CN108154986B - Y-containing high-abundance rare earth permanent magnet and preparation method thereof - Google Patents
Y-containing high-abundance rare earth permanent magnet and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 229910016285 MxNy Inorganic materials 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 28
- 238000003723 Smelting Methods 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005496 tempering Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000009694 cold isostatic pressing Methods 0.000 claims description 7
- 238000000462 isostatic pressing Methods 0.000 claims description 7
- 238000010902 jet-milling Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims 1
- 229910001172 neodymium magnet Inorganic materials 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 7
- 238000012876 topography Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 5
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- -1 L a Inorganic materials 0.000 description 2
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- H—ELECTRICITY
- 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
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- 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
- H01F1/0573—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 obtained by reduction or by hydrogen decrepitation or embrittlement
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- H—ELECTRICITY
- 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
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- 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
- H01F1/0576—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 pressed, e.g. hot working
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- H—ELECTRICITY
- 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
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- 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
- H01F1/0577—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 sintered
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- H—ELECTRICITY
- 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
- H01F41/0266—Moulding; Pressing
Abstract
The invention provides a Y-containingThe high-abundance rare earth permanent magnet comprises the following components: reαYβBγMxNyFe100‑α‑β‑γ‑x‑yThe main phase crystal grain of the Y-containing high-abundance rare earth permanent magnet is in a core-shell structure, wherein more elements Y are distributed at the core, and more Ce and Nd are distributed at the shell layer, so that loss of coercive force caused by adding Ce in Nd-Fe-B can be compensated, and the temperature stability of the use of the Y-containing high-abundance rare earth permanent magnet is improved.
Description
Technical Field
The invention belongs to the field of rare earth permanent magnet material preparation, and particularly relates to a Y-containing high-abundance rare earth permanent magnet and a preparation method thereof.
Background
The rare earth neodymium iron boron permanent magnet material is developed in the beginning of the eighties of the twentieth century, is called as 'magical king' due to extremely high coercive force and maximum magnetic energy product, and is widely applied to various industries of national economy such as instruments, microwave communication, wind power generation, electric vehicles and the like.
At present, a great deal of light rare earth elements Nd and Pr and heavy rare earth elements Dy and Tb are still used for preparing the neodymium iron boron permanent magnet, on one hand, the price of the neodymium iron boron magnet is high due to the high price of the light rare earth elements Nd and Pr and the heavy rare earth elements Dy and Tb, on the other hand, the contents of the rare earth elements in the earth crust are sequentially Ce, Y, L a, Nd, Pr, Sm, Gd, Dy and Tb 56, and the great deal of use of the rare earth permanent magnet enables the Pr, Nd, Dy and Tb to be rapidly consumed, so that a great deal of accumulation of high-abundance rare earth elements L a, Ce and Y is caused, and the utilization of rare earth resources is unbalanced.
At present, research on high-abundance rare earth permanent magnets mainly focuses on the preparation of rare earth permanent magnets by replacing Nd with Ce. In patent document CN1035737A, researchers have replaced part of Nd with Ce by direct smelting, and found that as the Ce content increases, both the coercive force and remanence of the magnet decrease. This is because of Ce2Fe14Intrinsic Property of B (H)a＝26kOe，4πMs11.7kGs) is much lower than Nd2Fe14Intrinsic Property of B (H)a＝73kOe，4πMs16.0 kGs); meanwhile, the microstructure of the magnet is remarkably deteriorated after Ce replaces Nd, which is also a reason for greatly reducing the coercive force and remanence.
Disclosure of Invention
The invention aims to provide a high-abundance rare earth permanent magnet which has higher coercive force and temperature stability.
In order to achieve the technical purpose, the team of the invention discovers that a core-shell structure can be formed in the obtained main phase crystal grains by replacing part of Ce with a high-abundance rare earth element Y when the Nd-Ce-Fe-B rare earth permanent magnet is prepared through a large number of experiments. That is, more Y is distributed at the core, more Nd and Ce are distributed at the shell, and the coercive force and the temperature stability of the permanent magnet are improved.
Namely, the technical scheme of the invention is as follows: a high-abundance rare earth permanent magnet containing Y comprises the following components:
ReαYβBγMxNyFe100-α-β-γ-x-y
wherein Re is a rare earth element, including Nd and Ce, and also can include one or more elements of L a, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, L u, Y and SC;
m is an additive element selected from one or two elements of Co and Cu;
n is an additive element selected from one or more of Nb, Ti, Zn, Ga, Al, Zr, Sn, Sb, Ta and W;
α, β, gamma, x and y are the weight percentage of each element, 23 is equal to or more than α is equal to or less than 35, β is greater than 0 and equal to or less than 10, gamma is equal to or more than 0.95 and equal to or less than 1.2, x is equal to or more than 0 and equal to or less than 2, and y is equal to or more than 0 and equal to or less than 2;
the main phase crystal grain of the Y-containing high-abundance rare earth permanent magnet is in a core-shell structure, wherein more of element Y is distributed at the core, and more of Nd and Ce are distributed at the shell layer.
Preferably, 1.5 < β < 7, more preferably, 3 < β < 6.5.
B is necessary to form the magnetic phase and is therefore at least 0.95 wt.% in the permanent magnetic material of the present invention, but excessive addition deteriorates magnetic properties.
The invention also provides a manufacturing method of the Y-containing high-abundance rare earth permanent magnet, which comprises the following steps:
1) quick setting: grinding after mixing the elements according to the nominal composition, smelting at 1300-1420 ℃ by using a rapid hardening flail vacuum induction smelting furnace under the protection of argon, and casting molten steel onto a rotating cooling copper roller to prepare a rapid hardening sheet with the average thickness of 0.3-0.5 mm;
2) hydrogen breaking: placing the obtained quick-setting sheet in a hydrogen breaking furnace, and absorbing hydrogen under the hydrogen pressure of 0.2-0.25 MPa; then, fully dehydrogenating at 380-550 ℃ for a long time, and crushing the quick-setting pieces into alloy coarse powder with the diameter of about 100-5000 microns;
3) and (3) jet milling: further crushing the coarse powder obtained in the step 2) into fine powder of 0.5-5 microns through an airflow mill;
4) orientation forming: orienting and molding the powder obtained in the step 3) under a 2T magnetic field by using a magnetic field press;
5) isostatic pressing: carrying out cold isostatic pressing on the formed blank obtained in the step 4) under the pressure of 100-200 MPa to prepare a green blank;
6) sintering and tempering: and placing the obtained green body in a vacuum sintering furnace, sintering for 2-4 hours at 850-1020 ℃, and tempering for 2-6 hours at 400-800 ℃ to finally obtain the sintered magnet.
Preferably, in the step 1), the rotation speed of the copper roller is kept within the range of 0m/s to 1.5 m/s.
Preferably, in the step 6), sintering is carried out at 950-1015 ℃.
Preferably, in the step 3), the grinding pressure of the jet mill is 0.4-0.8 Mpa, and the sorting rotation speed is 70-100 Hz, so as to obtain magnetic powder with fine particle size and uniform distribution.
Preferably, in the step 3), the content of oxygen is controlled to be less than 10ppm during the grinding process, so as to avoid oxidation of the magnetic powder.
In conclusion, Y is added into the high-abundance rare earth permanent magnet Nd-Ce-Fe-B, and the occupation energy of Y atoms in the 2:14:1 phase is lower than that of Nd atoms and Ce atoms, so that Y can more easily enter a main phase in the sintering and tempering processes to replace Nd and Ce, and a core-shell structure is formed in main phase grains. In the core-shell structure, Y is more distributed at the core, Nd and Ce are more distributed at the shell, so that a structure with a surface layer anisotropy field higher than that of the interior can be formed, and the anisotropy field of the magnet is enhanced. Compared with the prior art, the invention has the following advantages and effects:
(1) loss of coercive force caused by adding Ce into Nd-Fe-B can be compensated;
(2) y is the element with the second highest abundance in the rare earth elements, and the price of Y is higher than that of Ce but lower than that of Nd, so that the use of Nd can be reduced under the condition of the same performance, and the cost of the magnet is effectively reduced.
(3) Due to Y2Fe14Curie temperature of B is Tc565K, and Ce2Fe14Curie temperature T of Bc424K, the temperature stability of the magnet can therefore be increased by the addition of Y.
Drawings
FIG. 1 shows [ Nd ] obtained in example 1 of the present invention0.5Ce0.5]30.5Al0.1Cu0.1Fe68.3B1A micro-topography of the magnet;
FIG. 2 shows [ Nd ] obtained in example 2 of the present invention0.5(Ce0.45Y0.05)]30.5Al0.1Cu0.1Fe68.3B1A micro-topography of the magnet;
FIG. 3 shows an embodiment of the present invention3 produced [ Nd0.5(Ce0.4Y0.10)]30.5Al0.1Cu0.1Fe68.3B1A micro-topography of the magnet;
FIG. 4 shows [ Nd ] obtained in example 4 of the present invention0.5(Ce0.35Y0.15)]30.5Al0.1Cu0.1Fe68.3B1A micro-topography of the magnet;
FIG. 5 shows [ Nd ] obtained in example 5 of the present invention0.5(Ce0.30Y0.20)]30.5Al0.1Cu0.1Fe68.3B1A micro-topography of the magnet.
Detailed Description
The present invention will be further described with reference to examples, which are provided only for illustrating the technical solutions of the present invention and are not intended to limit the present invention.
Example 1:
in this embodiment, the high-abundance rare earth permanent magnet has a nominal composition, in mass percent, of: [ Nd ]0.5Ce0.5]30.5Al0.1Cu0.1Fe68.3B1。
The preparation method of the high-abundance rare earth permanent magnet comprises the following steps:
1) quick setting: polishing the proportioned master alloy, and then putting the polished master alloy into a rapid hardening furnace for smelting, wherein the main parameters in the smelting step are as follows: controlling the smelting temperature to 1350 ℃, keeping the rotating speed of a copper roller at 1.2m/s during smelting, and obtaining the average thickness of the master alloy quick-setting sheet by a quick-setting process to be 0.3-0.5 mm;
2) hydrogen breaking: placing the obtained quick-setting sheet in a hydrogen breaking furnace, and absorbing hydrogen under the hydrogen pressure of 0.2-0.25 MPa; then, fully dehydrogenating at 550 ℃ for a long time, and crushing the quick-setting pieces into alloy coarse powder of about 100-150 microns;
3) and (3) jet milling: further crushing the coarse powder obtained in the step 2) into fine powder of 1-5 microns through an airflow mill;
4) orientation forming: orienting and molding the powder obtained in the step 3) under a 1.7T magnetic field by using a magnetic field press;
5) isostatic pressing: carrying out cold isostatic pressing on the formed blank obtained in the step 4) under the pressure of 150MPa to prepare a green blank;
6) sintering and tempering: the obtained green compact was placed in a vacuum sintering furnace, sintered at 960 ℃ for 2 hours, and tempered at 700 ℃ for 2 hours to finally obtain a sintered magnet.
The prepared magnet is placed in a closed NIM-500C type permanent magnet material measuring system, and the magnetic performance results are as follows: remanence Br1.227T, coercive force Hcj7.13kOe, maximum magnetic energy product (BH)max34.59MGOe, a remanence temperature coefficient α of-0.1724%/DEG C, and a coercive force temperature coefficient β of-0.5613%/DEG C.
Example 2:
in this embodiment, the high-abundance rare earth permanent magnet has a nominal composition, in mass percent, of: [ Nd ]0.5(Ce0.45Y0.05)]30.5Al0.1Cu0.1Fe68.3B1。
The preparation method of the high-abundance rare earth permanent magnet comprises the following steps:
1) quick setting: polishing the proportioned master alloy, and then putting the polished master alloy into a rapid hardening furnace for smelting, wherein the main parameters in the smelting step are as follows: controlling the smelting temperature to 1350 ℃, keeping the rotating speed of a copper roller at 1.2m/s during smelting, and obtaining the average thickness of the master alloy quick-setting sheet by a quick-setting process to be 0.3-0.5 mm;
2) hydrogen breaking: placing the obtained quick-setting sheet in a hydrogen breaking furnace, and absorbing hydrogen under the hydrogen pressure of 0.2-0.25 MPa; then, fully dehydrogenating at 550 ℃ for a long time, and crushing the quick-setting pieces into alloy coarse powder of about 100-150 microns;
3) and (3) jet milling: further crushing the coarse powder obtained in the step 2) into fine powder of 1-5 microns through an airflow mill; .
4) Orientation forming: orienting and molding the powder obtained in the step 3) under a 1.7T magnetic field by using a magnetic field press;
5) isostatic pressing: carrying out cold isostatic pressing on the formed blank obtained in the step 4) under the pressure of 150MPa to prepare a green blank;
6) sintering and tempering: the obtained green compact was placed in a vacuum sintering furnace, sintered at 960 ℃ for 2 hours, and tempered at 700 ℃ for 2 hours to finally obtain a sintered magnet.
The prepared magnet is placed in a closed NIM-500C type permanent magnet material measuring system, and the magnetic performance results are as follows: remanence Br1.155T, coercive force HcjMaximum energy product (BH) of 8.75kOemax31.05MGOe, a remanence temperature coefficient α of-0.1652%/DEG C, and a coercive force temperature coefficient β of-0.5484%/DEG C.
Example 3:
in this embodiment, the high-abundance rare earth permanent magnet has a nominal composition, in mass percent, of: [ Nd ]0.5(Ce0.4Y0.10)]30.5Al0.1Cu0.1Fe68.3B1。
The preparation method of the high-abundance rare earth permanent magnet comprises the following steps:
1) quick setting: polishing the proportioned master alloy, and then putting the polished master alloy into a rapid hardening furnace for smelting, wherein the main parameters in the smelting step are as follows: controlling the smelting temperature to 1350 ℃, keeping the rotating speed of a copper roller at 1.2m/s during smelting, and obtaining the average thickness of the master alloy quick-setting sheet by a quick-setting process to be 0.3-0.5 mm;
2) hydrogen breaking: placing the obtained quick-setting sheet in a hydrogen breaking furnace, and absorbing hydrogen under the hydrogen pressure of 0.2-0.25 MPa; then, fully dehydrogenating at 550 ℃ for a long time, and crushing the quick-setting pieces into alloy coarse powder of about 100-150 microns;
3) and (3) jet milling: further crushing the coarse powder obtained in the step 2) into fine powder of 1-5 microns through an airflow mill;
4) orientation forming: orienting and molding the powder obtained in the step 3) under a 1.7T magnetic field by using a magnetic field press;
5) isostatic pressing: carrying out cold isostatic pressing on the formed blank obtained in the step 4) under the pressure of 150MPa to prepare a green blank;
6) sintering and tempering: the obtained green compact was placed in a vacuum sintering furnace, sintered at 960 ℃ for 2 hours, and tempered at 700 ℃ for 2 hours to finally obtain a sintered magnet.
The prepared magnet is placed in a closed NIM-500C type permanent magnet material measuring system, and the magnetic performance results are as follows: remanence Br1.175T, coercive force Hcj9.55kOe, maxMagnetic energy product (BH)max31.55MGOe, a remanence temperature coefficient α of-0.1558%/DEG C, and a coercive force temperature coefficient β of-0.5376%/DEG C.
Example 4:
in this embodiment, the high-abundance rare earth permanent magnet has a nominal composition, in mass percent, of: [ Nd ]0.5(Ce0.35Y0.15)]30.5Al0.1Cu0.1Fe68.3B1。
The preparation method of the high-abundance rare earth permanent magnet comprises the following steps:
1) quick setting: polishing the proportioned master alloy, and then putting the polished master alloy into a rapid hardening furnace for smelting, wherein the main parameters in the smelting step are as follows: controlling the smelting temperature to 1350 ℃, keeping the rotating speed of a copper roller at 1.2m/s during smelting, and obtaining the average thickness of the master alloy quick-setting sheet by a quick-setting process to be 0.3-0.5 mm;
2) hydrogen breaking: placing the obtained quick-setting sheet in a hydrogen breaking furnace, and absorbing hydrogen under the hydrogen pressure of 0.2-0.25 MPa; and then, fully dehydrogenating at 550 ℃ for a long time, and crushing the quick-setting pieces into alloy coarse powder with the diameter of about 100-150 microns.
3) And (3) jet milling: further crushing the coarse powder obtained in the step 2) into fine powder of 1-5 microns through an airflow mill; .
4) Orientation forming: orienting and molding the powder obtained in the step 3) under a 1.7T magnetic field by using a magnetic field press;
5) isostatic pressing: carrying out cold isostatic pressing on the formed blank obtained in the step 4) under the pressure of 150MPa to prepare a green blank;
6) sintering and tempering: the obtained green compact was placed in a vacuum sintering furnace, sintered at 960 ℃ for 2 hours, and tempered at 700 ℃ for 2 hours to finally obtain a sintered magnet.
The prepared magnet is placed in a closed NIM-500C type permanent magnet material measuring system, and the magnetic performance results are as follows: remanence Br1.158T, coercive force Hcj9.73kOe, maximum magnetic energy product (BH)max29.12MGOe, a remanence temperature coefficient α of-0.1516%/DEG C, and a coercive force temperature coefficient β of-0.5145%/DEG C.
Example 5:
in this example, gaofengThe rare earth permanent magnet comprises the following nominal components in percentage by mass: [ Nd ]0.5(Ce0.30Y0.20)]30.5Al0.1Cu0.1Fe68.3B1。
The preparation method of the high-abundance rare earth permanent magnet comprises the following steps:
1) quick setting: polishing the proportioned master alloy, and then putting the polished master alloy into a rapid hardening furnace for smelting, wherein the main parameters in the smelting step are as follows: controlling the smelting temperature to 1350 ℃, keeping the rotating speed of a copper roller at 1.2m/s during smelting, and obtaining the average thickness of the master alloy quick-setting sheet by a quick-setting process to be 0.3-0.5 mm;
2) hydrogen breaking: placing the obtained quick-setting sheet in a hydrogen breaking furnace, and absorbing hydrogen under the hydrogen pressure of 0.2-0.25 MPa; then, fully dehydrogenating at 550 ℃ for a long time, and crushing the quick-setting pieces into alloy coarse powder of about 100-150 microns;
3) and (3) jet milling: further crushing the coarse powder obtained in the step 2) into fine powder of 1-5 microns through an airflow mill;
4) orientation forming: orienting and molding the powder obtained in the step 3) under a 1.7T magnetic field by using a magnetic field press;
5) isostatic pressing: carrying out cold isostatic pressing on the formed blank obtained in the step 4) under the pressure of 150MPa to prepare a green blank;
6) sintering and tempering: the obtained green compact was placed in a vacuum sintering furnace, sintered at 960 ℃ for 2 hours, and tempered at 700 ℃ for 2 hours to finally obtain a sintered magnet.
The prepared magnet is placed in a closed NIM-500C type permanent magnet material measuring system, and the magnetic performance results are as follows: remanence Br1.124T, coercivity HcjMaximum energy product (BH) of 8.75kOemax24.35MGOe, a remanence temperature coefficient α of-0.1476%/DEG C, and a coercive force temperature coefficient β of-0.5052%/DEG C.
The micro-topography of the magnets prepared in examples 1-5 is shown in FIGS. 1-5. It can be seen that in example 1, Y is not added, and the elements in the main phase grains are uniformly distributed without a core-shell structure. In examples 2 to 5, Y was added, and the main phase grains were each in a core-shell structure, wherein the reference symbol a was a core and the reference symbol B was a shell. The elemental composition in the core-shell structure of the magnet in example 4 was tested by EDS elemental analysis, with the following results:
the elemental composition in core a is (wt.%): fe 73.99, Y5.29, Ce 7.19, Nd 13.53;
the element composition in shell layer B is (wt.%): fe 73.09, Y3.39, Ce 9.14, Nd 14.37.
That is, in the core-shell structure, elements Y and Ce are more distributed at the core, and Nd is more distributed at the shell.
The elemental composition in the core-shell structure of the magnet in examples 2, 3, 5 was tested by EDS elemental analysis, and results similar to those in example 4 were obtained, i.e., in the core-shell structure, element Y was more distributed at the core, and elements Nd and Ce were more distributed at the shell.
The coercive force H of the example magnet to which Y was added was found by comparisoncjIs improved compared with the magnet without Y.
The comparison shows that the temperature stability of the magnet with Y is improved compared with the magnet without Y.
The preparation process of the magnet without the Y magnet is the same as that of the magnet with the corresponding Y magnet. Further, the coercive force and the temperature stability of the magnet added with Y in a reasonable range are greatly improved compared with those of the magnet without Y added with the same component. In addition, the price of the metal Y is lower than that of the metal Nd, so that the cost can be effectively reduced.
Although particular embodiments of the invention have been described and illustrated, the invention is not limited thereto but may also be embodied in other ways within the scope of the technical solution defined in the following claims.
Claims (8)
1. A method for improving the coercive force and the temperature stability of an Nd-Ce-Fe-B rare earth permanent magnet is characterized by comprising the following steps: the high-abundance rare earth element Y is adopted to replace part of Ce, and the obtained Nd-Ce-Fe-B rare earth permanent magnet molecule consists of:
ReαYβBγMxNyFe100-α-β-γ-x-y
wherein Re is a rare earth element including Nd and Ce;
m is an additive element selected from one or two elements of Co and Cu;
n is an additive element selected from one or more than two of Nb, Ti, Zn, Ga, Al, Zr, Sn, Sb, Ta and W;
α, β, gamma, x and y are the weight percentage of each element, 23 is equal to or more than α is equal to or less than 35, β is greater than 0 and equal to or less than 10, gamma is equal to or more than 0.95 and equal to or less than 1.2, x is equal to or more than 0 and equal to or less than 2, and y is equal to or more than 0 and equal to or less than 2;
the main phase crystal grain of the Y-containing high-abundance rare earth permanent magnet is in a core-shell structure, wherein more elements Y are distributed at the core, and more elements Nd and Ce are distributed at the shell layer;
the preparation method of the Nd-Ce-Fe-B rare earth permanent magnet comprises the following steps:
1) quick setting: grinding the elements after being prepared according to the nominal composition, then smelting at 1300-1420 ℃ by using a rapid hardening flail vacuum induction smelting furnace under the protection of argon, and casting molten steel onto a rotating cooling copper roller to prepare a rapid hardening sheet with the average thickness of 0.1-0.5 mm;
2) hydrogen breaking: placing the obtained quick-setting sheet in a hydrogen breaking furnace, and absorbing hydrogen under the hydrogen pressure of 0.1-0.3 MPa; then, fully dehydrogenating at 380-550 ℃ for a long time, and crushing the quick-setting pieces into alloy coarse powder of 0.1-5 mm;
3) and (3) jet milling: further crushing the coarse powder obtained in the step 2) into fine powder of 0.5-5 microns through an airflow mill;
4) orientation forming: orienting and molding the powder obtained in the step 3) under a magnetic field by utilizing a magnetic field press;
5) isostatic pressing: carrying out cold isostatic pressing on the formed blank obtained in the step 4) under the pressure of 100-200 MPa to prepare a green blank;
6) sintering and tempering: and placing the obtained green body in a vacuum sintering furnace, sintering for 2-4 hours at 850-1020 ℃, and tempering for 2-6 hours at 400-800 ℃ to finally obtain the sintered magnet.
2. The method for improving the coercive force and the temperature stability of the Nd-Ce-Fe-B rare earth permanent magnet as claimed in claim 1, wherein the coercive force and the temperature stability are 1.5- β -7.
3. The method for improving the coercive force and the temperature stability of the Nd-Ce-Fe-B rare earth permanent magnet as claimed in claim 1, wherein 3 is more than β and less than or equal to 6.5.
4. The method for improving the coercive force and the temperature stability of the Nd-Ce-Fe-B rare earth permanent magnet according to claim 1, wherein the element Re further comprises one element or more than two elements of L a, Pr, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, L u and Sc.
5. The method for improving the coercivity and the temperature stability of the Nd-Ce-Fe-B rare earth permanent magnet according to claim 1, wherein the method comprises the following steps: in the step 1), the rotating speed of the copper roller is kept within the range of 0 m/s-1.5 m/s.
6. The method for improving the coercivity and the temperature stability of the Nd-Ce-Fe-B rare earth permanent magnet according to claim 1, wherein the method comprises the following steps: and in the step 6), sintering at 950-1015 ℃.
7. The method for improving the coercivity and the temperature stability of the Nd-Ce-Fe-B rare earth permanent magnet according to claim 1, wherein the method comprises the following steps: in the step 3), the grinding pressure of the jet mill is 0.4-0.8 Mpa, and the sorting rotating speed is 70-100 Hz.
8. The method for improving the coercivity and the temperature stability of the Nd-Ce-Fe-B rare earth permanent magnet according to claim 1, wherein the method comprises the following steps: in the step 3), the content of oxygen is controlled to be less than 10ppm in the grinding process.
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| CN109637768B (en) * | 2018-12-29 | 2020-07-28 | 中国科学院宁波材料技术与工程研究所 | Yttrium-containing rare earth permanent magnetic material and preparation method thereof |
| CN109509605B (en) * | 2019-01-11 | 2019-12-13 | 宁波复能新材料股份有限公司 | Rare earth permanent magnet with multilayer structure and preparation method thereof |
| CN111210963B (en) * | 2020-02-07 | 2021-01-01 | 钢铁研究总院 | High-performance yttrium cerium based rare earth permanent magnet and preparation method thereof |
| CN112071544A (en) * | 2020-08-20 | 2020-12-11 | 钢铁研究总院 | Low-density Y-containing permanent magnet and preparation method thereof |
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| CN104112555A (en) * | 2013-04-22 | 2014-10-22 | Tdk株式会社 | R-t-b based sintered magnet |
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