CN106298133B - Permanent-magnet material and its preparation method and application based on the primary norium of total association - Google Patents

Abstract

The present invention provides a dual main phase permanent magnet material based on co-associated primary mixed rare earth metals and its preparation method and application, which consists of: (R _Ma Fe _{100‑a‑b‑c} M _b B _c ) _1‑x { [(Pr _1‑y Nd _y ) _1‑z R _z ] _d Fe _{100‑d‑e‑f} M _e B _f } _x , the permanent magnet material includes R _Ma Fe _{100‑a‑b‑ c} M _b B _c and [(Pr _1‑y Nd _y ) _1‑z R _z ] _d Fe _{100‑d‑e‑f} M _e B _f two main phases, where R _M is the co-associated primary mixed rare earth metal, and its mass composition Including: 20%~32%La, 48%~58%Ce, 4%~6%Pr and 15%~17%Nd; M is Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga, One or more of In, Sn, Ge and Si; R is one or more of Y, La, Ce, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Since the permanent magnet of the invention is cheap and has excellent comprehensive permanent magnetic properties, it has very wide application value.

Description

Permanent magnet material based on co-associated primary mixed rare earth metals and its preparation method and application

technical field

The invention relates to a permanent magnet material based on co-associated primary mixed rare earth metals, a preparation method and application thereof.

Background technique

As the third-generation rare earth permanent magnet material, NdFeB has the characteristics of high remanence B _r , high coercivity H _cj , and high magnetic energy product (BH) _m , and has been used in high-tech fields such as aerospace, information and energy. It is one of the important basic materials of modern industry. However, as the global demand for NdFeB continues to increase, the use of rare earth element neodymium has also greatly increased, resulting in metal neodymium accounting for more than 90% of the cost of NdFeB raw materials. It has caused a lot of pressure on magnetic material manufacturers and users. Moreover, since rare earths are associated ores, the demand for scarce resources such as Pr, Nd, Tb, and Dy on the one hand leads to a large backlog of high-abundance rare earths such as La, Ce, and Y, resulting in a waste of rare earth resources. On the other hand, the process of extracting and separating single high-purity rare earth metals from co-associated primary mixed rare earth metals is complicated, which not only consumes a lot of energy and resources, but also seriously increases the environmental load.

If the co-occurring primary mixed rare earth metals can be directly used to replace the separated single high-purity rare earth metals such as Pr, Nd, Tb, Dy to prepare permanent magnets, then not only can the complicated rare earth purification process be greatly reduced, energy and resource consumption can be reduced, It can reduce costs, and can basically solve the problem of balanced utilization of rare earth resources in our country, and reduce environmental load, which has very important application value and strategic significance.

At present, much attention has been paid to the research of reducing costs, using no heavy rare earth or using less metal neodymium (CN102436892A, CN102800454A, CN102969112A, CN103137314A, CN103035350A). Combining with the characteristics of rare earth resources in China, replacing single Nd with the most abundant reserves of Ce and LaCe alloys or mixed rare earths ( _LaCePrNd ) has become a research hotspot. However, since La ₂ Fe ₁₄ B and Ce ₂ Fe ₁₄ B have much lower Anisotropic field of Fe ₁₄ B, and not easy to form a phase. Therefore, in actual production, the replacement of rare earth Ce or La will cause the performance of the permanent magnet to decline, especially when the replacement amount of La or Ce exceeds 60%, the cost performance of the magnet is extremely low, and it has no practical value (JOURNAL OF APPLIED PHYSICS115, 113912 (2014).

Although the permanent magnet material with slightly higher performance can be obtained by using melt-spinning technology (spinning belt process) (JOURNAL OFAPPLIED PHYSICS 111, 07A718 (2012)), on the one hand, the magnetic properties of this material are still very low; on the other hand, this A magnet is a thin sheet (fixed in shape) and cannot be used in large areas. Therefore, how to prepare high-performance co-associated primary mixed rare earth metal-based sintered permanent magnets is still an urgent problem to be solved.

In 2007, Zhongke Sanhuan (CN 101471165B) used double alloys to prepare permanent magnets with high coercive force and almost no decrease in remanence, which made people see the advantages of double alloys. In 2012, the General Institute of Iron and Steel Research (CN 102800454A, CN 103187133A, CN 103714939A) announced dual-primary-phase or multi-primary-phase magnets and their manufacturing methods, and predicted that permanent magnets with excellent comprehensive properties could be prepared by the above preparation methods.

Generally speaking, the reason why the comprehensive performance of dual (multiple) main phase magnets is higher than that of single main phase magnets is that in addition to the "mixing" effect it exhibits, the coupling between magnets is an important reason, so the use of high-abundance rare earth Or the performance of the single main phase magnet prepared by partially replacing Nd by mixed rare earth is not high, and the effect of 1+1>2 cannot be realized. Although the performance can be improved by using dual main phase magnets (CN102800454A), the improvement effect is still not obvious. At present, in the dual main phase magnets prepared by using high-abundance rare earths or mixed rare earths, it is necessary to prepare high-abundance rare earths or mixed rare earths into single main phase magnets by adding other rare earth elements, and then prepare them with another main phase. into dual main phase magnets without directly using La, Ce or mixed rare earth (MM) iron boron magnets as one of the main phases. Although this method is beneficial to the realization of the magnet preparation process (you can directly use the single main phase preparation method without a new preparation process), it reduces the coupling advantages of this dual main phase magnet to a certain extent, which is not conducive to the magnet The improvement of comprehensive performance and the effective utilization of rare earth resources.

Contents of the invention

In order to overcome the deficiencies in the prior art, the present invention provides a dual-main-phase permanent magnet material based on co-associated primary mixed rare earth metals and a preparation method thereof. The price is low, which is conducive to environmental protection and the balanced utilization of rare earth resources, and one of the main phases only contains co-associated primary mixed rare earth metals without adding other rare earth elements, which is conducive to improving the coupling advantages of the dual main phase magnet and the comprehensive magnetic properties of the magnet able to improve.

For the convenience of description, the following names or terms are defined and explained:

1. Preparation of raw materials: use shot blasting and grinding to remove the oxide layer on the surface of the raw materials, and weigh the raw materials in proportion.

2. Preparation of quick-setting tablets: Mix the raw materials weighed in proportion, put them into the crucible in the ZGSN-0.003 vacuum induction quick-setting furnace, heat them under the protection of argon until all the raw materials melt, and then cool down to keep it at 1200 ~1600°C, and finally cast the solution onto a water-cooled copper roller with a line speed of 1-5 m/s to prepare a quick-setting sheet with a thickness of 0.1-0.5 mm.

3. Hydrogen crushing: Put the quick-setting sheet into the hydrogen breaking furnace, first evacuate to below 5Pa, then fill in about 0.2Mpa of H ₂ , replenish H ₂ at any time, so that the pressure of H ₂ is basically maintained at 0.2Mpa , absorb hydrogen at room temperature for 1 to 2 hours, then evacuate to below 5 Pa, and dehydrogenate at 200 to 600°C for 1 to 2 hours to obtain hydrogen broken powder.

4. Jet mill: put the raw material to be ground (generally hydrogen broken powder) into the QLM-100T jet mill, and carry out the jet mill at an oxygen content of less than 0.1ppm. The average particle size is obtained by adjusting the speed of the air selection wheel. 1~5μm jet milling.

In order to realize the purpose of the invention, the invention provides the following technical solutions:

A dual main phase permanent magnet material based on co-associated primary mixed rare earth metals, whose elemental composition is (R _Ma Fe _100-abc M _b B _c ) _1-x {[(Pr _1-y Nd _y ) _{1 -z} R _z ] _d Fe _100-def M _e B _f } _x , the permanent magnetic material includes R _Ma Fe _100-abc M _b B _c and [(Pr _1-y Nd _y ) _1-z R _z ] _d Fe _100-def M _e B _f two main phases, in which R _M is the primary mixed rare earth metal associated with it, and its mass composition includes: 20-32% La, 48-58% Ce, 4-6% Pr and 15- 17% Nd; M is one or more of Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga, In, Sn, Ge and Si; R is Y, La, Ce, Eu, Gd , one or more of Tb, Dy, Ho, Er, Tm, Yb and Lu, and 27≤a≤33, 0≤b≤5, 0.9≤c≤1.3, 0.1≤x≤0.9, 0≤y ≤1, 0≤z≤0.1, 28≤d≤32, 0≤e≤5, 0.9≤f≤1.2.

Preferably, in the dual main phase permanent magnet material, the value range of x is: 0.4≤x≤0.9, more preferably 0.6≤x≤0.9.

According to the dual main-phase permanent magnet material provided by the present invention, the "co-associated primary mixed rare earth metal" refers to those extracted from the co-associated primary rare earth ore without separation of a single rare earth element, and the rare earth distribution is consistent with that of the original ore Miscellaneous rare earth metals. The associated primary mixed rare earth metals used in the present invention may be the associated primary mixed rare earth metals from the Baiyan Obo Mine.

In the co-associated primary mixed rare earth metals, the following components may also be included: Sm<0.5%, Fe<0.04%, Si<0.02%, Mg<0.06%, Zn<0.01%, W<0.01%, Mo<0.01 %, Cu<0.01%, Ti<0.01%, Ca<0.01%, Pb<0.01%, Cr<0.01%, C<0.01%.

Preferably, the dual main phase permanent magnet material can be one of the following materials:

(R _M32 Fe ₆₃ Zr ₃ Al _0.9 B _1.1 ) ₃₀ ((Pr _0.4 Nd _0.6 ) ₃₀ Fe ₆₇ Al ₂ B ₁ ) ₇₀ ;

(R _M32 Fe ₆₆ Al ₁ B ₁ ) ₁₀ ((Nd _0.97 Dy _0.03 ) ₃₀ Fe ₆₉ B ₁ ) ₉₀ ;

(R _M31 Fe ₆₃ Zr ₂ Al ₁ Si ₂ B ₁ ) ₄₀ ((Pr _0.2 Nd _0.8 ) ₃₁ Fe ₆₇ Co ₁ B ₁ ) ₆₀ ;

(R _M33 Fe ₆₂ Zr ₁ Al _1.8 Si ₁ B _1.2 ) ₆₀ ((Pr _0.2 Nd _0.8 ) ₃₂ Fe ₆₆ Ga _0.8 Sn _0.2 B ₁ ) ₄₀ .

The present invention also provides the preparation method of above-mentioned permanent magnetic material, described method comprises the following steps:

(1) Prepare R _Ma Fe _100-abc M _b B _c and ((Pr _1-y Nd _y ) _1-z R _z ) _d Fe _100-def M _e B _f two main phase alloys respectively, and make them thick It is a quick-setting tablet of 0.1-0.5 mm, and then undergoes hydrogen crushing to obtain a hydrogen-broken powder of 1-3 mm (a sheet-shaped powder with a width of 1-3 mm and a thickness of 0.1-0.5 mm);

(2) R _Ma Fe _100-abc M _b B _c hydrogen broken powder and ((Pr _1-y Nd _y ) _1-z R _z ) _d Fe _100-def M _e B _f hydrogen broken powder according to the mass ratio of 10 : Mix evenly in the ratio of 90-90:10, put it into the jet mill to make jet mill powder with an average particle size of 1-5 μm;

(3) Under the protection of an inert gas, the jet mill powder is oriented and formed in a magnetic field of 0.5-2T;

(4) Put the oriented magnet into a hot isostatic pressing machine, and press it for 0.01-4 hours under an isostatic pressure of 50-400 MPa and an isostatic pressing temperature of 400°C-1100°C.

According to the preparation method provided by the present invention, preferably, in step (1), R _Ma Fe _100-abc M _b B _c : ((Pr _{1- y} Nd _y ) _1-z R _z ) _d Fe _100-def M The mass component ratio of _e B _f ranges from 10:90 to 60:40.

According to the preparation method provided by the present invention, preferably, the hot isostatic pressure in step (4) is 50-200Mpa; preferably, the hot isostatic pressing temperature is 650-1040°C; preferably, the hot isostatic pressing time is 0.5 ~2h.

According to the preparation method provided by the present invention, the preparation method may further include step (5): put the magnet after compression molding in step (4) into a high-vacuum sintering furnace for sintering at a sintering temperature of 800-1060°C 0.01 to 2 hours.

According to the preparation method provided by the present invention, the preparation method may further include step (6): tempering the sintered body obtained in step (5) at a temperature of 200-500° C. for 0.01-2 hours.

The present invention also provides the above-mentioned dual-main-phase permanent magnet material or the dual-main-phase permanent magnet material prepared according to the method of the present invention to be used in instruments and meters, household appliances, motors, wind power generation, aerospace, mobile phones, communication equipment, rotating machinery, magnetic Applications in medical equipment and sporting goods.

Compared with the currently prepared La, Ce or MM-based sintered rare earth permanent magnet materials, the present invention adopts the co-associated primary mixed rare earth metal raw materials without rare earth purification treatment to prepare permanent magnets, so the raw material process is simple, and the energy and resource consumption is small. The price is low, and it is beneficial to environmental protection and balanced utilization of rare earth resources. In addition, since one of the main phases of the double main phase magnet prepared by the present invention only contains the co-associated primary mixed rare earth metals without adding other rare earth elements, the coupling advantage of the double main phase magnet is improved, thereby increasing the magnet's Comprehensive magnetic properties. Thirdly, because the preparation method of the present invention adopts a special hot isostatic pressing process that is beneficial to the double main phase magnet, it not only simplifies the preparation process, but also further improves the magnetic properties.

Detailed ways

The present invention will be further described in detail below in conjunction with specific embodiments, and the given examples are only for clarifying the present invention, not for limiting the scope of the present invention.

The mixed rare earth R _M used in the following examples is purchased from Suzhou Kangming Chemical Co., Ltd., and its chemical composition is about by mass ratio: 27.8% La, 51.9% Ce, 5.1% Pr and 15.1% Nd, and the rest are Sm, Fe, Si , Al, C and other impurities.

Example 1

(1) Prepare two main alloys R _M32 Fe ₆₃ Zr ₃ Al _0.9 B _1.1 and (Pr _0.4 Nd _0.6 ) ₃₀ Fe ₆₇ Al ₂ B ₁ , the total mass of the two main alloys is 2.5Kg, and the thickness is 0.3 mm quick-setting tablets.

(2) The above two main alloys are subjected to hydrogen crushing respectively to obtain particles with an average particle size distribution of about 1-3 mm, and then respectively jet milled to obtain particles with an average particle size of about 2 μm.

(3) According to the mass ratio R _M32 Fe ₆₃ Zr ₃ Al _0.9 B _1.1 : (Pr _0.4 Nd _0.6 ) ₃₀ Fe ₆₇ Al ₂ B ₁ in the ratio of 30:70, mix the above jet mill powder, and weigh 10g of it, after sealing Put it into an argon-protected magnetic field orientation mold, and perform orientation molding under a magnetic field of 1.5T (pressure is about 20MPa).

(4) Put the molded magnet into a hot isostatic pressing machine to press it for 0.5 hour at a temperature of 700° C. under an isostatic pressure of 150 MPa, and then rapidly cool it through a built-in cooler.

(5) Put the hot isostatically pressed magnet into a high-vacuum sintering furnace for sintering at a sintering temperature of 1000° C. for 0.5 hour, and air-cool to room temperature.

(6) After tempering the sintered magnet at 490° C. for 2 hours, the dual main phase permanent magnet material of this embodiment is obtained.

The prepared material is processed into a small cylinder of Φ10mm × 10mm, and the permanent magnetic properties of the magnet are measured in the permanent magnet B-H hysteresis loop instrument of the NIM-2000HF type (the measurement temperature is room temperature, about 20～22 ℃, the following examples same). The test results are listed in Table 1.

It can be seen from the results in Table 1 that the dual-main-phase magnet produced in this example has excellent performance. When the content of the primary rare earth is 30%, the coercive force of the magnet exceeds 10kOe, and the magnetic energy product exceeds 40MGOe. practical application.

Comparative example 1

According to the same steps as in Example 1 to prepare a dual main phase magnet, the difference is that step (4) described in Example 1 is not carried out, and step (4) is changed to: implement cold isostatic under a pressure of 150Mpa pressure treatment. The test results of the materials prepared in this comparative example are also listed in Table 1.

From the comparison with Example 1, it can be seen that after the hot isostatic pressing step in Example 1 is replaced by the cold isostatic pressing step of this comparative example, the magnetic properties of the material are greatly reduced.

Comparative example 2

According to the same steps as in Example 1 to prepare a dual main phase magnet, the difference is that step (4) is: cold isostatic pressing is carried out under a pressure of 150Mpa; and step (5) is: step (4) is processed The finished magnet is put into a high-vacuum sintering furnace for sintering at a sintering temperature of 1000°C for 8 hours, and air-cooled to room temperature. The test results of the materials prepared in this comparative example are also listed in Table 1.

From the comparison with Example 1, it can be seen that after replacing the hot isostatic pressing step in Example 1 with the cold isostatic pressing step of this comparative example, even if the sintering time is increased, the magnetic properties of the material will still be greatly reduced.

Comparative example 3

According to the same steps as in Example 1 to prepare a dual main phase magnet, the difference is that step (4) is: cold isostatic pressing is carried out under a pressure of 150Mpa; and step (5) is: step (4) is processed The finished magnet is put into a high-vacuum sintering furnace for sintering at a sintering temperature of 1040° C. for 2 hours, and air-cooled to room temperature. The test results of the materials prepared in this comparative example are also listed in Table 1.

By comparing with Example 1, it can be seen that after replacing the hot isostatic pressing step in Example 1 with the cold isostatic pressing step of this comparative example, by adjusting the sintering temperature, the sintering time can also achieve better magnetic properties , but compared to the results of Example 1, its magnetic properties are still low.

Comparative example 4

The magnet was prepared according to the same steps as in Example 1, except that step (1) was to prepare a single main phase alloy ( _RM32 Fe ₆₃ Zr ₃ Al _0.9 B _1.1 ) ₃₀ [(Pr _0.4 Nd _0.6 ) ₃₀ Fe ₆₇ Al ₂ B ₁ ] ₇₀ , instead of separately preparing alloys with two main phases; and step (2) is to hydrogen-break and jet-mill the single-main-phase alloy to obtain particles with an average particle size of 2 μm. The test results of the materials prepared in this comparative example are also listed in Table 1.

By comparing with Example 1, it can be seen that the dual main phase magnet is not used, but a single main phase is prepared by element substitution, even if the hot isostatic pressing technique is used, its magnetic properties are increased (see Comparative Example 5) , and its magnetic properties are much lower than those of dual main phase magnets.

Comparative example 5

The magnet was prepared according to the same steps as in Example 1, except that step (1) was to prepare a single main phase alloy ( _RM32 Fe ₆₃ Zr ₃ Al _0.9 B _1.1 ) ₃₀ [(Pr _0.4 Nd _0.6 ) ₃₀ Fe ₆₇ Al ₂ B ₁ ] ₇₀ , instead of separately preparing alloys of two main phases; step (2) is to hydrogen-break and jet mill the single main phase alloy to obtain particles with an average particle size of 2 μm; step (4) is: Implement cold isostatic pressing under the pressure of 150Mpa; and step (5) is: put the magnet after step (4) into a high-vacuum sintering furnace for sintering, the sintering temperature is 1040°C, sintering for 2 hours, and air-cooled to room temperature. The test results of the materials prepared in this comparative example are also listed in Table 1.

By comparing with Example 1 and Comparative Example 4, it can be seen that even for single main phase magnets, the magnetic properties will be reduced if the hot isostatic pressing treatment is replaced by cold isostatic pressing treatment, which also shows that the hot isostatic pressing treatment Hydrostatic technology is also applicable to single main phase magnets. However, this substitution has slightly less effect on the magnetic properties compared to the dual main phase magnet.

Comparative example 6

(1) Prepare two main alloys R _M16 Pr ₁₆ Fe ₆₃ Zr ₃ Al _0.9 B _1.1 and (R _M0.22 Pr _0.18 Nd _0.6 ) ₃₀ Fe ₆₇ Al ₂ B ₁ respectively according to the mass ratio, the total mass of the two main alloys Both are 2.5Kg, and then prepared into quick-setting sheets with a thickness of 0.3mm;

(2) The quick-setting tablets in step (1) are subjected to hydrogen crushing to obtain particles with an average particle size of about 1 to 3 mm, and then jet milled to obtain particles with an average particle size of about 2 μm.

(3) According to the mass ratio of R _M16 Pr ₁₆ Fe ₆₃ Zr ₃ Al _0.9 B _1.1 : (R _M0.22 Pr _0.18 Nd _0.6 ) ₃₀ Fe ₆₇ Al ₂ B ₁ in the ratio of 30:70, mix the above jet mill powder, and weigh Take 10g of it, seal it, put it into an argon-protected magnetic field orientation mold, and perform orientation molding under a magnetic field of 1.5T (the pressure is about 20MPa).

(4) Put the formed magnet into a hot isostatic pressing machine to press for 0.5 hour at a temperature of 700° C. under an isostatic pressure of 150 MPa, and then rapidly cool it through a built-in cooler.

(5) Put the hot isostatically pressed magnet into a high-vacuum sintering furnace for sintering at a sintering temperature of 1000° C. for 0.5 hour, and air-cool to room temperature.

(6) After tempering the sintered magnet at 490° C. for 2 hours, the magnet of this comparative example was obtained.

The sintered magnet prepared above was processed into a small cylinder of Φ10mm×10mm, and the permanent magnetic properties of the magnet were measured on a NIM-2000HF permanent magnet B-H hysteresis loop instrument (the measurement temperature was room temperature, about 20-22°C). The test results are also listed in Table 1.

By comparison with Example 1, it can be seen from the data in Table 1 that using Pr to partially replace R _M will weaken the coupling interaction in the case of the same rare earth content, resulting in a decline in the performance of the magnet.

Example 2

According to the same steps as in Example 1 to prepare a dual main phase magnet, the difference is that step (4) is: put the formed magnet into a hot isostatic press under an isostatic pressure of 120 MPa at a temperature of 900 ° C , pressed for 0.5 hour, and then rapidly cooled by a built-in cooler; and steps (5) and (6) were not carried out. The test results are listed in Table 1.

It can be seen from the data in Table 1 that as long as the temperature and time of hot isostatic pressing are appropriate, the direct production of magnets without sintering and tempering in the later stage will not lead to a significant decrease in magnetic properties. This is very beneficial for reducing preparation time.

Example 3

(1) Prepare two main alloys R _M32 Fe ₆₆ Al ₁ B ₁ and (Nd _0.97 Dy _0.03 ) ₃₀ Fe ₆₉ B ₁ , both of which have a total mass of 2.5Kg, and make quick-setting sheets of 0.3mm respectively.

(2) The above two main alloys are subjected to hydrogen crushing to obtain particles with an average particle size distribution of about 1-3 mm, and then jet milled to obtain jet mill particles with an average particle size of 1.5 μm and 3 μm respectively.

(3) According to the mass ratio of R _M32 Fe ₆₆ Al ₁ B ₁ : (Nd _0.97 Dy _0.03 ) ₃₀ Fe ₆₉ B ₁ in the ratio of 10:90, mix the above airflow milling powder, and weigh 10g of it, seal it and put it into argon gas In the protected magnetic field orientation mold, orientation molding is performed under a magnetic field of 1.5T (pressure is about 20MPa).

(4) Put the molded magnet into a hot isostatic press to press it for 0.5 hour at a temperature of 1040° C. under an isostatic pressure of 100 MPa, and then rapidly cool it through a built-in cooler.

The magnet prepared above was processed into a small cylinder of Φ10mm×10mm and tested in a B-H loop instrument. The test results are listed in Table 1.

Example 4

(1) Prepare two main alloys R _M31 Fe ₆₃ Zr ₂ Al ₁ Si ₂ B ₁ and (Pr _0.2 Nd _0.8 ) ₃₁ Fe ₆₇ Co ₁ B ₁ , the total mass of the two main alloys is 2.5Kg, respectively made into 0.3 mm quick-setting tablets.

(2) The above two main alloys are subjected to hydrogen crushing to obtain particles with an average particle size distribution of about 1-3 mm, and then jet milled to obtain jet mill particles with an average particle size of 2 μm and 3 μm respectively.

(3) According to the mass ratio of R _M31 Fe ₆₃ Zr ₂ Al ₁ Si ₂ B ₁ : (Pr _0.2 Nd _0.8 ) ₃₁ Fe ₆₇ Co ₁ B ₁ in the ratio of 40:60, mix the above jet mill powder, and weigh 10g of it, After sealing, put it into an argon-protected magnetic field orientation mold, and perform orientation molding under a magnetic field of 1.5T (the pressure is about 20MPa).

(4) Put the molded magnet into a hot isostatic pressing machine under an isostatic pressure of 200 MPa and a temperature of 970° C. for 0.8 hours, and then quickly cool it through a built-in cooler.

The magnet prepared above was processed into a small cylinder of Φ10mm×10mm and tested in a B-H loop instrument. The test results are listed in Table 1.

Example 5

(1) Two main alloys, R _M33 Fe ₆₂ Zr ₁ Al _1.8 Si ₁ B _1.2 and (Pr _0.2 Nd _0.8 ) ₃₂ Fe ₆₅ Ga _0.8 Sn _0.2 Co ₁ B ₁ were prepared, both with a total mass of 2.5Kg, respectively made into 0.3 mm quick-setting tablets.

(2) The above two main alloys are subjected to hydrogen crushing to obtain particles with an average particle size distribution of about 1-3 mm, and then jet milled to obtain jet mill particles with an average particle size of 2 μm and 3 μm respectively.

(3) According to the mass ratio R _M33 Fe ₆₂ Zr ₁ Al _1.8 Si ₁ B _1.2 : (Pr _0.2 Nd _0.8 ) ₃₂ Fe ₆₅ Ga _0.8 Sn _0.2 Co ₁ B ₁ in the ratio of 60:40, mix the above jet mill powder, and weigh Take 10g of it, seal it, put it into an argon-protected magnetic field orientation mold, and perform orientation molding under a magnetic field of 2T (the pressure is about 20MPa).

(4) Put the molded magnet into a hot isostatic pressing machine to press for 2 hours at a temperature of 650° C. under an isostatic pressure of 50 MPa, and then rapidly cool it through a built-in cooler.

The magnet prepared above was processed into a small cylinder of Φ10mm×10mm and tested in a B-H loop instrument. The test results are listed in Table 1.

Table 1

From the results of Examples 3-5, it can be seen that as long as two main phases are maintained, and the rare earth element in one of the main phases only contains R _M , a sintered magnet with excellent performance can be obtained by adjusting the preparation process. The magnetic properties can be further improved by the isostatic pressing process.

The embodiments described above have described the technical solutions of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the present invention. All technical solutions can realize the present invention, and the embodiments are not listed one by one here; any modification, supplement or similar substitution made within the scope of the principle of the present invention shall be included in the protection scope of the present invention.

Claims (6)

1. a kind of preparation method of double main phase permanent-magnet materials based on the primary norium of total association, double main phases are forever Magnetic material is one of following material:

(R_M32Fe₆₃Zr₃Al_0.9B_1.1)₃₀((Pr_0.4Nd_0.6)₃₀Fe₆₇Al₂B₁)₇₀；

(R_M32Fe₆₆Al₁B₁)₁₀((Nd_0.97Dy_0.03)₃₀Fe₆₉B₁)₉₀；

(R_M31Fe₆₃Zr₂Al₁Si₂B₁)₄₀((Pr_0.2Nd_0.8)₃₁Fe₆₇Co₁B₁)₆₀；With

(R_M33Fe₆₂Zr₁Al_1.8Si₁B_1.2)₆₀((Pr_0.2Nd_0.8)₃₂Fe₆₆Ga_0.8Sn_0.2B₁)₄₀,

Wherein, R_MFor the primary norium of total association, quality composition include: 20%~32%La, 48%~58%Ce, 4%~6%Pr and 15%~17%Nd,

The preparation method comprises the following steps:

(1) two kinds of main-phase alloys, and the rapid-hardening flake being made with a thickness of 0.1~0.5mm are prepared respectively, are put down using hydrogen breaking The hydrogen that equal granularity is 1~3mm breaks powder；

(2) two kinds of main-phase alloy hydrogen are broken powder to be uniformly mixed according to the ratio that mass ratio is 10:90~90:10, is put into airflow milling The air-flow that average particle size is 1~5 μm is made to be milled；

(3) by air-flow milling under the protection of inert gas, the oriented moulding in the magnetic field of 0.5~2T；

(4) magnet being orientated is put into hot isostatic press, under the isostatic pressure of 50~200Mpa, at 650~1040 DEG C At a temperature of equal static pressure, 0.5~2h is suppressed.

2. preparation method according to claim 1, wherein airflow milling Powder Particle Size described in step (2) is 1~3 μm.

3. preparation method according to claim 1, wherein the preparation method further includes step

(5): the blank after step (4) compression moulding is put into the sintering furnace of high vacuum in 800~1060 DEG C of sintering temperature 0.01~2h of lower sintering.

4. preparation method according to claim 3, wherein the preparation method further includes step

(6): the sintered body that step (5) is obtained 200~500 DEG C at a temperature of be tempered 0.01~2h.

5. a kind of double main phase permanent-magnet materials based on the primary norium of total association, double main phase permanent-magnet materials are by weighing Benefit requires any one of 1 to 4 the method to be made.

6. according to described in double main phase permanent-magnet materials made from any one of claims 1 to 4 the method or claim 5 Double main phase permanent-magnet materials are in instrument and meter, household electrical appliances, motor, wind-power electricity generation, aerospace, mobile phone, communication equipment, whirler Application in tool, magnetotherapy appliance and sports goods.