CN103903824B - A kind of rare earth permanent magnet material and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of rare earth permanent-magnetic material, the material includes principal phase and auxiliary phase, it is characterised in that the composition of the principal phase is：R1_xR2_yFe_{100‑x‑y‑z‑u}Co_zB_u；The composition of the auxiliary phase is：R1_aR2_bFe_{100‑a‑b‑c‑n‑v}Co_cB_nM_v；On the basis of the gross mass of the principal phase and auxiliary phase, the mass content of the auxiliary phase is more than 0 and less than or equal to 20%.The rare earth permanent-magnetic material prepared present invention also offers a kind of preparation method of rare earth permanent-magnetic material and by this method.The rare earth permanent-magnetic material that the present invention is provided, with higher coercivity, relatively low temperature coefficient, and effectively increases operating temperature, also significantly reduces the content of dysprosium and/or terbium, reduce the production cost of permanent-magnet material while magnetic residual loss very little is ensured.

Description

A kind of rare earth permanent magnet material and preparation method thereof

technical field

The invention relates to a rare earth permanent magnet material, a preparation method of the rare earth permanent magnet material, and a rare earth permanent magnet material prepared by the method.

Background technique

Compared with other types of permanent magnet materials, sintered NdFeB permanent magnet materials have outstanding advantages such as high magnetic performance and low price, which makes its development and application have achieved extraordinary development. At present, its comprehensive magnetic properties have reached a high level, and its application has involved various fields of the national economy.

However, new energy and environmental protection are increasingly concerned and become an inevitable development trend, and the requirements for high coercive force and high remanence are also put forward for the permanent magnet materials used. High-coercivity magnets require more expensive dysprosium and/or terbium elements, but magnets with more of these two elements cannot better meet the needs of high remanence, which is not conducive to the lightweight and high-power motor and Efficient use of electricity and wind energy.

CN102534358A discloses a method for manufacturing high-coercivity R-Fe-B series sintered permanent magnet materials, characterized in that the method comprises the following steps: step 1, the raw materials are prepared in proportion, at 200-700Kg/time melted in the strip continuous casting furnace, and cast into alloy flakes with a roll speed of 1m/s-10m/s, and the thickness of the alloy flakes is 0.1-0.4mm; step 2, put the alloy flakes prepared in step 1 into Hydrogen crushing is carried out in the hydrogen treatment furnace, and the hydrogen is dehydrogenated at a temperature of 400-600 ° C to a hydrogen pressure <10Pa; in an oxygen-free environment under the protection of an inert gas, the alloy flakes after hydrogen crushing are sent to an intermediate mill for crushing to The particle size is less than 0.5mm, and then finely pulverized by jet mill, and classified into NdFeB alloy powder with particle size d=2-4um; Step 3, in an oxygen-free environment under the protection of inert gas, reduce the particle size to less than 100nm At least one of nano-dysprosium oxide, nano-terbium oxide, and nano-holmium oxide is added to the prepared NdFeB alloy powder, and the addition ratio is 1-3% of the NdFeB alloy powder weight, and mixed uniformly; step 4, In an oxygen-free environment under the protection of an inert gas, the homogeneously mixed powder in step 3 is oriented by a magnetic field of 1.5-3T and pressed into a compact; in step 5, in an oxygen-free environment under the protection of an inert gas, the The prepared compact is sent into a vacuum sintering furnace for primary sintering at 600-700°C×2-4hr, followed by secondary sintering at 800-900°C×2-4hr, rapid cooling, and then 1000-1100°C×1 Three times of high-temperature sintering and rapid cooling for -2hr, and finally aging treatment at 850-950℃×1-6hr and 450-600℃×1-6hr in turn to produce high-coercivity high-temperature-resistant R-Fe-B sintering permanent magnet material. The remanence of the permanent magnet material prepared by the method is 13.6-14.5 (kGs), and the coercive force is 14.5-18 (kOe).

The coercive force of the currently produced permanent magnet materials is still far from the theoretical limit of 80kOe, and the content of dysprosium and/or terbium required to increase the coercive force is still relatively high. In addition, while increasing the coercivity of permanent magnet materials, the remanence will inevitably decrease. How to increase the coercivity while ensuring a low drop in remanence (that is, to ensure high coercivity and high remanence at the same time), and To reduce the usage of dysprosium and/or terbium has become a research hotspot at present.

Contents of the invention

The purpose of the present invention is to solve the technical problems that the permanent magnet materials in the prior art cannot obtain higher coercive force, lower temperature coefficient and higher working temperature at the same time, and the usage of dysprosium and/or terbium is relatively high, Provide a kind of rare earth permanent magnet material with higher coercive force, lower temperature coefficient and higher working temperature, and the usage amount of dysprosium and/or terbium is lower, and the preparation method of the rare earth permanent magnet material and by the method Prepared rare earth permanent magnet materials.

The inventor of the present invention notices that magnet only adopts the rare-earth element that Pr and/or Nd forms, and in essential feature, it is difficult to obtain magnets such as high coercive force such as automobile motor, wind-driven generator and adapting to high working temperature, therefore mainly The phase requires a certain content of heavy rare earth Dy and/or Tb to increase the coercive force, but the presence of Dy and/or Tb inevitably leads to a decrease in remanence and an increase in cost.

However, the inventors of the present invention have finally found through many experiments that the main phase with a certain composition and content cooperates with the auxiliary phase with a certain composition and content and a higher content of Dy and/or Tb, effectively reducing the magnetic induction of the final magnet. Loss, high coercive force can be obtained under the condition of low magnetic induction loss. Although the content of Dy and/or Tb in the auxiliary phase is relatively high, because the amount of the auxiliary phase added in the rare earth permanent magnet material can obtain a better effect in less cases, so compared with the prior art, It is still possible to obtain high coercive force, low temperature coefficient and high operating temperature under the condition of low magnetic induction loss under the condition of low content of Dy and/or Tb. In addition, when the performance of the rare earth permanent magnet material provided by the present invention is close to that of the rare earth permanent magnet material provided by the prior art, the content of dysprosium and/or terbium of the rare earth permanent magnet material provided by the present invention is higher than that of the existing rare earth permanent magnet. Materials are significantly lower.

In order to achieve the above object, the present invention provides a rare earth permanent magnet material, which includes a main phase and an auxiliary phase, wherein the composition of the main phase is: R1 _x R2 _y Fe 100 _{- xyzu} Co _z Bu , R1 is selected from From Pr and/or Nd; R2 is selected from Dy and/or Tb, where x, y, z, u are mass percentages, and 26%≤x+y≤36%, 0.01%≤y≤6%, 0% ≤z≤5%, 0.8%≤u≤1.2%; the composition of the auxiliary phase is: R1 _a R2 _b Fe _100-abcnv Co _c B _n M _v , R1 is selected from Pr and/or Nd; R2 is selected from Dy And/or Tb, M is selected from one or more of Zr, Ga, Cu, Nb, Sn, Mo, Al, V, W, Si, Hf, Ti, wherein, a, b, c, n, v It is a mass percentage, and 35%≤a+b≤80%, 5%≤b≤40%, 0%≤c≤40%, 0%≤n≤1.2%, 0%≤v≤30%; The total mass of the main phase and the auxiliary phase is used as the basis, and the mass content of the auxiliary phase is greater than 0 and less than or equal to 20%.

The present invention also provides a method for preparing a rare earth permanent magnet material. The method includes sequentially performing mixed molding, sintering and tempering on the main phase alloy raw material and the auxiliary phase alloy raw material, wherein the composition of the main phase alloy raw material is: R1 _x R2 _y Fe 100 _{- xyzu} Co _z Bu , R1 is selected from Pr and/or Nd; R2 is selected from Dy and/or Tb, wherein, x, y, z, u are mass percentages, and 26%≤x+ y≤36%, 0.01%≤y≤6%, 0%≤z≤5%, 0.8%≤u≤1.2%; the composition of the auxiliary phase alloy raw material is: R1 _a R2 _b Fe _100-abcnv Co _c B _n M _v , R1 is selected from Pr and/or Nd; R2 is selected from Dy and/or Tb, M is selected from Zr, Ga, Cu, Nb, Sn, Mo, Al, V, W, Si, Hf, Ti One or more, among which, a, b, c, n, v are mass percentages, and 35%≤a+b≤80%, 5%≤b≤40%, 0%≤c≤40%, 0% ≤n≤1.2%, 0%≤v≤30%; relative to the total amount of 100 parts by weight of the main phase alloy raw material and the auxiliary phase alloy raw material, the amount of the auxiliary phase alloy raw material is greater than 0 parts by weight and Less than or equal to 20 parts by weight.

The present invention also provides the rare earth permanent magnet material prepared by the above method.

Compared with the prior art, the rare earth permanent magnet material provided by the present invention has higher coercive force, lower temperature coefficient and higher operating temperature under the condition that the remanence is guaranteed to decrease little, and reduces dysprosium and and/or the amount of terbium used.

Other features and advantages of the present invention will be described in detail in the following detailed description.

detailed description

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The present invention provides a rare earth permanent magnet material, which comprises a main phase and an auxiliary phase, wherein the composition of the main phase is: R1 _x R2 _y Fe 100 _{- xyzu} Co _z Bu, R1 is selected from Pr and/or Nd; R2 is selected from Dy and/or Tb, where x, y, z, u are mass percentages, and 26%≤x+y≤36%, 0.01%≤y≤6%, 0%≤z≤5% , 0.8%≤u≤1.2%; the composition of the auxiliary phase is: R1 _a R2 _b Fe _100-abcnv Co _c B _n M _v , R1 is selected from Pr and/or Nd; R2 is selected from Dy and/or Tb, M is selected from one or more of Zr, Ga, Cu, Nb, Sn, Mo, Al, V, W, Si, Hf, Ti, wherein a, b, c, n, v are mass percentages, and 35%≤a+b≤80%, 5%≤b≤40%, 0%≤c≤40%, 0%≤n≤1.2%, 0%≤v≤30%; the main phase and auxiliary phase The total mass of is used as a benchmark, and the mass content of the auxiliary phase is greater than 0 and less than or equal to 20%.

According to the rare earth permanent magnet material provided by the present invention, preferably, in the composition of the main phase, the mass percentages of x, y, z, and u are: 28%≤x+y≤32%, 1.5%≤y≤4 %, 1%≤z≤2.5%, 0.9%≤u≤1.1%. When the composition of the main phase is within the above range, it is more beneficial to obtain rare earth permanent magnets with higher coercive force, lower temperature coefficient and higher operating temperature with little reduction in remanence Material.

According to the rare earth permanent magnet material provided by the present invention, preferably, in the composition of the auxiliary phase, the mass percentages of a, b, c, n, and v are: 38%≤a+b≤67%, 10%≤b ≤25%, 0%≤c≤17%, 0%≤n≤1%, 8%≤v≤28%. When the composition of the auxiliary phase is within the above range, it is more conducive to obtaining rare earth permanent magnets with higher coercive force, lower temperature coefficient and higher operating temperature with little reduction in remanence Material.

According to the rare earth permanent magnet material provided by the present invention, preferably, based on the total mass of the main phase and the auxiliary phase, the mass content of the auxiliary phase is greater than 0 and less than or equal to 15%, for example, it can be greater than 1%. And less than or equal to 15%. When the mass content of the auxiliary phase of the rare earth permanent magnet material is within the above range, it is more favorable to realize the object of the present invention.

The invention provides a method for preparing a rare earth permanent magnet material. The method includes sequentially mixing and molding, sintering and tempering the main phase alloy raw material and the auxiliary phase alloy raw material, wherein the composition of the main phase alloy raw material is: R1 _x R2 _y Fe 100 _{- xyzu} Co _z Bu , R1 is selected from Pr and/or Nd; R2 is selected from Dy and/or Tb, wherein, x, y, z, u are mass percentages, and 26%≤x+y ≤36%, 0.01%≤y≤6%, 0%≤z≤5%, 0.8%≤u≤1.2%; the composition of the auxiliary phase alloy raw material is: R1 _a R2 _b Fe _100-abcnv Co _c B _n Mv, R1 is selected from Pr and/or Nd; R2 is selected from Dy and/or Tb, M is selected from one of Zr, Ga, Cu, Nb, Sn, Mo, Al, _V , W, Si, Hf, Ti One or several kinds, where a, b, c, n, v are mass percentages, and 35%≤a+b≤80%, 5%≤b≤40%, 0%≤c≤40%, 0%≤ n≤1.2%, 0%≤v≤30%; relative to the total amount of 100 parts by weight of the main phase alloy raw material and the auxiliary phase alloy raw material, the amount of the auxiliary phase alloy raw material is greater than 0 weight part and less than Or equal to 20 parts by weight.

According to the preparation method of the rare earth permanent magnet material provided by the present invention, preferably, in the composition of the main phase alloy raw material, the mass percentages of x, y, z, u are: 28%≤x+y≤32%, 1.5% %≤y≤4%, 1%≤z≤2.5%, 0.9%≤u≤1.1%. When the composition of the main phase alloy raw material is within the above range, adopting this method is more conducive to preparing the alloy with higher coercive force, lower temperature coefficient and higher Rare earth permanent magnet materials at working temperature.

According to the preparation method of the rare earth permanent magnet material provided by the present invention, preferably, in the composition of the auxiliary phase alloy raw materials, the mass percentages of a, b, c, n, and v are: 38%≤a+b≤67% , 10%≤b≤25%, 0%≤c≤17%, 0%≤n≤1%, 8%≤v≤28%. When the composition of the auxiliary phase alloy raw material is within the above range, adopting this method is more conducive to preparing a compound with higher coercive force, lower temperature coefficient and higher Rare earth permanent magnet materials at working temperature.

According to the preparation method of the rare earth permanent magnet material provided by the present invention, preferably, relative to the total amount of 100 parts by weight of the main phase alloy raw material and the auxiliary phase alloy raw material, the amount of the auxiliary phase alloy raw material is greater than 0 weight part and less than or equal to 15 parts by weight, for example, it may be greater than 1 part by weight and less than or equal to 15 parts by weight. When the mass content of the auxiliary phase of the rare earth permanent magnet material is within the above range, it is more beneficial to realize the purpose of the present invention.

According to the preparation method of the rare earth permanent magnet material provided by the present invention, the double alloy method (that is, the main phase alloy raw material and the auxiliary phase alloy raw material are smelted separately to form a rare earth permanent magnet material) and the single alloy method (that is, an alloy Composition, smelting, and the obtained material contains two phases, that is, the main phase and the auxiliary phase) to prepare rare earth permanent magnet materials to achieve the purpose of the present invention.

When the present invention adopts the single alloy method to prepare the rare earth permanent magnet material, the alloy of one component is smelted to obtain the ingot or quick-setting thin slice of the alloy raw material, and the ingot or quick-setting thin slice of the alloy raw material is broken and manufactured. powder, and then molded.

When the present invention adopts the double alloy method to prepare rare earth permanent magnet materials, the main phase alloy raw material and the auxiliary phase alloy raw material are smelted separately to obtain ingots or quick-setting flakes of the main phase alloy raw material and ingots or quick-setting alloy raw materials of the auxiliary phase. Solidified flakes, there is no special requirement for the order of mixing, crushing and pulverizing the ingots or quick-setting flakes of the main phase alloy raw materials and the ingots or quick-setting flakes of the auxiliary phase alloy raw materials, and can be mixed first, then crushed and pulverized; It can also be crushed, mixed, and powdered first; it can also be crushed, powdered, and then mixed; and then the obtained fine powder of the main phase alloy raw material and the auxiliary phase alloy raw material can be shaped.

Preferably, the present invention adopts a double alloy method to prepare rare earth permanent magnet materials. That is, before forming the main-phase alloy raw material and the auxiliary-phase alloy raw material, the main-phase alloy raw material and the auxiliary-phase alloy raw material are melted separately. The inventors of the present invention found that the performance of the rare earth permanent magnet material prepared by the double alloy method is better than that of the rare earth permanent magnet material prepared by the single alloy method. This may be due to the reaction of the auxiliary phase alloy raw materials at the grain boundary to obtain the main phase with a high anisotropy field and the formation of a rare earth-rich phase. At the same time, the trace elements in the auxiliary phase alloy raw materials can well improve the microstructure at the grain boundary. In addition, since the auxiliary phase alloy raw materials are added separately, Dy and/or Tb and trace elements in the auxiliary phase alloy raw materials are completely avoided from entering the main phase, but located in the epitaxial layer and grain boundary of the main phase. Therefore, compared with the rare earth permanent magnet material prepared by the single alloy method with similar properties, the content of Dy and/or Tb is significantly reduced in the rare earth permanent magnet material prepared by the double alloy method.

The smelting method is a conventional smelting method in the art, and the obtained alloy is in the form of ingot or strip. The smelting temperature is 1200-1500°C, and the smelting time is 20min-1h.

The crushing method is a variety of conventional crushing methods in the art, as long as the ingot or quick-setting flake of the main phase alloy raw material and the ingot or quick-setting flake of the auxiliary phase alloy raw material can be fully broken, preferably hydrogen broken way. The conditions of hydrogen crushing can also be the conditions known in the art. It is preferred to absorb hydrogen at room temperature (20±5°C) for 0.1-5h under the hydrogen pressure of 0.02-1.5Mpa in ingot or quick-setting flakes, and at 300- Dehydrogenation at 650°C for 2-10 hours to obtain crushed hydrogen powder.

The pulverizing method is various conventional pulverizing methods in the art, as long as the hydrogen pulverized powder can be made into a fine powder with a target particle size, the jet milling method is preferably used, and an antioxidant is added before the jet milling. The antioxidant can be any special antioxidant for NdFeB, for example, it can be a special antioxidant for NdFeB purchased from Beijing Juncefeng Technology Development Co., Ltd., the brand name is KM-01. Based on the total weight of the crushed hydrogen powder, the added amount of the antioxidant is 0.02-0.15% by weight. The hydrogen crushed powder is made into a fine powder with an average particle size of 1.0-4.5 μm by jet milling (when the double alloy method is used, the average particle size of the fine powder of the main phase alloy raw material is preferably 2.5-4.5 μm).

Preferably, a lubricant is added to the fine powder obtained after milling, and the lubricant is preferably one of gasoline, oleic acid, stearic acid, polyethylene glycol, sorbitan and glyceryl stearate or Various. Based on the weight of the fine powder, the added amount of the lubricant is 0.02-0.15% by weight.

According to the preparation method of the rare earth permanent magnet material provided by the present invention, the molding method can adopt conventional methods in the art, preferably, the molding is carried out in a constant magnetic field or a pulsed magnetic field of 1.5-4T for orientation compression molding, And after 170-220MPa isostatic pressure to maintain 30-120s.

According to the preparation method of the rare earth permanent magnet material provided by the present invention, the conditions of the sintering and the step of tempering can be any one known to those skilled in the art, preferably, the conditions of the sintering are: the sintering temperature is 1040-1120°C, sintering time is 3-8 hours; the tempering steps are: firstly perform primary tempering at 860-940°C, and keep for 1-5h, then perform secondary tempering at 470-560°C , and keep it for 1-8h.

The present invention also provides the rare earth permanent magnet material prepared by the above preparation method of the rare earth permanent magnet material.

The present invention will be described in detail below by way of examples.

In the following examples, according to the GB/T 3217-1992 test standard, the Chinese Institute of Science and Metrology NIM-10000H is used to test (or test and calculate) the remanence (Br) and coercivity (Hcj) of rare earth permanent magnet materials at 22°C ), the maximum magnetic energy product ((BH)max), the maximum operating temperature and the β temperature coefficient;

where the β temperature coefficient is calculated by the following formula:

Among them, β (Hcj): temperature coefficient of intrinsic coercive force, %/℃;

T ₁ : base temperature, °C; T ₂ : upper limit temperature of temperature change, °C;

Hcj (T ₁ ): Intrinsic coercive force at temperature T ₁ , kA/m;

Hcj (T ₂ ): Intrinsic coercive force at temperature T ₂ , kA/m.

Example 1

The raw material with the formula of Pr ₅ Nd ₂₃ Dy ₃ Tb _0.5 Fe _66.5 Co ₁ B ₁ was strip-spun at a copper roller surface speed of 1.8m/s to prepare strip strips as the main phase alloy raw material. The main phase alloy raw material was absorbed hydrogen at 15° C. for 2 hours under a hydrogen pressure of 0.15 MPa, and then dehydrogenated at 560° C. for 6 hours, thereby obtaining hydrogen crushed powder of the main phase alloy raw material. Then, mix 100 parts by weight of hydrogen crushed powder of the main phase alloy raw material with 0.05 parts by weight of NdFeB special antioxidant (purchased from Beijing Juncefeng Technology Development Co., Ltd., brand KM-01), and then pass The jet mill grinds to make the main phase alloy raw material fine powder with an average particle diameter of 3.2um, then mix the obtained main phase alloy raw material fine powder with 0.03 parts by weight of gasoline based on the main phase alloy raw material fine powder of 100 parts by weight Mix evenly to obtain the main phase precursor.

The raw material with the formula of Pr _9.6 Nd _29.3 Dy ₁₀ Fe _15.5 Co _16.5 B _0.96 Al _5.5 Cu _3.2 Zr _2.4 Ga ₇ was melted and cast at 1300°C for 25 minutes to prepare an ingot as a supplementary phase alloy raw material. The auxiliary phase alloy raw material was absorbed hydrogen at 15° C. for 2 hours under a hydrogen pressure of 0.15 MPa, and then dehydrogenated at 560° C. for 6 hours to obtain hydrogen crushed powder of the auxiliary phase alloy raw material. Then, 100 parts by weight of the hydrogen crushed powder of the auxiliary phase alloy raw material and 0.05 parts by weight of NdFeB special antioxidant (purchased from Beijing Juncefeng Technology Development Co., Ltd., brand KM-01) were evenly mixed, and then passed The jet mill is ground to make an auxiliary phase alloy raw material fine powder with an average particle diameter of 3um, and then the obtained auxiliary phase alloy raw material fine powder is mixed with 0.03 parts by weight of gasoline based on 100 parts by weight of the auxiliary phase alloy raw material fine powder Uniformly, the auxiliary phase precursor is obtained.

The main phase precursor and the auxiliary phase precursor are uniformly mixed, and the amount of the auxiliary phase precursor is 1.5 parts by weight relative to 100 parts by weight of the total amount of the main phase precursor and the auxiliary phase precursor. The homogeneously mixed main phase precursor and auxiliary phase precursor were molded in a constant magnetic field of 2T, then subjected to 190MPa isostatic pressure for 70s, then sintered at 1090°C for 5h, and performed primary tempering at 920°C for 1.5h ; Then carry out secondary tempering at 480°C for 3.5h. Finally, the rare earth permanent magnet material described in the present invention is obtained. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Comparative example 1

The preparation method of the rare earth permanent magnet material in Example 1 is adopted, the difference is that no auxiliary phase alloy raw material is added. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Example 2

Adopting the preparation method of the rare earth permanent magnet material of embodiment 1, the difference is that relative to the total amount of the main phase precursor and the auxiliary phase precursor of 100 parts by weight, the consumption of the auxiliary phase precursor is 3.5 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Example 3

Adopting the preparation method of the rare earth permanent magnet material of embodiment 1, the difference is that relative to the total amount of the main phase precursor and the auxiliary phase precursor of 100 parts by weight, the consumption of the auxiliary phase precursor is 5 parts by weight. The total composition of the main phase alloy raw material and the auxiliary phase alloy raw material is: Pr _5.23 Nd _23.315 Dy _3.35 Tb _0.475 Fe _63.95 Co _1.775 B _0.998 Al _0.275 Cu _0.16 Zr _0.12 Ga _{0.3 5} . The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Example 4

Using the content of trace elements (i.e. Co, B, Al, Cu, Zr, Ga) in Example 3, and adjusting the content of rare earth and iron, the main phase alloy raw material can be prepared into the preparation of rare earth permanent magnet material in Example 1 method (that is, equivalent to a single alloy preparation method), so that the performance of the prepared rare earth permanent magnet material is similar to that of the rare earth permanent magnet material in Example 3. The composition of the raw material is: Pr _4.5 Nd ₂₂ Dy _5.35 Tb _0.475 Fe ₆₄ Co _1.775 B ₁ Al _0.275 Cu _0.16 Zr _0.12 Ga _0.35 . The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Example 5

Adopt the preparation method of the rare earth permanent magnet material of embodiment 1, difference is, relative to the total consumption of described main phase precursor and described auxiliary phase precursor of 100 parts by weight, the consumption of described auxiliary phase precursor is 8 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Example 6

Adopting the preparation method of the rare earth permanent magnet material of embodiment 1, the difference is that relative to the total amount of the main phase precursor and the auxiliary phase precursor of 100 parts by weight, the consumption of the auxiliary phase precursor is 15 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Example 7

Using the preparation method of the rare earth permanent magnet material in Example 1, relative to the total amount of 100 parts by weight of the main phase precursor and the auxiliary phase precursor, the amount of the auxiliary phase precursor is 18 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Comparative example 2

The preparation method of the rare earth permanent magnet material in Example 1 is adopted, the difference is that all Dy in the auxiliary phase alloy raw material is replaced by Pr and Nd components, and the auxiliary phase alloy raw material is Pr _12.1 Nd _36.8 Fe _15.5 Co _16.5 B _0.96 Al _5.5 Cu _3.2 Zr _2.4 Ga ₇ . The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Comparative example 3

The preparation method of the rare earth permanent magnet material in Example 1 is adopted, the difference is that all Dy in the auxiliary phase alloy raw material is replaced by Pr and Nd components, and the auxiliary phase alloy raw material is Pr _12.1 Nd _36.8 Fe _15.5 Co _16.5 B _0.96 Al _5.5 Cu _3.2 Zr _2.4 Ga ₇ , and relative to 100 parts by weight of the total amount of the main phase precursor and the auxiliary phase precursor, the amount of the auxiliary phase precursor is 3.5 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Comparative example 4

The preparation method of the rare earth permanent magnet material in Example 1 is adopted, the difference is that all Dy in the auxiliary phase alloy raw material is replaced by Pr and Nd components, and the auxiliary phase alloy raw material is Pr _12.1 Nd _36.8 Fe _15.5 Co _16.5 B _0.96 Al _5.5 Cu _3.2 Zr _2.4 Ga ₇ , and relative to 100 parts by weight of the total amount of the main phase precursor and the auxiliary phase precursor, the amount of the auxiliary phase precursor is 5 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 1.

Table 1

Example 8

The raw material with the formula of Pr ₇ Nd ₂₁ Dy _3.7 Tb _0.3 Fe _65.6 Co _1.5 B _0.9 was strip-spun at a copper roller surface speed of 1.8m/s to prepare strip strips as the main phase alloy raw material. The main phase alloy raw material was absorbed hydrogen at 20° C. for 2.5 hours under a hydrogen pressure of 0.2 MPa, and then dehydrogenated at 550° C. for 5.5 hours, so as to obtain hydrogen crushed powder of the main phase alloy raw material. Then, mix 100 parts by weight of the hydrogen crushed powder of the main phase alloy raw material with 0.04 parts by weight of NdFeB special antioxidant (purchased from Beijing Juncefeng Technology Development Co., Ltd., brand KM-01), and then pass The jet mill is ground to make the main phase alloy raw material fine powder with an average particle diameter of 3.5um, and then the obtained main phase alloy raw material fine powder is mixed with 0.02 parts by weight of oil based on the main phase alloy raw material fine powder of 100 parts by weight. The acid is mixed evenly to obtain the main phase precursor.

The raw material with the formula of Pr _9.6 Nd _29.3 Dy ₁₀ Fe _15.5 Co _16.5 B _0.96 Al _5.5 Cu _3.2 Zr _2.4 Ga ₇ was melted and cast at 1300°C for 25 minutes to prepare an ingot as a supplementary phase alloy raw material. The auxiliary phase alloy raw material was subjected to hydrogen absorption at 20° C. for 2.5 hours under a hydrogen pressure of 0.2 MPa, and then dehydrogenated at 550° C. for 5.5 hours, thereby obtaining hydrogen crushed powder of the auxiliary phase alloy raw material. Then, 100 parts by weight of the hydrogen crushed powder of the auxiliary phase alloy raw material and 0.04 parts by weight of NdFeB special antioxidant (purchased from Beijing Juncefeng Technology Development Co., Ltd., brand KM-01) were evenly mixed, and then passed The jet mill is ground to make an auxiliary phase alloy raw material fine powder with an average particle diameter of 3.2um, and then the obtained auxiliary phase alloy raw material fine powder is mixed with 0.02 parts by weight of oil based on the auxiliary phase alloy raw material fine powder of 100 parts by weight. The acid is mixed evenly to obtain the auxiliary phase precursor.

The main phase precursor and the auxiliary phase precursor are uniformly mixed, and the amount of the auxiliary phase precursor is 1.5 parts by weight relative to 100 parts by weight of the total amount of the main phase precursor and the auxiliary phase precursor. The homogeneously mixed main phase precursor and auxiliary phase precursor were molded in a constant magnetic field of 3.5T, and then subjected to 220MPa isostatic pressure for 30s, then sintered at 1100°C for 3h, and performed primary tempering at 940°C to maintain 1.5h; then carry out secondary tempering at 500°C and keep for 3h. Finally, the rare earth permanent magnet material described in the present invention is obtained. The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 9

The raw material with the formula of Pr _6.625 Nd _19.875 Tb _1.5 Fe _68.4 Co _2.5 B _1.1 was subjected to strip-spinning treatment at a surface speed of 1.8m/s on the surface of the copper roller to prepare a strip-spinning sheet as the main phase alloy raw material. The main phase alloy raw material was subjected to hydrogen absorption at 25° C. for 3 hours under a hydrogen pressure of 0.5 MPa, and then dehydrogenated at 500° C. for 7 hours to obtain hydrogen crushed powder of the main phase alloy raw material. Then, mix 100 parts by weight of the hydrogen crushed powder of the main phase alloy raw material with 0.03 parts by weight of NdFeB special antioxidant (purchased from Beijing Juncefeng Technology Development Co., Ltd., brand KM-01), and then pass Jet mill is ground, and the main phase alloy raw material micropowder that makes average particle diameter is 3um, then with the stearin of 0.04 weight part of the main phase alloy raw material micropowder that obtains with the main phase alloy raw material micropowder of 100 weight parts The acid is mixed evenly to obtain the main phase precursor.

The raw material with the formula of Pr _9.6 Nd _29.3 Dy ₁₀ Fe _15.5 Co _16.5 B _0.96 Al _5.5 Cu _3.2 Zr _2.4 Ga ₇ was melted and cast at 1300°C for 25 minutes to prepare an ingot as a supplementary phase alloy raw material. The auxiliary phase alloy raw material was absorbed hydrogen at 25° C. for 3 hours under a hydrogen pressure of 0.5 MPa, and then dehydrogenated at 500° C. for 7 hours, thereby obtaining hydrogen crushed powder of the auxiliary phase alloy raw material. Then, 100 parts by weight of the hydrogen crushed powder of the auxiliary phase alloy raw material and 0.03 parts by weight of NdFeB special antioxidant (purchased from Beijing Juncefeng Technology Development Co., Ltd., brand KM-01) were evenly mixed, and then passed The jet mill is ground to make an auxiliary phase alloy raw material fine powder with an average particle diameter of 2.8um, and then the obtained auxiliary phase alloy raw material fine powder is mixed with 0.04 parts by weight of hard powder based on the auxiliary phase alloy raw material fine powder of 100 parts by weight. Fatty acids are mixed uniformly to obtain auxiliary phase precursors.

The main phase precursor and the auxiliary phase precursor are uniformly mixed, and the amount of the auxiliary phase precursor is 1.5 parts by weight relative to 100 parts by weight of the total amount of the main phase precursor and the auxiliary phase precursor. The homogeneously mixed main phase precursor and auxiliary phase precursor were molded in a constant magnetic field of 3T, then subjected to 170MPa isostatic pressure for 120s, then sintered at 1080°C for 6h, and performed primary tempering at 900°C for 2h; Then carry out secondary tempering at 490°C for 4h. Finally, the rare earth permanent magnet material described in the present invention is obtained. The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 10

Adopt the preparation method of the rare earth permanent magnet material of embodiment 1, the difference is that the main phase alloy raw material composition is: Pr _{6.575 Nd 19.725 Dy 1} Tb _0.2 Fe _70.84 Co _0.8 B _0.86 ; the auxiliary phase alloy raw material composition is: Pr ₃ Nd ₉ Dy _25.5 Fe _36.4 Co ₁₈ B _1.1 Al ₂ Cu ₁ Zr ₂ Ga ₂ . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 11

The preparation method of the rare earth permanent magnet material in Example 1 is adopted, the difference is that the raw material composition of the auxiliary phase alloy is Pr _9.6 Nd _29.3 Dy ₂₀ Fe _15.5 Co _16.5 B ₁ Al _2.36 Cu _1.57 Zr _1.57 Ga _2.6 . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 12

Adopt the preparation method of the rare earth permanent magnet material of Example 1, the difference is that the auxiliary phase alloy raw material composition is Pr _9.6 Nd _29.3 Dy ₂₀ Fe _15.5 Co _16.5 B ₁ Al _2.36 Cu _1.57 Zr _1.57 Ga _2.6 , and relative to 100 parts by weight The total amount of the main phase precursor and the auxiliary phase precursor, the amount of the auxiliary phase precursor is 3.5 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 13

Adopt the preparation method of the rare earth permanent magnet material of Example 1, the difference is that the auxiliary phase alloy raw material composition is Pr _9.6 Nd _29.3 Dy ₂₀ Fe _15.5 Co _16.5 B ₁ Al _2.36 Cu _1.57 Zr _1.57 Ga _2.6 , and relative to 100 parts by weight The total amount of the main phase precursor and the auxiliary phase precursor, the amount of the auxiliary phase precursor is 5 parts by weight. The total composition of the main phase alloy raw material and the auxiliary phase alloy raw material is: Pr _5.23 Nd _23.315 Dy _3.85 Tb _0.475 Fe _63.95 Co _1.775 B ₁ Al _0.118 Cu _0.0785 Zr _0.0785 Ga _0.13 . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 14

Using the content of trace elements (i.e. Co, B, Al, Cu, Zr, Ga) in Example 13, and adjusting the content of rare earth and iron, the main phase alloy raw material can be prepared into the preparation of rare earth permanent magnet material in Example 1 method (that is, equivalent to a single alloy preparation method), so that the performance of the prepared rare earth permanent magnet material is similar to that of the rare earth permanent magnet material in Example 13. The composition of the raw material is: Pr ₄ Nd _22.7 Dy _5.7 Tb _0.475 Fe _63.95 Co _1.77 B ₁ Al _0.118 Cu _0.0785 Zr _0.0785 Ga _0.13 . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 15

The preparation method of the rare earth permanent magnet material in Example 1 is adopted, the difference is that the raw material composition of the auxiliary phase alloy is Pr _10.3 Nd _31.7 Dy ₂₅ Fe ₈ Al _6.95 Cu _8.1 Zr _6.95 Ga ₃ . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 16

Using the preparation method of the rare earth permanent magnet material in Example 1, the difference is that the auxiliary phase alloy raw material composition is Pr _10.3 Nd _31.7 Dy ₂₅ Fe ₈ Al _6.95 Cu _8.1 Zr _6.95 Ga ₃ , and relative to 100 parts by weight of the main The total amount of the phase precursor and the auxiliary phase precursor, the amount of the auxiliary phase precursor is 3.5 parts by weight. The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 17

Using the preparation method of the rare earth permanent magnet material in Example 1, the difference is that the auxiliary phase alloy raw material composition is Pr _10.3 Nd _31.7 Dy ₂₅ Fe ₈ Al _6.95 Cu _8.1 Zr _6.95 Ga ₃ , and relative to 100 parts by weight of the main The total amount of the phase precursor and the auxiliary phase precursor, the amount of the auxiliary phase precursor is 5 parts by weight. The total composition of the main phase alloy raw material and the auxiliary phase alloy raw material is: Pr _5.265 Nd _23.435 Dy _4.1 Tb _0.475 Fe _63.575 Co _0.95 B _0.95 Al _0.3475 Cu _0.405 Zr _0.3475 Ga _0.15 . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Example 18

Using the content of trace elements (i.e. Co, B, Al, Cu, Zr, Ga) in Example 17, and adjusting the content of rare earth and iron, the main phase alloy raw material can be prepared into the preparation of rare earth permanent magnet material in Example 1 method (that is, equivalent to a single alloy preparation method), so that the performance of the prepared rare earth permanent magnet material is similar to that of the rare earth permanent magnet material in Example 17. The composition of the raw material is: Pr ₄ Nd _22.8 Dy ₆ Tb _0.475 Fe _63.575 Co _0.95 B _0.95 Al _0.3475 Cu _0.405 Zr _0.3475 Ga _0.15 . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Comparative example 5

The method of Example 2 in CN102534358A is adopted to adjust the element content of the permanent magnet material, so that the performance of the obtained permanent magnet material is similar to that of Example 18. The composition of the raw material is: Nd _18.72 Pr _4.68 Dy ₇ Tb _0.6 Fe _67.9 Cu _0.1 B ₁ . The magnetic properties of the rare earth permanent magnet material are shown in Table 2.

Table 2

It can be seen from the test results in Table 1 that the remanence of the rare earth permanent magnet materials prepared in Examples 1-7 is 11.3-13.18 (kGs), and the coercive force is 21-26 (kOe). Compared with the rare earth permanent magnet material prepared in Comparative Example 1 without auxiliary phase, the remanence of the rare earth permanent magnet material prepared in Examples 1-7 decreased by a maximum of 14.4%, but the coercive force increased by a maximum of 30%, and the β The temperature coefficient is improved significantly, and the maximum working temperature of rare earth permanent magnet materials can be increased by 30°C.

In addition, in the case of obtaining rare earth permanent magnet materials with similar properties, the content of dysprosium and/or terbium in the rare earth permanent magnet materials prepared by the double alloy method is lower than that of the single alloy method. Moreover, compared with the rare earth permanent magnet material provided by the present invention (Example 18) and the rare earth permanent magnet material (Comparative Example 5) with similar properties provided by the prior art, the content of dysprosium has decreased by 14.28% by weight, and the content of terbium has decreased by 20.83% by weight. This shows that the rare earth permanent magnet material provided by the present invention has higher coercive force while ensuring higher remanence, and also significantly reduces the content of dysprosium and/or terbium, reducing the production cost of the rare earth permanent magnet material.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (8)

1. a kind of rare earth permanent-magnetic material, the material includes principal phase and auxiliary phase, it is characterised in that

The composition of the principal phase is：R1_xR2_yFe_100-x-y-z-uCo_zB_u, R1 is selected from Pr and/or Nd；R2 is selected from Dy and/or Tb, its In, x, y, z, u are mass percent, and 28%≤x+y≤32%, 1.5%≤y≤4%, 1%≤z≤2.5%, 0.9%≤u ≤ 1.1%；

The composition of the auxiliary phase is：R1_aR2_bFe_{100-a-b-c-n-v}Co_cB_nM_v, R1 is selected from Pr and/or Nd；R2 is selected from Dy and/or Tb, M One or more in Zr, Ga, Cu, Nb, Sn, Mo, Al, V, W, Si, Hf, Ti, wherein, a, b, c, n, v are quality percentage Than, and 38%≤a+b≤67%, 10%≤b≤25%, 0%≤c≤17%, 0%≤n≤1%, 8%≤v≤28%；

On the basis of the gross mass of the principal phase and auxiliary phase, the mass content of the auxiliary phase is more than 0 and less than or equal to 20%.

2. material according to claim 1, wherein, on the basis of the gross mass of the principal phase and auxiliary phase, the auxiliary phase Mass content is more than 0 and less than or equal to 15%.

3. a kind of preparation method of rare earth permanent-magnetic material, this method includes entering main-phase alloy raw material and auxiliary phase alloy raw material successively Row mixed-forming, sintering and tempering, it is characterised in that

The composition of the main-phase alloy raw material is：R1_xR2_yFe_100-x-y-z-uCo_zB_u, R1 is selected from Pr and/or Nd；R2 be selected from Dy and/ Or Tb, wherein, x, y, z, u are mass percent, and 28%≤x+y≤32%, 1.5%≤y≤4%, 1%≤z≤2.5%, 0.9%≤u≤1.1%；

The composition of the auxiliary phase alloy raw material is：R1_aR2_bFe_{100-a-b-c-n-v}Co_cB_nM_v, R1 is selected from Pr and/or Nd；R2 is selected from Dy And/or the one or more of Tb, M in Zr, Ga, Cu, Nb, Sn, Mo, Al, V, W, Si, Hf, Ti, wherein, a, b, c, n, v are Mass percent, and 38%≤a+b≤67%, 10%≤b≤25%, 0%≤c≤17%, 0%≤n≤1%, 8%≤v≤ 28%；

Relative to the main-phase alloy raw material and total consumption of the auxiliary phase alloy raw material of 100 parts by weight, the auxiliary phase alloy The consumption of raw material is more than 0 parts by weight and less than or equal to 20 parts by weight.

4. method according to claim 3, wherein, relative to 100 parts by weight the main-phase alloy raw material and auxiliary be harmonious Total consumption of golden raw material, the consumption of the auxiliary phase alloy raw material is more than 0 parts by weight and less than or equal to 15 parts by weight.

5. method according to claim 3, wherein, the main-phase alloy raw material and the auxiliary phase alloy raw material are each with casting The form of ingot or rapid hardening thin slice is used, and the ingot casting or rapid hardening thin slice are made by melting.

6. the method according to claim 3 or 5, wherein, the process of shaping includes：In 1.5-4T Constant charge soil or pulsed magnetic Orientation is carried out in compressing, and isostatic pressed keeps 30-120s under 170-220MPa.

7. method according to claim 3, wherein, the condition of the sintering includes：Sintering temperature is 1040-1120 DEG C, Sintering time is 3-8 hours；The step of tempering is：One-level tempering first is carried out at 860-940 DEG C, and keeps 1-5h, then 470-560 DEG C of progress second annealing, and keep 1-8h.

8. the rare earth permanent-magnetic material prepared as the method described in any one in claim 3-7.