CN105575577A - Sintered cerium-rich rare earth permanent magnetic material and preparation method thereof - Google Patents

Abstract

The invention provides a sintered cerium-rich rare earth permanent magnetic material. The sintered cerium-rich rare earth permanent magnetic material is prepared from, by mass, RE1 20%-28%, RE2 4%-15%, Fe 60.5%-70.5%, B 0.8%-1.2% and Tm 0.1%-5%. A main phase is Nd2Fe14B or (Nd, Pr) 2Fe14B, and Ce or Ce and La are distributed around the main phase grains. The RE1 is Nd, Nd and Pr, a rare earth element dominated by Nd or a rare earth element dominated by Nd and Pr, the RE2 is Ce or Ce and La, and the Tm is at least one of Co, Cu, Al, Ga, Nb, Zr, Mo, Mn and Cr. The invention further provides a preparation method of the rare earth permanent magnetic material. The problem that the Ce and La are used for replacing the Nd and Pr in part to prepare the cerium-rich rare earth permanent magnetic material and the intrinsic magnetic properties of the material are influenced can be solved, and meanwhile the cost of the rare earth permanent magnetic material can be reduced.

Description

Sintered cerium-rich rare earth permanent magnet material and preparation method thereof

technical field

The invention belongs to the field of rare earth permanent magnet material preparation, in particular to a sintered cerium-rich rare earth permanent magnet material and a preparation method thereof.

Background technique

Nd-Fe-B series rare earth permanent magnet materials have been widely used in many fields such as electronic products, medical equipment, and automobile industry due to their superior comprehensive magnetic properties. In recent years, with the continuous increase in the global production of rare earth permanent magnet materials, the consumption of rare earth Nd and Pr resources has continued to decrease, and the cost of raw materials has continued to rise, which has greatly restricted the development of the rare earth permanent magnet industry. However, the high-abundance elements Ce and La in my country's rare earth mines have a low utilization rate, insufficient deep processing, and a large amount of low-value-added primary products have seriously affected the comprehensive and balanced utilization of rare earth resources. Ce, La, Pr, Nd and other elements belong to the lanthanide metals and have a similar 4f electron layer structure. Using Ce and La to replace Pr and Nd to prepare cerium-rich rare earth permanent magnet materials can reduce the cost of permanent magnet materials, and it is also the realization of rare earth Ce , An effective way to increase the value of resources.

Some research reports on the preparation of cerium-rich rare earth permanent magnet materials by replacing Pr and Nd with Ce and La are disclosed in the prior art. However, due to the limitations of the inherent magnetic properties of light rare earth elements, the performance of the prepared magnets is seriously lower than that of Nd-Fe-B magnets. There are three main ways to control the limitation of Ce and La light rare earth elements on the intrinsic magnetic properties of magnets: one is to control the deterioration of magnet performance by limiting the substitution amount of Ce to Nd and Pr elements within a relatively low range; The second is to improve the performance of the Ce-containing magnet by mixing and sintering the (Nd,Ce)-Fe-B alloy obtained by smelting and the high-magnetic Nd-Fe-B alloy cast sheet; the third is to dope the magnet with other Improve elements to ensure certain magnetic properties. But these methods did not fundamentally solve the problem. The main reason for the decline in magnet performance is that in the existing preparation methods of cerium-rich rare earth permanent magnet materials, the introduction of rare earth Ce, La or mixed rare earth alloy MM is mostly smelted and alloyed with Nd or Pr-Nd alloy. , a large amount of Ce in the rare earth permanent magnet material prepared in this way replaces the Nd and Pr elements in the main phase, and the Ce element mainly exists in the form of (Nd,Ce) ₂ Fe ₁₄ B or (Nd,Pr,Ce) ₂ Fe ₁₄ B , with the increase of the replacement amount, the intrinsic magnetic parameters such as the saturation magnetic polarization J _s of the main phase, the magnetocrystalline anisotropy field H _A , and the Curie temperature T _c are severely reduced, and the performance of the magnet is severely reduced.

Contents of the invention

The purpose of the present invention is to address the deficiencies in the prior art, to provide a sintered cerium-rich rare earth permanent magnet material and a preparation method thereof, so as to effectively solve the problem of using Ce and La to partially replace Nd and Pr to prepare cerium-rich rare earth permanent magnet materials. The influence of magnetic properties, while reducing the cost of rare earth permanent magnet materials.

The sintered cerium-rich rare earth permanent magnet material of the present invention contains the following components and the mass percentage of each component: RE1 is 20% to 28%, RE2 is 4% to 15%, Fe is 60.5% to 70.5%, and B is 0.8% to 1.2%, and Tm is 0.1% to 5%. The main phase of the sintered cerium-rich rare earth permanent magnet material is Nd ₂ Fe ₁₄ B or (Nd,Pr) ₂ Fe ₁₄ B, and there are Ce, or Ce and La; the RE1 is Nd, Nd and Pr, Nd-based rare earth elements, or Nd and Pr-based rare earth elements, the RE2 is Ce, or Ce and La, and the T _m is at least one of Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, and Cr.

In the above-mentioned sintered cerium-rich rare earth permanent magnet material, said RE1 is a rare earth element mainly composed of Nd, which means that the mass of Nd is greater than or equal to 95% of the mass of RE1, and said RE1 is a rare earth element mainly composed of Nd and Pr. The mass of Nd and Pr is greater than or equal to 95% of the mass of RE1. When RE1 is a rare earth element mainly composed of Nd or composed of Nd and Pr, RE1 also includes at least Dy, Tb, Gd, and Ho A rare earth element.

The above-mentioned sintered cerium-rich rare earth permanent magnet material also contains a small amount of Ce ₂ Fe ₁₄ B phase or (Ce,La) ₂ Fe ₁₄ B phase. When RE1 is a rare earth element mainly composed of Nd or a rare earth element mainly composed of Nd and Pr element, it also includes a small amount of at least one of Dy ₂ Fe ₁₄ B, Tb ₂ Fe ₁₄ B, Gd ₂ Fe ₁₄ B, Ho ₂ Fe ₁₄ B.

The preparation method of the sintered cerium-rich rare earth permanent magnet material of the present invention, the process steps are as follows:

(1) Preparation of main alloy flakes, intergranular auxiliary alloy flakes or blocks

① Ingredients

The main alloy RE3-Fe-BM _A contains the components and the mass percentage of each component: RE3 is 27%~30%, Fe is 65%~72%, _B is 0.9%~1.1%, MA is 0.1%~ 4%, the RE3 is Nd, Nd and Pr, Nd-based rare earth elements, or Nd and Pr-based rare earth elements, and the _MA is Co, Cu, Al, Ga, Nb, Zr, Mo At least one of , Mn, Cr;

The components contained in the intergranular supplementary alloy RE4-Fe-BM _B and the mass percentages of each component: RE4 is 38% to 85%, Fe is 6% to 60%, B is 0.1% to 1.2%, M _B is 0.1 %～20%; the RE4 is Ce, or a rare earth element mainly composed of Ce and La, and the _MB is at least one of Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr;

According to the above-mentioned components of the main alloy RE3-Fe-BM _A and the intergranular auxiliary alloy RE4-Fe-BM _B and the mass percentage of each component;

②Casting or casting and crushing

Melting and casting the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step 1 respectively to obtain the main alloy cast sheet and the intergranular auxiliary alloy cast sheet;

Or the main alloy raw material prepared in step ① is prepared into a cast sheet by melting and casting, and the intergranular auxiliary alloy raw material prepared in step ① is melted and cast into an intergranular auxiliary alloy ingot, and the intergranular auxiliary alloy ingot is homogenized and annealed Then it is crushed into an intergranular auxiliary alloy block with a size of 10-30mm;

(2) Preparation of main alloy powder, intergranular auxiliary alloy powder or mixed powder of main alloy and intergranular auxiliary alloy

The main alloy cast sheet and the intergranular auxiliary alloy block obtained in step (1) are subjected to hydrogen absorption-dehydrogenation treatment respectively to obtain coarsely broken particles of the main alloy with a particle size of 10-300 μm and an intergranular auxiliary alloy with a particle size of 0.1-3 mm Coarsely crushing the particles, crushing the coarsely crushing particles of the main alloy with a jet mill under the protection of nitrogen or inert gas to obtain a main alloy powder with a particle size of 1-5 μm, and ball milling the coarsely crushed particles of the intergranular auxiliary alloy to obtain Intergranular auxiliary alloy powder with a diameter of 0.5-3 μm;

Or according to the components of the prepared rare earth permanent magnet material and the mass percentage of each component, weigh the main alloy casting sheet and the intergranular auxiliary alloy casting sheet obtained in step (2), carry out hydrogen absorption-dehydrogenation treatment after they are mixed , obtaining coarsely crushed mixed alloy particles with a particle size of 10-300 μm, performing jet mill crushing of the obtained mixed alloy coarsely broken particles under the protection of nitrogen or an inert gas, to obtain mixed alloy powder with a particle size of 1-5 μm;

(3) Preparation of green body

Adding an antioxidant and a lubricant to the mixed alloy powder obtained in step (2) and mixing uniformly to form a billet, then putting the billet into a cavity and placing it in a magnetic field, and pressing and molding at room temperature under nitrogen protection to obtain a green billet;

Or weigh the main alloy powder and intergranular auxiliary alloy powder obtained in step (2) according to the component of the prepared rare earth permanent magnet material and the mass percentage of each component and mix them uniformly to form mixed alloy powder, then add antioxidant and After the lubricant is mixed evenly to form a billet, then the billet is put into the cavity and placed in a magnetic field, and pressed and formed under the protection of nitrogen to obtain a green billet;

(4) Cold isostatic pressing of green body

The cold isostatic pressed green body obtained by cold isostatic pressing the green body obtained in step (3);

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, sinter under vacuum conditions at 990-1070°C for 1-6 hours, and pass inert gas or nitrogen to cool to room temperature after sintering to obtain a sintered magnet ;

(6) heat treatment

Heat the sintered magnet obtained in step (5) to 800-950°C for 0.5-4 hours, cool to 100-40°C after the heat preservation is completed, and then heat to 460-600°C for 1-6 hours, and then pass inert gas or nitrogen after the heat preservation is completed After cooling to room temperature, the sintered cerium-rich rare earth permanent magnet material is obtained.

In the preparation method of the above sintered cerium-rich rare earth permanent magnet material, in the step (1), the homogenization annealing of the intergranular auxiliary alloy ingot is carried out at 600-1000° C. for 1-20 hours under the protection of an inert gas, and then cooled with the furnace to room temperature.

In the preparation method of the above sintered cerium-rich rare earth permanent magnet material, in step (2), the main alloy cast sheet and the intergranular auxiliary alloy block are subjected to hydrogen absorption-dehydrogenation treatment respectively, or the main alloy cast sheet and the intergranular auxiliary alloy are cast When the hydrogen absorption-dehydrogenation treatment is carried out after the sheets are mixed, the hydrogen pressure of the hydrogen absorption treatment is 0.1-0.3MPa, and the hydrogen absorption treatment is completed when the hydrogen absorption reaches saturation (the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method, and within 10 minutes The hydrogen pressure drop in the furnace is less than or equal to 0.02MPa, that is, the hydrogen absorption reaches saturation), the dehydrogenation treatment is carried out at 500-600°C by vacuuming and dehydrogenation, and it will be completed when the hydrogen content of the cast piece or block undergoing dehydrogenation treatment is ≤250ppm Dehydrogenation treatment.

In the preparation method of the above sintered cerium-rich rare earth permanent magnet material, in the step (3), the magnetic field strength for preparing the green body is 1.5-3T, the forming pressure is 40-100MPa, and the holding time is 1-15s.

In the above method for preparing the sintered cerium-rich rare earth permanent magnet material, in the step (4), the pressure of cold isostatic pressing of the green body is 120-320 MPa, and the holding time is 10-300 s.

In the preparation method of the above sintered cerium-rich rare earth permanent magnet material, in step (3), the sum of the mass of the antioxidant and the lubricant is 0.05% to 0.5% of the mass of the mixed alloy powder, and the mass ratio of the antioxidant to the lubricant is 1 :1. Antioxidants are commercially available NdFeB special antioxidants, which are produced by many domestic companies, such as Tianjin Yuesheng New Material Research Institute, Hangzhou Yadong New Material Co., Ltd., Taiyuan Jiaci Co., Ltd., Beijing Juncefeng Technology Development Co., Ltd. Etc.; lubricant can be oleic acid, stearic acid, zinc stearate etc., the present invention selects zinc stearate for use.

In the preparation method of the above-mentioned sintered cerium-rich rare earth permanent magnet material, in the step (1), the RE3 is a rare earth element mainly composed of Nd, which means that the quality of Nd is greater than or equal to 95% of the mass of RE3, and the RE3 is composed of Nd The rare earth element mainly composed of Nd and Pr means that the mass of Nd and Pr is greater than or equal to 95% of the mass of RE3. When RE3 is the rare earth element mainly composed of Nd or the rare earth element mainly composed of Nd and Pr, Ce is also included in RE3 , La, Dy, Tb, Gd, Ho at least one rare earth element; said RE4 is a rare earth element mainly composed of Ce and La means that the mass of Ce and La is greater than or equal to 75% of the mass of RE4, when RE4 is When Ce and La are the main rare earth elements, RE4 also includes at least one rare earth element among Nd, Pr, Dy, Tb, Gd, and Ho.

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

1. The sintered cerium-rich rare earth permanent magnet material of the present invention contains 4% to 15% of Ce by mass fraction, or Ce and La, that is, part of Nd and Pr is replaced by Ce and La, thereby promoting rare earth Ce and La resources comprehensive utilization, while effectively reducing the cost of raw materials for rare earth permanent magnet materials.

2. The rare earth permanent magnet material prepared by the method of the present invention, contained RE2 is mainly distributed in the intergranular phase, which can reduce the melting point of the intergranular phase, and combine a certain amount of Tm elements (Cu, Ga, Al, etc.) to further reduce The melting point of the intergranular phase (for example, the melting point of CeCu is only 424 ° C), serves the purpose of providing a sintering liquid phase and reducing the sintering temperature, and at the same time improves the wettability of the intergranular phase. The sintering and tempering temperature of the magnetic material, so the grains of the rare earth permanent magnet material are uniform, fine and evenly distributed, and have excellent magnetic properties.

3. The method of the present invention adopts the double alloy method, that is, RE3-Fe-BM _A is used as the main alloy, mainly to provide the main phase Nd ₂ Fe ₁₄ B or ( Nd,Pr) ₂ Fe ₁₄ B, to ensure that the permanent magnet material has high saturation magnetic polarization Js and magnetocrystalline anisotropy field H _A , with RE4-Fe-BM _B as the intergranular auxiliary alloy, mainly to make the cerium-rich rare earth permanent Magnetic materials are sintered and densified and provide Ce-rich, or Ce- and La-rich intergranular phases required for magnetostatic coupling of the main phase, so as to control the distribution of rare earth elements and avoid large amounts of Ce, La and other elements from entering Nd ₂ Fe ₁₄ B or ( Nd, Pr) ₂ Fe14 _B phase leads to the decline of its intrinsic magnetic properties, so it can effectively reduce the influence of Ce and La partially replacing Pr and Nd on the intrinsic magnetic properties of cerium-rich rare earth permanent magnet materials.

4. The method of the present invention first prepares the main alloy and the intergranular auxiliary alloy, and then conducts compositional design based on the main alloy and the intergranular auxiliary alloy according to the composition and performance requirements of the sintered cerium-rich rare earth permanent magnet material, so flexibility and freedom The high degree is conducive to the promotion of industrialization.

detailed description

The following examples will further illustrate the sintered cerium-rich rare earth permanent magnet material and its preparation method of the present invention.

In the following examples, the numbers in front of each component in the alloy chemical formula represent the mass percentage of the component in the alloy.

Example 1

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure metal neodymium, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the ingredients in the main alloy 27.67Nd-70.59Fe-1.02B-0.72Al and the mass percentage of each component, and remove the oxides and inclusions on the surface of each raw material;

Dosing according to the mass percentage content of each component and each component in the auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 24.90Nd-5.92Ce-67.14Fe-0.98B-1.06T _m , and according to the above ratio, the mass ratio of the main alloy cast sheet and the intergranular auxiliary alloy cast sheet is 90 : 10 Weigh the main alloy cast sheet and the intergranular auxiliary alloy cast sheet that step (1) obtains, put into the rotary hydrogen crushing furnace after mixing the two alloy cast sheets and carry out hydrogen absorption-dehydrogenation treatment, the hydrogen pressure of the hydrogen absorption treatment When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, it means that the hydrogen absorption has reached saturation). Vacuum dehydrogenation at 560°C for hydrogen treatment. Dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm. After the hydrogen absorption-dehydrogenation treatment is completed, a mixed alloy with a particle size of 10-300μm is obtained. Particles, the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen to obtain mixed alloy powder with an average particle size of 3.2 μm;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.1% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is a NdFeB special antioxidant purchased from Tianjin Yuesheng New Material Research Institute, and the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 2T. Under the protection of nitrogen, press molding at room temperature and 80MPa molding pressure for a holding time of 4s to obtain a green body;

(4) Cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 150 MPa for 100 seconds, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1065°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool to room temperature by passing in argon gas after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 930°C for 1.5h, cool to below 100°C after the heat preservation, and then heat to 570°C for 4h, and then pass in argon to cool to room temperature after the heat preservation is completed, and the sintered cerium-rich rare earth permanent magnet is obtained. magnetic material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.32T, H _cj =826.5kA/m, (BH) _max =335.2kJ/m ³ .

Example 2

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure metal neodymium, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the ingredients in the main alloy 27.67Nd-70.59Fe-1.02B-0.72Al and the mass percentage of each component, and remove the oxides and inclusions on the surface of each raw material;

Dosing according to the mass percentage content of each component and each component in the auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 23.52Nd-8.88Ce-65.41Fe-0.96B-1.23T _m , according to the above ratio, the mass ratio of the main alloy cast sheet and the intergranular auxiliary alloy cast sheet is 85 : 15 Weigh the main alloy cast sheet and the intergranular auxiliary alloy cast sheet that step (1) obtains, put into the rotary hydrogen crushing furnace after mixing the two alloy cast sheets and carry out hydrogen absorption-dehydrogenation treatment, the hydrogen pressure of the hydrogen absorption treatment When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, it means that the hydrogen absorption has reached saturation). Vacuum dehydrogenation at 560°C for hydrogen treatment. Dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm. After the hydrogen absorption-dehydrogenation treatment is completed, a mixed alloy with a particle size of 10-300μm is obtained. Particles, the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen to obtain mixed alloy powder with an average particle size of 3.6 μm;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.1% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is a NdFeB special antioxidant purchased from Tianjin Yuesheng New Material Research Institute, and the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 2T. Under the protection of nitrogen, press molding at room temperature and 80MPa molding pressure for a holding time of 4s to obtain a green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 150 MPa for 100 seconds, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1065°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool to room temperature by passing in argon gas after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 930°C for 1 hour, cool to below 100°C after the heat preservation, and then heat to 550°C for 4 hours. After the heat preservation is completed, pass in argon and cool to room temperature to obtain a sintered cerium-rich rare earth permanent magnet. Material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.298T, H _cj =904.5kA/m, (BH) _max =324.7kJ/m ³ .

Example 3

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure metal neodymium, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the ingredients in the main alloy 27.67Nd-70.59Fe-1.02B-0.72Al and the mass percentage content of each component, and remove the oxides and inclusions on the surface of each raw material metal;

Dosing according to the mass percentage content of each component and each component in the auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25 mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 22.13Nd-11.84Ce-63.69Fe-0.94B-1.40T _m . According to the above ratio, the mass ratio of the main alloy cast sheet and the intergranular auxiliary alloy cast sheet is 80 : 20 Weighing the main alloy cast sheet and the intergranular auxiliary alloy cast sheet that step (1) obtains, put into the rotary hydrogen crushing furnace after mixing the two alloy cast sheets and carry out hydrogen absorption-dehydrogenation treatment, the hydrogen pressure of the hydrogen absorption treatment When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, it means that the hydrogen absorption has reached saturation). The hydrogen treatment is vacuum dehydrogenation at 560°C. When the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, the dehydrogenation treatment is completed. After the hydrogen absorption-dehydrogenation treatment is completed, a mixed alloy with a particle size of 10-300μm is obtained. Crushing the particles, crushing the obtained mixed alloy coarsely broken particles under the protection of nitrogen by jet milling to obtain mixed alloy powders with an average particle size of 4.1 μm;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.25% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is NdFeB special antioxidant purchased from Tianjin Yuesheng New Material Research Institute, the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 1.8T , under the protection of nitrogen, at room temperature and 70MPa molding pressure, press molding for a holding time of 4s to obtain a green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 150s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1065°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool to room temperature by passing in argon gas after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 900°C for 1 hour, cool it to below 100°C after the heat preservation is over, and then heat it to 530°C and hold it for 4 hours. Material.

The magnetic properties of the sintered cerium-rich rare earth permanent magnet material were measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.24T, H _cj =858.9kA/m, (BH) _max =286.7kJ/m ³ .

Example 4

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure praseodymium neodymium alloy with a praseodymium content of 20% by mass, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the main alloy 27.57(Nd _0.8 Pr _0.2 )-70.69Fe-1.02B-0.72Al each component and the mass percentage content of each component are mixed, and the oxides and inclusions on the surface of each raw material metal are cleaned;

According to the intergranular auxiliary alloy 56.34Ce-40.80Fe-2.05Cu-0.81B, each component and the mass percentage content of each component are batched, and the oxides and inclusions on the surface of each raw material metal are cleaned;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25 mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 23.44(Nd,Pr)-8.45Ce-66.21Fe-0.99B-0.91T _m , according to the above ratio according to the main alloy casting sheet and the intergranular auxiliary alloy casting sheet The mass ratio is 85:15. Weigh the main alloy cast flakes and intergranular auxiliary alloy cast flakes obtained in step (1), mix the two alloy cast flakes and put them into a rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation treatment. The pressure of the hydrogen to be treated is 0.15MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, the hydrogen absorption reaches saturated), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, and the dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, and the particle size is 10-300μm after the hydrogen absorption-dehydrogenation treatment is completed The mixed alloy coarsely crushed particles, the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen, and the mixed alloy powder with an average particle size of 4.1 μm is obtained;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.25% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is NdFeB special antioxidant purchased from Hangzhou Yadong New Material Co., Ltd., and the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 1.8T , under the protection of nitrogen, at room temperature and 70MPa molding pressure, press molding for a holding time of 4s to obtain a green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 150s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1035°C for 6 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool down to room temperature with argon after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 910°C for 1.5h, cool to below 100°C after the heat preservation is completed, and then heat to 520°C for 4 hours, and then pass in argon to cool to room temperature after the heat preservation is completed, and the sintered cerium-rich rare earth permanent magnet is obtained. magnetic material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material were measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.30T, H _cj =873.3kA/m, (BH) _max =326.4kJ/m ³ .

Example 5

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure praseodymium neodymium alloy with a praseodymium content of 20% by mass, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the main alloy 27.57(Nd _0.8 Pr _0.2 )-70.69Fe-1.02B-0.72Al each component and the mass percentage content of each component are mixed, and the oxides and inclusions on the surface of each raw material metal are cleaned;

Dosing according to the mass percentage content of each component and each component in the auxiliary alloy 56.34Ce-40.80Fe-2.05Cu-0.81B, and remove the oxide and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25 mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 20.68(Nd,Pr)-14.08Ce-63.22Fe-0.97B-1.05T _m , according to the above ratio according to the main alloy casting sheet and the intergranular auxiliary alloy casting sheet The mass ratio is 75:25. Weigh the main alloy cast flakes and intergranular auxiliary alloy cast flakes obtained in step (1), mix the two alloy cast flakes and put them into a rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation treatment. The pressure of the hydrogen to be treated is 0.15MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, the hydrogen absorption reaches saturated), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, and the dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, and the particle size is 10-300μm after the hydrogen absorption-dehydrogenation treatment is completed The mixed alloy coarsely crushed particles, the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen, and the mixed alloy powder with an average particle size of 4.5 μm is obtained;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.4% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is NdFeB special antioxidant purchased from Hangzhou Yadong New Materials Co., Ltd., and the lubricant is zinc stearate; the blank is packed into the cavity and placed in a magnetic field with a magnetic field strength of 2T. Under the protection of nitrogen, press molding at room temperature and 60MPa molding pressure for a holding time of 4s to obtain a green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 150s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1025°C for 6 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool down to room temperature with argon after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 870°C for 1.5h, cool to below 100°C after the heat preservation, and then heat to 480°C for 5h, and then pass in argon gas to cool to room temperature after the heat preservation is completed, to obtain the sintered cerium-rich rare earth permanent magnet. magnetic material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.19T, H _cj =765.5kA/m, (BH) _max =244.3kJ/m ³ .

Example 6

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure praseodymium neodymium alloy with praseodymium content of 20% by mass, dysprosium iron alloy with 80% dysprosium content by mass, pure iron, pure aluminum, pure copper, niobium iron alloy with 70% niobium content by mass, metal cobalt, metal Gallium, and boron-iron alloys with a boron content of 20% by mass;

According to the main alloy 28.25 (Nd _0.8 Pr _0.15 Dy _0.05 )-68.01Fe-1.02B-0.42Al-1.9Co-0.4Nb in each component and the mass percentage content of each component, and the oxidation of each raw material metal surface Clean up the objects and inclusions;

According to the proportioning of each component in the auxiliary alloy 64.6Ce-26.9Fe-4.5Co-1.0Ga-2.5Cu-0.5B and the mass percentage content of each component, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25 mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 24.86(Nd,Pr,Dy)-7.75Ce-63.08Fe-0.96B-3.35T _m . The mass ratio of the sheet is 88:12. Weigh the main alloy cast sheet and the intergranular auxiliary alloy cast sheet obtained in step (1), mix the two alloy cast sheets and put them into a rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation treatment. The hydrogen pressure of the hydrogen absorption treatment is 0.24MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. hydrogen reaches saturation), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, and the dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, and the particle size is 10 after the hydrogen absorption-dehydrogenation treatment is completed. Mixed alloy coarsely crushed particles of ~300 μm, the obtained mixed alloy coarsely crushed particles are jet milled under the protection of argon to obtain mixed alloy powder with an average particle size of 2.7 μm;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.3% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is NdFeB special antioxidant purchased from Hangzhou Yadong New Material Co., Ltd., the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 2.5T , under the protection of nitrogen, at room temperature and 70MPa molding pressure, press molding for a holding time of 4s to obtain a green body;

(4) Cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 150s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1045°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool down to room temperature with argon after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 905°C for 1 hour, cool to below 100°C after the heat preservation, and then heat to 510°C for 4 hours. After the heat preservation is completed, pass in argon and cool to room temperature to obtain a sintered cerium-rich rare earth permanent magnet. Material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.32T, H _cj =1089.3kA/m, (BH) _max =343.1kJ/m ³ .

Example 7

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure praseodymium neodymium alloy with a praseodymium content of 20% by mass, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the main alloy 27.56 (Nd _0.8 Pr _0.15 Ce _0.05 )-70.70Fe-1.02B-0.72Al each component and the mass percentage content of each component are mixed, and the oxides and inclusions on the surface of each raw material metal are cleaned;

Dosing according to the mass percentage content of each component and each component in the auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25 mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 23.43(Nd,Pr)-8.88Ce-65.51Fe-0.96B-1.23T _m , according to the above ratio according to the main alloy cast sheet and intergranular auxiliary alloy cast sheet The mass ratio is 85:15. Weigh the main alloy cast flakes and intergranular auxiliary alloy cast flakes obtained in step (1), mix the two alloy cast flakes and put them into a rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation treatment. The pressure of the hydrogen to be treated is 0.2MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, the hydrogen absorption reaches saturated), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, and the dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, and the particle size is 10-300μm after the hydrogen absorption-dehydrogenation treatment is completed The mixed alloy coarsely crushed particles, the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen, and the mixed alloy powder with an average particle size of 3.8 μm is obtained;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.25% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is NdFeB special antioxidant purchased from Hangzhou Yadong New Material Co., Ltd., and the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 1.8T , under the protection of nitrogen, at room temperature and 70MPa molding pressure, press molding for a holding time of 4s to obtain a green body;

(4) Cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 150s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1050°C for 2.5 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool to room temperature with argon after sintering , to obtain a sintered magnet;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 905°C for 1.5 hours, cool to below 100°C after the heat preservation, and then heat to 540°C for 1 hour. permanent magnet material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.26T, H _cj =810.3kA/m, (BH) _max =292.6kJ/m ³ .

Example 8

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure praseodymium neodymium alloy with a praseodymium content of 20% by mass, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the main alloy 28.66(Nd _0.8 Pr _0.2 )-69.60Fe-1.02B-0.72Al each component and the mass percentage content of each component are mixed, and the oxides and inclusions on the surface of each raw material metal are cleaned;

Dosing according to the mass percentage content of each component and each component in the auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 24.36(Nd,Pr)-8.88Ce-64.58Fe-0.96B-1.22T _m , according to the above ratio according to the main alloy casting sheet and the intergranular auxiliary alloy casting sheet The mass ratio is 85:15. Weigh the main alloy cast flakes and intergranular auxiliary alloy cast flakes obtained in step (1), mix the two alloy cast flakes and put them into a rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation treatment. The pressure of the hydrogen to be treated is 0.2MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, the hydrogen absorption reaches saturated), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, and the dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, and the particle size is 10-300μm after the hydrogen absorption-dehydrogenation treatment is completed The mixed alloy coarsely crushed particles, the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen, and the mixed alloy powder with an average particle size of 3.8 μm is obtained;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.25% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant 1:1, the antioxidant is the NdFeB special antioxidant purchased from Taiyuan Jiaci Co., Ltd., the lubricant is zinc stearate; the blank is packed into the cavity and placed in a magnetic field with a magnetic field strength of 2T, and the Under protection, press molding at room temperature and 70MPa molding pressure for a holding time of 4s to obtain a green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 150s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1050°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and after sintering, pass in nitrogen to cool to room temperature to obtain Sintered magnet;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 910°C for 1.5h, cool to below 100°C after the heat preservation, and then heat to 510°C for 4h, and then pass nitrogen into it to cool to room temperature to obtain the sintered cerium-rich rare earth permanent magnet. magnetic material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.286T, H _cj =912.7kA/m, (BH) _max =313.68kJ/m ³ .

Example 9

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

Raw materials are industrially pure praseodymium neodymium alloy with a praseodymium content of 20% by mass, metal cerium, pure iron, pure aluminum, pure copper and boron-iron alloy with a boron content of 20% by mass;

According to the main alloy 28.66(Nd _0.8 Pr _0.2 )-69.60Fe-1.02B-0.72Al each component and the mass percentage content of each component are mixed, and the oxides and inclusions on the surface of each raw material metal are cleaned;

According to the ingredients in the auxiliary alloy 69.3Ce-14.48Fe-16.01Cu-0.21B and the mass percentage content of each component, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 25.22(Nd,Pr)-8.32Ce-62.99Fe-0.92B-2.55T _m , according to the above ratio according to the main alloy casting sheet and the intergranular auxiliary alloy casting sheet The mass ratio is 88:12. Weigh the main alloy cast flakes and intergranular auxiliary alloy cast flakes obtained in step (1), mix the two alloy cast flakes and put them into a rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation treatment. The pressure of the hydrogen to be treated is 0.2MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, the hydrogen absorption reaches saturated), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, and the dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, and the particle size is 10-300μm after the hydrogen absorption-dehydrogenation treatment is completed The mixed alloy coarsely crushed particles, the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen, and the mixed alloy powder with an average particle size of 3.8 μm is obtained;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.25% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant 1:1, the antioxidant is the NdFeB special antioxidant purchased from Taiyuan Jiaci Co., Ltd., the lubricant is zinc stearate; the blank is packed into the cavity and placed in a magnetic field with a magnetic field strength of 2T, and the Under protection, press molding at room temperature and 70MPa molding pressure for a holding time of 6s to obtain a green body;

(4) Cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 150s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1050°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and after sintering, pass in nitrogen to cool to room temperature to obtain Sintered magnet;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 850°C for 1.5h, cool to below 100°C after the heat preservation is completed, and then heat to 520°C for 4h, and then pass in nitrogen to cool to room temperature after the heat preservation is completed, and the sintered cerium-rich rare earth permanent magnet is obtained. magnetic material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.293T, H _cj =822.65kA/m, (BH) _max =312.3kJ/m ³ .

Example 10

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy block

① Ingredients

Raw materials are industrially pure praseodymium neodymium alloys with a praseodymium content of 20% by mass, pure iron, pure aluminum, pure copper, niobium-iron alloys with a niobium content of 70% by mass, metal cobalt, and boron-iron alloys with a boron content of 20% by mass;

According to the main alloy 29.71 (Nd _0.8 Pr _0.2 )-67.73Fe-1.01B-0.70Al-0.75Co-0.1Nb in each component and the mass percentage content of each component, the oxides and Clean up the inclusions;

Dosing according to the mass percentage content of each component in the intergranular auxiliary alloy 81.13Ce-8.40Fe-10.33Cu-0.14B, and remove the oxides and inclusions on the surface of each raw material metal;

②Melting and crushing

Put the main alloy raw material prepared in step ① into a vacuum induction melting furnace, melt it under the protection of argon, and pour the alloy liquid on a water-cooled copper roller with a linear speed of 3m/s for rapid cooling to obtain a speed alloy with an average thickness of 0.25mm. Congeal the main alloy casting sheet; put the intergranular auxiliary alloy raw material prepared in step (1) into a vacuum induction melting furnace, melt under argon condition, and pour the alloy liquid obtained by melting on the water-cooled copper mold to obtain an average A quick-solidified intergranular auxiliary alloy ingot with a thickness of 10mm, and then put the intergranular auxiliary ingot into a vacuum heating furnace, and keep it at 650°C for 3 hours under the protection of argon for homogenization annealing, and then cool it to room temperature with the furnace. Coarse crushing into 10-30mm intergranular auxiliary alloy block;

(2) Preparation of main alloy powder and intergranular auxiliary alloy powder

Put the main alloy cast piece and intergranular auxiliary alloy block obtained in step (1) into the rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation treatment. When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, the hydrogen absorption reaches saturation), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, The dehydrogenation treatment is completed when the hydrogen content of the dehydrogenated cast piece or block is ≤250ppm. After the hydrogen absorption-dehydrogenation treatment is completed, the coarsely broken particles of the main alloy with a particle size of 10-300 μm and a particle size of 0.1-300 μm are obtained. 3mm intergranular auxiliary alloy coarsely crushed particles, the obtained main alloy coarsely crushed particles are subjected to jet mill crushing under the protection of nitrogen, and the main alloy powder with an average particle size of 3.5 μm is obtained, and the obtained intercrystalline auxiliary alloy coarsely crushed particles are dissolved in gasoline Carrying out ball milling, the ball-to-material ratio is 12:1, the ball milling speed is 450r/min, and the ball milling time is 60min, to obtain an intergranular auxiliary alloy powder with an average particle size of 1 μm;

(3) Preparation of green body

The component distribution ratio of the rare earth permanent magnet material to be prepared is 26.74(Nd,Pr)-8.11Ce-61.79Fe-0.92B-2.44T _m , according to the above ratio, the mass ratio of the main alloy powder to the intergranular auxiliary alloy powder is 90:10 Weigh the main alloy powder and intergranular auxiliary alloy powder obtained in step (2) and mix them uniformly to obtain mixed alloy powder; add antioxidant and lubricant to the mixed alloy powder and mix uniformly to form a billet, the anti-oxidant The sum of the mass of oxidant and lubricant is 0.25% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant is 1:1, and the antioxidant is NdFeB special antioxidant and lubricant purchased from Taiyuan Jiaci Co., Ltd. It is zinc stearate; the blank is packed into the mold cavity and placed in a magnetic field with a magnetic field strength of 2T, under the protection of nitrogen, at room temperature and under a molding pressure of 90MPa for a dwell time of 4s and press-molded to obtain a green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 240MPa for 200s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1045°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool down to room temperature with argon after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 890°C for 1.5 hours, cool to below 100°C after the heat preservation, and then heat to 505°C for 4 hours. permanent magnet material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.261T, H _cj =1093.1kA/m, (BH) _max =300.7kJ/m ³ .

Example 11

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

The raw materials are industrially pure praseodymium neodymium alloy with praseodymium content of 20% by mass, pure iron, pure aluminum, pure copper, ferroboron alloy with boron content of 20% by mass, and components of 51.56% Ce, 25.31% La, 16.94% Nd , 6.19% Pr mass of mixed rare earth MM.

According to the main alloy 27.57(Nd _0.8 Pr _0.2 )-70.69Fe-1.02B-0.72Al each component and the mass percentage content of each component are mixed, and the oxides and inclusions on the surface of each raw material metal are cleaned;

According to the ingredients in the auxiliary alloy 61.8MM-33.5Fe-4.1Cu-0.6B and the mass percentage content of each component, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 25.57(Nd,Pr)-7.13(Ce,La)-65.11Fe-0.96B-1.23T _m . The mass ratio of the alloy flakes is 85:15. Weigh the main alloy flakes and the intergranular auxiliary alloy flakes obtained in step (1), mix the two alloy flakes and put them into a rotary hydrogen crushing furnace for hydrogen absorption-dehydrogenation Treatment, the hydrogen pressure of the hydrogen absorption treatment is 0.18MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. For hydrogen absorption to reach saturation), the dehydrogenation treatment is vacuum dehydrogenation at 560°C. When the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is less than or equal to 250ppm, the dehydrogenation treatment is completed, and the particle size is obtained after the hydrogen absorption-dehydrogenation treatment is completed. Mixed alloy coarsely crushed particles of 10 to 300 μm, the obtained mixed alloy coarsely broken particles are subjected to jet mill crushing under the protection of nitrogen to obtain mixed alloy powder with an average particle size of 4.0 μm;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.25% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is NdFeB special antioxidant purchased from Beijing Juncefeng Technology Development Co., Ltd., and the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 1.8T , under nitrogen protection at room temperature, 50MPa molding pressure holding time 12s compression molding, to obtain green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 200s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1045°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool down to room temperature with argon after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 910°C for 1.5h, cool it to below 100°C after the heat preservation is over, heat it to 520°C and keep it for 4h, pass it into argon to cool to room temperature after the heat preservation is completed, and obtain the sintered cerium-rich rare earth permanent magnet material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.273T, H _cj =702.4kA/m, (BH) _max =295.6kJ/m ³ .

Example 12

The preparation method of the rare earth permanent magnet material described in the present embodiment is as follows:

(1) Preparation of main alloy cast sheet and intergranular auxiliary alloy cast sheet

① Ingredients

The raw materials are praseodymium neodymium alloy with 20% praseodymium content of industrial purity, pure iron, pure aluminum, pure copper, boron iron alloy with 20% boron content by mass, and 53.93% Ce, 29.35% La, 12.01% Nd , 4.71% Pr mass of mixed rare earth MM.

According to the main alloy 27.57(Nd _0.8 Pr _0.2 )-70.69Fe-1.02B-0.72Al each component and the mass percentage content of each component are mixed, and the oxides and inclusions on the surface of each raw material metal are cleaned;

According to the ingredients in the auxiliary alloy 61.6MM-33.7Fe-4.1Cu-0.6B and the mass percentage content of each component, and remove the oxides and inclusions on the surface of each raw material metal;

② Casting

Put the main alloy raw material and the intergranular auxiliary alloy raw material prepared in step ① into the vacuum induction melting furnace respectively, and after melting under the protection of argon, pour the alloy liquid on the water-cooled copper roller with a linear speed of 3m/s for rapid cooling. Obtain quick-setting main alloy cast sheets and intergranular auxiliary alloy cast sheets with an average thickness of 0.25mm;

(2) Preparation of mixed powder of main alloy and intergranular auxiliary alloy

The component distribution ratio of the rare earth permanent magnet material to be prepared is 24.96(Nd,Pr)-7.71(La,Ce)-65.14Fe-0.96B-1.23T _m . The mass ratio of the auxiliary alloy cast flakes is 85:15. Weigh the main alloy cast flakes and the intergranular auxiliary alloy cast flakes obtained in step (1), mix the two alloy cast flakes and put them into a rotary hydrogen crushing furnace for hydrogen absorption-desorption Hydrogen treatment, the hydrogen pressure of the hydrogen absorption treatment is 0.18MPa, and the hydrogen in the furnace is supplemented by the dynamic hydrogen replenishment method. When the hydrogen absorption reaches saturation, the hydrogen absorption treatment is completed (when the hydrogen pressure drop in the furnace within 10 minutes is less than or equal to 0.02MPa, That is, the hydrogen absorption reaches saturation), the dehydrogenation treatment is vacuum dehydrogenation at 560°C, and the dehydrogenation treatment is completed when the hydrogen content of the mixed cast sheet undergoing dehydrogenation treatment is ≤250ppm, and the hydrogen absorption-dehydrogenation treatment is completed. Mixed alloy coarsely crushed particles with a diameter of 10-300 μm, and the obtained mixed alloy coarsely crushed particles are subjected to jet mill crushing under nitrogen protection to obtain mixed alloy powders with an average particle size of 4.5 μm;

(3) Preparation of green body

Add antioxidant and lubricant to the mixed alloy powder obtained in step (2) and mix uniformly to form a billet, the sum of the quality of the antioxidant and lubricant is 0.5% of the mixed alloy powder mass, the mass ratio of antioxidant to lubricant The ratio is 1:1, the antioxidant is NdFeB special antioxidant purchased from Beijing Juncefeng Technology Development Co., Ltd., and the lubricant is zinc stearate; the blank is loaded into the cavity and placed in a magnetic field with a magnetic field strength of 1.8T , under nitrogen protection at room temperature, 50MPa molding pressure holding time 12s compression molding, to obtain green body;

(4) cold isostatic pressing of green body

The green body obtained in step (3) is placed in a cold isostatic press and pressed at a pressure of 200MPa for 200s, and the cold isostatic pressed green body is obtained after pressure relief;

(5) Sintering

Put the cold isostatic pressed green body obtained in step (4) into a vacuum sintering furnace, heat-preserve and sinter at 1050°C for 4 hours under a vacuum condition of 10 ^-3 ~ 10 ^-2 Pa, and cool to room temperature by passing in argon gas after sintering. A sintered magnet is obtained;

(6) heat treatment

Heat the sintered magnet obtained in step (5) at 910°C for 1.5h, cool it to below 100°C after the heat preservation is over, heat it to 520°C and keep it for 4h, pass it into argon to cool to room temperature after the heat preservation is completed, and obtain the sintered cerium-rich rare earth permanent magnet material.

The magnetic properties of the obtained sintered cerium-rich rare earth permanent magnet material are measured by the AMT-4 magnetization characteristic automatic measuring instrument: B _r =1.267T, H _cj =693.2kA/m, (BH) _max =286.2kJ/m ³ .

Claims (9)

1. sinter cerium-rich rare earth permanent magnetic material, it is characterized in that the mass percent of the component that this sintering cerium-rich rare earth permanent magnetic material comprises and each component is as follows: RE1 is 20% ~ 28%, RE2 be 4% ~ 15%, Fe is 60.5% ~ 70.5%, B is 0.8% ~ 1.2%, Tm is 0.1% ~ 5%; The principal phase of this sintering cerium-rich rare earth permanent magnetic material is Nd ₂fe ₁₄b or (Nd, Pr) ₂fe ₁₄b, is distributed with Ce around main phase grain, or Ce and La;

Described RE1 is Nd, Nd and Pr, rare earth element based on Nd or based on the rare earth element of Nd and Pr, described RE2 is Ce, or Ce and La, described T _mfor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr.

2. sinter cerium-rich rare earth permanent magnetic material according to claim 1, it is characterized in that described RE1 is that rare earth element based on Nd refers to that the quality of Nd is more than or equal to 95% of RE1 quality, based on the rare earth element of Nd and Pr, described RE1 refers to that the quality of Nd and Pr is more than or equal to 95% of RE1 quality, when RE1 be the rare earth element based on Nd or the rare earth element based on Nd and Pr time, also comprise at least one rare earth element in Dy, Tb, Gd, Ho in RE1.

3. sinter a preparation method for cerium-rich rare earth permanent magnetic material, it is characterized in that processing step is as follows:

(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular or block

1. prepare burden

Master alloying RE3-Fe-B-M _athe mass percent of the component comprised and each component: RE3 is 27% ~ 30%, Fe is 65% ~ 72%, B is 0.9% ~ 1.1%, M _abe 0.1% ~ 4%, described RE3 be Nd, Nd and Pr, rare earth element based on Nd or based on the rare earth element of Nd and Pr, described M _afor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr;

The auxiliary alloy RE4-Fe-B-M of intergranular _bthe mass percent of the component comprised and each component: RE4 is 38% ~ 85%, Fe is 6% ~ 60%, B is 0.1% ~ 1.2%, M _bbe 0.1% ~ 20%; Described RE4 is Ce, or based on the rare earth element of Ce and La, described M _bfor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr;

According to master alloying RE3-Fe-B-M _a, the auxiliary alloy RE4-Fe-B-M of intergranular _bsaid components and each component mass percent batching;

2. founding or founding and fragmentation

Master alloying raw material step 1. prepared, the auxiliary alloy raw material of intergranular carry out founding respectively and obtain master alloying slab and the auxiliary alloy casting piece of intergranular;

Or master alloying raw material step 1. to be prepared is prepared into slab by founding, pour into the auxiliary alloy cast ingot of intergranular after the melting of intergranular step 1. prepared auxiliary alloy raw material, after auxiliary for intergranular alloy cast ingot is carried out homogenizing annealing, be broken into the auxiliary alloy block of the intergranular being of a size of 10 ~ 30mm again;

(2) preparation of master alloying powder, the auxiliary alloy powder of intergranular or master alloying and the auxiliary mixed powder for alloy of intergranular

Master alloying slab step (1) obtained, the auxiliary alloy block of intergranular carry out suction hydrogen-Dehydroepiandrosterone derivative respectively, obtain the master alloying coarse crushing particle of particle diameter 10 ~ 300 μm and the intergranular auxiliary alloy coarse crushing particle of particle diameter 0.1 ~ 3mm, described master alloying coarse crushing particle is broken by airflow milling under nitrogen or inert gas shielding, obtain the master alloying powder of particle diameter 1 ~ 5 μm, auxiliary for described intergranular alloy coarse crushing particle is carried out ball milling, obtains the auxiliary alloy powder of intergranular of particle diameter 0.5 ~ 3 μm;

Or weigh according to the mass percent of the component of prepared rare earth permanent-magnetic material and each component the master alloying slab and the auxiliary alloy casting piece of intergranular that step (2) obtains, suction hydrogen-Dehydroepiandrosterone derivative is carried out after they being mixed, obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen or inert gas shielding, obtains the hybrid alloys powder that particle diameter is 1 ~ 5 μm;

(3) preparation of green compact

In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, then blank being loaded die cavity juxtaposition in magnetic field, obtain green compact in room temperature is compressing under nitrogen protection;

Or weigh step (2) gained master alloying powder, the auxiliary alloy powder of intergranular they mixed and form hybrid alloys powder according to the mass percent of the component of prepared rare earth permanent-magnetic material and each component, formation blank is mixed after adding antioxidant and lubricant again, then blank is loaded die cavity juxtaposition in magnetic field, compressingly under nitrogen protection obtain green compact;

(4) isostatic cool pressing of green compact

The green compact that step (3) obtains are carried out the isostatic cool pressing green compact that isostatic cool pressing obtains;

(5) sinter

The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, under vacuum in 990 ~ 1070 DEG C of sintering 1 ~ 6h, passes into inert gas after terminating or nitrogen is cooled to room temperature, obtain sintered magnet;

(6) heat treatment

Step (5) gained sintered magnet is heated to 800 ~ 950 DEG C of insulation 0.5 ~ 4h, 100 ~ 40 DEG C are cooled to after insulation terminates, be heated to 460 ~ 600 DEG C of insulation 1 ~ 6h again, after insulation terminates, pass into inert gas or nitrogen is cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.

4. sinter the preparation method of cerium-rich rare earth permanent magnetic material according to claim 3; it is characterized in that in step (1); the homogenizing annealing of the auxiliary alloy cast ingot of intergranular is incubated 1 ~ 20h in 600 ~ 1000 DEG C under inert gas shielding, then cools to room temperature with the furnace.

5. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (2), the auxiliary alloy block of master alloying slab, intergranular carries out suction hydrogen-Dehydroepiandrosterone derivative respectively, or when carrying out suction hydrogen-Dehydroepiandrosterone derivative after master alloying slab and the mixing of intergranular auxiliary alloy casting piece, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.1 ~ 0.3MPa, namely complete after suction hydrogen reaches capacity and inhale hydrogen process, Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 500 ~ 600 DEG C, when namely completing Dehydroepiandrosterone derivative after the slab of carrying out Dehydroepiandrosterone derivative or block hydrogen content≤250ppm.

6. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (3), the magnetic field intensity preparing green compact is 1.5 ~ 3T, and briquetting pressure is 40 ~ 100MPa, and the dwell time is 1 ~ 15s.

7. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (4), the pressure of green compact isostatic cool pressing is 120 ~ 320MPa, and the dwell time is 10 ~ 300s.

8. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (3), the quality sum of antioxidant and lubricant is 0.05% ~ 0.5% of hybrid alloys powder quality, and the mass ratio of antioxidant and lubricant is 1:1.

9. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (1), described RE3 is that the rare earth element based on Nd refers to that the quality of Nd is more than or equal to 95% of RE3 quality, based on the rare earth element of Nd and Pr, described RE3 refers to that the quality of Nd and Pr is more than or equal to 95% of RE3 quality, when RE3 be the rare earth element based on Nd or the rare earth element based on Nd and Pr time, also comprise at least one rare earth element in Ce, La, Dy, Tb, Gd, Ho in RE3; Based on the rare earth element of Ce and La, described RE4 refers to that the quality of Ce and La is more than or equal to 75% of RE4 quality, when RE4 is the rare earth element based on Ce and La, also comprise at least one rare earth element in Nd, Pr, Dy, Tb, Gd, Ho in RE4.