neodymium-iron-boron magnet material and preparation method and application thereof
阅读说明：本技术 一种钕铁硼磁体材料及其制备方法和应用 (neodymium-iron-boron magnet material and preparation method and application thereof ) 是由 牟维国 黄佳莹 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种钕铁硼磁体材料及其制备方法和应用。该钕铁硼磁体材料,以重量百分比计,包括如下组分：R 29.5～31.5wt％且RH＞1.5wt％；Cu 0.05～0.25wt％；Co 0.42～2.6wt％；Ga 0.20～0.3wt％；N 0.25～0.3wt％；Al 0.46～0.6wt％或Al≤0.04wt％但不为0；B 0.98～1wt％；Fe 64～68wt％；其中：R为稀土元素,R包括Nd和RH；RH为重稀土元素,RH包括Tb；Tb与Co的重量比≤15但不为0。本发明中钕铁硼磁体材料的矫顽力和剩磁均较高,并具有较低的剩磁温度系数和矫顽力温度系数。(The invention discloses a neodymium iron boron magnet material and a preparation method and application thereof. The neodymium iron boron magnet material comprises the following components in percentage by weight: r29.5-31.5 wt% and RH > 1.5 wt%; 0.05-0.25 wt% of Cu; 0.42-2.6 wt% of Co; 0.20-0.3 wt% of Ga; 0.25-0.3 wt% of N; 0.46-0.6 wt% of Al or less than or equal to 0.04 wt% of Al but not 0; 0.98-1 wt% of B; fe 64-68 wt%; wherein: r is rare earth element, and R comprises Nd and RH; RH is heavy rare earth element, and RH comprises Tb; the weight ratio of Tb to Co is less than or equal to 15 but not 0. The neodymium iron boron magnet material has high coercive force and remanence, and has low temperature coefficient of remanence and temperature coefficient of coercive force.)
1. The neodymium-iron-boron magnet material is characterized by comprising the following components in percentage by weight: r: 29.5-31.5 wt% and RH > 1.5 wt%;
Cu：0.05～0.25wt％；
Co：0.42～2.6wt％；
Ga：0.20～0.3wt％；
N: 0.25-0.3 wt%, wherein the N comprises one or more of Zr, Nb, Hf and Ti;
Al: 0.46-0.6 wt% or Al is less than or equal to 0.04 wt% but not 0 wt%;
B：0.98～1wt％；
Fe：64～68wt％；
Wherein: the R is a rare earth element and at least comprises Nd and RH; the RH is a heavy rare earth element, and the RH comprises Tb;
the weight ratio of Tb to Co is not more than 15 but not 0.
2. the ndfeb magnet material according to claim 1, wherein the content of R is 30.15 to 31 wt%, preferably 30.1 to 30.6 wt%, more preferably 30.42 wt% or 30.48 wt%;
And/or said R further comprises a light rare earth element, preferably Pr;
and/or the content of Nd is 27-28 wt%, more preferably 27.13 wt% or 27.44 wt%;
and/or the weight percentage of the RH in the R is 9.7-13 wt%, preferably 9.7-11 wt%, preferably 9.7 wt%;
and/or the RH is 2.8-4 wt%, preferably 2.9-3.4 wt%, more preferably 2.98 wt% or 3.35 wt%;
And/or the Cu content is 0.05-0.16 wt%, preferably 0.05 wt% or 0.15 wt%;
And/or the Co content is 1.48-2.7 wt%, preferably 1.49 wt%, 1.51 wt% or 2.6 wt%, preferably 1.48-1.51 wt%;
And/or the Ga content is 0.2 to 0.26 wt%, preferably 0.2 wt% or 0.25 wt%;
And/or the content of N is 0.26-0.3 wt%, preferably 0.26 wt%, 0.27 wt% or 0.3 wt%;
And/or the N is one or more of Zr, Nb, Hf and Ti; preferably Zr and/or Ti;
And/or the Al content is 0.46-0.5 wt% or 0.02-0.04 wt%, preferably 0.03 wt%, 0.45 wt% or 0.46 wt%;
And/or the content of B is 0.98-0.99 wt%, preferably 0.99 wt%;
And/or the Fe content is 64-66 wt%, preferably 64.86 wt%, 65.7 wt%, 65.72 wt% or 65.74 wt%;
and/or the weight ratio of Tb to Co is (1-15): 1, preferably (1-3): 1; more preferably 3.35:1.49 or 2: 1;
And/or the neodymium iron boron magnet material also comprises Mn;
And/or Tb is distributed at the grain boundary and the central part of crystal grains in the neodymium iron boron magnet material; preferably, the content of Tb distributed at the grain boundaries is higher than the content of Tb distributed at the central portions of the grains;
And/or, the N is distributed at the grain boundary;
And/or, the Co is distributed in a grain boundary triangular region;
And/or, at the grain boundary triangular region of the neodymium iron boron magnet material, the distribution of Tb is not overlapped with the distribution of Co.
3. The ndfeb magnet material according to claim 2, wherein the Mn content is 0.035 wt% or less but not 0 wt%, preferably 0.01 to 0.035 wt%, more preferably 0.03 wt%.
4. The neodymium-iron-boron magnet material as claimed in claim 1, characterized by comprising the following components in percentage by weight: 27-28 wt% of Nd, 2.8-4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.25-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B and 64-66 wt% of Fe, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-13 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-15): 1;
Preferably, the neodymium iron boron magnet material comprises the following components in percentage by weight: 27-28 wt% of Nd, 2.8-4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.25-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B, 64-66 wt% of Fe and 0.01-0.035 wt% of Mn, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-13 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-15): 1;
More preferably, the neodymium iron boron magnet material comprises the following components in percentage by weight: 27-28 wt% of Nd, 2.9-3.4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.26-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B, and 64-66 wt% of Fe, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-11 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-3): 1; preferably, the neodymium iron boron magnet material comprises the following components in percentage by weight: 27-28 wt% of Nd, 2.9-3.4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.26-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B, 64-66 wt% of Fe and 0.01-0.035 wt% of Mn, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-11 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-3): 1.
5. The main alloy for preparing the neodymium-iron-boron magnet material is characterized by comprising the following components of Nd a -Fe b -B c -Tb d -Co e -Cu f -Ga g -Al x -Mn y -N h, wherein a, B, c, d, e, f, g, h, x and y are the weight fractions of the elements in the main alloy, a is 26-30 wt%, B is 64-68 wt%, c is 0.96-1.1 wt%, d is 0.5-5 wt%, e is 0.5-2.6 wt%, f is 0.05-0.3 wt%, g is 0.05-0.3 wt%, x is not more than 0.04 wt% but not 0 wt% or 0.46-0.6 wt%, y is 0-0.04 wt%, and h is 0.2-0.5 wt%, and the percentages are in percentage by weight in the main alloy;
Preferably, a is 28 to 29 wt%, more preferably 28.46 wt%; and/or b is 65.5 to 67.5 wt%, preferably 65.62 wt%, 66.63 wt%, 66.7 wt%, 66.73 wt%, 66.78 wt%, 66.83 wt% or 67.16 wt%; and/or, c is 0.98-1 wt%, preferably 0.99 wt%; and/or d is 1 to 1.5 wt%, preferably 1.1 to 1.3 wt%, more preferably 1.2 wt% or 1.3 wt%; and/or e is 1.4 to 2.6 wt%, preferably 1.49 wt% or 2.6 wt%; and/or f is 0.05 to 0.16 wt%, preferably 0.05 wt% or 0.15 wt%; and/or the g is 0.1 to 0.25 wt%, preferably 0.2 wt% or 0.25 wt%; and/or, h is 0.25 to 0.3 wt%, preferably 0.27 wt%; and/or, the x is 0.02 to 0.04 wt% or 0.45 to 0.47 wt%, preferably 0.03 wt% or 0.46 wt%; and/or y is 0.02-0.04 wt%, preferably 0.03 wt%, and the percentage refers to the weight percentage in the main alloy.
6. The master alloy of claim 5, wherein the composition of the master alloy is Nd a -Fe b -B c -Tb d -Co e -Cu f -Ga g -Al x -Mn y -N h, wherein a, B, c, d, e, f, g, h, x and y are weight fractions of the elements in the master alloy, a is 28 to 29 wt%, B is 65.5 to 67.5 wt%, c is 0.98 to 1 wt%, d is 1 to 1.5 wt%, e is 1.4 to 2.6 wt%, f is 0.05 to 0.16 wt%, g is 0.1 to 0.25 wt%, x is 0.02 to 0.04 wt% or 0.45 to 0.47 wt%, y is 0.02 to 0.04 wt%, and h is 0.25 to 0.3 wt%, the percentages being by weight of the master alloy.
7. an auxiliary alloy for preparing a neodymium-iron-boron magnet material is characterized by comprising the following components of Nd i -Fe j -B k -Tb l -Co m -Cu n -Ga o -Al r -Mn t -N p, wherein i, j, k, l, m, N, o, p, r and t are weight fractions of the elements in the auxiliary alloy, i is 5-30 wt%, j is 59-65 wt%, k is 0.98-1 wt%, l is 5-25 wt%, m is 0.5-2.7 wt%, N is 0.05-0.3 wt%, o is 0.05-0.3 wt%, r is not more than 0.04 wt% but not 0 wt% or 0.46-0.6 wt%, t is 0-0.04 wt%, p is 0-0.5 wt%, and the percentages are weight percentages in the auxiliary alloy;
preferably, i is 15 to 25 wt%, preferably 19 to 21 wt%; and/or, j is 59 to 61 wt%, preferably 59.25 wt%, 60.33 wt%, 60.36 wt%, 60.39 wt%, 60.41 wt%, 60.46 wt% or 60.79 wt%; and/or k is 0.98-0.99 wt%; and/or, the l is 15 to 20 wt%, preferably 16 wt%; and/or m is 1.45 to 2.6 wt%, preferably 1.49 wt% or 2.6 wt%; and/or n is 0.05 to 0.16 wt%, preferably 0.05 wt% or 0.15 wt%; and/or o is 0.2 to 0.26 wt%, preferably 0.2 wt% or 0.25 wt%; and/or r is 0.01 to 0.04 wt% or 0.46 to 0.47 wt%, preferably 0.03 wt% or 0.46 wt%; and/or, t is 0.01 to 0.04 wt%, preferably 0.03 wt%; and/or p is 0.26 to 0.3 wt%, preferably 0.27 wt% or 0.3 wt%;
More preferably, the auxiliary alloy is Nd i -Fe j -B k -Tb l -Co m -Cu n -Ga o -Al r -Mn t -N p, wherein i, j, k, l, m, N, o, p, r and t are weight fractions of the elements in the auxiliary alloy, i is 19-21 wt%, j is 59-61 wt%, k is 0.98-0.99 wt%, l is 15-20 wt%, m is 1.45-2.6 wt%, N is 0.05-0.16 wt%, o is 0.2-0.26 wt%, r is 0.01-0.04 wt% or 0.46-0.47 wt%, t is 0-0.04 wt%, and p is 0.26-0.3 wt%.
8. A preparation method of a neodymium-iron-boron magnet material is characterized in that the main alloy of claim 5 or 6 and the auxiliary alloy of claim 7 are adopted to prepare the neodymium-iron-boron magnet material through a double-alloy method, and the weight ratio of the main alloy to the auxiliary alloy is (9-30): 1, preferably (6-15): 1, more preferably (6-8): 1;
preferably, the preparation process of the double alloy method comprises the steps of uniformly mixing the main alloy and the auxiliary alloy to obtain mixed alloy powder, and sequentially sintering and aging the mixed alloy powder; preferably, the uniformly mixing is to mix the main alloy and the auxiliary alloy and then carry out hydrogen breaking and airflow milling treatment, or to mix the main alloy and the auxiliary alloy after the hydrogen breaking and airflow milling treatment respectively;
More preferably, the hydrogen breaking is to absorb hydrogen in a saturated way under the hydrogen pressure of 0.067-0.098 MPa and dehydrogenate at 480-530 ℃; preferably, the particle size of the powder after the jet milling treatment is between 3.7 and 4.2 mu m; more preferably, the sintering temperature is 1050-1085 ℃, more preferably 1070-1085 ℃, and the sintering time is 4-7 hours; more preferably, the temperature of the aging treatment is 460-520 ℃, and the time of the aging treatment is 4-10 hours.
9. A neodymium iron boron magnet material, which is characterized by being prepared by the preparation method of claim 8.
10. use of a neodymium-iron-boron magnet material according to any one of claims 1-4 and 9 as an electronic component in an electrical machine; the motor is preferably a new energy automobile driving motor, an air conditioner compressor or an industrial servo motor.
Technical Field
The invention particularly relates to a neodymium iron boron magnet material and a preparation method and application thereof.
Background
The neodymium iron boron (Nd-Fe-B) magnet material taking Nd 2 Fe 14 B as a main component has higher remanence, coercive force and maximum magnetic energy product, has excellent comprehensive magnetic performance, and is applied to the aspects of new energy automobile driving motors, air-conditioning compressors, industrial servo motors and the like.
At present, the remanence Br of a sintered Nd-Fe-B permanent magnet material is close to more than 90% of the theoretical value of magnetic performance, while the coercive force of the sintered Nd-Fe-B permanent magnet material is only 12% of the anisotropy field of Nd 2 Fe 14 B, so that the coercive force of the sintered Nd-Fe-B permanent magnet material has great improvement potential.
Therefore, it is an urgent technical problem to select an appropriate amount and manner of adding the heavy rare earth metal to simultaneously improve the coercive force and remanence of the magnet.
disclosure of Invention
The invention aims to overcome the defect of low coercive force of a neodymium iron boron magnet material obtained by a neodymium iron boron magnet in the prior art, and provides the neodymium iron boron magnet material and a preparation method and application thereof. The neodymium iron boron magnet material is high in coercive force and remanence, and has a low temperature coefficient of remanence and a low temperature coefficient of coercive force.
The invention solves the technical problems through the following technical scheme.
The invention provides a neodymium iron boron magnet material which comprises the following components in percentage by weight:
R: 29.5-31.5 wt% and RH > 1.5 wt%;
Cu：0.05～0.25wt％；
Co：0.42～2.6wt％；
Ga：0.20～0.3wt％；
N: 0.25-0.3 wt%, wherein the N comprises one or more of Zr, Nb, Hf and Ti;
al: 0.46-0.6 wt% or Al is less than or equal to 0.04 wt% but not 0 wt%;
B：0.98～1wt％；
Fe：64～68wt％；
Wherein: the R is a rare earth element and at least comprises Nd and RH; the RH is a heavy rare earth element, and the RH comprises Tb;
The weight ratio of Tb to Co is not more than 15 but not 0.
In the present invention, the content of R is preferably 30.15 to 31 wt%, such as 30.1 to 30.6 wt%, more preferably 30.4 to 30.5 wt%, such as 30.42 wt% or 30.48 wt%, which is the weight percentage in the ndfeb magnet material.
In the present invention, the R may further include a light rare earth element, such as Pr, which is conventional in the art.
In the present invention, the content of Nd is preferably 27 to 28 wt%, for example, 27.13 wt% or 27.44 wt%, which is a weight percentage in the neodymium iron boron magnet material.
In the present invention, the weight percentage of the RH in the R is 9.7 to 13 wt%, preferably 9.7 to 11 wt%, and more preferably 9.7 wt%.
In the present invention, the content of RH is preferably 2.8 to 4 wt%, more preferably 2.9 to 3.4 wt%, for example 2.98 wt% or 3.35 wt%, which refers to the weight percentage in the neodymium iron boron magnet material.
in the present invention, the content of Cu is preferably 0.05 to 0.16 wt%, for example, 0.05 wt% or 0.15 wt%, and the percentage refers to the weight percentage in the neodymium iron boron magnet material.
In the present invention, the content of Co is preferably 1.48 to 2.7 wt%, for example, 1.49 wt%, 1.51 wt% or 2.6 wt%, preferably 1.49 to 1.51 wt%, and the percentage refers to the weight percentage in the neodymium iron boron magnet material.
In the present invention, the content of Ga is preferably 0.2 to 0.26 wt%, for example, 0.2 wt% or 0.25 wt%, and the percentage refers to the weight percentage in the neodymium iron boron magnet material.
In the present invention, the content of N is preferably 0.26 to 0.3 wt%, for example, 0.26 wt%, 0.27 wt% or 0.3 wt%, and the percentage refers to the weight percentage in the neodymium iron boron magnet material.
in the present invention, the N is preferably one or more of Zr, Nb, Hf and Ti, such as Zr and/or Ti.
In the present invention, the Al content is preferably 0.46 to 0.5 wt%, or 0.02 to 0.04 wt%, for example, 0.03 wt%, 0.45 wt%, or 0.46 wt%, and the percentage refers to the weight percentage in the neodymium iron boron magnet material.
In the present invention, the content of B is preferably 0.98 to 0.99 wt%, and more preferably 0.99 wt%, where the percentage refers to the weight percentage in the neodymium iron boron magnet material.
In the present invention, the content of Fe is preferably 64 to 66 wt%, for example 64.86 wt%, 65.7 wt%, 65.72 wt% or 65.74 wt%, where the percentage refers to the weight percentage in the neodymium iron boron magnet material.
In the present invention, the weight ratio of Tb to Co is preferably (1-15): 1, e.g., 3.35:1.49 or 2:1, more preferably (1-3): 1.
In the present invention, the neodymium iron boron magnet material preferably further includes Mn.
Wherein, the content of Mn is preferably less than or equal to 0.035 wt% but less than 0 wt%, preferably 0.01-0.035 wt%, for example 0.03 wt%, the percentage refers to the weight percentage in the neodymium iron boron magnet material.
In the invention, the neodymium iron boron magnet material comprises the following components in percentage by weight: 27-28 wt% of Nd, 2.8-4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.25-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B and 64-66 wt% of Fe, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-13 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-15): 1.
In the invention, the neodymium iron boron magnet material comprises the following components in percentage by weight: 27-28 wt% of Nd, 2.8-4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.25-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B, 64-66 wt% of Fe and 0.01-0.035 wt% of Mn, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-13 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-15): 1.
In the invention, the neodymium iron boron magnet material comprises the following components in percentage by weight: 27-28 wt% of Nd, 2.9-3.4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.26-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B, and 64-66 wt% of Fe, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-11 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-3): 1.
In the invention, the neodymium iron boron magnet material comprises the following components in percentage by weight: 27-28 wt% of Nd, 2.9-3.4 wt% of Tb, 0.05-0.16 wt% of Cu, 1.48-2.7 wt% of Co, 0.2-0.26 wt% of Ga, 0.26-0.3 wt% of N, 0.46-0.5 wt% or 0.02-0.04 wt% of Al, 0.98-0.99 wt% of B, 64-66 wt% of Fe and 0.01-0.035 wt% of Mn, wherein the percentages refer to the weight percentage in the neodymium iron boron magnet material; wherein N is Zr and/or Ti; tb accounts for 9.7-11 wt% of the total weight of Nd and Tb, and the weight ratio of Tb to Co is (1-3): 1.
In the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% Nd, 2.98 wt% Tb, 0.15 wt% Cu, 1.49 wt% Co, 0.25 wt% Ga, 0.27 wt% Zr, 0.46 wt% Al, 0.99 wt% B, 65.72 wt% Fe, percentages refer to weight percentages in the NdFeB magnet material; the balance being unavoidable impurities.
In the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.13 wt% of Nd, 3.35 wt% of Tb, 0.15 wt% of Cu, 1.49 wt% of Co, 0.25 wt% of Ga, 0.26 wt% of Zr, 0.45 wt% of Al, 0.99 wt% of B, 65.74 wt% of Fe, the percentages refer to the weight percentage in the neodymium iron boron magnet material, and the balance is inevitable impurities.
In the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% Nd, 2.98 wt% Tb, 0.15 wt% Cu, 1.49 wt% Co, 0.25 wt% Ga, 0.27 wt% Ti, 0.46 wt% Al, 0.99 wt% B, 65.70 wt% Fe, percentages refer to weight percentages in the NdFeB magnet material; the balance being unavoidable impurities.
in the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% Nd, 2.98 wt% Tb, 0.15 wt% Cu, 1.49 wt% Co, 0.25 wt% Ga, 0.27 wt% Zr, 0.46 wt% Al, 0.99 wt% B, 65.72 wt% Fe, 0.03 wt% Mn, percentages referring to weight percentages in the NdFeB magnet material; the balance being unavoidable impurities.
In the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% Nd, 2.98 wt% Tb, 0.15 wt% Cu, 2.6 wt% Co, 0.25 wt% Ga, 0.27 wt% Zr, 0.46 wt% Al, 0.99 wt% B, 64.86 wt% Fe, percentages referring to weight percentages in the neodymium iron boron magnet material.
In the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% Nd, 2.98 wt% Tb, 0.15 wt% Cu, 1.49 wt% Co, 0.25 wt% Ga, 0.3 wt% Zr, 0.46 wt% Al, 0.99 wt% B, 65.72 wt% Fe, percentages refer to weight percentages in the NdFeB magnet material; the balance being unavoidable impurities.
in the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% Nd, 2.98 wt% Tb, 0.15 wt% Cu, 1.49 wt% Co, 0.25 wt% Ga, 0.27 wt% Zr, 0.03 wt% Al, 0.99 wt% B, 65.72 wt% Fe, percentages refer to weight percentages in the NdFeB magnet material; the balance being unavoidable impurities.
In the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% Nd, 2.98 wt% Tb, 0.05 wt% Cu, 1.49 wt% Co, 0.25 wt% Ga, 0.27 wt% Zr, 0.46 wt% Al, 0.99 wt% B, 65.72 wt% Fe, percentages refer to weight percentages in the NdFeB magnet material; the balance being unavoidable impurities.
in the invention, the neodymium iron boron magnet material preferably comprises the following components in percentage by weight: 27.44 wt% of Nd, 2.98 wt% of Tb, 0.15 wt% of Cu, 1.49 wt% of Co, 0.2 wt% of Ga, 0.27 wt% of Zr, 0.46 wt% of Al, 0.99 wt% of B, 65.72 wt% of Fe, the percentages refer to the weight percentage in the neodymium iron boron magnet material, and the balance is inevitable impurities.
In the invention, Tb is preferably distributed at the grain boundary and the central part of crystal grains in the neodymium iron boron magnet material; preferably, the content of Tb distributed at the grain boundary is higher than the content of Tb distributed at the central portion of the crystal grain. Wherein the crystallization refers to the separation between the two main phases.
In the present invention, preferably, the N is distributed at the grain boundary.
In the present invention, preferably, the Co is distributed in the grain boundary triangular region.
In the present invention, preferably, at the grain boundary triangle of the ndfeb magnet material, the distribution of Tb and the distribution of Co do not overlap.
in the present invention, as known to those skilled in the art, the grain boundary triangle refers to a gap formed between three grains, and the grains refer to neodymium iron boron magnet material grains.
In the present invention, one skilled in the art knows that Nd is neodymium, Fe is iron, B is boron, Tb is terbium, Co is cobalt, Cu is copper, Ga is gallium, Al is aluminum, Mn is manganese, Zr is zirconium, Ti is titanium, Nb is niobium, and Hf is hafnium.
The invention also provides a main alloy for preparing the neodymium iron boron magnet material, which comprises Nd a -Fe b -B c -Tb d -Co e -Cu f -Ga g -Al x -Mn y -N h, wherein a, B, c, d, e, f, g, h, x and y are weight fractions of the elements in the main alloy, a is 26-30 wt%, B is 64-68 wt%, c is 0.96-1.1 wt%, d is 0.5-5 wt%, e is 0.5-2.6 wt%, f is 0.05-0.3 wt%, g is 0.05-0.3 wt%, x is not more than 0.04 wt% but not 0 wt% or 0.46-0.6 wt%, y is 0-0.04 wt%, and h is 0.2-0.5 wt%, and the percentages are weight percentages in the main alloy.
In the present invention, a is preferably 28 to 29 wt%, for example, 28.46 wt%, and the percentage refers to the weight percentage in the main alloy.
In the present invention, b is preferably 65.5 to 67.5 wt%, for example, 65.62 wt%, 66.63 wt%, 66.7 wt%, 66.73 wt%, 66.78 wt%, 66.83 wt% or 67.16 wt%, which is the weight percentage in the main alloy.
In the present invention, c is preferably 0.98 to 1 wt%, for example, 0.99 wt%, which is the weight percentage in the main alloy.
In the present invention, d is preferably 1 to 1.5 wt%, more preferably 1.1 to 1.3 wt%, for example, 1.2 wt% or 1.3 wt%, and the percentage refers to the weight percentage in the main alloy.
In the present invention, e is preferably 1.4 to 2.6 wt%, for example, 1.49 wt% or 2.6 wt%, and the percentage refers to the weight percentage in the main alloy.
In the present invention, f is preferably 0.05 to 0.16 wt%, such as 0.05 wt% or 0.15 wt%, which is the weight percentage in the main alloy.
In the present invention, the g is preferably 0.1 to 0.25 wt%, for example, 0.2 wt% or 0.25 wt%, which is the weight percentage in the main alloy.
in the present invention, h is preferably 0.25 to 0.3 wt%, for example, 0.27 wt% or 0.3 wt%, which is the weight percentage in the main alloy.
In the present invention, x is preferably 0.02 to 0.04 wt% or 0.45 to 0.47 wt%, for example, 0.03 wt% or 0.46 wt%, and the percentage refers to the weight percentage in the main alloy.
In the present invention, y is preferably 0.02 to 0.04 wt%, for example 0.03 wt%, which is the weight percentage in the main alloy.
In the invention, the main alloy preferably comprises Nd a -Fe b -B c -Tb d -Co e -Cu f -Ga g -Al x -Mn y -N h, wherein a, B, c, d, e, f, g, h, x and y are weight fractions of the elements in the main alloy, a is 28-29 wt%, B is 65.5-67.5 wt%, c is 0.98-1 wt%, d is 1-1.5 wt%, e is 1.4-2.6 wt%, f is 0.05-0.16 wt%, g is 0.1-0.25 wt%, x is 0.02-0.04 wt% or 0.45-0.47 wt%, y is 0.02-0.04 wt%, h is 0.25-0.3 wt%, and the percentages refer to the weight percentage in the main alloy.
In the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 66.73 B 0.99 Tb 1.2 Co 1.49 Cu 0.15 Ga 0.25 Zr 0.27 Al 0.46, wherein the subscript value is the weight percentage of each element in the main alloy.
In the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 66.63 B 0.99 Tb 1.3 Co 1.49 Cu 0.15 Ga 0.25 Zr 0.27 Al 0.46, wherein the subscript value is the weight percentage of each element in the main alloy.
In the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 66.73 B 0.99 Tb 1.2 Co 1.49 Cu 0.15 Ga 0.25 Ti 0.27 Al 0.46, wherein the subscript value is the weight percentage of each element in the main alloy.
in the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 66.7 B 0.99 Tb 1.2 Co 1.49 Cu 0.15 Ga 0.25 Zr 0.27 Al 0.46 Mn 0.03, wherein the subscript value is the weight percentage of each element in the main alloy.
In the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 65.62 B 0.99 Tb 1.2 Co 2.6 Cu 0.15 Ga 0.25 Zr 0.27 Al 0.46, wherein the subscript value is the weight percentage of each element in the main alloy.
in the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 67.16 B 0.99 Tb 1.2 Co 1.49 Cu 0.15 Ga 0.25 Zr 0.27 Al 0.03, wherein the subscript value is the weight percentage of each element in the main alloy.
In the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 66.83 B 0.99 Tb 1.2 Co 1.49 Cu 0.05 Ga 0.25 Zr 0.27 Al 0.46, wherein the subscript value is the weight percentage of each element in the main alloy.
In the present invention, the composition of the main alloy is preferably Nd 28.46 Fe 66.78 B 0.99 Tb 1.2 Co 1.49 Cu 0.15 Ga 0.2 Zr 0.27 Al 0.46, wherein the subscript value is the weight percentage of each element in the main alloy.
In the present invention, the preparation method of the main alloy may be a preparation method conventional in the art, and generally as follows: (1) preparing a main alloy solution containing the components; (2) and (3) cooling the main alloy solution through a rotating roller to form a main alloy cast sheet.
In the step (2), the cooling is generally to 700-900 ℃.
In the step (2), after the main alloy cast piece is formed, the main alloy cast piece is generally collected by a collector and cooled to below 50 ℃.
The invention also provides an auxiliary alloy for preparing the neodymium iron boron magnet material, which comprises Nd i -Fe j -B k -Tb l -Co m -Cu n -Ga o -Al r -Mn t -N p, wherein i, j, k, l, m, N, o, p, r and t are weight fractions of the elements in the auxiliary alloy, i is 5-30 wt%, j is 59-65 wt%, k is 0.98-1 wt%, l is 5-25 wt%, m is 0.5-2.7 wt%, N is 0.05-0.3 wt%, o is 0.05-0.3 wt%, r is not more than 0.04 wt% but not 0 wt% or 0.46-0.6 wt%, t is 0-0.04 wt%, and p is 0-0.5 wt%, and the percentages are weight percentages in the auxiliary alloy.
in the present invention, i is preferably 15 to 25 wt%, more preferably 19 to 21 wt%, for example, 20 wt%, which is the weight percentage of the secondary alloy.
In the present invention, j is preferably 59 to 61 wt%, for example, 59.25 wt%, 60.33 wt%, 60.36 wt%, 60.39 wt%, 60.41 wt%, 60.46 wt% or 60.79 wt%, which is the weight percentage in the secondary alloy.
in the present invention, k is preferably 0.98 to 0.99 wt%, for example, 0.99 wt%, which is the weight percentage of the secondary alloy.
in the present invention, l is preferably 15 to 20 wt%, for example, 16 wt%, which is the weight percentage in the secondary alloy.
in the present invention, m is preferably 1.45 to 2.6 wt%, for example, 1.49 wt% or 2.6 wt%, and the percentage refers to the weight percentage in the secondary alloy.
In the present invention, n is preferably 0.05 to 0.16 wt%, for example, 0.05 wt% or 0.15 wt%, which is the weight percentage in the secondary alloy.
In the present invention, o is preferably 0.2 to 0.26 wt%, for example, 0.2 wt% or 0.25 wt%, which is the weight percentage in the secondary alloy.
In the present invention, r is preferably 0.02 to 0.04 wt% or 0.46 to 0.47 wt%, for example 0.03 wt% or 0.46 wt%, which is the weight percentage in the secondary alloy.
In the present invention, t is preferably 0.01 to 0.04 wt%, for example, 0.03 wt%, which is the weight percentage of the secondary alloy.
in the present invention, p is preferably 0.26 to 0.3 wt%, for example, 0.27 wt% or 0.3 wt%, which is the weight percentage in the secondary alloy.
In the invention, the composition of the auxiliary alloy is preferably Nd i -Fe j -B k -Tb l -Co m -Cu n -Ga o -Al r -Mn t -N p, wherein i, j, k, l, m, N, o, p, r and t are weight fractions of the elements in the auxiliary alloy, i is 19-21 wt%, j is 59-61 wt%, k is 0.98-0.99 wt%, l is 15-20 wt%, m is 1.45-2.6 wt%, N is 0.05-0.16 wt%, o is 0.2-0.26, r is 0.02-0.04 wt% or 0.46-0.47 wt%, t is 0-0.04 wt%, p is 0.26-0.3 wt%, and the percentage refers to the weight percentage in the auxiliary alloy.
in the present invention, the composition of the secondary alloy is preferably Nd 20 Fe 60.36 B 0.99 Tb 16 Co 1.49 Cu 0.15 Ga 0.25 Zr 0.3 Al 0.46, and the subscript values are the weight percentages of the respective elements in the secondary alloy.
In the present invention, the composition of the secondary alloy is preferably Nd 20 Fe 60.39 B 0.99 Tb 16 Co 1.49 Cu 0.15 Ga 0.25 Ti 0.27 Al 0.46, and the subscript value is the weight percentage of each element in the secondary alloy.
In the present invention, the composition of the secondary alloy is preferably Nd 20 Fe 60.33 B 0.99 Tb 16 Co 1.49 Cu 0.15 Ga 0.25 Zr 0.3 Al 0.46 Mn 0.03, and the subscript value is the weight percentage of each element in the secondary alloy.
In the present invention, the composition of the secondary alloy is preferably Nd 20 Fe 59.25 B 0.99 Tb 16 Co 2.6 Cu 0.15 Ga 0.25 Zr 0.3 Al 0.46, and the subscript values are the weight percentages of the respective elements in the secondary alloy.
In the present invention, the composition of the secondary alloy is preferably Nd 20 Fe 60.79 B 0.99 Tb 16 Co 1.49 Cu 0.15 Ga 0.25 Zr 0.3 Al 0.03, and the subscript values are the weight percentages of the respective elements in the secondary alloy.
In the present invention, the composition of the secondary alloy is preferably Nd 20 Fe 60.46 B 0.99 Tb 16 Co 1.49 Cu 0.05 Ga 0.25 Zr 0.3 Al 0.46, and the subscript values are the weight percentages of the respective elements in the secondary alloy.
In the present invention, the composition of the secondary alloy is preferably Nd 20 Fe 60.41 B 0.99 Tb 16 Co 1.49 Cu 0.15 Ga 0.2 Zr 0.3 Al 0.46, and the subscript values are the weight percentages of the respective elements in the secondary alloy.
in the present invention, the preparation method of the secondary alloy may be a preparation method conventional in the art, and is generally as follows: (1) preparing an auxiliary alloy solution containing the components; (2) and (3) cooling the auxiliary alloy solution through a rotating roller to form an auxiliary alloy casting sheet, thus obtaining the auxiliary alloy casting sheet.
In the step (2), the cooling is generally to 700-900 ℃.
In the step (2), after the secondary alloy cast pieces are formed, the secondary alloy cast pieces are collected by a collector and cooled to below 50 ℃.
The invention also provides a preparation method of the neodymium iron boron magnet material, the prepared main alloy and auxiliary alloy are prepared into the neodymium iron boron magnet material by a double-alloy method, and the weight ratio of the main alloy to the auxiliary alloy is (9-30): 1.
in the present invention, the weight ratio of the main alloy to the auxiliary alloy is preferably (6-15): 1, more preferably (6-8): 1, e.g., 88:12 or 86: 14.
In the invention, the preparation process of the double-alloy method is generally to uniformly mix the main alloy and the auxiliary alloy to obtain mixed alloy powder, and the mixed alloy powder is sintered and aged in sequence.
The uniform mixing can be conventional in the field, and the main alloy and the auxiliary alloy are usually mixed and then subjected to hydrogen breaking and airflow milling treatment, or the main alloy and the auxiliary alloy are respectively subjected to hydrogen breaking and airflow milling treatment and then uniformly mixed.
The operation condition of the hydrogen breaking treatment can be conventional in the field, and preferably saturated hydrogen absorption is carried out under the hydrogen pressure of 0.067-0.098 MPa, and dehydrogenation is carried out at 480-530 ℃; more preferably at 510 deg.C to 530 deg.C.
Wherein, the technicians in the field know that the treatment of hydrogen breaking and airflow milling also comprises the treatment of mixing materials. The mixing time is preferably 3 hours or more, more preferably 3 to 6 hours.
The mixing device can be conventional in the field, and is preferably a three-dimensional mixer.
The operation and conditions of the jet milling treatment can be conventional in the art, and the particle size of the powder after the jet milling treatment is preferably 3.7-4.2 μm, more preferably 3.7-4 μm.
The operation and conditions of the sintering treatment can be conventional in the art, the sintering temperature is preferably 1050-1085 ℃, more preferably 1070-1085 ℃, and the sintering time is 4-7 hours.
wherein the aging treatment may be conventional in the art. The temperature of the aging treatment is usually 460-520 ℃, and the time of the aging treatment is usually 4-10 hours.
the invention also provides the neodymium iron boron magnet material prepared by the preparation method.
The invention also provides application of the neodymium iron boron magnet material as an electronic element in a motor.
In the invention, the motor is preferably a new energy automobile driving motor, an air conditioner compressor or an industrial servo motor.
on the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the coercive force and the remanence of the magnet material are high, and the temperature coefficients of the remanence and the coercive force are low; wherein the coercive force can reach more than 13.39kOe, and the remanence can reach more than 26.8 kGs; and the temperature coefficient | alpha | of Br at 20-100 ℃ can reach below 0.092 (Br)%/° C, and the temperature coefficient | beta | of Hcj at 20-100 ℃ can reach below 0.46 (Hcj)%/° C.
Drawings
fig. 1 is a distribution of elements in the microstructure of the neodymium-iron-boron magnet material in example 7.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
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