A heavy rare earth alloy, neodymium iron boron material and its manufacturing method and application

Abstract

The present invention discloses a heavy rare earth alloy, a neodymium iron boron material, and a manufacturing method and application thereof. The heavy rare earth alloy comprises the following components, measured in weight percentage: 35.00 wt.% ≤ TRE ≤ 50.00 wt.%, wherein HRE ≥ 35.00 wt.% of the TRE; Fe ≤ 50.00 wt.%; 5.00 wt.% ≤ M1 ≤ 50.00 wt.%, wherein M1 is two or more of Co, Cu, Ga, Al, Zr, and Ti, wherein the sum of Cu, Ga, and Al is ≥ 3.00 wt.%, and the sum of Zr and Ti is ≥ 3.00 wt.%; and 0.30 wt.% ≤ B ≤ 0.60 wt.%. The neodymium iron boron material of the present invention can be used to produce a neodymium iron boron magnet material with high Br and high Hcj while using less heavy rare earth, effectively improving the performance of the neodymium iron boron magnet material.

Description

Technical Field

[0001] The present invention relates to a heavy rare earth alloy, a neodymium iron boron material, and a manufacturing method and application thereof. Background Art

[0002] The single alloy and dual alloy processes currently used in the manufacture of NdFeB have a single phase or multiple dispersed phases in the intergranular triangular region. The magnetic domain nucleation field at the contact area between the above phase and the main phase is low, and magnetic coupling is easily generated between the main phase grains, resulting in a low Hcj of the product.

[0003] Existing patent CN 111710489A prepares dispersed iron-rich and iron-poor phases with varying iron contents within the triple grain boundaries. The demagnetizing coupling effect of the iron-poor phase reduces the coupling between the main phases, thereby increasing Hcj. This existing patent utilizes the dispersed iron-poor phase for demagnetizing coupling, but its demagnetizing coupling effect is limited.

[0004] Therefore, how to further improve the phase distribution of the intercrystalline triangle region of NdFeB materials so that they can more effectively play the role of demagnetization coupling is a technical problem that needs to be solved urgently in this field. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the defect of low coercivity (Hcj) caused by the presence of a single phase or multiple dispersed phases in the intergranular triangular region of NdFeB magnet materials in the prior art. By providing a heavy rare earth alloy, NdFeB material, and its manufacturing method and application, the present invention can produce NdFeB magnet materials with high Br and high Hcj while using less heavy rare earth, effectively improving the performance of NdFeB magnet materials.

[0006] The present invention provides a heavy rare earth alloy comprising the following components in weight percentage:

[0007] 35.00wt.%≤TRE≤50.00wt.%, of the TRE, HRE≥35.00wt.%;

[0008] Fe≤50.00wt.%;

[0009] 5.00wt.%≤M1≤50.00wt.%, M1 is two or more of Co, Cu, Ga, Al, Zr and Ti, wherein: M1 contains at least one of Cu, Ga and Al, and the sum of "Cu, Ga and Al" is ≥3.00wt.%; M1 further contains at least one of Zr and Ti, and the sum of "Zr and Ti" is ≥3.00wt.%;

[0010] 0.30 wt.% ≤ B ≤ 0.60 wt.%; the percentage refers to the weight percentage in the heavy rare earth alloy.

[0011] In the present invention, TRE refers to total rare earth elements, and HRE refers to heavy rare earth elements.

[0012] In the present invention, the content of TRE may be 35.00-48.00wt.%, for example, 35.00wt.%, 40.00wt.%, 41.00wt.%, 42.00wt.%, 43.00wt.%, 45.00wt.%, 46.00wt.%, 47.00wt.% or 48.00wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0013] In the present invention, the content of the HRE may be 35.00-48.00 wt.%, for example, 35.00 wt.%, 38.00 wt.%, 40.00 wt.%, 41.00 wt.%, 42.00 wt.%, 43.00 wt.%, 45.00 wt.% or 48.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0014] In the present invention, the type of the HRE may be a type of heavy rare earth element conventional in the art, such as Tb and / or Dy.

[0015] When the type of the HRE is Tb, the content of Tb may be 35.00-48.00 wt.%, for example, 35.00 wt.%, 38.00 wt.%, 40.00 wt.%, 41.00 wt.%, 42.00 wt.%, 43.00 wt.%, 45.00 wt.% or 48.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0016] When the type of the HRE is Dy, the content of Dy may be 40.00-48.00 wt.%, for example, 45.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0017] In the present invention, the heavy rare earth alloy may contain light rare earth elements LRE, such as Pr and / or Nd.

[0018] The content of the LRE may be 0.00-15.00 wt.%, but not 0, such as 2.00 wt.%, 6.00 wt.%, 7.00 wt.% or 10.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0019] When the heavy rare earth alloy contains PrNd, the content of PrNd may be 1.00-15.00 wt.%, for example, 2.00 wt.%, 6.00 wt.%, 7.00 wt.% or 10.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0020] In the present invention, the Fe content may be ≤47.00wt.%, for example, 19.40wt.%, 35.60wt.%, 38.60wt.%, 39.70wt.%, 41.40wt.%, 42.50wt.%, 42.60wt.%, 43.50wt.%, 43.70wt.%, 44.40wt.%, 45.50wt.%, 46.20wt.%, 46.40wt.% or 46.50wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0021] In the present invention, the content of M1 may be 5.00-40.00wt.%, for example, 9.00wt.%, 11.50wt.%, 12.00wt.%, 13.00wt.%, 15.00wt.%, 18.00wt.%, 19.00wt.% or 35.00wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0022] In the present invention, the sum of "Cu, Ga and Al" may be 4.00-20.00wt.%, for example, 4.00wt.%, 5.00wt.%, 6.00wt.%, 7.00wt.%, 8.00wt.%, 10.00wt.%, 12.00wt.%, 14.00wt.% or 20.00wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0023] In the present invention, the sum of "Zr and Ti" may be 3.00-10.00 wt.%, for example, 3.00 wt.%, 4.00 wt.%, 5.00 wt.%, 6.00 wt.% or 10.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0024] In the present invention, when M1 contains Co, the content of Co may be 0.00-10.00 wt.%, but not 0, for example, 1.00 wt.%, 2.00 wt.%, 2.50 wt.%, 3.00 wt.% or 5.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0025] In the present invention, when M1 contains Cu, the content of Cu may be 0.00-15.00 wt.%, but not 0, for example, 1.00 wt.%, 3.50 wt.%, 4.00 wt.%, 5.00 wt.%, 8.00 wt.% or 10.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0026] In the present invention, when the M1 contains Al, the content of the Al may be 0.00-15.00 wt.%, but not 0, for example, 2.00 wt.%, 3.00 wt.%, 4.00 wt.%, 5.00 wt.%, 6.00 wt.% or 10.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0027] In the present invention, when Ga is contained in M1, the content of Ga may be 0.00-15.00 wt.%, but not 0, for example, 1.00 wt.%, 4.00 wt.%, 4.50 wt.%, 6.00 wt.%, 8.00 wt.% or 10.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0028] In the present invention, when the M1 contains Zr, the content of Zr may be 0.00-8.00 wt.%, but not 0, for example, 1.00 wt.%, 2.00 wt.%, 3.00 wt.%, 4.00 wt.% or 5.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0029] In the present invention, when M1 contains Ti, the content of Ti may be 0.00-8.00 wt.%, but not 0, for example, 1.00 wt.%, 2.00 wt.%, 3.00 wt.%, 4.00 wt.% or 5.00 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0030] In the present invention, preferably, the M1 comprises Cu, Ga, Al, "Cu and Al" or "Cu, Ga and Al".

[0031] When the M1 contains "Cu and Al", the Cu content may be 5.00-15.00 wt.%, and the Al content may be 5.00-15.00 wt.%; for example, the Cu content is 10.00 wt.%, and the Al content is 10.00 wt.%, where percentages refer to weight percentages in the heavy rare earth alloy.

[0032] When the M1 contains "Cu, Ga and Al", the Cu content may be 1.00-5.00wt.%, the Al content may be 1.00-5.00wt.%, and the Ga content may be 1.00-6.00wt.%; for example, Cu 1.00wt.%, Al 5.00wt.%, Ga 1.00wt.%, Cu 5.00wt.%, Al 3.00wt.%, Ga 6.00wt.%, Cu 4.00wt.%, Al 2.00wt.%, Ga 4.00wt.%, or, Cu 3.50wt.%, Al 4.00wt.%, Ga 4.50wt.%; the percentages refer to the weight percentages in the heavy rare earth alloy.

[0033] In the present invention, preferably, the M1 contains Zr and Ti.

[0034] When the M1 contains Zr and Ti, the Zr content may be 1.00-8.00wt.%, and the Ti content may be 1.00-8.00wt.%; for example, Zr 2.00wt.%, Ti 2.00wt.%, Zr 1.00wt.%, Ti 3.00wt.%, Zr3.00wt.%, Ti 1.00wt.%, Zr 2.00wt.%, Ti 3.00wt.%, Zr 3.00wt.%, Ti 2.00wt.%, Zr2.00wt.%, Ti 1.00wt.%, Zr 3.00wt.%, Ti 3.00wt.%, or Zr 5.00wt.%, Ti5.00wt.%; the percentages refer to the weight percentages in the heavy rare earth alloy.

[0035] In the present invention, preferably, the content of B is 0.40-0.60 wt.%, such as 0.40 wt.%, 0.50 wt.% or 0.60 wt.%, where the percentage refers to the weight percentage in the heavy rare earth alloy.

[0036] In a preferred embodiment of the present invention, the heavy rare earth alloy comprises the following components by weight:

[0037] HRE ≥ 35.00 wt.%;

[0038] Fe≤50.00wt.%;

[0039] Co: 0.00-10.00wt.%;

[0040] Cu: 0.00-15.00wt.%;

[0041] Al: 0.00-15.00wt.%;

[0042] Ga: 0.00-15.00wt.%;

[0043] B: 0.30-0.60wt.%;

[0044] Zr: 0.00-8.00wt.%;

[0045] Ti: 0.00-8.00wt.%;

[0046] The percentages refer to the weight percentages in the heavy rare earth alloy.

[0047] In a preferred embodiment of the present invention, the heavy rare earth alloy comprises the following components by weight:

[0048] HRE ≥ 35.00 wt.%;

[0049] Fe≤50.00wt.%;

[0050] Co: 1.00-5.00wt.%;

[0051] Al: 1.00-10.00wt.%;

[0052] B: 0.30-0.60wt.%;

[0053] Zr: 1.00-8.00wt.%;

[0054] Ti: 1.00-8.00wt.%;

[0055] The percentages refer to the weight percentages in the heavy rare earth alloy.

[0056] In a preferred embodiment of the present invention, the heavy rare earth alloy is composed of any of the following formulas by weight:

[0057]

[0058]

[0059] In a preferred embodiment of the present invention, the heavy rare earth alloy is composed of the following formula in weight percentage:

[0060] PnN Dy Fe Co Cu Al B Zr Ti 0.00 45.00 19.40 5.00 10.00 10.00 0.60 5.00 5.00

[0061] The present invention also provides a method for producing a heavy rare earth alloy, which comprises the following steps: mixing and smelting the raw material composition of the heavy rare earth alloy;

[0062] The raw material composition of the heavy rare earth alloy includes the following components:

[0063] 35.00wt.%≤TRE≤50.00wt.%, of the TRE, HRE≥35.00wt.%;

[0064] Fe≤50.00wt.%;

[0065] 5.00wt.%≤M1≤50.00wt.%, M1 is two or more of Co, Cu, Ga, Al, Zr and Ti, wherein M1 contains at least one of Cu, Ga and Al, and the sum of “Cu, Ga and Al” is ≥3.00wt.%, M1 further contains at least one of Zr and Ti, and the sum of “Zr and Ti” is ≥3.00wt.%;

[0066] 0.30 wt.% ≤ B ≤ 0.60 wt.%; the percentage refers to the weight percentage in the raw material composition of the heavy rare earth alloy.

[0067] The composition of the raw material composition of the heavy rare earth alloy may be the same as the composition of the heavy rare earth alloy.

[0068] The smelting temperature may be 1520±30°C, such as 1500°C or 1490°C.

[0069] The present invention also provides a heavy rare earth alloy produced by the above-mentioned method for producing the heavy rare earth alloy.

[0070] The present invention also provides a method for manufacturing NdFeB material, which comprises the following steps: mixing, pressing, sintering and aging the powder of alloy A and the powder of the heavy rare earth alloy;

[0071] In terms of weight percentage, the alloy A comprises the following components: 28.00 wt.% ≤ TRE ≤ 30.00 wt.%; 0.50 wt.% ≤ M2 ≤ 3.00 wt.%, M2 being selected from one or more of Cu, Co, Ga, Zr, Ti, Al, and Nb; 0.80 wt.% ≤ B ≤ 1.00 wt.%, with the balance being Fe. The percentages refer to the weight percentages in the alloy A.

[0072] The mass ratio of the alloy A to the heavy rare earth alloy is (9-99):1.

[0073] In the present invention, preferably, the particle size of the powder of alloy A is 4.0-4.3 μm or 4.1-4.4 μm.

[0074] In the present invention, preferably, the particle size of the heavy rare earth alloy powder is 3.7-4.0 μm or 4.1-4.4 μm.

[0075] In the present invention, the content of TRE may be 29.00-30.00 wt.%, such as 29.20 wt.%, 29.50 wt.% or 29.80 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0076] In the present invention, the type of the TRE may be PrNd.

[0077] When the alloy A includes PrNd, the content of PrNd may be 29.00-30.00 wt.%, for example, 29.20 wt.%, 29.50 wt.%, or 29.80 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0078] In the present invention, the content of M2 may be 0.50-2.50 wt.%, for example, 0.50 wt.%, 2.00 wt.% or 2.11 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0079] In the present invention, when M2 contains Co, the content of Co may be 0.00-5.00 wt.%, but not 0, such as 1.00 wt.% or 1.50 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0080] In the present invention, when M2 contains Cu, the content of Cu may be 0.00-0.50 wt.%, but not 0, such as 0.10 wt.% or 0.15 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0081] In the present invention, when the M1 contains Al, the content of Al may be 0.00-0.50 wt.%, but not 0, for example, 0.10 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0082] In the present invention, when M2 contains Ga, the content of Ga may be 0.00-0.50 wt.%, but not 0, such as 0.15 wt.%, 0.25 wt.% or 0.30 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0083] In the present invention, when M2 contains Zr, the content of Zr may be 0.10-0.20 wt.%, for example, 0.11 wt.% or 0.16 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0084] In the present invention, when M2 contains Ti, the content of Ti may be 0.05-0.20 wt.%, but not 0, for example, 0.10 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0085] In the present invention, preferably, the content of B is 0.90-1.00 wt.%, for example, 0.96 wt.%, where the percentage refers to the weight percentage in the alloy A.

[0086] In a preferred embodiment of the present invention, the alloy A consists of the following components in weight percentage:

[0087] PnN Fe Co Cu Ga B Zr 29.20 68.38 1.00 0.10 0.25 0.96 0.11

[0088] In a preferred embodiment of the present invention, the alloy A consists of the following components in weight percentage:

[0089] PnN Fe Cu Ga B Ti 29.80 68.74 0.10 0.30 0.96 0.10

[0090] In the present invention, the powder of the alloy A can be prepared by the following method: the raw material composition of the alloy A is mixed, smelted, hydrogen-decomposed, and pulverized;

[0091] The raw material composition of the alloy A includes the following components: 28.00 wt.% ≤ TRE ≤ 30.00 wt.%; 0.50 wt.% ≤ M2 ≤ 3.00 wt.%, M2 is selected from one or more of Cu, Co, Ga, Zr, Ti, Al and Nb; 0.80 wt.% ≤ B ≤ 1.00 wt.%, and the balance is Fe. The percentages refer to the weight percentages in the raw material composition of the alloy A.

[0092] The composition of the raw material composition of the alloy A can be the same as the composition of the alloy A.

[0093] The smelting temperature may be 1520±30°C, for example 1530°C.

[0094] The hydrogen cracking process may include hydrogen absorption and dehydrogenation. The hydrogen absorption temperature may be 350±70°C, for example, 350°C. The dehydrogenation temperature may be 550±70°C, for example, 550°C.

[0095] The pulverization can be carried out by conventional pulverization methods in the art, such as jet mill pulverization.

[0096] In the present invention, the heavy rare earth alloy powder can be prepared by the following method: hydrogen-crushing and pulverizing the heavy rare earth alloy.

[0097] The hydrogen cracking process may include hydrogen absorption and dehydrogenation. The temperature of the hydrogen absorption may be 350±70°C, for example, 350°C. The temperature of the dehydrogenation may be 550±70°C, for example, 550°C.

[0098] The pulverization can be carried out by conventional pulverization methods in the art, such as jet mill pulverization.

[0099] In the present invention, when the particle size of the alloy A powder is 4.0-4.3 μm and the particle size of the heavy rare earth alloy powder is 3.7-4.0 μm, the rare earth-rich phase can better wrap the main phase, the Hcj of the obtained NdFeB material is higher, the Hcj of the magnet can be improved, and the magnet consistency is good.

[0100] In the present invention, the mass ratio of the alloy A to the heavy rare earth alloy may be (20-50):1, for example (20-40):1, and further for example 97.5:2.5, 97:3, 96:4 or 96.5:3.5.

[0101] In the present invention, the intensity of the pressing magnetic field may be 1.6±0.2T, for example, 1.6T.

[0102] In the present invention, the pressed orientation magnetic field may be ≥1500Ka / m.

[0103] In the present invention, the sintering temperature may be 1090±15°C, for example, 1090°C or 1085°C.

[0104] In the present invention, the sintering time may be 4-10 hours, for example 6 hours.

[0105] In the present invention, the aging treatment may include primary aging treatment and secondary aging treatment.

[0106] The temperature of the primary aging treatment may be 900±30°C, such as 880°C or 920°C.

[0107] The time of the primary aging treatment may be 2-6 hours, for example 3 hours.

[0108] The temperature of the secondary aging treatment may be 460±40°C, such as 470°C or 480°C.

[0109] The secondary aging treatment may last for 2-6 hours, for example, 3 hours.

[0110] The present invention also provides a NdFeB material produced by the above-mentioned method for producing the NdFeB material.

[0111] The present invention also provides a neodymium iron boron material, (1) comprising the following components in weight percentage:

[0112] 28.00wt.%≤TRE≤33.00wt.%, of the TRE, 1.00wt.%≤HRE≤3.00wt.%;

[0113] 1.00wt.%≤M≤5.00wt.%, M is two or more of Co, Cu, Ga, Al, Zr and Ti, wherein M contains at least one of Cu, Ga and Al, and the sum of Cu, Ga and Al is ≥0.30wt.%, M further contains at least one of Zr and Ti, and the sum of Zr and Ti is ≥0.15wt.%;

[0114] 0.80wt.%≤B≤1.20wt.%;

[0115] The balance is Fe, and the percentage refers to the weight percentage in the NdFeB material;

[0116] (2) The intergranular triangular region of the NdFeB material contains phase A, and the phase A is a core-shell structure comprising a core and a shell; the core is R6T 13 M phase, wherein R refers to TRE, T refers to Fe and / or Co, and M refers to at least one of Al, Cu and Ga; the shell is a rare earth-rich phase.

[0117] In the present invention, the main phase is RE2Fe 14 Phase B, grain boundary phase refers to the nanoscale thin layer of rare earth-rich phase between the two main phase particles, and the intergranular triangle area refers to the area where the blocky rare earth-rich phase is located at the coupling point of three or more main phases.

[0118] In the present invention, the NdFeB material can form two phases in the intergranular triangle region, one of which is a 6:13:1 phase. The formation of this phase can reduce the Fe content of the two-particle grain boundary phase, enhance the demagnetizing coupling ability of the two-particle grain boundary phase, and thus improve Hcj; at the same time, a layer of rare earth-rich phase is formed on the periphery of the 6:13:1 phase. The above-mentioned rare earth-rich phase can wrap the 6:13:1 phase, effectively blocking the contact of the same main phase particles of 6:13:1, reducing the defects of the outer layer of the main phase particles, and improving Hcj.

[0119] In the present invention, the content of TRE may be 28.50-30.50wt.%, for example, 29.40wt.%, 29.52wt.%, 29.55wt.%, 29.58wt.%, 29.60wt.%, 29.62wt.%, 29.71wt.%, 29.76wt.%, 29.83wt.%, 29.91wt.%, 29.95wt.% or 30.41wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0120] In the present invention, the content of the HRE may be 1.00-2.00 wt.%, for example, 1.00 wt.%, 1.08 wt.%, 1.13 wt.%, 1.20 wt.%, 1.23 wt.%, 1.26 wt.%, 1.44 wt.%, 1.52 wt.%, 1.60 wt.%, 1.68 wt.% or 1.80 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0121] In the present invention, the type of the HRE may be a type of heavy rare earth element conventional in the art, such as Tb and / or Dy.

[0122] When the type of the HRE is Tb, the content of Tb may be 1.00-2.00 wt.%, for example, 1.00 wt.%, 1.08 wt.%, 1.13 wt.%, 1.20 wt.%, 1.23 wt.%, 1.26 wt.%, 1.44 wt.%, 1.52 wt.%, 1.60 wt.%, 1.68 wt.% or 1.80 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0123] When the type of the HRE is Dy, the content of Dy may be 1.50-2.00 wt.%, for example, 1.80 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0124] In the present invention, the NdFeB material may contain light rare earth elements (LRE), such as Pr and / or Nd.

[0125] Among them, the content of the LRE may be 28.00-29.00wt.%, for example, 28.03wt.%, 28.18wt.%, 28.31wt.%, 28.32wt.%, 28.38wt.%, 28.43wt.%, 28.47wt.%, 28.61wt.% or 28.62wt.%, and the percentage refers to the weight percentage in the NdFeB material.

[0126] When the NdFeB material contains PrNd, the content of PrNd may be 28.00-29.00 wt.%, for example, 28.03 wt.%, 28.18 wt.%, 28.31 wt.%, 28.32 wt.%, 28.38 wt.%, 28.43 wt.%, 28.47 wt.%, 28.61 wt.% or 28.62 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0127] In the present invention, the content of M may be 1.50-2.50wt.%, for example, 1.69wt.%, 1.75wt.%, 1.76wt.%, 1.80wt.%, 1.81wt.%, 1.86wt.%, 1.87wt.%, 1.88wt.%, 1.90wt.%, 1.92wt.% or 2.04wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0128] In the present invention, the sum of "Cu, Ga and Al" may be 0.30-1.50wt.%, for example, 0.46wt.%, 0.50wt.%, 0.54wt.%, 0.55wt.%, 0.58wt.%, 0.59wt.%, 0.64wt.%, 0.66wt.%, 0.69wt.%, 0.76wt.% or 1.18wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0129] In the present invention, the sum of "Zr and Ti" may be 0.15-0.50wt.%, for example, 0.18wt.%, 0.23wt.%, 0.26wt.%, 0.27wt.%, 0.31wt.%, 0.32wt.% or 0.50wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0130] In the present invention, when Co is included in the M, the content of Co may be 0.20-1.50 wt.%, for example, 0.20 wt.%, 0.96 wt.%, 0.97 wt.%, 0.98 wt.%, 1.00 wt.%, 1.03 wt.%, 1.06 wt.%, 1.08 wt.% or 1.12 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0131] In the present invention, when Cu is included in the M, the content of Cu may be 0.10-0.50 wt.%, for example, 0.10 wt.%, 0.13 wt.%, 0.20 wt.%, 0.22 wt.%, 0.26 wt.%, 0.34 wt.%, 0.40 wt.% or 0.50 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0132] In the present invention, when Al is contained in the M, the content of the Al may be 0.00-0.50 wt.%, but not 0, for example, 0.05 wt.%, 0.08 wt.%, 0.12 wt.%, 0.14 wt.%, 0.15 wt.%, 0.20 wt.%, 0.24 wt.% or 0.40 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0133] In the present invention, when Ga is included in the M, the content of Ga may be 0.10-0.60wt.%, for example, 0.24wt.%, 0.27wt.%, 0.29wt.%, 0.34wt.%, 0.36wt.%, 0.39wt.%, 0.40wt.%, 0.49wt.% or 0.56wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0134] In the present invention, when the M contains Zr, the content of Zr may be 0.05-0.30 wt.%, for example, 0.11 wt.%, 0.14 wt.%, 0.16 wt.%, 0.17 wt.%, 0.18 wt.%, 0.19 wt.%, 0.20 wt.%, 0.21 wt.% or 0.23 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0135] In the present invention, when M contains Ti, the content of Ti may be 0.00-0.30wt.%, but not 0, for example, 0.03wt.%, 0.04wt.%, 0.05wt.%, 0.06wt.%, 0.08wt.%, 0.09wt.%, 0.11wt.%, 0.12wt.%, 0.16wt.%, 0.20wt.% or 0.30wt.%, where the percentage refers to the weight percentage in the NdFeB material.

[0136] In the present invention, preferably, the content of B is 0.90-1.00 wt.%, such as 0.93 wt.%, 0.94 wt.% or 0.95 wt.%, where percentage refers to the weight percentage in the NdFeB material.

[0137] In a preferred embodiment of the present invention, the NdFeB material is composed of any of the following formulas by weight:

[0138]

[0139]

[0140] In a preferred embodiment of the present invention, the NdFeB material is composed of the following formula in weight percentage:

[0141] PnN Dy Fe Co Cu Al Ga B Zr Ti 28.61 1.80 66.77 0.20 0.50 0.40 0.29 0.95 0.20 0.30

[0142] In the present invention, the R6T 13 The volume ratio of the M phase in the intercrystalline triangular region may be 5.0-10.0%, for example, 5.6%, 5.9%, 6.0%, 6.1%, 6.3%, 6.4%, 6.5%, 6.8%, 6.9% or 7.0%.

[0143] In the present invention, the thickness of the rare earth rich phase may be 100-250 nm, for example, 125-180 nm, 135-210 nm, 140-185 nm, 140-200 nm, 140-205 nm, 140-215 nm, 145-180 nm, 145-200 nm, 145-220 nm or 150-200 nm.

[0144] In the present invention, the volume ratio of the rare earth-rich phase shell in the intercrystalline triangular region may be 0.5-3.0%, for example, 1.10%, 1.20% or 1.30%.

[0145] The present invention also provides an application of the NdFeB material as a raw material for preparing electronic components.

[0146] 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.

[0147] The reagents and raw materials used in the present invention are commercially available.

[0148] The positive progress effect of the present invention is:

[0149] 1. The NdFeB material of the present invention can form two phases in the intergranular triangular region: the rare earth-rich phase can wet the grain boundaries, increasing Hcj; and the 6-13-1 phase can play a role in magnetization reversal coupling, thereby increasing Hcj. In this structure, compared with two dispersed phases (such as the phase distribution shown in the EPMA image of the NdFeB material in Comparative Example 1), the 6-13-1 phase occupying the middle portion and the vast majority of the area can better play a role in magnetization reversal coupling.

[0150] 2. The NdFeB material of the present invention has excellent magnetic properties and can achieve high Br and high Hcj while using less heavy rare earth. BRIEF DESCRIPTION OF THE DRAWINGS

[0151] Figure 1 This is an EPMA image of the NdFeB material prepared in Example 1, wherein the “circle” represents a schematic diagram of the triple boundary of the 6:13:1 phase surrounded by the rare earth-rich phase.

[0152] Figure 2 This is the EPMA image of the NdFeB material prepared in Example 1 (partially enlarged).

[0153] Figure 3 This is an EPMA image of the NdFeB material prepared in Example 1, wherein the area circled by the dotted line refers to the rare earth-rich phase encapsulating the 6:13:1 phase.

[0154] Figure 4This is an EPMA image of the NdFeB material prepared in Example 1, wherein the black scale and white numbers refer to the shell thickness of the rare earth-rich phase encapsulating the 6:13:1 phase.

[0155] Figure 5 This is the EPMA image of the NdFeB material prepared in Example 1, wherein the area circled by the dotted line refers to the 6:13:1 phase.

[0156] Figure 6 This is the EPMA graph of the NdFeB material prepared in Comparative Example 1. DETAILED DESCRIPTION

[0157] 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.

[0158] Example 1 (Formulations 1-1 to 1-10, 1-3)

[0159] Example 1: A double alloy process is used to prepare NdFeB material. The specific preparation steps are as follows:

[0160] 1. A vacuum induction furnace was used to prepare master alloy A, sub-alloys 1-1 to 1-10, and sub-alloy 1-3. The melting temperature of master alloy A was 1530°C, and the melting temperatures of sub-alloys 1-1 to 1-10 and sub-alloy 1-3 were 1500°C respectively.

[0161] The formulas of master alloy A, sub-alloys 1-1 to 1-10, and sub-alloy 1-3 are shown in Table 1 below. The proportions of each element in Table 1 are weight percentages (wt%) in master alloy A, sub-alloys 1-1 to 1-10, or sub-alloy 1-3.

[0162] Table 1

[0163]

[0164] 2. Hydrogen-crushed powders of master alloy A, sub-alloys 1-1 to 1-10, and sub-alloy 1-3 were prepared in a hydrogen-crushed furnace, wherein: hydrogen absorption temperature: 350°C, dehydrogenation temperature: 550°C;

[0165] 3. Using a jet mill, powders of master alloy A, sub-alloys 1-1 to 1-10, and sub-alloy 1-3 were prepared respectively. The powder particle size of master alloy A was controlled at 4.0-4.3 μm, and the powder particle size of sub-alloys was controlled at 3.7-4.0 μm (powder particle size refers to D50 particle size).

[0166] 4. The powders of master alloy A, sub-alloys 1-1 to 1-10, and sub-alloy 1-3 were mixed according to the ratios shown in Table 2 to obtain the raw material ratio of NdFeB material. The ratios of each element in Table 2 are the weight percentages (wt%) in the raw material of NdFeB material.

[0167] Table 2

[0168]

[0169]

[0170] Note: The ratio in Table 2 refers to the mass ratio of the master alloy powder to the daughter alloy powder;

[0171] The content of each element in Table 2 is calculated based on the ratio of the sub-alloy to the master alloy. The sum of the mass of each element may be ≥ 100%. This is caused by the way the decimal places are rounded. For example, the original sum of two 0.005 is 0.005 + 0.005 = 0.01. If the decimal places are rounded to two digits, the sum becomes 0.01 + 0.01 = 0.02. These changes in values ​​do not affect the properties of the product.

[0172] 5. Press the powder (orientation magnetic field ≥ 1500Ka / m, magnetic field strength: 1.6T);

[0173] 6. The obtained compact is subjected to isostatic pressing, pressure sintering and vacuum sintering, wherein: the sintering temperature is 1090°C and the aging time is 6 hours;

[0174] 7. The sintered body blank is subjected to primary aging and secondary aging treatment; wherein: primary aging temperature & time: 880℃*3h, secondary aging temperature & time: 480℃*3h.

[0175] Example 2 (Formula 4)

[0176] The double alloy process is used to prepare NdFeB materials. The specific preparation steps are as follows:

[0177] 1. A vacuum induction furnace was used to prepare master alloy B and daughter alloy 4. The melting temperature of master alloy B was 1530°C, and the melting temperature of daughter alloy 4 was 1490°C.

[0178] The formulas of the master alloy B and the sub-alloy 4 are shown in Table 3 below. The proportions of the elements in Table 3 are weight percentages (wt%) in the master alloy B or sub-alloy 4.

[0179] Table 3

[0180] element PnN Dy Fe Co Cu Al Ga B Zr Ti Master alloy B / wt% 29.80 0.00 68.74 0.00 0.10 0.00 0.30 0.96 0.00 0.10 Sub-alloy 4 / wt% 0.00 45.00 19.40 5.00 10.00 10.00 0.00 0.60 5.00 5.00

[0181] 2. Use hydrogen crushing furnace to prepare hydrogen crushing powder of master alloy B and daughter alloy 4 respectively, where: hydrogen absorption temperature: 350℃, dehydrogenation temperature: 550℃;

[0182] 3. Prepare powders of master alloy B and daughter alloy 4 respectively using a jet mill, wherein the powder particle size of master alloy B is controlled at 4.0-4.3 μm, and the powder particle size of daughter alloy 4 is controlled at 3.7-4.0 μm (powder particle size refers to D50 particle size);

[0183] 4. The powders of master alloy B and sub-alloy 4 are mixed according to the ratios shown in Table 4 below to obtain the raw material ratio of NdFeB material; the ratios of each element in the table are weight percentages (wt%) in the raw material of NdFeB material;

[0184] Table 4

[0185]

[0186] 5. Press the powder (orientation magnetic field ≥ 1500Ka / m, magnetic field strength: 1.6T);

[0187] 6. The obtained green compact is subjected to isostatic pressing, pressure sintering and vacuum sintering, wherein: the sintering temperature is 1085°C and the aging time is 6 hours;

[0188] 7. The sintered body blank is subjected to primary aging and secondary aging treatment; wherein: primary aging temperature & time: 920℃*3h, secondary aging temperature & time: 470℃*3h.

[0189] Comparative Example 1 (Formula 5)

[0190] According to the formula shown in Table 5, NdFeB material was prepared.

[0191] Table 5

[0192]

[0193]

[0194] 1. A vacuum induction furnace was used to prepare the master alloy C and daughter alloy 5 shown in Table 5. The melting temperature of the master alloy C was 1530°C, and the melting temperature of the daughter alloy 5 was 1500°C.

[0195] 2. After mixing according to the mass ratio in the table above, use a hydrogen decomposition furnace for hydrogen decomposition, and the dehydrogenation temperature is 550℃;

[0196] 3. Use air jet mill equipment to prepare powders respectively, and the powder particle size is controlled at 4.1-4.4μm;

[0197] 4. Press the powder (orientation magnetic field ≥ 1500Ka / m, magnetic field strength: 1.6T);

[0198] 5. The obtained compact is subjected to isostatic pressing, pressure sintering and vacuum sintering, wherein: the sintering temperature is 1090°C and the aging time is 6 hours;

[0199] 6. The sintered body blank is subjected to primary aging and secondary aging treatment; wherein: primary aging temperature & time: 880℃*3h, secondary aging temperature & time: 480℃*3h.

[0200] Comparative Example 2 (Formula 6)

[0201] Table 6

[0202]

[0203] 1. A vacuum induction furnace was used to prepare the master alloy D and daughter alloy 6 shown in Table 6. The melting temperature of the master alloy D was 1520°C, and the melting temperature of the daughter alloy 6 was 1480°C.

[0204] 2. After mixing according to the mass ratio shown in Table 6 above, use a hydrogen decomposition furnace for hydrogen decomposition, and the dehydrogenation temperature is 550°C;

[0205] 3. Use air jet mill equipment to prepare powders respectively, and the powder particle size is controlled at 4.1-4.4μm;

[0206] 4. Press the powder (orientation magnetic field ≥ 1500Ka / m, magnetic field strength: 1.6T);

[0207] 5. The obtained green compact is subjected to isostatic pressing, pressure sintering and vacuum sintering, wherein: the sintering temperature is 1080°C and the aging time is 6 hours;

[0208] 6. The sintered body blank is subjected to primary aging and secondary aging treatment; wherein: primary aging temperature & time: 900℃*3h, secondary aging temperature & time: 480℃*3h.

[0209] Effect Example 1

[0210] (1) The NdFeB blanks prepared from Formulas 1-1 to 1-10, Formula 1, Formula 2, Formula 3, Formula 4, and Formula 6 were tested for magnetic properties. The test methods for Br, Hcb, Hcj, (BH)max, and Hk were as follows: Tests were performed using the NIM-10000H equipment from the China National Institute of Metrology in accordance with GB / T 3217-2013 Magnetic Test Methods for Permanent Magnet (Hard Magnetic) Materials.

[0211] Its magnetic properties are shown in Table 7 below.

[0212] Table 7

[0213]

[0214] The microstructure of the NdFeB material prepared in Example 1 is as follows: Figure 1 、 Figure 2 As shown. Figure 1 、 Figure 2 It can be seen that NdFeB material forms two phases in the intergranular triangle area, one of which is the 6:13:1 phase. The formation of this phase can reduce the Fe content of the two-particle grain boundary phase and enhance the demagnetizing coupling ability of the two-particle grain boundary phase; at the same time, a layer of rare earth-rich phase is formed on the periphery of the 6:13:1 phase. The above rare earth-rich phase can wrap the 6:13:1 phase and can effectively block the contact of the same main phase particles of 6:13:1, thereby reducing the defects of the outer layer of the main phase particles.

[0215] (2) The NdFeB material blank prepared in Comparative Example 1 was tested for magnetic properties. The testing method for Br, Hcb, Hcj, (BH)max, and Hk was as follows: Testing was performed using the NIM-10000H equipment from the China National Institute of Metrology in accordance with GB / T 3217-2013 Magnetic Test Methods for Permanent Magnet (Hard Magnetic) Materials.

[0216] Its magnetic properties are shown in Table 8 below.

[0217] Table 8

[0218]

[0219] Note: In Table 8, performance 1 and performance 2 refer to the test results obtained by testing multiple samples from the same batch of samples in Comparative Example 1.

[0220] The microstructure of the NdFeB material prepared in Comparative Example 1 is as follows: Figure 6 As shown. Figure 6 It can be seen that although the 6-13-1 phase and the rare earth-rich phase coexist in Comparative Example 1, they are dispersed in this example, while in the present invention, the rare earth-rich phase envelops the 6-13-1 phase, forming a shell structure. Therefore, the NdFeB material in Comparative Example 1 (Formula 5) has inferior performance to Formulations 1, 2, 3, 4, and 1-1 to 1-10.

[0221] (3) The NdFeB materials prepared from Recipes 1-6 and 1-1 to 1-10 were photographed and the shell dimensions were measured using a scanning electron microscope (S4800). PS software was then used to identify the rare earth-rich phase and the 6-13-1 phase in the images taken by the electron microscope, and the corresponding proportions were calculated. Specific data are shown in Tables 9 and 10.

[0222] Figure 3-5This is an example calculation of the proportion of the rare earth-rich phase, the shell thickness, and the proportion of the 6:13:1 phase of the NdFeB material of Formula 1 in Example 1.

[0223] Table 9

[0224]

[0225] Note: The volume percentage of the 6:13:1 phase in the above table refers to the volume percentage in the intergranular triangular region, and the volume percentage of the rare earth-rich phase shell refers to the volume percentage in the intergranular triangular region.

[0226] Table 10

[0227]

Claims

1. A neodymium iron boron material, characterized in that: (1) In terms of weight percentage, it comprises the following components: 28.00wt.%≤TRE≤33.00wt.%, of the TRE, 1.00wt.%≤HRE≤3.00wt.%; wherein the TRE is total rare earth elements and the HRE is heavy rare earth elements; 1.00wt.%≤M≤5.00wt.%, M is two or more of Co, Cu, Ga, Al, Zr and Ti, wherein M contains at least one of Cu, Ga and Al, and the sum of Cu, Ga and Al is ≥0.30wt.%, M further contains at least one of Zr and Ti, and the sum of Zr and Ti is ≥0.15wt.%; 0.80wt.%≤B≤1.20wt.%; The balance is Fe, and the percentage refers to the weight percentage in the NdFeB material; (2) The intergranular triangular region of the NdFeB material contains phase A, and the phase A is a core-shell structure comprising a core and a shell; the core is R6T 13 M phase, wherein R refers to TRE, T refers to Fe and / or Co, and M refers to at least one of Al, Cu and Ga; the shell is a rare earth-rich phase; Among them, the R6T 13 The volume ratio of the M phase in the intercrystalline triangular region is 5.0-10.0%; The thickness of the rare earth-rich phase is 100-250 nm; The volume ratio of the rare earth-rich phase shell in the intercrystalline triangular region is 0.5-3.0%; The NdFeB material contains light rare earth element LRE; the LRE contains Nd.

2. The NdFeB material according to claim 1, wherein: The R6T 13 The volume ratio of the M phase in the intercrystalline triangular region is 5.6%, 5.9%, 6.0%, 6.1%, 6.3%, 6.4%, 6.5%, 6.8%, 6.9% or 7.0%.

3. The NdFeB material according to claim 1, wherein: The thickness of the rare earth-rich phase is 125-180 nm, 135-210 nm, 140-185 nm, 140-200 nm, 140-205 nm, 140-215 nm, 145-180 nm, 145-200 nm, 145-220 nm or 150-200 nm.

4. The NdFeB material according to claim 1, wherein: The volume ratio of the rare earth-rich phase shell in the intercrystalline triangular region is 1.10%, 1.20% or 1.30%.

5. The NdFeB material according to claim 1, wherein: The NdFeB material meets one or more of the following conditions: ① The content of TRE is 28.50-30.50wt.%, where the percentage refers to the weight percentage in the NdFeB material; ② The content of HRE is 1.00-2.00wt.%, where the percentage refers to the weight percentage in the NdFeB material; ③ The type of HRE is Tb and / or Dy; ④ The content of the LRE is 28.00-29.00wt.%, where the percentage refers to the weight percentage in the NdFeB material; ⑤ The content of M is 1.50-2.50wt.%, where the percentage refers to the weight percentage in the NdFeB material; ⑥ The sum of "Cu, Ga and Al" is 0.30-1.50wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑦ The sum of "Zr and Ti" is 0.15-0.50wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑧When M contains Co, the content of Co is 0.20-1.50wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑨ When M contains Cu, the content of Cu is 0.10-0.50wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑩ When the M contains Al, the content of Al is 0.00-0.50 wt.%, but not 0, and the percentage refers to the weight percentage in the NdFeB material; When Ga is included in M, the content of Ga is 0.10-0.60 wt.%, where the percentage refers to the weight percentage in the NdFeB material; When the M contains Zr, the content of Zr is 0.05-0.30wt.%, and the percentage refers to the weight percentage in the NdFeB material; When M contains Ti, the content of Ti is 0.00-0.30 wt.%, but not 0, and the percentage refers to the weight percentage in the NdFeB material; and The content of B is 0.90-1.00 wt.%, where the percentage refers to the weight percentage in the NdFeB material.

6. The NdFeB material according to claim 1, wherein: The NdFeB material meets one or more of the following conditions: ① The content of TRE is 29.40wt.%, 29.52wt.%, 29.55wt.%, 29.58wt.%, 29.58wt.%, 29.60wt.%, 29.62wt.%, 29.71wt.%, 29.76wt.%, 29.83wt.%, 29.91wt.%, 29.95wt.% or 30.41wt.%, and the percentage refers to the weight percentage in the NdFeB material; ② The content of the HRE is 1.00wt.%, 1.08wt.%, 1.13wt.%, 1.20wt.%, 1.23wt.%, 1.26wt.%, 1.44wt.%, 1.52wt.%, 1.60wt.%, 1.68wt.% or 1.80wt.%, and the percentage refers to the weight percentage in the NdFeB material; ③ The LRE is Pr and Nd; The content of the LRE is 28.03wt.%, 28.18wt.%, 28.31wt.%, 28.32wt.%, 28.38wt.%, 28.43wt.%, 28.47wt.%, 28.61wt.% or 28.62wt.%, and the percentage refers to the weight percentage in the NdFeB material; ④ The content of M is 1.69wt.%, 1.75wt.%, 1.76wt.%, 1.80wt.%, 1.81wt.%, 1.86wt.%, 1.87wt.%, 1.88wt.%, 1.90wt.%, 1.92wt.% or 2.04wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑤ The sum of “Cu, Ga and Al” is 0.46wt.%, 0.50wt.%, 0.54wt.%, 0.55wt.%, 0.58wt.%, 0.59wt.%, 0.64wt.%, 0.66wt.%, 0.69wt.%, 0.76wt.% or 1.18wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑥ The sum of “Zr and Ti” is 0.18wt.%, 0.23wt.%, 0.26wt.%, 0.27wt.%, 0.31wt.%, 0.32wt.% or 0.50wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑦ When M contains Co, the content of Co is 0.20wt.%, 0.96wt.%, 0.97wt.%, 0.98wt.%, 1.00wt.%, 1.03wt.%, 1.06wt.%, 1.08wt.% or 1.12wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑧ When M contains Cu, the content of Cu is 0.10wt.%, 0.13wt.%, 0.20wt.%, 0.22wt.%, 0.22wt.%, 0.26wt.%, 0.34wt.%, 0.40wt.% or 0.50wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑨ When the M contains Al, the content of the Al is 0.05wt.%, 0.08wt.%, 0.12wt.%, 0.14wt.%, 0.15wt.%, 0.20wt.%, 0.24wt.% or 0.40wt.%, and the percentage refers to the weight percentage in the NdFeB material; ⑩ When Ga is contained in M, the content of Ga is 0.24 wt.%, 0.27 wt.%, 0.29 wt.%, 0.34 wt.%, 0.36 wt.%, 0.39 wt.%, 0.40 wt.%, 0.49 wt.% or 0.56 wt.%, and the percentage refers to the weight percentage in the NdFeB material; When the M contains Zr, the content of Zr is 0.11 wt.%, 0.14 wt.%, 0.16 wt.%, 0.17 wt.%, 0.18 wt.%, 0.19 wt.%, 0.20 wt.%, 0.21 wt.% or 0.23 wt.%, and the percentage refers to the weight percentage in the NdFeB material; When M contains Ti, the content of Ti is 0.03wt.%, 0.04wt.%, 0.05wt.%, 0.06wt.%, 0.08wt.%, 0.09wt.%, 0.11wt.%, 0.12wt.%, 0.16wt.%, 0.20wt.% or 0.30wt.%, and the percentage refers to the weight percentage in the NdFeB material; and, The B content is 0.93 wt.%, 0.94 wt.% or 0.95 wt.%, where percentage refers to the weight percentage in the NdFeB material.

7. Use of the NdFeB material according to any one of claims 1 to 6 as a raw material for preparing electronic components.

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