CN104575906B - 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 PDF

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CN104575906B
CN104575906B CN201410763584.8A CN201410763584A CN104575906B CN 104575906 B CN104575906 B CN 104575906B CN 201410763584 A CN201410763584 A CN 201410763584A CN 104575906 B CN104575906 B CN 104575906B
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rare earth
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CN104575906A (en
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郝忠彬
洪群峰
吴美浩
王成胜
章晓峰
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GANZHOU DONGCI RARE EARTH CO., LTD.
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Ganzhou Dongci Rare Earth Co Ltd
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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

A kind of high-performance and low-cost rare earth permanent-magnetic material and preparation method thereof
Technical field
The invention belongs to rare earth permanent magnet field, more particularly to a kind of high-performance and low-cost rare earth permanent-magnetic material and its preparation side Method.
Background technology
Rare-earth-iron-boron series permanent magnetic material with neodymium iron boron as representative be magnetic property (energy density) highest, range of application most Extensively, permanent-magnet material of new generation with the fastest developing speed, is described as " magnetic king ", using widely in various electric equipments.R- Fe-B magnets microscopic structure is as shown in figure 1, ferromagnetic phase maximum to magnetic property contribution in the magnet is R2Fe14B phases, this is claimed It is principal phase, such as white portion.Grain-Boundary Phase is additionally there are, in general Grain-Boundary Phase is a kind of rich R phases, such as black region.In master There is transition zone of the composition of layer between principal phase and crystal boundary in the intersection of phase and Grain-Boundary Phase.
The important function of wherein richness R phases is:
(1) richness R phases have low melting point, therefore it becomes liquid phase in the sintering step of magnet generation technique, so richness R phases Promote the densification of magnet, thus improve the intensity of magnetization;
(2) richness R phases eliminate R2Fe14The defect of B phase crystal boundaries, the defect causes the nucleating point of reverse magnetic domain, so due to this The reduction of nucleating point and increase coercivity;
(3) because rich R phases are nonmagnetic, so the principal phase is what is be magnetically mutually isolated, so increase coercivity Plus.
The main magnetic property index of R-Fe-B magnets includes remanent magnetism and coercivity.The height of magnet remanent magnetism depends primarily on master The factors such as the percent by volume of phase, the saturated pole intensity of principal phase and the degree of orientation.The coercitive factor of influence magnet is a lot, just For at present, addition dysprosium, terbium are the most frequently used, the maximally effective raising coercitive methods of magnet, because dysprosium terbium-iron-boron mutually has Times over the anisotropy field of Nd-Fe-B phase.But dysprosium, terbium belong to scarce resource, expensive, a large amount of additions are difficult, so Dysprosium, terbium minimizing have become the research theme of many scholars.In general, magnet crystal boundary and transition zone are easier to turn into reverse The forming core point of magnetic domain, so hardening crystal boundary can significantly more improve the coercivity of magnet.That is, R2Fe14B compounds have Have and be more beneficial for improving the coercivity of magnet into crystal boundary and transition zone compared with the rare earth element that waits of high anisotropy.Thus, The preferable crystal structure of R-Fe-B magnets should be R2Fe14B compounds enter brilliant with the rare earth element compared with high anisotropy Boundary's phase.Such as CN200680003392.0, CN200810179949.7 are the technical methods of this respect.
In actual production, people are typically for the common melting of various rare earth elements such as praseodymium, neodymium, dysprosium, terbium to prepare R-Fe-B Alloy.According to R2Fe14The intrinsic characteristic of B compounds, substantially R2Fe14B compound anisotropies rare earth element knot high Brilliant temperature 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 from high temperature to low temperature Preferential crystallization generation dysprosium terbium-iron-boron phase in cooling, and make R2Fe14The rare earth such as B compound anisotropies relatively low praseodymium, neodymium unit Element enters Grain-Boundary Phase, and this is on the contrary with preferable magnet model.
The content of the invention
The present invention provides a kind of high-performance and low-cost rare earth permanent-magnetic material, and the principal phase of the rare earth permanent-magnetic material has a crystalline substance The characteristics of grain only has single rare earth.
The present invention also provides the preparation method of the 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, the material is main to press 1: 0.005- by principal phase and crystal-boundary phase alloy 0.2 weight is formed than mixed sintering,
Described principal phase is by R1- Fe-M-B alloys, R2- Fe-M-B alloys, R3- Fe-M-B alloys, R4- Fe-M-B alloys, R5The mixture of any two or more composition in-Fe-M-B alloys, wherein R1It is praseodymium, R2It is neodymium, R3It is lanthanum, R4It is Cerium, R5It is yttrium, M is selected from one or more in Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga,
Foregoing RxIn-Fe-M-B alloys, x takes the positive integer of 1-5,26wt%≤Rx≤ 33wt%;0wt%≤M≤ 10wt%;0.9wt%≤B≤2wt%;Remaining is iron and inevitable impurity;
Described crystal-boundary phase alloy is a kind of rich rare earth alloy, and the composition of the alloy is RQ, in formula R be praseodymium, neodymium, gadolinium, promethium, One or more in europium, samarium, dysprosium, terbium, Q be one kind in Fe, Co, Ni, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, B or It is several;In crystal-boundary phase alloy, 0≤Q≤72wt%, remaining is R and inevitable impurity.
Preferably, the particle mean size of crystal-boundary phase alloy is 0.5~5 μm.When particle mean size is more than 5 μm, crystal boundary can be made Distributed mutually is uneven and part crystal boundary is hardened;If particle mean size is less than 0.5 μm, magnetic activity is very high, easily oxygen Change spontaneous combustion, so as to crystal boundary hardening, also danger close cannot be played a part of.
A kind of preparation method of described high-performance and low-cost rare earth permanent-magnetic material, the method comprises the following steps:
1. principal phase is prepared, principal phase is by R1- Fe-M-B alloys, R2- Fe-M-B alloys, R3- Fe-M-B alloys, R4-Fe-M-B Alloy, R5The mixture of any two or more composition in-Fe-M-B alloys, wherein R1It is praseodymium, R2It is neodymium, R3Be lanthanum, R4It is cerium, R5It is yttrium, M is selected from one or more in Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, (R1- Fe-M-B alloys +R2- Fe-M-B alloys) than (R3- Fe-M-B alloys+R4- Fe-M-B alloys+R5- Fe-M-B alloys)=1: 0~1.
Foregoing RxIn-Fe-M-B alloys, x takes the positive integer of 1-5,26wt%≤Rx≤ 35wt%;0wt%≤M≤ 10wt%;0.9wt%≤B≤2wt%;Remaining is iron and inevitable impurity;Because as conventional principal phase rare earth element Praseodymium, neodymium, lanthanum, cerium, yttrium, their crystallization temperature and anisotropy field equally have difference, also substantially conform to R2Fe14B compounds are each Anisotropy rare earth element crystallization temperature high also this rule high.If (PrNdLaCeY)-Fe-M-B alloys melted together Refining, its result is exactly that preferential praseodymium neodymium enters principal phase, and R2Fe14The relatively low LaCeY elements of B compound anisotropies enter crystal boundary Phase, and make magnet coercivity very low.The step selects different rare earth elements that R-Fe-M-B systems alloy is obtained respectively, by each R- Fe-M-B systems 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, and the composition of the alloy is RQ, and R is in formula One or more in praseodymium, neodymium, gadolinium, promethium, europium, samarium, dysprosium, terbium, Q be Fe, Co, Ni, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, One or more in Ga, B;
In crystal-boundary phase alloy, 0≤Q≤72wt%, remaining is R and inevitable impurity;The rare earth element of Grain-Boundary Phase with Rare earth element in principal phase is compared, R2Fe14B compounds have anisotropy field higher.In sintering and drawing process, crystal boundary Rare earth element in phase also form small part R2Fe14B compounds are dispersed in crystal boundary and transition zone so as to play hardening crystal boundary Improve coercitive effect.Rare earth element can harden crystal boundary after adding rich rare earth alloy, improve magnetic property;
3. principal phase and crystal-boundary phase alloy are put well mixed alloy powder by 1: 0.005-0.1 weight ratio mixing Orientation is pressed into green compact in magnetic field, green compact is 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 1~5h of sintering at a temperature of 1030~1120 DEG C, are warming up to again after cooling 750~950 DEG C, insulation 1~10h tempering, then cooling down, and be warming up to 400~680 DEG C again carries out Ageing Treatment, and 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, according to production Can be used in mixed way for main-phase alloy with several rare earths by needs, but every kind of main-phase alloy is all manufactured separately.Then will R2Fe14There is B compounds the rare earth element of high anisotropy to be directly prepared into Grain-Boundary Phase addition, obtained by this method Magnet closer to ideal model, the characteristics of with high magnetic characteristics, low cost.
The beneficial effects of the invention are as follows:Principal phase is resolved into several R-Fe-M-B systems alloys, first prepare comprise only it is single The R of rare earthx- Fe-M-B alloys, then again by each Rx- Fe-M-B alloys mix, and add crystal-boundary phase alloy carry out magnetic field orientating, Base is pressed into, it is hereby achieved that more preferably crystal structure, is made high magnetic characteristics, the rare-earth permanent magnet of low cost.
After using the technical method, magnet has the special feature that is:A kind of rare earth of 80% intra-die accounts for rare earth in magnet More than the 95% of total amount;R in magnet2Fe14B compound anisotropies highest rare earth element crystal boundary concentration ratio in crystal grain It is internal high.
Brief description of the drawings
Fig. 1 is R-Fe-B magnet microscopic structure schematic diagrames;
Fig. 2 R2Fe14The corresponding relation figure of B compounds crystallization temperature and anisotropy field.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail.It should be appreciated that this hair Bright implementation is not limited to the following examples, and any formal accommodation and/or change made to the present invention will all fall Enter the scope of the present invention.
In the present invention, if not refering in particular to, all of part, percentage are unit of weight, equipment and raw material for being used etc. It is commercially available or commonly used in the art.Method in following embodiments, unless otherwise instructed, is the normal of this area Rule method.
Embodiment 1:
Main-phase alloy is by a kind of R1- Fe-M-B alloys and R3- Fe-M-B alloys are constituted, R1- Fe-M-B alloying components by The neodymium of 32wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Ti of the Cr of the W of the Mo of the V of the Ga of 0.10wt%, 0.10wt%, 0.10wt%, 0.10wt%, 0.10wt%, 0.10wt%, The Zr of 0.10wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
R3- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.30wt%, The Nb of the Cu of 0.10wt%, 0.50wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
By R1- Fe-M-B alloys and R3- Fe-M-B alloys use HD+JM powder, R1The μ of-Fe-M-B alloys particle mean size 3.5 M, R34.0 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys and R3- Fe-M-B alloys are by 5: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1070 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 2:
Main-phase alloy is by a kind of R1- Fe-M-B alloys and R4- Fe-M-B alloys are constituted, R1- Fe-M-B alloying components by The neodymium of 32wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Zr of the Ti of the Ga of 0.10wt%, 0.10wt%, 0.10wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
R4- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, The Nb of the Cu of 0.20wt%, 0.40wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
By R1- Fe-M-B alloys and R4- Fe-M-B alloys use HD+JM powder, R1The μ of-Fe-M-B alloys particle mean size 3.5 M, R44.0 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys and R4- Fe-M-B alloys are by 4: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1070 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 3:
Main-phase alloy is by a kind of R1- Fe-M-B alloys and R5- Fe-M-B alloys are constituted, R1- Fe-M-B alloying components by The neodymium of 32wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Zr of the V of the Ga of 0.10wt%, 0.10wt%, 0.10wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
R5- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.30wt%, The Nb of the V of the Cu of 0.150wt%, 0.10wt%, 0.50wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
By R1- Fe-M-B alloys and R5- Fe-M-B alloys use HD+JM powder, R1The μ of-Fe-M-B alloys particle mean size 3.5 M, R54.0 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys and R5- Fe-M-B alloys are by 3: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1060 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 4:
Main-phase alloy is by a kind of R2- Fe-M-B alloys and R3- Fe-M-B alloys are constituted, R2- Fe-M-B alloying components by The neodymium of 34wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Zr of the Ti of the Cr of the W of the Ga of 0.10wt%, 0.10wt%, 0.10wt%, 0.10wt%, 0.10wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;
R3- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.30wt%, The Nb of the Cu of 0.10wt%, 0.50wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
By R2- Fe-M-B alloys and R3- Fe-M-B alloys use HD+JM powder, R2The μ of-Fe-M-B alloys particle mean size 3.5 M, R34.0 μm of-Fe-M-B alloys particle mean size, by R2- Fe-M-B alloys and R3- Fe-M-B alloys are by 2: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1070 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 5:
Main-phase alloy is by a kind of R2- Fe-M-B alloys and R4- Fe-M-B alloys are constituted, R2- Fe-M-B alloying components by The neodymium of 35wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Zr of the Ti of the Ga of 0.10wt%, 0.10wt%, 0.10wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
R4- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, The Nb of the Cu of 0.20wt%, 0.40wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
By R2- Fe-M-B alloys and R4- Fe-M-B alloys use HD+JM powder, R2The μ of-Fe-M-B alloys particle mean size 3.5 M, R44.0 μm of-Fe-M-B alloys particle mean size, by R2- Fe-M-B alloys and R4- Fe-M-B alloys are by 1: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1070 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 6:
Main-phase alloy is by a kind of R2- Fe-M-B alloys and R5- Fe-M-B alloys are constituted, R2- Fe-M-B alloying components by The neodymium of 31wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Zr of the V of the Ga of 0.10wt%, 0.10wt%, 0.10wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
R5- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.30wt%, The Nb of the V of 0., 150wt% Cu, 0.10wt%, 0.50wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
By R2- Fe-M-B alloys and R5- Fe-M-B alloys use HD+JM powder, R2The μ of-Fe-M-B alloys particle mean size 3.5 M, R54.0 μm of-Fe-M-B alloys particle mean size, by R2- Fe-M-B alloys and R5- Fe-M-B alloys are by 10: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1060 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 7:
Main-phase alloy is by a kind of R1- Fe-M-B alloys and R2- Fe-M-B alloys are constituted, R1- Fe-M-B alloying components by The neodymium of 31wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Zr of the V of the Ga of 0.10wt%, 0.10wt%, 0.10wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
R2- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.30wt%, The Nb of the V of 0., 150wt% Cu, 0.10wt%, 0.50wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
By R1- Fe-M-B alloys and R2- Fe-M-B alloys use HD+JM powder, R1The μ of-Fe-M-B alloys particle mean size 3.5 M, R53.5 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys and R2- Fe-M-B alloys are by 3: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1080 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 8:
Main-phase alloy is by a kind of R1- Fe-M-B alloys, R2- Fe-M-B alloys and R4- Fe-M-B alloys are constituted, R1-Fe-M-B Alloying component by 31wt% neodymium, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, The Zr of the Ga of the Nb of 0.50wt%, 0.10wt%, 0.10wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
R2- Fe-M-B alloying components by 33wt% neodymium, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.30wt%, The Ga of the Nb of the Cu of 0.15wt%, 0.50wt%, 0.10wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
R4- Fe-M-B alloying components by 27wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.30wt%, The Nb of the V of 0., 150wt% Cu, 0.10wt%, 0.50wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
By R1- Fe-M-B alloys, R2- Fe-M-B alloys and R4- Fe-M-B alloys all use HD+JM powder, R1-Fe-M-B Alloy and R22.5 μm of-Fe-M-B alloys particle mean size, R44.5 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys, R2- Fe-M-B alloys and R4- Fe-M-B alloys are by 3: 1: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1070 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 9:
Main-phase alloy is by a kind of R1- Fe-M-B alloys, R2- Fe-M-B alloys, R3- Fe-M-B alloys, R4- Fe-M-B alloys And R5- Fe-M-B alloys are constituted, R1- Fe-M-B alloying components by 31wt% neodymium, the B of 1.00wt%, the Co of 1.00wt%, The Zr of the Ga of the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, 0.10wt%, 0.10wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R2- Fe-M-B alloying components by 33wt% neodymium, the B of 1.00wt%, The Ga of the Nb of the Cu of the Al of the Co of 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R3- Fe-M-B alloying components by 27wt% lanthanum, the B of 1.00wt%, The Nb of the Al of the Co of 1.00wt%, 0.30wt%, 0., 150wt% Cu, the V of 0.10wt%, 0.50wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R4- Fe-M-B alloying components by 33wt% neodymium, the B of 1.00wt%, The Ga of the Nb of the Cu of the Al of the Co of 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R5- Fe-M-B alloying components by 28wt% lanthanum, the B of 1.00wt%, The Nb of the Al of the Co of 1.00wt%, 0.30wt%, 0., 150wt% Cu, the V of 0.10wt%, 0.50wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;
By R1- Fe-M-B alloys, R2- Fe-M-B alloys, R3- Fe-M-B alloys, R4- Fe-M-B alloys and R5- Fe-M-B is closed Gold all uses HD+JM powder, R1- Fe-M-B alloys and R23 μm of-Fe-M-B alloys particle mean size, R3- Fe-M-B alloys, R4-Fe- M-B alloys, R45.0 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys, R2- Fe-M-B alloys and R4- Fe-M-B is closed Gold is by 3: 1: 1: 1: 1 mixing.
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1060 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Embodiment 10:
Main-phase alloy is by a kind of R1- Fe-M-B alloys and R4- Fe-M-B alloys are constituted, R1- Fe-M-B alloying components by The neodymium of 32wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, The Zr of the Ti of the Ga of 0.10wt%, 0.10wt%, 0.10wt% and the Fe compositions of surplus, are obtained using rapid hardening (SC) technique and closed Gold;
R4- Fe-M-B alloying components by 31wt% lanthanum, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, The Nb of the Cu of 0.20wt%, 0.40wt% and the Fe compositions of surplus, alloy is obtained using rapid hardening (SC) technique;
By R1- Fe-M-B alloys and R4- Fe-M-B alloys use HD+JM powder, R1The μ of-Fe-M-B alloys particle mean size 3.5 M, R44.0 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys and R4- Fe-M-B alloys are by 4: 1 mixing composition principal phase magnetic Powder.
Crystal boundary phase constituent by 45.00wt% iron, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, The Ga of the Nb of the Cu of 0.20wt%, 0.50wt%, 0.10wt% and the dysprosium composition of surplus, are obtained using rapid hardening (SC) technique and closed Gold;Crystal-boundary phase alloy uses HD+JM powder, and particle mean size is 3.0 μm.
Green compact then by mixed-powder oriented moulding, and are put into vacuum-sintering by main-phase alloy and crystal boundary Phase Proportion 10: 1 1070 DEG C × 4.5h sintering+910 DEG C × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet in stove, and magnetic property is shown in Table 1.
Embodiment 11:
Main-phase alloy is by a kind of R1- Fe-M-B alloys, R2- Fe-M-B alloys, R3- Fe-M-B alloys, R4- Fe-M-B alloys And R5- Fe-M-B alloys are constituted, R1- Fe-M-B alloying components by 31wt% neodymium, the B of 1.00wt%, the Co of 1.00wt%, The Zr of the Ga of the Nb of the Cu of the Al of 0.50wt%, 0.10wt%, 0.50wt%, 0.10wt%, 0.10wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R2- Fe-M-B alloying components by 33wt% neodymium, the B of 1.00wt%, The Ga of the Nb of the Cu of the Al of the Co of 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R3- Fe-M-B alloying components by 27wt% lanthanum, the B of 1.00wt%, The Nb of the Al of the Co of 1.00wt%, 0.30wt%, 0., 150wt% Cu, the V of 0.10wt%, 0.50wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R4- Fe-M-B alloying components by 33wt% neodymium, the B of 1.00wt%, The Ga of the Nb of the Cu of the Al of the Co of 1.00wt%, 0.30wt%, 0.15wt%, 0.50wt%, 0.10wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;R5- Fe-M-B alloying components by 28wt% lanthanum, the B of 1.00wt%, The Nb of the Al of the Co of 1.00wt%, 0.30wt%, 0., 150wt% Cu, the V of 0.10wt%, 0.50wt% and the Fe groups of surplus Into using the prepared alloy of rapid hardening (SC) technique;
By R1- Fe-M-B alloys, R2- Fe-M-B alloys, R3- Fe-M-B alloys, R4- Fe-M-B alloys and R5- Fe-M-B is closed Gold all uses HD+JM powder, R1- Fe-M-B alloys and R23 μm of-Fe-M-B alloys particle mean size, R3- Fe-M-B alloys, R4-Fe- M-B alloys, R45.0 μm of-Fe-M-B alloys particle mean size, by R1- Fe-M-B alloys, R2- Fe-M-B alloys and R4- Fe-M-B is closed Gold is by 3: 1: 1: 1: 1 mixing.
Grain-Boundary Phase is metal dysprosium commercially, and crystal-boundary phase alloy uses HD+JM powder, and particle mean size is 1.0 μm. By principal phase magnetic and Grain-Boundary Phase magnetic by 1: 0.005 weight than mixing;
Then by mixed-powder oriented moulding, and green compact are put into+910 DEG C of 1060 DEG C × 4.5h sintering in vacuum sintering furnace × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Comparative example 1:
Composition:The neodymium of 15.00wt%, the praseodymium of 4.00wt%, the lanthanum of 4.00wt%, the cerium of 4.00wt%, 4.00wt%'s Yttrium, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, the Nb of 0.50wt%, 0.10wt%'s The Fe of Ga and surplus, alloy is obtained using rapid hardening (SC) technique, and alloy is used into HD+JM powder, and particle mean size is 3.5 μm.So Afterwards by mixed-powder oriented moulding, and green compact are put into+910 DEG C × 2h+510 DEG C of 1070 DEG C × 4.5h sintering in vacuum sintering furnace × 4h Ageing Treatments obtain permanent magnet, and magnetic property is shown in Table 1.
Comparative example 2:
Composition:The neodymium of 14.50wt%, the praseodymium of 4.00wt%, the lanthanum of 4.00wt%, the cerium of 4.00wt%, 4.00wt%'s Yttrium, the dysprosium of 0.50wt%, the B of 1.00wt%, the Co of 1.00wt%, the Al of 0.50wt%, the Cu of 0.10wt%, 0.50wt%'s The Ga of Nb, the 0.10wt% and Fe of surplus, alloy is obtained using rapid hardening (SC) technique, and alloy is used into HD+JM powder, average grain Spend is 3.8 μm.Then by mixed-powder oriented moulding, and green compact are put into 1060 DEG C × 4.5h sintering+910 in vacuum sintering furnace DEG C × 2h+510 DEG C × 4h Ageing Treatments obtain permanent magnet, magnetic property is shown in Table 1.
As it can be seen from table 1 embodiment 1~9 is praseodymium, neodymium and lanthanum, cerium, yttrium element alloy being mixed to get by different proportion As a result, even if lanthanum, cerium, the accounting of yttrium reach 50% can also be obtained commercially valuable magnet, this is due to crystal boundary in magnet Still there is a certain amount of praseodymium neodymium hardening crystal boundary in phase.And in comparative example 1, magnetic property is very low, this is due to magnet Grain-Boundary Phase base Originally it is made up of lanthanum cerium yttrium, it is impossible to form continuous crystal boundary, so coercivity is very low.
Embodiment 10 and embodiment 11 be crystal boundary addition containing the magnetic property result after disprosium alloy, after addition dysprosium in Grain-Boundary Phase and A small amount of Dy is formd in transition zone2Fe14The alloy hardening crystal boundaries of MB, make the magnetic property of magnet be significantly improved.And in comparative example 2 In, dysprosium element enters intra-die, and coercitive effect also can be to a certain degree improved certainly, but effect is much worse than dysprosium and enters crystal boundary Phase.
The magnetic property comparing result of table 1
Remanent magnetism Br(kGs) Coercivity HcJ(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
Embodiment described above is a kind of preferably scheme of the invention, not makees any formal to the present invention Limitation, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.

Claims (2)

1. a kind of high-performance and low-cost rare earth permanent-magnetic material, it is characterised in that the material is main to press 1 by principal phase and crystal-boundary phase alloy : the weight of 0.005-0.2 is formed than mixed sintering,
Described principal phase is by R1- Fe-M-B alloys, R2- Fe-M-B alloys, R3- Fe-M-B alloys, R4- Fe-M-B alloys, R5- The mixture of any two or more composition in Fe-M-B alloys, wherein R1It is praseodymium, R2It is neodymium, R3It is lanthanum, R4It is cerium, R5 It is yttrium, M is selected from one or more in Co, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga,
Foregoing RxIn-Fe-M-B alloys, x takes the positive integer of 1-5,26 wt%≤Rx≤ 33wt%;0 wt%≤M≤ 10wt%;0.9 wt%≤B≤2wt%;Remaining is iron and inevitable impurity;
Described crystal-boundary phase alloy is a kind of rich rare earth alloy, and the composition of the alloy is RQ, in formula R be praseodymium, neodymium, gadolinium, promethium, europium, One or more in samarium, dysprosium, terbium, Q is the one kind or several in Fe, Co, Ni, Nb, V, Mo, W, Cr, Al, Ti, Zr, Cu, Ga, B Kind;In crystal-boundary phase alloy, 0≤Q≤72wt%, remaining is R and inevitable impurity;The particle mean size of crystal-boundary phase alloy is 0.5~5μm;
The preparation method of the high-performance and low-cost rare earth permanent-magnetic material comprises the following steps:
1. principal phase is prepared, R is obtained using strip castingx- Fe-M-B alloys, by Rx- Fe-M-B uses HD+JM powder;
2. crystal-boundary phase alloy is prepared, crystal-boundary phase alloy is obtained using strip casting, crystal-boundary phase alloy is used into HD+JM powder;
3. well mixed alloy powder is put into magnetic by principal phase and crystal-boundary phase alloy by 1: 0.005-0.2 weight ratio mixing Orientation is pressed into green compact in, green compact is sintered in sintering furnace and obtains rare-earth permanent magnet.
2. a kind of high-performance and low-cost rare earth permanent-magnetic material according to claim 1, it is characterised in that:Step 3. in, burn Knot process is:Green compact are put into vacuum sintering furnace 1~5h of sintering at a temperature of 1030~1120 DEG C, are warming up to again after cooling 750~950 DEG C, insulation 1~10h tempering, then cooling down, and be warming up to 400~680 DEG C again carries out Ageing Treatment, and the time is 1 ~10h.
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