CN109550945B - Permanent magnet material prepared from bayan obo associated raw ore mixed rare earth and preparation method thereof - Google Patents

Permanent magnet material prepared from bayan obo associated raw ore mixed rare earth and preparation method thereof Download PDF

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CN109550945B
CN109550945B CN201811623971.6A CN201811623971A CN109550945B CN 109550945 B CN109550945 B CN 109550945B CN 201811623971 A CN201811623971 A CN 201811623971A CN 109550945 B CN109550945 B CN 109550945B
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李柱柏
张雪峰
张志新
刘飞
刘艳丽
李永峰
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Inner Mongolia University of Science and Technology
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    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
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    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
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    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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Abstract

The invention discloses a permanent magnet material prepared from bayan obo associated raw ore mixed rare earth and a preparation method thereof. The method takes the Bayan Obo associated raw ore mixed rare earth MM as a raw material, uses at least more than two alloys to prepare the rare earth permanent magnet, and optimizes and designs the components of the alloy (MM, RE) -Fe-B and the alloy (Nd, Pr) -Fe-B so as to improve the magnetic performance. The chemical formula of the alloy (MM, RE) -Fe-B is MM in atomic percentagea1REa2Fe100‑a1‑a2‑b‑cBbAcThe chemical formula of (Nd, Pr) -Fe-B is (Nd, Pr)a3Fe100‑a3‑b‑cBbAcThe content of rare earth in the (MM, RE) -Fe-B alloy is much lower than that in the (Nd, Pr) -Fe-B alloy, namely a1+ a2+2 is less than or equal to a 3. The method can improve the content of mixed rare earth MM and reduce the dosage of Nd and Pr while keeping higher coercivity, thereby obviously reducing the raw material and production cost, further reducing the separation steps and the separation requirements of the rare earth, comprehensively utilizing the rare earth resources to a greater extent, and reducing the negative influence of the mining, purification and separation of the rare earth on the environment.

Description

Permanent magnet material prepared from bayan obo associated raw ore mixed rare earth and preparation method thereof
Technical Field
The invention relates to a permanent magnet material prepared from bayan obo associated raw ore mixed rare earth and a preparation method thereof, belonging to the field of rare earth permanent magnet material preparation.
Background
The rare earth permanent magnet (Nd, Pr) -Fe-B has the advantages of high remanence, high coercivity and high magnetic energy product, and becomes an indispensable key material in modern scientific technology, particularly in the fields of transportation, computers, aerospace, clean energy and the like. However, the production and application of rare earth permanent magnets cause excessive consumption of important rare earth elements such as Nd and Pr, and the saving and reasonable utilization of the rare earth elements become a very concern in China and industry.
The rare earth elements La, Ce, Pr and Nd coexist in the rare earth ore, the La and Ce are abundant in the rare earth ore, and the Nd and Pr are low in abundance in the rare earth ore. Excessive consumption of Nd and Pr elements simultaneously causes La and Ce to be exploited but not utilized and overstocked. In the rare earth purification process, unseparated rare earth elements are mixed rare earth, and in order to efficiently and balancedly utilize the rare earth elements, the mixed rare earth MM can be used for partially replacing Nd-Pr to prepare the rare earth permanent magnet, so that the high-abundance rare earth elements La and Ce can be utilized, the use amount of Nd and Pr can be reduced, the exploitation amount of rare earth ores can be reduced, the separation processes such as extraction and purification of the rare earth elements are reduced, the raw material cost is reduced, and the pollution of the rare earth exploitation and separation to the environment is reduced.
China is a large country with rare earth resources, and the rare earth content of bayuneboite, Bayun, which is the first place in the world, is the most important rare earth permanent magnet raw material and product production base. The Bayan obo ore contains La, Ce, Pr and Nd coexisting with Fe in a coexisting form, the La-Ce content exceeds 75 percent, the Nd-Pr content is about 20 percent, and a small amount of heavy rare earth Dy and Tb is contained. In the Chinese patent with the publication number of CN104700973B, the rare earth permanent magnet can be prepared by compounding the Bayan obo associated raw ore mischmetal MM-Fe-B with the traditional (Nd, Pr) -Fe-B, but the (La, Ce) formed by La and Ce elements in the mischmetal2Fe14The B phase has lower intrinsic magnetism, so the content of the mixed rare earth MM in the total rare earth is not more than 35 wt%. In patent application publication No. CN104715876A, increasing the content of misch metal MM in the total rare earth, the magnetic performance of the magnet is significantly reduced.
Disclosure of Invention
Aiming at the defect that the content of the existing mixed rare earth MM in the total rare earth is not high,the invention aims to provide a permanent magnet material prepared by utilizing bayan obo associated raw ore mixed rare earth and a preparation method thereof. The rare earth permanent magnet is prepared by mixing (MM, RE) -Fe-B and (Nd, Pr) -Fe-B alloy powder, and the magnetic performance of the magnet and the content of mixed rare earth MM are improved by properly reducing the content of rare earth in the (MM, RE) -Fe-B alloy and improving the content of rare earth in the (Nd, Pr) -Fe-B alloy. Because of the low rare earth content in the (MM, RE) -Fe-B alloy, close to RE2Fe14The positive component content of B, therefore, the content of intercrystalline phase is small, the possibility of La and Ce in the misch metal MM diffusing into the intercrystalline phase is reduced, the degree of diffusion into the (Nd, Pr) -Fe-B alloy to replace Nd-Pr is reduced, and thus the high magnetocrystalline anisotropy field of the (Nd, Pr) -Fe-B phase is maintained. Meanwhile, because the content of rare earth elements in the (Nd, Pr) -Fe-B alloy is relatively high, Nd-Pr diffuses towards an intercrystalline liquid phase and can also replace La and Ce elements at the grain boundary of the (MM, RE) -Fe-B alloy phase, so that the magnetocrystalline anisotropy field at the grain boundary of the (MM, RE) -Fe-B alloy phase is improved. By combining the two factors, the (Nd, Pr) -Fe-B phase high magnetocrystalline anisotropy field is maintained, the (MM, RE) -Fe-B alloy phase crystal grain surface layer magnetocrystalline anisotropy field is improved, the magnet coercive force can be obviously enhanced, the proportion of the mixed rare earth MM in the total rare earth can be increased, and the dosage of Nd-Pr can be reduced.
In order to achieve the purpose, the invention adopts the technical scheme that:
a permanent magnet material prepared by utilizing Bayan Obo associated raw ore mixed rare earth comprises (MM, RE) -Fe-B alloy powder and (Nd, Pr) -Fe-B alloy powder which contain mixed rare earth MM, wherein the chemical formula of the (MM, RE) -Fe-B alloy powder is MM in atomic percentagea1REa2Fe100-a1-a2-b-cBbAcThe chemical formula of (Nd, Pr) -Fe-B is (Nd, Pr)a3Fe100-a3-b-cBbAcWherein a1 is more than or equal to 6 and less than or equal to 10, a2 is more than or equal to 2 and less than or equal to 6, a1+ a2 is more than or equal to 11.7 and less than or equal to 13.5, a3 is more than or equal to 20, B is more than or equal to 5 and less than or equal to 8, c is more than or equal to 0 and less than or equal to 15, and the percentage content of rare earth atoms in the (MM, RE) -Fe-B alloy is less than that of rare earth atoms in the (Nd, Pr) -Fe-B alloy, namely a1+ a;
the mixed rare earth MM is a bayan obo associated raw ore mixed rare earth, Fe is iron, B is boron, and RE is selected from one or more of rare earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc;
in the chemical formula, the element A is an additive element and is selected from one or more of Co, Ni, Cu, Zn, Al, Ga, Nb, Mo, Ti, Zr, V, Cr, Mn, C, Si, P, S, Ge, Se, Sn, Ta and Pb.
The main phases of the (MM, RE) -Fe-B alloy and the (Nd, Pr) -Fe-B alloy are both RE2Fe14B。
The Baiyunebo associated raw ore mixed rare earth comprises the following rare earth components in percentage by weight: 10-30% of La, 78-60% of Ce40, 5-10% of Pr, 5-20% of Nd, 0-0.05% of Sm, 0-0.04% of Gd, 0-0.01% of Tb, 0-0.01% of Dy and 0-0.01% of Y.
In the mixture of the (MM, RE) -Fe-B alloy powder containing the mixed rare earth MM and the (Nd, Pr) -Fe-B alloy powder, the weight percentage of the (MM, RE) -Fe-B alloy powder containing the mixed rare earth MM is more than or equal to 40 percent, and the weight percentage of the (Nd, Pr) -Fe-B alloy powder is less than or equal to 60 percent.
The raw materials of the permanent magnetic material also comprise other alloys or metal powder, and the weight percentage of the other alloys or metal powder in the permanent magnetic material is less than or equal to 20 percent.
The other alloy or metal powder is selected from one or more of RE, Fe, B, Co, Cu, Al, Ga, Nb, Zr and Ti.
A method for preparing a permanent magnet material by utilizing Bayan Obo associated raw ore mixed rare earth comprises the following steps:
step 1: weighing the components of the raw materials according to the component design requirements, and mixing the components in proportion to prepare a component mixture of the raw materials;
step 2: respectively placing the raw material component mixtures prepared in the step 1 into a crucible of an induction melting rapid hardening furnace, vacuumizing, introducing argon, then transmitting power for heating, pouring molten liquid onto a water-cooled copper roller with the linear speed of 1-3m/s when the raw material component mixtures are molten into liquid, and obtaining a rapid hardening thin strip with the average thickness of 0.1-2.0 mm; or melting the mixture of the raw material components into liquid by adopting an induction heating mode under the vacuum condition, ensuring the alloy components to be uniform, and then cooling the alloy ingot;
and step 3: putting the rapid hardening thin strip or the alloy cast ingot prepared in the step 2 into a hydrogen crushing furnace for crushing to obtain primary crushing powder; adding nitrogen into the primary crushed powder to perform jet milling, or adding an antioxidant into the primary crushed powder under a protective atmosphere to prevent oxidation and agglomeration of the powder, and preparing the primary crushed powder into alloy powder with the average particle size of 1-6 mu m by the jet milling;
and 4, step 4: uniformly mixing the alloy powder obtained in the step 3;
and 5: orienting and pressing the uniformly mixed powder in the step 4 in a magnetic field of 1-3T for forming, and preparing a blank in a cold isostatic press;
step 6: putting the blank obtained in the step 5 into a sintering furnace, vacuumizing the furnace, then filling argon, heating to 970-1080 ℃ for sintering, preserving heat for 1-6 hours, and cooling to normal temperature to obtain a compact sintered magnet;
and 7: and (3) performing heat treatment on the compact sintered magnet obtained in the step (6) at the temperature of 700-980 ℃ and 400-700 ℃ for 1-4h respectively to obtain the permanent magnet material.
The nitrogen in the step 3 is 5-7 atm.
Step 6 vacuum of 3X 10-3Pa。
The density of the blank is 3-5g/cm3
The (MM, RE) -Fe-B alloy containing the mixed rare earth MM has low rare earth content; the rare earth element Nd-Pr in the (Nd, Pr) -Fe-B alloy is high in content and provides a high magnetocrystalline anisotropy field. In the sintering annealing process, rare earth elements are mainly diffused from the alloy phase with high rare earth content to the alloy phase with low rare earth content, La and Ce elements in the mixed rare earth MM are diffused from the alloy phase with low rare earth content to the alloy phase with high rare earth content to replace Nd-Pr for weakening, the magnetocrystalline anisotropy field with high (Nd, Pr) -Fe-B phase is maintained, and the magnet can maintain higher coercive force.
The rare earth element Nd-Pr in the (Nd, Pr) -Fe-B alloy is high in content, the diffusion degree of elements such as Nd-Pr to intergranular phases is more obvious in the sintering annealing process, the elements are further diffused to the surface layer of the (MM, RE) -Fe-B phase crystal grains with low rare earth content, the magnetocrystalline anisotropy field of the surface layer of the (MM, RE) -Fe-B alloy phase crystal grains is improved, and the coercive force of a magnet is improved.
The (MM, RE) -Fe-B main phase has low rare earth content, so the total rare earth content in the magnet is lower, the Fe content is high, the saturation magnetization of the magnet is higher, the remanence is higher, and good comprehensive magnetic performance can be obtained.
Compared with the prior art, the invention has the beneficial effects that:
1) the rare earth content of the mixed rare earth (MM, RE) -Fe-B alloy is low, the rare earth content of the (Nd, Pr) -Fe-B alloy is high, and a magnet prepared by compounding the two alloy powders has higher coercive force and improved magnetic performance.
2) The amount of the (MM, RE) -Fe-B alloy powder in the mixed powder can be increased, the total content of MM in the magnet can be moderately increased, the high-price Nd-Pr consumption is reduced, and the raw material cost of the magnet is obviously reduced.
3) The method has the advantages of reducing the Nd-Pr consumption and improving the mixed rare earth MM content, thereby obviously reducing the rare earth separation steps and the separation requirements, comprehensively utilizing the rare earth resources to a greater extent and reducing the negative influence of the rare earth mining and purification separation on the environment.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
The Baiyunebo associated raw ore mixed rare earth comprises the following rare earth components in percentage by weight: 10-30% of La, 78-60% of Ce40, 5-10% of Pr, 5-20% of Nd, 0-0.05% of Sm, 0-0.04% of Gd, 0-0.01% of Tb, 0-0.01% of Dy and 0-0.01% of Y.
Example 1
A permanent magnet material prepared by utilizing Bayan Obo associated raw ore mixed rare earth comprises (MM, RE) -Fe-B alloy powder and (Nd, Pr) -Fe-B alloy powder which contain mixed rare earth MM, wherein the chemical formula of the (MM, RE) -Fe-B alloy powder is MM in atomic percentage8.8Nd3.4Fe81.8B6The chemical formula of (Nd, Pr) -Fe-B is Nd according to atomic percent15Fe79B6。
The preparation method comprises the following steps:
step 1: weighing MM according to the design requirements of components8.8Nd3.4Fe81.8B6And Nd15Fe79B6Mixing the components of (1) and preparing a component mixture of two alloys;
step 2: respectively melting the alloy component mixture prepared in the step 1 into liquid by adopting an induction heating mode (1100 ℃ and 2 hours) under the vacuum condition, and then cooling to obtain MM8.8Nd3.4Fe81.8B6And Nd15Fe79B6Alloy ingot casting, which ensures uniform components during smelting to ensure that the main phase of the alloy is RE2Fe14B；
And step 3: the MM prepared in the step 2 is8.8Nd3.4Fe81.8B6And Nd15Fe79B6Crushing the alloy cast ingot in a hydrogen crushing furnace to obtain primary crushed powder; then adding 5-7atm high-pressure nitrogen gas into the primary crushed powder to carry out jet milling, and respectively preparing MM with the average particle size of about 3.5 mu m8.8Nd3.4Fe81.8B6And Nd15Fe79B6Alloying powder;
and 4, step 4: 7g MM obtained in step 38.8Nd3.4Fe81.8B6Alloy powder and 3g Nd15Fe79B6Mixing the alloy powder uniformly;
and 5: the powder evenly mixed in the step 4 is pressed and formed in a 2T magnetic field in an orientation mode, and the powder is made into the powder with the density of 4g/cm in a cold isostatic press3The blank of (2);
step 6: putting the blank obtained in the step 5 into a sintering furnace, and pumping the furnace to 3 x 10-3Pa high vacuum, then filling argon, heating to 1030 ℃ for sintering, keeping the temperature for 2h, and then cooling to normal temperature to obtain a compact sintered magnet;
and 7: and (4) respectively carrying out heat treatment on the compact sintered magnet obtained in the step (6) at 900 ℃ and 550 ℃ for 2h to obtain the permanent magnet material.
Two alloys having a rare earth content similar to that of example 1 were used as raw materials to prepare permanent magnetic materials according to the method of example 1, and the results are shown in table 1.
Table 1: magnetic properties of magnet and content of misch metal MM in example 1 and comparative examples 1 and 2
Figure BDA0001927573880000041
Figure BDA0001927573880000051
As can be seen from table 1, the magnets of comparative examples 1 and 2 have lower coercive force and lower magnetic energy product than the magnet of example 1, which shows that the method adopted in example 1 has a better effect on improving the magnetic properties.
Example 2
A permanent magnet material prepared by utilizing Bayan Obo associated raw ore mixed rare earth comprises (MM, RE) -Fe-B alloy powder and (Nd, Pr) -Fe-B alloy powder which contain mixed rare earth MM, wherein the chemical formula of the (MM, RE) -Fe-B alloy powder is MM in atomic percentage8.8Nd3.4Fe81.8B6The chemical formula of (Nd, Pr) -Fe-B is Nd according to atomic percent15Fe79B6。
The preparation method comprises the following steps:
step 1: weighing MM according to the design requirements of components8.8Nd3.4Fe81.8B6And Nd15Fe79B6Mixing the components of (1) and preparing a component mixture of two alloys;
step 2: respectively melting the alloy component mixture prepared in the step 1 into liquid by adopting an induction heating mode (1100 ℃ and 2 hours) under the vacuum condition, and then cooling to obtain MM8.8Nd3.4Fe81.8B6And Nd15Fe79B6Alloy ingot casting, which ensures uniform components during smelting to ensure that the main phase of the alloy is RE2Fe14B；
And step 3: the MM prepared in the step 2 is8.8Nd3.4Fe81.8B6And Nd15Fe79B6Crushing the alloy cast ingot in a hydrogen crushing furnace to obtain primary crushed powder; then, the coarsely pulverized powder was subjected to jet milling with 5 to 7atm of high-pressure nitrogen gas to prepare MM having an average particle size of about 3.5 μm, respectively8.8Nd3.4Fe81.8B6And Nd15Fe79B6Alloying powder;
and 4, step 4: mixing 6g MM obtained in step 38.8Nd3.4Fe81.8B6Alloy powder and 4g Nd15Fe79B6Mixing the alloy powder uniformly;
and 5: the powder uniformly mixed in the step 4 is oriented and pressed in a 1T magnetic field to be molded, and the powder is prepared into the powder with the density of 3g/cm in a cold isostatic press3The blank of (2);
step 6: putting the blank obtained in the step 5 into a sintering furnace, and pumping the furnace to 3 x 10-3Pa high vacuum, then filling argon, heating to 1030 ℃ for sintering, keeping the temperature for 2h, and then cooling to normal temperature to obtain a compact sintered magnet;
and 7: and (4) respectively carrying out heat treatment on the compact sintered magnet obtained in the step (6) at 900 ℃ and 550 ℃ for 2h to obtain the permanent magnet material.
Permanent magnet materials were prepared according to the method of example 2 using as raw materials an alloy having a rare earth content similar to that of example 2 and the alloy of patent application No. CN 201310671574.7, and the results are shown in table 2.
Table 2: magnetic properties and mixed rare earth MM content of magnet of example 2 and comparative example
Figure BDA0001927573880000052
Figure BDA0001927573880000061
As can be seen from table 2, the magnet of comparative example 3 has a lower coercive force and magnetic energy product than the magnet of example 2, which indicates that the method adopted in example 2 has a better effect in improving magnetic properties. The magnet of comparative example 4 has lower magnetic properties than the magnet of example 2, and the content of misch metal MM in the total amount of rare earth is only 35 wt%. This shows that the method adopted in example 2 has a better effect in simultaneously improving the magnetic properties and increasing the content of mixed rare earth MM.
In conclusion, the rare earth permanent magnet is prepared by mixing the alloy with higher rare earth content and the alloy powder with lower rare earth content, so that the higher coercive force and magnetic performance are obtained, the content of mixed rare earth MM can be increased, and the high-abundance cheap rare earth elements can be utilized to a greater extent.
Example 3
A permanent magnet material prepared by utilizing Bayan Obo associated raw ore mixed rare earth comprises (MM, RE) -Fe-B alloy powder and (Nd, Pr) -Fe-B alloy powder which contain mixed rare earth MM, wherein the chemical formula of the (MM, RE) -Fe-B alloy powder is MM in atomic percentage8.8Nd3.4Fe80.8B6Co1The chemical formula of (Nd, Pr) -Fe-B is Nd according to atomic percent15Fe79B6。
The preparation method comprises the following steps:
step 1: weighing MM according to the design requirements of components8.8Nd3.4Fe80.8B6Co1And Nd15Fe79B6Mixing the components of (1) and preparing a component mixture of two alloys;
step 2: respectively melting the alloy component mixture prepared in the step 1 into liquid by adopting an induction heating mode (1100 ℃ and 2 hours) under the vacuum condition, and then cooling to obtain MM8.8Nd3.4Fe80.8B6Co1And Nd15Fe79B6Alloy ingot casting, which ensures uniform components during smelting to ensure that the main phase of the alloy is RE2Fe14B；
And step 3: the MM prepared in the step 2 is8.8Nd3.4Fe80.8B6Co1And Nd15Fe79B6Crushing the alloy cast ingot in a hydrogen crushing furnace to obtain primary crushed powder; then the primary crushed powder is mixedSubjecting to jet milling with 5-7atm high pressure nitrogen gas to obtain MM with average particle size of about 3.5 μm8.8Nd3.4Fe80.8B6Co1And Nd15Fe79B6Alloying powder;
and 4, step 4: mixing 6g MM obtained in step 38.8Nd3.4Fe81.8B6Alloy powder and 4g Nd15Fe79B6Mixing the alloy powder uniformly;
and 5: the uniformly mixed powder in the step 4 is subjected to orientation compression molding in a 2T magnetic field, and is prepared into the powder with the density of about 4g/cm in a cold isostatic press3The blank of (2);
step 6: putting the blank obtained in the step 5 into a sintering furnace, and pumping the furnace to 3 x 10-3Pa high vacuum, then filling argon, heating to 1030 ℃ for sintering, keeping the temperature for 2h, and then cooling to normal temperature to obtain a compact sintered magnet;
and 7: and (4) respectively carrying out heat treatment on the compact sintered magnet obtained in the step (6) at 900 ℃ and 550 ℃ for 2h to obtain the permanent magnet material.
Testing the performance of the magnet, and measuring the coercive force H of the magnetcIs 7.91kOe, remanence BrIs 12.23kGs, magnetic energy product (BH)maxIt was 32.56 MGsOe. The mixed rare earth MM accounts for 40 wt% of the rare earth.
Example 4
A permanent magnet material prepared by utilizing Bayan Obo associated raw ore mixed rare earth comprises (MM, RE) -Fe-B alloy powder and (Nd, Pr) -Fe-B alloy powder which contain mixed rare earth MM, wherein the chemical formula of the (MM, RE) -Fe-B alloy powder is MM in atomic percentage8.8Nd3.4Fe81.8B6The chemical formula of (Nd, Pr) -Fe-B is Nd according to atomic percent15Fe79B6。
The preparation method comprises the following steps:
step 1: weighing MM according to the design requirements of components8.8Nd3.4Fe81.8B6And Nd15Fe79B6Mixing the components of (1) and preparing a component mixture of two alloys;
step 2: respectively melting the alloy component mixture prepared in the step 1 into liquid by adopting an induction heating mode (1100 ℃ and 2 hours) under the vacuum condition, and then cooling to obtain MM8.8Nd3.4Fe81.8B6And Nd15Fe79B6Alloy ingot casting, which ensures uniform components during smelting to ensure that the main phase of the alloy is RE2Fe14B；
And step 3: the MM prepared in the step 2 is8.8Nd3.4Fe81.8B6And Nd15Fe79B6Crushing the alloy cast ingot in a hydrogen crushing furnace to obtain primary crushed powder; then, the coarsely pulverized powder was subjected to jet milling with 5 to 7atm of high-pressure nitrogen gas to prepare MM having an average particle size of about 3.5 μm, respectively8.8Nd3.4Fe81.8B6And Nd15Fe79B6Alloying powder;
and 4, step 4: mixing 6.7g MM obtained in step 38.8Nd3.4Fe81.8B6Alloy powder and 3g Nd15Fe79B6Mixing the alloy powder, adding 0.3g of Nd powder, and uniformly mixing; the Nd powder is obtained by putting metal Nd into a hydrogen crushing furnace for crushing and then ball-milling;
and 5: the uniformly mixed powder in the step 4 is subjected to orientation compression molding in a 2T magnetic field, and is prepared into the powder with the density of about 4g/cm in a cold isostatic press3The blank of (2);
step 6: putting the blank obtained in the step 5 into a sintering furnace, and pumping the furnace to 3 x 10-3Pa high vacuum, then filling argon, heating to 1030 ℃ for sintering, keeping the temperature for 2h, and then cooling to normal temperature to obtain a compact sintered magnet;
and 7: and (4) respectively carrying out heat treatment on the compact sintered magnet obtained in the step (6) at 900 ℃ and 550 ℃ for 2h to obtain the permanent magnet material.
Testing the performance of the magnet, and measuring the coercive force H of the magnetc8.16kOe, remanence BrIs 12.15kGs, magnetic energy product (BH)maxIs 31.69 MGsOe. The weight ratio of the mixed rare earth to the rare earth is 42 wt%.

Claims (6)

1. A preparation method of a permanent magnet material prepared by utilizing Bayan Obo associated raw ore mixed rare earth is characterized in that the raw materials comprise (MM, RE) -Fe-B alloy powder and (Nd, Pr) -Fe-B alloy powder containing mixed rare earth MM, and the chemical formula of the (MM, RE) -Fe-B alloy powder is MM in atomic percentagea1REa2Fe100-a1-a2-b-cBbAcThe chemical formula of (Nd, Pr) -Fe-B is (Nd, Pr)a3Fe100-a3-b-cBbAcWherein a1 is more than or equal to 6 and less than or equal to 10, a2 is more than or equal to 2 and less than or equal to 6, a1+ a2 is more than or equal to 11.7 and less than or equal to 13.5, a3 is more than or equal to 20, B is more than or equal to 5 and less than or equal to 8, c is more than or equal to 0 and less than or equal to 15, and the percentage content of rare earth atoms in the (MM, RE) -Fe-B alloy is less than that of rare earth atoms in the (Nd, Pr) -Fe-B alloy, namely a1+ a;
the mixed rare earth MM is a bayan obo associated raw ore mixed rare earth, Fe is iron, B is boron, and RE is selected from one or more of rare earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc;
in the chemical formula, the element A is an additive element and is selected from one or more of Co, Ni, Cu, Zn, Al, Ga, Nb, Mo, Ti, Zr, V, Cr, Mn, C, Si, P, S, Ge, Se, Sn, Ta and Pb;
the main phases of the (MM, RE) -Fe-B alloy and the (Nd, Pr) -Fe-B alloy are both RE2Fe14B; in the mixture of the (MM, RE) -Fe-B alloy powder containing the mixed rare earth MM and the (Nd, Pr) -Fe-B alloy powder, the weight percentage of the (MM, RE) -Fe-B alloy powder containing the mixed rare earth MM is more than or equal to 40 percent, and the weight percentage of the (Nd, Pr) -Fe-B alloy powder is less than or equal to 60 percent;
the preparation method of the permanent magnetic material comprises the following steps:
step 1: weighing the components of the raw materials according to the component design requirements, and mixing the components in proportion to prepare a component mixture of the raw materials;
step 2: respectively placing the raw material component mixtures prepared in the step 1 into a crucible of an induction melting rapid hardening furnace, vacuumizing, introducing argon, then transmitting power for heating, pouring molten liquid onto a water-cooled copper roller with the linear speed of 1-3m/s when the raw material component mixtures are molten into liquid, and obtaining a rapid hardening thin strip with the average thickness of 0.1-2.0 mm; or melting the mixture of the raw material components into liquid by adopting an induction heating mode under the vacuum condition, ensuring the alloy components to be uniform, and then cooling the alloy ingot;
and step 3: putting the rapid hardening thin strip or the alloy cast ingot prepared in the step 2 into a hydrogen crushing furnace for crushing to obtain primary crushing powder; adding nitrogen into the primary crushed powder to perform jet milling, or adding an antioxidant into the primary crushed powder under a protective atmosphere to prevent oxidation and agglomeration of the powder, and preparing the primary crushed powder into alloy powder with the average particle size of 1-6 mu m by the jet milling;
and 4, step 4: uniformly mixing the alloy powder obtained in the step 3;
and 5: orienting and pressing the uniformly mixed powder in the step 4 in a magnetic field of 1-3T for forming, and preparing a blank in a cold isostatic press;
step 6: putting the blank obtained in the step 5 into a sintering furnace, vacuumizing the furnace, then filling argon, heating to 970-1080 ℃ for sintering, preserving heat for 1-6 hours, and cooling to normal temperature to obtain a compact sintered magnet;
and 7: and (3) performing heat treatment on the compact sintered magnet obtained in the step (6) at the temperature of 700-980 ℃ and 400-700 ℃ for 1-4h respectively to obtain the permanent magnet material.
2. The method for preparing a permanent magnet material by using the Baiyunebo associated raw ore misch metal according to claim 1, wherein the Baiyunebo associated raw ore misch metal comprises the following rare earth components in percentage by weight: 10-30% of La, 40-60% of Ce, 5-10% of Pr, 5-20% of Nd, 0-0.05% of Sm, 0-0.04% of Gd, 0-0.01% of Tb, 0-0.01% of Dy and 0.01% of Y0.
3. The method for preparing a permanent magnet material by using the bayan obo associated raw ore mixed rare earth as claimed in claim 1, wherein the raw material of the permanent magnet material further comprises metal powder, and the weight percentage of the metal powder in the permanent magnet material is less than or equal to 20%.
4. The method for preparing a permanent magnet material from the bayan obo associated raw ore mixed rare earth according to claim 3, wherein the metal powder is one or more selected from RE, Fe, Co, Cu, Al, Ga, Nb, Zr and Ti.
5. The method for preparing a permanent magnet material from the bayan obo associated raw ore mixed rare earth according to claim 1, wherein the vacuum degree in step 6 is 3 x 10-3Pa。
6. The method for preparing a permanent magnet material from the bayan obo associated raw ore misch metal according to claim 1, wherein the density of the blank is 3-5g/cm3。
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