Neodymium iron boron magnet material and its preparation method and application
Preparation of neodymium iron boron magnet materials through specific formulas and dual alloy processes solves the problems of both ultra-high residual magnetism and high coercivity in the existing technology, and realizes the preparation of high-performance magnets, which are suitable for rail transit, military equipment and other fields.
Patent Information
- Application Number
- CN202510614937.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-14
- Publication Date
- 2025-08-12
- Estimated Expiration
- 2045-05-14
AI Technical Summary
The existing neodymium iron boron magnet materials are difficult to have both ultra-high residual magnetism and high coercivity, and cannot meet the modern industry's demand for high-performance magnets.
A specific ratio of PrNd and Nd elemental alloys are used to combine with Al, Cu, Ga and other elements. Through a dual alloy process, combined with hydrogen breaking, airflow grinding, pressing, sintering and grain boundary diffusion, a neodymium iron boron magnet material with excellent magnetic properties is prepared.
The prepared neodymium iron boron magnet material has a high volume fraction, low content of impurity elements, and significantly improved residual magnetism and coercivity. The residual magnetism can reach more than 14.95kGs, the coercivity can reach more than 20.5kOe, and Hk/Hcj can reach more than 96%.
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Abstract
Description
Technical Field
[0001] The invention relates to a neodymium iron boron magnet material and a preparation method and application thereof. Background Art
[0002] Sintered NdFeB permanent magnets are widely used due to their ultra-high energy density, earning them the nickname "King of Magnets." Their high magnetic energy density, excellent temperature resistance, and excellent cost-effectiveness have led to their widespread application in my country's pillar industries and emerging sectors, such as rail transit, military equipment, wind power generation, low-altitude flight, artificial intelligence, aerospace, medical devices, and precision manufacturing. With the trend toward miniaturization, lightweighting, efficiency, and intelligent devices across various fields, the performance requirements of rare earth permanent magnets are increasing. The development of ultra-high-performance magnets has become a key focus of industry development, and the development of dual-high remanence and high coercivity magnets has become an increasingly popular topic. However, few dual-high magnets have been certified by authoritative organizations and publicly reported. Summary of the Invention
[0003] The technical problem to be solved by the present invention is to overcome the defect of existing magnetic materials that cannot achieve both ultra-high remanence and high coercivity, and to provide a neodymium iron boron magnet material, its preparation method, and application. The neodymium iron boron magnet material described in the present invention has excellent magnetic properties and can achieve both ultra-high remanence and high coercivity.
[0004] In order to achieve the above objectives, the present invention adopts the following technical solutions.
[0005] In a first aspect, the present invention provides a method for preparing a neodymium iron boron magnet material, comprising the following steps:
[0006] S1. Melting and casting the first alloy raw material composition and the second alloy raw material composition respectively to obtain a first alloy sheet and a second alloy sheet;
[0007] S2. Mixing the first alloy flakes and the second alloy flakes and then performing hydrogen crushing to obtain a coarse powder; or hydrogen crushing the first alloy flakes and the second alloy flakes separately to obtain a first coarse powder and a second coarse powder, and mixing the first coarse powder and the second coarse powder to obtain a coarse powder;
[0008] Then, the coarse powder is subjected to air jet milling to obtain fine powder;
[0009] S3, pressing the fine powder to obtain a green body;
[0010] S4, sintering the green body to obtain a NdFeB matrix;
[0011] S5, performing grain boundary diffusion on the NdFeB matrix to obtain the NdFeB magnet material;
[0012] The first alloy raw material composition and the second alloy raw material composition each independently include the following components:
[0013] R: 25.0-30.0 mass%, wherein R is a rare earth element, and R includes PrNd and Nd; the contents of PrNd and Nd satisfy the following: 0.03≤PrNd / (PrNd+Nd)≤0.84;
[0014] M: 0-3.0 mass%. Wherein, the content of M is not 0, and M includes Al, Cu, Ga, and X; the contents of Al, Cu, and Ga satisfy the following conditions: 0 mass.%<Al+Cu+Ga≤0.46 mass.%, and Al<Cu≤Ga; X includes one or more of Ti, Zr, Nb, W, and Mo;
[0015] B: 0.87-1.02mass.%;
[0016] And the balance of Fe and inevitable impurities;
[0017] mass.% represents the mass percentage of the total mass of the first alloy raw material composition or the second alloy raw material composition;
[0018] Furthermore, the mass ratio of the first alloy raw material composition to the second alloy raw material composition is (30-70): (30-70).
[0019] In the present invention, “PrNd / (PrNd+Nd)” represents the ratio of the PrNd content to the “sum of the PrNd and Nd contents”.
[0020] In the present invention, "Al+Cu+Ga" refers to the sum of the contents of Al, Cu and Ga.
[0021] In the present invention, “Al<Cu≤Ga” represents the magnitude relationship among the Al content, the Cu content, and the Ga content.
[0022] In the present invention, the PrNd may be a conventional PrNd alloy in the art. The mass ratio of the Pr element to the Nd element in the PrNd may be (10-25):(75-90), for example, 10:90, 20:80, or 25:75.
[0023] In some embodiments of the present invention, the contents of PrNd and Nd in the first alloy raw material composition satisfy the following relationship: 0.05≤PrNd / (PrNd+Nd)≤0.20.
[0024] In some preferred embodiments of the present invention, the contents of PrNd and Nd in the first alloy raw material composition satisfy the following ratio: 0.15≤PrNd / (PrNd+Nd)≤0.20.
[0025] In some specific embodiments of the present invention, in the first alloy raw material composition, the contents of PrNd and Nd satisfy: PrNd / (PrNd+Nd)=0.15 or PrNd / (PrNd+Nd)=0.08.
[0026] In some preferred embodiments of the present invention, the content of R in the first alloy raw material composition is 25.0-28.5 mass%.
[0027] In some specific embodiments of the present invention, the content of R in the first alloy raw material composition is 28.3 mass % or 29.4 mass %.
[0028] In some preferred embodiments of the present invention, the Nd content in the first alloy raw material composition is 23.0-25.0 mass%.
[0029] In some specific embodiments of the present invention, the Nd content in the first alloy raw material composition is 24.0 mass % or 27.0 mass %.
[0030] In some preferred embodiments of the present invention, the content of PrNd in the first alloy raw material composition is 3.0-5.0 mass%.
[0031] In some specific embodiments of the present invention, the content of PrNd in the first alloy raw material composition is 2.4 mass % or 4.3 mass %.
[0032] In some embodiments of the present invention, the content of B in the first alloy raw material composition is 0.89-1.02 mass%. For example, 0.98 mass%.
[0033] In some embodiments of the present invention, in the first alloy raw material composition, the R further comprises one or more of Dy, Tb, Pr, Y and Ho.
[0034] In some embodiments of the present invention, the content of M in the first alloy raw material composition is 1.0-2.0 mass%., for example, 1.25 mass%. or 1.42 mass%.
[0035] In some embodiments of the present invention, in the first alloy raw material composition, the M further comprises Co, and the content of the Co is 0.1-0.9 mass%.
[0036] In some preferred embodiments of the present invention, in the first alloy raw material composition, the M further comprises Co, and the content of the Co is 0.1-0.6 mass%.
[0037] In some specific embodiments of the present invention, in the first alloy raw material composition, the M further comprises Co, and the content of the Co is 0.6 mass % or 0.8 mass %.
[0038] In some embodiments of the present invention, the contents of Al, Cu and Ga in the first alloy raw material composition satisfy the following: 0.35 mass.%≤Al+Cu+Ga≤0.40 mass.%, for example, 0.37 mass.% or 0.39 mass.%.
[0039] In some embodiments of the present invention, the content of Al in the first alloy raw material composition is 0-0.05 mass%., preferably 0.01-0.03 mass%., for example, 0.01 mass%. or 0.03 mass%.
[0040] In some embodiments of the present invention, the content of Cu in the first alloy raw material composition is 0.1-0.2 mass%., for example, 0.16 mass%.
[0041] In some embodiments of the present invention, the Ga content in the first alloy raw material composition is 0.1-0.3 mass%., for example, 0.2 mass%.
[0042] In some embodiments of the present invention, the content of X in the first alloy raw material composition is 0.1-0.3 mass%., for example, 0.25 mass%. or 0.26 mass%.
[0043] In some embodiments of the present invention, in the first alloy raw material composition, X includes Ti and / or Zr.
[0044] In some embodiments of the present invention, in the first alloy raw material composition, X comprises Ti; wherein the content of Ti is preferably 0.05-0.1 mass%., for example, 0.06 mass%. or 0.09 mass%.
[0045] In some embodiments of the present invention, in the first alloy raw material composition, X includes Zr; wherein the content of Zr is preferably 0.15-0.2 mass%., such as 0.17 mass%. or 0.19 mass%.
[0046] In some embodiments of the present invention, in the first alloy raw material composition, X includes Ti and Zr; wherein the content of Ti is 0.05-0.1 mass %; and the content of Zr is 0.15-0.2 mass %.
[0047] In some specific embodiments of the present invention, in the first alloy raw material composition, X includes Ti and Zr; wherein the content of Ti is 0.09 mass.%; and the content of Zr is 0.17 mass.%.
[0048] In some specific embodiments of the present invention, in the first alloy raw material composition, X includes Ti and Zr; wherein the content of Ti is 0.06 mass.%; and the content of Zr is 0.19 mass.%.
[0049] In some embodiments of the present invention, the first alloy raw material composition includes the following components:
[0050] PrNd: 3.0-5.0 mass.%;
[0051] Nd: 23.0-25.0 mass.%;
[0052] Al: 0.01-0.03 mass.%;
[0053] Cu: 0.1-0.2 mass.%;
[0054] Ga: 0.1-0.3 mass.%;
[0055] Co: 0.1-0.6 mass.%;
[0056] Ti: 0.05-0.1 mass.%;
[0057] Zr: 0.15-0.2 mass.%;
[0058] B: 0.89-1.02 mass.%;
[0059] Fe: 67.0-75.0 mass.%;
[0060] The mass.% refers to the percentage of the total weight of the first alloy raw material composition.
[0061] In some specific embodiments of the present invention, the first alloy raw material composition includes the following components:
[0062] PrNd: 4.3 mass.%;
[0063] Nd: 24.0 mass.%;
[0064] Al: 0.03 mass.%;
[0065] Cu: 0.16 mass.%;
[0066] Ga: 0.2 mass.%;
[0067] Co: 0.6 mass.%;
[0068] Ti: 0.09 mass.%;
[0069] Zr: 0.17 mass.%;
[0070] B:0.98 mass.%;
[0071] Fe: 69.47 mass.%;
[0072] The mass.% refers to the percentage of the total weight of the first alloy raw material composition.
[0073] In some specific embodiments of the present invention, the first alloy raw material composition includes the following components:
[0074] PrNd: 2.4 mass.%;
[0075] Nd: 27.0 mass.%;
[0076] Al: 0.01 mass.%;
[0077] Cu: 0.16 mass.%;
[0078] Ga: 0.2 mass.%;
[0079] Co: 0.8 mass.%;
[0080] Ti: 0.06 mass.%;
[0081] Zr: 0.19 mass.%;
[0082] B:0.98 mass.%;
[0083] Fe: 68.2 mass.%;
[0084] The mass.% refers to the percentage of the total weight of the first alloy raw material composition.
[0085] In some embodiments of the present invention, the contents of PrNd and Nd in the second alloy raw material composition satisfy the following relationship: 0.05≤PrNd / (PrNd+Nd)≤0.20.
[0086] In some embodiments of the present invention, the contents of PrNd and Nd in the second alloy raw material composition satisfy the following relationship: 0.05≤PrNd / (PrNd+Nd)≤0.10.
[0087] In some specific embodiments of the present invention, in the second alloy raw material composition, the contents of PrNd and Nd satisfy: PrNd / (PrNd+Nd)=0.15 or PrNd / (PrNd+Nd)=0.08.
[0088] In some embodiments of the present invention, the content of R in the second alloy raw material composition is 27.0-30.0 mass%.
[0089] In some specific embodiments of the present invention, the content of R in the second alloy raw material composition is 28.3 mass % or 29.4 mass %.
[0090] In some embodiments of the present invention, the Nd content in the second alloy raw material composition is 26.0-27.0 mass%.
[0091] In some specific embodiments of the present invention, the Nd content in the second alloy raw material composition is 24.0 mass % or 27.0 mass %.
[0092] In some embodiments of the present invention, the content of PrNd in the second alloy raw material composition is 1.0-2.5 mass%.
[0093] In some specific embodiments of the present invention, the content of PrNd in the second alloy raw material composition is 2.4 mass % or 4.3 mass %.
[0094] In some embodiments of the present invention, the content of B in the second alloy raw material composition is 0.87-1.0 mass%., for example, 0.98 mass%.
[0095] In some embodiments of the present invention, in the second alloy raw material composition, the R further comprises one or more of Dy, Tb, Pr, Y and Ho.
[0096] In some embodiments of the present invention, the content of M in the second alloy raw material composition is 1.0-2.0 mass%., for example, 1.25 mass%. or 1.42 mass%.
[0097] In some embodiments of the present invention, in the second alloy raw material composition, the M further comprises Co, and the content of the Co is 0.1-0.9 mass%.
[0098] In some preferred embodiments of the present invention, in the second alloy raw material composition, the M further comprises Co, and the content of the Co is 0.7-0.9 mass%.
[0099] In some specific embodiments of the present invention, in the second alloy raw material composition, the M further comprises Co, and the content of the Co is 0.6 mass % or 0.8 mass %.
[0100] In some embodiments of the present invention, the contents of Al, Cu and Ga in the second alloy raw material composition satisfy the following: 0.35 mass.%≤Al+Cu+Ga≤0.40 mass.%, for example, 0.37 mass.% or 0.39 mass.%.
[0101] In some embodiments of the present invention, the content of Al in the second alloy raw material composition is 0-0.05 mass%., preferably 0.01-0.03 mass%., for example, 0.01 mass%. or 0.03 mass%.
[0102] In some embodiments of the present invention, the content of Cu in the second alloy raw material composition is 0.1-0.2 mass%., for example, 0.16 mass%.
[0103] In some embodiments of the present invention, the Ga content in the second alloy raw material composition is 0.1-0.3 mass%., for example, 0.2 mass%.
[0104] In some embodiments of the present invention, the content of X in the second alloy raw material composition is 0.1-0.3 mass%., for example, 0.25 mass%. or 0.26 mass%.
[0105] In some embodiments of the present invention, in the second alloy raw material composition, X includes Ti and / or Zr.
[0106] In some embodiments of the present invention, in the second alloy raw material composition, X comprises Ti; wherein the content of Ti is preferably 0.05-0.1 mass%., for example, 0.06 mass%. or 0.09 mass%.
[0107] In some embodiments of the present invention, in the second alloy raw material composition, X includes Zr; wherein the content of Zr is preferably 0.15-0.2 mass%., such as 0.17 mass%. or 0.19 mass%.
[0108] In some embodiments of the present invention, in the second alloy raw material composition, X includes Ti and Zr; wherein the content of Ti is 0.05-0.1 mass %; and the content of Zr is 0.15-0.2 mass %.
[0109] In some specific embodiments of the present invention, in the second alloy raw material composition, X includes Ti and Zr; wherein the content of Ti is 0.09 mass.%; and the content of Zr is 0.17 mass.%.
[0110] In some specific embodiments of the present invention, in the second alloy raw material composition, X includes Ti and Zr; wherein the content of Ti is 0.06 mass.%; and the content of Zr is 0.19 mass.%.
[0111] In some embodiments of the present invention, the second alloy raw material composition includes the following components:
[0112] PrNd: 1.0-2.5 mass.%;
[0113] Nd: 26.0-27.0 mass.%;
[0114] Al: 0.01-0.03 mass.%;
[0115] Cu: 0.1-0.2 mass.%;
[0116] Ga: 0.1-0.3 mass.%;
[0117] Co: 0.7-0.9 mass.%;
[0118] Ti: 0.05-0.1 mass.%;
[0119] Zr: 0.15-0.2 mass.%;
[0120] B: 0.87-1.0 mass.%;
[0121] Fe: 65.0-73.0 mass.%;
[0122] The mass.% refers to the percentage of the total weight of the second alloy raw material composition.
[0123] In some specific embodiments of the present invention, the second alloy raw material composition includes the following components:
[0124] PrNd: 2.4 mass.%;
[0125] Nd: 27.0 mass.%;
[0126] Al: 0.01 mass.%;
[0127] Cu: 0.16 mass.%;
[0128] Ga: 0.2 mass.%;
[0129] Co: 0.8 mass.%;
[0130] Ti: 0.06 mass.%;
[0131] Zr: 0.19 mass.%;
[0132] B:0.98 mass.%;
[0133] Fe: 68.2 mass.%;
[0134] The mass.% refers to the percentage of the total weight of the second alloy raw material composition.
[0135] In some specific embodiments of the present invention, the second alloy raw material composition includes the following components:
[0136] PrNd: 4.3 mass.%;
[0137] Nd: 24.0 mass.%;
[0138] Al: 0.03 mass.%;
[0139] Cu: 0.16 mass.%;
[0140] Ga: 0.2 mass.%;
[0141] Co: 0.6 mass.%;
[0142] Ti: 0.09 mass.%;
[0143] Zr: 0.17 mass.%;
[0144] B:0.98 mass.%;
[0145] Fe: 69.47 mass.%;
[0146] The mass.% refers to the percentage of the total weight of the second alloy raw material composition.
[0147] In some embodiments of the present invention, the first alloy raw material composition includes the following components:
[0148] PrNd: 3.0-5.0 mass.%;
[0149] Nd: 23.0-25.0 mass.%;
[0150] Al: 0.01-0.03 mass.%;
[0151] Cu: 0.1-0.2 mass.%;
[0152] Ga: 0.1-0.3 mass.%;
[0153] Co: 0.1-0.6 mass.%;
[0154] Ti: 0.05-0.1 mass.%;
[0155] Zr: 0.15-0.2 mass.%;
[0156] B: 0.89-1.02 mass.%;
[0157] Fe: 67.0-75.0 mass.%;
[0158] The mass.% is the percentage of the total weight of the first alloy raw material composition;
[0159] Furthermore, the second alloy raw material composition includes the following components in weight percentage:
[0160] PrNd: 1.0-2.5 mass.%;
[0161] Nd: 26.0-27.0 mass.%;
[0162] Al: 0.01-0.03 mass.%;
[0163] Cu: 0.1-0.2 mass.%;
[0164] Ga: 0.1-0.3 mass.%;
[0165] Co: 0.7-0.9 mass.%;
[0166] Ti: 0.05-0.1 mass.%;
[0167] Zr: 0.15-0.2 mass.%;
[0168] B: 0.87-1.0 mass.%;
[0169] Fe: 65.0-73.0 mass.%;
[0170] The mass.% is the percentage of the total weight of the second alloy raw material composition;
[0171] Wherein, the mass ratio of the first alloy raw material composition to the second alloy raw material composition is (30-50): (50-70).
[0172] In some specific embodiments of the present invention, the first alloy raw material composition includes the following components:
[0173] PrNd: 4.3 mass.%;
[0174] Nd: 24.0 mass.%;
[0175] Al: 0.03 mass.%;
[0176] Cu: 0.16 mass.%;
[0177] Ga: 0.2 mass.%;
[0178] Co: 0.6 mass.%;
[0179] Ti: 0.09 mass.%;
[0180] Zr: 0.17 mass.%;
[0181] B:0.98 mass.%;
[0182] Fe: 69.47 mass.%;
[0183] The mass.% is the percentage of the total weight of the first alloy raw material composition;
[0184] Furthermore, the second alloy raw material composition includes the following components:
[0185] PrNd: 2.4 mass.%;
[0186] Nd: 27.0 mass.%;
[0187] Al: 0.01 mass.%;
[0188] Cu: 0.16 mass.%;
[0189] Ga: 0.2 mass.%;
[0190] Co: 0.8 mass.%;
[0191] Ti: 0.06 mass.%;
[0192] Zr: 0.19 mass.%;
[0193] B:0.98 mass.%;
[0194] Fe: 68.2 mass.%;
[0195] The mass.% refers to the percentage of the total weight of the second alloy raw material composition.
[0196] In some embodiments of the present invention, the mass ratio of the first alloy raw material composition to the second alloy raw material composition is (30-50):(50-70), for example, 40:60.
[0197] In the present invention, in step S1, the smelting and the casting can be performed in a conventional manner in the art, and can be performed in a continuous furnace.
[0198] In some embodiments of the present invention, in step S1, the smelting temperature is 1400-1500°C, for example, 1445°C or 1451°C.
[0199] In some embodiments of the present invention, in step S1, the casting process parameters include: copper roller speed 20-30r / min, supercooling 160-180°C, casting flow 140-145cm 3 / s.
[0200] In some specific embodiments of the present invention, in step S1, the casting process parameters include: copper roller speed 28r / min, supercooling 170°C, casting flow 140.3cm 3 / s.
[0201] In some specific embodiments of the present invention, in step S1, after the casting is completed, the temperature is cooled to 40-60°C, for example, 45°C.
[0202] In some embodiments of the present invention, in step S1, the thickness of the first alloy sheet is 0.20-0.30 mm, for example, 0.26 mm, 0.27 mm or 0.28 mm.
[0203] In some embodiments of the present invention, in step S1, the width of the columnar crystals of the first alloy sheet is 1.0-4.0 μm, preferably 2.0-3.0 μm, such as 2.7 μm or 2.8 μm.
[0204] In some embodiments of the present invention, in step S1, the thickness of the second alloy sheet is 0.20-0.30 mm, for example, 0.27 mm or 0.28 mm.
[0205] In some embodiments of the present invention, in step S1, the width of the columnar crystals of the second alloy sheet is 1.0-4.0 μm, preferably 2.0-3.0 μm, such as 2.6 μm, 2.7 μm or 2.8 μm.
[0206] In some embodiments of the present invention, step S1 further includes: performing a gas atomization treatment on the first alloy sheet using PrNd. The gas atomization treatment can fill and repair the rare earth elements at the grain boundaries of the first alloy sheet to a certain extent, thereby achieving both a main phase with an ultra-high main phase volume fraction and a relatively continuous grain boundary phase structure in the first alloy sheet. This can significantly reduce the risk of powder oxidation during subsequent powder making and prevent subsequent densification failure during sintering.
[0207] Preferably, the atomization treatment comprises: performing physical vapor deposition on the first alloy sheet using PrNd; the temperature of the physical vapor deposition is 600-800° C., and the time of the physical vapor deposition is 4-20 h.
[0208] Preferably, after the gas atomization treatment, the PrNd weight gain of the first alloy sheet is 0.5%-1.0%, for example, 0.75%. The PrNd weight gain refers to the percentage of the mass increase of PrNd in the first alloy sheet after the gas atomization treatment relative to the mass of the first alloy sheet before the gas atomization treatment.
[0209] In the present invention, in step S2, the hydrogen cracking can be performed using a continuous hydrogen cracking furnace.
[0210] In some embodiments of the present invention, in step S2, the reaction pressure of the hydrogen cracking is 0.08-0.1 MPa, for example, 0.098 MPa.
[0211] In some embodiments of the present invention, in step S2, during the hydrogen cracking process, the temperature of the dehydrogenation treatment is 500-600°C, for example, 570°C.
[0212] In the present invention, in step S2, the air flow milling can be performed using a multi-nozzle opposing fluidized bed air flow mill.
[0213] In some specific embodiments of the present invention, in step S2, the parameter settings of the jet mill include: the classifying wheel gap maintains the disc cleaning pressure of 70Kpa, the classifying wheel speed is 3490r / min, the grinding chamber mass is 58kg, the grinding pressure is 0.57MPa, and the side spray pressure is 25Kpa.
[0214] In some embodiments of the present invention, in step S2, a powder additive is added to the coarse powder.
[0215] Preferably, the powder additive is added in an amount of 1.7 g per kg of coarse powder.
[0216] In some embodiments of the present invention, in step S2, a powder additive is added to the fine powder.
[0217] Preferably, the powder additive is added in an amount of 0.8 g per kg of coarse powder.
[0218] In some embodiments of the present invention, in step S2, a powder additive is added to the coarse powder before the jet milling, and a powder additive is added to the fine powder obtained by the jet milling.
[0219] In some embodiments of the present invention, the powder additive is added via an online dosing system.
[0220] In some specific embodiments of the present invention, the average particle size SMD of the fine powder obtained by the jet mill is 2.0-2.5 μm, for example, 2.2 μm.
[0221] In the present invention, adding powder additives during the airflow milling process is a conventional operation in the field, which can prevent particle agglomeration, control particle size distribution, improve grinding efficiency, reduce equipment wear, protect the grinding cavity, prevent oxidation or hydrolysis, improve product stability, and improve downstream process adaptability.
[0222] In the present invention, in step S3, the pressing can be performed in a conventional manner in the art.
[0223] In some embodiments of the present invention, in step S3, the pressing is performed using an all-electric floating press and a modular mold.
[0224] In some embodiments of the present invention, in step S3, the pressing comprises orientation pressing.
[0225] Among them, preferably, the process parameters of the orientation pressing include: pressing orientation direction dimension 55mm, pressing blank gram weight 780g, mold forming position minimum orientation field >1.95T, and the oxygen content throughout the pressing process is less than 50ppm.
[0226] In some embodiments of the present invention, in step S3, pre-pressing is further included before the orientation pressing.
[0227] Preferably, the pre-pressing is a two-stage pre-pressing, including:
[0228] The first section: pre-pressed density is 2.2g / cm 3 , suppressing current 20A;
[0229] Second stage: pre-pressed density 3.0 g / cm 3 , suppressing current 100A.
[0230] Preferably, the orientation pressing satisfies: pressing density 4.0 g / cm 3 , suppressing current 210A.
[0231] Preferably, the holding time of the orientation pressing is 1-3s, for example, 2s.
[0232] In some embodiments of the present invention, in step S3, the pressing further comprises isostatic pressing.
[0233] Preferably, the isostatic pressing pressure is 200 MPa.
[0234] In the present invention, in step S4, the sintering can be performed in a conventional manner in the art.
[0235] In some embodiments of the present invention, in step S4, the sintering uses one or more of a high-density graphite box, a molybdenum box, a tungsten box, and a carbon ceramic box; preferably, the sintering uses a combination box of a high-density graphite box and a molybdenum box.
[0236] In some embodiments of the present invention, in step S4, the sintering uses a high-density graphite box and a molybdenum box combination box.
[0237] In some embodiments of the present invention, in step S4, the sintering is performed in a gradient temperature increase manner.
[0238] In some embodiments of the present invention, in step S4, the sintering process includes: keeping warm at 100-300°C, 350-450°C, 550-600°C, 620-680°C, 700-780°C, 810-980°C and 1000-1200°C respectively.
[0239] Preferably, the holding time at 1000-1200°C is 4-15h.
[0240] In some specific embodiments of the present invention, in step S4, the sintering process includes: keeping warm at 250°C, 420°C, 580°C, 640°C, 760°C, 830°C and 1085°C, with the keeping time being 1.5h, 2.5h, 1.5h, 2.5h, 2h, 3h and 9h respectively.
[0241] In some embodiments of the present invention, in step S4, the heating rate during the sintering process is 1-3°C / min, for example, 1.5°C / min.
[0242] In some embodiments of the present invention, in step S4, aging treatment is further performed after sintering, wherein preferably, the aging treatment is a two-stage aging treatment.
[0243] In some embodiments of the present invention, the two-stage aging treatment comprises: keeping at 880-930° C. for 3-10 hours, and then keeping at 450-550° C. for 3-10 hours.
[0244] In some specific embodiments of the present invention, the two-stage aging treatment includes: keeping at 905° C. for 3 hours and then keeping at 505° C. for 5 hours.
[0245] In the present invention, in step S5, the grain boundary diffusion can be performed using conventional methods in the art.
[0246] In some embodiments of the present invention, in step S5, the grain boundary diffusion operation includes: applying a diffusion source to the surface of the NdFeB substrate and performing heat treatment.
[0247] In some embodiments of the present invention, the applying method is screen printing, spraying or magnetron sputtering.
[0248] In some embodiments of the present invention, the grain boundary diffusion is performed using a staged heat treatment process.
[0249] In some embodiments of the present invention, in step S5, the grain boundary diffusion is performed using a staged heat treatment process, including:
[0250] The first stage: the holding temperature is 880-950℃, and the holding time is 5-36h;
[0251] The second stage: the insulation temperature is 450-550℃ and the time is 3-10h.
[0252] In some specific embodiments of the present invention, in step S5, the staged heat treatment process for grain boundary diffusion includes:
[0253] The first stage: keep the temperature at 900℃, 908℃, 916℃ and 905℃ for 4h, 4h, 3h and 5h respectively; after the temperature is kept at 900℃, 908℃, 916℃ and 905℃ respectively; cool the temperature to below 70℃ with argon air;
[0254] The second stage: heat to 505℃ and keep warm for 5h.
[0255] In some embodiments of the present invention, in step S5, the vacuum degree during the grain boundary diffusion process is controlled to be 10 -1 -10 -4 Pa.
[0256] In some embodiments of the present invention, in step S5, the diffusion source of the grain boundary diffusion includes a heavy rare earth element RH, and the RH includes Dy and / or Tb.
[0257] In some embodiments of the present invention, the mass of the heavy rare earth element RH in the diffusion source accounts for 0.1-0.8 mass %, for example, 0.5 mass %, of the NdFeB matrix.
[0258] In some embodiments of the present invention, the diffusion source is one or more of a simple substance, a fluoride, a hydride, and an alloy of RH.
[0259] In some specific embodiments of the present invention, the diffusion source is a (Tb-Co-Fe-Cu-PrNd)H alloy; wherein the mass ratio of Tb, Co, Fe, Cu and PrNd is 76:4:4:8:8.
[0260] In a second aspect, the present invention provides a NdFeB magnet material, which is prepared using the method for preparing the NdFeB magnet material as described above.
[0261] In some embodiments of the present invention, the volume fraction of the main phase grains in the NdFeB magnet material is greater than 95.8%, for example, 96.1%, 97.51% or 97.59%.
[0262] In some embodiments of the present invention, the carbon content in the NdFeB magnet material is ≤600 ppm, the oxygen content is ≤400 ppm, and the nitrogen content is ≤210 ppm.
[0263] In a third aspect, the present invention further provides a use of the aforementioned NdFeB magnet material as a magnetic device.
[0264] The NdFeB magnet material is used as a magnetic device in many fields such as rail transportation, military equipment, wind power generation, low-altitude flight, artificial intelligence, aerospace, medical equipment, precision manufacturing, etc.
[0265] In the present invention, the symbols of each element have conventional meanings in the art, specifically: "Pr" for praseodymium, "Nd" for neodymium, "Dy" for dysprosium, "Tb" for terbium, "Y" for yttrium, "Ho" for holmium, "Al" for aluminum, "Cu" for copper, "Ga" for gallium, "Co" for cobalt, "Ti" for titanium, "Zr" for zirconium, "Nb" for niobium, "W" for tungsten, "Mo" for molybdenum, "Fe" for iron, and "B" for boron.
[0266] In the present invention, unless otherwise specified, an element appearing alone means a simple substance of the element.
[0267] On the basis of conforming to the common sense in this field, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.
[0268] The reagents and raw materials used in the present invention are commercially available.
[0269] The positive progress effect of the present invention is:
[0270] The present invention utilizes a unique formula design, combining a PrNd alloy and a single Nd element in specific ratios, with controlled amounts of elements such as Al, Cu, and Ga. This dual-alloy process improves production stability, resulting in uniform, high-quality microscopic grain boundaries and ultimately achieving a further breakthrough in the performance of NdFeB magnet materials. This NdFeB magnet material boasts a primary phase grain volume fraction exceeding 95.8%, significantly reduced levels of impurity elements such as carbon, oxygen, and nitrogen, and exhibits excellent magnetic properties, combining ultra-high remanence with high coercivity. Specifically, the remanence can reach over 14.95 kGs, the coercivity can reach over 20.5 kOe, and the Hk / Hcj ratio can reach over 96%. DETAILED DESCRIPTION
[0271] The present invention is further illustrated by way of examples below, but the present invention is not limited to the scope of the examples. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.
[0272] The sources of the following reagents and instruments used in the following examples are shown in Table 1:
[0273] Table 1
[0274]
[0275] Example 1
[0276] S1. Melting and Casting
[0277] (1) Preparation of the first alloy sheet: The raw materials were weighed and mixed according to Table 2, smelted in a continuous furnace at 1451°C, and cast on a copper roller (copper roller speed 28 r / min, undercooling 170°C, casting flow 140.3 cm 3 / s), cooled to 45°C and taken out of the furnace to obtain a first alloy sheet. The specific thickness and columnar crystal width of the first alloy sheet are shown in Table 3; the first alloy sheet was placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for standby use.
[0278] The first alloy sheet was subjected to gas atomization treatment. The gas atomization treatment involved physical vapor deposition of a PrNd alloy (Pr:Nd in a ratio of 20:80) at 690°C for 8 hours, resulting in a PrNd weight gain of 0.75%. The PrNd weight gain refers to the percentage increase in PrNd mass in the first alloy sheet after gas atomization treatment compared to the mass of the first alloy sheet before gas atomization treatment. The gas atomization treatment can fill and repair the grain boundaries of the first alloy sheet to a certain extent.
[0279] (2) Preparation of the second alloy sheet: The raw materials were weighed and mixed according to Table 2, smelted in a continuous furnace at 1445°C, and cast on a copper roller (copper roller speed 28 r / min, undercooling 170°C, casting flow 140.3 cm 3 / s), cooled to 45°C and taken out of the furnace to obtain a second alloy sheet. The specific thickness and columnar crystal width of the second alloy sheet are shown in Table 3; the second alloy sheet was placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for standby use.
[0280] S2, flour making
[0281] (1) Hydrogen rupture:
[0282] The first alloy sheet and the second alloy sheet were respectively subjected to hydrogen cracking treatment in a continuous hydrogen cracking furnace with a reaction pressure of 0.098 MPa and dehydrogenation treatment at 570°C. The sheets were cooled to below 40°C and taken out of the furnace in a fully sealed manner to obtain first coarse powder and second coarse powder; the first coarse powder and the second coarse powder were mixed (mass ratio of 40:60) to obtain coarse powder, which was loaded into a coarse powder tank that had been fully deoxygenated to below 50pm in advance, and filled with argon to maintain pressure.
[0283] Powder additives were added to the obtained coarse powder. The powder additives consisted of Tianjin agent Yuesheng agent YSH-01, Dongyang agent YKJ-10 and 120# gasoline in a mass ratio of 1:1:1.8. The addition ratio was 1.7 g of powder additive per kg of coarse powder. The mixed powders were stirred for 120 minutes.
[0284] (2) Jet mill:
[0285] A multi-nozzle, opposed-type fluidized bed jet mill was used for grinding. First, the bottom material in the mill was completely blown out to prevent any impurities from entering. Argon was then used to fully deoxygenate the mill to below 2 ppm before the coarse powder was loaded. The mill was then started, with key parameters set to maintain a cleaning pressure of 70 kPa for the separation wheel gap, a separation wheel speed of 3490 r / min, a mill chamber mass of 58 kg, a grinding pressure of 0.57 MPa, and a side spray pressure of 25 kPa. A highly spherical fine powder with an average particle size (SMD) of approximately 2.2 μm was produced. The main phase of the fine powder produced by this process exhibited a high degree of rare earth-rich coating.
[0286] During the grinding process, an online dosing system is used to add powder additives (with the same composition as the aforementioned powder additives) to the fine powder receiving tank at a ratio of 0.8 g of powder additive per kg of fine powder, and the powders are mixed and stirred for 120 minutes.
[0287] The fine powder after air jet milling is screened, and the oxygen content during the whole screening process is less than 50ppm.
[0288] S3, Suppression
[0289] A fully electric floating press and a combined mold are used to orient the fine powder. The pressing orientation direction dimension is 55mm, the pressed blank weighs 780g, the minimum orientation field at the mold forming position is >1.95T, and the oxygen content during the entire pressing process is <50ppm.
[0290] The pressing process adopts a two-stage pre-pressing and pre-orientation process design, with the pre-pressing density of 2.2g / cm 3 , pressing current 20A, and pre-pressing density 3.0 g / cm 3 , pressing current 100A; then start pressing, pressing density 4.0 g / cm 3 , pressing current 210A, and appropriately extending the holding pressure orientation time (holding pressure orientation time is 2s) to obtain a higher orientation degree.
[0291] The obtained compact was isostatically pressed at a pressure of 200 MPa.
[0292] S4, sintering
[0293] A high-density graphite box and a molybdenum box are used for sintering. Before use, the blank obtained in step S3 is placed in the box and evacuated. The temperature is raised at a rate of approximately 1.5°C / min, and the blanks are kept at 250°C, 420°C, 580°C, 640°C, 760°C, 830°C, and 1085°C for 1.5 hours, 2.5 hours, 1.5 hours, 2.5 hours, 2 hours, 3 hours, and 9 hours, respectively. After sintering, two-stage aging treatments are performed in vacuum (905°C for 3 hours and 505°C for 5 hours) to obtain the NdFeB matrix.
[0294] S5, Grain Boundary Diffusion
[0295] The NdFeB substrate was processed into a 30*12*3.5mm sample and then surface activated by degreasing and ultrasonic cleaning. A diffusion film was then attached to the NdFeB substrate using screen printing. The composition of the diffusion film is (Tb-Co-Fe-Cu-PrNd)H (Tb, Co, Fe, Cu, and PrNd in a mass ratio of 76:4:4:8:8), with Tb accounting for 0.5 mass% of the NdFeB substrate.
[0296] Diffusion is carried out using a staged heat treatment process, specifically:
[0297] The first stage: keep the temperature at 900℃, 908℃, 916℃ and 905℃ for 4h, 4h, 3h and 5h respectively; after the temperature is kept at 900℃, 908℃, 916℃ and 905℃ respectively; cool the temperature to below 70℃ with argon air;
[0298] The second stage: heating to 505°C, keeping the temperature for 5 hours, cooling to below 60°C with nitrogen, and taking out of the furnace to obtain NdFeB magnet material.
[0299] Example 2
[0300] S1. Melting and Casting
[0301] (1) Preparation of the first alloy sheet: Weigh and mix the raw materials according to Table 2, melt them in a continuous furnace at 1445°C, and cast them on a copper roller (copper roller speed 28 r / min, supercooling 170°C, casting flow 140.3 cm 3 / s), cooled to 45°C and taken out of the furnace to obtain a first alloy sheet. The specific thickness and columnar crystal width of the first alloy sheet are shown in Table 3; the first alloy sheet was placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for standby use.
[0302] The first alloy sheet was subjected to gas atomization treatment. The gas atomization treatment involved physical vapor deposition of a PrNd alloy (Pr:Nd in a ratio of 20:80) at 690°C for 8 hours, resulting in a PrNd weight gain of 0.75%. The PrNd weight gain refers to the percentage increase in PrNd mass in the first alloy sheet after gas atomization treatment compared to the mass of the first alloy sheet before gas atomization treatment. The gas atomization treatment can fill and repair the grain boundaries of the first alloy sheet to a certain extent.
[0303] (2) Preparation of the second alloy sheet: The raw materials were weighed and mixed according to Table 2, smelted in a continuous furnace at 1445°C, and cast on a copper roller (copper roller speed 28 r / min, undercooling 170°C, casting flow 140.3 cm 3 / s), cooled to 45°C and removed from the furnace to produce a second alloy sheet. The specific thickness and columnar crystal width of the second alloy sheet are shown in Table 3. The second alloy sheet was placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for future use. The second alloy sheet was not subjected to atomization treatment.
[0304] The operations and conditions of steps S2, S3, S4 and S5 are the same as those in Example 1, and a NdFeB magnet material is obtained.
[0305] Example 3
[0306] S1. Melting and Casting
[0307] (1) Preparation of the first alloy sheet: The raw materials were weighed and mixed according to Table 2, smelted in a continuous furnace at 1451°C, and cast on a copper roller (copper roller speed 28 r / min, undercooling 170°C, casting flow 140.3 cm 3 / s), cooled to 45°C and taken out of the furnace to obtain a first alloy sheet. The specific thickness and columnar crystal width of the first alloy sheet are shown in Table 3; the first alloy sheet was placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for standby use.
[0308] The first alloy sheet was subjected to gas atomization treatment. The gas atomization treatment involved physical vapor deposition of a PrNd alloy (Pr:Nd in a ratio of 20:80) at 690°C for 8 hours, resulting in a PrNd weight gain of 0.75%. The PrNd weight gain refers to the percentage increase in PrNd mass in the first alloy sheet after gas atomization treatment compared to the mass of the first alloy sheet before gas atomization treatment. The gas atomization treatment can fill and repair the grain boundaries of the first alloy sheet to a certain extent.
[0309] (2) Preparation of the second alloy sheet: The raw materials were weighed and mixed according to Table 2, smelted in a continuous furnace at 1451°C, and cast on a copper roller (copper roller speed 28 r / min, undercooling 170°C, casting flow 140.3 cm 3 / s), cooled to 45°C and taken out of the furnace to obtain a second alloy sheet. The specific thickness and columnar crystal width of the second alloy sheet are shown in Table 3; the second alloy sheet was placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for standby use.
[0310] The operations and conditions of steps S2, S3, S4 and S5 are the same as those in Example 1.
[0311] Comparative Example 1
[0312] This comparative example is based on Example 2, but does not use the dual alloy method. In step S1, the first alloy raw material composition and the second alloy raw material composition are first mixed, and then melted and cast. Specifically:
[0313] S1. Melting and Casting
[0314] (1) Preparation of alloy flakes: The raw material components of the first alloy raw material composition and the second alloy raw material composition of Example 2 in Table 2 were weighed, the first alloy raw material composition and the second alloy raw material composition were mixed in a mass ratio of 40:60, smelted in a continuous furnace at 1445°C, and cast on a copper roller (copper roller speed 28 r / min, undercooling 170°C, casting flow rate 140.3 cm 3 / s), cooled to 45℃ and taken out of the furnace to obtain alloy sheets; the alloy sheets were placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for standby use.
[0315] The alloy sheet was subjected to gas atomization treatment. Physical vapor deposition of a PrNd alloy (Pr:Nd in a ratio of 20:80) was performed at 690°C for 8 hours, resulting in a PrNd weight gain of 0.75%. The PrNd weight gain refers to the percentage of PrNd mass increase after gas atomization compared to the pre-treatment mass of the alloy sheet. Gas atomization can fill and repair the grain boundaries of the alloy sheet to a certain extent.
[0316] S2, flour making
[0317] (1) Hydrogen rupture:
[0318] The alloy sheets were subjected to hydrogen cracking treatment in a continuous hydrogen cracking furnace with a reaction pressure of 0.098 MPa and dehydrogenation treatment at 570°C. They were cooled to below 40°C and taken out of the furnace in a fully sealed manner to obtain coarse powder, which was loaded into a coarse powder tank that had been fully deoxygenated to below 50pm in advance and filled with argon to maintain pressure.
[0319] Powder additives were added to the obtained coarse powder. The powder additives consisted of Tianjin agent Yuesheng agent YSH-01, Dongyang agent YKJ-10 and 120# gasoline in a mass ratio of 1:1:1.8. The addition ratio was 1.7 g of powder additive per kg of coarse powder. The mixed powders were stirred for 120 minutes.
[0320] The operations and conditions of steps S2 (2), S3, S4 and S5 are the same as those in Example 1, and a NdFeB magnet material is obtained.
[0321] Comparative Example 2
[0322] This comparative example is based on Example 3, but does not use the dual alloy method. In step S1, the first alloy raw material composition and the second alloy raw material composition are first mixed, and then melted and cast. Specifically:
[0323] S1. Melting and Casting
[0324] (1) Preparation of alloy flakes: The raw material components of the first alloy raw material composition and the second alloy raw material composition of Example 3 in Table 2 were weighed, the first alloy raw material composition and the second alloy raw material composition were mixed in a mass ratio of 40:60, smelted in a continuous furnace at 1451°C, and cast on a copper roller (copper roller speed 28 r / min, undercooling 170°C, casting flow rate 140.3 cm 3 / s), cooled to 45℃ and taken out of the furnace to obtain alloy sheets; the alloy sheets were placed in a sealed stainless steel barrel, fully deoxygenated with argon gas, and then sealed for standby use.
[0325] The alloy sheet was subjected to gas atomization treatment. Physical vapor deposition of a PrNd alloy (Pr:Nd in a ratio of 20:80) was performed at 690°C for 8 hours, resulting in a PrNd weight gain of 0.75%. The PrNd weight gain refers to the percentage of PrNd mass increase after gas atomization compared to the pre-treatment mass of the alloy sheet. Gas atomization can fill and repair the grain boundaries of the alloy sheet to a certain extent.
[0326] The operations and conditions of steps S2, S3, S4 and S5 are the same as those in Comparative Example 1, and a NdFeB magnet material is obtained.
[0327] Table 2
[0328]
[0329] Note: 1 The mass proportion of Pr in PrNd is 20%.
[0330] Table 3
[0331]
[0332] The columnar crystal width of the first and second alloy flakes was measured as follows: After polishing the alloy flakes, microscopic photographs were taken using a scanning electron microscope (SEM). The columnar crystal width was analyzed and calculated using the streak method using ImageJ software. As shown in Table 3, the alloy flakes in this embodiment were less than 0.3 mm thick and had a columnar crystal width of less than 3 μm.
[0333] Effect Example 1: Material Composition Determination and Structural Characterization
[0334] (1) Compositions of NdFeB magnet material (after diffusion) and NdFeB matrix (before diffusion)
[0335] The components of the NdFeB matrix (before diffusion) and the NdFeB magnet material (after diffusion) in Examples 1-3 and Comparative Examples 1-2 were measured using a high-frequency inductively coupled plasma optical emission spectrometer (ICP-OES) using conventional methods in the art. The measurement results are shown in Tables 4 and 5, respectively.
[0336] Table 4 Content of each component in NdFeB matrix
[0337]
[0338] Table 5 Content of each component of NdFeB magnet material
[0339]
[0340] (2) Impurity element content test
[0341] The NdFeB magnet materials (after diffusion) obtained in Examples 1-3 and Comparative Examples 1-2 were crushed into small particles, and carbon and oxygen and nitrogen were tested and analyzed using a carbon-sulfur analyzer CS-3000 and an oxygen-nitrogen-hydrogen analyzer ONH836, respectively. The test data are shown in Table 6 below.
[0342] Table 6
[0343]
[0344] As can be seen from Table 6, the contents of impurity elements carbon, oxygen, and nitrogen in the NdFeB magnet material prepared in the embodiment of the present invention are significantly reduced, which is also one of the important factors for the significant improvement of the magnetic properties Br and Hcj.
[0345] (3) Main phase grain volume fraction test
[0346] The volume fraction of the primary phase grains in the NdFeB matrix (before diffusion) and NdFeB magnet materials (after diffusion) from Examples 1-3 and Comparative Examples 1-2 were measured. The samples were ground and prepared, and X-ray spectroscopy was performed to obtain diffraction peak data. Image J was used to compare the primary phase grains, and the volume fraction of the primary phase grains in the samples was determined by analysis and processing. The test results are shown in Table 7.
[0347] Table 7
[0348]
[0349] As can be seen from Table 7, the volume fraction of the main phase grains in the NdFeB magnet material prepared in the embodiment of the present invention is higher. In addition, the volume fraction of the main phase grains in the material before and after diffusion does not change much.
[0350] Effect Example 2
[0351] The NdFeB matrix (before diffusion) and NdFeB magnet material (after diffusion) prepared in Examples 1-3 and Comparative Examples 1-2 were respectively processed into standard sample columns of ø10*10 mm. The magnetic properties were tested using NIM62000 at a constant temperature of 20°C. The test data are shown in Table 8.
[0352] Table 8
[0353]
[0354] In Table 8, "Br" represents remanence; Hcj represents intrinsic coercivity; and "Hk / Hcj" represents knee coercivity and intrinsic coercivity. Hk / Hcj is a quantitative indicator of squareness, reflecting the rectangularity of the demagnetization curve. The closer its value is to 100%, the stronger the irreversibility of magnetization reversal under a reverse magnetic field, the more stable the magnetic domains remain before the knee point (Hk), and the better the demagnetization resistance. As shown in Table 8, the NdFeB magnet material produced in the embodiment of the present invention can achieve a remanence Br of over 14.95 kGs, an intrinsic coercivity Hcj of over 20.5 kOe, and an Hk / Hcj ratio of over 96%. However, the NdFeB magnet material produced in the comparative example cannot achieve these results simultaneously.
[0355] Although specific embodiments of the present invention have been described above, those skilled in the art will appreciate that these are merely illustrative and that the scope of the present invention is defined by the appended claims. Those skilled in the art may make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, and such changes and modifications are intended to fall within the scope of the present invention.
Claims
1. A method for preparing a neodymium iron boron magnet material, characterized in that: It includes the following steps: S1. Melting and casting a first alloy raw material composition and a second alloy raw material composition respectively to obtain a first alloy sheet and a second alloy sheet; step S1 further includes: performing a gas atomization treatment on the first alloy sheet using PrNd; S2. Mixing the first alloy flakes and the second alloy flakes and then performing hydrogen crushing to obtain a coarse powder; or hydrogen crushing the first alloy flakes and the second alloy flakes separately to obtain a first coarse powder and a second coarse powder, and mixing the first coarse powder and the second coarse powder to obtain a coarse powder; Then, the coarse powder is subjected to air jet milling to obtain fine powder; S3, pressing the fine powder to obtain a green body; S4, sintering the green body to obtain a NdFeB matrix; S5, performing grain boundary diffusion on the NdFeB matrix to obtain the NdFeB magnet material; The first alloy raw material composition and the second alloy raw material composition each independently include the following components: R: 25.0-30.0 mass%, wherein R is a rare earth element, and R includes PrNd and Nd; the content of PrNd and Nd satisfies: 0.05≤PrNd / (PrNd+Nd)≤0.20; M: 0-3.0 mass%. Wherein, the content of M is not 0, and M includes Al, Cu, Ga, and X; the contents of Al, Cu, and Ga satisfy the following conditions: 0 mass.%<Al+Cu+Ga≤0.46 mass.%, and Al<Cu≤Ga; X includes one or more of Ti, Zr, Nb, W, and Mo; B: 0.87-1.02mass.%; And the balance of Fe and inevitable impurities; mass.% represents the mass percentage of the total mass of the first alloy raw material composition or the second alloy raw material composition; Furthermore, the mass ratio of the first alloy raw material composition to the second alloy raw material composition is (30-70): (30-70).
2. The method for preparing a NdFeB magnet material according to claim 1, wherein: The first alloy raw material composition satisfies one or more of the following conditions (1)-(5): (1) The contents of PrNd and Nd satisfy the following conditions: 0.15≤PrNd / (PrNd+Nd)≤0.20; (2) The content of R is 25.0-28.5 mass%. (3) The Nd content is 23.0-25.0 mass%. (4) The content of PrNd is 3.0-5.0 mass%. (5) The content of B in the first alloy raw material composition is 0.89-1.02 mass%.
3. The method for preparing a NdFeB magnet material according to claim 1, wherein: The second alloy raw material composition satisfies one or more of the following conditions (1) to (5): (1) The contents of PrNd and Nd satisfy the following conditions: 0.05≤PrNd / (PrNd+Nd)≤0.10; (2) The content of R is 27.0-30.0 mass%. (3) The Nd content is 26.0-27.0 mass%. (4) The content of PrNd is 1.0-2.5 mass%. (5) The content of B in the second alloy raw material composition is 0.87-1.0 mass%.
4. The method for preparing a NdFeB magnet material according to claim 1, wherein: The first alloy raw material composition and the second alloy raw material composition each independently satisfy one or more of the following conditions (1)-(9): (1) The R further comprises one or more of Dy, Tb, Pr, Y and Ho; (2) The content of M is 1.0-2.0 mass.%; (3) The M also includes Co, and the content of Co is 0.1-0.9 mass.%; (4) The contents of Al, Cu and Ga satisfy the following requirements: 0.35 mass.% ≤ Al+Cu+Ga ≤ 0.40 mass.%; (5) The Al content is 0-0.05 mass%.% (6) The Cu content is 0.1-0.2 mass%. (7) The Ga content is 0.1-0.3 mass%. (8) The content of X is 0.1-0.3 mass%. (9) The X comprises Ti and Zr; wherein the content of Ti is 0.05-0.1 mass %; and the content of Zr is 0.15-0.2 mass %.
5. The method for preparing a NdFeB magnet material according to claim 1, wherein: The first alloy raw material composition includes the following components: PrNd: 3.0-5.0 mass.%; Nd: 23.0-25.0 mass.%; Al: 0.01-0.03 mass.%; Cu: 0.1-0.2 mass.%; Ga: 0.1-0.3 mass.%; Co: 0.1-0.6 mass.%; Ti: 0.05-0.1 mass.%; Zr: 0.15-0.2 mass.%; B: 0.89-1.02 mass.%; Fe: 67.0-75.0 mass.%; The mass.% is the percentage of the total weight of the first alloy raw material composition; Furthermore, the second alloy raw material composition includes the following components in weight percentage: PrNd: 1.0-2.5 mass.%; Nd: 26.0-27.0 mass.%; Al: 0.01-0.03 mass.%; Cu: 0.1-0.2 mass.%; Ga: 0.1-0.3 mass.%; Co: 0.7-0.9 mass.%; Ti: 0.05-0.1 mass.%; Zr: 0.15-0.2 mass.%; B: 0.87-1.0 mass.%; Fe: 65.0-73.0 mass.%; The mass.% is the percentage of the total weight of the second alloy raw material composition; Wherein, the mass ratio of the first alloy raw material composition to the second alloy raw material composition is (30-50): (50-70).
6. The method for preparing a NdFeB magnet material according to claim 1, wherein: In step S1, the atomization treatment includes: performing physical vapor deposition on the first alloy sheet using PrNd; the physical vapor deposition temperature is 600-800° C., and the physical vapor deposition time is 4-20 hours; and / or, in step S1, after the gas atomization treatment, the PrNd weight gain of the first alloy sheet is 0.5%-1.0%; and / or, in step S3, the pressing includes orientation pressing; And / or, in step S4, the sintering uses a high-density graphite box and a molybdenum box combination box; And / or, in step S4, the sintering further includes a two-stage aging treatment.
7. The method for preparing a NdFeB magnet material according to claim 1, wherein: In step S5, the grain boundary diffusion is performed using a staged heat treatment process, including: The first stage: the holding temperature is 880-950℃, and the holding time is 5-36h; The second stage: the holding temperature is 450-550℃, and the holding time is 3-10h; And / or, the vacuum degree during the grain boundary diffusion process is controlled to be 10 -1 -10 -4 Pa; And / or, in step S5, the diffusion source of the grain boundary diffusion includes a heavy rare earth element RH, and the RH includes Dy and / or Tb.
8. A neodymium iron boron magnet material, characterized in that: The NdFeB magnet is prepared by the method for preparing the NdFeB magnet material according to any one of claims 1 to 7.
9. The NdFeB magnet material according to claim 8, characterized in that: The volume fraction of the main phase grains in the NdFeB magnet material is greater than 95.8%; And / or, the carbon content in the NdFeB magnet material is ≤600ppm, the oxygen content is ≤400ppm, and the nitrogen content is ≤210ppm.
10. Use of the NdFeB magnet material according to claim 8 or 9 as a magnetic device.
Citation Information
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