CN109273183B - Corrosion-resistant monocrystalline magnetic powder and preparation method and application thereof - Google Patents
Corrosion-resistant monocrystalline magnetic powder and preparation method and application thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 61
- 230000007797 corrosion Effects 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 69
- 238000009792 diffusion process Methods 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 51
- 239000013078 crystal Substances 0.000 claims abstract description 50
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005266 casting Methods 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 84
- 239000000956 alloy Substances 0.000 claims description 84
- 239000002245 particle Substances 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000002344 surface layer Substances 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000005121 nitriding Methods 0.000 claims description 13
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- 230000008018 melting Effects 0.000 claims description 12
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- 239000000470 constituent Substances 0.000 claims description 5
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- 229910052748 manganese Inorganic materials 0.000 claims description 3
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- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
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- 238000003723 Smelting Methods 0.000 claims description 2
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- 239000000696 magnetic material Substances 0.000 claims 1
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- PRQMIVBGRIUJHV-UHFFFAOYSA-N [N].[Fe].[Sm] Chemical compound [N].[Fe].[Sm] PRQMIVBGRIUJHV-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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Abstract
The invention relates to corrosion-resistant single crystal magnetic powder and a preparation method and application thereof, belonging to the technical field of rare earth permanent magnet materials. The corrosion-resistant monocrystalline magnetic powder comprises the following components: raFe100‑a‑b‑c‑d‑ vM1bM2cM3dNv. Wherein R is Sm or a combination of Sm and other rare earth elements, and a is more than or equal to 5 and less than or equal to 20; m1 is at least one element of Nb, Zr, Ga, Hf and Ta, and b is more than or equal to 0.2 and less than or equal to 5; m2 is at least one of Co, Al, Cr and Ni, c is more than or equal to 1 and less than or equal to 10; m3 is at least one element of Cu and Zn, d is more than or equal to 0.1 and less than or equal to 10; v is more than or equal to 0.5 and less than or equal to 20. The magnetic powder has low cost, high magnetic performance, high oxidation resistance and high corrosion resistance. The preparation method comprises the following steps: preparing a casting sheet, carrying out first heat treatment, diffusion heat treatment, hydrogenation treatment, dehydrogenation treatment, powder preparation and nitridation. The method is simple, and the obtained magnetic powder can be used for preparing anisotropic bonded permanent magnet materials and the like.
Description
Technical Field
The invention belongs to the technical field of rare earth permanent magnet materials, and particularly relates to corrosion-resistant single crystal magnetic powder and a preparation method and application thereof.
Background
At present, rare earth permanent magnets are widely applied to industries such as computers, automobiles, instruments, household appliances, petrochemical industry, medical care, aerospace and the like as important basic materials in modern society.
Wherein Sm is2Fe17NxWith Nd (Fe, M)12NxIs considered as a candidate for the next generation rare earth permanent magnet. But Sm prepared by the prior art2Fe17N3The magnetic powder has fine particle size and high specific surface area, so the magnetic powder is easy to oxidize and is not corrosion-resistant. Therefore, a new process for preparing magnetic powder having an oxidation-resistant surface layer needs to be studied.
Disclosure of Invention
One of the objects of the present invention is to provide a corrosion-resistant single crystal magnetic powder which is low in cost and has high magnetic properties, oxidation resistance and corrosion resistance.
The second purpose of the invention is to provide a preparation method of the corrosion-resistant single crystal magnetic powder, which is simple to operate, not only is beneficial to preparing the corrosion-resistant single crystal magnetic powder with better performance, but also is suitable for industrial production.
The invention also aims to provide application of the corrosion-resistant single crystal magnetic powder, such as application of the corrosion-resistant single crystal magnetic powder in preparation of anisotropic bonded permanent magnet materials and anisotropic sintered magnets.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention provides corrosion-resistant single crystal magnetic powder which comprises the following components in atomic percentage: raFe100-a-b-c-d-vM1bM2cM3dNv。
In the formula, R is rare earth element Sm or the combination of Sm and other rare earth elements, and a is more than or equal to 5 and less than or equal to 20; m1 is at least one element of Nb, Zr, Ga, Hf and Ta, and b is more than or equal to 0.2 and less than or equal to 5; m2 is at least one of Co, Al, Cr, Ni, Ti, V, Si, Mn, Mo and W, and c is more than or equal to 1 and less than or equal to 10; m3 is at least one element of Cu and Zn, d is more than or equal to 0.1 and less than or equal to 10; v is more than or equal to 0.5 and less than or equal to 20.
The corrosion-resistant single crystal magnetic powder is obtained by nitriding mother alloy magnetic powder, and the mother alloy magnetic powder consists of a first phase, a second phase and a third phase.
The first phase is composed of R, Fe, M1 and M2 and has Th2Zn17Or Th2Ni17The main phase of the structure.
The second phase is an R-rich auxiliary phase which is formed by the first auxiliary phase and the second auxiliary phase. The first auxiliary phase is a non-magnetic phase RM3 phase consisting of R and M3 and having a melting point below 800 ℃. The second auxiliary phase is R (Fe, M1, M2) consisting of R, Fe, M1 and M22Phase or R (Fe, M1, M2)3And (4) phase(s).
The third phase comprises oxides of R and unavoidable impurities.
The invention also provides a preparation method of the corrosion-resistant single crystal magnetic powder, which comprises the following steps:
r, Fe and M2 as raw materials according to RaFe100-a-b-c-d-vM1bM2cM3dNvThe elements except M2 and N are proportioned, smelted and cast into cast pieces, and the cast pieces are subjected to primary heat treatment.
Mixing M2 powder with volatile organic solvent, spraying on the surface of the cast piece after the first heat treatment, drying, and sequentially carrying out the second heat treatment, hydrogenation treatment, dehydrogenation treatment, powder preparation and nitridation.
The invention also provides an application of the corrosion-resistant single crystal magnetic powder, for example, the corrosion-resistant single crystal magnetic powder can be used for preparing anisotropic bonded permanent magnet materials and anisotropic sintered magnets.
The corrosion-resistant single crystal magnetic powder provided by the preferred embodiment of the invention and the preparation method and application thereof have the beneficial effects that:
the corrosion-resistant single crystal magnetic powder provided by the preferred embodiment of the invention has lower cost and higher magnetic property, oxidation resistance and corrosion resistance. The preparation method is simple to operate, is beneficial to preparing the corrosion-resistant monocrystalline magnetic powder with better performance, and is suitable for industrial production. The obtained corrosion-resistant single crystal magnetic powder can be used for preparing anisotropic bonded permanent magnet materials and sintered magnets.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The corrosion-resistant single crystal magnetic powder of the embodiment of the invention, the preparation method and the application thereof are specifically explained below.
The corrosion-resistant single crystal magnetic powder provided by the application comprises the following components in atomic percentage: raFe100-a-b-c-d- vM1bM2cM3dNv。
In the formula, R is rare earth element Sm or the combination of Sm and other rare earth elements, and a is more than or equal to 5 and less than or equal to 20; m1 is at least one element of Nb, Zr, Ga, Hf and Ta, and b is more than or equal to 0.2 and less than or equal to 5; m2 is at least one of Co, Al, Cr, Ni, Ti, V, Si, Mn, Mo and W, and c is more than or equal to 1 and less than or equal to 10; m3 is at least one element of Cu and Zn, d is more than or equal to 0.1 and less than or equal to 10; v is more than or equal to 0.5 and less than or equal to 20. In order to obtain a sufficiently high coercive force, when R is a combination of Sm and other rare earth elements other than Sm, at most 30 at% of the Sm element is replaced with the other rare earth elements.
The corrosion-resistant single crystal magnetic powder is obtained by nitriding mother alloy magnetic powder. The master alloy magnetic powder has a surface layer rich in M2 element, and the surface layer rich in M2 element may have a thickness of 0.1-1 μ M. In a preferred embodiment, the corrosion-resistant single crystal magnetic powder has a surface layer rich in M2 element with a thickness of 0.2 μ M, an average Co content of 7 to 25 at%, and a remaining M2 element content of 7 to 20 at%.
In the present application, the master alloy magnetic powder is composed of a first type phase, a second type phase, and a third type phase.
Wherein the first phase is composed of R, Fe, M1 and M2 and has Th2Zn17Or Th2Ni17The main phase of the structure. The composition atoms of the first phase account for 80-99 at% of the master alloy magnetic powder. The main phase mainly has the function of providing magnetic property for the corrosion-resistant single crystal magnetic powder.
The second type of phase is an R-rich auxiliary phase, which is specifically composed of the first auxiliary phase and the second auxiliary phase together. The first auxiliary phase is a non-magnetic phase RM3 phase composed of R and M3, and the melting point of the non-magnetic phase RM3 phase is lower than 800 ℃. The second auxiliary phase is R (Fe, M1, M2) consisting of R, Fe, M1 and M32Phase or R (Fe, M1, M2)2And (4) phase(s).
In some embodiments, constituent atoms of the non-magnetic phase RM3 phase constitute 1-20 at% of the master alloy magnetic powder, and/or R (Fe, M1, M2)2Constituent atoms of the phases or R (Fe, M1, M2)3The composition atoms of the phase account for 0.5-5 at% of the mother alloy magnetic powder.
The third phase comprises oxides of R and unavoidable impurities. The third phase should be reduced as much as possible in the process of preparing the corrosion-resistant monocrystalline magnetic powder.
The preparation method of the corrosion-resistant monocrystalline magnetic powder can comprise the following steps:
and smelting the master alloy and casting into a cast sheet. Specifically, R, Fe, M1 and M3 are used as raw materials according to RaFe100-a-b-c-d- vM1bM2cM3dNvIn the proportion of elements except M2 and N, in argonInduction melting under protection, and casting the melt into cast pieces (cast alloy flakes) by using a water-cooled copper roller with the speed of 2-20 m/s.
In some embodiments, when the rapid solidification ingot casting technology is used for preparing cast pieces, for example, the surface linear velocity range of the copper roller is controlled to be 2-20m/s, and the thickness of the obtained cast alloy scale is controlled to be 50-1000 μm, so that the microstructure cast pieces with the following characteristics can be obtained: the main phase composed of R, Fe and M1 elements has Th2Zn17Or Th2Ni17A mold structure with a grain size of 0.2-5 μm; the R-rich auxiliary phase is uniformly distributed among the main phase grains and has the size of 0.01-1.5 mu m.
The adoption of the rapid hardening cast piece technology is beneficial to forming the cast piece structure with uniform main phase crystal grain size and R-rich phase distributed around the crystal grain, and is convenient for the subsequent secondary heat treatment and the preparation of single crystal. In order to make the average contents of M2 element in the center and surface of the master alloy cast piece after the second heat treatment as uniform as possible, the thickness of the cast piece is preferably less than 300 μ M.
Further, the obtained cast alloy scale is subjected to a first heat treatment. In some embodiments, the first heat treatment may be performed to the cast alloy flakes at 750 ℃ -. The argon gas is preferably high-purity argon gas, and the purity of the argon gas is preferably more than 99.9999%.
The first heat treatment of the obtained cast alloy scale can eliminate α -Fe and other impurity phases which can not react completely in the original cast alloy scale, and can regulate the grain size of the main phase to 2-12 microns, reduce sharp corners on the main phase grains and form grains with regular shapes, and eliminate metastable phase generated by rapid cooling to form stable main phase and R-rich auxiliary phase, wherein the R-rich auxiliary phase is distributed uniformly among the main phase grains and has the size of about 0.2-2 microns.
The M2 powder is mixed with a volatile organic solvent (e.g., alcohol) in a suspension, where the volume ratio of volatile organic solvent to M1 powder can be (1:0.1) - (1:5), such as 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1: 5. And spraying the suspension on the surface of the cast alloy scale subjected to the first heat treatment to achieve the effect of uniform dispersion.
In addition, the cast alloy flakes can be pre-crushed into coarse powder with the particle diameter of 100-400 μ M, and then the M1 powder and the cast alloy flakes are uniformly mixed in a mixer.
Preferably, the M2 powder has a particle size of less than 5 μ M, because when the diffusion source powder has a small particle size, the diffusion source powder has a high specific surface area and is easy to react with the master alloy and diffuse into the main phase grain boundary, preferably, the oxygen content of the diffusion source alloy powder is less than 2 wt%, so that the phenomenon that an excessive oxygen content forms an oxide film to reduce the atomic diffusion rate is avoided, and on the other hand, the oxygen consumes rare earth elements to finally cause α -Fe to be precipitated from the master alloy to influence the magnetic performance is avoided.
Further, the cast alloy flakes coated with the diffusion source alloy are dried, for example, may be vacuum dried. After drying, a second heat treatment (i.e., diffusion heat treatment as described below) is performed.
The second heat treatment may be performed at a temperature of 750-. The argon gas is preferably high-purity argon gas, and the purity of the argon gas is preferably more than 99.9999%.
By the second heat treatment, M2 can be made to pass through the RM3 phase with low melting point and R (Fe, M1)2Facies or R (Fe, M1)3The phases react and diffuse to the main phase through grain boundaries, so that partial Fe atoms on the surfaces of the main phase grains are replaced by M2, and the local component is R2(Fe,M1,M2)17Thereby forming a grain surface layer of M-rich 2.
The second heat treatment is carried out at a lower temperature, the grain growth is less than 0.5 mu M during diffusion treatment, and meanwhile, the diffusion range of M2 element is localized near the grain boundary, so that the M2 atom is prevented from being diffused in a large range.
Preferably, in the present application, the magnetic powder particles contain M2 element only in the surface layer of 0.1-1 μ M, so as to improve the oxidation resistance and corrosion resistance of the magnetic powder while maintaining the magnetic properties. After the diffusion reaction, the content and the distribution of the M2 element on the section of the master alloy cast sheet can be tested. The 10 positions from the surface layer to the center of the cross section are selected, the average content of Co in the outer layer with the thickness of 0.2 μ M on the main phase grains is preferably 7 to 25 at%, and the remaining M2 element is preferably 7 to 20 at%.
And then, carrying out hydrogenation treatment on the cast alloy scale after the second heat treatment. By reference, the hydrotreatment of H can be carried out at 25-450 deg.C2Middle treatment for 60-300min, H2The pressure of (a) is 1 atmosphere. By hydrogenation treatment, the mother alloy can generate hydrogen absorption reaction, crystal lattices expand, grain boundary fracture is promoted, the bonding force of the grain boundaries is reduced, and the part rich in M2 element in the main phase grain is promoted to become the surface layer of the single crystal magnetic powder.
And carrying out dehydrogenation treatment after hydrogenation treatment. The dehydrogenation treatment may, for example, be carried out under vacuum at 400-650 c to remove hydrogen atoms from the master alloy.
And (5) carrying out powder preparation after dehydrogenation treatment. The powder may be crushed by low energy ball or jet milling to break the mother alloy along the crystal to obtain single crystal magnetic powder with surface rich in M2 element.
Further, nitriding the obtained corrosion-resistant single crystal magnetic powder. For reference, the nitridation can be performed in 400-. The nitrogen source is preferably high purity nitrogen gas, preferably greater than 99.9999% pure.
By the nitriding reaction, nitrogen atoms enter the main phase, and promote the main phase compound to be transformed from easy basal plane magnetization to easy c-axis magnetization. In some preferred embodiments, the nitriding reaction may be performed in a rotary furnace equipped with a stirring device to uniformly nitride the magnetic powder.
In summary, the master alloy of the corrosion-resistant single crystal magnetic powder prepared by the method mainly comprises two phases, namely a main phase and an R-rich phase. The magnetic property of the magnetic powder is represented by R2(Fe,M1,M2)17The main phase provides, and the auxiliary phase itself does not provide magnetic properties, which serve to facilitate the adjustment of the microstructure of the master alloy. The melting point of the RM3 phase is lower than 800 ℃, and the RM3 phase melts at the heat treatment temperature higher than 800 ℃, and the RM 3578 phase has the function of regulating the grain growth speed and providing a rapid diffusion channel for M2 atoms. Meanwhile, R-rich RM3, R (Fe, M1) in the cast piece2Or R (Fe, M1)3The phase is capable of providing R atoms, which form R containing M2 element together with M2 and Fe atoms upon the second heat treatment2(Fe,M1,M2)17And (4) shell layer. R-rich phase R (Fe, M1)2Or R (Fe, M1)3The phases tend to distribute at the grain boundaries of the main phase during high temperature heat treatment, enabling the M2 atoms to diffuse uniformly throughout the surface layers of the grains. R (Fe, M1, M2)2Or R (Fe, M1, M2)3Compatible and easily absorbed H2And after absorption of hydrogen occurs significantly (>10 v%) of the crystal lattice, promoting the occurrence of intergranular cracks of the master alloy cast sheet during hydrogen explosion treatment, and finally causing the occurrence of intergranular fracture during grinding.
Compared with the corrosion-resistant single crystal magnetic powder prepared by the traditional powder metallurgy method, the corrosion-resistant single crystal magnetic powder prepared by the method contains the master alloy with the low-melting-point crystal boundary phase, and Co and other elements capable of improving the oxidation resistance and the corrosion resistance of the magnetic powder are doped on the surface layer of the magnetic powder through crystal boundary diffusion, so that the magnetic performance is kept while the oxidation resistance and the corrosion resistance of the magnetic powder are improved, and the raw material cost of the magnetic powder is reduced.
In addition, the application also provides an application of the corrosion-resistant single crystal magnetic powder, for example, the corrosion-resistant single crystal magnetic powder can be used for preparing anisotropic bonded permanent magnet materials and anisotropic sintered magnets.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Rare earth Sm with the purity of 99.9%, pure Fe, Nb-Fe alloy and pure Cu are used as raw materials, and the materials are prepared according to the following chemical formula: sm11.58Fe87.02Nb0.4Cu1.00. As Sm is easy to volatilize, 10 percent more is added on the basis of theoretical value to compensate.
And putting the prepared metal raw materials into an induction melting furnace to be melted in high-purity Ar. And (3) heating the alloy by induction until the raw materials are completely and uniformly melted, wherein the temperature of the melt is about 1550 ℃, and preparing the rapid-hardening alloy flakes by using the water-cooled copper roller speed, wherein the linear speed of the surface of the copper roller is 10 m/s.
And (3) placing the cast alloy flakes in a corundum crucible, carrying out primary heat treatment for 20min under the protection of argon at 950 ℃, and air-cooling. The diffusion source is Co powder and Cr powder, the average particle size of the Co powder is 3 mu m, and the weight of the Co powder is 3 wt% of the master alloy; the Cr powder had an average particle size of 2 μm and a weight of 1.5 wt% of the master alloy.
Mixing the two diffusion source powders, and adding anhydrous alcohol according to the volume ratio of 1:2 to mix into paste.
The diffusion source was double coated on top of the master alloy cast sheet to increase the weight by 4.5 wt% after drying.
And (3) placing the coated master alloy in a vacuum furnace under the protection of high-purity Ar for diffusion heat treatment. The diffusion heat treatment temperature is 750-.
Placing the casting sheet subjected to diffusion heat treatment at 200 deg.C in H2And (5) performing intermediate treatment for 2h, and performing hydrogen explosion treatment. The furnace temperature is adjusted to 580 ℃, and the vacuum-pumping dehydrogenation treatment is carried out for 2 hours. And (3) carrying out low-energy ball milling on the casting piece subjected to dehydrogenation treatment by using 6mm stainless steel balls, wherein the ball-material ratio is 5:1, the rotating speed of a planetary ball mill is set to be 150rpm, and the milling time is 2 h.
Nitriding the magnetic powder for 15 hours at 430 ℃ by using high-purity nitrogen, and nitriding the magnetic powder into samarium-iron-nitrogen magnetic powder through gas-solid reaction.
The element distribution in the master alloy after diffusion heat treatment and the particle size of the ground magnetic powder are observed by using an electron microscope. 200 magnetic powder particles within the field of view were measured and counted, and the particle size was characterized using the arithmetic mean. The magnetic powder and the hot paraffin were mixed in proportion, and after orientation by a magnetic field, the oriented sample was tested using a vibrating magnetometer (VSM). The direction of the loading magnetic field is parallel to the easy magnetization axis of the sample. The method for testing the oxidation resistance and the corrosion resistance of the magnetic powder comprises the following steps: and heating the magnetic powder in air to 120 ℃ and keeping the temperature for 2 hours, and retesting the coercive force and residual magnetism of the magnetic powder. Magnetic powder sample properties are shown in tables 1 and 2.
TABLE 1 magnetic Properties of Corrosion-resistant Single-crystal magnetic powder
Note: the content of Co in the surface layer and the content of Cr in the surface layer in Table 1 mean values measured by an energy spectrometer at the edge of the grain boundary.
TABLE 2 magnetic powder heated to 120 deg.C in air and maintained magnetic properties for 2h or so
Example 2
Rare earth Sm with the purity of 99.9%, pure Fe and pure Cu are used as raw materials, and the raw materials are mixed according to the following chemical formula: sm11.58Fe87.02Nb0.4Cu1.00. As Sm is easy to volatilize, 10 percent more is added on the basis of theoretical value to compensate.
And putting the prepared metal raw materials into an induction melting furnace to be melted in high-purity Ar. And (3) heating the alloy by induction until the raw materials are completely and uniformly melted, wherein the temperature of the melt is about 1550 ℃, and preparing the rapid-hardening alloy flakes by using the water-cooled copper roller speed, wherein the linear speed of the surface of the copper roller is 10 m/s.
And (3) placing the cast alloy flakes in a corundum crucible, carrying out primary heat treatment for 20min under the protection of argon at 950 ℃, and air-cooling. The diffusion source is Co powder and Si powder, the average particle size of the Co powder is 3 mu m, and the weight of the Co powder is 3 wt% of the master alloy; the average particle size of the Si powder was 2 μm and the weight was 1.5 wt% of the master alloy.
Mixing the two diffusion source powders, and adding anhydrous alcohol according to the volume ratio of 1:2 to mix into paste.
The diffusion source was double coated on top of the master alloy cast sheet to increase the weight by 4.5 wt% after drying.
And (3) placing the coated master alloy in a vacuum furnace under the protection of high-purity Ar for diffusion heat treatment. The diffusion heat treatment temperature is 750-.
Placing the casting sheet subjected to diffusion heat treatment at 200 deg.C in H2And (5) performing intermediate treatment for 2h, and performing hydrogen explosion treatment. The furnace temperature is adjusted to 580 ℃, and the vacuum-pumping dehydrogenation treatment is carried out for 2 hours. Using low-energy ball mill to perform dehydrogenation treatment on the cast pieceGrinding with 6mm stainless steel balls at a ball-to-material ratio of 5:1, a planetary ball mill rotation speed of 150rpm, and a grinding time of 2 h.
Nitriding the magnetic powder into Sm by using high-purity nitrogen for 15h at 430 ℃ through gas-solid reaction2Fe17N3。
The element distribution in the master alloy after diffusion heat treatment and the particle size of the ground magnetic powder are observed by using an electron microscope. 200 magnetic powder particles within the field of view were measured and counted, and the particle size was characterized using the arithmetic mean. The magnetic powder and the hot paraffin were mixed in proportion, and after orientation by a magnetic field, the oriented sample was tested using a vibrating magnetometer (VSM). The direction of the loading magnetic field is parallel to the easy magnetization axis of the sample. The method for testing the oxidation resistance and the corrosion resistance of the magnetic powder comprises the following steps: and heating the magnetic powder in air to 120 ℃ and keeping the temperature for 2 hours, and retesting the coercive force and residual magnetism of the magnetic powder. Magnetic powder sample properties are shown in tables 3 and 4.
TABLE 3 magnetic Properties of Corrosion-resistant Single-crystal magnetic powder
Note: the content of the surface layer Co and the content of the surface layer Si in Table 3 mean values measured by an energy spectrometer at the grain boundary edge.
TABLE 4 magnetic powder heating to 120 deg.C in air and keeping magnetic property before and after 2h
Example 3
Rare earth Sm with the purity of 99.9%, pure Fe and pure Cu are used as raw materials, and the raw materials are mixed according to the following chemical formula: sm11.58Fe87.02Nb0.4Cu1.00. As Sm is easy to volatilize, 10 percent more is added on the basis of theoretical value to compensate.
And putting the prepared metal raw materials into an induction melting furnace to be melted in high-purity Ar. And (3) heating the alloy by induction until the raw materials are completely and uniformly melted, wherein the temperature of the melt is about 1550 ℃, and preparing the rapid-hardening alloy flakes by using the water-cooled copper roller speed, wherein the linear speed of the surface of the copper roller is 10 m/s.
And (3) placing the cast alloy flakes in a corundum crucible, carrying out primary heat treatment for 20min under the protection of argon at 950 ℃, and air-cooling. The diffusion source is Co powder and Al powder, the average particle size of the Co powder is 3 mu m, and the weight of the Co powder is 3.5 wt% of the master alloy; the Al powder had an average particle size of 2 μm and a weight of 1.0 wt% of the master alloy.
Mixing the two diffusion source powders, and adding anhydrous alcohol according to the volume ratio of 1:2 to mix into paste.
The diffusion source was double coated on top of the master alloy cast sheet to increase the weight by 4.5 wt% after drying.
And (3) placing the coated master alloy in a vacuum furnace under the protection of high-purity Ar for diffusion heat treatment. The diffusion heat treatment temperature is 750-.
Placing the casting sheet subjected to diffusion heat treatment at 200 deg.C in H2And (5) performing intermediate treatment for 2h, and performing hydrogen explosion treatment. The furnace temperature is adjusted to 580 ℃, and the vacuum-pumping dehydrogenation treatment is carried out for 2 hours. And (3) carrying out low-energy ball milling on the casting piece subjected to dehydrogenation treatment by using 6mm stainless steel balls, wherein the ball-material ratio is 5:1, the rotating speed of a planetary ball mill is set to be 150rpm, and the milling time is 2 h.
Nitriding the magnetic powder into Sm by using high-purity nitrogen for 15h at 430 ℃ through gas-solid reaction2Fe17N3。
The element distribution in the master alloy after diffusion heat treatment and the particle size of the ground magnetic powder are observed by using an electron microscope. 200 magnetic powder particles within the field of view were measured and counted, and the particle size was characterized using the arithmetic mean. The magnetic powder and the hot paraffin were mixed in proportion, and after orientation by a magnetic field, the oriented sample was tested using a vibrating magnetometer (VSM). The direction of the loading magnetic field is parallel to the easy magnetization axis of the sample. The method for testing the oxidation resistance and the corrosion resistance of the magnetic powder comprises the following steps: and heating the magnetic powder in air to 120 ℃ and keeping the temperature for 2 hours, and retesting the coercive force and residual magnetism of the magnetic powder. Magnetic powder sample properties are shown in tables 5 and 6.
TABLE 5 magnetic Properties of Corrosion-resistant Single-crystal magnetic powder
Note: the surface Co content and the surface Al content in Table 5 mean values measured by an energy spectrometer at the grain boundary edge.
TABLE 6 magnetic powder heating to 120 deg.C in air and keeping magnetic properties before and after 2h
Example 4
Rare earth Sm with the purity of 99.9%, pure Fe and pure Cu are used as raw materials, and the raw materials are mixed according to the following chemical formula: sm11.58Fe87.42Cu1.00. As Sm is easy to volatilize, 10 percent more is added on the basis of theoretical value to compensate.
And putting the prepared metal raw materials into an induction melting furnace to be melted in high-purity Ar. And (3) heating the alloy by induction until the raw materials are completely and uniformly melted, wherein the temperature of the melt is about 1550 ℃, and preparing the rapid-hardening alloy flakes by using the water-cooled copper roller speed, wherein the linear speed of the surface of the copper roller is 10 m/s.
And (3) placing the cast alloy flakes in a corundum crucible, carrying out primary heat treatment for 20min under the protection of argon at 950 ℃, and air-cooling. The diffusion source is Co powder and Mn powder, the average particle size of the Co powder is 3 mu m, and the weight of the Co powder is 3.0 wt% of the master alloy; the Mn powder had an average particle size of 2 μm and a weight of 1.5 wt% of the master alloy.
Mixing the two diffusion source powders, and adding anhydrous alcohol according to the volume ratio of 1:2 to mix into paste.
The diffusion source was double coated on top of the master alloy cast sheet to increase the weight by 4.5 wt% after drying.
And (3) placing the coated master alloy in a vacuum furnace under the protection of high-purity Ar for diffusion heat treatment. The diffusion heat treatment temperature is 750-.
Placing the casting sheet subjected to diffusion heat treatment at 200 deg.C in H2And (5) performing intermediate treatment for 2h, and performing hydrogen explosion treatment. The furnace temperature is adjusted to 580 ℃, and the vacuum-pumping dehydrogenation treatment is carried out for 2 hours. Will be subjected to dehydrogenation treatmentThe cast piece is ground by using a low-energy ball mill, 6mm stainless steel balls are used, the ball-material ratio is 5:1, the rotating speed of a planetary ball mill is set to be 150rpm, and the grinding time is 2 hours.
Nitriding the magnetic powder into Sm by using high-purity nitrogen for 15h at 430 ℃ through gas-solid reaction2Fe17N3。
The element distribution in the master alloy after diffusion heat treatment and the particle size of the ground magnetic powder are observed by using an electron microscope. 200 magnetic powder particles within the field of view were measured and counted, and the particle size was characterized using the arithmetic mean. The magnetic powder and the hot paraffin were mixed in proportion, and after orientation by a magnetic field, the oriented sample was tested using a vibrating magnetometer (VSM). The direction of the loading magnetic field is parallel to the easy magnetization axis of the sample. The method for testing the oxidation resistance and the corrosion resistance of the magnetic powder comprises the following steps: and heating the magnetic powder in air to 120 ℃ and keeping the temperature for 2 hours, and retesting the coercive force and residual magnetism of the magnetic powder. Magnetic powder sample properties are shown in tables 7 and 8.
TABLE 7 magnetic Properties of Corrosion-resistant Single-crystal magnetic powder
Note: the content of the surface layer Co and the content of the surface layer Mn in Table 7 mean values measured by an energy spectrometer at the grain boundary edge.
TABLE 8 magnetic powder heating to 120 deg.C in air and magnetic property before and after 2h
Example 5
Rare earth Sm with the purity of 99.9%, pure Fe and pure Cu are used as raw materials, and the raw materials are mixed according to the following chemical formula: sm11.58Fe87.42Cu1.00. As Sm is easy to volatilize, 10 percent more is added on the basis of theoretical value to compensate.
And putting the prepared metal raw materials into an induction melting furnace to be melted in high-purity Ar. And (3) heating the alloy by induction until the raw materials are completely and uniformly melted, wherein the temperature of the melt is about 1550 ℃, and preparing the rapid-hardening alloy flakes by using the water-cooled copper roller speed, wherein the linear speed of the surface of the copper roller is 2 m/s.
And (3) placing the cast alloy flakes in a corundum crucible, carrying out primary heat treatment for 120min under the protection of argon at 750 ℃, and cooling in air. The diffusion source is Co powder and Mn powder, the average particle size of the Co powder is 3 mu m, and the weight of the Co powder is 3.0 wt% of the master alloy; the Mn powder had an average particle size of 2 μm and a weight of 1.5 wt% of the master alloy.
Mixing the two diffusion source powders, and adding anhydrous alcohol according to the volume ratio of 1:2 to mix into paste.
The diffusion source was double coated on top of the master alloy cast sheet to increase the weight by 4.5 wt% after drying.
And (3) placing the coated master alloy in a vacuum furnace under the protection of high-purity Ar for diffusion heat treatment. The diffusion heat treatment temperature is 750 ℃, and the heat treatment time is 10 h.
Subjecting the cast sheet to diffusion heat treatment to H at 25 deg.C2Performing medium treatment for 300min, and performing hydrogen explosion treatment. The furnace temperature is adjusted to 400 ℃, and the vacuum-pumping dehydrogenation treatment is carried out for 2.5 h. And (3) carrying out low-energy ball milling on the casting piece subjected to dehydrogenation treatment by using 6mm stainless steel balls, wherein the ball-material ratio is 10:1, the rotating speed of a planetary ball mill is set to be 150rpm, and the milling time is 2 h.
Nitriding the magnetic powder into Sm by using high-purity nitrogen gas at 400 ℃ for 30h through gas-solid reaction2Fe17N3。
Example 6
Rare earth Sm with the purity of 99.9%, pure Fe and pure Cu are used as raw materials, and the raw materials are mixed according to the following chemical formula: sm11.58Fe87.42Cu1.00. As Sm is easy to volatilize, 10 percent more is added on the basis of theoretical value to compensate.
And putting the prepared metal raw materials into an induction melting furnace to be melted in high-purity Ar. And (3) heating the alloy by induction until the raw materials are completely and uniformly melted, wherein the temperature of the melt is about 1550 ℃, and preparing the rapid-hardening alloy flakes by using the water-cooled copper roller speed, wherein the linear speed of the surface of the copper roller is 20 m/s.
And (3) placing the cast alloy flakes in a corundum crucible, carrying out primary heat treatment for 5min under the protection of argon at 1000 ℃, and cooling in air. The diffusion source is Co powder and Mn powder, the average particle size of the Co powder is 3 mu m, and the weight of the Co powder is 3.0 wt% of the master alloy; the Mn powder had an average particle size of 2 μm and a weight of 1.5 wt% of the master alloy.
Mixing the two diffusion source powders, and adding anhydrous alcohol according to the volume ratio of 1:2 to mix into paste.
The diffusion source was double coated on top of the master alloy cast sheet to increase the weight by 4.5 wt% after drying.
And (3) placing the coated master alloy in a vacuum furnace under the protection of high-purity Ar for diffusion heat treatment. The diffusion heat treatment temperature is 1000 ℃, and the heat treatment time is 1 h.
Placing the casting sheet subjected to diffusion heat treatment at 450 deg.C in H2Performing medium treatment for 60min, and performing hydrogen explosion treatment. The furnace temperature is increased to 650 ℃, and the vacuum-pumping dehydrogenation treatment is carried out for 1.5 h. And (3) carrying out low-energy ball milling on the casting piece subjected to dehydrogenation treatment by using 6mm stainless steel balls, wherein the ball-material ratio is 8:1, the rotating speed of a planetary ball mill is set to be 150rpm, and the milling time is 2 h.
Nitriding the magnetic powder into Sm by using high-purity nitrogen gas at 500 ℃ for 3h through gas-solid reaction2Fe17N3。
The results of the tests conducted in the same manner as in examples 1-4 show that the corrosion-resistant single crystal magnetic powders obtained in examples 5 and 6 also have good magnetic properties, oxidation resistance and corrosion resistance.
In summary, the corrosion-resistant single crystal magnetic powder provided by the application has the advantages of low cost, and high magnetic property, oxidation resistance and corrosion resistance. The preparation method is simple to operate, is beneficial to preparing the corrosion-resistant monocrystalline magnetic powder with better performance, and is suitable for industrial production. The obtained corrosion-resistant single crystal magnetic powder can be used for preparing anisotropic bonded permanent magnet materials.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (11)
1. The corrosion-resistant single crystal magnetic powder is characterized by comprising the following components in atomic percentage: raFe100-a-b-c-d-vM1bM2cM3dNv；
In the formula, R is rare earth element Sm or the combination of Sm and other rare earth elements, and a is more than or equal to 5 and less than or equal to 20; m1 is at least one element of Nb, Zr, Ga, Hf and Ta, and b is more than or equal to 0.2 and less than or equal to 5; m2 is at least one of Co, Al, Cr, Ni, Ti, V, Si, Mn, Mo and W, and c is more than or equal to 1 and less than or equal to 10; m3 is at least one element of Cu and Zn, d is more than or equal to 0.1 and less than or equal to 10; v is more than or equal to 0.5 and less than or equal to 20;
the corrosion-resistant single crystal magnetic powder is obtained by nitriding mother alloy magnetic powder, and the mother alloy magnetic powder consists of a first phase, a second phase and a third phase;
the first phase is composed of R, Fe, M1 and M2 and has Th2Zn17Or Th2Ni17A main phase of type structure;
the second type of phase is an R-rich auxiliary phase which is formed by a first auxiliary phase and a second auxiliary phase together, and the first auxiliary phase is a non-magnetic phase RM3 phase which is composed of R and M3 and has a melting point lower than 800 ℃; the second auxiliary phase is R (Fe, M1, M2) consisting of R, Fe, M1 and M22Phase or R (Fe, M1, M2)3Phase (1);
the third type of phase comprises R oxide and inevitable impurities;
the corrosion-resistant monocrystalline magnetic powder has a surface layer rich in M2 element, and the thickness of the surface layer rich in M2 element is 0.1-1 μ M.
2. The corrosion resistant single crystal magnetic powder of claim 1, wherein the constituent atoms of the first type of phase comprise 80-99 at% of the master alloy magnetic powder;
or, the constituent atoms of the RM3 phase account for 1-20 at% of the master alloy magnetic powder;
or, the R (Fe, M1, M2)2Phase or the R (Fe, M1, M2)3The constituent atoms of the phase account for 0.5-5 at% of the master alloy magnetic powder.
3. The corrosion-resistant single crystal magnetic powder according to claim 1, wherein when the thickness of the M2-rich surface layer of the corrosion-resistant single crystal magnetic powder is 0.2 μ M, the average content of Co in the surface layer is 7 to 25 at%, and the content of the remaining M2 element is 7 to 20 at%.
4. A method of producing a corrosion resistant single crystal magnetic powder according to any of claims 1 to 3, comprising the steps of:
using R, Fe, M1 and M3 as raw materials according to RaFe100-a-b-c-d-vM1bM2cM3dNvProportioning the elements except M2 and N, smelting and casting into cast sheets, and carrying out primary heat treatment;
mixing M2 powder with volatile organic solvent, spraying on the surface of the cast piece after the first heat treatment, drying, and sequentially carrying out second heat treatment, hydrogenation treatment, dehydrogenation treatment, powder preparation and nitridation.
5. The production method according to claim 4, wherein the thickness of the cast sheet is 50 μm to 1000 μm.
6. The method of claim 5, wherein the cast sheet has a thickness of less than 300 μm.
7. The method according to claim 5, wherein the M2 powder as a diffusion source has a particle size of less than 5 μ M during the second heat treatment.
8. The method of claim 7, wherein the M2 powder has an oxygen content of less than 2 wt%.
9. The method as claimed in claim 5, wherein the second heat treatment is performed at 750-1000 ℃ under argon protection for 1-10 h.
10. The method as claimed in claim 9, wherein the temperature of the second heat treatment is 800-950 ℃.
11. Use of a corrosion resistant single crystal magnetic powder according to any one of claims 1 to 3 for the preparation of anisotropically bonded permanent magnetic material and anisotropically sintered magnets.
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Application publication date: 20190125 Assignee: Huizhou xinhongda Intelligent Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980042099 Denomination of invention: A corrosion-resistant single crystal magnetic powder and its preparation method and application Granted publication date: 20200616 License type: Common License Record date: 20230919 Application publication date: 20190125 Assignee: Dongguan Yaluo Environmental Protection Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980042119 Denomination of invention: A corrosion-resistant single crystal magnetic powder and its preparation method and application Granted publication date: 20200616 License type: Common License Record date: 20230919 Application publication date: 20190125 Assignee: Liuzhou Xutang Environmental Protection Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980042110 Denomination of invention: A corrosion-resistant single crystal magnetic powder and its preparation method and application Granted publication date: 20200616 License type: Common License Record date: 20230919 |
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Application publication date: 20190125 Assignee: Guangzhou Hefu Technology Innovation and Development Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980047222 Denomination of invention: A corrosion-resistant single crystal magnetic powder and its preparation method and application Granted publication date: 20200616 License type: Common License Record date: 20231115 |
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Application publication date: 20190125 Assignee: Zhongshan Zircon Lighting Technology Co.,Ltd. Assignor: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Contract record no.: X2023980053729 Denomination of invention: A corrosion-resistant single crystal magnetic powder and its preparation method and application Granted publication date: 20200616 License type: Common License Record date: 20231222 |