阅读说明：本技术 耐高温磁体及其制造方法 (High-temperature-resistant magnet and manufacturing method thereof ) 是由 王传申 彭众杰 杨昆昆 丁开鸿 于 2021-09-24 设计创作，主要内容包括：本发明公开了一种耐高温磁体及制造方法,属于磁体制备领域,通过设计晶界为低熔点磁体,并在该磁体上形成具有特殊扩散源,进行扩散、时效处理,得到高性能耐高温的钕铁硼磁体。低重稀土扩散源化学式为R-(1x)R-(2y)H-(z)M-(1-x-y-z),其中R-(1)是指Nd,Pr中的至少一种,R-(2)为Ho、Gd中至少一种,H是指Tb,Dy中的至少一种,M是指Al、Cu、Ga、Ti、Co、Mg、Zn、Sn中至少一种,其中15＜x＜50,0＜y≤10,40≤z≤70,比例为重量百分比,得到具有晶界结构包括主相,壳层和特定成分的三角区点扫成分。本发明所述的一种耐高温磁体及制造方法,耐高温性能和矫顽力均有大幅度地提升。(The invention discloses a high-temperature resistant magnet and a manufacturing method thereof, belonging to the field of magnet preparation. The chemical formula of the low heavy rare earth diffusion source is R 1x R 2y H z M 1‑x‑y‑z Wherein R is 1 Refers to at least one of Nd and Pr, R 2 At least one of Ho and Gd, H is at least one of Tb and Dy, M is at least one of Al, Cu, Ga, Ti, Co, Mg, Zn and Sn, wherein x is more than 15 and less than 50, y is more than 0 and less than or equal to 10, z is more than or equal to 40 and less than or equal to 70, and the proportion is weight percentage, so that the point scanning component with a grain boundary structure comprising a main phase, a shell layer and specific components is obtained. The high-temperature resistant magnet and the manufacturing method thereof greatly improve the high-temperature resistance and the coercive force.)

1. A high temperature resistant magnet characterized by: the grain boundary structure of the magnet comprises a main phase structure, an R shell layer, a transition metal shell layer and a triangular region, wherein the R shell layer is at least one of Nd, Pr, Ho and Gd, the transition metal shell layer is at least one of Cu, Al and Ga, the triangular region point scanning component comprises a component I, a component II and/or a component III, and the component III,

the component I is Nd_aFe_bR_cM_dThe material is characterized in that R is at least one of Pr, Ce and La, M is at least three of Al, Cu, Ga, Ti, Co, Mg, Zn, Sn and Zr, the weight percentage of Nd is a, 30% to 70% of a, the weight percentage of Fe is b, 5% to 40% of b, the weight percentage of R is c, 5% to 35% of c, and 0% to 15% of d;

the component II is Nd_eFe_fR_gH_hK_iM_jThe material is characterized in that R is at least one of Pr, Ce and La, H is at least one of Dy and Tb, K is one of Ho and Gd, M is at least three of Al, Cu, Ga, Ti, Co, Mg, Zn, Sn and Zr, the weight percentage of Nd is e, e is more than or equal to 25% and less than or equal to 65%, the weight percentage of Fe is f, f is more than or equal to 5% and less than or equal to 35%, the weight percentage of R is g, g is more than or equal to 5% and less than or equal to 30%, the weight percentage of H is H, H is more than or equal to 5% and less than or equal to 30%, the weight percentage of K is i, i is more than or equal to 1% and less than or equal to 12%, and j is more than or equal to 0% and less than or equal to 10%;

the component III is Nd_kFe_lR_mD_nM_oThe material is characterized in that R is at least one of Pr, Ce and La, D is at least one of Al, Cu and Ga, M is at least one of Ti, Co, Mg, Zn, Sn and Zr, the weight percentage of Nd is k, k is more than or equal to 30% and less than or equal to 70%, the weight percentage of Fe is l, l is more than or equal to 5% and less than or equal to 35%, the weight percentage of R is M, M is more than or equal to 5% and less than or equal to 35%, the weight percentage of D is n, n is more than or equal to 5% and less than or equal to 25%, the weight percentage of M is o, and o is more than or equal to 0% and less than or equal to 10%.

2. The high temperature resistant magnet of claim 1, wherein: the thickness of the magnet is 0.3-6 mm.

3. A method of manufacturing the high temperature resistant magnet of claim 1, comprising the steps of:

(S1) smelting and quickly solidifying the prepared neodymium iron boron alloy raw material to obtain a neodymium iron boron alloy sheet, and mechanically crushing the prepared alloy sheet into 150-400 mu m scale-shaped alloy sheets;

(S2) mechanically mixing and stirring the flaky alloy flakes, the low-melting-point powder and the lubricant, then putting the mixture into a hydrogen treatment furnace for hydrogen absorption and dehydrogenation treatment, and preparing neodymium-iron-boron powder through airflow milling, wherein the particle size of the neodymium-iron-boron powder is 3-5 microns;

(S3) pressing and molding the neodymium iron boron powder, and sintering to obtain the required neodymium iron boron magnet;

(S4) machining the sintered NdFeB magnet into a required shape, and then forming a low-gravity rare earth diffusion source film on a surface of the magnet perpendicular to or parallel to the C axis direction in a coating mode, wherein the preparation method of the diffusion source is atomizing powder preparation, amorphous melt spinning or ingot casting;

(S5) finally, diffusion and tempering are carried out, and the neodymium iron boron magnet with the structural characteristics is obtained.

4. The manufacturing method according to claim 3, characterized in that: in the step (S1), the neodymium iron boron alloy comprises the following raw materials, by weight, 28% to 30% of R, 0.8% to 1.2% of B, 0% to 3% of M, and the balance Fe, wherein the R is at least two of Nd, Pr, Ce, La, Tb, Dy, Ho, and Gd, and the M is at least one of Co, Mg, Ti, Zr, Nb, and Mo.

5. The manufacturing method according to claim 3, characterized in that: in the step (S2), the low-melting-point powder material includes at least one of NdCu, NdAl, and NdGa in an amount of 0% to 3% NdCu, 0% to 3% NdAl, and 0% to 3% NdGa, and the low-melting-point powder material is 200nm to 4 μm.

6. The manufacturing method according to claim 3, characterized in that: in the step (S2), the dehydrogenation temperature is 400-600 ℃.

7. The manufacturing method according to claim 3, characterized in that: in the step (S3), argon gas is needed to be introduced for cooling after sintering is completed, and then primary tempering treatment and secondary aging treatment are carried out, wherein the sintering temperature is 980 and 1060 ℃, and the sintering time is 6-15 h; the primary aging temperature is 850 ℃, and the primary aging time is 3 h; the secondary aging temperature is 450-660 ℃, and the secondary aging time is 3 h.

8. The manufacturing method according to claim 3, characterized in that: in the step (S4), the low heavy rare earth diffusion source film has a composition of R_1xR_2yH_zM_1-x-y-zWherein, said R₁Is at least one of Nd and Pr, and the R₁X is more than 15 percent and less than 50 percent, and R is₂Is at least one of Ho and Gd, and the R₂The weight percentage of the metal oxide is y, y is more than 0% and less than or equal to 10%, H is at least one of Tb and Dy, the weight percentage of H is z, z is more than or equal to 40% and less than or equal to 70%, M is at least one of Al, Cu, Ga, Ti, Co, Mg, Zn and Sn, and the weight percentage of M is 1-x-y-z.

9. The manufacturing method according to claim 3, characterized in that: in the step (S5), the diffusion temperature of the NdFeB magnet is 850-.

10. The manufacturing method according to claim 7, characterized in that: the heating speed of the aging temperature of the neodymium iron boron magnet is 1-5 ℃/min, and the cooling speed is 5-20 ℃/min.

Technical Field

The invention relates to the field of magnets and magnet preparation, in particular to a high-temperature-resistant magnet and a manufacturing method thereof.

Background

The neodymium iron boron sintered permanent magnet is widely applied to high and new technical fields of electronic information, medical equipment, new energy automobiles, household appliances, robots and the like. In the development process of the past decades, the neodymium iron boron permanent magnet is rapidly developed, and the remanence basically reaches the theoretical limit. However, the coercivity is far from the theoretical value, so that the improvement of the coercivity of the magnet is a great research hotspot.

Since the conventional manufacturing process consumes a large amount of Tb or Dy heavy rare earth metal, the cost increases. Although the content of the heavy rare earth can be greatly reduced by the grain boundary diffusion technology, the cost is still high along with the rapid price rise of the current heavy rare earth Tb. Therefore, it is still important to continuously reduce the content of heavy rare earths. The coercive force can be increased by forming a large number of core-shell structures through diffusion hardening of the Nd2Fe14B main phase containing heavy rare earth elements. Therefore, research on magnets and research on diffusion sources have become the focus of this solution.

Although the effect of enhancing the coercive force is most remarkably diffused by the heavy rare earth, the abundance of the heavy rare earth is low and the price is expensive. Therefore, more and more researchers achieve the purpose of increasing the coercive force of the magnet through diffusion by preparing the low-melting-point heavy rare earth alloy as a diffusion source. The patent with the special grain boundary phase is mainly designed on the magnetism itself, and the application is more, such as the patent with the publication number of CN112735717A, namely the name of a neodymium iron boron material and a preparation method thereof, in the patent, the surface of a magnet is coated with a magnet with a special structure of heavy rare earth Tb and Dy diffusion, so that the diffusion depth of the magnet is improved, and the coercive force is improved; the patent with the publication number of CN105513734A, namely the light and heavy rare earth mixture for the neodymium iron boron magnet, the neodymium iron boron magnet and the preparation method thereof, mainly has high Hcj performance increase range after the light and heavy rare earth mixture is diffused, but the light and heavy rare earth mixture has poor uniformity and is difficult to play a special role of improving the diffusion coefficient of the magnet after the alloy is formed. Although the coercive force of the magnet can be greatly increased by the low-melting-point heavy rare earth diffusion source, the high-temperature resistance of the magnet is poor, namely the residual magnetism and the coercive force of the magnet are low in high-temperature performance.

Therefore, it is necessary to find a method which can improve the diffusion depth, i.e. the depth of the core-shell structure, through the melting point alloy phase and can also improve the high temperature resistance of the magnet.

Disclosure of Invention

The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides a high-temperature resistant magnet and a manufacturing method thereof.

The technical scheme is as follows: in order to achieve the above purpose, the grain boundary structure of the magnet of the present invention comprises a main phase structure, an R shell layer, a transition metal shell layer and a triangular region, wherein the R shell layer is at least one of Nd, Pr, Ho and Gd, the transition metal shell layer is at least one of Cu, Al and Ga, the triangular region point-scanning component comprises a component i, a component ii and/or a component iii,

the component I is Nd_aFe_bR_cM_dThe material is characterized in that R is at least one of Pr, Ce and La, M is at least three of Al, Cu, Ga, Ti, Co, Mg, Zn, Sn and Zr, the weight percentage of Nd is a, 30% to 70% of a, the weight percentage of Fe is b, 5% to 40% of b, the weight percentage of R is c, 5% to 35% of c, and 0% to 15% of d;

the component II is Nd_eFe_fR_gH_hK_iM_jThe material is characterized in that R is at least one of Pr, Ce and La, H is at least one of Dy and Tb, K is one of Ho and Gd, M is at least three of Al, Cu, Ga, Ti, Co, Mg, Zn, Sn and Zr, the weight percentage of Nd is e, e is more than or equal to 25% and less than or equal to 65%, the weight percentage of Fe is f, f is more than or equal to 5% and less than or equal to 35%, the weight percentage of R is g, g is more than or equal to 5% and less than or equal to 30%, the weight percentage of H is H, H is more than or equal to 5% and less than or equal to 30%, the weight percentage of K is i, i is more than or equal to 1% and less than or equal to 12%, and j is more than or equal to 0% and less than or equal to 10%;

the component III is Nd_kFe_lR_mD_nM_oR is at least one of Pr, Ce and La, D is at least one of Al, Cu and Ga, M is at least one of Ti, Co, Mg, Zn, Sn and Zr, the weight percentage of Nd is k, k is more than or equal to 30% and less than or equal to 70%, the weight percentage of Fe is l, l is more than or equal to 5% and less than or equal to 35%, the weight percentage of R is M, M is more than or equal to 5% and less than or equal to 35%, the weight percentage of D is n, n is more than or equal to 5% and less than or equal to 25%, and the weight percentage of M isThe ratio of o is more than or equal to 0% and less than or equal to 10%.

Further, the thickness of the magnet is 0.3-6 mm.

A method of manufacturing the high temperature resistant magnet, comprising the steps of:

(S1) smelting and quickly solidifying the prepared neodymium iron boron alloy raw material to obtain a neodymium iron boron alloy sheet, and mechanically crushing the prepared alloy sheet into 150-400 mu m scale-shaped alloy sheets;

(S2) mechanically mixing and stirring the flaky alloy flakes, the low-melting-point powder and the lubricant, then putting the mixture into a hydrogen treatment furnace for hydrogen absorption and dehydrogenation treatment, and preparing neodymium-iron-boron powder through airflow milling, wherein the particle size of the neodymium-iron-boron powder is 3-5 microns;

(S3) pressing and molding the neodymium iron boron powder, and sintering to obtain the required neodymium iron boron magnet;

(S4) machining the sintered NdFeB magnet into a required shape, and then forming a low-gravity rare earth diffusion source film on a surface of the magnet perpendicular to or parallel to the C axis direction in a coating mode, wherein the preparation method of the diffusion source is atomizing powder preparation, amorphous melt spinning or ingot casting.

(S5) finally, diffusion and tempering are carried out, and the neodymium iron boron magnet with the structural characteristics is obtained.

Preferably, in the step (S1), the neodymium iron boron alloy raw material components and weight percentages thereof are respectively, R is equal to or greater than 28% and equal to or less than 30%, B is equal to or greater than 0.8% and equal to or less than 1.2%, M is equal to or greater than 0% and equal to or less than 3%, and the balance is Fe, wherein R is at least two of Nd, Pr, Ce, La, Tb and Dy, and M is at least one of Co, Mg, Ti, Zr, Nb and Mo.

Preferably, in the step (S2), the low melting point frit includes NdCu, NdAl and NdGa in respective weight percentages of 0% or more and 3% or less NdCu, 0% or more and 3% or less NdAl, and 0% or more and 3% or less NdGa, and the low melting point frit is 200nm to 4 μm.

Preferably, in the step (S2), the dehydrogenation temperature is 400-600 ℃.

Preferably, in the step (S3), after sintering, argon gas is introduced for cooling, and then primary tempering treatment and secondary aging treatment are performed, wherein the sintering temperature is 980-; the primary aging temperature is 850 ℃, and the primary aging time is 3 h; the secondary aging temperature is 450-660 ℃, and the aging time is 3 h.

Preferably, in the step (S4), the composition of the low heavy rare earth diffusion source thin film is R_1xR_2yH_zM_1-x-y-zWherein, said R₁Is at least one of Nd and Pr, and the R₁X is more than 15 percent and less than 50 percent, and R is₂Is at least one of Ho and Gd, and the R₂The weight percentage of the metal oxide is y, y is more than 0% and less than or equal to 10%, H is at least one of Tb and Dy, the weight percentage of H is z, z is more than or equal to 40% and less than or equal to 70%, M is at least one of Al, Cu, Ga, Ti, Co, Mg, Zn and Sn, and the weight percentage of M is 1-x-y-z.

Preferably, in the step (S5), the diffusion temperature of the ndfeb magnet is 850-.

Preferably, the temperature rising speed of the aging temperature of the neodymium iron boron magnet is 1-5 ℃/min, and the temperature reduction speed is 5-20 ℃/min.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) by designing the crystal boundary as a low-melting-point magnet and forming a diffusion source with a special function on the magnet, performing diffusion and aging treatment to obtain the neodymium iron boron magnet with a specific crystal boundary structure and low heavy rare earth content; the coercive force is greatly improved by regulating and controlling the components of the magnet and the diffusion source structure;

(2) the magnet has high temperature resistance, overcomes the defect that the coercivity of a low-melting-point magnet and a diffusion source is greatly improved and the high temperature resistance is poor, and can realize the mass production of products;

(3) performing an optimization process test on the designed magnet, then performing a diffusion test on the magnet to achieve the optimal performance, wherein the coercivity increase amplitude after the Dy alloy is diffused can reach 8-10.5 kOe;

(4) the diffusion magnet matrix contains NdCu, NdAl and NdGa of low melting point phases, which is beneficial to increasing the diffusion coefficient of the magnet grain boundary, thereby improving the diffusion efficiency of a diffusion source;

(5) the diffusion source not only enables the low-melting-point phase and the heavy rare earth to rapidly enter the magnet when the low-melting-point phase and the heavy rare earth are the same, greatly improves the high-temperature resistance of the magnet, but also can well form a shell layer with a magnetic isolation effect, thereby improving the coercivity.

Drawings

FIG. 1 is a schematic representation of SEM-based experimental sampling using a ZISS electron microscope.

Detailed Description

The principles and features of the present invention are described below in conjunction with fig. 1, which is provided by way of example only to illustrate the present invention and not to limit the scope of the present invention.

It is also noted that the term "and/or" is intended to be inclusive and not exclusive, such that the term includes not only the listed elements, but also elements that are not expressly listed as elements of a method, process, article, or apparatus.

A method for manufacturing a high-temperature resistant magnet comprises the following steps:

(S1) preparing a neodymium iron boron alloy sheet by rapidly solidifying the prepared neodymium iron boron alloy raw material through smelting, and mechanically crushing the prepared alloy sheet into a 150-400-micron scaly alloy sheet;

(S2) mechanically mixing and stirring the flake-like alloy, the low-melting-point powder containing NdCu, NdAl and NdGa, and the lubricant, wherein the numbers of the flake-like alloy, the low-melting-point powder containing NdCu, NdAl and NdGa, and the lubricant are respectively 1-22 according to the content of each element, and the numbers are shown in the following Table 1; then placing the neodymium iron boron powder into a hydrogen treatment furnace for hydrogen absorption and dehydrogenation treatment, wherein the dehydrogenation temperature is 600 ℃, and preparing neodymium iron boron powder through jet milling D50, and the particle size of the neodymium iron boron powder is 3-5 μm;

(S3) performing orientation forming and cold isostatic pressing on the alloy powder after the jet milling to prepare a blank, performing vacuum sintering on a pressed compact, introducing argon for rapid cooling, then performing primary tempering and secondary aging, and testing the performance of the magnet, wherein the specific process is shown in Table 2;

(S4) machining the blank, cutting the machined blank into samples with corresponding sizes, and coating the diffusion source slurry on two sides of the samples, which are perpendicular to the C axis;

(S5) finally, diffusion and tempering are carried out, and the neodymium iron boron magnet with the structural characteristics is obtained.

The examples were carried out with Ho or Gd in the diffusion source and the comparative examples without Ho or Gd in the diffusion source, and the respective process conditions of the examples are shown in table 3, and the corresponding process conditions of the comparative examples are shown in table 4.

TABLE 1 alloy flakes, quick setting flakes and lubricant mixed elements and their contents

TABLE 2 Process conditions in the Components

Table 3 diffusion sources and process condition performance for each example

TABLE 4 comparative diffusional sources and their process condition performance

Based on the data, NdCu, NdAl or NdGa phase powder is added into the grain boundary of the melt-spun sheet to prepare the NdFeB permanent magnet with the grain boundary having a low-melting point grain boundary channel and suitable for magnet diffusion, the diffusion is facilitated, particularly the diffusion of a heavy rare earth dysprosium alloy diffusion source, after the diffusion, the Delta Hcj is more than 7.5kOe, the coercive force is obviously increased, and the coercive force high temperature resistance coefficient is obviously superior to that of a comparative example.

Specifically, each of examples and comparative examples was analyzed as follows:

example 1, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature and the like, compared with the condition before diffusion, Br of PrHoDyCu diffused in example 1 is reduced by 0.23kGS, Hcj is increased by 10.61kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.50%; comparative example 1 Br of diffused PrDyCu was decreased by 0.2kGS, Hcj was increased by 10.21kOe, and the coercive force of the magnet had a coefficient of-0.53% at 150 ℃; the advantages of example 1 are evident.

Example 2, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature and the like, compared with the condition before diffusion, Br of PrHoDyCu diffused in example 2 is reduced by 0.26kGS, Hcj is increased by 9.08kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.495%; comparative example 2 Br of diffused PrDyCu was decreased by 0.24kGS, Hcj was increased by 8.78kOe, and the coercive force of the magnet had a coefficient of-0.510% at 150 ℃; the advantages of example 2 are evident.

Example 3, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature and the like, compared with the condition before diffusion, Br of PrHoDyCu diffused in example 3 is reduced by 0.24kGS, Hcj is increased by 8.08kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.45%; comparative example 3 Br of diffused PrDyCu was decreased by 0.22kGS, Hcj was increased by 7.58kOe, and the coercive force of the magnet had a coefficient of-0.51% high temperature resistance at 150 ℃; the advantages of example 3 are evident.

Example 4, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, Br of PrHoDyCu diffused in example 4 is reduced by 0.26kGS, Hcj is increased by 8.02kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.497%; comparative example 4 Br of diffused PrDyCu was decreased by 0.24kGS, Hcj was increased by 7.52kOe, and the coercive force of the magnet had a coefficient of-0.52% at 150 ℃; the advantages of example 4 are evident.

Example 5, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, the Br of the diffused NdHoDyCu in example 5 is reduced by 0.27kGS, the Hcj is increased by 10.11kOe, and the coefficient of the coercive force of the magnet for resisting high temperature of 150 ℃ is-0.49%; comparative example 5 Br of diffused NdDyCu was decreased by 0.25kGS, Hcj was increased by 9.51kOe, and the coercive force of the magnet had a coefficient of high temperature resistance of 150 ℃ of-0.51%; the advantages of example 5 are evident.

Example 6, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, Br of the NdHoDyCu diffused in example 6 is reduced by 0.25kGS, Hcj is increased by 8.71kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.492%; comparative example 6 Br of diffused NdDyCu was decreased by 0.23kGS, Hcj was increased by 8.31kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.52%; the advantages of example 6 are evident.

Example 7, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, the Br of the diffused NdHoDyCu in example 7 is reduced by 0.24kGS, the Hcj is increased by 9.32kOe, and the coefficient of the coercive force of the magnet for resisting high temperature of 150 ℃ is-0.482%; comparative example 7 Br of diffused NdDyCu was decreased by 0.22kGS, Hcj was increased by 8.82kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.515%; the advantages of example 7 are evident.

Example 8, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, the Br of the PrGdDyCu diffused in example 8 is reduced by 0.26kGS, the Hcj is increased by 9.85kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.49%; comparative example 8 Br of diffused PrDyCu was decreased by 0.21kGS, Hcj was increased by 9.35kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.51%; the advantages of example 8 are evident.

Example 9, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, the Br of the PrGdDyCu diffused in example 9 is reduced by 0.24kGS, the Hcj is increased by 9.75kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.47%; comparative example 9 Br of diffused PrDyCu decreased by 0.24kGS, Hcj increased by 9.35kOe, and coercive force of the magnet had a high temperature coefficient of resistance of-0.5%; the advantages of example 9 are evident.

Example 10, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of the PrGdDyCu diffused in example 10 is reduced by 0.27kGS, the Hcj is increased by 10.88kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.48%; comparative example 10 Br of diffused PrDyCu was decreased by 0.22kGS, Hcj was increased by 9.88kOe, and the coercive force of the magnet had a coefficient of high temperature resistance of 150 ℃ of-0.515%; the advantages of example 10 are evident.

Example 11, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, the Br of PrGdDyCu diffused by the example 11 is reduced by 0.21kGS, the Hcj is increased by 8.24kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.49 percent compared with the Br before diffusion; comparative example 11 Br of diffused PrDyCu was decreased by 0.21kGS, Hcj was increased by 7.74kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.525%; the advantages of example 11 are evident.

Example 12, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of the PrGdDyCu diffused in example 12 is reduced by 0.27kGS, the Hcj is increased by 8.1kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.457%; comparative example 12 Br of diffused PrDyCu was decreased by 0.22kGS, Hcj was increased by 7.6kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.51%; the advantages of example 12 are evident.

Example 13, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of PrHoDyCuGa diffused in example 13 is reduced by 0.25kGS, Hcj is increased by 7.9kOe, and the coefficient of coercive force of the magnet for resisting high temperature of 150 ℃ is-0.46%; comparative example 13 Br of diffused PrDyCuGa was decreased by 0.25kGS, Hcj was increased by 7.6kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.51%; the advantages of example 13 are evident.

Example 14, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of PrHoDyCuGa diffused in example 14 is reduced by 0.27kGS, Hcj is increased by 8.85kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.47%; comparative example 14 Br of diffused PrDyCuGa was decreased by 0.22kGS, Hcj was increased by 8.25kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.52%; the advantages of example 14 are evident.

Example 15, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, the Br of PrHoDyCuGa diffused in example 15 is reduced by 0.27kGS, Hcj is increased by 9.48kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.46%; comparative example 15 Br of diffused PrDyCuGa was decreased by 0.25kGS, Hcj was increased by 8.98kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.505%; the advantages of example 15 are evident.

Example 16, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, the Br of PrHoDyCuAl diffused in example 16 is reduced by 0.26kGS, the Hcj is increased by 9.44kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.47%; comparative example 16 Br of diffused PrDyCuAl was decreased by 0.2kGS, Hcj was increased by 10.21kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.51%; the advantages of example 16 are evident.

Example 17, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of PrHoDyCuAl diffused in example 17 is reduced by 0.2kGS, Hcj is increased by 8.77kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.48%; comparative example 17 Br of diffused PrDyCuAl was decreased by 0.2kGS, Hcj was increased by 10.21kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.52%; the advantages of example 17 are evident.

Example 18, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of PrHoDyCuAl diffused in example 18 is reduced by 0.28kGS, Hcj is increased by 9.1kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.49%; comparative example 18 Br of diffused PrDyCuAl was decreased by 0.26kGS, Hcj was increased by 8.6kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.505%; the advantages of example 18 are evident.

Example 19, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of the PrGdDyCu diffused in example 19 is reduced by 0.3kGS, the Hcj is increased by 9.1kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.47%; comparative example 19 Br of diffused PrDyCu decreased by 0.2kGS, Hcj increased by 10.21kOe, and coercive force of the magnet had a high temperature coefficient of resistance of-0.53%; the advantages of example 19 are evident.

Example 20, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of the PrGdDyCu diffused in example 20 is reduced by 0.2kGS, Hcj is increased by 7.7kOe, and the coefficient of coercive force of the magnet at high temperature of 150 ℃ is-0.475%; comparative example 20 Br of diffused PrDyCu was decreased by 0.2kGS, Hcj was increased by 7.5kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.5%; the advantages of example 20 are evident.

Example 21, under the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and other conditions, compared with before diffusion, the Br of the PrGdDyCu diffused in example 21 is reduced by 0.25kGS, the Hcj is increased by 9.8kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.46%; comparative example 21 Br of diffused PrDyCu was decreased by 0.25kGS, Hcj was increased by 9.5kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.51%; the advantages of example 21 are evident.

Example 22, under the conditions of the same neodymium iron boron magnet and size, the same diffusion temperature and aging temperature, and the like, compared with the condition before diffusion, the Br of PrGdDyCu diffused in example 22 is reduced by 0.22kGS, the Hcj is increased by 7.9kOe, and the coefficient of the coercive force of the magnet at high temperature of 150 ℃ is-0.455%; comparative example 22 Br of diffused PrDyCu was decreased by 0.2kGS, Hcj was increased by 7.5kOe, and the coercive force of the magnet had a high temperature coefficient of resistance of-0.51%; the advantages of example 22 are evident.

From the above, the effect of the high temperature resistance of the heavy rare earth alloy after diffusion is obviously better than that of the heavy rare earth alloy in the comparative example. Therefore, we carried out microstructure determination on the magnet after diffusion of the heavy rare earth alloy. SEM was performed mainly using a ZISS electron microscope and oxford EDS performed on the composition of the sample magnet elements. Wherein the definition: the rare earth shell layer, namely the R shell layer, is more than 60 percent of the continuity of the surrounding crystal grains, and the transition metal shell layer is more than 40 percent of the continuity of the surrounding crystal grains. In addition, three points a, b and c are sampling points at different positions, but are characterized by a 6:14 phase type Cu-rich EDS formula of Fe in a small triangular area with the size of less than 1 mu m_30-51(NdPr)_45-60Cu_2-15Ga_0-5Co_0-5Or Fe_30-51(NdPr)_45-60Dy_2-15Cu_2-15Ga_0-5Co_0-5Wherein the number of the foot side of the element is the weight percentage of the element. The other three points, sample points at SEM3, are shown in FIG. 1. By diffusion ofThe source diffusion forms an R shell layer and a transition metal shell layer, and the statistical analysis of three points a, b and c is as follows:

example 1, after a magnet was diffused with PrHoDyCu, the magnet had Pr, Dy, Ho rare earth shell and transition metal shell Cu, forming a dot scan composition of 1: nd (neodymium)_50-70Fe_10-30Pr_10-20Cu_0-5(ii) a Dot scanning component 2: nd (neodymium)_50-55Fe_10-30Pr_5-15Dy_5-15Ho_2-9Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_50-70Fe_10-35Pr_10-20Cu_10-20Co_0-5。

Example 2 the magnet was diffused with PrHoDyCu to have Pr, Dy, Ho rare earth shell and transition metal shell Cu to form a dot scan composition 1: nd (neodymium)_50-65Fe_10-30Pr_10-25Cu_0-5Ga_0-5Al_0-3(ii) a Dot scanning component 2: nd (neodymium)_50-55Fe_10-30Pr_5-15Dy_5-15 Ho_{3- 10}Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_50-70Fe_10-35Pr_10-20Cu_10-15Co_0-5。

Example 3, the composition magnet was subjected to diffusion of PrHoDyCu and then the magnet had Pr, Dy, Ho rare earth shell and transition metal shell Cu and Al, forming a dot scan composition of 1: nd (neodymium)_45-65Fe_10-35Pr_10-25Cu_0-5Ga_0-5Al_3-5(ii) a Dot scanning component 2: nd (neodymium)_{45- 55}Fe_10-30Pr_5-20Dy_5-10 Ho_3-8Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_50-65Fe_10-35Pr_10-20Cu_10-15Co_0-5Al_0-5。

Example 4 this component magnet was subjected to diffusion of PrHoDyCu and the magnet had Pr, Dy, Ho rare earth shell and transition metal shell Cu and Al forming a dot scan component 1: nd (neodymium)_45-60Fe_10-35Pr_10-20Cu_3-8Ga_0-5Al_3-5(ii) a Dot scanning component 2: nd (neodymium)_{45- 55}Fe_10-30Pr_5-20Dy_5-10Ho_3-6Cu_2-5Al_2-10(ii) a Dot-broom component3：Nd_45-65Fe_10-30Pr_10-20Cu_10-25Co_0-5Al_0-5。

Example 5, this component magnet was subjected to ndho dycu diffusion to provide a Nd, Dy, Ho rare earth shell and a transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_50-65Pr_10-15Fe_10-30Cu_2-6Go_0-5(ii) a Dot scanning component 2: nd (neodymium)_45-60Fe_5-30Pr_{5- 15}Dy_5-15Ho_3-10(ii) a Dot scanning component 3: nd (neodymium)_45-60Pr_10-20Fe_5-30Cu_10-20Co_0-5。

Example 6, the component magnet was subjected to ndho dycu diffusion to provide a Nd, Dy, Ho rare earth shell and a transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_45-60Pr_10-20Fe_10-30Cu_2-5Ga_0-5(ii) a Dot scanning component 2: nd (neodymium)_45-60Fe_5-25Pr_{5- 12}Dy_5-20Ho_2-9(ii) a Dot scanning component 3: nd (neodymium)_50-60Pr_10-15Fe_5-25Cu_5-25Co_0-5。

Example 7, this component magnet was subjected to ndho dycu diffusion to provide a Nd, Dy, Ho rare earth shell and transition metal shells Cu and Al, forming a dot scan component 1: nd (neodymium)_50-65Pr_10-15Fe_10-40Cu_5-10Al_0-5(ii) a Dot scanning component 2: nd (neodymium)_50-60Fe_{5- 30}Pr_5-15Dy_5-25Ho_3-12Al_2-10(ii) a Dot scanning component 3: nd (neodymium)_50-60Pr_10-15Fe_5-25Cu_5-15Co_0-5Al_0-5。

Example 8, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_40-65Pr_20-35Fe_10-25Cu_5-10(ii) a Dot scanning component 2: nd (neodymium)_25-40Fe_10-30Pr_{10- 25}Dy_15-20Gd_1-7Co_0-5Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_35-45Pr_15-35Fe_5-25Cu_10-25Co_0-5。

Example 9, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_40-60Pr_20-30Fe_10-30Cu_3-8(ii) a Dot scanning component 2: nd (neodymium)_35-45Fe_10-30Pr_10-25Dy_{5- 25}Gd_2-12Co_0-5Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_35-50Pr_15-30Fe_5-25Cu_5-20Co_0-5。

Example 10, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_40-60Pr_20-35Fe_10-30Cu_0-5(ii) a Dot scanning component 2: nd (neodymium)_25-40Fe_10-30Pr_10-25Dy_{5- 15}Gd_2-7Co_0-5Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_35-45Pr_15-35Fe_5-30Cu_5-20Co_0-5。

Example 11, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_50-65Fe_10-25Pr_10-20Cu_0-5Ga_0-5Al_0-5(ii) a Dot scanning component 2: nd (neodymium)_45-55Fe_{10- 30}Pr_5-20Dy_5-20Gd_3-9Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_45-70Fe_10-30Pr_10-25Cu_10-25Co_0-5Ga_0-5。

Example 12, the component magnet was subjected to diffusion of PrGdDyCu to give a magnet having Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_50-65Fe_10-30Pr_10-25Cu_0-5Ga_2-7Al_3-7(ii) a Dot scanning component 2: nd (neodymium)_45-55Fe_{10- 30}Pr_5-20Dy_5-10Gd_2-5Cu_0-5Ga_0-5(ii) a Dot scanning component 3: nd (neodymium)_50-65Fe_10-35Pr_5-20Cu_10-20Co_0-5Al_0-5。

Example 13, the composition magnet was subjected to diffusion of PrHoDyCuGa and the magnet had Pr, Dy, Ho rare earth shell and transition metal shell Cu and Ga, forming a dot-scan composition of 1: nd (neodymium)_45-55Pr_20-25Fe_15-30Ga_2-10Cu_3-5(ii) a Dot scanning component 2: nd (neodymium)_30-45Fe_{5- 25}Pr_25-30Dy_5-20Ho_1-10Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_35-45Pr_20-35Fe_10-35Cu_5-15Ga_5-10Co_2-5。

Example 14, the composition magnet was subjected to diffusion of PrHoDyCuGa and the magnet had Pr, Dy, Ho rare earth shell and transition metal shell Cu and Ga, forming a dot-scan composition of 1: nd (neodymium)_40-55Pr_20-30Fe_15-30Ga_2-10Cu_3-5(ii) a Dot scanning component 2: nd (neodymium)_30-40Fe_{5- 25}Pr_25-30Dy_5-15Ho_2-9Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_30-50Pr_25-30Fe_10-30Cu_5-10Ga_5-10Co_2-5。

Example 15, the composition magnet was subjected to diffusion of PrHoDyCuGa and the magnet had Pr, Dy, Ho rare earth shell and transition metal shell Cu and Ga, forming a dot-scan composition of 1: nd (neodymium)_40-55Pr_20-30Fe_15-25Ga_5-10Cu_3-10(ii) a Dot scanning component 2: nd (neodymium)_30-40Fe_{5- 25}Pr_15-30Dy_5-20Ho_3-12Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_30-45Pr_25-35Fe_10-30Cu_5-10Ga_5-10Co_2-5。

Example 16, the composition magnet was subjected to diffusion of PrHoDyCuAl and the magnet had Pr, Dy, Ho rare earth shell and transition metal shells Cu and Al, forming a dot-scan composition of 1: nd (neodymium)_45-65Fe_10-35Pr_5-15Cu_5-15Al_5-10(ii) a Dot sweeping component 2Nd_45-65Fe_{5- 30}Pr_5-20Dy_5-10Ho_2-11Cu_5-10Al_2-10(ii) a Dot scanning component 3: nd (neodymium)_50-65Fe_10-20Pr_10-15Cu_10-25Al_0-5。

Example 17, the composition magnet was subjected to diffusion of PrHoDyCuAl and the magnet had Pr, Dy, Ho rare earth shell and transition metal shells Cu and Al, forming a dot-scan composition of 1: nd (neodymium)_45-55Fe_10-30Pr_5-20Cu_5-10Al_2-5(ii) a Dot scanning component 2: nd (neodymium)_45-60Fe_{5- 25}Pr_5-25Dy_5-15Ho_2-10Cu_5-10Al_3-5(ii) a Dot scanning component 3: nd (neodymium)_45-60Fe_10-20Pr_10-20Cu_10-20Ga_0-5Al_0-5。

Example 18, the composition magnet was subjected to diffusion of PrHoDyCuAl and the magnet had Pr, Dy, Ho rare earth shell and transition metal shells Cu and Al, forming a dot-scan composition of 1: nd (neodymium)_50-65Fe_10-30Pr_5-20Cu_5-10Al_2-5(ii) a Dot scanning component 3: nd (neodymium)_45-65Fe_{5- 30}Pr_5-20Dy_5-15Ho_1-6Cu_5-10Al_5-10(ii) a Dot scanning component 2: nd (neodymium)_45-60Fe_10-25Pr_10-20Cu_10-20Ga_0-5Al_0-5。

Example 19, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_45-55Fe_5-30Pr_20-35Cu_0-5(ii) a Dot scanning component 2: nd (neodymium)_45-55Fe_5-10Pr_10-30Dy_{5- 20}Gd_2-8Cu_0-5(ii) a Dot scanning component 3: nd (neodymium)_35-55Fe_5-30Pr_10-35Cu_5-10Ga_0-5Co_0-5。

Example 20, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_35-50Fe_15-40Pr_15-30Cu_0-10Ga_0-3Al_0-3(ii) a Dot scanning component 2: nd (neodymium)_40-60Fe_{3- 30}Pr_10-20Gd_1-7Dy_5-25(ii) a Dot scanning component 3: nd (neodymium)_40-55Fe_5-35Pr_15-30Cu_5-25Ga_0-5Co_0-5。

Example 21, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_30-45Fe_10-30Pr_20-25Cu_5-10Ga_0-5Co_0-5Ti_0-5(ii) a Dot scanning component 2: nd (neodymium)_{30- 40}Fe_5-25Pr_10-15Dy_10-30Gd_2-6Ho_3-9(ii) a Dot scanning component 3: nd (neodymium)_35-45Fe_5-30Pr_15-30Cu_5-25Ga_0-3Co_0-5。

Example 22, after subjecting the component magnet to diffusion of PrGdDyCu, the magnet had Pr, Dy, Gd rare earth shell and transition metal shell Cu, forming a dot-scan component 1: nd (neodymium)_25-35Fe_20-30Pr_20-30Cu_0-10Ga_0-5(ii) a Dot scanning component 2: nd (neodymium)_45-55Fe_10-20Pr_{20- 30}Dy_5-20Gd_4-10(ii) a Dot scanning component 3: nd (neodymium)_40-55Fe_10-25Pr_15-40Cu_5-20Ga_0-10Co_0-5。

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.