WO2022077679A1 - 一种Sr掺杂锰镓合金及其高矫顽力纳米晶磁体的制备方法 - Google Patents

一种Sr掺杂锰镓合金及其高矫顽力纳米晶磁体的制备方法 Download PDF

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WO2022077679A1
WO2022077679A1 PCT/CN2020/127968 CN2020127968W WO2022077679A1 WO 2022077679 A1 WO2022077679 A1 WO 2022077679A1 CN 2020127968 W CN2020127968 W CN 2020127968W WO 2022077679 A1 WO2022077679 A1 WO 2022077679A1
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deformation
thermal deformation
alloy
pressure
temperature
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路清梅
李虹霏
岳明
张红国
刘卫强
张东涛
李玉卿
吴琼
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北京工业大学
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure
    • C22C2200/04—Nanocrystalline
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic

Definitions

  • the invention relates to a Sr-doped manganese gallium alloy and a preparation method of a high coercive force nanocrystalline magnet, belonging to the technical field of magnetic material preparation.
  • Permanent magnet materials are an important field of magnetic materials and play an extremely important role in various industries.
  • permanent magnets that are widely used and have excellent performance such as NdFeB and Samarium Cobalt alloys, usually contain a large amount of rare earth elements, even expensive heavy rare earth elements.
  • my country is a big country of rare earths, the shortage of rare earth resources in my country has become increasingly prominent due to decades of cheap and excessive exploitation. Therefore, the development and research of a high-performance, high-stability non-rare earth magnetic material has become a new trend in the magnetic industry of various countries. research direction.
  • Mn x Ga (1 ⁇ x ⁇ 3) alloy As a non-rare earth material, Mn x Ga (1 ⁇ x ⁇ 3) alloy has rich phase structure, diverse magnetic properties, and high theoretical intrinsic magnetic properties. It is one of the technical reserves in the field of new non-rare earth magnetic materials. First, research reports on its preparation, changes in magnetic properties and application value have been common. For example, the high spin polarizability and high Curie temperature of D0 22 -Mn 3 Ga make it suitable for new spin transfer torque materials; while the tetragonal L1 0 -MnGa alloys have become one of the main candidates for non-rare earth permanent magnet materials due to their high saturation magnetization, Curie temperature, strong magnetocrystalline anisotropy, and high theoretical magnetic energy product.
  • Alloy plastic deformation is an effective way to realize the magnetic hardening of Mn x Ga ( 1 ⁇ x ⁇ 3 ) alloy. Deformation, and magnetic hardening of alloys with different compositions is achieved through the recovery and recrystallization of grains. The study found that on the basis of ensuring the tetragonal structure, the lower the temperature, the higher the deformation rate, and the larger the deformation, the higher the degree of recrystallization and the more conducive to the formation of fine grains. But for alloys with a specific composition, the deformation parameters are closely related to the chemical composition and crystal structure.
  • the temperature range for maintaining the single-phase tetragonal L10 structure tends to decrease; on the other hand, the material is brittle, so it is difficult to control thermal deformation. craft.
  • the single-phase tetragonal Mn 1.80 Ga alloy has a maximum deformation of 92%.
  • the remanence and coercivity of the deformed magnet are increased to 2.52kG and 4.73kOe, respectively.
  • the coercivity of the Mn 1.33 Ga hot-deformed magnet with a deformation amount of 88% reaches 5.65 kOe, and its grain size is reduced from 30 ⁇ m of the ingot before deformation to 1-3 ⁇ m, but there is still a big gap compared with its single domain size of 605 nm. , and only adjusting the deformation process can no longer meet the requirements of further reducing the grain size.
  • Modification of Mn x Ga (1 ⁇ x ⁇ 3) alloy by appropriate element doping can enhance the plastic deformation ability of the alloy on the basis of maintaining its intrinsic magnetic properties, and then optimize the thermal deformation process parameters (especially reducing the deformation temperature). ), is a more effective means to further reduce the grain size of thermally deformed magnets and improve their coercivity.
  • Sr has a low melting point and a "soft" quality.
  • the rapid thermal deformation technology is used for magnetic hardening.
  • the existence of Sr-rich phase as a liquid phase promotes thermal deformation, which not only reduces the deformation temperature, but also increases the thermal deformation rate and deformation amount, and achieves refined grains, The effect of improving the magnetic properties.
  • the thermal deformation process of Sr-doped MnxyGaSry alloys requires strict control of process conditions.
  • the lowest possible deformation temperature and large deformation rate are used to optimize its magnetic properties, and finally a high coercivity manganese gallium nanocrystalline magnet is obtained.
  • the invention comprehensively adopts various technologies such as smelting, heat treatment, discharge plasma sintering, etc., and proposes a Sr-doped manganese gallium alloy and a preparation method for a high coercive force nanocrystalline magnet, which overcomes the insufficient crystal grains of the existing manganese gallium permanent magnet material.
  • the technical purpose of the present invention is achieved through the following technical solutions:
  • the first technical purpose of the present invention is a kind of preparation method of Sr-doped manganese gallium alloy, comprising the following steps:
  • Step 1 After weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, Mn xy GaSr y (1 ⁇ x ⁇ 3.0, 0 ⁇ y ⁇ 0.5) is obtained under vacuum or inert gas protection by using smelting technology alloy ingot;
  • step 2 the Mn xy GaSr y (1 ⁇ x ⁇ 3.0, 0 ⁇ y ⁇ 0.5) ingot obtained in step 1 is subjected to different heat treatment processes to obtain a tetragonal phase alloy under vacuum or inert gas protection conditions.
  • the smelting and heat treatment process is carried out under vacuum or inert gas protection conditions, and the inert gas can be nitrogen, argon or helium, etc., preferably argon.
  • the heat treatment conditions described in the above step 2 are adjusted according to the difference of the Mn-Ga composition, the heat treatment temperature is 465-610° C., and the heat treatment time is 1-7 days.
  • the second technical purpose of the present invention is a kind of preparation method of Sr-doped manganese gallium alloy high coercivity nanocrystalline magnet, the concrete steps are:
  • the above-mentioned tetragonal doped alloy block is placed in a mold, and a spark plasma sintering (SPS) process is used to perform rapid thermal deformation under vacuum or inert gas protection conditions to obtain Sr-doped manganese gallium nanocrystalline magnets with high coercivity .
  • SPS spark plasma sintering
  • the rapid thermal deformation described in the above steps is carried out under the protection of high vacuum or inert gas, preferably high vacuum conditions.
  • the rapid thermal deformation process described in the above steps is as follows: the temperature can be raised to the thermal deformation temperature at a certain rate and then pressure is applied, or the temperature increase and the pressure can be carried out simultaneously, preferably at a certain rate to the thermal deformation temperature and then pressure is applied; thermal deformation After completion, the pressure can be released immediately, or the pressure can be released after holding for 1 to 5 minutes.
  • the rapid thermal deformation process parameters described in the above steps are: the heating rate range is 30-100°C/min, preferably 60°C/min; the thermal deformation pressure range is 30-1000MPa, preferably 500MPa; the thermal deformation temperature range is 400-520 °C, according to the different properties of different composition alloys, the lowest temperature without phase transformation is preferred; the deformation range is more than 30%, and the maximum deformation amount at the specified temperature and pressure is selected according to the different properties of different composition alloys; the deformation rate range is 0.01 mm/s ⁇ 0.1mm/s, the deformation rate as fast as possible is preferred according to the different properties of alloys with different compositions.
  • the rapid thermal deformation technology is used in the above steps.
  • the mold can be a graphite mold or a cemented carbide mold.
  • a graphite mold can be used.
  • a cemented carbide mold should be used.
  • the invention adopts the spark plasma sintering (SPS) thermal deformation method, while increasing the deformation amount of the Sr-doped Mn x Ga alloy, the thermal deformation temperature is reduced, the thermal deformation rate and the deformation amount are increased, and the fine-grained, high-correction alloy is obtained.
  • SPS spark plasma sintering
  • VSM vibrating sample magnetometer
  • Table 1 shows the specific numerical values of the magnetic properties of the Mn xy GaSry (1 ⁇ x ⁇ 3.0, 0 ⁇ y ⁇ 0.5) magnet samples.
  • Figure 1 shows the room temperature hysteresis loops of Mn 1.33 Ga and Mn 1.32 GaSr 0.01 thermally deformed magnets.
  • Figure 2 shows the comparison of fracture morphologies of Mn 1.33 Ga and Mn 1.32 GaSr 0.01 hot-deformed magnets.
  • Example 1 A Mn 1.145 GaSr 0.005 magnet with a deformation amount of 86% was prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the medium frequency induction melting technology is used to obtain a Mn 1.145 GaSr 0.005 alloy ingot under argon protection;
  • step 2 the Mn 1.145 GaSr 0.005 ingot obtained in step 1 is annealed at 465° C. for 2 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 400 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 86%, and the deformation rate during thermal deformation was kept at 0.02 mm/s. Then, after holding for 1 min, the pressure is released and the temperature is lowered.
  • the obtained manganese gallium magnet has a coercivity H cj and an average grain size in the vertical pressure direction of 6.82 kOe and 685 nm, respectively.
  • Example 2 A Mn 1.14 GaSr 0.01 magnet with a deformation amount of 86% was prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 1.14 GaSr 0.01 alloy ingot under argon protection;
  • step 2 the Mn 1.14 GaSr 0.01 ingot obtained in step 1 is annealed at 465° C. for 2 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 400 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 86%, and the deformation rate during thermal deformation was kept at 0.02 mm/s. After holding for 1 min, the pressure was released and the temperature was lowered.
  • the coercive force H cj and the average grain size of the obtained manganese gallium magnet in the vertical pressure direction were 7.54 kOe and 646 nm, respectively.
  • Example 3 A Mn 1.13 GaSr 0.02 magnet with a deformation amount of 86% was prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 1.13 GaSr 0.02 alloy ingot under argon protection;
  • step 2 the Mn 1.13 GaSr 0.02 ingot obtained in step 1 is annealed at 465° C. for 2 days under the protection of argon to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 400 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 86%, and the deformation rate during thermal deformation was kept at 0.02 mm/s. After holding for 1 min, the pressure is released and the temperature is lowered.
  • the obtained manganese gallium magnets have a coercivity H cj and an average grain size in the vertical pressure direction of 6.75 kOe and 698 nm, respectively.
  • Example 4 A Mn 1.10 GaSr 0.05 magnet with a deformation amount of 86% was prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, using medium frequency induction melting technology to obtain Mn 1.10 GaSr 0.05 gold ingots under argon protection;
  • step 2 the Mn 1.10 GaSr 0.05 ingot obtained in step 1 is annealed at 465° C. for 2 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 400 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 86%, and the deformation rate during thermal deformation was kept at 0.02 mm/s. After holding for 1 min, the pressure was released and the temperature was lowered.
  • the coercive force H cj and the average grain size of the obtained manganese gallium magnet in the vertical pressure direction were 5.72 kOe and 842 nm, respectively.
  • Example 5 A Mn 1.05 GaSr 0.1 magnet with a deformation amount of 86% was prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 1.05 GaSr 0.1 alloy ingot under argon protection;
  • step 2 the Mn 1.05 GaSr 0.1 ingot obtained in step 1 is annealed at 465° C. for 2 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 400 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 86%, and the deformation rate during thermal deformation was kept at 0.02 mm/s. After holding for 1 min, the pressure is released and the temperature is lowered.
  • the obtained manganese gallium magnet has a coercive force H cj perpendicular to the pressure direction and an average grain size of 4.69 kOe and 1452 nm, respectively.
  • Example 6 A Mn 0.95 GaSr 0.2 magnet with a deformation amount of 86% was prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 0.95 GaSr 0.2 alloy ingot under argon protection;
  • step 2 the Mn 0.95 GaSr 0.2 ingot obtained in step 1 is annealed at 465° C. for 2 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 390 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 86%, and the deformation rate during thermal deformation was kept at 0.02 mm/s. After holding for 1 min, the pressure is released and the temperature is lowered.
  • the obtained manganese gallium magnets have a coercivity H cj perpendicular to the pressure direction and an average grain size of 3.76 kOe and 2012 nm, respectively.
  • Example 7 A Mn 0.65 GaSr 0.5 magnet with a deformation amount of 86% was prepared according to the following specific steps.
  • step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, a Mn 0.65 GaSr 0.5 alloy ingot is obtained by using an intermediate frequency induction melting technology under argon protection;
  • step 2 the Mn 0.65 GaSr 0.5 ingot obtained in step 1 is annealed at 465° C. for 2 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 390 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 86%, and the deformation rate during thermal deformation was kept at 0.02 mm/s. After holding for 1 min, the pressure was released and the temperature was lowered.
  • the obtained manganese gallium magnets had a coercivity H cj perpendicular to the pressure direction and an average grain size of 2.98 kOe and 2876 nm, respectively.
  • Examples 8 to 14 Mn 1.33-x GaSr x series magnets with a deformation amount of 92% were prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 1.33-x GaSr x alloy ingot under argon protection;
  • step 2 the Mn 1.33-x GaSr x ingot obtained in step 1 is annealed at 520° C. for 4 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 410 °C at a heating rate of 60 °C/min. After the temperature is maintained, the pressure is 500 MPa, and the deformation is controlled to 92%, and the deformation rate during thermal deformation is maintained at 0.03 mm/s. After holding for 1 min, the pressure is released and the temperature is lowered.
  • SPS spark plasma sintering
  • Examples 15-18 Mn 1.80-x GaSr x series magnets with a deformation amount of 93% were prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 1.80-x GaSr x alloy ingot under argon protection;
  • step 2 the Mn 1.80-x GaSr x ingot obtained in step 1 is annealed at 610° C. for 4 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 460 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 93%, and the deformation rate during thermal deformation was kept at 0.03 mm/s. After holding for 1 min, the pressure is released and the temperature is lowered.
  • the coercive force H cj and the average grain size of the obtained Mn 1.80-x GaSr x series magnets in the vertical pressure direction are shown in Table 1, respectively.
  • Examples 19 to 22 Mn 2.50-x GaSr x series magnets with a deformation amount of 93% were prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 2.50-x GaSr x alloy ingot under argon protection;
  • step 2 the Mn 2.50-x GaSr x ingot obtained in step 1 is annealed at 600° C. for 6 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy block was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 500 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 93%, and the deformation rate during thermal deformation was kept at 0.04 mm/s. After holding for 1 min, the pressure is released and the temperature is lowered.
  • SPS spark plasma sintering
  • Examples 23-26 Mn 3.00-x GaSr x series magnets with a deformation amount of 94% were prepared according to the following specific steps.
  • Step 1 after weighing Mn, Ga, and Sr with a purity of more than 99 wt.% in proportion, the intermediate frequency induction melting technology is used to obtain a Mn 3.00-x GaSr x alloy ingot under argon protection;
  • step 2 the Mn 3.00-x GaSr x ingot obtained in step 1 is annealed at 600° C. for 7 days under argon protection to obtain a tetragonal doped alloy bulk.
  • the obtained tetragonal doped alloy bulk was placed in a cemented carbide mold, and under vacuum conditions, the spark plasma sintering (SPS) thermal deformation technology was used for rapid thermal deformation treatment, and the temperature was increased to 520 °C at a heating rate of 60 °C/min. After °C, the pressure was kept at 500 MPa, and the deformation was controlled to 94%, and the deformation rate during thermal deformation was kept at 0.04 mm/s. After holding for 1 min, the pressure is released and the temperature is lowered.
  • SPS spark plasma sintering

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Abstract

一种Sr掺杂锰镓合金及其高矫顽力纳米晶磁体的制备方法，属于非稀土磁性材料技术领域。其具体方法为：首先采用熔炼及热处理的工艺，制备出四方相Sr掺杂锰镓合金，其化学式为Mnx-yGaSry(1＜x≤3.0,0＜y≤0.5)。再将该合金快速热变形，获得具有高矫顽力的Sr掺杂锰镓纳米晶磁体。采用Sr元素掺杂对MnxGa(1≤x≤3)合金进行改性，在保持其内禀磁性的基础上，增强合金塑性变形能力，降低了热变形温度，提高了热变形速率和变形量，达到细化晶粒、提高磁性能的效果。

Description

一种Sr掺杂锰镓合金及其高矫顽力纳米晶磁体的制备方法 技术领域
本发明涉及一种Sr掺杂锰镓合金及其高矫顽力纳米晶磁体的制备方法，属于磁性材料制备技术领域。
背景技术
永磁材料是磁性材料的一个重要领域，在各个行业都发挥着极其重要的作用。目前获得广泛应用、性能优异的永磁体中，如钕铁硼、钐钴合金等通常含有大量的稀土元素，甚至昂贵的重稀土元素。虽然我国是稀土大国，但几十年的廉价、过度开采使我国的稀土资源短缺问题日益突出，因此，开发和研究一种高性能、高稳定性的非稀土磁性材料已成为各国磁性行业新的研究方向。
Mn xGa(1≤x≤3)合金作为一种非稀土材料，具有丰富的相结构、多样的磁特性，以及较高的理论内禀磁性能，是新型非稀土磁性材料领域的技术储备之一，关于其制备、磁性能变化和应用价值的研究报道也已屡见不鲜,如D0 22-Mn 3Ga的高自旋极化率和高居里温度使其应用于新型自旋转移矩材料；而四方L1 0-MnGa合金因其较高的饱和磁化强度、居里温度、强磁晶各向异性，以及较高的理论磁能积，成为非稀土永磁材料的主要候选之一。实际上，随着Mn元素的降低，四方Mn xGa(1≤x≤3)合金的磁性能逐渐从亚铁磁性转变为铁磁性，但是其相结构也更易发生失稳，更难进行磁硬化。
合金塑性变形是一种实现Mn xGa(1≤x≤3)合金磁硬化的有效途径，此前我们(ZL201710011067.9)利用放电等离子烧结方法对 Mn xGa(1≤x≤3)铸锭热变形，通过晶粒的回复再结晶，实现了不同成分合金的磁硬化。研究发现，在保证四方结构的基础上，温度越低、变形速率越高，变形量越大，则再结晶程度越高，越有利于形成细晶。但是对于特定成分的合金，其变形参数与化学组成和晶体结构密切相关。就Mn xGa(1≤x≤3)而言，随着Mn含量降低，一方面保持单相四方L1 0结构的温度区间趋于减小，另一方面，材料脆性大，因此难于调控热变形工艺。如单相四方Mn 1.80Ga合金，其最大变形量为92％，此时变形磁体的剩磁和矫顽力分别提高到2.52kG，4.73kOe。而Mn 1.33Ga在最佳热变形工艺条件下，最大变形量为88％，热变形磁体的剩磁、矫顽力分别提高到3.87kG，5.65kOe。结合显微结构分析，我们发现，尽管热变形引发了再结晶，使得晶粒急剧减小，矫顽力获得了数量级的提升，但是与理论值相比，依然差距甚远。如变形量88％的Mn 1.33Ga热变形磁体的矫顽力达到5.65kOe，其晶粒尺寸从变形前铸锭的30μm降低到1-3μm，但相比其单畴尺寸605nm仍有很大差距，而仅仅通过调控变形工艺已无法满足进一步减小晶粒尺寸的要求。
通过适当的元素掺杂对Mn xGa(1≤x≤3)合金进行改性，在保持其内禀磁性的基础上，增强合金塑性变形能力，进而优化热变形工艺参数(特别是降低变形温度)，是进一步降低热变形磁体晶粒尺寸，提高其矫顽力的更有效手段。通过第一性原理计算所得到的元素中，Sr熔点低且质“软”。我们通过一系列熔炼、热处理工艺，制备四方相Mn x-yGaSr y(1＜x≤3.0，0＜y≤0.5)掺杂合金，发现Sr以网状富Sr 相形态分布在Mn-Ga基体中。再采用快速热变形技术进行磁硬化，在热变形过程中，富Sr相作为液相存在促进了热变形，不但降低了变形温度，还提高了热变形速率和变形量，达到细化晶粒、提高磁性能的效果。另外，由于锰镓合金相结构丰富，相变复杂，且不同成分合金的塑性不同，因此Sr掺杂Mn x-yGaSr y合金的热变形过程需要严格控制工艺条件，在保证其足够大变形量的基础上，采用尽可能低的变形温度、大的变形速率来优化其磁性能，最终获得高矫顽力锰镓纳米晶磁体。
发明内容
本发明综合采用熔炼、热处理、放电等离子烧结等多种技术，提出一种Sr掺杂锰镓合金及其高矫顽力纳米晶磁体的制备方法，克服了现有锰镓永磁材料晶粒不够细小均匀、矫顽力低的技术难题。本发明的技术目的通过下述技术方案予以实现：
本发明的第一个技术目的是一种Sr掺杂锰镓合金的制备方法，包括以下步骤：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用熔炼技术在真空或惰性气体保护条件下获得Mn x-yGaSr y(1＜x≤3.0，0＜y≤0.5)合金铸锭；
步骤二，将步骤一得到的Mn x-yGaSr y(1＜x≤3.0，0＜y≤0.5)铸锭在真空或惰性气体保护条件下，通过不同的热处理工艺获得四方相合金。
上述步骤一和步骤二中，熔炼和热处理过程在真空或惰性气体保护条件下进行，惰性气体可以为氮气、氩气或氦气等，优选氩气。
上述步骤二中所述的热处理条件因Mn-Ga成分的不同而调整，热处理温度为465～610℃，热处理时间为1～7天。
本发明的第二个技术目的是一种Sr掺杂锰镓合金高矫顽力纳米晶磁体的制备方法，具体步骤为：
将上述四方相掺杂合金块体置于模具中，采用放电等离子烧结(SPS)工艺，在真空或惰性气体保护条件下进行快速热变形，获得高矫顽力的Sr掺杂锰镓纳米晶磁体。
上述步骤中所述的快速热变形在高真空或惰性气体保护下进行，优选高真空条件。
上述步骤中所述的快速热变形工艺为：可以以一定的速率升温至热变形温度然后施加压力，或者升温与加压同时进行，优选以一定的速率升温至热变形温度然后施加压力；热变形完成后可立即卸压，或者保温1～5min再卸压，优选热变形完成后保温1min再卸压。
上述步骤中所述的快速热变形工艺参数为：升温速率范围为30～100℃/min，优选60℃/min；热变形压强范围为30～1000MPa，优选500MPa；热变形温度范围为400～520℃，根据不同成分合金的不同性能优选不发生相变的最低温度；变形量范围在30％以上，根据不同成分合金的不同性能优选其指定温度及压强下的最大变形量；变形速率范围为0.01mm/s～0.1mm/s，根据不同成分合金的不同性能优选尽可能快的变形速率。
上述步骤中采用快速热变形技术，模具可以是石墨模具，也可以是硬质合金模具，热变形压强在100MPa以下时可以采用石墨模具，大于等于100MPa时应采用硬质合金模具，本工艺根据热变形工艺参数500MPa压强选择硬质合金模具。
本发明采用放电等离子烧结(SPS)热变形的方法，在提高Sr掺杂Mn xGa合金变形量的同时，降低了热变形温度，提高了热变形速率和变形量，获得了细晶、高矫顽力的锰镓磁体，极大提升了锰镓合金在磁性材料领域的应用潜力。
附图说明
以下，结合附图来详细说明本发明的实施方案，其中使用振动样品磁强计(VSM)在-3T～3T范围内的室温下测试样品的磁滞回线，使用Jade软件分析得样品的XRD数据。
表1为Mn x-yGaSr y(1＜x≤3.0，0＜y≤0.5)磁体样品磁性能的具体数值。
图1为Mn 1.33Ga和Mn 1.32GaSr 0.01热变形磁体的室温磁滞回线。
图2为Mn 1.33Ga和Mn 1.32GaSr 0.01热变形磁体的断口形貌对比。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明并不限于以下实施例。
实施例1：按照以下具体步骤制备变形量86％的Mn 1.145GaSr 0.005磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 1.145GaSr 0.005合金铸锭；
步骤二，将步骤一得到的Mn 1.145GaSr 0.005铸锭在氩气保护条件下，于465℃下退火处理2天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至400℃后保温施压500MPa，控制变形量到86％，其中热变形期间的变形速率保持在0.02mm/s。然后保温1min后卸压降温，获得的锰镓磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别为6.82kOe和685nm。
实施例2：按照以下具体步骤制备变形量86％的Mn 1.14GaSr 0.01磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 1.14GaSr 0.01合金铸锭；
步骤二，将步骤一得到的Mn 1.14GaSr 0.01铸锭在氩气保护条件下，于465℃下退火处理2天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件 下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至400℃后保温施压500MPa，控制变形量到86％，其中热变形期间的变形速率保持在0.02mm/s。然后保温1min后卸压降温，获得的锰镓磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别为7.54kOe和646nm。
实施例3：按照以下具体步骤制备变形量86％的Mn 1.13GaSr 0.02磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 1.13GaSr 0.02合金铸锭；
步骤二，将步骤一得到的Mn 1.13GaSr 0.02铸锭在氩气保护条件下，于465℃下退火处理2天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至400℃后保温施压500MPa，控制变形量到86％，其中热变形期间的变形速率保持在0.02mm/s。然后保温1min后卸压降温，获得的锰镓磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别为6.75kOe和698nm。
实施例4：按照以下具体步骤制备变形量86％的Mn 1.10GaSr 0.05磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 1.10GaSr 0.05金铸锭；
步骤二，将步骤一得到的Mn 1.10GaSr 0.05铸锭在氩气保护条件下，于465℃下退火处理2天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至400℃后保温施压500MPa，控制变形量到86％，其中热变形期间的变形速率保持在0.02mm/s。然后保温1min后卸压降温，获得的锰镓磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别为5.72kOe和842nm。
实施例5：按照以下具体步骤制备变形量86％的Mn 1.05GaSr 0.1磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 1.05GaSr 0.1合金铸锭；
步骤二，将步骤一得到的Mn 1.05GaSr 0.1铸锭在氩气保护条件下，于465℃下退火处理2天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至400℃后保温施压500MPa，控制变形量 到86％，其中热变形期间的变形速率保持在0.02mm/s。然后保温1min后卸压降温，获得的锰镓磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别为4.69kOe和1452nm。
实施例6：按照以下具体步骤制备变形量86％的Mn 0.95GaSr 0.2磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 0.95GaSr 0.2合金铸锭；
步骤二，将步骤一得到的Mn 0.95GaSr 0.2铸锭在氩气保护条件下，于465℃下退火处理2天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至390℃后保温施压500MPa，控制变形量到86％，其中热变形期间的变形速率保持在0.02mm/s。然后保温1min后卸压降温，获得的锰镓磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别为3.76kOe和2012nm。
实施例7：按照以下具体步骤制备变形量86％的Mn 0.65GaSr 0.5磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 0.65GaSr 0.5合金铸锭；
步骤二，将步骤一得到的Mn 0.65GaSr 0.5铸锭在氩气保护条件下，于465℃下退火处理2天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至390℃后保温施压500MPa，控制变形量到86％，其中热变形期间的变形速率保持在0.02mm/s。然后保温1min后卸压降温，获得的锰镓磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别为2.98kOe和2876nm。
实施例8～14：按照以下具体步骤制备变形量92％的Mn 1.33-xGaSr x系列磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 1.33-xGaSr x合金铸锭；
步骤二，将步骤一得到的Mn 1.33-xGaSr x铸锭在氩气保护条件下，于520℃下退火处理4天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至410℃后保温施压500MPa，控制变形量到92％，其中热变形期间的变形速率保持在0.03mm/s。然后保温1min后卸压降温，获得的Mn 1.33-xGaSr x系列垂直压力方向的矫顽力H cj 和平均晶粒尺寸分别如表1所示。
实施例15～18：按照以下具体步骤制备变形量93％的Mn 1.80-xGaSr x系列磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 1.80-xGaSr x合金铸锭；
步骤二，将步骤一得到的Mn 1.80-xGaSr x铸锭在氩气保护条件下，于610℃下退火处理4天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至460℃后保温施压500MPa，控制变形量到93％，其中热变形期间的变形速率保持在0.03mm/s。然后保温1min后卸压降温，获得的Mn 1.80-xGaSr x系列磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别如表1所示。
实施例19～22：按照以下具体步骤制备变形量93％的Mn 2.50-xGaSr x系列磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 2.50-xGaSr x合金铸锭；
步骤二，将步骤一得到的Mn 2.50-xGaSr x铸锭在氩气保护条件下，于600℃下退火处理6天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至500℃后保温施压500MPa，控制变形量到93％，其中热变形期间的变形速率保持在0.04mm/s。然后保温1min后卸压降温，获得的Mn 2.50-xGaSr x系列磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别如表1所示。
实施例23～26：按照以下具体步骤制备变形量94％的Mn 3.00-xGaSr x系列磁体。
(1)掺杂合金的制备：
步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用中频感应熔炼技术在氩气保护条件下获得Mn 3.00-xGaSr x合金铸锭；
步骤二，将步骤一得到的Mn 3.00-xGaSr x铸锭在氩气保护条件下，于600℃下退火处理7天，获得四方相掺杂合金块体。
(2)热变形磁体的制备：
将得到的四方相掺杂合金块体置于硬质合金模具中，在真空条件下，使用放电等离子烧结(SPS)热变形技术进行快速热变形处理，以60℃/min的升温速率升温至520℃后保温施压500MPa，控制变形量到94％，其中热变形期间的变形速率保持在0.04mm/s。然后保温1min后卸压降温，获得的Mn 3-xGaSr x系列磁体垂直压力方向的矫顽力H cj和平均晶粒尺寸分别如表1所示。
表1.实施例1-25中Mn x-yGaSr y(1＜x≤3.0，0＜y≤0.5)变形磁体的矫顽力和晶粒尺寸
Figure PCTCN2020127968-appb-000001
Figure PCTCN2020127968-appb-000002

Claims (9)

  1. 一种Sr掺杂锰镓合金的制备方法，其特征在于，包括以下步骤：
    包括以下步骤：
    步骤一，将纯度99wt.％以上的Mn、Ga、Sr按比例称重后，利用熔炼技术在真空或惰性气体保护条件下获得Mn x-yGaSr y合金铸锭，1＜x≤3.0，0＜y≤0.5；
    步骤二，将步骤一得到的Mn x-yGaSr y铸锭在真空或惰性气体保护条件下，通过不同的热处理工艺获得四方相合金。
  2. 按照权利要求1所述的方法，其特征在于，步骤一和步骤二中，熔炼和热处理过程在真空或惰性气体保护条件下进行，惰性气体为氮气、氩气或氦气，优选氩气。
  3. 按照权利要求1所述的方法，其特征在于，上述步骤二中所述的热处理条件因Mn-Ga成分的不同而调整，热处理温度为465～610℃，热处理时间为1～7天。
  4. 一种Sr掺杂锰镓合金高矫顽力纳米晶磁体的制备方法，其特征在于，具体步骤为：
    将权利要求1-3任一项所得四方相合金置于模具中，采用放电等离子烧结(SPS)工艺，在真空或惰性气体保护条件下进行快速热变形，获得高矫顽力的Sr掺杂锰镓纳米晶磁体；
    快速热变形：升温速率范围为30～100℃/min，优选60℃/min；热变形压强范围为30～1000MPa，优选500MPa；热变形温度范围为400～520℃，根据不同成分合金的不同性能优选不发生相变的最低温度；变形量范围在30％以上，根据不同成分合金的不同性能优选其指 定温度及压强下的最大变形量；变形速率范围为0.01mm/s～0.1mm/s，根据不同成分合金的不同性能优选尽可能快的变形速率。
  5. 按照权利要求4所述的方法，其特征在于，所述的快速热变形在高真空或惰性气体保护下进行，优选高真空条件。
  6. 按照权利要求4所述的方法，其特征在于，可以以一定的速率升温至热变形温度然后施加压力，或者升温与加压同时进行，优选以一定的速率升温至热变形温度然后施加压力；
  7. 按照权利要求4所述的方法，其特征在于，热变形完成后可立即卸压，或者保温1～5min再卸压，优选热变形完成后保温1min再卸压。
  8. 按照权利要求4所述的方法，其特征在于，采用快速热变形技术，模具是石墨模具，或是硬质合金模具，热变形压强在100MPa以下时采用石墨模具，大于等于100MPa时应采用硬质合金模具。优选硬质合金模具。
  9. 按照权利要求1-8任一项所述的方法制备得到的一种高矫顽力锰镓磁体。
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