CN112195381A - Preparation method of Sr-doped manganese-gallium alloy and high-coercivity nanocrystalline magnet thereof - Google Patents
Preparation method of Sr-doped manganese-gallium alloy and high-coercivity nanocrystalline magnet thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910000807 Ga alloy Inorganic materials 0.000 title claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 86
- 239000000956 alloy Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 52
- 238000005516 engineering process Methods 0.000 claims description 27
- 229910052786 argon Inorganic materials 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 238000002490 spark plasma sintering Methods 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- -1 tetragonal phase alloy Chemical class 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 9
- 239000000696 magnetic material Substances 0.000 abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 32
- 230000001276 controlling effect Effects 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000000137 annealing Methods 0.000 description 11
- 230000006698 induction Effects 0.000 description 11
- 238000003825 pressing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005308 ferrimagnetism Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000009862 microstructural analysis Methods 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
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Abstract
A preparation method of Sr-doped manganese-gallium alloy and a high-coercivity nanocrystalline magnet thereof belongs to the technical field of non-rare earth magnetic materials. The specific method comprises the following steps: firstly, the smelting and heat treatment process is adopted to prepare the tetragonal phase Sr-doped manganese-gallium alloy with the chemical formula of Mnx‑yGaSry(x is more than 1 and less than or equal to 3.0, and y is more than 0 and less than or equal to 0.5). And then the alloy is subjected to rapid thermal deformation to obtain the Sr-doped manganese-gallium nanocrystalline magnet with high coercivity. The invention is characterized in thatSr element doped to MnxAnd the Ga (x is more than or equal to 1 and less than or equal to 3) alloy is modified, so that the plastic deformation capacity of the alloy is enhanced, the thermal deformation temperature is reduced, the thermal deformation rate and the deformation are improved, and the effects of refining crystal grains and improving the magnetic property are achieved on the basis of keeping the intrinsic magnetism of the alloy.
Description
Technical Field
The invention relates to a preparation method of a Sr-doped manganese-gallium alloy and a high-coercivity nanocrystalline magnet thereof, belonging to the technical field of magnetic material preparation.
Background
The permanent magnetic material is an important field of magnetic materials and plays an extremely important role in various industries. In the permanent magnets which are widely applied and have excellent performance, such as neodymium iron boron, samarium cobalt alloy and the like, a large amount of rare earth elements and even expensive heavy rare earth elements are usually contained. Although China is a big rare earth country, the rare earth resource shortage problem of China is increasingly highlighted by decades of low-cost and excessive exploitation, so that the development and research of a high-performance and high-stability non-rare earth magnetic material becomes a new research direction in the magnetic industry of various countries.
MnxAs a non-rare earth material, Ga (x is more than or equal to 1 and less than or equal to 3) alloy has rich phase structure, various magnetic properties and higher theoretical intrinsic magnetic property, is one of technical reserves in the field of novel non-rare earth magnetic materials, and has been reported frequently on the research of preparation, magnetic property change and application value thereof, such as D022-Mn3The high spin polarizability and high curie temperature of Ga make it applicable to novel spin transfer torque materials; and square L10The MnGa alloy is one of the main candidates of the non-rare earth permanent magnetic material due to higher saturation magnetization, Curie temperature, strong magnetocrystalline anisotropy and higher theoretical magnetic energy product. In fact, as the Mn element decreases, tetragonal MnxThe magnetic property of Ga (1 ≤ x ≤ 3) alloy gradually changes from ferrimagnetism to ferromagnetism, but the phase structure is more prone to instability, and magnetic hardening is more difficult to perform.
The plastic deformation of the alloy is realized by MnxAn effective way for magnetic hardening of Ga (x is more than or equal to 1 and less than or equal to 3) alloy, and in the past, we (ZL201710011067.9) utilized a discharge plasma sintering method to carry out MnxGa (x is more than or equal to 1 and less than or equal to 3) cast ingot is thermally deformed, and magnetic hardening of the alloy with different components is realized through recovery recrystallization of crystal grains. Research shows that on the basis of ensuring the tetragonal structure, the lower the temperature, the higher the deformation rate, and the larger the deformation amount, the higher the recrystallization degree, and the more favorable the formation of fine crystals. However, for an alloy of a particular composition, the deformation parameters are closely related to the chemical composition and crystal structure. In the case of MnxGa (1. ltoreq. x. ltoreq.3), as the Mn content decreases, on the one hand, single-phase tetragonal L1 is maintained0The temperature range of the structure tends to decrease, and on the other hand, the material is brittle, so that it is difficult to regulate the thermal deformation process. Such as single phase tetragonal Mn1.80The maximum deformation amount of the Ga alloy is 92%, and the remanence and the coercive force of the deformed magnet are respectively improved to 2.52kG and 4.73 kOe. And Mn1.33Under the optimal thermal deformation process condition, the maximum deformation of Ga is 88 percent, and the remanence and the coercive force of the thermal deformation magnet are respectively improved to 3.87kG and 5.65 kOe. In combination with microstructural analysis, we found that although recrystallization is induced by thermal deformation, so that the crystal grains are sharply reduced and the coercive force is improved by orders of magnitude, the difference is still far from the theoretical value. Such as Mn with a deformation of 88%1.33The coercive force of the Ga thermal deformation magnet reaches 5.65kOe, the grain size of the Ga thermal deformation magnet is reduced to 1-3 mu m from 30 mu m of an ingot before deformation, but the Ga thermal deformation magnet has a large difference compared with the single domain size of 605nm, and the requirement of further reducing the grain size cannot be met only by regulating and controlling the deformation process.
Mn by doping with appropriate elementsxThe Ga (x is more than or equal to 1 and less than or equal to 3) alloy is modified, the plastic deformation capacity of the alloy is enhanced on the basis of keeping the intrinsic magnetism of the alloy, and further thermal deformation process parameters (particularly the deformation temperature) are optimized, so that the method is a more effective means for further reducing the grain size of the thermal deformation magnet and improving the coercive force of the thermal deformation magnet. Among the elements obtained by the calculation of the first principle, Sr has a low melting point and is soft. The tetragonal phase Mn is prepared by a series of smelting and heat treatment processesx-yGaSry(x is more than 1 and less than or equal to 3.0, y is more than 0 and less than or equal to 0.5) doping the alloy, and the Sr is found to be in a net-shaped Sr-rich phaseThe form is distributed in the Mn-Ga matrix. And then, a rapid thermal deformation technology is adopted for magnetic hardening, and in the thermal deformation process, the Sr-rich phase exists as a liquid phase to promote thermal deformation, so that the deformation temperature is reduced, the thermal deformation rate and the deformation are improved, and the effects of grain refinement and magnetic property improvement are achieved. In addition, because the Mn-Ga alloy has rich phase structure, complex phase change and different plasticity of alloys with different components, Sr is doped with Mnx-yGaSryThe thermal deformation process of the alloy needs to strictly control process conditions, and on the basis of ensuring enough large deformation amount, the magnetic property of the alloy is optimized by adopting the deformation temperature and the deformation rate which are as low as possible, and finally the high-coercivity manganese-gallium nanocrystalline magnet is obtained.
Disclosure of Invention
The invention comprehensively adopts various technologies such as smelting, heat treatment, discharge plasma sintering and the like, provides a preparation method of Sr-doped manganese-gallium alloy and a high-coercivity nanocrystalline magnet thereof, and overcomes the technical problems that the existing manganese-gallium permanent magnet material is not fine and uniform enough in crystal grains and low in coercivity. The technical purpose of the invention is realized by the following technical scheme:
the first technical purpose of the invention is a preparation method of Sr-doped manganese-gallium alloy, which comprises the following steps:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn by utilizing a smelting technology under the protection of vacuum or inert gasx-yGaSry(x is more than 1 and less than or equal to 3.0, and y is more than 0 and less than or equal to 0.5) alloy ingot casting;
step two, Mn obtained in the step onex-yGaSry(x is more than 1 and less than or equal to 3.0, y is more than 0 and less than or equal to 0.5) under the protection of vacuum or inert gas, and the tetragonal phase alloy is obtained by different heat treatment processes.
In the first step and the second step, the smelting and the heat treatment are carried out under the protection of vacuum or inert gas, and the inert gas can be nitrogen, argon or helium, preferably argon.
The heat treatment conditions in the second step are adjusted according to different Mn-Ga components, the heat treatment temperature is 465-610 ℃, and the heat treatment time is 1-7 days.
The second technical purpose of the invention is a preparation method of a Sr-doped manganese-gallium alloy high-coercivity nanocrystalline magnet, which comprises the following steps:
and (3) placing the tetragonal phase doped alloy block in a mould, and performing rapid thermal deformation under the protection of vacuum or inert gas by adopting a Spark Plasma Sintering (SPS) process to obtain the Sr-doped manganese-gallium nanocrystalline magnet with high coercivity.
The rapid thermal deformation in the above steps is performed under high vacuum or inert gas protection, preferably under high vacuum conditions.
The rapid thermal deformation process in the steps comprises the following steps: the temperature may be raised to the heat distortion temperature and then the pressure applied at a rate, or the temperature and pressure may be raised simultaneously, preferably at a rate; and (3) immediately releasing the pressure after thermal deformation is finished, or releasing the pressure after heat preservation for 1-5 min, and preferably releasing the pressure after heat preservation for 1min after thermal deformation is finished.
The rapid thermal deformation process parameters in the steps are as follows: the temperature rise rate ranges from 30 to 100 ℃/min, preferably 60 ℃/min; the thermal deformation pressure intensity range is 30-1000 MPa, and 500MPa is preferred; the thermal deformation temperature range is 400-520 ℃, and the lowest temperature without phase change is preferably selected according to different performances of alloys with different components; the deformation range is more than 30%, and the maximum deformation under the specified temperature and pressure is optimized according to the different performances of the alloy with different components; the deformation rate range is 0.01 mm/s-0.1 mm/s, and the deformation rate is preferably as fast as possible according to different properties of the alloy with different components.
The rapid thermal deformation technology is adopted in the steps, the mold can be a graphite mold or a hard alloy mold, the graphite mold can be adopted when the thermal deformation pressure is below 100MPa, the hard alloy mold is adopted when the thermal deformation pressure is more than or equal to 100MPa, and the hard alloy mold is selected according to the thermal deformation process parameter of 500MPa pressure.
The invention adopts the thermal deformation method of Spark Plasma Sintering (SPS) to improve Sr-doped MnxWhile the Ga alloy deforms, the heat deformation temperature is reduced, the heat deformation rate and the deformation are improved, and fine grains are obtainedAnd the high-coercivity manganese-gallium magnet greatly improves the application potential of the manganese-gallium alloy in the field of magnetic materials.
Drawings
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which a hysteresis loop of a sample is tested at room temperature in the range of-3T to 3T using a Vibrating Sample Magnetometer (VSM), and XRD data of the sample is analyzed using Jade software.
Table 1 shows Mnx-yGaSry(x is more than 1 and less than or equal to 3.0, and y is more than 0 and less than or equal to 0.5) specific numerical values of the magnetic property of the magnet sample.
FIG. 1 shows Mn1.33Ga and Mn1.32GaSr0.01Room temperature hysteresis loop of a thermally deformed magnet.
FIG. 2 shows Mn1.33Ga and Mn1.32GaSr0.01And comparing fracture morphology of the thermal deformation magnet.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1: mn with a strain capacity of 86% was prepared according to the following specific procedure1.145GaSr0.005A magnet.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology1.145GaSr0.005Alloy ingot casting;
step two, Mn obtained in the step one1.145GaSr0.005And annealing the cast ingot at 465 ℃ for 2 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 400 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure at 500MPa, and controlling the deformation amount to 86%, wherein the deformation rate during the thermal deformation is kept at 0.02 mm/s.Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced, so as to obtain the coercive force H of the manganese-gallium magnet in the direction vertical to the pressurecjAnd average grain sizes of 6.82kOe and 685nm, respectively.
Example 2: mn with a strain capacity of 86% was prepared according to the following specific procedure1.14GaSr0.01A magnet.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology1.14GaSr0.01Alloy ingot casting;
step two, Mn obtained in the step one1.14GaSr0.01And annealing the cast ingot at 465 ℃ for 2 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 400 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure at 500MPa, and controlling the deformation amount to 86%, wherein the deformation rate during the thermal deformation is kept at 0.02 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced, so as to obtain the coercive force H of the manganese-gallium magnet in the direction vertical to the pressurecjAnd average grain sizes of 7.54kOe and 646nm, respectively.
Example 3: mn with a strain capacity of 86% was prepared according to the following specific procedure1.13GaSr0.02A magnet.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology1.13GaSr0.02Alloy ingot casting;
step two, Mn obtained in the step one1.13GaSr0.02And annealing the cast ingot at 465 ℃ for 2 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 400 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure at 500MPa, and controlling the deformation amount to 86%, wherein the deformation rate during the thermal deformation is kept at 0.02 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced, so as to obtain the coercive force H of the manganese-gallium magnet in the direction vertical to the pressurecjAnd average grain sizes of 6.75kOe and 698nm, respectively.
Example 4: mn with a strain capacity of 86% was prepared according to the following specific procedure1.10GaSr0.05A magnet.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology1.10GaSr0.05Casting a gold ingot;
step two, Mn obtained in the step one1.10GaSr0.05And annealing the cast ingot at 465 ℃ for 2 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 400 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure at 500MPa, and controlling the deformation amount to 86%, wherein the deformation rate during the thermal deformation is kept at 0.02 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced, so as to obtain the coercive force H of the manganese-gallium magnet in the direction vertical to the pressurecjAnd average grain sizes of 5.72kOe and 842nm, respectively.
Example 5: mn with a strain capacity of 86% was prepared according to the following specific procedure1.05GaSr0.1A magnet.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology1.05GaSr0.1Alloy ingot casting;
step two, Mn obtained in the step one1.05GaSr0.1And annealing the cast ingot at 465 ℃ for 2 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 400 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure at 500MPa, and controlling the deformation amount to 86%, wherein the deformation rate during the thermal deformation is kept at 0.02 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced, so as to obtain the coercive force H of the manganese-gallium magnet in the direction vertical to the pressurecjAnd average grain sizes of 4.69kOe and 1452nm, respectively.
Example 6: mn with a strain capacity of 86% was prepared according to the following specific procedure0.95GaSr0.2A magnet.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology0.95GaSr0.2Alloy ingot casting;
step two, Mn obtained in the step one0.95GaSr0.2And annealing the cast ingot at 465 ℃ for 2 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 390 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure of 500MPa, and controlling the deformation amount to 86%, wherein the deformation rate during the thermal deformation is kept at 0.02 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced, so as to obtain the coercive force H of the manganese-gallium magnet in the direction vertical to the pressurecjAnd average grain sizes of 3.76kOe and 2012nm, respectively.
Example 7:mn with a strain capacity of 86% was prepared according to the following specific procedure0.65GaSr0.5A magnet.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology0.65GaSr0.5Alloy ingot casting;
step two, Mn obtained in the step one0.65GaSr0.5And annealing the cast ingot at 465 ℃ for 2 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 390 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure of 500MPa, and controlling the deformation amount to 86%, wherein the deformation rate during the thermal deformation is kept at 0.02 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced, so as to obtain the coercive force H of the manganese-gallium magnet in the direction vertical to the pressurecjAnd average grain sizes of 2.98kOe and 2876nm, respectively.
Examples 8 to 14: mn with a strain of 92% was prepared according to the following specific procedure1.33-xGaSrxA series of magnets.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology1.33-xGaSrxAlloy ingot casting;
step two, Mn obtained in the step one1.33-xGaSrxAnd annealing the ingot for 4 days at 520 ℃ under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
placing the obtained tetragonal phase doped alloy block in a hard alloy mould, and performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition to obtain a material with a thermal deformation rate of 6Heating to 410 ℃ at a heating rate of 0 ℃/min, then preserving heat and pressurizing to 500MPa, and controlling the deformation amount to 92%, wherein the deformation rate during thermal deformation is kept at 0.03 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced to obtain Mn1.33-xGaSrxSeries of coercive forces H perpendicular to the direction of pressurecjAnd the average grain sizes are shown in table 1, respectively.
Examples 15 to 18: mn with a strain of 93% was prepared according to the following specific procedure1.80-xGaSrxA series of magnets.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology1.80-xGaSrxAlloy ingot casting;
step two, Mn obtained in the step one1.80-xGaSrxAnd annealing the ingot for 4 days at 610 ℃ under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 460 ℃ at a heating rate of 60 ℃/min, then preserving heat and applying pressure at 500MPa, and controlling the deformation amount to 93%, wherein the deformation rate during the thermal deformation is kept at 0.03 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced to obtain Mn1.80-xGaSrxCoercive force H of series magnet in vertical pressure directioncjAnd the average grain sizes are shown in table 1, respectively.
Examples 19 to 22: mn with a strain of 93% was prepared according to the following specific procedure2.50-xGaSrxA series of magnets.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology2.50-xGaSrxAlloy ingot casting;
step two, Mn obtained in the step one2.50-xGaSrxAnd annealing the cast ingot at 600 ℃ for 6 days under the protection of argon to obtain the tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 500 ℃ at a heating rate of 60 ℃/min, then keeping the temperature and applying pressure at 500MPa, and controlling the deformation amount to 93%, wherein the deformation rate during the thermal deformation is kept at 0.04 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced to obtain Mn2.50-xGaSrxCoercive force H of series magnet in vertical pressure directioncjAnd the average grain sizes are shown in table 1, respectively.
Examples 23 to 26: mn with a 94% strain was prepared according to the following specific procedure3.00-xGaSrxA series of magnets.
(1) Preparation of doped alloy:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn under the protection of argon by using a medium-frequency induction melting technology3.00-xGaSrxAlloy ingot casting;
step two, Mn obtained in the step one3.00-xGaSrxAnd annealing the cast ingot at 600 ℃ for 7 days under the protection of argon to obtain a tetragonal phase doped alloy block.
(2) Preparation of a Heat-deformed magnet:
and placing the obtained tetragonal phase doped alloy block in a hard alloy die, performing rapid thermal deformation treatment by using a Spark Plasma Sintering (SPS) thermal deformation technology under a vacuum condition, heating to 520 ℃ at a heating rate of 60 ℃/min, then keeping the temperature and pressurizing to 500MPa, and controlling the deformation amount to 94%, wherein the deformation rate during the thermal deformation is kept at 0.04 mm/s. Then the temperature is preserved for 1min, and the pressure is relieved and the temperature is reduced to obtain Mn3-xGaSrxCoercive force H of series magnet in vertical pressure directioncjAnd the average grain sizes are shown in table 1, respectively.
TABLE 1 Mn in examples 1-25x-yGaSry(1＜x is less than or equal to 3.0, y is more than 0 and less than or equal to 0.5) coercive force and grain size of the deformed magnet
Claims (9)
1. The preparation method of the Sr-doped manganese-gallium alloy is characterized by comprising the following steps of:
the method comprises the following steps:
step one, weighing Mn, Ga and Sr with the purity of more than 99 wt.% in proportion, and obtaining Mn by utilizing a smelting technology under the protection of vacuum or inert gasx-yGaSryCasting an alloy ingot, wherein x is more than 1 and less than or equal to 3.0, and y is more than 0 and less than or equal to 0.5;
step two, Mn obtained in the step onex-yGaSryAnd (3) obtaining the tetragonal alloy from the ingot through different heat treatment processes under the protection of vacuum or inert gas.
2. The method according to claim 1, wherein in the first and second steps, the smelting and heat treatment processes are performed under vacuum or inert gas protection, and the inert gas is nitrogen, argon or helium, preferably argon.
3. The method according to claim 1, wherein the heat treatment conditions in the second step are adjusted depending on the Mn-Ga content, the heat treatment temperature is 465 to 610 ℃, and the heat treatment time is 1 to 7 days.
4. A preparation method of a Sr-doped manganese-gallium alloy high-coercivity nanocrystalline magnet is characterized by comprising the following specific steps:
placing the tetragonal phase alloy obtained in any one of claims 1-3 in a mold, and performing rapid thermal deformation under the protection of vacuum or inert gas by adopting a Spark Plasma Sintering (SPS) process to obtain a Sr-doped manganese-gallium nanocrystalline magnet with high coercivity;
rapid thermal deformation: the temperature rise rate ranges from 30 to 100 ℃/min, preferably 60 ℃/min; the thermal deformation pressure intensity range is 30-1000 MPa, and 500MPa is preferred; the thermal deformation temperature range is 400-520 ℃, and the lowest temperature without phase change is preferably selected according to different performances of alloys with different components; the deformation range is more than 30%, and the maximum deformation under the specified temperature and pressure is optimized according to the different performances of the alloy with different components; the deformation rate range is 0.01 mm/s-0.1 mm/s, and the deformation rate is preferably as fast as possible according to different properties of the alloy with different components.
5. The method according to claim 4, wherein the rapid thermal deformation is performed under high vacuum or inert gas shielding, preferably high vacuum conditions.
6. A method according to claim 4, wherein the temperature is raised to the heat distortion temperature and then pressure is applied at a rate, or the temperature is raised simultaneously with the application of pressure, preferably at a rate and then pressure is applied.
7. The method according to claim 4, wherein the pressure is released immediately after completion of the hot deformation or after holding for 1-5 min, preferably after holding for 1 min.
8. A method according to claim 4, characterized in that rapid thermal deformation is used, the mold being a graphite mold or a cemented carbide mold, the graphite mold being used at a thermal deformation pressure below 100MPa and the cemented carbide mold being used at a pressure greater than or equal to 100 MPa. Cemented carbide molds are preferred.
9. A high coercivity manganese gallium magnet produced by the process according to any one of claims 1 to 8.
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