CN111145973B - Samarium-cobalt permanent magnet containing grain boundary phase and preparation method thereof - Google Patents
Samarium-cobalt permanent magnet containing grain boundary phase and preparation method thereof Download PDFInfo
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- CN111145973B CN111145973B CN201811313384.7A CN201811313384A CN111145973B CN 111145973 B CN111145973 B CN 111145973B CN 201811313384 A CN201811313384 A CN 201811313384A CN 111145973 B CN111145973 B CN 111145973B
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- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 title claims abstract description 164
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 104
- 239000000956 alloy Substances 0.000 claims abstract description 104
- 239000000843 powder Substances 0.000 claims abstract description 74
- 239000010949 copper Substances 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 36
- 230000032683 aging Effects 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000006104 solid solution Substances 0.000 claims abstract description 22
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 230000006835 compression Effects 0.000 claims abstract description 6
- 238000007906 compression Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 15
- 230000008520 organization Effects 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000006872 improvement Effects 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 229910052786 argon Inorganic materials 0.000 description 14
- 238000003825 pressing Methods 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Classifications
-
- 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
- H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
- H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 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
- 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 samarium cobalt permanent magnet containing a grain boundary phase and a preparation method thereof. The samarium cobalt permanent magnet containing the grain boundary phase has an organization structure of crystal grains wrapped by the grain boundary phase rich in copper elements. The preparation method comprises the following steps: firstly, smelting a samarium cobalt alloy ingot by adopting a traditional powder metallurgy process, and preparing the samarium cobalt alloy ingot into micron-sized samarium cobalt alloy powder; and uniformly mixing micron-sized or nano-sized CuO powder with the samarium cobalt alloy powder, and then sequentially carrying out magnetic field orientation compression, cold isostatic pressing, sintering, solid solution and aging treatment to obtain the samarium cobalt permanent magnet containing the grain boundary phase. Compared with the samarium cobalt permanent magnet without the microstructure, the samarium cobalt permanent magnet has the structure of crystal grain wrapped by the grain boundary phase rich in copper element and high coercive force, and the room-temperature coercive force of the samarium cobalt permanent magnet is greatly improved along with the increase of the addition of CuO, and the improvement range reaches 1.5 to 2.5 times.
Description
Technical Field
The invention relates to a samarium cobalt permanent magnet material, in particular to a samarium cobalt permanent magnet containing a copper-rich element grain boundary phase and a preparation method thereof, belonging to the technical field of rare earth permanent magnet materials.
Background
Samarium cobalt permanent magnet is mainly composed of samarium, cobalt, iron, copper, zirconium and other elements, and rare earth permanent magnet materials are obtained by high-temperature sintering and aging. Because of its high magnetic energy product, excellent temperature stability and corrosion resistance, it can be widely used in the fields of aerospace, national defense and military industry, communication, microwave device, instrument and meter, motor, etc.
Conventional samarium cobalt permanent magnets consume a large amount of cobalt, which is an expensive strategic element, has a limited reserve and is not renewable. Therefore, on the premise of basically maintaining the magnetic performance of the samarium cobalt permanent magnet, the dosage of the cobalt element is reduced, the dosage of the iron element is increased, the cost of the samarium cobalt permanent magnet is reduced, and the cobalt element is protected. However, increasing the amount of iron in samarium cobalt permanent magnets can affect the achievement of high coercivity samarium cobalt permanent magnets.
In the traditional samarium cobalt sintered permanent magnet, because of the loss of a grain boundary phase, the magnet grains have stronger magnetic coupling effect, and a region with lower copper element content than the inside of the grains is formed around the grains, namely a copper element poor region, thereby restricting the improvement of the magnet coercive force. At present, the common method for improving the coercive force of the samarium cobalt permanent magnet is to improve the content of a copper element in the samarium cobalt permanent magnet alloy. But this can greatly reduce the remanence of the magnet and limit the improvement of the magnetic performance of the samarium cobalt permanent magnet. Therefore, how to eliminate the magnetic coupling effect among grains and the phenomenon of poor copper element in the grain boundary area is a key way for improving the coercive force of the samarium-cobalt permanent magnet.
In the current patent technology, the Chinese invention patent application CN102568807A discloses that nano Cu is added into a samarium cobalt permanent magnet so as to improve the coercive force of the samarium cobalt permanent magnet, but the method does not form obvious grain boundary phase around the crystal grains of the samarium cobalt permanent magnet and does not form grain boundary phase rich in Cu element. In addition, chinese patent application CN102650004A discloses a method for preparing samarium cobalt permanent magnets by adding calcium oxide and magnesium oxide during the melting process of samarium cobalt alloy, wherein calcium oxide or magnesium oxide enters the grain boundary of samarium cobalt magnet, but does not form the texture structure of grains wrapped by the grain boundary phase rich in Cu element in samarium cobalt magnet.
Disclosure of Invention
The invention mainly aims to provide a samarium cobalt permanent magnet containing a grain boundary phase and a preparation method thereof, so as to overcome the defects of the conventional samarium cobalt permanent magnet.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a samarium cobalt permanent magnet containing a grain boundary phase, which has an organization structure of grain boundary phase wrapped grains rich in copper elements.
The embodiment of the invention also provides a preparation method of the samarium cobalt permanent magnet containing the grain boundary phase, which comprises the following steps:
smelting a raw material containing alloy elements of Sm, Co, Fe, Cu and Zr to form a samarium-cobalt alloy ingot and preparing into samarium-cobalt alloy powder;
and uniformly mixing CuO powder and the samarium-cobalt alloy powder, wherein the particle size of the CuO powder is in a micron level or a nanometer level, and the mass ratio of the CuO powder to the samarium-cobalt alloy powder is (0.1-20): 100, respectively; and then sequentially carrying out magnetic field orientation compression, cold isostatic pressing, sintering, solid solution and aging treatment to obtain the samarium-cobalt permanent magnet with the microstructure of the grain boundary phase wrapped grains rich in the copper element.
The embodiment of the invention also provides the samarium cobalt permanent magnet containing the grain boundary phase prepared by the method.
Compared with the prior art, the samarium cobalt permanent magnet provided by the invention has an organization structure of crystal grain wrapped by a grain boundary phase rich in copper element and high coercive force, and the room-temperature coercive force of the samarium cobalt permanent magnet is greatly improved along with the increase of the addition amount of CuO compared with the samarium cobalt permanent magnet without the organization structure, and the improvement range is up to 1.5-2.5 times.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1a is a back-scattered electron diagram of an original alloy magnet a of undoped CuO powder in example 13 of the present invention.
Figure 1b is a back-scattered electron image of samarium cobalt permanent magnets doped with CuO powder according to example 13 of the present invention.
Fig. 2 is a graph of the distribution of elemental copper at the grain boundary locations of samarium cobalt permanent magnets after doping with CuO powder in example 13 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has found through long-term research and a great deal of practice that the technical scheme of the present invention is provided. The technical solution, its implementation and principles, etc. will be further explained as follows.
An embodiment of one aspect of the invention provides a samarium cobalt permanent magnet comprising an intergranular phase having an organization of grains surrounded by an intergranular phase rich in a copper element.
In some embodiments, the content of copper in the grain boundary phase is higher than the content of copper in the interior of the grains.
Furthermore, the content of the copper element in the grain boundary phase is 1-50 wt% (by mass) higher than that in the crystal grains.
In some embodiments, the grain boundary phase has a width of 0.01 to 4 μm, and the grains have a size of 10 to 100 μm.
In some embodiments, the samarium cobalt permanent magnet is prepared from an alloy magnet comprising, in mass percent: sm 23-28 wt%, Fe 10-25 wt%, Cu 1-6 wt%, Zr 1-4 wt%, and the balance of Co.
Another aspect of an embodiment of the present invention also provides a method for preparing a samarium cobalt permanent magnet including a grain boundary phase, including:
smelting a raw material containing alloy elements of Sm, Co, Fe, Cu and Zr to form a samarium-cobalt alloy ingot and preparing into samarium-cobalt alloy powder;
and uniformly mixing CuO powder and the samarium-cobalt alloy powder, wherein the particle size of the CuO powder is in a micron level or a nanometer level, and the mass ratio of the CuO powder to the samarium-cobalt alloy powder is (0.1-20): 100, respectively; and then sequentially carrying out magnetic field orientation compression, cold isostatic pressing, sintering, solid solution and aging treatment to obtain the samarium-cobalt permanent magnet with the microstructure of the grain boundary phase wrapped grains rich in the copper element.
In some embodiments, the samarium cobalt permanent magnet comprises the following alloy compositions, calculated by mass percent: sm 23-28 wt%, Fe 10-25 wt%, Cu 1-6 wt%, Zr 1-4 wt%, and the balance of Co.
In some embodiments, the preparation method specifically comprises:
smelting a raw material containing alloy elements of Sm, Co, Fe, Cu and Zr to form a samarium-cobalt alloy ingot;
and then crushing the obtained samarium cobalt alloy ingot into micron-sized samarium cobalt alloy powder.
Further, the smelting temperature is 1300-1900 ℃, and the time is 15-35 min.
Furthermore, the particle size of the samarium cobalt alloy powder is 1-20 μm.
In some embodiments, the preparation method specifically comprises: and uniformly mixing micron-sized CuO powder and the samarium-cobalt alloy powder, performing orientation molding in a magnetic field with the magnetic field intensity of 1-2T, and performing cold isostatic pressing in a fluid with the pressure of 100-300 MPa to obtain a samarium-cobalt alloy pressed blank.
Further, the particle size of the CuO powder is 0.1-3 μm.
In some embodiments, the preparation method specifically comprises: and sintering the samarium cobalt alloy pressed compact for 30-120 minutes at 1190-1230 ℃ in an inert atmosphere, then carrying out solid solution for 3-10 hours at 1160-1190 ℃, and cooling to obtain the precursor magnet.
In some embodiments, the preparation method specifically comprises: and carrying out isothermal aging on the precursor magnet at 750-880 ℃ for 10-25 h, then cooling to 300-500 ℃ at the speed of 0.3-1.5 ℃/min, preserving heat at 300-500 ℃ for 1-10 h, and cooling to obtain the samarium-cobalt permanent magnet containing the grain boundary phase.
Wherein, in a more specific exemplary embodiment, the preparation method comprises the steps of:
s1, according to the components, smelting the samarium cobalt alloy into an alloy ingot by using a traditional powder metallurgy process to prepare samarium cobalt alloy powder;
s2, mixing the CuO powder with the samarium cobalt alloy powder uniformly according to the proportion of 0.1-20% (by mass) of the CuO powder in the samarium cobalt alloy powder, and performing magnetic field orientation compression and oil-cooled isostatic pressing to obtain a samarium cobalt alloy pressed compact;
s3, sintering a samarium cobalt alloy pressed blank at 1190-1230 ℃ for 30-120 minutes in an inert atmosphere, performing solid solution at 1160-1190 ℃ for 3-10 hours, and then rapidly cooling to room temperature to obtain a precursor magnet;
s4, the precursor magnet obtained in the step S3 is subjected to heat preservation for 10-25 hours at the temperature of 750-880 ℃, cooled to 300-500 ℃ at the temperature control rate of 0.3-1.5 ℃/min, then subjected to heat preservation for 1-10 hours at the temperature of 300-500 ℃, and finally rapidly cooled to the room temperature.
Further, the preparation method comprises the following steps: the CuO powder with the average grain diameter of 0.1-3 mu m is evenly mixed with the samarium cobalt alloy powder according to the proportion of 0.1-20% (mass percentage). And (3) orienting and profiling in a magnetic field of 1-2T, and performing cold isostatic pressing under the pressure of 100-300 MPa to obtain the samarium cobalt alloy green compact. The samarium cobalt alloy pressed compact is sintered for 0.5-1 hour at 1190-1230 ℃ in an argon environment, then is subjected to solid solution for 3-5 hours at 1160-1190 ℃, and is cooled to room temperature by air to obtain the precursor magnet. And (3) preserving the heat of the precursor magnet for 10-20 hours at 800-850 ℃, cooling to 300-500 ℃ at a cooling speed of 0.7-1.0 ℃/min, and preserving the heat at 300-500 ℃ for 1-3 hours to obtain the sintered samarium-cobalt permanent magnet.
In summary, the method comprises the steps of firstly adopting a medium-frequency induction smelting furnace to smelt samarium, cobalt, iron, copper, zirconium and other raw materials with the purity of 99% into the samarium-cobalt alloy ingot, and preparing the samarium-cobalt alloy ingot into micron-sized samarium-cobalt alloy powder. The method comprises the steps of uniformly mixing commercial micron-sized or nano-sized CuO powder with alloy powder in proportion, and finally obtaining the sintered samarium cobalt permanent magnet through magnetic field orientation compression, cold isostatic pressing, sintering and aging. The CuO-doped samarium-cobalt permanent magnet has a structure that crystal grains are wrapped by a grain boundary phase rich in copper elements, and the high-coercivity samarium-cobalt permanent magnet is finally obtained.
In another aspect of an embodiment of the invention, there is also provided a samarium cobalt permanent magnet comprising a grain boundary phase prepared by the foregoing method.
In conclusion, by means of the technical scheme, the samarium cobalt permanent magnet provided by the invention has an organization structure of crystal grain wrapped by a grain boundary phase rich in copper element and high coercive force, and compared with the samarium cobalt permanent magnet without the organization structure, the room-temperature coercive force of the samarium cobalt permanent magnet is greatly improved along with the increase of the addition amount of CuO, and the improvement range reaches 1.5-2.5 times.
Technical solutions in the embodiments of the present invention will be described in detail below with reference to the drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
According to the scheme, samarium, cobalt, iron, copper and zirconium with the purity of 99% are selected as raw materials, the raw materials are smelted in a medium-frequency induction furnace, and the smelted raw materials are cast into a water-cooling copper mold to obtain samarium-cobalt alloy ingots with different components.
Alloy ingot A (mass percent): sm: 25%, Co: 49%, Fe: 20%, Cu: 4%, Zr: 2 percent.
Alloy ingot B (mass percent): sm: 25%, Co: 48%, Fe: 21%, Cu: 4%, Zr: 2 percent.
Alloy ingot C (mass percent): sm: 26%, Co: 44%, Fe: 23%, Cu: 4%, Zr: 2 percent.
Alloy ingot D (mass percent): sm: 23%, Co: 58%, Fe: 10%, Cu: 6%, Zr: 3 percent.
Alloy ingot E (mass percent): sm: 28%, Co: 42%, Fe: 25%, Cu: 1%, Zr: 4 percent.
Alloy ingot F (mass percent): sm: 25%, Co: 52%, Fe: 19%, Cu: 3%, Zr: 1 percent.
Alloy ingot G (mass percent): sm: 26%, Co: 45%, Fe: 23%, Cu: 4%, Zr: 2 percent.
The following examples were designed according to the mass percent of CuO powder incorporated and the initial composition of samarium cobalt alloy powder.
Example 1
And (2) uniformly mixing 0.2 wt% of CuO powder with the average particle size of 0.1 mu m and the alloy ingot powder A, orienting and pressing in a 2T magnetic field, and carrying out cold isostatic pressing under the pressure of 150MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 0.5 hour at 1210 ℃ in an argon environment, then is subjected to solid solution for 3.5 hours at 1170 ℃, and is cooled to room temperature by air to obtain a precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 16 hours at 830 ℃, reducing the temperature to 400 ℃ according to the cooling rate of 1.0 ℃/min, and then preserving the heat at 400 ℃ for 2 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.45 | 15.50 | 29.5 |
| Magnet of the present embodiment | 11.42 | 21.59 | 29.4 |
Example 2
And (2) uniformly mixing 0.4 wt% of CuO powder with the average particle size of 0.1 mu m and the alloy ingot powder A, orienting and pressing in a 2T magnetic field, and carrying out cold isostatic pressing under the pressure of 150MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy compact is sintered for 0.5 hour at 1210 ℃ in an argon environment, then is subjected to solid solution for 3.5 hours at 1180 ℃, and is cooled to room temperature by air to obtain the precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 16 hours at 830 ℃, reducing the temperature to 400 ℃ according to the cooling rate of 1.0 ℃/min, and then preserving the heat at 400 ℃ for 2 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
Example 3
And (2) uniformly mixing 0.7 wt% of CuO powder with the average particle size of 0.1 mu m and the alloy ingot powder A, orienting and pressing in a 2T magnetic field, and carrying out cold isostatic pressing under the pressure of 150MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 0.5 hour at 1210 ℃ in an argon environment, then is subjected to solid solution for 3.5 hours at 1170 ℃, and is cooled to room temperature by air to obtain a precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 14 hours at 830 ℃, reducing the temperature to 420 ℃ according to the cooling rate of 1.0 ℃/min, and then preserving the heat at 420 ℃ for 2 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.45 | 15.50 | 29.5 |
| Contrast magnet | 11.37 | 29.69 | 29.0 |
Example 4
And (2) uniformly mixing 0.1 wt% of CuO powder with the average particle size of 1 mu m and the alloy ingot powder B, orienting and pressing in a 1T magnetic field, and carrying out cold isostatic pressing under the pressure of 300MPa to obtain the samarium cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 1 hour at 1190 ℃ in an argon environment, then is subjected to solid solution for 5 hours at 1160 ℃, and is cooled to room temperature by air to obtain a precursor magnet.
Isothermal aging process: and (3) keeping the temperature of the precursor magnet at 800 ℃ for 20 hours, cooling to 500 ℃ at a cooling rate of 0.7 ℃/min, and then keeping the temperature for 3 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.62 | 12.50 | 31.5 |
| Magnet of the present embodiment | 11.60 | 17.24 | 30.9 |
Example 5
And (2) uniformly mixing 0.3 wt% of CuO powder with the average particle size of 1 mu m and the alloy ingot powder B, orienting and pressing in a 1.5T magnetic field, and carrying out cold isostatic pressing under the pressure of 100MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 0.5 hour at 1210 ℃ in an argon environment, then is subjected to solid solution for 3 hours at 1170 ℃, and is cooled to room temperature by air to obtain a precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 10 hours at 820 ℃, reducing the temperature to 300 ℃ according to the cooling rate of 0.8 ℃/min, and then preserving the heat for 1 hour to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.62 | 12.50 | 31.5 |
| Magnet of the present embodiment | 11.55 | 23.41 | 31.0 |
Example 6
And (2) uniformly mixing 5 wt% of CuO powder with the average particle size of 3 mu m and alloy ingot powder C, orienting and profiling in a 2T magnetic field, and carrying out cold isostatic pressing under the pressure of 200MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 2 hours at 1200 ℃ in an argon environment, then is subjected to solid solution for 4 hours at 1170 ℃, and is cooled to room temperature to obtain a precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 15 hours at 830 ℃, reducing the temperature to 400 ℃ according to the cooling rate of 0.7 ℃/min, and then preserving the heat for 2 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.71 | 10.45 | 29.6 |
| Magnet of the present embodiment | 11.21 | 14.63 | 27.3 |
Example 7
And (2) uniformly mixing 6 wt% of CuO powder with the average particle size of 3 mu m and alloy ingot powder C, orienting and profiling in a 1T magnetic field, and carrying out cold isostatic pressing under the pressure of 300MPa to obtain the samarium cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy compact is sintered for 45min at 1220 ℃ in an argon environment, then is subjected to solid solution for 10h at 1160 ℃, and is cooled to room temperature by air to obtain the precursor magnet.
Isothermal aging process: and (3) keeping the temperature of the precursor magnet at 800 ℃ for 25 hours, cooling to 300 ℃ at a cooling rate of 1.5 ℃/min, and then keeping the temperature for 10 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
Example 8
And (2) uniformly mixing 1 wt% of CuO powder with the average particle size of 0.1 mu m and the alloy ingot powder D, orienting and pressing in a 2T magnetic field, and carrying out cold isostatic pressing under the pressure of 250MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 2 hours at 1210 ℃ in an argon environment, then is subjected to solid solution for 3 hours at 1190 ℃, and is cooled to room temperature by air to obtain a precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 10 hours at 850 ℃, reducing the temperature to 500 ℃ according to the cooling rate of 0.3 ℃/min, and then preserving the heat for 2 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 9.5 | 23.25 | 19.3 |
| Contrast magnet | 9.5 | 25.60 | 19.0 |
Example 9
And (2) uniformly mixing 2 wt% of CuO powder with the average particle size of 1 mu m and alloy ingot powder E, orienting and profiling in a 1T magnetic field, and carrying out cold isostatic pressing under the pressure of 300MPa to obtain the samarium cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 1 hour at 1200 ℃ in an argon environment, then is subjected to solid solution for 5 hours at 1170 ℃, and is cooled to room temperature to obtain a precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 20 hours at 840 ℃, reducing the temperature to 400 ℃ according to the cooling rate of 0.7 ℃/min, and then preserving the heat for 3 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.82 | 12.10 | 31.2 |
| Contrast magnet | 11.46 | 16.32 | 30.2 |
Example 10
And (2) uniformly mixing 10 wt% of CuO powder with the average particle size of 1 mu m and alloy ingot powder E, orienting and profiling in a 2T magnetic field, and carrying out cold isostatic pressing under the pressure of 100MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 0.5 hour at 1210 ℃ in an argon environment, then is subjected to solid solution for 3 hours at 1170 ℃, and is cooled to room temperature by air to obtain a precursor magnet.
Isothermal aging process: and (3) keeping the temperature of the precursor magnet at 800 ℃ for 20 hours, cooling to 300 ℃ at a cooling rate of 1.0 ℃/min, and then keeping the temperature for 5 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.82 | 12.10 | 31.2 |
| Contrast magnet | 11.46 | 16.32 | 30.2 |
Example 11
And (2) uniformly mixing 20 wt% of CuO powder with the average particle size of 1 mu m and alloy ingot powder F, orienting and pressing in a 1.6T magnetic field, and carrying out cold isostatic pressing under the pressure of 180MPa to obtain the samarium cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy compact is sintered for 1 hour at 1210 ℃ in an argon environment, then is subjected to solid solution for 4 hours at 1180 ℃, and is cooled to room temperature by air to obtain the precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 18 hours at 820 ℃, reducing the temperature to 350 ℃ according to the cooling rate of 1.2 ℃/min, and then preserving the heat for 2 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
| Magnet body | Br(kGs) | Hci(kOe) | (BH)max(MGOe) |
| Original magnet | 11.56 | 24.34 | 30.3 |
| Contrast magnet | 11.36 | 26.45 | 29.9 |
Example 12
And (2) uniformly mixing 1.5 wt% of CuO powder with the average particle size of 0.5 mu m and alloy ingot powder G, orienting and profiling in a 2T magnetic field, and carrying out cold isostatic pressing under the pressure of 300MPa to obtain the samarium-cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 0.5 hour at 1230 ℃ in an argon environment, then is subjected to solid solution for 10 hours at 1160 ℃, and is cooled to room temperature by air to obtain a precursor magnet.
Isothermal aging process: and (3) keeping the temperature of the precursor magnet at 800 ℃ for 20 hours, cooling to 500 ℃ at a cooling rate of 0.7 ℃/min, and then keeping the temperature for 3 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, and the room temperature magnetic property is as follows.
Example 13
And (2) uniformly mixing 0.6 wt% of CuO powder with the average particle size of 0.1 mu m and the alloy ingot powder A, orienting and profiling in a 1T magnetic field, and carrying out cold isostatic pressing under the pressure of 300MPa to obtain the samarium cobalt alloy green compact.
The sintering process comprises the following steps: the samarium cobalt alloy pressed compact is sintered for 0.5 hour at 1210 ℃ in an argon environment, then is subjected to solid solution for 5 hours at 1175 ℃, and is cooled to room temperature by air to obtain the precursor magnet.
Isothermal aging process: and (3) preserving the heat of the precursor magnet for 10 hours at 850 ℃, reducing the temperature to 500 ℃ according to the cooling rate of 1.0 ℃/min, and then preserving the heat for 5 hours to obtain the sintered samarium-cobalt permanent magnet.
The samarium cobalt permanent magnet is obtained by the sintering aging process, the cross-sectional back scattering electron diagram of the original alloy magnet A is shown in figure 1a, and the cross-sectional back scattering electron diagram of the sintered samarium cobalt permanent magnet obtained after the CuO powder is doped in the embodiment is shown in figure 1 b. The distribution of elemental copper at the grain boundary position of samarium cobalt permanent magnets after incorporation of CuO powder is shown in fig. 2.
Microstructure analysis is carried out on the CuO-doped samarium cobalt permanent magnet in the embodiment, and the samarium cobalt permanent magnet has an organization structure with obvious grain boundary phase wrapping grains, and the grain boundary is rich in Cu elements. And the undoped samarium cobalt permanent magnet does not have a microstructure of grain boundary phase wrapped grains rich in Cu elements.
In summary, according to the technical scheme of the invention, the samarium cobalt permanent magnet has an organization structure of crystal grain wrapped by a grain boundary phase rich in copper element and high coercive force, and compared with the samarium cobalt permanent magnet without the organization structure, the room-temperature coercive force of the samarium cobalt permanent magnet is greatly improved along with the increase of the addition amount of CuO, and the improvement range reaches 1.5-2.5 times.
In addition, the inventors of the present invention conducted experiments using other materials and conditions listed in the present specification, and the like, in the manner of examples 1 to 13, and also produced samarium-cobalt permanent magnets having an organization structure of grain boundary phase-wrapped grains rich in copper element and a high coercive force.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (11)
1. A preparation method of samarium cobalt permanent magnet containing grain boundary phase is characterized by comprising the following steps:
smelting a raw material containing alloy elements of Sm, Co, Fe, Cu and Zr to form a samarium-cobalt alloy ingot and preparing into samarium-cobalt alloy powder;
and uniformly mixing CuO powder and the samarium-cobalt alloy powder, wherein the particle size of the CuO powder is in a micron level or a nanometer level, and the mass ratio of the CuO powder to the samarium-cobalt alloy powder is (0.1-20): 100, respectively; and then sequentially carrying out magnetic field orientation compression, cold isostatic pressing, sintering, solid solution and aging treatment to obtain the samarium-cobalt permanent magnet with the microstructure of the grain boundary phase wrapped grains rich in the copper element.
2. The method according to claim 1, comprising:
smelting a raw material containing alloy elements of Sm, Co, Fe, Cu and Zr to form a samarium-cobalt alloy ingot;
and then crushing the obtained samarium cobalt alloy ingot into micron-sized samarium cobalt alloy powder.
3. The method of claim 2, wherein: the smelting temperature is 1300-1900 ℃, and the time is 15-35 min.
4. The method of claim 2, wherein: the particle size of the samarium cobalt alloy powder is 1-20 mu m.
5. The method according to claim 1, comprising: and uniformly mixing micron-sized CuO powder and the samarium-cobalt alloy powder, performing orientation molding in a magnetic field with the magnetic field intensity of 1-2T, and performing cold isostatic pressing in a fluid with the pressure of 100-300 MPa to obtain a samarium-cobalt alloy pressed blank.
6. The method of claim 5, wherein: the particle size of the CuO powder is 0.1-3 mu m.
7. The preparation method according to claim 5, characterized by specifically comprising: and sintering the samarium cobalt alloy pressed compact for 30-120 minutes at 1190-1230 ℃ in an inert atmosphere, then carrying out solid solution for 3-10 hours at 1160-1190 ℃, and cooling to obtain the precursor magnet.
8. The preparation method according to claim 7, characterized by specifically comprising: sintering the samarium cobalt alloy pressed blank in an inert atmosphere at 1190-1230 ℃ for 30-60 minutes, then carrying out solid solution at 1160-1190 ℃ for 3-5 hours, and cooling to obtain the precursor magnet.
9. The preparation method according to claim 7, characterized by specifically comprising: and carrying out isothermal aging on the precursor magnet at 750-880 ℃ for 10-25 h, then cooling to 300-500 ℃ at the speed of 0.3-1.5 ℃/min, preserving heat at 300-500 ℃ for 1-10 h, and cooling to obtain the samarium-cobalt permanent magnet containing the grain boundary phase.
10. The method according to claim 9, comprising: and carrying out isothermal aging on the precursor magnet at 800-850 ℃ for 10-20 h, then cooling to 300-500 ℃ at the speed of 0.7-1.0 ℃/min, preserving heat at 300-500 ℃ for 1-3 h, and cooling to obtain the samarium-cobalt permanent magnet containing the grain boundary phase.
11. A samarium cobalt permanent magnet comprising a grain boundary phase made by the method of any of claims 1-10.
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| CN113205955B (en) * | 2021-04-30 | 2022-07-19 | 太原科技大学 | Preparation method of high-performance sintered samarium-cobalt magnet |
| CN113421760B (en) * | 2021-06-11 | 2023-01-17 | 太原科技大学 | Preparation method of samarium-cobalt magnet with low sintering temperature and high knee point magnetic field |
| CN113744987B (en) * | 2021-08-25 | 2022-09-30 | 北京航空航天大学 | Method for preparing high-performance samarium-cobalt magnet through grain boundary structure reconstruction |
| CN113936905B (en) * | 2021-09-30 | 2022-09-13 | 宁波宁港永磁材料有限公司 | Preparation method of samarium cobalt permanent magnet material |
| CN114255945A (en) | 2021-11-30 | 2022-03-29 | 福建省长汀卓尔科技股份有限公司 | Additive and application thereof, 2-17 type samarium-cobalt magnet and preparation method thereof |
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| JPH04102303A (en) * | 1990-08-22 | 1992-04-03 | Seiko Electronic Components Ltd | Manufacture of rare earth magnet |
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| CN106531383B (en) * | 2016-11-08 | 2018-11-20 | 中国科学院宁波材料技术与工程研究所 | Samarium-cobalt alloy material, samarium-cobalt alloy powder and preparation method thereof and SmCo base magnet |
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| JPH04102303A (en) * | 1990-08-22 | 1992-04-03 | Seiko Electronic Components Ltd | Manufacture of rare earth magnet |
| CN103839652A (en) * | 2012-11-20 | 2014-06-04 | 株式会社东芝 | Permanent magnet, and motor and power generator using the same |
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