Master alloy and sub-alloy system neodymium iron boron magnet material and method for producing the same

Abstract

The present invention discloses a raw material composition of a neodymium iron boron magnet material based on a main alloy and a sub-alloy, and a method for producing the same. [Solution] The raw material composition of the main alloy and secondary alloy NdFeB magnet material includes a main alloy raw material and a secondary alloy raw material, and the mass percentage of the secondary alloy raw material in the raw material composition of the main alloy and secondary alloy NdFeB magnet material is 1.0-15.0 mass%. The main alloy and secondary alloy NdFeB magnet material produced using the raw material composition has improved coercivity while maintaining a high residual magnetic flux density, and the production method thereof realizes engineering applications.

Description

Technical Field

[0001] The present invention relates to a master alloy and a sub-alloy system neodymium iron boron magnet material and a manufacturing method thereof.

Background Art

[0002] Neodymium iron boron is currently attracting attention as the permanent magnet with the largest room-temperature magnetic energy product, and is widely used in fields such as traction motors, servo motors, main drive motors of new energy vehicles, magnetic elements, and wind turbines. However, the demagnetization resistance of commercial magnets is only 1 / 4 of the theoretical value (about 71 kOe). The demagnetization resistance of neodymium iron boron is generally indicated by the coercive force, and the magnitude of the coercive force is greatly affected by the microstructure of neodymium iron boron and is controlled by two mechanisms, namely, the nucleation region and the pinning region. Centering on the nucleation region, the route to improve HcJ in the nucleation region is to eliminate the antiphase domain nucleation points. From a microscopic perspective, there are generally three routes to improve the coercive force.

[0003] 1) Enhance the demagnetization coupling ability of the grain boundary phase between the main phases. Specifically, by including Nd6Fe 13 X in the main phase to absorb Fe in the grain boundary, convert the grain boundary phase into a non-magnetic phase or an antiferromagnetic phase, and expand the grain boundary. Or, increase the total rare earth content to increase the volume of the grain boundary phase. By adding grain boundary elements such as Cu, Ga, Co, and Al, the fluidity of the neodymium-rich phase is improved, the main phase particle boundaries are optimized, the main phase defects are repaired, the formation of the antiphase domain is reduced, and HcJ is increased. In such a method, the improvement of HcJ is limited, and it is difficult to increase HcJ to 25 kOe or more.

[0004] 2) By refining the crystal grains, reduce the antiphase domain nucleation points of the main phase particles. The closer the single-phase region dimension is approached, the less likely the antiphase domain is to be formed. Or, Nd6Fe 13The formation of grain boundary phases such as X eliminates the sharp angles of the main phase particles, smoothens the main phase grain boundaries, and reduces the inverse domain nucleation points. Such a method has a strong effect of improving HcJ, and the HcJ of magnets manufactured by the thin film method can reach 29 kOe, but it is difficult for engineering applications.

[0005] 3) By adding heavy rare earths, the anisotropic region of the main phase is enhanced. However, the reserves of heavy rare earth resources are small, the price is high, and the application of neodymium iron boron magnets in various industries is severely restricted. Usually, the double alloy or diffusion method is adopted to distribute heavy rare earths in the epitaxial layer of the main phase to improve the utilization rate of heavy rare earths. However, the diffusion method cannot be applied to magnets with a thickness greater than 15 mm, and in the existing double alloy method, HcJ can only be increased by about 1 - 1.5 kOe, and its improvement effect is limited.

Summary of the Invention

Problems to be Solved by the Invention

[0006] In order to solve the drawback that the coercivity of neodymium iron boron magnets manufactured by the conventional double alloy method is low, the present invention provides a main alloy and a secondary alloy system neodymium iron boron magnet material or a manufacturing method thereof. The main alloy and secondary alloy system neodymium iron boron magnet material of the present invention improves the coercivity while ensuring a high residual magnetic flux density, and its manufacturing method realizes engineering applications.

Means for Solving the Problems

[0007] To achieve the above object, the present invention adopts the following technical conceptions.

[0008] The present invention provides a raw material composition of a main alloy and a secondary alloy system neodymium iron boron magnet material including a main alloy raw material and a secondary alloy raw material, where the main alloy raw material includes the following components, LR: 10.0 - 33.0 mas%, where LR is a light rare earth element, and LR is one or more of Y, La, Ce, Pr, Nd, HR: 0 to 20.0 mas%, where the HR is a heavy rare earth element, and the HR is one or more of Gd, Dy, Tb, and Ho. M: 0.1 to 5.0 mas%, where the M is one or more of Co, Cu, Al, and Ga. X: 0.05 to 0.7 mas%, where the X is one or more of Zr, Ti, and Nb. B: 0.94 to 1.1 mas% The balance is Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The sub-alloy raw material contains the following components: LR: 0 to 30.0 mas%, where the LR is a light rare earth element, and the LR is Nd and / or Pr. HR: 1 to 80 mas%, where the HR is a heavy rare earth element, and the HR is Dy and / or Tb. M: 5.0 to 20.0 mas%, where the M is one or more of Co, Cu, Al, and Ga. X: 3.0 to 12.0 mas%, where the X is one or more of Ti, Zr, Hf, Nb, W, and Ta. B: 0 to 0.6 mas% The balance is Fe. Here, mas% means the mass percentage of the component in the sub-alloy raw material. The mass percentage of the sub-alloy raw material in the raw material composition of the main alloy and sub-alloy system neodymium iron boron magnet material is 1.0 to 15.0 mas%.

[0009] In the present invention, preferably, the total rare earth content TRE in the main alloy raw material is 26.0 to 40.0 mas%, more preferably 29.0 to 32.0 mas%, for example, 29.5 mas%, 30.5 mas%, or 31.5 mas%. Here, mas% means the mass percentage of the component in the main alloy raw material.

[0010] In the present invention, preferably, the content of the LR in the master alloy raw material is 25.0 to 30.0 mas%, for example, 25.2 mas%, 29.5 mas% or 30 mas%, and mas% means the mass percentage of the component in the master alloy raw material.

[0011] In the present invention, when the LR in the master alloy raw material contains Nd, the content of the Nd is preferably 18.9 to 22.5 mas%, for example, 22.125 mas%, and mas% means the mass percentage of the component in the master alloy raw material.

[0012] In the present invention, when the LR in the master alloy raw material contains Pr, the content of the Pr is preferably 6.0 to 7.5 mas%, for example, 6.3 mas% or 7.375 mas%, and mas% means the mass percentage of the component in the master alloy raw material.

[0013] Preferably, the LR in the master alloy raw material contains Nd and Pr. More preferably, the content of the Nd is 22.125 mas% and the content of the Pr is 7.375 mas%, or the content of the Nd is 22.5 mas% and the content of the Pr is 7.5 mas%, or the content of the Nd is 18.9 mas% and the content of the Pr is 6.3 mas%, where mas% means the mass percentage of the component in the master alloy raw material.

[0014] In the present invention, the content of the HR in the master alloy raw material is preferably 1.0 to 10.0 mas%, for example, 1.5 mas% or 5.3 mas%, and mas% means the mass percentage of the component in the master alloy raw material.

[0015] In the present invention, when the HR in the master alloy raw material contains Dy, the content of Dy is preferably 1.0 to 5.0 mas%, for example, 1.5 mas% or 4.3 mas%. Preferably, the HR in the master alloy raw material is Dy, and the content of Dy is preferably 1.5 mas%. Here, mas% means the mass percentage of the component in the master alloy raw material.

[0016] In the present invention, when the HR in the master alloy raw material contains Ho, the content of Ho is preferably 0.5 to 2.0 mas%, for example, 1.0 mas%. Here, mas% means the mass percentage of the component in the master alloy raw material.

[0017] Preferably, the HR in the master alloy raw material contains Dy and Ho. Here, the content of Dy is preferably 4.3 mas%, and the content of Ho is preferably 1.0 mas%. Here, mas% means the mass percentage of the component in the master alloy raw material.

[0018] In the present invention, the content of M in the master alloy raw material is preferably 0.5 to 2.0 mas%, for example, 0.88 mas%, 1.5 mas% or 1.65 mas%. Here, mas% means the mass percentage of the component in the master alloy raw material.

[0019] In the present invention, when M in the master alloy raw material contains Ga, the content of Ga is preferably 0.2 to 0.4 mas%, for example, 0.25 mas%. Here, mas% means the mass percentage of the component in the master alloy raw material.

[0020] In the present invention, when M in the master alloy raw material contains Al, the content of Al is preferably 0.01 to 0.1 mas%, for example, 0.03 mas%. Here, mas% means the mass percentage of the component in the master alloy raw material.

[0021] In the present invention, when M in the master alloy raw material contains Cu, the content of Cu is preferably 0.1 to 0.25 mas%, for example, 0.15 mas%, and mas% means the mass percentage in the master alloy raw material of the component.

[0022] In the present invention, when M in the master alloy raw material contains Co, the content of Co is preferably 0.5 to 1.0 mas%, and mas% means the mass percentage in the master alloy raw material of the component.

[0023] Preferably, M in the master alloy raw material contains Ga, Al, Cu or Co. Here, the content of Ga is preferably 0.25 mas%, the content of Al is preferably 0.03 mas%, the content of Cu is preferably 0.1 mas%, the content of Co is preferably 0.5 mas%, and mas% means the mass percentage in the master alloy raw material of the component.

[0024] In the present invention, the content of X in the master alloy raw material is preferably 0.1 to 0.35 mas%, for example, 0.11 mas% or 0.15 mas%, and mas% means the mass percentage in the master alloy raw material of the component. Preferably, X in the master alloy raw material is Zr or Ti.

[0025] In the present invention, the content of B in the master alloy raw material is preferably 0.97 to 0.99 mas%, for example, 0.98 mas%, and mas% means the mass percentage in the master alloy raw material of the component.

[0026] In one preferred embodiment, the master alloy raw material contains the following components: 22.125 mas% of Nd, 7.375 mas% of Pr, 0.25 mas% of Ga, 0.03 mas% of Al, 0.1 mas% of Cu, 0.5 mas% of Co, 0.11 mas% of Zr, 0.98 mas% of B, and the balance is Fe. Here, mas% means the mass percentage in the master alloy raw material of the component.

[0027] In one preferred embodiment, the main alloy raw material contains the following components: 22.5 mas% of Nd, 7.5 mas% of Pr, 1.5 mas% of Dy, 0.4 mas% of Ga, 0.25 mas% of Cu, 1.0 mas% of Co, 0.35 mas% of Zr, 0.97 mas% of B, and the balance is Fe, where mas% means the mass percentage of the component in the main alloy raw material.

[0028] In one preferred embodiment, the main alloy raw material contains the following components: 18.9 mas% of Nd, 6.3 mas% of Pr, 4.3 mas% of Dy, 1.0 mas% of Ho, 0.25 mas% of Ga, 0.1 mas% of Al, 0.15 mas% of Cu, 1.0 mas% of Co, 0.15 mas% of Ti, 0.97 mas% of B, and the balance is Fe, where mas% means the mass percentage of the component in the main alloy raw material.

[0029] In the present invention, the total rare earth content TRE in the secondary alloy raw material is preferably 35.0 to 50.0 mas%, more preferably 40.0 to 45.0 mas%, and mas% means the mass percentage of the component in the secondary alloy raw material.

[0030] In the present invention, the content of the LR in the secondary alloy raw material is preferably 20.0 to 30.0 mas%, for example, 25.0 mas%, and mas% means the mass percentage of the component in the secondary alloy raw material.

[0031] In the present invention, when the LR in the secondary alloy raw material contains Nd, the content of the Nd is preferably 10.0 to 20.0 mas%, for example, 15.0 mas%, and mas% means the mass percentage of the component in the secondary alloy raw material.

[0032] In the present invention, when the LR in the secondary alloy raw material contains Pr, the content of the Pr is preferably 15.0 to 25.0 mas%, for example, 20.0 mas%, and mas% means the mass percentage of the component in the secondary alloy raw material.

[0033] Preferably, the LR in the sub-alloy raw material is Nd and Pr, the content of Nd is 15.0 mas%, the content of Pr is 15.0 mas%, and mas% means the mass percentage in the sub-alloy raw material of the component.

[0034] In the present invention, the content of the HR in the sub-alloy raw material is preferably 15.0 to 20.0 mas%, and mas% means the mass percentage in the sub-alloy raw material of the component.

[0035] Preferably, the HR in the sub-alloy raw material is Tb, the content of Tb is 15.0 mas%, and mas% means the mass percentage in the sub-alloy raw material of the component.

[0036] Preferably, the HR in the sub-alloy raw material is Dy, the content of Dy is 20.0 mas%, and mas% means the mass percentage in the sub-alloy raw material of the component.

[0037] In the present invention, when the M in the sub-alloy raw material contains Ga, the content of Ga is preferably 2.0 to 10.0 mas%, for example 5.0 mas%, and mas% means the mass percentage in the sub-alloy raw material of the component.

[0038] In the present invention, when the M in the sub-alloy raw material contains Co, the content of Co is preferably 10.0 to 20.0 mas%, for example 15.0 mas%, and mas% means the mass percentage in the sub-alloy raw material of the component.

[0039] Preferably, the M in the sub-alloy raw material is Ga and Co, where the content of Ga is preferably 5.0 mas%, the content of Co is preferably 15.0 mas%, and mas% means the mass percentage in the sub-alloy raw material of the component.

[0040] In the present invention, the content of X in the sub-alloy raw material is preferably 4.0 to 10.0 mas%, for example, 4.5 mas% or 5.0 mas%. Here, mas% means the mass percentage in the sub-alloy raw material of the component. Preferably, X in the sub-alloy raw material is Zr.

[0041] In the present invention, the content of B in the sub-alloy raw material is preferably 0.3 to 0.6 mas%, for example, 0.4 mas% or 0.5 mas%. Here, mas% means the mass percentage in the sub-alloy raw material of the component.

[0042] In one preferred embodiment, the sub-alloy raw material contains the following components: 15.0 mas% of Nd, 15.0 mas% of Pr, 15.0 mas% of Tb, 10.0 mas% of Zr, 0.5 mas% of B, and the balance is Fe. Here, mas% means the mass percentage in the sub-alloy raw material of the component.

[0043] In one preferred embodiment, the sub-alloy raw material contains the following components: 25.0 mas% of Pr, 20.0 mas% of Dy, 4.5 mas% of Zr, 0.5 mas% of B, and the balance is Fe. Here, mas% means the mass percentage in the sub-alloy raw material of the component.

[0044] In one preferred embodiment, the sub-alloy raw material contains the following components: 20.0 mas% of Pr, 20.0 mas% of Dy, 5.0 mas% of Ga, 15.0 mas% of Co, 5.0 mas% of Zr, 0.4 mas% of B, and the balance is Fe. Here, mas% means the mass percentage in the sub-alloy raw material of the component.

[0045] In the present invention, the mass percentage of the sub-alloy raw material in the raw material composition of the main alloy and the sub-alloy system neodymium iron boron magnet material is preferably 2.0 to 5.0 mas%, for example, 4.0 mas%.

[0046] In one more preferred embodiment, the raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material includes a main alloy raw material and a secondary alloy raw material. Here, the main alloy raw material includes the following components: 22.125 mas% of Nd, 7.375 mas% of Pr, 0.25 mas% of Ga, 0.03 mas% of Al, 0.1 mas% of Cu, 0.5 mas% of Co, 0.11 mas% of Zr, 0.98 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The secondary alloy raw material includes the following components: 15.0 mas% of Nd, 15.0 mas% of Pr, 15.0 mas% of Tb, 10.0 mas% of Zr, 0.5 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the secondary alloy raw material. The mass percentage of the secondary alloy raw material in the raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material is 4.0 mas%.

[0047] In one more preferred embodiment, the raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material includes a main alloy raw material and a secondary alloy raw material. Here, the main alloy raw material includes the following components: 22.5 mas% of Nd, 7.5 mas% of Pr, 1.5 mas% of Dy, 0.4 mas% of Ga, 0.25 mas% of Cu, 1.0 mas% of Co, 0.35 mas% of Zr, 0.97 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The secondary alloy raw material includes the following components: 25.0 mas% of Pr, 20.0 mas% of Dy, 4.5 mas% of Zr, 0.5 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the secondary alloy raw material. The mass percentage of the secondary alloy raw material in the raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material is 5.0 mas%.

[0048] In a more preferred embodiment, the raw material composition of the main alloy and the sub-alloy system neodymium iron boron magnet material includes a main alloy raw material and a sub-alloy raw material. Here, the main alloy raw material includes the following components: 18.9 mas% Nd, 6.3 mas% Pr, 4.3 mas% Dy, 1.0 mas% Ho, 0.25 mas% Ga, 0.1 mas% Al, 0.15 mas% Cu, 1.0 mas% Co, 0.2 mas% Zr, 0.97 mas% B, with the balance being Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The sub-alloy raw material includes the following components: 20.0 mas% Pr, 20.0 mas% Dy, 5.0 mas% Ga, 15.0 mas% Co, 5.0 mas% Zr, 0.4 mas% B, with the balance being Fe. Here, mas% means the mass percentage of the component in the sub-alloy raw material. The mass percentage of the sub-alloy raw material in the raw material composition of the main alloy and the sub-alloy system neodymium iron boron magnet material is 4.0 mas%.

[0049] The present invention further provides a method for manufacturing a main alloy and a sub-alloy system neodymium iron boron magnet material, including the following steps:

[0050] S1: After melting the main alloy raw material and the sub-alloy raw material in the raw material composition of the main alloy and the sub-alloy system neodymium iron boron magnet material respectively and then casting, a main alloy and a sub-alloy are obtained respectively.

[0051] S2: After performing hydrogen crushing and fine pulverization on the main alloy and the sub-alloy respectively, they are mixed, and then formed and sintered to obtain the main alloy and the sub-alloy system neodymium iron boron magnet material.

[0052] In the present invention, the melting, casting, hydrogen crushing, fine pulverization, forming, and sintering are all normal operations and conditions in this field.

[0053] In the present invention, the melting can be carried out by a normal method in this field. For example, it can be melted and refined in a melting furnace. The vacuum degree of the melting furnace is approximately 5×10 -2It is Pa. The temperature of the melting and smelting can be 1300 to 1600 °C, preferably 1500 °C to 1550 °C.

[0054] In the present invention, the casting process can be a normal casting process in this field, for example, a strip continuous casting method, an ingot method, a centrifugal casting method or a rapid cooling method.

[0055] In the present invention, the hydrogen crushing process can be a normal process in this field. The dehydrogenation temperature of the hydrogen crushing can be 400 °C to 650 °C, for example, 500 to 620 °C.

[0056] In the present invention, the fine pulverization process can be a normal fine pulverization process in this field. The fine pulverization is preferably carried out in a jet mill. The fine pulverization is preferably carried out in an oxygen-containing atmosphere, and the oxygen content in the oxygen-containing atmosphere is 80 ppm or less, preferably 50 ppm or less. The powder particle size after the fine pulverization is 1 to 20 μm.

[0057] In the present invention, the molding conditions can be normal ones in this field. For example, it is pressed with a press to obtain a green compact. The magnetic field strength of the press is preferably 0.5 T to 3.0 T, for example, 1.0 T to 2.0 T. The pressure of the press can be 200 to 300 MPa, for example, 260 MPa. The time of the press can be normal ones in this field and can be 3 to 30 s, for example, 15 s.

[0058] In the present invention, the sintering conditions can be normal ones in this field. The sintering temperature can be 1000 to 1150 °C, preferably 1060 to 1090 °C. The sintering time can be 4 to 20 hours. The sintering atmosphere is preferably a vacuum or argon gas atmosphere.

[0059] The present invention further provides a main alloy and a main alloy and sub-alloy system neodymium iron boron magnet material manufactured by the method for manufacturing the main alloy and the sub-alloy system neodymium iron boron magnet material.

[0060] In the present invention, the main alloy and the main alloy and sub-alloy system neodymium iron boron magnet material include a main phase and a grain boundary phase, where the main phase has a core-shell structure, and the core is LR2T 14 B, and the shell is HR2T 14 B, and the grain boundary phase includes a neodymium-rich phase, an XB2 phase, and an R6T 13 M phase, where R is LR and / or HR, LR is one or more of Y, La, Ce, Pr, or Nd, HR is one or more of Gd, Dy, Tb, or Ho, M is one or more of Cu, Al, or Ga, X is one or more of Ti, Zr, Hf, Nb, W, or Ta, T is Fe and / or Co.

[0061] Preferably, in the main alloy and the main alloy and sub-alloy system neodymium iron boron magnet material, LR is Pr and Nd, HR is Tb, M is Cu, Al, and Ga, X is Zr, and T is Fe and Co.

[0062] Preferably, in the main alloy and the main alloy and sub-alloy system neodymium iron boron magnet material, LR is Pr and Nd, HR is Dy, M is Cu and Ga, X is Zr, and T is Fe and Co.

[0063] Preferably, in the main alloy and the main alloy and sub-alloy system neodymium iron boron magnet material, LR is Pr and Nd, HR is Dy and Ho, M is Cu, Al, and Ga, X is Ti, and T is Fe and Co.

[0064] In the present invention, the main alloy is LR2Fe 14The B main phase or a certain neodymium-rich phase is provided, and the sub-alloy provides HR as a diffusion source. During the sintering process, HR in the sub-alloy diffuses to the surface layer of the main-phase particles by replacing LR of the main-phase particles through the molten neodymium-rich phase, and a heavy rare-earth shell layer HR2Fe 14 B is formed. The low content of B in the sub-alloy exists as a solid solution, and HR2T 14 The presence of B is reduced, and it becomes easier for HR to form a shell layer on the epitaxial layer of the main-phase particles during the mixing process, improving the utilization efficiency of HR. At the same time, the low content of B makes the sub-alloy pieces easier to pulverize, which is beneficial to the stable operation of the melting equipment and facilitates the subsequent hydrogen crushing. After mixing the main alloy and the sub-alloy, heat treatment is carried out. At high temperature, the X element in the neodymium-rich phase combines with B to form a precipitate XB2, and Fe in the original R-Fe-X and Fe-X is released, increasing the fluidity of the neodymium-rich phase and promoting the formation of the R6T 13 M phase (tetragonal phase, non-magnetic phase or antiferromagnetic phase), ensuring a high residual magnetic flux density (Br) and increasing the intrinsic coercive force (HcJ) of the magnet.

[0065] Based on the common general knowledge in this field, by arbitrarily combining the above-mentioned suitable conditions, each preferred example of the present invention can be obtained.

[0066] The reagents and raw materials used in the present invention are all commercially available.

Advantages of the Invention

[0067] The positive and progressive effects of the present invention are as follows: That is, the present invention constructs a combination of a main alloy and a sub-alloy, combines a specific raw material mixing ratio, forms a heavy rare-earth shell layer on the neodymium-iron-boron main-phase particles, improves the fluidity of the neodymium-rich phase, and increases the intrinsic coercive force of the magnet while ensuring a high residual magnetic flux density. The manufacturing method of the present invention is simple and easy to implement, and can realize engineering applications.

Brief Description of the Drawings

[0068]

Figure 1

Figure 2

Embodiments for Carrying out the Invention

[0069] Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited to the scope of the above examples. In the following examples, experimental methods for which specific conditions are not specified are selected according to normal methods and conditions or according to the product specification sheets. Examples 1 to 3

[0070] (1) Casting process: According to the mixing ratios shown in Examples 1 to 3 in Table 1 below, the main alloy raw material and the secondary alloy raw material in the raw material composition of the main alloy and the secondary alloy system neodymium iron boron magnet material are respectively put into a vacuum melting furnace, and vacuum melting is carried out at a temperature of 1500 - 1550 °C in a vacuum of about 5×10 -2 Pa, and then the molten liquid obtained by melting by the strip continuous casting method is respectively cast to produce a main alloy piece and a secondary alloy piece.

[0071] (2) Hydrogen crushing process: At room temperature, the main alloy piece and the secondary alloy piece in step (1) are respectively suctioned with hydrogen, and then vacuum dehydrogenation treatment is carried out at 500 - 620 °C to obtain coarsely pulverized powder.

[0072] (3) Fine pulverization treatment: The coarsely pulverized powder in step (2) is finely pulverized in a jet mill in an atmosphere with an oxygen content of 50 ppm or less to obtain finely pulverized powder with an average particle size D50 of 1 - 20 μm.

[0073] (4) Molding process: Press with a press machine with a magnetic field strength of 1.0 - 2.0 T to form a green compact, and then maintain it for 15 seconds under the condition of a pressure of 260 MPa, that is, a molded body is obtained.

[0074] (5) Sintering process: The compact is sintered at a temperature of 1060 - 1090 °C, and the sintering atmosphere is a vacuum or an argon gas atmosphere, i.e., a neodymium iron boron permanent magnet material is obtained.

[0075] Table 1 Components and contents (mas%) of the raw material compositions of the main alloy and the secondary alloy system neodymium iron boron magnet material JPEG0007711200000001.jpg214161 Here, " / " indicates that the component is not included. Effect implementation examples

[0076] (1) Transmission electron microscope (TEM) test The main alloy and the secondary alloy system neodymium iron boron magnet material obtained in Example 3 were taken, and the phase structure of the magnet material was observed using TEM, and the results are shown in Fig. 1. Fig. 1 shows the elemental distribution in the grain boundary phase in the Ti-rich region. It can be seen that Ti is closely related to the B element. Combining the phase diagram and thermodynamic calculations, this phase is TiB2. However, Zr, Ti, Hf, etc. are homologous elements, and it can be seen that any of them can produce this phase in the production of neodymium iron boron. TiB2 is a high-temperature ceramic phase, which maintains stability in a wide temperature range, purifies the B in the grain boundary, makes the fluidity of the Nd-rich phase better, and provides favorable conditions for the formation of phases such as tetragonal Nd6Fe 13 Ga, etc.

[0077] (2) Magnetic property test The main alloy and the secondary alloy system neodymium iron boron magnet material obtained in Examples 1 - 3 were taken, and the magnetic properties were inspected using a PFM14.CN type ultra-high coercivity permanent magnet measuring instrument of the National Institute of Metrology of China.

[0078] Table 2 Magnetic properties of the main alloy and the secondary alloy system neodymium iron boron magnet material JPEG0007711200000002.jpg36161

[0079] "Br" means the residual magnetic flux density. After the permanent magnet material is saturated magnetized, the magnetism that can be retained after removing the external magnetic field is called the residual magnetic flux density. The magnetic polarization intensity coercivity is H cJIt is (intrinsic coercive force).

[0080] (3) FE-EPMA test Taking the master alloy and the sub-alloy system neodymium iron boron magnet material obtained in Example 1, as shown in Fig. 2, an elemental analysis diagram (Tb, Al, Ga, Co, B, CP, Nd, Cu, Zr, etc.) is formed by FE-EPMA surface scanning. As can be seen from Fig. 2, heavy rare earth elements such as Tb form a rich shell layer in the epitaxial layer of the main phase, high-temperature elements such as Zr are uniformly distributed in the grain boundary phase, B in the neodymium-rich phase is purified, and tetragonal Nd6Fe 13 Antiferromagnetic phases such as Ga are more likely to be generated, and both of them enhance the coercive force of the magnet.

Claims

1. A raw material composition for a master alloy and a sub-alloy system neodymium iron boron magnet material, comprising a master alloy raw material and a sub-alloy raw material, wherein the master alloy raw material contains the following components: LR: 10.0 to 33.0 mas%, where LR is a light rare earth element, LR is one or more of Y, La, Ce, Pr, Nd, and LR contains Nd, HR: 0 to 20.0 mas%, where HR is a heavy rare earth element, HR is one or more of Gd, Dy, Tb, Ho, M: 0.1 to 5.0 mas%, where M is one or more of Co, Cu, Al, Ga, X: 0.05 to 0.7 mas%, where X is one or more of Zr, Ti, Nb, B: 0.94 to 1.1 mas%, the balance is Fe, where mas% means the mass percentage of the component in the master alloy raw material, the sub-alloy raw material contains the following components: LR: 20.0 to 30.0 mas%, where LR is a light rare earth element, LR is Nd and / or Pr, HR: 1 to 20 mas%, where HR is a heavy rare earth element, HR is Dy and / or Tb, M: 5.0 to 20.0 mas%, where M is one or more of Co, Cu, Al, Ga, X: 3.0 to 12.0 mas%, where X is one or more of Ti, Zr, Hf, Nb, W, Ta, B: 0 to 0.6 mas%, the balance is Fe, where mas% means the mass percentage of the component in the sub-alloy raw material, the mass percentage of the sub-alloy raw material in the raw material composition of the master alloy and the sub-alloy system neodymium iron boron magnet material is 1.0 to 5.0 mas%, A raw material composition for a master alloy and a sub-alloy system neodymium iron boron magnet material, characterized by the above.

2. The total rare earth content TRE in the master alloy raw material is 26.0 to 40.0 mas%, where mas% means the mass percentage of the component in the master alloy raw material, and / or the content of LR in the master alloy raw material is 25.0 to 30.0 mas%, where mas% means the mass percentage of the component in the master alloy raw material, And / or, when the LR in the master alloy raw material contains Nd, the content of the Nd is 18.9 to 22.5 mas%, and when the LR in the master alloy raw material contains Pr, the content of the Pr is 6.0 to 7.5 mas%. Here, mas% means the mass percentage in the master alloy raw material of the component. And / or, the LR in the master alloy raw material contains Nd and Pr. And / or, the content of the HR in the master alloy raw material is 1.0 to 10.0 mas%. Here, mas% means the mass percentage in the master alloy raw material of the component. And / or, when the HR in the master alloy raw material contains Dy, the content of the Dy is 1.0 to 5.0 mas%, and when the HR in the master alloy raw material contains Ho, the content of the Ho is 0.5 to 2.0 mas%. Here, mas% means the mass percentage in the master alloy raw material of the component. And / or, the content of the M in the master alloy raw material is 0.5 to 2.0 mas%. Here, mas% means the mass percentage in the master alloy raw material of the component. And / or, when the M in the master alloy raw material contains Ga, the content of the Ga is 0.2 to 0.4 mas%, when the M in the master alloy raw material contains Al, the content of the Al is 0.01 to 0.1 mas%, when the M in the master alloy raw material contains Cu, the content of the Cu is 0.1 to 0.25 mas%, and when the M in the master alloy raw material contains Co, the content of the Co is 0.5 to 1.0 mas%. Here, mas% means the mass percentage in the master alloy raw material of the component. And / or, the content of the X in the master alloy raw material is 0.1 to 0.35 mas%. Here, mas% means the mass percentage in the master alloy raw material of the component. The X in the master alloy raw material is Zr or Ti. And / or, the content of the B in the master alloy raw material is 0.97 to 0.99 mas%. Here, mas% means the mass percentage in the master alloy raw material of the component. The raw material composition of the master alloy and the sub-alloy system neodymium iron boron magnet material according to claim 1, characterized by the above.

3. The main alloy raw material contains the following components: 22.125 mas% of Nd, 7.375 mas% of Pr, 0.25 mas% of Ga, 0.03 mas% of Al, 0.1 mas% of Cu, 0.5 mas% of Co, 0.11 mas% of Zr, 0.98 mas% of B, with the balance being Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. Alternatively, the main alloy raw material contains the following components: 22.5 mas% of Nd, 7.5 mas% of Pr, 1.5 mas% of Dy, 0.4 mas% of Ga, 0.25 mas% of Cu, 1.0 mas% of Co, 0.35 mas% of Zr, 0.97 mas% of B, with the balance being Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. Alternatively, the main alloy raw material contains the following components: 18.9 mas% of Nd, 6.3 mas% of Pr, 4.3 mas% of Dy, 1.0 mas% of Ho, 0.25 mas% of Ga, 0.1 mas% of Al, 0.15 mas% of Cu, 1.0 mas% of Co, 0.15 mas% of Ti, 0.97 mas% of B, with the balance being Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The raw material composition of the main alloy and the sub-alloy system neodymium iron boron magnet material according to claim 1, characterized in that.

4. The total rare earth content TRE in the sub-alloy raw material is 35.0 to 50.0 mas%. Here, mas% means the mass percentage of the component in the sub-alloy raw material. And / or when the LR in the sub-alloy raw material contains Nd, the content of Nd is 10.0 to 20.0 mas%. When the LR in the sub-alloy raw material contains Pr, the content of Pr is 15.0 to 25.0 mas%. Here, mas% means the mass percentage of the component in the sub-alloy raw material. And / or the LR in the sub-alloy raw material is Nd and Pr, the content of Nd is 15.0 mas%, and the content of Pr is 15.0 mas%. Here, mas% means the mass percentage of the component in the sub-alloy raw material. And / or the content of the HR in the sub-alloy raw material is 15.0 to 20.0 mas%. Here, mas% means the mass percentage of the component in the sub-alloy raw material. And / or, when the HR in the sub-alloy raw material is Tb, the content of Tb is 15.0 mas%, where mas% means the mass percentage in the sub-alloy raw material of the component, And / or, when the HR in the sub-alloy raw material is Dy, the content of Dy is 20.0 mas%, where mas% means the mass percentage in the sub-alloy raw material of the component, And / or, when the M in the sub-alloy raw material contains Ga, the content of Ga is 2.0 - 10.0 mas%, and when the M in the sub-alloy raw material contains Co, the content of Co is 10.0 - 20.0 mas%, here, mas% means the mass percentage in the sub-alloy raw material of the component, And / or, the content of X in the sub-alloy raw material is 4.0 - 10.0 mas%, where mas% means the mass percentage in the sub-alloy raw material of the component, And / or, the content of B in the sub-alloy raw material is 0.3 - 0.6 mas%, where mas% means the mass percentage in the sub-alloy raw material of the component, And / or, the mass percentage of the sub-alloy raw material in the raw material composition of the main alloy and sub-alloy system neodymium iron boron magnet material is 2.0 - 5.0 mas%, The raw material composition of the main alloy and sub-alloy system neodymium iron boron magnet material according to claim 1, characterized in that.

5. The sub-alloy raw material contains the following components: 15.0 mas% of Nd, 15.0 mas% of Pr, 15.0 mas% of Tb, 10.0 mas% of Zr, 0.5 mas% of B, and the balance is Fe, here, mas% means the mass percentage in the sub-alloy raw material of the component, Or, the sub-alloy raw material contains the following components: 25.0 mas% of Pr, 20.0 mas% of Dy, 4.5 mas% of Zr, 0.5 mas% of B, and the balance is Fe, here, mas% means the mass percentage in the sub-alloy raw material of the component, Or, the sub-alloy raw material contains the following components: 20.0 mas% of Pr, 20.0 mas% of Dy, 5.0 mas% of Ga, 15.0 mas% of Co, 5.0 mas% of Zr, 0.4 mas% of B, and the balance is Fe, here, mas% means the mass percentage in the sub-alloy raw material of the component, The raw material composition of the main alloy and sub-alloy system neodymium iron boron magnet material according to claim 1, characterized in that.

6. The raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material includes a main alloy raw material and a secondary alloy raw material. Here, the main alloy raw material includes the following components: 22.125 mas% of Nd, 7.375 mas% of Pr, 0.25 mas% of Ga, 0.03 mas% of Al, 0.1 mas% of Cu, 0.5 mas% of Co, 0.11 mas% of Zr, 0.98 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The secondary alloy raw material includes the following components: 15.0 mas% of Nd, 15.0 mas% of Pr, 15.0 mas% of Tb, 10.0 mas% of Zr, 0.5 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the secondary alloy raw material. The mass percentage of the secondary alloy raw material in the raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material is 4.0 mas%. Alternatively, the raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material includes a main alloy raw material and a secondary alloy raw material. Here, the main alloy raw material includes the following components: 22.5 mas% of Nd, 7.5 mas% of Pr, 1.5 mas% of Dy, 0.4 mas% of Ga, 0.25 mas% of Cu, 1.0 mas% of Co, 0.35 mas% of Zr, 0.97 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The secondary alloy raw material includes the following components: 25.0 mas% of Pr, 20.0 mas% of Dy, 4.5 mas% of Zr, 0.5 mas% of B, and the balance is Fe. Here, mas% means the mass percentage of the component in the secondary alloy raw material. The mass percentage of the secondary alloy raw material in the raw material composition of the main alloy and the secondary alloy-based neodymium iron boron magnet material is 5.0 mas%. Alternatively, the raw material composition of the main alloy and the secondary alloy system neodymium iron boron magnet material includes a main alloy raw material and a secondary alloy raw material. Here, the main alloy raw material includes the following components: 18.9 mas% Nd, 6.3 mas% Pr, 4.3 mas% Dy, 1.0 mas% Ho, 0.25 mas% Ga, 0.1 mas% Al, 0.15 mas% Cu, 1.0 mas% Co, 0.2 mas% Zr, 0.97 mas% B, and the balance is Fe. Here, mas% means the mass percentage of the component in the main alloy raw material. The secondary alloy raw material includes the following components: 20.0 mas% Pr, 20.0 mas% Dy, 5.0 mas% Ga, 15.0 mas% Co, 5.0 mas% Zr, 0.4 mas% B, and the balance is Fe. Here, mas% means the mass percentage of the component in the secondary alloy raw material. The mass percentage of the secondary alloy raw material in the raw material composition of the main alloy and the secondary alloy system neodymium iron boron magnet material is 4.0 mas%. The raw material composition of the main alloy and the secondary alloy system neodymium iron boron magnet material according to claim 1, characterized in that.

7. A method for manufacturing a main alloy and a secondary alloy system neodymium iron boron magnet material, comprising the following steps: S1: After melting the main alloy raw material and the secondary alloy raw material in the raw material composition of the main alloy and the secondary alloy system neodymium iron boron magnet material according to any one of claims 1 to 6, respectively, casting is performed to obtain a main alloy and a secondary alloy, respectively. S2: After performing hydrogen crushing and fine pulverization on the main alloy and the secondary alloy, respectively, mixing is performed, and then shaping and sintering treatment are performed to obtain the main alloy and the secondary alloy system neodymium iron boron magnet material. A method for manufacturing a main alloy and a secondary alloy system neodymium iron boron magnet material, characterized in that.

8. The melting is carried out by melting and smelting in a melting furnace, and the vacuum degree of the melting furnace is 5×10 －２ Pa, and the temperature of the melting and smelting is 1300 to 1600 °C, And / or, the casting process is a strip continuous casting method, an ingot method, a centrifugal casting method or a rapid cooling method. And / or, the dehydrogenation temperature of the hydrogen crushing is 400°C to 650°C. And / or, the fine pulverization is performed in a jet mill. And / or, the fine pulverization is performed in an oxygen-containing atmosphere, and the oxygen content in the oxygen-containing atmosphere is 80 ppm or less. And / or, the powder particle size after the fine pulverization is 1 to 20 μm. And / or, the molding conditions are to press with a press machine to form a green compacted powder, the magnetic field strength of the press machine is 0.5 T to 3.0 T, the pressure of the press is 200 to 300 MPa, and the time of the press is 3 to 30 s. And / or, the sintering temperature is 1000 to 1150 °C. And / or, the sintering time is 4 to 20 hours. And / or, the sintering atmosphere is a vacuum or argon gas atmosphere. The method for manufacturing a main alloy and secondary alloy system neodymium iron boron magnet material according to claim 7, characterized by the above.

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