CN104637643A - Rare-earth permanent magnet material mixed with bayan obo co-existence and associated crude ores and method for manufacturing rare-earth permanent magnet material - Google Patents
Rare-earth permanent magnet material mixed with bayan obo co-existence and associated crude ores and method for manufacturing rare-earth permanent magnet material Download PDFInfo
- Publication number
- CN104637643A CN104637643A CN201510097712.4A CN201510097712A CN104637643A CN 104637643 A CN104637643 A CN 104637643A CN 201510097712 A CN201510097712 A CN 201510097712A CN 104637643 A CN104637643 A CN 104637643A
- Authority
- CN
- China
- Prior art keywords
- rare
- earth permanent
- permanent magnet
- powder
- nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a rare-earth permanent magnet mixed with bayan obo co-existence and associated crude ores and a method for manufacturing the rare-earth permanent magnet. Compositions of the rare-earth permanent magnet are shown as a following formula of MM<x>Fe<y>A<z>B, the x is larger than or equal to 2 and is smaller than or equal to 2.5, the y is larger than or equal to 11 and is smaller than or equal to 14, the z is larger than or equal to 0 and is smaller than or equal to 0.6, the MM represents rare-earth mixed with the bayan obo co-existence and associated crude ores, and the A represents nanometer auxiliary alloy which includes one type of Nd elements, Pr elements, Al elements and Cu elements or a plurality of types of the Nd elements, the Pr elements, the Al elements and Cu elements. The rare-earth permanent magnet can be manufactured by the aid of a powder metallurgy technology and rapid quenching and thermal pressure and thermal deformation technologies. The rare-earth permanent magnet and the method have the advantages that the novel resource-saving rare-earth permanent magnet which is developed from the rare-earth mixed with the bayan obo co-existence and associated crude ores can replace the traditional rare-earth permanent magnet and is low in cost, and environmental pollution can be reduced; the magnetic energy product scope of the magnet ranges from 20MGOe to 40MGOe, and applicable scope gaps of ferrites and SmCo rare-earth permanent magnets can be effectively filled.
Description
Technical field
The present invention relates to and utilize the common association raw ore mishmetal of Bayan Obo directly to prepare rare earth permanent-magnetic material and method thereof, belong to rare earth permanent-magnetic material preparation field.
Background technology
Rare earth permanent-magnetic material is indispensable material in fields such as national security, information, the energy, environmental protection, and China is that rare earth permanent-magnetic material produces the first big country.Reach more than 50% according to correlation report display Nd-Fe-B permanent magnet in tradition application (loud speaker, magnetic separation, magneto, VCM, MRI etc.) market penetration rate, demand is in the steady growth phase, and annual growth is about 10%.China is global rare earth resource big country, packet header baiyuneboite content of rare earth occupies first place in the world, topmost rare earth permanent magnet raw material and production base, many metals intergrowth mineral bed that this Kuang Shi world is rare, there is poor, thin, assorted feature, Bayan Obo is total in association raw ore mishmetal not only containing praseodymium, neodymium, lanthanum, cerium, simultaneously containing the heavy rare earth element such as dysprosium, terbium, rare earth element coexists with common association form and iron, and finds the ore deposit Entropy density deviation consistent appearance of praseodymium, neodymium, lanthanum, cerium mischmetal element.Traditional rare-earth permanent magnet consumes a large amount of low abundance, resource scarcity praseodymium, neodymium, samarium, dysprosium, terbium rare earth element, and high abundance lanthanum, Ce elements are not utilized effectively and overstock in a large number, causes the utilization of rare earth resources uneven.And original technique does not consider the common association natural formula attribute of rare earth element, the undue purity pursuing raw material, rare earth adopt-select-separating-purifying-smelting process in cause serious ecological environmental pollution and the wasting of resources.
Summary of the invention
According to an aspect of the present invention, the invention provides one directly utilizes the common association raw ore mishmetal of Bayan Obo to prepare rare earth permanent-magnetic material and method thereof.
According to a further aspect in the invention, the present invention adds the auxiliary alloying pellet of nanometer in rare-earth permanent magnet, reaches while improving magnet performance, significantly reduces the object of metal praseodymium neodymium use amount.
The rare-earth permanent magnet be made up of the common association raw ore mishmetal of Bayan Obo, it is characterized in that, the composition of described rare-earth permanent magnet is shown below: MM
xfe
ya
zb, wherein, 2≤x≤2.5,11≤y≤14,0≤z≤0.6, MM is Bayan Obo association raw ore mishmetal altogether, and Fe is ferro element, and A is the auxiliary alloy of nanometer, comprises one or more in Nd, Pr, Al, Cu element, and B is boron element.
Preferably, the common natural constituent of association raw ore mishmetal of described Bayan Obo comprises following rare earth composition by weight percentage: La:10%-30%, Ce:20%-60%, Pr:5%-10%, Nd:5%-15%, Sm:0-0.05%, Gd:0-0.04%, Tb:0-0.01%, Dy:0-0.01%, Y:0-0.01%.
According to the present invention, Bayan Obo altogether association raw ore norium is by adopting Novel mineral method to baiyuneboite---X-fluorescence is chosen, carry out separating-purifying as required, direct smelting and obtaining, wherein Bayan Obo altogether association raw ore norium comprise natural constituent as shown in table 1.It needs to be noted, not only containing praseodymium, neodymium, lanthanum, cerium in the common association raw ore mishmetal of raw material Bayan Obo that the present invention is used, simultaneously also containing the heavy rare earth element such as dysprosium, terbium, rare earth element coexists with common association form and iron, and finding the ore deposit Entropy density deviation consistent appearance of praseodymium, neodymium, lanthanum, cerium mischmetal element, the common association natural formula attribute of rare earth element plays vital effect to the combination property improving material.
Table 1. Bayan Obo is association raw ore mishmetal constituent altogether
Be total to a preparation method for the rare-earth permanent magnet that association raw ore mishmetal is made by Bayan Obo, it is characterized in that, first directly utilize Bayan Obo to be total to association raw ore mishmetal MM and prepare MM
xfe
yb powder, then alloying pellet auxiliary with nanometer is mixed with into MM
xfe
ya
zb rare earth permanent-magnetic material.
Preferably, described preparation method comprises powder metallurgic method, hot-pressing thermal deformation technique.
Wherein, powder metallurgic method possesses following steps:
(1) Feedstock treating: carry out surface treatment to raw material, mechanically removes surface oxide layer by ready raw material, and wherein said raw material comprises Bayan Obo association raw ore mishmetal MM altogether;
(2) prepare burden: the raw material mix according to a certain percentage after step (1) is processed; In process for preparation, first by the oxide of metal surface and impurity removing;
(3) smelt: batching is carried out in vaccum sensitive stove be smelted into MM
xfe
yb ingot casting; Maybe batching is made the MM of thickness between 0.1-1mm in vacuum induction rapid hardening furnace
xfe
yb alloy sheet, controls it and forms column crystal;
(4) powder process: employing hydrogen is quick-fried, air-flow abrasive dust, by MM
xfe
yb alloy grinds into the fine powder of 2.5 ~ 5 microns of sizes;
(5) mixed powder: add auxiliary for nanometer alloying pellet to prepared MM
xfe
yin B powder, mix in vacuum environment;
(6) die mould: the powder that step (5) is mixed is pressed into certain shape in magnetic field, pressure 3T/cm
2, magnetic field H > 15000 oersted;
(7) sinter: in vacuum degree higher than 10
-3in the vacuum environment of Pa, the pressed compact obtained by step (6) is placed in heat-treatment furnace and sinters, described sintering process is: insulation 1.5 ~ 2.5 hours at being first heated to 560 ~ 630 DEG C by room temperature, then 2.5 ~ 3.5 hours are incubated at being warming up to 860 ~ 930 DEG C, be incubated 1.5 ~ 2.5 hours at being warming up to 1050 ~ 1060 DEG C afterwards, take out after finally cooling to room temperature with the furnace;
(8) Post isothermal treatment: in vacuum degree higher than 10
-3in the vacuum environment of Pa, the sintered body that step (7) obtains is increased to 870-890 DEG C by room temperature, insulation 80-240 minute, is cooled to room temperature afterwards, and then temperature is increased to 470-560 DEG C, be incubated after 80-240 minute, then be cooled to room temperature;
(9) magnetic-field heat treatment: the magnet after step (8) Post isothermal treatment being placed on magnetic field intensity is that the heat-treatment furnace of 1.5-15T carries out tempering in 1000 ~ 1100 DEG C of temperature ranges in vacuum environment.
Preferably, magnetic field orientating is one of following method with forming method in step (6): parallel punching block pressure, vertical steel mold pressing, parallel punching block is pressed and isostatic pressed, vertical steel mold pressing and isostatic pressed.
Wherein, hot-pressing thermal deformation technique possesses following steps:
(1) prepare burden: with is by weight percentage: the master alloying raw material of MM:26-50%, Fe:49.5-72%, B:0.5-2%, wherein, MM is Bayan Obo association raw ore mishmetal altogether;
(2) fast quenching: by the master alloying raw material melting fast quenching in (1), fast quenching is carried out with the speed of quenching of 10-80m/s by behind master alloying heating raw materials to 1200 ~ 1250 DEG C, nozzle is circular or elongated aperture, nozzle distance chill roll 2mm-10mm, gained rapid tempering belt vacuum heat 1 minute-2 hours at 300-1000 DEG C;
(3) powder process: the master alloying rapid tempering belt ball milling in (2) was obtained MM after 0.5-4 hour
xfe
yb master alloying powder; By after quick-fried through hydrogen to auxiliary alloy raw material Pr, Nd, PrNd, PrCu, NdCu and AlCu, airflow milling, high-energy ball milling, grind into the auxiliary alloying pellet of nanometer that particle diameter is 10-500nm or make through using vaporization condensation process the auxiliary alloying pellet of nanometer that particle diameter is 10-500nm, in auxiliary alloy raw material PrCu, NdCu and AlCu, the mass percent of Cu is 1%-90%;
(4) mixed powder: obtain mixed powder after being mixed with the auxiliary alloying pellet of nanometer by master alloying powder in (3), wherein, the mixed powder ratio of the auxiliary alloying pellet of nanometer is mass percent 0-8%;
(5) hot pressing: the mixed powder in (4) is carried out hot pressing, described heat pressing process is: hot pressing is vacuum environment, and vacuum degree is higher than 10
-3pa, hot pressing temperature 500-800 DEG C, hot pressing pressure 100-500MPa, heating rate 10-80 DEG C/min; In hot pressing, to reach after default hot pressing temperature pressurize 1.5 ~ 2.5 minutes until magnet temperature, the density of gained hot-pressed magnets is 7-7.60g/cm
3;
(6) thermal deformation: the hot-pressed magnets in (5) is carried out thermal deformation, described thermal deformation technique is: thermal deformation process is vacuum environment, and vacuum degree is higher than 10
-3pa, heat distortion temperature 850-1050 DEG C, thermal deformation pressure 700-1000MPa, thermal deformation speed is 12-15mm/s, heating rate 10-80 DEG C/min; In thermal deformation process, reach pressurize 40 ~ 60s after default thermal deformation pressure until magnet pressure; The density of gained heat distortion magnet is 7-7.68g/cm
3.
The present invention has following beneficial effect, the invention provides a kind of utilization and directly utilizes the common association raw ore mishmetal of Bayan Obo to prepare rare earth permanent-magnetic material and method thereof.This new rare-earth permanent magnetic material possesses cheap, reduces environmental pollution, and magnetic energy product scope, at 20 ~ 40MGOe, can be filled up ferrite well, the SmCo rare-earth permanent magnet scope of application is blank.
embodiment:
The rare-earth permanent magnet be made up of the common association raw ore mishmetal of Bayan Obo, it is characterized in that, the composition of described rare-earth permanent magnet is shown below: MM
xfe
ya
zb, wherein, 2≤x≤2.5,11≤y≤14,0≤z≤0.6, MM is Bayan Obo association raw ore mishmetal altogether, and Fe is ferro element, and A is the auxiliary alloy of nanometer, comprises one or more in Nd, Pr, Al, Cu element, and B is boron element.
Preferably, the common natural constituent of association raw ore mishmetal of described Bayan Obo comprises following rare earth composition by weight percentage: La:10%-30%, Ce:20%-60%, Pr:5%-10%, Nd:5%-15%, Sm:0-0.05%, Gd:0-0.04%, Tb:0-0.01%, Dy:0-0.01%, Y:0-0.01%.
Be total to a preparation method for the rare-earth permanent magnet that association raw ore mishmetal is made by Bayan Obo, it is characterized in that, first directly utilize Bayan Obo to be total to association raw ore mishmetal MM and prepare MM
xfe
yb powder, then alloying pellet auxiliary with nanometer is mixed with into MM
xfe
ya
zb rare earth permanent-magnetic material.
Preferably, described preparation method comprises powder metallurgic method, hot-pressing thermal deformation technique.
Wherein, powder metallurgic method possesses following steps:
(1) Feedstock treating: carry out surface treatment to raw material, mechanically removes surface oxide layer by ready raw material, and wherein said raw material comprises Bayan Obo association raw ore mishmetal MM altogether;
(2) prepare burden: the raw material mix according to a certain percentage after step (1) is processed; In process for preparation, first by the oxide of metal surface and impurity removing;
(3) smelt: batching is carried out in vaccum sensitive stove be smelted into MM
xfe
yb ingot casting; Maybe batching is made the MM of thickness between 0.1-1mm in vacuum induction rapid hardening furnace
xfe
yb alloy sheet, controls it and forms column crystal;
(4) powder process: employing hydrogen is quick-fried, air-flow abrasive dust, by MM
xfe
yb alloy grinds into the fine powder of 2.5 ~ 5 microns of sizes;
(5) mixed powder: add auxiliary for nanometer alloying pellet to prepared MM
xfe
yin B powder, mix in vacuum environment;
(6) die mould: the powder that step (5) is mixed is pressed into certain shape in magnetic field, pressure 3T/cm
2, magnetic field H > 15000 oersted;
(7) sinter: in vacuum degree higher than 10
-3in the vacuum environment of Pa, the pressed compact obtained by step (6) is placed in heat-treatment furnace and sinters, described sintering process is: insulation 1.5 ~ 2.5 hours at being first heated to 560 ~ 630 DEG C by room temperature, then 2.5 ~ 3.5 hours are incubated at being warming up to 860 ~ 930 DEG C, be incubated 1.5 ~ 2.5 hours at being warming up to 1050 ~ 1060 DEG C afterwards, take out after finally cooling to room temperature with the furnace;
(8) Post isothermal treatment: in vacuum degree higher than 10
-3in the vacuum environment of Pa, the sintered body that step (7) obtains is increased to 870-890 DEG C by room temperature, insulation 80-240 minute, is cooled to room temperature afterwards, and then temperature is increased to 470-560 DEG C, be incubated after 80-240 minute, then be cooled to room temperature;
(9) magnetic-field heat treatment: the magnet after step (8) Post isothermal treatment being placed on magnetic field intensity is that the heat-treatment furnace of 1.5-15T carries out tempering in 1000 ~ 1100 DEG C of temperature ranges in vacuum environment.
Preferably, magnetic field orientating is one of following method with forming method in step (6): parallel punching block pressure, vertical steel mold pressing, parallel punching block is pressed and isostatic pressed, vertical steel mold pressing and isostatic pressed.
Wherein, hot-pressing thermal deformation technique possesses following steps:
(1) prepare burden: with is by weight percentage: the master alloying raw material of MM:26-50%, Fe:49.5-72%, B:0.5-2%, wherein, MM is Bayan Obo association raw ore mishmetal altogether;
(2) fast quenching: by the master alloying raw material melting fast quenching in (1), fast quenching is carried out with the speed of quenching of 10-80m/s by behind master alloying heating raw materials to 1200 ~ 1250 DEG C, nozzle is circular or elongated aperture, nozzle distance chill roll 2mm-10mm, gained rapid tempering belt vacuum heat 1 minute-2 hours at 300-1000 DEG C;
(3) powder process: the master alloying rapid tempering belt ball milling in (2) was obtained MM after 0.5-4 hour
xfe
yb master alloying powder; By after quick-fried through hydrogen to auxiliary alloy raw material Pr, Nd, PrNd, PrCu, NdCu and AlCu, airflow milling, high-energy ball milling, grind into the auxiliary alloying pellet of nanometer that particle diameter is 10-500nm or make through using vaporization condensation process the auxiliary alloying pellet of nanometer that particle diameter is 10-500nm, in auxiliary alloy raw material PrCu, NdCu and AlCu, the mass percent of Cu is 1%-90%;
(4) mixed powder: obtain mixed powder after being mixed with the auxiliary alloying pellet of nanometer by master alloying powder in (3), wherein, the mixed powder ratio of the auxiliary alloying pellet of nanometer is mass percent 0-8%;
(5) hot pressing: the mixed powder in (4) is carried out hot pressing, described heat pressing process is: hot pressing is vacuum environment, and vacuum degree is higher than 10
-3pa, hot pressing temperature 500-800 DEG C, hot pressing pressure 100-500MPa, heating rate 10-80 DEG C/min; In hot pressing, to reach after default hot pressing temperature pressurize 1.5 ~ 2.5 minutes until magnet temperature, the density of gained hot-pressed magnets is 7-7.60g/cm
3;
(6) thermal deformation: the hot-pressed magnets in (5) is carried out thermal deformation, described thermal deformation technique is: thermal deformation process is vacuum environment, and vacuum degree is higher than 10
-3pa, heat distortion temperature 850-1050 DEG C, thermal deformation pressure 700-1000MPa, thermal deformation speed is 12-15mm/s, heating rate 10-80 DEG C/min; In thermal deformation process, reach pressurize 40 ~ 60s after default thermal deformation pressure until magnet pressure; The density of gained heat distortion magnet is 7-7.68g/cm
3.
Rare earth permanent-magnetic material provided by the present invention and preparation method thereof has the following advantages:
(1) directly utilize Bayan Obo to be total to association raw ore mishmetal and prepare sintered rare-earth permanent magnetic material, Rare Earth Separation step can be reduced significantly and reduce separation requirement, protection of the environment while being conducive to reducing manufacture of materials cost;
(2) due to the common concomitant characteristics of Bayan Obo altogether association raw ore mishmetal, the magnet adding separately pure rare earth element or the mishmetal manually prepared in proportion and produce is higher than with the magnet performance of Bayan Obo altogether prepared by association raw ore mishmetal;
(3) Bayan Obo altogether association raw ore mishmetal except containing except a large amount of La, Ce, Pr, Nd, also have other elements such as heavy rare earth element and Al such as Dy, Tb, these elements are all of value to raising magnetism of material energy, are the advantages not available for common artificial mishmetal;
(4) mishmetal is directly utilized to prepare permanent magnetic material, be difficult to obtain the higher product of performance, preparation method utilized mishmetal to replace part praseodymium neodymium alloy to reach the operable product of preparation in the past, and in the present invention, add the Grain-Boundary Phase that the auxiliary alloying pellet of nanometer effectively can improve material, while remarkable reduction praseodymium neodymium use amount, greatly can also improve the performance of material;
(5) this new rare-earth permanent magnetic material is conducive to the utilance improving the high abundance rare earths such as La, Ce, reduces Pr, Nd price fluctuation greatly on the impact of the price of rare earth permanent-magnetic material, is conducive to applying of rare earth permanent-magnetic material;
(6) this new rare-earth permanent magnetic material magnetic energy product coverage is wide, and the application that effectively can make up ferrite and SmCo permanent magnetism is not enough;
(7) owing to also having a large amount of La, Ce elements in Bayan Obo altogether association raw ore mishmetal, can effectively reduce sintering temperature and time, enter the production cost that is reduced material.
embodiment 1:
A kind of sintered rare-earth permanent magnetic material utilizing the common association raw ore mishmetal of Bayan Obo directly to prepare.
It is as follows that batching presses table 2:
Table 2
| Composition | Bayan Obo is association raw ore mishmetal altogether | Fe | B |
| Percentage by weight | 35 | 64 | 1 |
Adopt powder metallurgical technique, by such as: the Bayan Obo of the raw material containing certain proportioning, association raw ore mishmetal, ferro-boron etc. smelt into alloy steel ingot by induction melting furnace altogether, then the broken powder making 3 ~ 5 μm, and add the auxiliary alloying pellet of NdCu nanometer wherein, wherein the addition of the auxiliary alloying pellet of NdCu nanometer is that 100% its percentage by weight is as shown in table 3 in the weight of alloy steel ingot, and compressing in magnetic field, the densified sintering product in vacuum freezing of a furnace after shaping tempering.The magnetism testing result of gained rare earth permanent-magnetic material is as shown in table 3.
Table 3
| The addition of PrCu | B r(kGs) | H cj(kOe) | BH max(MGOe) |
| 0 | 10.33 | 4.69 | 10.92 |
| 4% | 11.23 | 7.02 | 18.37 |
| 8% | 11.65 | 10.87 | 23.75 |
As can be seen from the table 3 of embodiment 1, Bayan Obo altogether association raw ore mishmetal is very easily oxidized, thus is difficult to the product that obtains applying, then after adding a small amount of auxiliary alloying pellet of PdCu nanometer, the performance of material significantly improves.While material can be applied, the utilance of lanthanum, cerium also significantly increases.
embodiment 2
Table 4
| Method | B r(kGs) | H cj(kOe) | BH max(MGOe) |
| Raw ore mishmetal | 11.23 | 7.02 | 18.37 |
| Common mishmetal | 10.65 | 5.87 | 15.38 |
As can be seen from the table 4 of embodiment 2, when composition and engineering condition is identical, use the performance of common mishmetal will be total to the performance of association raw ore mishmetal well below use Bayan Obo.
embodiment 3
Table 5
| Method | Ce content | La content | B r(kGs) | H cj(kOe) | BH max(MGOe) |
| Independent interpolation La | 0.9% | 11.1 | 8.91 | 25 | |
| Independent interpolation Ce | 35% | 11.36 | 6.47 | 25.94 | |
| Bayan Obo is association raw ore mishmetal magnet altogether | 18.75% | 9.06% | 11.33 | 8.69 | 25.92 |
As can be seen from the table 5 of embodiment 3, when magnet performance is close, the utilance that Bayan Obo is total to lanthanum in association raw ore mishmetal is 10 times that add separately lanthanum, effectively can solve high abundance rare earth problem of complex utilization.And use the performance of common mishmetal will be total to the performance of association raw ore mishmetal well below use Bayan Obo.
embodiment 4
Utilize the hot-pressing thermal deformable rare earth permanent magnetic material that the common association raw ore mishmetal of Bayan Obo is directly prepared, the preparation method of described rare earth permanent-magnetic material is as follows:
(1) prepare burden: with is by weight percentage: the master alloying raw material of MM:31%, Fe:68%, B:1%, wherein, MM is Bayan Obo association raw ore mishmetal altogether;
(2) fast quenching: by the master alloying raw material melting fast quenching in (1), carry out fast quenching by after master alloying heating raw materials to 1250 DEG C with the speed of quenching of 30m/s, nozzle is circular aperture, nozzle distance chill roll 8mm, gained rapid tempering belt vacuum heat 5 minutes at 500 DEG C;
(3) powder process: the master alloying rapid tempering belt ball milling in (2) was obtained MM after 1.5 hours
xfe
yb master alloying powder; Auxiliary alloy raw material AlCu is made through using vaporization condensation process the auxiliary alloying pellet of nanometer that particle diameter is 100nm, and in auxiliary alloy raw material AlCu, the mass percent of Cu is 50%;
(4) mixed powder: obtain mixed powder after being mixed with the auxiliary alloying pellet of nanometer by master alloying powder in (3), wherein, the mixed powder ratio of the auxiliary alloying pellet of nanometer is mass percent 5%;
(5) hot pressing: the mixed powder in (4) is carried out hot pressing, described heat pressing process is: hot pressing is vacuum environment, and vacuum degree is higher than 10
-3pa, hot pressing temperature 600 DEG C, hot pressing pressure 500MPa, heating rate 60 DEG C/min; In hot pressing, to reach after default hot pressing temperature pressurize 2 minutes until magnet temperature, the density of gained hot-pressed magnets is 7.58g/cm
3;
(6) thermal deformation: the hot-pressed magnets in (5) is carried out thermal deformation, described thermal deformation technique is: thermal deformation process is vacuum environment, and vacuum degree is higher than 10
-3pa, heat distortion temperature 900 DEG C, thermal deformation pressure 800MPa, thermal deformation speed is 13mm/s, heating rate 60 DEG C/min; In thermal deformation process, reach pressurize 60s after default thermal deformation pressure until magnet pressure; The density of gained heat distortion magnet is 7.65g/cm
3.
The magnetism testing result of gained hot pressing heat distortion magnet is as shown in table 6 below.
Table 6
| The addition of AlCu | B r(kGs) | H cj(kOe) | BH max(MGOe) |
| 5% | 10.42 | 12.89 | 26.37 |
Claims (6)
1. the rare-earth permanent magnet be made up of the common association raw ore mishmetal of Bayan Obo, it is characterized in that, the composition of described rare-earth permanent magnet is shown below: MM
xfe
ya
zb, wherein, 2≤x≤2.5,11≤y≤14,0≤z≤0.6, MM is Bayan Obo association raw ore mishmetal altogether, and Fe is ferro element, and A is the auxiliary alloy of nanometer, comprises one or more in Nd, Pr, Al, Cu element, and B is boron element.
2. rare-earth permanent magnet according to claim 1, it is characterized in that, the described Bayan Obo altogether natural constituent of association raw ore mishmetal comprises following rare earth composition by weight percentage: La:10%-30%, Ce:20%-60%, Pr:5%-10%, Nd:5%-15%, Sm:0-0.05%, Gd:0-0.04%, Tb:0-0.01%, Dy:0-0.01%, Y:0-0.01%.
3. a preparation method for the rare-earth permanent magnet described in any one of claim 1-2, is characterized in that, first directly utilizes Bayan Obo to be total to association raw ore mishmetal MM and prepares MM
xfe
yb powder, then alloying pellet auxiliary with nanometer is mixed with into MM
xfe
ya
zb rare earth permanent-magnetic material, wherein, A is the auxiliary alloy of nanometer, comprises one or more in Nd, Pr, Al, Cu element.
4. preparation method according to claim 3, is characterized in that, possesses following steps:
(1) Feedstock treating: carry out surface treatment to raw material, mechanically removes surface oxide layer by ready raw material, and wherein said raw material comprises Bayan Obo association raw ore mishmetal MM altogether;
(2) prepare burden: the raw material mix according to a certain percentage after step (1) is processed; In process for preparation, first by the oxide of metal surface and impurity removing;
(3) smelt: batching is carried out in vaccum sensitive stove be smelted into MM
xfe
yb ingot casting; Maybe batching is made the MM of thickness between 0.1-1mm in vacuum induction rapid hardening furnace
xfe
yb alloy sheet, controls it and forms column crystal;
(4) powder process: employing hydrogen is quick-fried, air-flow abrasive dust, by MM
xfe
yb alloy grinds into the fine powder of 2.5 ~ 5 microns of sizes;
(5) mixed powder: add auxiliary for nanometer alloying pellet to prepared MM
xfe
yin B powder, mix in vacuum environment;
(6) die mould: the powder that step (5) is mixed is pressed into certain shape in magnetic field, pressure 3T/cm
2, magnetic field H > 15000 oersted;
(7) sinter: in vacuum degree higher than 10
-3in the vacuum environment of Pa, the pressed compact obtained by step (6) is placed in heat-treatment furnace and sinters, described sintering process is: insulation 1.5 ~ 2.5 hours at being first heated to 560 ~ 630 DEG C by room temperature, then 2.5 ~ 3.5 hours are incubated at being warming up to 860 ~ 930 DEG C, be incubated 1.5 ~ 2.5 hours at being warming up to 1050 ~ 1060 DEG C afterwards, take out after finally cooling to room temperature with the furnace;
(8) Post isothermal treatment: in vacuum degree higher than 10
-3in the vacuum environment of Pa, the sintered body that step (7) obtains is increased to 870-890 DEG C by room temperature, insulation 80-240 minute, is cooled to room temperature afterwards, and then temperature is increased to 470-560 DEG C, be incubated after 80-240 minute, then be cooled to room temperature;
(9) magnetic-field heat treatment: the magnet after step (8) Post isothermal treatment being placed on magnetic field intensity is that the heat-treatment furnace of 1.5-15T carries out tempering in 1000 ~ 1100 DEG C of temperature ranges in vacuum environment.
5. preparation method according to claim 3, is characterized in that, possesses following steps:
(1) prepare burden: with is by weight percentage: the master alloying raw material of MM:26-50%, Fe:49.5-72%, B:0.5-2%, wherein, MM is Bayan Obo association raw ore mishmetal altogether;
(2) fast quenching: by the master alloying raw material melting fast quenching in (1), fast quenching is carried out with the speed of quenching of 10-80m/s by behind master alloying heating raw materials to 1200 ~ 1250 DEG C, nozzle is circular or elongated aperture, nozzle distance chill roll 2mm-10mm, gained rapid tempering belt vacuum heat 1 minute-2 hours at 300-1000 DEG C;
(3) powder process: the master alloying rapid tempering belt ball milling in (2) was obtained MM after 0.5-4 hour
xfe
yb master alloying powder; By after quick-fried through hydrogen to auxiliary alloy raw material Pr, Nd, PrNd, PrCu, NdCu and AlCu, airflow milling, high-energy ball milling, grind into the auxiliary alloying pellet of nanometer that particle diameter is 10-500nm or make through using vaporization condensation process the auxiliary alloying pellet of nanometer that particle diameter is 10-500nm, in auxiliary alloy raw material PrCu, NdCu and AlCu, the mass percent of Cu is 1%-90%;
(4) mixed powder: obtain mixed powder after being mixed with the auxiliary alloying pellet of nanometer by master alloying powder in (3), wherein, the mixed powder ratio of the auxiliary alloying pellet of nanometer is mass percent 0-8%;
(5) hot pressing: the mixed powder in (4) is carried out hot pressing, described heat pressing process is: hot pressing is vacuum environment, and vacuum degree is higher than 10
-3pa, hot pressing temperature 500-800 DEG C, hot pressing pressure 100-500MPa, heating rate 10-80 DEG C/min; In hot pressing, to reach after default hot pressing temperature pressurize 1.5 ~ 2.5 minutes until magnet temperature, the density of gained hot-pressed magnets is 7-7.60g/cm
3;
(6) thermal deformation: the hot-pressed magnets in (5) is carried out thermal deformation, described thermal deformation technique is: thermal deformation process is vacuum environment, and vacuum degree is higher than 10
-3pa, heat distortion temperature 850-1050 DEG C, thermal deformation pressure 700-1000MPa, thermal deformation speed is 12-15mm/s, heating rate 10-80 DEG C/min; In thermal deformation process, reach pressurize 40 ~ 60s after default thermal deformation pressure until magnet pressure; The density of gained heat distortion magnet is 7-7.68g/cm
3.
6. preparation method according to claim 3, is characterized in that, the particle diameter of the auxiliary alloying pellet of described nanometer is 10nm-500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510097712.4A CN104637643B (en) | 2015-03-05 | 2015-03-05 | Bayan Obo is total to association raw ore mischmetal permanent-magnet material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510097712.4A CN104637643B (en) | 2015-03-05 | 2015-03-05 | Bayan Obo is total to association raw ore mischmetal permanent-magnet material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104637643A true CN104637643A (en) | 2015-05-20 |
| CN104637643B CN104637643B (en) | 2018-08-14 |
Family
ID=53216288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510097712.4A Expired - Fee Related CN104637643B (en) | 2015-03-05 | 2015-03-05 | Bayan Obo is total to association raw ore mischmetal permanent-magnet material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104637643B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105321646A (en) * | 2015-11-25 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Nanocrystalline thermal deformation rare-earth permanent magnet with high coercivity and preparation method of nanocrystalline thermal deformation rare-earth permanent magnet |
| CN106210997A (en) * | 2016-08-26 | 2016-12-07 | 广东欧珀移动通信有限公司 | A kind of speaker and terminal |
| CN106548843A (en) * | 2016-10-17 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Rare earth permanent-magnetic material and preparation method thereof |
| CN106782971A (en) * | 2016-12-05 | 2017-05-31 | 湖南航天磁电有限责任公司 | A kind of NdFeB material and preparation method thereof |
| CN107578869A (en) * | 2016-07-05 | 2018-01-12 | 中国科学院物理研究所 | A kind of mischmetal-iron-base permanent magnetic material and its preparation method and application |
| CN108666127A (en) * | 2018-06-04 | 2018-10-16 | 安徽天宇磁业股份有限公司 | Based on energy-saving and environment-friendly permanent magnet processing technology |
| CN109550945A (en) * | 2018-12-28 | 2019-04-02 | 内蒙古科技大学 | A kind of permanent-magnet material and preparation method thereof being total to the preparation of association raw ore mischmetal using Bayan Obo |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070012380A1 (en) * | 2002-06-27 | 2007-01-18 | Tetsurou Tayu | Rare earth magnet, method for manufacturing the same, and motor using rare earth magnet |
| CN101958171A (en) * | 2010-04-14 | 2011-01-26 | 无锡南理工科技发展有限公司 | Method for preparing corrosion-resistant sintered neodymium iron boron (NdFeB) magnet |
| CN102534358A (en) * | 2012-01-16 | 2012-07-04 | 烟台正海磁性材料股份有限公司 | Manufacturing method of high-coercivity R-Fe-B sintered permanent magnet material |
| CN103123838A (en) * | 2013-01-30 | 2013-05-29 | 浙江大学 | Rare earth permanent magnet produced by applying abundant rare earth MM and preparation method thereof |
| CN103151161A (en) * | 2013-03-22 | 2013-06-12 | 四川大学 | Method for preparing anisotropic neodymium iron boron magnetic powder through directionally breaking thermal deformed magnet |
| CN103426624A (en) * | 2013-08-14 | 2013-12-04 | 林建强 | Production method for neodymium-iron-boron permanent magnet |
| CN103834863A (en) * | 2014-03-31 | 2014-06-04 | 内蒙古科技大学 | Method for preparing neodymium iron boron permanent magnet material by using associated mixed rare earth |
| CN103928204A (en) * | 2014-04-10 | 2014-07-16 | 重庆科技学院 | Low-rare earth content anisotropy nanocrystalline NdFeB compact magnet and preparation method thereof |
-
2015
- 2015-03-05 CN CN201510097712.4A patent/CN104637643B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070012380A1 (en) * | 2002-06-27 | 2007-01-18 | Tetsurou Tayu | Rare earth magnet, method for manufacturing the same, and motor using rare earth magnet |
| CN101958171A (en) * | 2010-04-14 | 2011-01-26 | 无锡南理工科技发展有限公司 | Method for preparing corrosion-resistant sintered neodymium iron boron (NdFeB) magnet |
| CN102534358A (en) * | 2012-01-16 | 2012-07-04 | 烟台正海磁性材料股份有限公司 | Manufacturing method of high-coercivity R-Fe-B sintered permanent magnet material |
| CN103123838A (en) * | 2013-01-30 | 2013-05-29 | 浙江大学 | Rare earth permanent magnet produced by applying abundant rare earth MM and preparation method thereof |
| CN103151161A (en) * | 2013-03-22 | 2013-06-12 | 四川大学 | Method for preparing anisotropic neodymium iron boron magnetic powder through directionally breaking thermal deformed magnet |
| CN103426624A (en) * | 2013-08-14 | 2013-12-04 | 林建强 | Production method for neodymium-iron-boron permanent magnet |
| CN103834863A (en) * | 2014-03-31 | 2014-06-04 | 内蒙古科技大学 | Method for preparing neodymium iron boron permanent magnet material by using associated mixed rare earth |
| CN103928204A (en) * | 2014-04-10 | 2014-07-16 | 重庆科技学院 | Low-rare earth content anisotropy nanocrystalline NdFeB compact magnet and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105321646A (en) * | 2015-11-25 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Nanocrystalline thermal deformation rare-earth permanent magnet with high coercivity and preparation method of nanocrystalline thermal deformation rare-earth permanent magnet |
| CN107578869A (en) * | 2016-07-05 | 2018-01-12 | 中国科学院物理研究所 | A kind of mischmetal-iron-base permanent magnetic material and its preparation method and application |
| CN107578869B (en) * | 2016-07-05 | 2020-03-17 | 中国科学院物理研究所 | Mixed rare earth-iron-based permanent magnet material and preparation method and application thereof |
| CN106210997A (en) * | 2016-08-26 | 2016-12-07 | 广东欧珀移动通信有限公司 | A kind of speaker and terminal |
| CN106548843A (en) * | 2016-10-17 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Rare earth permanent-magnetic material and preparation method thereof |
| CN106782971A (en) * | 2016-12-05 | 2017-05-31 | 湖南航天磁电有限责任公司 | A kind of NdFeB material and preparation method thereof |
| CN108666127A (en) * | 2018-06-04 | 2018-10-16 | 安徽天宇磁业股份有限公司 | Based on energy-saving and environment-friendly permanent magnet processing technology |
| CN109550945A (en) * | 2018-12-28 | 2019-04-02 | 内蒙古科技大学 | A kind of permanent-magnet material and preparation method thereof being total to the preparation of association raw ore mischmetal using Bayan Obo |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104637643B (en) | 2018-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104700973B (en) | A kind of rare-earth permanent magnet being made up of the common association raw ore mischmetal of Bayan Obo and preparation method thereof | |
| CN103212714B (en) | Method for preparing neodymium iron boron material | |
| CN104637643A (en) | Rare-earth permanent magnet material mixed with bayan obo co-existence and associated crude ores and method for manufacturing rare-earth permanent magnet material | |
| CN101266855B (en) | Rare earth permanent magnetism material and its making method | |
| CN103834863B (en) | The method of Nd-Fe-Bo permanent magnet material is manufactured with common association mishmetal | |
| CN103280290B (en) | Containing cerium low melting point rare earth permanent magnetic liquid phase alloy and permanent magnet preparation method thereof | |
| CN103187133B (en) | A kind of RE permanent magnetic alloy and Magnetic Phase composite preparation process thereof | |
| CN101834045B (en) | Yttrium-containing neodymium iron boron permanent magnet material and manufacturing method thereof | |
| CN107275027B (en) | Using the cerium-rich rare earth permanent magnet and preparation method thereof of yttrium | |
| CN105170976A (en) | Method for preparing high-coercivity neodymium iron boron by means of low-temperature sintering after blank compacting permeation | |
| CN103903823A (en) | Rare earth permanent magnetic material and preparation method thereof | |
| CN108183021B (en) | Rare earth permanent magnetic material and preparation method thereof | |
| CN104575920A (en) | Rare-earth permanent magnet and production method thereof | |
| CN104576021A (en) | NdFeB magnet sintering method | |
| CN107958760B (en) | Rare earth permanent magnetic material and preparation method thereof | |
| CN104966607A (en) | Sintered Nd-Fe-B permanent magnet producing method | |
| WO2021223436A1 (en) | High-performance neodymium iron boron permanent magnet material and preparation method therefor | |
| CN109192489A (en) | A kind of preparation method of high-performance heavy rare earth neodymium iron boron magnetic body | |
| CN111916285A (en) | Preparation method of low-heavy rare earth high-coercivity sintered neodymium-iron-boron magnet | |
| CN112509775A (en) | Neodymium-iron-boron magnet with low-amount heavy rare earth addition and preparation method thereof | |
| CN104759628A (en) | Method for preparing heat-resistance sintering NdFeB permanent magnet material | |
| CN103310972A (en) | Method for preparing high-performance sintered Nd-Fe-B magnet | |
| CN110895985A (en) | Mixed rare earth sintered neodymium-iron-boron permanent magnet and preparation method thereof | |
| CN106158213A (en) | A kind of high-coercivity neodymium-iron-boronpermanent-magnet permanent-magnet material and preparation method thereof | |
| CN108806910B (en) | Method for improving coercive force of neodymium iron boron magnetic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180814 Termination date: 20210305 |