
2-Fe-M-B alloying component by the neodymium of 31wt%, the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, the Ga of the Nb of the Cu of 0.10wt%, 0.50wt%, 0.10wt%, the Zr of the V of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
5-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0., 150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
2-Fe-M-B alloy and R
5-Fe-M-B alloy adopts HD+JM powder process, R
2-Fe-M-B alloy particle mean size 3.5 μm, R
5-Fe-M-B alloy particle mean size 4.0 μm, by R
2-Fe-M-B alloy and R
5-Fe-M-B alloy is by 10: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1060 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 7:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy and R
2-Fe-M-B alloy composition, R
1-Fe-M-B alloying component by the neodymium of 31wt%, the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, the Ga of the Nb of the Cu of 0.10wt%, 0.50wt%, 0.10wt%, the Zr of the V of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
2-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0., 150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy and R
2-Fe-M-B alloy adopts HD+JM powder process, R
1-Fe-M-B alloy particle mean size 3.5 μm, R
5-Fe-M-B alloy particle mean size 3.5 μm, by R
1-Fe-M-B alloy and R
2-Fe-M-B alloy is by 3: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1080 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 8:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy, R
2-Fe-M-B alloy and R
4-Fe-M-B alloy composition, R
1-Fe-M-B alloying component by the neodymium of 31wt%, the Co of the B of 1.00wt%, 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Zr of the Ga of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
2-Fe-M-B alloying component is by the neodymium of 33wt%, and the Ga of the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
4-Fe-M-B alloying component is by the lanthanum of 27wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0., 150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy, R
2-Fe-M-B alloy and R
4-Fe-M-B alloy all adopts HD+JM powder process, R
1-Fe-M-B alloy and R
2-Fe-M-B alloy particle mean size 2.5 μm, R
4-Fe-M-B alloy particle mean size 4.5 μm, by R
1-Fe-M-B alloy, R
2-Fe-M-B alloy and R
4-Fe-M-B alloy is by 3: 1: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1070 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 9:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy and R
5-Fe-M-B alloy composition, R
1-Fe-M-B alloying component by the neodymium of 31wt%, the Co of the B of 1.00wt%, 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Zr of the Ga of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
2-Fe-M-B alloying component is by the neodymium of 33wt%, and the Ga of the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
3-Fe-M-B alloying component is by the lanthanum of 27wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0., 150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
4-Fe-M-B alloying component is by the neodymium of 33wt%, and the Ga of the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
5-Fe-M-B alloying component is by the lanthanum of 28wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0., 150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy and R
5-Fe-M-B alloy all adopts HD+JM powder process, R
1-Fe-M-B alloy and R
2-Fe-M-B alloy particle mean size 3 μm, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy, R
4-Fe-M-B alloy particle mean size 5.0 μm, by R
1-Fe-M-B alloy, R
2-Fe-M-B alloy and R
4-Fe-M-B alloy is by 3: 1: 1: 1: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1060 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 10:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy and R
4-Fe-M-B alloy composition, R
1-Fe-M-B alloying component is by the neodymium of 32wt%, the B of 1.00wt%, the Co of 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Ga of 0.10wt%, the Zr of the Ti of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
R
4-Fe-M-B alloying component is by the lanthanum of 31wt%, and the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, 0.20wt%, 0.40wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy and R
4-Fe-M-B alloy adopts HD+JM powder process, R
1-Fe-M-B alloy particle mean size 3.5 μm, R
4-Fe-M-B alloy particle mean size 4.0 μm, by R
1-Fe-M-B alloy and R
4-Fe-M-B alloy is by 4: 1 mixing composition principal phase magnetics.
Grain-Boundary Phase composition is by the iron of 45.00wt%, and the Ga of the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, 0.20wt%, 0.50wt%, 0.10wt% and the dysprosium composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; Crystal-boundary phase alloy adopts HD+JM powder process, and particle mean size is 3.0 μm.
Main-phase alloy and Grain-Boundary Phase ratio 10: 1, then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1070 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Embodiment 11:
Main-phase alloy is by a kind of R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy and R
5-Fe-M-B alloy composition, R
1-Fe-M-B alloying component by the neodymium of 31wt%, the Co of the B of 1.00wt%, 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Zr of the Ga of 0.10wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
2-Fe-M-B alloying component is by the neodymium of 33wt%, and the Ga of the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
3-Fe-M-B alloying component is by the lanthanum of 27wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0., 150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
4-Fe-M-B alloying component is by the neodymium of 33wt%, and the Ga of the Nb of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy; R
5-Fe-M-B alloying component is by the lanthanum of 28wt%, and the Nb of the V of the Cu of the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.30wt%, 0., 150wt%, 0.10wt%, 0.50wt% and the Fe composition of surplus, adopt rapid hardening (SC) technique to obtain alloy;
By R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy and R
5-Fe-M-B alloy all adopts HD+JM powder process, R
1-Fe-M-B alloy and R
2-Fe-M-B alloy particle mean size 3 μm, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy, R
4-Fe-M-B alloy particle mean size 5.0 μm, by R
1-Fe-M-B alloy, R
2-Fe-M-B alloy and R
4-Fe-M-B alloy is by 3: 1: 1: 1: 1 mixing.
Grain-Boundary Phase is metal dysprosium commercially, and crystal-boundary phase alloy adopts HD+JM powder process, and particle mean size is 1.0 μm.Principal phase magnetic and Grain-Boundary Phase magnetic are pressed the weight ratio mixing of 1: 0.005;
Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1060 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Comparative example 1:
The neodymium of composition: 15.00wt%, the praseodymium of 4.00wt%, the lanthanum of 4.00wt%, the cerium of 4.00wt%, the yttrium of 4.00wt%, the B of 1.00wt%, the Co of 1.00wt%, the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, the Ga of 0.10wt% and the Fe of surplus, adopt rapid hardening (SC) technique to obtain alloy, alloy is adopted HD+JM powder process, particle mean size is 3.5 μm.Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1070 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
Comparative example 2:
The neodymium of composition: 14.50wt%, the praseodymium of 4.00wt%, the lanthanum of 4.00wt%, the cerium of 4.00wt%, the yttrium of 4.00wt%, the dysprosium of 0.50wt%, the Al of the Co of the B of 1.00wt%, 1.00wt%, 0.50wt%, the Cu of 0.10wt%, the Ga of the Nb of 0.50wt%, 0.10wt% and the Fe of surplus, adopts rapid hardening (SC) technique to obtain alloy, alloy is adopted HD+JM powder process, particle mean size is 3.8 μm.Then by mixed-powder oriented moulding, and green compact are put into vacuum sintering furnace 1060 DEG C × 4.5h and sinter+910 DEG C × 2h+510 DEG C × 4h Ageing Treatment and obtain permanent magnet, magnetic property is in table 1.
As can be seen from Table 1, the result that embodiment 1 ~ 9 is praseodymiums, neodymium and lanthanum, cerium, yttrium element alloy are mixed to get by different proportion, even if the accounting of lanthanum, cerium, yttrium reaches the magnet that 50% also can obtain commercial value, this is owing to still having a certain amount of praseodymium neodymium sclerosis crystal boundary in Grain-Boundary Phase in magnet.And in comparative example 1, magnetic property is very low, this is because magnet Grain-Boundary Phase is made up of lanthanum cerium yttrium substantially, cannot form continuous print crystal boundary, so coercive force is very low.
Embodiment 10 and embodiment 11 are that crystal boundary adds containing the magnetic property result after disprosium alloy, define a small amount of Dy after adding dysprosium in Grain-Boundary Phase and transition zone
2fe
14the alloy hardening crystal boundary of MB, makes the magnetic property of magnet be significantly improved.And in comparative example 2, dysprosium element enters intra-die, certainly also can to a certain degree improve coercitive effect, but effect is much worse than dysprosium enters Grain-Boundary Phase.
Table 1 magnetic property comparing result
| Remanent magnetism B r(kGs) | Coercive force H cJ(kOe) | |
| Embodiment 1 | 13.3 | 13.2 |
| Embodiment 2 | 12.7 | 12.7 |
| Embodiment 3 | 12.1 | 12.3 |
| Embodiment 4 | 11.5 | 11.8 |
| Embodiment 5 | 10.9 | 10.5 |
| Embodiment 6 | 13.9 | 13.6 |
| Embodiment 7 | 14.3 | 14.1 |
| Embodiment 8 | 12.9 | 14.2 |
| Embodiment 9 | 11.7 | 11.5 |
| Embodiment 10 | 12.9 | 12.1 |
| Embodiment 11 | 11.8 | 12.5 |
| Comparative example 1 | 9.3 | 7.6 |
| Comparative example 2 | 11.9 | 8.8 |
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (4)
1. a high-performance and low-cost rare earth permanent-magnetic material, is characterized in that, this material primarily of principal phase and crystal-boundary phase alloy by 1: 0.005-0.2 weight ratio mixed sintering form,
Described principal phase is by R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy, R
5the mixture of two or more composition any in-Fe-M-B alloy, wherein R
1praseodymium, R
2neodymium, R
3lanthanum, R
4cerium, R
5be yttrium, M is selected from one or more in Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga,
Aforesaid R
xin-Fe-M-B alloy, x gets the positive integer of 1-5,26 wt%≤R
x≤ 33wt%; 0 wt%≤M≤10wt%; 0.9 wt%≤B≤2wt%; All the other are iron and inevitable impurity;
Described crystal-boundary phase alloy is a kind of rich rare earth alloy, the composition of this alloy is RQ, in formula, R is one or more in praseodymium, neodymium, gadolinium, promethium, europium, samarium, dysprosium, terbium, and Q is one or more in Fe, Co, Ni, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, B; In crystal-boundary phase alloy, 0≤Q≤72wt%, all the other are R and inevitable impurity.
2. high-performance and low-cost rare earth permanent-magnetic material according to claim 1, is characterized in that: the particle mean size of crystal-boundary phase alloy is 0.5 ~ 5 μm.
3. a preparation method for high-performance and low-cost rare earth permanent-magnetic material according to claim 1, is characterized in that the method comprises the steps:
1. prepare principal phase, principal phase is by R
1-Fe-M-B alloy, R
2-Fe-M-B alloy, R
3-Fe-M-B alloy, R
4-Fe-M-B alloy, R
5the mixture of two or more composition any in-Fe-M-B alloy, wherein R
1praseodymium, R
2neodymium, R
3lanthanum, R
4cerium, R
5be yttrium, M is selected from one or more in Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga,
Aforesaid R
xin-Fe-M-B alloy, x gets the positive integer of 1-5,26 wt%≤R
x≤ 33wt%; 0 wt%≤M≤10wt%; 0.9 wt%≤B≤2wt%; All the other are iron and inevitable impurity;
2. crystal-boundary phase alloy is prepared, crystal-boundary phase alloy is a kind of rich rare earth alloy, the composition of this alloy is RQ, in formula, R is one or more in praseodymium, neodymium, gadolinium, promethium, europium, samarium, dysprosium, terbium, and Q is one or more in Fe, Co, Ni, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, B;
In crystal-boundary phase alloy, 0≤Q≤72wt%, all the other are R and inevitable impurity;
3. principal phase and crystal-boundary phase alloy are pressed the weight ratio mixing of 1: 0.005-0.2, the alloy powder mixed is put into orientation in magnetic field and is pressed into green compact, green compact are sintered in sintering furnace and obtains rare-earth permanent magnet.
4. preparation method according to claim 3, it is characterized in that: step 3. in, sintering process is: green compact are put into vacuum sintering furnace and sinter 1 ~ 5h at 1030 ~ 1120 DEG C of temperature, 750 ~ 950 DEG C are warming up to again after cooling, insulation 1 ~ 10h tempering, then cool, and be again warming up to 400 ~ 680 DEG C and carry out Ageing Treatment, the time is 1 ~ 10h.
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