CN102568729A - Method for preparing bulk composite nanocrystalline rare earth permanent magnetic material - Google Patents
Method for preparing bulk composite nanocrystalline rare earth permanent magnetic material Download PDFInfo
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Abstract
The invention discloses a method for preparing bulk composite nanocrystalline rare earth permanent magnetic material. The method comprises the steps of: firstly, preparing an alloy ingot by vacuum smelting method; secondly, melting the alloy ingot and applying an external pulsed electric field in the molten alloy ingot to carry out electric pulse modification treatment; thirdly, preparing the bulk composite nanocrystalline rare earth permanent magnetic material by rapid solidification method in a copper mold under the action of an external pulsed magnetic field; finally, subjecting the material to proper thermal treatment according to the concrete condition. The method provided by the invention is simple and has short production period, and the prepared bulk composite nanocrystalline rare earth permanent magnetic material has fine grains, uniform texture, high density, and good comprehensive permanent magnetic performance.
Description
Technical field
The invention belongs to the magnetic material preparation field, be specifically related to a kind of method for preparing the bulk nano-crystalline composite permanent magnetic RE material.
Background technology
Nanocrystalline composite permanent magnetic RE material by nanocrystalline hard magnetic phase (like Nd
2Fe
14B, Sm
2Fe
17N
3) with soft magnetism mutually (like α-Fe, Fe
3B) constitute; Hard magnetic has high HCJ mutually, and soft magnetism has high saturation magnetization mutually, and there is the magnetic exchange-coupling interaction in the two-phase interface place; Make material have the high saturation and magnetic intensity and hard magnetic high-coercive force mutually of soft magnetism phase simultaneously, thereby have high energy product.The magnetic energy product theoretical value of nano-crystal composite permanent magnetic body can reach 1000kJ/m
3, higher nearly 1 times than the theoretical magnetic energy product of Sintered NdFeB magnet.And the content of rare earth of nanocrystalline composite permanent-magnet material is few, and low price has the wide development application prospect, has caused domestic and international investigation of materials personnel's attention.
At present, the preparation method of said material mainly contains melt-quenching method and mechanical alloying method, and resulting product mainly is strip and powder, drop into actual use and must be made into block.Adopt the conventional powder sintering process to prepare fully dense block materials and can cause nanocrystal to grow up, thereby significantly reduce magnetic property.Therefore people mix Magnaglo and binding agent, process bonded permanent magnet, but because the magnetic property of magnetic has been diluted in the adding of non magnetic binding agent and auxiliary agent, are unfavorable for the raising of magnet magnetic property.Simultaneously owing to have kind and the addition of uniformity consistency, the binding agent of magnetic, the problems such as flowability of magnetic, often cause the density of bonded permanent magnet relatively low, mechanical strength is relatively poor, in use is easy to generate distortion or breaks.Also there are some researchers to adopt discharge plasma sintering technique (Spark Plasma Sintering; Be called for short the SPS technology; One Chinese patent application number: 200510087114.5 and 2006910089122.8); The superelevation hot pressing and sintering technique (one Chinese patent application number: 200810063723.0), electric field activation pressure assisted sintering technology (one Chinese patent application number: 200510021982.3) prepare the bulk nano-crystalline composite permanent magnetic RE material.These methods can obtain the higher nanocrystalline composite block permanent magnetic material of density; But still can not avoid the complex process of foundry alloy melting-broken powder process-magnetic compacting-sinter molding-machining, and technology is loaded down with trivial details, and the production cycle is long; Magnetic is easy to generate oxidation and pollution; And high to agglomerating plant and technology controlling and process requirement, otherwise excessively growing up of nanocrystal taken place easily, cause magnetism of material to worsen.Also have some researchers to adopt the copper mold technology to prepare amorphous block material, prepare nanocrystalline composite permanent-magnet material through crystallization and thermal treatment then.But the cooling capacity of copper mold is limited; The amorphous formation ability of RE permanent magnetic alloy such as Nd-Fe-B and Sm-Co all a little less than; Have to improve the amorphous formation ability of alloy, thereby sacrificed the magnetic property of magnet through the mode that improves boron content or add nonmagnetic elements in a large number.On the other hand; Soft magnetism mutually with Hard Magnetic mutually the crystallization temperature of two kinds of magnetic phases differ bigger; And can occur metastable phase in the amorphous crystallization process and influence magnetic property (seeing IEEE Transactions On Magnetics 31 (1995) 3596-3601); Therefore control has all proposed very high requirement with technological parameter to Equipment for Heating Processing during crystallization, otherwise the phenomenon that crystallization is incomplete or crystal grain is grown up unusually takes place easily, causes the decline of magnet magnetic property.
In order to overcome above-mentioned deficiency; The present invention adopts impulse electric field that alloy melt is carried out inoculated; Rapid solidification under pulsed magnetic field action then can obtain that crystal grain is tiny, even tissue, density is high, magnetic property is good bulk nano-crystalline composite permanent magnetic RE material.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the bulk nano-crystalline composite permanent magnetic RE material.The inventive method technology is simple, and is with short production cycle, and prepared bulk nano-crystalline permanent magnetic material crystal grain is tiny, even tissue, density high, has good comprehensive permanent magnetism performance.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of concrete steps that prepare the method for bulk nano-crystalline rare earth permanent-magnetic material are:
1) at first prepared composition is R
xTM
100-x-yM
yAlloy cast ingot, R is a rare earth element in the formula, wherein the content of Nd or Pr is no less than the 70at% of R total amount; TM is transition metal, IIIA family metal or IVA family metal, and wherein the content of Fe is no less than the 60at% of TM total amount; M is a metalloid, and wherein B content is no less than the 80at% of M total amount; X is 3.5 ~ 11.6at%, and y is 5 ~ 30at%; Ingot casting melting in arc furnace, induction furnace or magnetic levitation melting stove, melting is carried out under vacuum or high-purity argon gas protection.
2) ingot casting is put into the bottom and open the quartz glass tube of aperture, and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, place water cooled copper mould in the lower end of quartz ampoule.Ingot casting induction melting under the high-purity argon gas protection becomes liquid, then electrode is inserted in the melt, applies impulse electric field, carries out electro-pulse modification and handles.When the alloy melt electro-pulse modification was handled, the impulse electric field parameter of employing was: pulse frequency 50 ~ 2500Hz, pulse current peak density 10 ~ 5000A/cm
2, pulse duration 5 ~ 500 μ s, processing time 5 ~ 120s.With after-applied pulsed magnetic field, the magnetic line of force passes the copper mold cavity, then opens the air valve that links to each other with quartz ampoule, and melt injects the copper mold cavity through the aperture of quartz ampoule bottom fast under the effect of spraying air pressure, make the foundry goods of the shape that designs.When alloy melt injected water cooled copper mould, the pulsed magnetic field parameter of employing was: pulse frequency 20 ~ 500Hz, and pulsed magnetic field peak strength 0.3 ~ 5T, pulse duration 10 ~ 600 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.The cooling rate of alloy melt in water cooled copper mould is 100 ~ 5000 ℃/second.
3) as the case may be above-mentioned foundry goods is carried out appropriate heat treatment, heat treatment is carried out under vacuum or high-purity argon gas protection, and heat treatment temperature is 300 ~ 800 ℃, and temperature retention time 0 ~ 10 minute is chilled to room temperature then soon.
Remarkable advantage of the present invention is:
1) the present invention is owing to adopted the impulse electric field inoculated in alloy melt; And under pulsed magnetic field action, the melt spray to cast is gone into the water-cooled copper mold; The block rare earth permanent-magnetic material of preparation has tiny, uniform nanometer crystal microstructure structure; Thereby strengthened soft magnetism mutually with the hard magnetic exchange-coupling interaction between nanocrystal mutually, and the magnet density is high, can obtain good comprehensive permanent magnetism performance and mechanical strength.
2) the bulk nano-crystalline rare earth permanent-magnetic material of the inventive method preparation, required ree content is less, and is with low cost, and can prepare the magnet of different shape through changing the shape and the size of copper mold cavity, satisfies the needs of practical applications.
3) bulk nano-crystalline rare earth permanent-magnetic material preparation method of the present invention, production equipment is simple, and technological process is simple, is convenient to operation, and processes expend is few.
Description of drawings
Fig. 1 is the demagnetization curve figure of bulk nano-crystalline composite permanent magnetic RE material among the embodiment 1.
Fig. 2 is the X ray diffracting spectrum of bulk nano-crystalline composite permanent magnetic RE material among the embodiment 1.
Fig. 3 is micro-organization chart's (transmission electron microscope photo) of bulk nano-crystalline composite permanent magnetic RE material among the embodiment 1.
Embodiment
Elaborate below in conjunction with embodiment.
Adopt purity greater than the Nd of 99.7wt%, Pr, Tb, Dy, Fe, Co, Zr, Ti, Ga, B, C etc. as raw material, be R according to composition
xTM
100-x-yM
yThe proportioning of (R is a rare earth element, and TM is transition metal, IIIA family metal or IVA family metal, and M is a metalloid) prepares, and x is 3.5 ~ 11.6at% in the formula, and y is 5 ~ 30at%, puts into induction furnace, arc furnace or magnetic levitation melting stove, is evacuated down to 10
-5Pa or more than, feed 0.5 * 10 then
5~ 1.3 * 10
5The high-purity argon gas of Pa, melt back 4 ~ 8 times is to guarantee to obtain the uniform ingot casting of composition under argon shield; Then, ingot casting is put into the bottom open the quartz glass tube of aperture, and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, place water cooled copper mould, be evacuated down to 10 in the lower end of quartz ampoule
-5Pa or more than, feed 0.5 * 10 then
5~ 1.3 * 10
5The high-purity argon gas of Pa, ingot casting induction melting under argon shield becomes liquid, then electrode is inserted in the melt, applies impulse electric field, carries out electro-pulse modification and handles.When the alloy melt electro-pulse modification was handled, the impulse electric field parameter of employing was: pulse frequency 50 ~ 2500Hz, pulse current peak density 10 ~ 5000A/cm
2, pulse duration is 5 ~ 500 μ s, the processing time is 5 ~ 120s.With after-applied pulsed magnetic field, the magnetic line of force passes the copper mold cavity, then opens the air valve that links to each other with quartz ampoule, and melt injects the copper mold cavity through the aperture of quartz ampoule bottom fast under the effect of spraying air pressure, make the foundry goods of the shape that designs.When alloy melt injected water cooled copper mould, the pulsed magnetic field parameter of employing was: pulse frequency 20 ~ 500Hz, and pulsed magnetic field peak strength 0.3 ~ 5T, pulse duration 10 ~ 600 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.At last, as the case may be the gained foundry goods is put into heat-treatment furnace, be evacuated to 10
-5Pa or more than, feed 1.0 * 10
5~ 1.5 * 10
5The high-purity argon gas of Pa is heated to 300 ~ 800 ℃, and temperature retention time 0 ~ 10 minute is chilled to room temperature then soon, obtains finished product.
Embodiment 1
Adopting purity is that Nd, Fe, Co, Zr, Nb, Cr, Mo and the B of 99.9wt% is as raw material, according to Nd
10.5Fe
56Co
12Zr
1Nb
2Cr
1Mo
0.5B
17Proportioning, put into the magnetic levitation melting stove, be evacuated down to 10
-5Pa feeds 1.1 * 10 then
5The high-purity argon gas of Pa, melt back is 6 times under argon shield, to guarantee to obtain the uniform ingot casting of composition, for the composition that guarantees ingot casting meets design mix basically, must pay close attention to the waste of alloying element in fusion process.Then; Alloy cast ingot is put into the bottom have the quartz glass tube of aperture (aperture is 0.7mm), and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, water cooled copper mould is placed in the quartz ampoule lower end; Copper mold cavity internal diameter is 2mm, and length is 50mm.The vacuum degree that is evacuated in the spray to cast furnace cavity is 10
-5Pa feeds 0.7 * 10 then
5The high-purity argon gas of Pa, ingot casting induction melting under the high-purity argon gas protection becomes liquid, then electrode is inserted in the melt; Apply impulse electric field; Carry out electro-pulse modification and handle, the impulse electric field parameter of employing is: pulse frequency 1200Hz, pulse current peak density 3000A/cm
2, pulse duration 100 μ s, the processing time is 60s.With after-applied pulsed magnetic field; Its magnetic line of force passes the copper mold cavity equably; And perpendicular to the axis direction of copper mold cavity, the pulsed magnetic field parameter of employing is: pulse frequency 300Hz, pulsed magnetic field peak strength 2T; Pulse duration 50 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.Then open the air valve that links to each other with quartz ampoule, the micropore jet bottom quartz ampoule is in water cooled copper mould under the effect of spraying air pressure for melt, and obtaining diameter is 2mm, and length is the bar-shaped alloy of 50mm.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.76T,
iH
c=605kA/m, (BH)
Max=102kJ/m
3, Fig. 1 is the demagnetization curve figure of this sample.With the phase constituent of X-ray diffractometer working sample, test result is seen Fig. 2, can know that this sample is by Nd
2Fe
14B phase and α-Fe phase composition.With this sample microscopic structure of transmission electron microscope observation, as shown in Figure 3, can find out that microscopic structure is fine and close, crystallite dimension is all less than 100nm.
The alloy cast ingot of identical component in the present embodiment adopts traditional conventional copper mold rapid solidification method (no pulse electric field and pulsed magnetic field are handled), and making diameter is 2mm, and length is the bar-shaped alloy of 50mm.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.63T,
iH
c=457kA/m, (BH)
Max=55kJ/m
3Can find out that than conventional copper mold rapid solidification method, remanent magnetism, HCJ and the maximum magnetic energy product of the nanocrystalline composite permanent magnetic RE material of the present invention's preparation all are significantly improved.
Embodiment 2
Adopting purity is that Nd, Dy, Fe, Y, Co, Nb, Zr, Ti, Si and the B of 99.9wt% is as raw material, according to Nd
9Dy
0.5Fe
59Y
2Co
9Nb
1Zr
1Ti
1.5Si
1B
16Proportioning, put into the magnetic levitation melting stove, be evacuated down to 10
-5Pa feeds 1.1 * 10 then
5The high-purity argon gas of Pa, melt back is 6 times under argon shield, to guarantee to obtain the uniform ingot casting of composition, for the composition that guarantees ingot casting meets design mix basically, must pay close attention to the waste of alloying element in fusion process.Then; Alloy cast ingot is put into the bottom have the quartz glass tube of aperture (aperture is 0.7mm), and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, water cooled copper mould is placed in the quartz ampoule lower end; Copper mold cavity internal diameter is 1.5mm, and length is 50mm.The vacuum degree that is evacuated in the spray to cast furnace cavity is 10
-5Pa feeds 0.7 * 10 then
5The high-purity argon gas of Pa, ingot casting induction melting under the high-purity argon gas protection becomes liquid, then electrode is inserted in the melt; Apply impulse electric field; Carry out electro-pulse modification and handle, the impulse electric field parameter of employing is: pulse frequency 1500Hz, pulse current peak density 2500A/cm
2, pulse duration 50 μ s, the processing time is 90s.With after-applied pulsed magnetic field; Its magnetic line of force passes the copper mold cavity equably; And perpendicular to the axis direction of copper mold cavity, the pulsed magnetic field parameter of employing is: pulse frequency 200Hz, pulsed magnetic field peak strength 3T; Pulse duration 100 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.Then open the air valve that links to each other with quartz ampoule, the micropore jet bottom quartz ampoule is in water cooled copper mould under the effect of spraying air pressure for melt, and obtaining diameter is 1.5mm, and length is the bar-shaped alloy of 50mm.The bar-shaped alloy of gained is packed in the vacuum heat treatment furnace, be evacuated to 10
-5Pa feeds 1.2 * 10
5The high-purity argon gas of Pa is heated to 600 ℃ under the high-purity argon gas protection, insulation 30s is chilled to room temperature soon.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.81T,
iH
c=623kA/m, (BH)
Max=115kJ/m
3
The alloy cast ingot of identical component in the present embodiment adopts traditional conventional copper mold rapid solidification method (no pulse electric field and pulsed magnetic field are handled), and making diameter is 1.5mm, and length is the bar-shaped alloy of 50mm, and through identical Technology for Heating Processing.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.67T,
iH
c=503kA/m, (BH)
Max=63kJ/m
3Can find out that than conventional copper mold rapid solidification method, remanent magnetism, HCJ and the maximum magnetic energy product of the nanocrystalline composite permanent magnetic RE material of the present invention's preparation all are significantly improved.
Embodiment 3
Adopting purity is that Nd, La, In, Fe, Co, Zr, Ti, Nb, Mo and the B of 99.9wt% is as raw material, according to (Nd
0.
95La
0.05)
4.5In
0.5Fe
53.5Co
10Zr
2Ti
1Nb
1Mo
1.5B
26Proportioning, put into the magnetic levitation melting stove, be evacuated down to 10
-5Pa feeds 1.1 * 10 then
5The high-purity argon gas of Pa, melt back is 6 times under argon shield, to guarantee to obtain the uniform ingot casting of composition, for the composition that guarantees ingot casting meets design mix basically, must pay close attention to the waste of alloying element in fusion process.Then; Alloy cast ingot is put into the bottom have the quartz glass tube of aperture (aperture is 0.7mm), and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, water cooled copper mould is placed in the quartz ampoule lower end; Copper mold cavity internal diameter is 5mm, and length is 50mm.The vacuum degree that is evacuated in the spray to cast furnace cavity is 10
-5Pa feeds 0.7 * 10 then
5The high-purity argon gas of Pa, ingot casting induction melting under the high-purity argon gas protection becomes liquid, then electrode is inserted in the melt; Apply impulse electric field; Carry out electro-pulse modification and handle, the impulse electric field parameter of employing is: pulse frequency 50Hz, pulse current peak density 5000A/cm
2, pulse duration 500 μ s, the processing time is 7s.With after-applied pulsed magnetic field; Its magnetic line of force passes the copper mold cavity equably; And perpendicular to the axis direction of copper mold cavity, the pulsed magnetic field parameter of employing is: pulse frequency 20Hz, pulsed magnetic field peak strength 5T; Pulse duration 600 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.Then open the air valve that links to each other with quartz ampoule, the micropore jet bottom quartz ampoule is in water cooled copper mould under the effect of spraying air pressure for melt, and obtaining diameter is 5mm, and length is the bar-shaped alloy of 50mm.The bar-shaped alloy of gained is packed in the vacuum heat treatment furnace, be evacuated to 10
-5Pa feeds 1.2 * 10
5The high-purity argon gas of Pa is heated to 350 ℃ under the high-purity argon gas protection, insulation 10min is chilled to room temperature soon.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.91T,
iH
c=315kA/m, (BH)
Max=67kJ/m
3
The alloy cast ingot of identical component in the present embodiment adopts traditional conventional copper mold rapid solidification method (no pulse electric field and pulsed magnetic field are handled), and making diameter is 5mm, and length is the bar-shaped alloy of 50mm, and through identical Technology for Heating Processing.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.65T,
iH
c=227kA/m, (BH)
Max=30kJ/m
3Can find out that than conventional copper mold rapid solidification method, remanent magnetism, HCJ and the maximum magnetic energy product of the nanocrystalline composite permanent magnetic RE material of the present invention's preparation all are significantly improved.
Embodiment 4
Adopting purity is that Nd, Pr, Tb, Fe, Co, Ga, Zr, Ti, Nb, V and the B of 99.9wt% is as raw material, according to Nd
7Pr
2Tb
0.
5Fe
59.5Co
6Ga
1Zr
1Ti
2Nb
1V
1B
19Proportioning, put into the magnetic levitation melting stove, be evacuated down to 10
-5Pa feeds 1.1 * 10 then
5The high-purity argon gas of Pa, melt back is 6 times under argon shield, to guarantee to obtain the uniform ingot casting of composition, for the composition that guarantees ingot casting meets design mix basically, must pay close attention to the waste of alloying element in fusion process.Then; Alloy cast ingot is put into the bottom have the quartz glass tube of aperture (aperture is 0.7mm), and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, water cooled copper mould is placed in the quartz ampoule lower end; Copper mold cavity internal diameter is 3mm, and length is 50mm.The vacuum degree that is evacuated in the spray to cast furnace cavity is 10
-5Pa feeds 0.7 * 10 then
5The high-purity argon gas of Pa, ingot casting induction melting under the high-purity argon gas protection becomes liquid, then electrode is inserted in the melt; Apply impulse electric field; Carry out electro-pulse modification and handle, the impulse electric field parameter of employing is: pulse frequency 2500Hz, pulse current peak density 10A/cm
2, pulse duration 8 μ s, the processing time is 120s.With after-applied pulsed magnetic field; Its magnetic line of force passes the copper mold cavity equably; And perpendicular to the axis direction of copper mold cavity, the pulsed magnetic field parameter of employing is: pulse frequency 500Hz, pulsed magnetic field peak strength 0.3T; Pulse duration 10 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.Then open the air valve that links to each other with quartz ampoule, the micropore jet bottom quartz ampoule is in water cooled copper mould under the effect of spraying air pressure for melt, and obtaining diameter is 3mm, and length is the bar-shaped alloy of 50mm.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.83T,
iH
c=557kA/m, (BH)
Max=108kJ/m
3
The alloy cast ingot of identical component in the present embodiment adopts traditional conventional copper mold rapid solidification method (no pulse electric field and pulsed magnetic field are handled), and making diameter is 3mm, and length is the bar-shaped alloy of 50mm.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.62T,
iH
c=405kA/m, (BH)
Max=52kJ/m
3Can find out that than conventional copper mold rapid solidification method, remanent magnetism, HCJ and the maximum magnetic energy product of the nanocrystalline composite permanent magnetic RE material of the present invention's preparation all are significantly improved.
Embodiment 5
Adopting purity is that Nd, Pr, Fe, Co, Y, Zr, Ti, Nb, Cr and the B of 99.9wt% is as raw material, according to Nd
3Pr
1Fe
71.5Co
8Y
1.5Zr
1Ti
2Nb
1Cr
1B
10Proportioning, put into the magnetic levitation melting stove, be evacuated down to 10
-5Pa feeds 1.1 * 10 then
5The high-purity argon gas of Pa, melt back is 6 times under argon shield, to guarantee to obtain the uniform ingot casting of composition, for the composition that guarantees ingot casting meets design mix basically, must pay close attention to the waste of alloying element in fusion process.Then; Alloy cast ingot is put into the bottom have the quartz glass tube of aperture (aperture is 0.7mm), and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, water cooled copper mould is placed in the quartz ampoule lower end; Copper mold cavity internal diameter is 2.5mm, and length is 50mm.The vacuum degree that is evacuated in the spray to cast furnace cavity is 10
-5Pa feeds 0.7 * 10 then
5The high-purity argon gas of Pa, ingot casting induction melting under the high-purity argon gas protection becomes liquid, then electrode is inserted in the melt; Apply impulse electric field; Carry out electro-pulse modification and handle, the impulse electric field parameter of employing is: pulse frequency 300Hz, pulse current peak density 500A/cm
2, pulse duration 250 μ s, the processing time is 25s.With after-applied pulsed magnetic field; Its magnetic line of force passes the copper mold cavity equably; And perpendicular to the axis direction of copper mold cavity, the pulsed magnetic field parameter of employing is: pulse frequency 70Hz, pulsed magnetic field peak strength 1T; Pulse duration 300 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.Then open the air valve that links to each other with quartz ampoule, the micropore jet bottom quartz ampoule is in water cooled copper mould under the effect of spraying air pressure for melt, and obtaining diameter is 2.5mm, and length is the bar-shaped alloy of 50mm.The bar-shaped alloy of gained is packed in the vacuum heat treatment furnace, be evacuated to 10
-5Pa feeds 1.2 * 10
5The high-purity argon gas of Pa is heated to 750 ℃ under the high-purity argon gas protection, insulation 2min is chilled to room temperature soon.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.94T,
iH
c=338kA/m, (BH)
Max=75kJ/m
3
The alloy cast ingot of identical component in the present embodiment adopts traditional conventional copper mold rapid solidification method (no pulse electric field and pulsed magnetic field are handled), and making diameter is 2.5mm, and length is the bar-shaped alloy of 50mm, and through identical Technology for Heating Processing.Use vibrating specimen magnetometer, the magnetic property result who measures magnet is following: B
r=0.68T,
iH
c=213kA/m, (BH)
Max=32kJ/m
3Can find out that than conventional copper mold rapid solidification method, remanent magnetism, HCJ and the maximum magnetic energy product of the nanocrystalline composite permanent magnetic RE material of the present invention's preparation all are significantly improved.
The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. method for preparing the bulk nano-crystalline composite permanent magnetic RE material, it is characterized in that: described preparation method's concrete steps are:
1) at first prepared composition is R
xTM
100-x-yM
yAlloy cast ingot, R is a rare earth element in the formula, wherein the content of Nd or Pr is no less than the 70at% of R total amount; TM is transition metal, IIIA family metal or IVA family metal, and wherein the content of Fe is no less than the 60at% of TM total amount; M is a metalloid, and wherein B content is no less than the 80at% of M total amount; X is 3.5 ~ 11.6at%, and y is 5 ~ 30at%; Ingot casting melting in arc furnace, induction furnace or magnetic levitation melting stove, melting is carried out under vacuum or high-purity argon gas protection;
2) ingot casting is put into the bottom and open the quartz glass tube of aperture, and place in the vacuum spray to cast stove that has impulse electric field and pulsed magnetic field apparatus, place water cooled copper mould in the lower end of quartz ampoule; Ingot casting induction melting under the high-purity argon gas protection becomes liquid, then electrode is inserted in the melt, applies impulse electric field, carries out electro-pulse modification and handles; With after-applied pulsed magnetic field, the magnetic line of force passes the copper mold cavity, then opens the air valve that links to each other with quartz ampoule, and melt injects the copper mold cavity through the aperture of quartz ampoule bottom fast under the effect of spraying air pressure, make the foundry goods of the shape that designs;
3) as the case may be above-mentioned foundry goods is carried out appropriate heat treatment: heat treatment is carried out under vacuum or high-purity argon gas protection, and heat treatment temperature is 300 ~ 800 ℃, and temperature retention time is 0 ~ 10 minute, is chilled to room temperature then soon.
2. the method for preparing the bulk nano-crystalline composite permanent magnetic RE material according to claim 1; It is characterized in that: when the alloy melt electro-pulse modification is handled; The impulse electric field parameter that adopts is pulse frequency 50 ~ 2500Hz, pulse current peak density 10 ~ 5000A/cm
2, pulse duration 5 ~ 500 μ s, processing time 5 ~ 120s.
3. the method for preparing the bulk nano-crystalline composite permanent magnetic RE material according to claim 1; It is characterized in that: when alloy melt injects water cooled copper mould; The pulsed magnetic field parameter that adopts is pulse frequency 20 ~ 500Hz; Pulsed magnetic field peak strength 0.3 ~ 5T, pulse duration 10 ~ 600 μ s, the processing time is for to begin until the alloy cool to room temperature from spray to cast.
4. the method for preparing the bulk nano-crystalline composite permanent magnetic RE material according to claim 1 is characterized in that: the cooling rate of alloy melt in water cooled copper mould is 100 ~ 5000 ℃/second.
5. product that preparation method as claimed in claim 1 makes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794355A (en) * | 2014-02-25 | 2014-05-14 | 刘洋 | Method for preparing neodymium iron boron magnet with high Curie point |
| CN103794320A (en) * | 2014-03-04 | 2014-05-14 | 南京信息工程大学 | Neodymium iron nitrogen permanent magnet material and preparation method |
| CN103894587A (en) * | 2014-03-20 | 2014-07-02 | 华南理工大学 | Neodymium-iron-boron permanent magnet material, preparation method and magnetic field auxiliary direct casting device |
| CN104588622A (en) * | 2014-12-24 | 2015-05-06 | 北方民族大学 | Metal melt bulk nanometer material preparing system |
| CN106057461A (en) * | 2016-05-20 | 2016-10-26 | 中国计量大学 | Anisotropic blocky nanocomposite permanent magnet and preparation method therefor |
| CN107790650A (en) * | 2016-09-06 | 2018-03-13 | 鞍钢股份有限公司 | A kind of micro alloyed steel directly fills the control method for rolling plate crackle |
| CN112201429A (en) * | 2020-10-14 | 2021-01-08 | 燕山大学 | Permanent magnet with nanoscale gradient structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002038245A (en) * | 2000-07-27 | 2002-02-06 | Hitachi Metals Ltd | Rare earth alloy powder for rermanent magnet and method for manufacturing rare earth permanent magnet |
| CN101086053A (en) * | 2007-07-13 | 2007-12-12 | 上海大学 | Nano crystal composite permanent-magnet alloy and its preparation method |
| CN102108452A (en) * | 2011-02-15 | 2011-06-29 | 江苏大学 | Method for synthesizing particle reinforced composite material under pulsed electric field and electromagnetic field |
-
2012
- 2012-01-10 CN CN201210005073.0A patent/CN102568729B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002038245A (en) * | 2000-07-27 | 2002-02-06 | Hitachi Metals Ltd | Rare earth alloy powder for rermanent magnet and method for manufacturing rare earth permanent magnet |
| CN101086053A (en) * | 2007-07-13 | 2007-12-12 | 上海大学 | Nano crystal composite permanent-magnet alloy and its preparation method |
| CN102108452A (en) * | 2011-02-15 | 2011-06-29 | 江苏大学 | Method for synthesizing particle reinforced composite material under pulsed electric field and electromagnetic field |
Non-Patent Citations (2)
| Title |
|---|
| 何力佳: "脉冲电场作用下金属组织的研究进展", 《辽宁工学院学报》, vol. 23, no. 5, 31 October 2003 (2003-10-31), pages 31 - 34 * |
| 朱继平等: "《无机材料合成与制备》", 31 December 2009, article "无机材料合成与制备", pages: 272 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794355A (en) * | 2014-02-25 | 2014-05-14 | 刘洋 | Method for preparing neodymium iron boron magnet with high Curie point |
| CN103794355B (en) * | 2014-02-25 | 2016-05-18 | 浙江爱特新能源汽车有限公司 | A kind of preparation method of the neodymium iron boron magnetic body with high-Curie-point |
| CN103794320A (en) * | 2014-03-04 | 2014-05-14 | 南京信息工程大学 | Neodymium iron nitrogen permanent magnet material and preparation method |
| CN103894587A (en) * | 2014-03-20 | 2014-07-02 | 华南理工大学 | Neodymium-iron-boron permanent magnet material, preparation method and magnetic field auxiliary direct casting device |
| CN104588622A (en) * | 2014-12-24 | 2015-05-06 | 北方民族大学 | Metal melt bulk nanometer material preparing system |
| CN106057461A (en) * | 2016-05-20 | 2016-10-26 | 中国计量大学 | Anisotropic blocky nanocomposite permanent magnet and preparation method therefor |
| CN107790650A (en) * | 2016-09-06 | 2018-03-13 | 鞍钢股份有限公司 | A kind of micro alloyed steel directly fills the control method for rolling plate crackle |
| CN107790650B (en) * | 2016-09-06 | 2019-03-26 | 鞍钢股份有限公司 | A kind of micro alloyed steel directly fills the control method for rolling plate crackle |
| CN112201429A (en) * | 2020-10-14 | 2021-01-08 | 燕山大学 | Permanent magnet with nanoscale gradient structure and preparation method thereof |
| CN112201429B (en) * | 2020-10-14 | 2021-12-21 | 燕山大学 | Permanent magnet with nanoscale gradient structure and preparation method thereof |
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