CN115424800A - Sintered neodymium-iron-boron material containing Cu-M phase and preparation method thereof - Google Patents

Sintered neodymium-iron-boron material containing Cu-M phase and preparation method thereof Download PDF

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CN115424800A
CN115424800A CN202211106467.5A CN202211106467A CN115424800A CN 115424800 A CN115424800 A CN 115424800A CN 202211106467 A CN202211106467 A CN 202211106467A CN 115424800 A CN115424800 A CN 115424800A
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phase
material containing
alloy
equal
oxygen
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陈运鹏
毛琮尧
赖欣
徐志欣
温平
苏权
吴海明
刘涛
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Jl Mag Rare Earth Co ltd
Jinli Permanent Magnet Baotou Technology Co ltd
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Jl Mag Rare Earth Co ltd
Jinli Permanent Magnet Baotou Technology Co ltd
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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
    • 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
    • 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

Abstract

The invention relates to the technical field of rare earth permanent magnet materials, in particular to a sintered neodymium iron boron material containing a Cu-M phase and a preparation method thereof, wherein the sintered neodymium iron boron material containing the Cu-M phase forms the Cu-M phase after a heat treatment process, so that the aims of improving coercive force and residual magnetism are fulfilled; the preparation method of the sintered neodymium iron boron material containing the Cu-M phase comprises the steps of smelting raw materials to obtain a casting sheet, crushing the casting sheet by hydrogen to obtain coarse powder, crushing the coarse powder by an airflow mill to obtain fine powder, and manufacturing a blank meeting the design requirement by a fine powder compression sintering process.

Description

Sintered neodymium-iron-boron material containing Cu-M phase and preparation method thereof
Technical Field
The invention relates to the technical field of permanent magnet materials, in particular to a sintered neodymium-iron-boron material containing a Cu-M phase and a preparation method thereof.
Background
As known, by Nd 2 Fe 14 The R-Fe-B rare earth sintered magnet with the B type compound as the main phase is a magnet with the highest performance in all permanent magnet materials, and is widely applied to new energy automobile motors, wind driven generators, variable frequency air conditioner motors, industrial motors, consumer electronics and the like.
Some high-end application fields have certain temperature resistance requirements on products and also have higher requirements on energy density, so that the rare earth permanent magnet material is required to improve the coercivity while not reducing or slightly reducing the remanence.
Therefore, there is a need to develop a material and method that can improve the overall performance of the product.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a sintered neodymium iron boron material containing a Cu-M phase, the Cu-M phase is formed after a heat treatment process, and the aims of improving coercive force and residual magnetism are fulfilled; the preparation method comprises the steps of smelting raw materials to obtain a casting sheet, crushing the casting sheet with hydrogen to obtain coarse powder, crushing the coarse powder with an airflow mill to obtain fine powder, and manufacturing a blank meeting design requirements through a fine powder compression sintering process.
The technical scheme for solving the technical problem is as follows:
a sintered nd-fe-b material containing a Cu-M phase, comprising: r is a -(Cu x -M y ) b -B c -N d -T e An alloy of, in which,
r is at least one element selected from La, ce, ho, gd, pr, nd, ho, dy and Tb, cu is copper element,
m is at least one element selected from the group consisting of Ti, V, cr, zr, nb, mo, hf, ta and W,
b is the element of boron, and B is the element of boron,
n is selected from at least one element of Al, in, and Ga and must contain Ga,
t is at least one element selected from Fe and Co.
As an improvement of the present invention, said R a -(Cu x -M y ) b -B c -N d -T e In the alloy, a is more than or equal to 28wt% and less than or equal to 33wt%, b is more than or equal to 0.65wt% and less than or equal to 1.35wt%, c is more than or equal to 0.85wt% and less than or equal to 0.94wt%, d is more than or equal to 0.30wt% and less than or equal to 0.95wt%, and a + b + c + d + e =100wt%.
In a further improvement of the invention, in the Cux-My phase of the Ra- (Cux-My) b-Bc-Nd-Te alloy, if M is Ti, V and Cr, x: y = 1.
As a further improvement of the invention, in the Cux-My phase of the Ra- (Cux-My) b-Bc-Nd-Te alloy, if M is Zr, nb and Mo, x: y =1 to 1.5.
In a further improvement of the invention, in the Cux-My phase of the Ra- (Cux-My) b-Bc-Nd-Te alloy, when M is Hf, ta and W, x: y = 1.
As a further improvement of the invention, in the Ra- (Cux-My) b-Bc-Nd-Te alloy, when T is Fe and Co, the mass percent of Co/T is less than 1.6%.
A preparation method of a sintered NdFeB material containing a Cu-M phase comprises the following steps:
s1, performing raw material proportioning on alloy components required by the Ra- (Cux-My) b-Bc-Nd-Te alloy according to requirements;
s2, smelting the proportioned raw materials to prepare a casting sheet;
s3, carrying out hydrogen crushing treatment on the cast sheet to obtain coarse powder;
s4, carrying out airflow milling treatment on the coarse powder to obtain fine powder;
and S5, performing magnetic field orientation compression and isostatic pressing treatment on the fine powder, and then performing vacuum sintering to obtain the neodymium iron boron magnet.
As a modification of the invention, in step S5, the magnetic field orientation compression treatment is carried out in a sealed oxygen-free or low-oxygen glove box, and the oxygen-free or low-oxygen is carried out in the whole running and isostatic pressing treatment processes.
As a further improvement of the invention, in step S6, in the vacuum sintering process, sintering is carried out in a vacuum sintering furnace for 6h at a sintering temperature of 1090 ℃.
As a further improvement of the invention, in step S6, a secondary aging heat treatment is adopted, wherein the temperature of the primary aging heat treatment is 880 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃ and the time is 5h.
In the invention, the sintered neodymium-iron-boron material containing the Cu-M phase forms the Cu-M phase through a heat treatment process, so that the aims of improving the coercive force and the residual magnetism are fulfilled; the preparation method of the sintered neodymium iron boron material containing the Cu-M phase comprises the steps of smelting raw materials to obtain a casting sheet, crushing the casting sheet by hydrogen to obtain coarse powder, crushing the coarse powder by an airflow mill to obtain fine powder, and manufacturing a blank with performance meeting design requirements by a fine powder compression sintering process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail with reference to the following embodiments; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention relates to a sintered neodymium iron boron material containing a Cu-M phase, which comprises the following components: ra- (Cux-My) b-Bc-Nd-Te alloy,
wherein R is at least one element selected from La, ce, ho, gd, pr, nd, ho, dy and Tb, cu is copper element,
m is at least one element selected from the group consisting of Ti, V, cr, zr, nb, mo, hf, ta and W,
b is the element of boron, and B is boron,
n is selected from at least one element of Al, in, and Ga and must contain Ga,
t is at least one element selected from Fe and Co.
The sintered neodymium iron boron material containing the Cu-M phase forms the Cu-M phase through a heat treatment process, so that the aims of improving the coercive force and improving the residual magnetism are fulfilled.
Within the present invention, br (kGs): residual magnetism, namely magnetism which can be kept by an external magnetic field is removed after the permanent magnetic material is subjected to saturation magnetization; hcj (kOe): the coercive force of the magnetic polarization strength is also called intrinsic coercive force.
In the invention, a is more than or equal to 28wt% and less than or equal to 33wt% in the Ra- (Cux-My) b-Bc-Nd-Te alloy, b is more than or equal to 0.65wt% and less than or equal to 1.35wt%, c is more than or equal to 0.85wt% and less than or equal to 0.94wt%, d is more than or equal to 0.30wt% and less than or equal to 0.95wt%, and a + b + c + d + e =100wt%.
In the invention, in a Cux-My phase in an Ra- (Cux-My) b-Bc-Nd-Te alloy, if M is Ti, V and Cr, x: y = 1; when M is Zr, nb and Mo, x: y =1 to 1.5; when M is Hf, ta or W, the ratio of x: y =1 2 The mass ratio of M is different, the residual magnetism can be greatly reduced when the M element enters the main phase, the M element can be inhibited from entering the main phase, the residual magnetism can be improved, and the formed Cu-M improves the coercive force in a grain boundary phase.
In the invention, in the Ra- (Cux-My) b-Bc-Nd-Te alloy, when T is Fe and Co, the mass percent of Co/T is less than 1.6%, if the Co element is too high, the Curie temperature is increased, so that the heat treatment temperature is not consistent with the process temperature, and the coercive force is not optimal.
Within the present invention, the microstructure of the neodymium iron boron magnet material comprises a main phase, a grain boundary phase and a rich phase;
according to a conventional formula, the effect of refining grains can be achieved by adding M element during smelting, so that the coercive force is improved, however, the residual magnetism can be greatly reduced when the M element mainly enters a main phase; and the separate addition of Cu element can cause the excessive increase of the wettability of the rich phase, and the rich phase enters the main phase in the sintering process, so that the remanence is reduced, and the rich phase and the poor phase can further reduce the coercive force, and the remanence or the coercive force is still adversely affected even if the simultaneous addition proportion of the two is not coordinated.
Under the current condition, excessive M enters a main phase to reduce remanence due to too low Cu proportion, and excessive Cu with too high Cu proportion forms R-Cu transition in a grain boundary phase to reduce the melting point of a rich phase and the rich phase enters the main phase to reduce coercive force, so that the M element addition plays a role in refining grains and improving coercive force, the M element addition mainly enters the main phase to replace an Fe element position so as to reduce remanence, and the Cu element distribution does not influence remanence in the grain boundary phase, so that the Cu element is introduced to be added according to a certain proportion to be combined with the M element to form a Cu2-M phase, the influence of the M entering the main phase on the remanence is reduced, the Cu2-M phase formed in the grain boundary phase improves the melting point of the rich phase to form a pinning effect and improve coercive force, and the Cu2-M phase has the function of improving coercive force and does not reduce the remanence; the rich phase contains a Cu-M phase, the Cu-M phase is formed in the smelting process at first, and a Cu2-M phase is also formed in the sintering and aging process again.
The Cu element and the M element are mainly generated into a Cu2-M phase in a grain boundary phase, cu and M raw materials are added according to a certain proportion, the Cu-M phase is firstly formed in the smelting process, and the Cu is formed under the condition of reasonable sintering temperature 2 -M phase, as follows:
Figure DEST_PATH_IMAGE001
Cu 2 m formation firstly reduces the M element into the main phase and thus increases the remanence, and secondly Cu in the grain boundary phase 2 The M phase is high melting point and increases the melting point of the rich phase to form a pinning effect to increase coercivity.
The invention provides a preparation method of a sintered neodymium iron boron material containing a Cu-M phase, which comprises the following steps:
s1, performing raw material proportioning on alloy components required by the Ra- (Cux-My) b-Bc-Nd-Te alloy according to requirements;
s2, smelting the proportioned raw materials to prepare a casting sheet;
s3, carrying out hydrogen crushing treatment on the cast sheet to obtain coarse powder;
s4, carrying out airflow milling treatment on the coarse powder to obtain fine powder;
and S5, carrying out magnetic field orientation compression and isostatic pressing treatment on the fine powder, and then carrying out vacuum sintering to obtain the neodymium iron boron magnet.
Wherein, in the step S2, the thickness of the casting sheet is 0.1mm to 0.6mm.
In step S3, in the hydrogen crushing treatment, the hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h, so as to obtain coarse powder.
In step S4, the size of the fine powder is 4.5um.
In step S5, the magnetic field orientation profiling process is performed in a sealed oxygen-free or low-oxygen glove box, and the oxygen-free or low-oxygen is performed during the whole operation and isostatic pressing process.
In step S6, in the vacuum sintering process, sintering is performed in a vacuum sintering furnace at a sintering temperature of 1090 ℃ for 6 hours.
In the step S6, secondary aging heat treatment is adopted, wherein the temperature of the primary aging heat treatment is 880 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h; specifically, the first aging temperature is 850-900 ℃, the sintering time is 2h-5h, and if the first aging temperature is higher than 900 ℃ or lower than 850 ℃, the formation of Cu2-M is not facilitated, so that the magnetic property is influenced; the secondary aging temperature is 450-500 ℃, the sintering time is 3-10h, and if the secondary aging temperature is higher than 500 ℃ or lower than 450 ℃, the secondary aging temperature is not beneficial to diffusion flow of a grain boundary phase to influence the structure distribution of a neodymium-rich phase, so that the magnetic performance is influenced.
Table 1 ingredient compounding table
Figure DEST_PATH_IMAGE003
The present invention provides several embodiments, as follows:
example 1:
1. according to the specific proportion of example 1 in the raw material component proportioning table in table 1, carrying out raw material proportioning according to proportioning components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and casting the proportioned raw materials to form a casting sheet with the thickness of 0.10-0.60mm;
3. hydrogen crushing (HD) treatment alloy sheet production technology, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an airflow mill to obtain fine powder with D50 particle size of 4.5 um;
5. magnetic field orientation profiling and isostatic pressing treatment, wherein magnetic field orientation molding is carried out in a sealed glove box without oxygen or low oxygen, and the product is ensured to be free from oxygen or low oxygen in the whole operation and isostatic pressing process;
6. vacuum sintering and aging heat treatment are carried out in a vacuum sintering furnace to obtain the neodymium iron boron magnet, and the sintering temperature is as follows: 1090 ℃ and the sintering time is as follows: 6h; the aging is carried out by two times, the temperature of the first aging heat treatment is 880 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h.
Comparative example 1A:
1. according to the proportion of a comparative example 1A in a raw material component proportioning table in a table 1, carrying out raw material proportioning according to proportioning components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and pouring proportioned raw materials to form a casting sheet with the thickness of 0.10mm to 0.60mm;
3. hydrogen crushing (HD) treatment alloy sheet production technology, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an air flow mill to obtain fine powder with D50 particle size of 4.5 um;
5. performing magnetic field orientation profiling and isostatic pressing treatment, namely performing magnetic field orientation profiling in a sealed oxygen-free or low-oxygen glove box, and ensuring that the product is oxygen-free or low-oxygen in the whole operation and isostatic pressing process;
6. vacuum sintering and aging heat treatment are carried out in a vacuum sintering furnace to obtain the neodymium iron boron magnet, and the sintering temperature is as follows: 1090 ℃ and the sintering time is as follows: 6h; the aging is carried out by two times, the temperature of the first aging heat treatment is 850 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃ and the time is 5h.
Comparative example 1B:
1. according to the proportion of a comparative example 1B in a raw material component proportioning table shown in a table 1, carrying out raw material proportioning according to proportioning components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and casting the proportioned raw materials to form a casting sheet with the thickness of 0.10-0.60mm;
3. hydrogen crushing (HD) treatment alloy sheet production technology, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an airflow mill to obtain fine powder with D50 particle size of 4.5 um;
5. magnetic field orientation profiling and isostatic pressing treatment, wherein magnetic field orientation molding is carried out in a sealed glove box without oxygen or low oxygen, and the product is ensured to be free from oxygen or low oxygen in the whole operation and isostatic pressing process;
6. carrying out vacuum sintering and aging heat treatment to obtain the neodymium-iron-boron magnet, wherein the sintering temperature is as follows: 1090 ℃ and the sintering time is as follows: 6h; the aging is carried out for two times, the temperature of the first aging heat treatment is 880 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h.
Magnetic properties of the ndfeb magnets prepared in example 1 and comparative examples 1A and 1B of the present invention were measured according to GB/T-3217-2-13 "magnetic test method for permanent (hard) magnetic material", and the measurement results are shown in table 2.
Table 2 example 1 and comparative examples 1A, 1B, magnetic properties of ndfeb magnets
Figure DEST_PATH_IMAGE005
It can be seen that comparative examples 1A and 1B do not satisfy the relationship (x: y =1:0.5 to 1.
Example 2:
1. according to the mixture ratio of the embodiment 2 in the raw material component mixture table in the table 1, the raw materials are mixed according to the mixture ratio components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and casting the proportioned raw materials to form a casting sheet with the thickness of 0.10mm-0.60mm;
3. a hydrogen crushing (HD) treatment alloy sheet production process, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with air jet mill to obtain fine powder with D50 particle size of 4.5um
5. Performing magnetic field orientation profiling and isostatic pressing treatment, namely performing magnetic field orientation profiling in a sealed oxygen-free or low-oxygen glove box, and ensuring that the product is oxygen-free or low-oxygen in the whole operation and isostatic pressing process;
6. vacuum sintering and aging heat treatment are carried out in a vacuum sintering furnace to obtain the neodymium iron boron magnet, and the sintering temperature is as follows: 1080 ℃, and the sintering time is as follows: 6h; the aging is carried out for two times, the temperature of the first aging heat treatment is 880 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h.
Comparative example 2A:
1. according to the proportion of a comparative example 1A in a raw material component proportioning table in a table 1, carrying out raw material proportioning according to proportioning components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and pouring proportioned raw materials to form a casting sheet with the thickness of 0.10mm to 0.60mm;
3. hydrogen crushing (HD) treatment alloy sheet production technology, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an air flow mill to obtain fine powder with D50 particle size of 4.5 um;
5. performing magnetic field orientation profiling and isostatic pressing treatment, namely performing magnetic field orientation profiling in a sealed oxygen-free or low-oxygen glove box, and ensuring that the product is oxygen-free or low-oxygen in the whole operation and isostatic pressing process;
6. carrying out vacuum sintering and aging heat treatment to obtain the neodymium-iron-boron magnet, wherein the sintering temperature is as follows: 1080 ℃, and the sintering time is as follows: 6h; the aging is carried out for two times, the temperature of the first aging heat treatment is 880 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h.
Comparative example 2B:
1. according to the proportion of a comparative example 2B in a raw material component proportioning table in a table 1, carrying out raw material proportioning according to proportioning components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and casting the proportioned raw materials to form a casting sheet with the thickness of 0.10-0.60mm;
3. hydrogen crushing (HD) treatment alloy sheet production technology, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an airflow mill to obtain fine powder with D50 particle size of 4.5 um;
5. magnetic field orientation profiling and isostatic pressing treatment, wherein magnetic field orientation molding is carried out in a sealed glove box without oxygen or low oxygen, and the product is ensured to be free from oxygen or low oxygen in the whole operation and isostatic pressing process;
6. carrying out vacuum sintering and aging heat treatment to obtain the neodymium-iron-boron magnet, wherein the sintering temperature is as follows: 1080 ℃, and the sintering time is as follows: 6h; the aging is carried out by two times, the temperature of the first aging heat treatment is 880 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h.
The magnetic properties of the ndfeb magnets prepared in example 2 of the present invention and comparative examples 2A and 2B were measured according to GB/T-3217-2-13 "magnetic test method for permanent (hard) magnetic material", and the results are shown in table 3.
Table 3 example 2 and comparative examples 2A, 2b, cu to M ratios and magnetic properties of neodymium iron boron magnets
Figure DEST_PATH_IMAGE007
It can be seen that the relationships (when M is Zr, nb, mo, x: y =1 to 1.5.
Example 3:
1. according to the mixture ratio of the raw material component in the example 3 of the raw material component mixture table in the table 1, the raw material mixture ratio is carried out according to the mixture ratio components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and casting the proportioned raw materials to form a casting sheet with the thickness of 0.10-0.60mm;
3. a hydrogen crushing (HD) treatment alloy sheet production process, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an air flow mill to obtain fine powder with D50 particle size of 4.5 um;
5. performing magnetic field orientation profiling and isostatic pressing treatment, namely performing magnetic field orientation profiling in a sealed oxygen-free or low-oxygen glove box, and ensuring that the product is oxygen-free or low-oxygen in the whole operation and isostatic pressing process;
6. carrying out vacuum sintering and aging heat treatment to obtain the neodymium-iron-boron magnet, wherein the sintering temperature is as follows: 1080 ℃, and the sintering time is as follows: 6h; the aging is carried out by two times, the temperature of the first aging heat treatment is 860 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h.
Comparative example 3A:
1. according to comparative example 3A of the raw material component batching table in the table 1, raw material proportioning is carried out according to proportioning components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and casting the proportioned raw materials to form a casting sheet with the thickness of 0.10-0.60mm;
3. a hydrogen crushing (HD) treatment alloy sheet production process, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an airflow mill to obtain fine powder with D50 particle size of 4.5 um;
5. magnetic field orientation profiling and isostatic pressing treatment, wherein magnetic field orientation molding is carried out in a sealed glove box without oxygen or low oxygen, and the product is ensured to be free from oxygen or low oxygen in the whole operation and isostatic pressing process;
6. carrying out vacuum sintering and aging heat treatment to obtain the neodymium-iron-boron magnet, wherein the sintering temperature is as follows: 1080 ℃, and the sintering time is as follows: 6h; the aging is carried out by two times, the temperature of the first aging heat treatment is 860 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃, and the time is 5h.
Comparative example 3B:
1. according to comparative example 3B of the raw material component batching table in the table 1, raw material proportioning is carried out according to proportioning components;
2. smelting: the method for manufacturing the alloy sheet by using a vacuum induction melting furnace comprises the steps of smelting and casting the proportioned raw materials to form a casting sheet with the thickness of 0.10-0.60mm;
3. hydrogen crushing (HD) treatment alloy sheet production technology, wherein hydrogen absorption time is 75min, then dehydrogenation is carried out for 5h at 580 ℃, and finally water cooling is carried out for 2h to obtain coarse powder;
4. treating the coarse powder with an airflow mill to obtain fine powder with D50 particle size of 4.5 um;
5. magnetic field orientation profiling and isostatic pressing treatment, wherein magnetic field orientation molding is carried out in a sealed glove box without oxygen or low oxygen, and the product is ensured to be free from oxygen or low oxygen in the whole operation and isostatic pressing process;
6. carrying out vacuum sintering and aging heat treatment to obtain the neodymium-iron-boron magnet, wherein the sintering temperature is as follows: 1080 ℃, and the sintering time is as follows: 6h; the aging is carried out by two times, the temperature of the first aging heat treatment is 860 ℃, and the time is 2 hours; the aging temperature of the second aging heat treatment is 490 ℃ and the time is 5h.
Magnetic properties of the ndfeb magnets prepared in example 3 of the present invention and comparative examples 3A and 3B were measured according to GB/T-3217-2-13 "magnetic test method for permanent (hard) magnetic material", and the results are shown in table 4.
Table 4 example 3 and comparative examples 3A, 3b, cu to M ratio and magnetic properties of ndfeb magnets
Figure DEST_PATH_IMAGE009
It is understood that the relationships (x: y =1:2 to 1.
The invention has the following advantages:
1. the M phase in the main phase is separated out by adding Cu and M in a composite ratio, so that the remanence is improved;
2. the grain boundary phases Cu and M are high melting points, so that the melting point of a rich phase is improved, a pinning effect is formed, and the coercivity is improved;
3. cu formation by a Heat treatment Process 2 phase-M, the first-grade heat treatment process is 850-900 DEG CSecond order 450 ℃ to 500 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A sintered neodymium iron boron material containing a Cu-M phase is characterized by comprising the following components: r a -(Cu x -M y ) b -B c -N d -T e An alloy comprising, in combination, at least one metal,
r is at least one element selected from La, ce, ho, gd, pr, nd, ho, dy and Tb, cu is copper element,
m is at least one element selected from the group consisting of Ti, V, cr, zr, nb, mo, hf, ta and W,
b is the element of boron, and B is the element of boron,
n is selected from at least one element of Al, in, and Ga and must contain Ga,
t is at least one element selected from Fe and Co.
2. The sintered NdFeB material containing the Cu-M phase according to claim 1, wherein R is a -(Cu x -M y ) b -B c -N d -T e In the alloy, a is more than or equal to 28wt% and less than or equal to 33wt%, b is more than or equal to 0.65wt% and less than or equal to 1.35wt%, c is more than or equal to 0.85wt% and less than or equal to 0.94wt%, d is more than or equal to 0.30wt% and less than or equal to 0.95wt%, and a + b + c + d + e =100wt%.
3. The sintered NdFeB material containing the Cu-M phase according to claim 1, wherein R is a -(Cu x -M y ) b -B c -N d -T e Cu in alloy x -M y In the phase, when M is Ti, V or Cr, x: y = 1.
4. The sintered NdFeB material containing the Cu-M phase according to claim 1, wherein R is a -(Cu x -M y ) b -B c -N d -T e Cu in alloy x -M y In phase, when M is Zr, nb, mo, x: y =1 to 1.5.
5. The sintered NdFeB material containing the Cu-M phase as claimed in claim 1, wherein R is selected from the group consisting of a -(Cu x -M y ) b -B c -N d -T e Cu in alloy x -M y In the phase, when M is Hf, ta or W, x: y = 1.
6. The sintered NdFeB material containing the Cu-M phase as claimed in claim 1, wherein R is selected from the group consisting of a -(Cu x -M y ) b -B c -N d -T e In the alloy, when T is Fe and Co, the mass percent of Co/T is less than 1.6 percent.
7. A preparation method of a sintered neodymium iron boron material containing a Cu-M phase is characterized by comprising the following steps:
step S1, according to the requirement, R is added a -(Cu x -M y ) b -B c -N d -T e The raw material proportioning of the alloy components required by the alloy is carried out;
s2, smelting the proportioned raw materials to prepare a casting sheet;
s3, carrying out hydrogen crushing treatment on the cast piece to obtain coarse powder;
s4, performing airflow milling treatment on the coarse powder to obtain fine powder;
and S5, performing magnetic field orientation compression and isostatic pressing treatment on the fine powder, and then performing vacuum sintering to obtain the neodymium iron boron magnet.
8. The method for preparing sintered NdFeB material containing Cu-M phase according to claim 7, wherein in step S5, the magnetic field orientation compression treatment is performed in a sealed glove box without oxygen or oxygen, and the whole process of operation and isostatic pressing treatment is performed without oxygen or oxygen.
9. The method for preparing the sintered NdFeB material containing the Cu-M phase according to the claim 8, wherein in the step S6, in the vacuum sintering process, the sintered NdFeB material is sintered for 1 to 8h in a vacuum sintering furnace at a sintering temperature of 990 to 1200 ℃.
10. The method for preparing the sintered NdFeB material containing the Cu-M phase according to the claim 9, wherein in the step S6, secondary aging heat treatment is adopted, wherein the temperature of the first aging heat treatment is 800 to 950 ℃, and the time is 1 to 3h; the aging temperature of the second aging heat treatment is 440 to 550 ℃, and the time is 2 to 6h.
CN202211106467.5A 2022-09-12 2022-09-12 Sintered neodymium-iron-boron material containing Cu-M phase and preparation method thereof Pending CN115424800A (en)

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