CN105575576A - NdFeB nanometre double-phase composite permanent magnet material and preparation method thereof - Google Patents
NdFeB nanometre double-phase composite permanent magnet material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 97
- 239000000956 alloy Substances 0.000 claims abstract description 97
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims description 28
- 238000005266 casting Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 229910052779 Neodymium Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010891 electric arc Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 241001062472 Stokellia anisodon Species 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 230000005291 magnetic effect Effects 0.000 abstract description 64
- 230000008569 process Effects 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000000137 annealing Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000009718 spray deposition Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
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- 230000006872 improvement Effects 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000001808 coupling effect Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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Abstract
本发明公开了一种NdFeB纳米双相复合永磁材料及其制备方法，NdFeB纳米双相复合永磁材料的成分及含量用公式表示为FeaNdbBBcMdPe，其中，M为选自Co、Nb、Ti、Zr和Cu元素中的至少一种元素或者多种元素的组合；a、b、c、d和e表示原子百分数，80≤a≤83，8≤b≤10，5≤c≤6.5，2≤d≤4，0.1≤e≤0.5且a+b+c+d+e＝100，在制备方法中控制母合金熔体喷射到铜轮上的速度来调整冷却速度，进而控制NdFeB纳米双相复合永磁材料的结晶速度，使软磁相和硬磁相的均匀形核长大，获得较小的晶粒尺寸；优点是NdFeB纳米双相复合永磁材料的内部微结构得到改善，其内部微结构接近微结构理想模型，软磁相和硬磁相之间的交换耦合作用得到增强，磁性能提升，制备方法不需要退火工艺，工艺简单且成本较低。
The invention discloses a NdFeB nano-two-phase composite permanent magnet material and a preparation method thereof. The composition and content of the NdFeB nano-two-phase composite permanent magnet material are expressed by a formula as Fe a Nd b BB c M d P e , wherein M is At least one element selected from Co, Nb, Ti, Zr and Cu elements or a combination of multiple elements; a, b, c, d and e represent atomic percentages, 80≤a≤83, 8≤b≤10, 5≤c≤6.5, 2≤d≤4, 0.1≤e≤0.5 and a+b+c+d+e=100, in the preparation method, control the speed at which the master alloy melt is sprayed onto the copper wheel to adjust the cooling rate , and then control the crystallization speed of the NdFeB nano-two-phase composite permanent magnet material, so that the uniform nucleation and growth of the soft magnetic phase and the hard magnetic phase can obtain a smaller grain size; the advantage is that the interior of the NdFeB nano-two-phase composite permanent magnet material The microstructure is improved, the internal microstructure is close to the ideal model of the microstructure, the exchange coupling between the soft magnetic phase and the hard magnetic phase is enhanced, the magnetic performance is improved, the preparation method does not require an annealing process, the process is simple and the cost is low.
Description
技术领域technical field
本发明涉及一种永磁材料，尤其是涉及一种NdFeB纳米双相复合永磁材料及其制备方法。The invention relates to a permanent magnet material, in particular to a NdFeB nanometer two-phase composite permanent magnet material and a preparation method thereof.
背景技术Background technique
纳米双相复合永磁材料又称交换耦合稀土永磁材料，是具有高磁晶各向异性的硬磁相和具有高饱和磁化强度的软磁相在纳米尺度范围内复合形成的两相共格永磁材料。自从1988年Coehoorn等人报道了Nd2Fe14B/α-Fe磁体以来，由于剩磁增强效应的出现而产生高的磁能积，这种新型的NdFeB纳米双相复合永磁材料得到了广泛的关注。其通过纳米尺度下两相晶粒间的铁磁交换耦合作用来获得理论磁能积高达106kJ/m3，比目前磁能积最高的烧结NdFeB永磁体的理论值高出1倍，被称为“兆焦耳永磁体”。另外，NdFeB纳米双相复合永磁材料具有稀土含量低，剩磁比和磁能积高，温度稳定性、耐热性和抗氧化性好等优点，因此，具有很高的实用价值，目前世界市场正在扩大其应用范围。Nano two-phase composite permanent magnet material, also known as exchange-coupled rare earth permanent magnet material, is a two-phase coherent composite formed by a hard magnetic phase with high magnetocrystalline anisotropy and a soft magnetic phase with high saturation magnetization in the nanoscale range. permanent magnet material. Since the Nd 2 Fe 14 B/α-Fe magnet was reported by Coehoorn et al. in 1988, due to the appearance of the remanence enhancement effect to produce a high magnetic energy product, this new type of NdFeB nano-two-phase composite permanent magnet material has been widely used focus on. It obtains a theoretical magnetic energy product of up to 106kJ/m 3 through ferromagnetic exchange coupling between two-phase grains at the nanometer scale, which is twice as high as the theoretical value of the sintered NdFeB permanent magnet with the highest magnetic energy product. Joule permanent magnet". In addition, the NdFeB nano-two-phase composite permanent magnet material has the advantages of low rare earth content, high remanence ratio and magnetic energy product, good temperature stability, heat resistance and oxidation resistance, etc. Therefore, it has high practical value and is currently in the world market Its scope of application is being expanded.
然而，实验与理论预言相差甚远，虽然NdFeB纳米双相复合永磁材料的剩磁有很大提高，但是矫顽力下降太多，限制了磁能积的提高。为了提高NdFeB纳米双相复合永磁材料的磁性能使其达到理论预期值，人们在理论和实验上进行了大量的研究。比如：在两纳米相间的磁交换耦合效应和矫顽力机制等理论方面，取向排列双相纳米磁体制备等实验方面都取得了重要研究进展。NdFeB纳米双相复合永磁材料的显微结构和磁性能与元素成分密切相关，通过调节成分进而优化纳米双相复合磁体的晶粒尺寸、形貌、相的分布及状态、显微结构，从而达到提高磁性能的效果。虽然目前已研制了多种NdFeB纳米双相复合永磁材料，但是这些NdFeB纳米双相复合永磁材料的磁性能远小于理论值。However, the experiment is far from the theoretical prediction. Although the remanence of the NdFeB nano-two-phase composite permanent magnet material has been greatly improved, the coercive force has dropped too much, which limits the improvement of the magnetic energy product. In order to improve the magnetic properties of NdFeB nano-two-phase composite permanent magnet materials to achieve theoretically expected values, a lot of research has been carried out in theory and experiments. For example, important research progress has been made in theoretical aspects such as the magnetic exchange coupling effect between two nanophases and the coercive force mechanism, and in experimental aspects such as the preparation of orientation-aligned dual-phase nanomagnets. The microstructure and magnetic properties of NdFeB nano-two-phase composite permanent magnet materials are closely related to the element composition. By adjusting the composition, the grain size, morphology, phase distribution and state, and microstructure of the nano-two-phase composite magnet can be optimized. To achieve the effect of improving the magnetic properties. Although a variety of NdFeB nano-two-phase composite permanent magnet materials have been developed, the magnetic properties of these NdFeB nano-two-phase composite permanent magnet materials are far smaller than the theoretical value.
鉴此，设计一种NdFeB纳米双相复合永磁材料及其制备方法来提高NdFeB纳米双相复合永磁材料的磁性能具有重要意义。In view of this, it is of great significance to design a NdFeB nano-two-phase composite permanent magnet material and its preparation method to improve the magnetic properties of the NdFeB nano-two-phase composite permanent magnet material.
发明内容Contents of the invention
本发明所要解决的技术问题之一是提供一种NdFeB纳米双相复合永磁材料，该NdFeB纳米双相复合材料通过在NdFeB纳米双相复合永磁材料中微量添加P元素，并控制P元素的含量，由此改进NdFeB纳米双相复合永磁材料的晶粒尺寸、形貌、相的分布及状态、显微结构，使其磁性能得到提升。One of the technical problems to be solved by the present invention is to provide a kind of NdFeB nano-two-phase composite permanent magnet material. The NdFeB nano-two-phase composite material adds P element in a small amount to the NdFeB nano-two-phase composite permanent magnet material, and controls the P element. content, thereby improving the grain size, morphology, phase distribution and state, and microstructure of the NdFeB nano-two-phase composite permanent magnet material, so as to improve its magnetic properties.
本发明解决上述技术问题之一所采用的技术方案为：一种NdFeB纳米双相复合永磁材料，其成分及含量用公式表示为FeaNdbBcMdPe，其中，M为选自Co、Nb、Ti、Zr和Cu元素中的一种元素或者多种元素的组合；a、b、c、d和e均表示原子百分数，80≤a≤83，8≤b≤10，5≤c≤6.5，2≤d≤4，0.1≤e≤0.5且a+b+c+d+e＝100。The technical scheme adopted by the present invention to solve one of the above-mentioned technical problems is: a kind of NdFeB nano-two-phase composite permanent magnet material, its composition and content are expressed as Fe a Nd b B c M d P e by formula, wherein, M is selected One or a combination of elements from Co, Nb, Ti, Zr and Cu; a, b, c, d and e all represent atomic percentages, 80≤a≤83, 8≤b≤10,5 ≤c≤6.5, 2≤d≤4, 0.1≤e≤0.5 and a+b+c+d+e=100.
Fe、Nd、B、Co、Nb、Ti、Zr、Cu和P元素的纯度均不低于99.9wt％。The purity of Fe, Nd, B, Co, Nb, Ti, Zr, Cu and P elements is not less than 99.9wt%.
与现有技术相比，本发明的NdFeB纳米双相复合永磁材料的优点在于通过在原有纳米双相复合永磁材料中添加原子百分含量为0.1～0.5的P元素，通过微量的P元素来改进NdFeB纳米双相复合永磁材料的晶粒尺寸、形貌、相的分布及状态、显微结构，使NdFeB纳米双相复合永磁材料的磁性能得到提升，同时具备具有较高的剩磁和磁能积。Compared with the prior art, the advantage of the NdFeB nano-two-phase composite permanent magnet material of the present invention is that by adding a P element with an atomic percentage of 0.1 to 0.5 in the original nano-two-phase composite permanent magnet material, a trace amount of P element To improve the grain size, morphology, phase distribution and state, and microstructure of NdFeB nano-two-phase composite permanent magnet materials, so that the magnetic properties of NdFeB nano-two-phase composite permanent magnet materials can be improved, and at the same time have a higher residual Magnetism and magnetic energy product.
本发明所要解决的技术问题之二是提供一种NdFeB纳米双相复合永磁材料的制备方法，该制备方法通过在NdFeB纳米双相复合永磁材料的原材料中微量添加P元素，并控制P元素的含量，由此改进制备得到的NdFeB纳米双相复合永磁材料的晶粒尺寸、形貌、相的分布及状态、显微结构，使其磁性能得到提升。The second technical problem to be solved by the present invention is to provide a preparation method of NdFeB nano-two-phase composite permanent magnet material. The preparation method adds a small amount of P element to the raw material of NdFeB nano-two-phase composite permanent magnet material, and controls the P element. content, thereby improving the grain size, morphology, phase distribution and state, and microstructure of the prepared NdFeB nano-two-phase composite permanent magnet material, so as to improve its magnetic properties.
本发明解决上述技术问题之二所采用的技术方案为：一种NdFeB纳米双相复合永磁材料的制备方法，包括如下步骤：The technical solution adopted by the present invention to solve the above-mentioned technical problem two is: a preparation method of a NdFeB nano-two-phase composite permanent magnet material, comprising the following steps:
①配比原材料：将元素Fe、Nd、B、M和P按照FeaNdbBcMdPe配比，其中，M为选自Co、Nb、Ti、Zr和Cu元素中的一种元素或者多种元素的组合；a、b、c、d和e均表示原子百分数，80≤a≤83，8≤b≤10，5≤c≤6.5，2≤d≤4，0.1≤e≤0.5且a+b+c+d+e＝100；① Proportioning of raw materials: the elements Fe, Nd, B, M and P are proportioned according to Fe a Nd b B c M d P e , wherein M is one of the elements selected from Co, Nb, Ti, Zr and Cu Elements or combinations of multiple elements; a, b, c, d and e all represent atomic percentages, 80≤a≤83, 8≤b≤10, 5≤c≤6.5, 2≤d≤4, 0.1≤e≤ 0.5 and a+b+c+d+e=100;
②制备母合金铸锭：将原材料放入电弧炉中，在钛吸附的氩气气氛下熔炼4次以上，混合均匀，冷却后得到母合金铸锭；②Preparation of master alloy ingots: Put the raw materials into an electric arc furnace, melt them for more than 4 times under the argon atmosphere adsorbed by titanium, mix them evenly, and obtain master alloy ingots after cooling;
③喷铸：使用金属熔体快淬的方法，将步骤②制得的母合金铸锭重新熔化，得到母合金熔体；将母合金熔体喷射到转速为24～26m/s的铜轮上，得到宽为1～2mm，厚25～30μm的快淬合金带材，该快淬合金带材即为NdFeB纳米双相复合永磁材料。③Spray casting: use the method of rapid quenching of metal melt to re-melt the master alloy ingot obtained in step ② to obtain the master alloy melt; spray the master alloy melt onto the copper wheel with a rotation speed of 24-26m/s , to obtain a quick-quenched alloy strip with a width of 1-2 mm and a thickness of 25-30 μm, and the quick-quenched alloy strip is a NdFeB nanometer dual-phase composite permanent magnet material.
Fe、Nd、B、Co、Nb、Ti、Zr、Cu和P元素的纯度均不低于99.9wt％。The purity of Fe, Nd, B, Co, Nb, Ti, Zr, Cu and P elements is not less than 99.9wt%.
与现有技术相比，本发明的NdFeB纳米双相复合永磁材料的制备方法的优点在于通过在原有纳米双相复合永磁材料中添加原子百分含量为0.1～0.5的P元素，由此优化母合金铸锭的成分，同时控制母合金熔体喷射到铜轮上的速度来调整冷却速度，直接制备出性能优异的NdFeB纳米双相复合永磁材料，不需要退火工艺处理，工艺简单且成本较低，并且改进制备得到的NdFeB纳米双相复合永磁材料的晶粒尺寸、形貌、相的分布及状态、显微结构，使其磁性能得到提升，同时具备具有较高的剩磁和磁能积。Compared with the prior art, the advantage of the preparation method of the NdFeB nano-two-phase composite permanent magnet material of the present invention is that by adding P elements with an atomic percentage of 0.1 to 0.5 in the original nano-two-phase composite permanent magnet material, thereby Optimize the composition of the master alloy ingot, and control the speed of the master alloy melt sprayed onto the copper wheel to adjust the cooling rate, and directly prepare the NdFeB nano-two-phase composite permanent magnet material with excellent performance, which does not require annealing process, the process is simple and The cost is low, and the grain size, morphology, phase distribution and state, and microstructure of the prepared NdFeB nano-two-phase composite permanent magnet material are improved, so that the magnetic properties are improved, and at the same time, it has high remanence and magnetic energy product.
附图说明Description of drawings
图1为本发明实施例一至实施例四制备得到的Fe81Nd10Co2Nb1B5.9P0.1、Fe81Nd10Co2Nb1B5.8P0.2、Fe81Nd10Co2Nb1B5.5P0.5和Fe82Nd11Nb1B5.8P0.2与对比例Fe81Nd10Co2Nb1B6快淬合金带材的磁滞回线图(VSM)；Figure 1 shows Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 , Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 , Fe 81 Nd 10 Co 2 Nb 1 B 5.5 prepared in Examples 1 to 4 of the present invention. Hysteresis loop diagram (VSM) of P 0.5 and Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 and comparative example Fe 81 Nd 10 Co 2 Nb 1 B 6 quenched alloy strip;
图2为本发明实施例一至实施例三制备的Fe81Nd10Co2Nb1B5.9P0.1、Fe81Nd10Co2Nb1B5.8P0.2、Fe81Nd10Co2Nb1B5.5P0.5与对比例Fe81Nd10Co2Nb1B6快淬合金带材的X射线衍射图(XRD)；Figure 2 shows Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 , Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 , Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P prepared in Examples 1 to 3 of the present invention 0.5 and the X-ray diffraction pattern (XRD) of comparative example Fe 81 Nd 10 Co 2 Nb 1 B 6 quick-quenching alloy strips;
图3为本发明实施例一制备的Fe81Nd10Co2Nb1B5.9P0.1与对比例Fe81Nd10Co2Nb1B6快淬合金带材的透射电镜图(TEM)。Fig. 3 is a transmission electron microscope image (TEM) of Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 prepared in Example 1 of the present invention and comparative example Fe 81 Nd 10 Co 2 Nb 1 B 6 quenched alloy strips.
具体实施方式detailed description
以下结合附图实施例对本发明作进一步详细描述。The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.
实施例一：一种NdFeB纳米双相复合永磁材料，其成分及含量用公式表示为Fe81Nd10Co2Nb1B5.9P0.1。Embodiment 1: A NdFeB nano-two-phase composite permanent magnet material, the composition and content of which are expressed by the formula Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 .
本实施例中，Fe、Nd、Co、Nb、B和P元素的纯度为99.9％(重量百分比)以上。In this embodiment, the purity of Fe, Nd, Co, Nb, B and P elements is above 99.9% (weight percentage).
本实施例的NdFeB纳米双相复合永磁材料Fe81Nd10Co2Nb1B5.9P0.1的制备方法，具体包括以下步骤：The preparation method of the NdFeB nano-two-phase composite permanent magnet material Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 in this embodiment specifically includes the following steps:
①配比原材料：将原料纯度为99.9％(重量百分比)以上的Fe、Nd、Co、Nb、B和P六种组分按原子比为81：10：2：1：5.9：0.1配好；① Proportioning of raw materials: the six components of Fe, Nd, Co, Nb, B and P with a raw material purity of more than 99.9% (weight percentage) are prepared according to the atomic ratio of 81:10:2:1:5.9:0.1;
②制备母合金铸锭：将原材料放入电弧炉中，在钛吸附的氩气气氛下反复熔炼4次以上，混合均匀，冷却后得到Fe81Nd10Co2Nb1B5.9P0.1母合金铸锭；②Preparation of master alloy ingots: Put the raw materials into an electric arc furnace, repeatedly smelt them for more than 4 times under the atmosphere of argon gas adsorbed by titanium, mix them evenly, and obtain Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 master alloy castings after cooling ingot;
③喷铸：使用常规的金属熔体快淬的方法，将步骤②制得的Fe81Nd10Co2Nb1B5.9P0.1母合金铸锭重新熔化，得到母合金熔体；将母合金熔体喷射到转速为25m/s的铜轮上，得到宽为1-2mm，厚25-30μm的Fe81Nd10Co2Nb1B5.9P0.1快淬合金带材，该快淬合金带材为NdFeB纳米双相复合永磁材料。③Spray casting: using the conventional metal melt rapid quenching method, re-melting the Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 master alloy ingot obtained in step ② to obtain a master alloy melt; melting the master alloy The body is sprayed onto a copper wheel with a rotational speed of 25m/s to obtain a Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 quenched alloy strip with a width of 1-2mm and a thickness of 25-30μm. The quenched alloy strip is NdFeB nano-two-phase composite permanent magnet material.
本实施例中，在步骤③的喷铸工艺中，可采用带有喷铸装置的铸造炉，Fe81Nd10Co2Nb1B5.9P0.1母合金铸锭在铸造炉中重新熔化后，利用铸造炉中的喷铸装置，将母合金熔体喷射到铜轮上。In this embodiment, in the spray casting process of step ③, a casting furnace with a spray casting device can be used. After the Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 master alloy ingot is re-melted in the casting furnace, A spray casting device in a casting furnace that sprays a master alloy melt onto a copper wheel.
对本实施例的成分为Fe81Nd10Co2Nb1B5.9P0.1的快淬合金带材进行检测，其磁滞回线(VSM)如图1所示，X射线衍射图(XRD)如图2所示，透射电镜图(TEM)如图3所示。The composition of this embodiment is Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 The rapid quenching alloy strip is detected, its hysteresis loop (VSM) is shown in Figure 1, and the X-ray diffraction pattern (XRD) is shown in Figure 1 2, and the transmission electron microscope (TEM) image is shown in Figure 3.
分析图1可知，本实施例的Fe81Nd10Co2Nb1B5.9P0.1快淬合金带材具有明显的剩磁效应，而且磁滞回线表现为单一永磁性能，这反映了该快淬合金带材内软磁相和硬磁相之间产生较强的交换耦合作用，从而使该成分快淬带材具有优异的磁性能：Hcj＝611kA/m，Br＝1.07T，(BH)max＝158kJ/m3，其硬磁性能明显优于现有的成分为Fe81Nd10Co2Nb1B6的合金条带，如表1所示。Analysis of Figure 1 shows that the Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 quenched alloy strip of this embodiment has obvious remanence effect, and the hysteresis loop shows a single permanent magnetic property, which reflects the fast Strong exchange coupling occurs between the soft magnetic phase and the hard magnetic phase in the quenched alloy strip, so that the quenched strip of this composition has excellent magnetic properties: H cj =611kA/m, B r =1.07T, ( BH) max =158kJ/m 3 , its hard magnetic performance is obviously better than that of the existing alloy strip with composition Fe 81 Nd 10 Co 2 Nb 1 B 6 , as shown in Table 1.
分析图2可知，本实施例的Fe81Nd10Co2Nb1B5.9P0.1快淬合金带材其衍射峰为多峰，表明快淬合金带材已结晶，而且通过衍射峰标定发现主要析出相为Nd2Fe14B硬磁相和α-Fe软磁相，证明该快淬合金带材为NdFeB纳米双相复合永磁材料，且相比Fe81Nd10Co2Nb1B6合金成分，增加微量的P元素后的快淬合金带材晶化度有一定的提升，同时软磁相的比例和尺寸有一定的增大，这也是造成Bs和Br提高的主要原因。根据谢乐公式得出两相的晶粒尺寸在15-35nm范围内，这个尺寸接近于交换耦合模型的理论尺寸，从而有利于材料磁性能的提高。通过图3的透射电镜照片进一步确认，加入微量的P元素使快淬合金带材的晶粒尺寸进一步细化，分布更加均匀。Analysis of Figure 2 shows that the Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 quenching alloy strip of this example has multiple peaks in its diffraction peaks, indicating that the quenching alloy strip has crystallized, and it is found that the main precipitation is through the calibration of the diffraction peaks The phases are Nd 2 Fe 14 B hard magnetic phase and α-Fe soft magnetic phase, which proves that the quenched alloy strip is a NdFeB nano-dual phase composite permanent magnet material, and compared with Fe 81 Nd 10 Co 2 Nb 1 B 6 alloy composition , the crystallinity of the quick-quenching alloy strip after adding a trace amount of P element has a certain increase, and at the same time the proportion and size of the soft magnetic phase have a certain increase, which is also the main reason for the increase of B s and B r . According to the Scherrer formula, the grain size of the two phases is in the range of 15-35nm, which is close to the theoretical size of the exchange coupling model, which is conducive to the improvement of the magnetic properties of the material. It is further confirmed by the transmission electron microscope photos in Figure 3 that adding a small amount of P element further refines the grain size of the quenching alloy strip and distributes it more uniformly.
综上所述，本实施例通过微量添加0.1％的P元素所制备的Fe81Nd10Co2Nb1B5.9P0.1快淬合金带材较现有的成分为Fe81Nd10Co2Nb1B6的快淬合金带材(本文中将该称成分为Fe81Nd10Co2Nb1B6的快淬合金带材称为对比例)具有更加优异的微观结构和良好的磁性能。In summary, the Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 quick-quenching alloy strip prepared by adding a small amount of 0.1% P element in this example is Fe 81 Nd 10 Co 2 Nb 1 The rapidly quenched alloy strip of B 6 (the rapidly quenched alloy strip with the composition Fe 81 Nd 10 Co 2 Nb 1 B 6 is referred to as a comparative example herein) has a more excellent microstructure and good magnetic properties.
实施例二：一种NdFeB纳米双相复合永磁材料，其成分及含量用公式表示为Fe81Nd10Co2Nb1B5.8P0.2。Embodiment 2: A NdFeB nano-two-phase composite permanent magnet material, the composition and content of which are expressed by the formula Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 .
本实施例中，Fe、Nd、Co、Nb、B和P元素的纯度为99.9％(重量百分比)以上。In this embodiment, the purity of Fe, Nd, Co, Nb, B and P elements is above 99.9% (weight percentage).
本实施例的Fe81Nd10Co2Nb1B5.8P0.2的制备方法，具体包括以下步骤：The preparation method of Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 in this embodiment specifically includes the following steps:
①配比原材料：将原料纯度为99.9％(重量百分比)以上的Fe、Nd、Co、Nb、B和P六种组分按原子比为81：10：2：1：5.8：0.2配好；① Proportioning of raw materials: the six components of Fe, Nd, Co, Nb, B and P with a raw material purity of 99.9% (weight percent) or more are prepared according to the atomic ratio of 81:10:2:1:5.8:0.2;
②制备母合金铸锭：将原材料放入电弧炉中，在钛吸附的氩气气氛下反复熔炼4次以上，混合均匀，冷却后得到Fe81Nd10Co2Nb1B5.8P0.2母合金铸锭；②Preparation of master alloy ingots: put the raw materials into an electric arc furnace, and repeatedly smelt them for more than 4 times in an argon atmosphere adsorbed by titanium, mix them evenly, and obtain Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 master alloy castings after cooling ingot;
③喷铸：使用常规的金属熔体快淬的方法，将步骤②制得的Fe81Nd10Co2Nb1B5.8P0.2母合金铸锭重新熔化，得到母合金熔体；将母合金熔体喷射到转速为25m/s的铜轮上，得到宽为1-2mm，厚25-30μm的Fe81Nd10Co2Nb1B5.8P0.2快淬合金带材，该快淬合金带材为NdFeB纳米双相复合永磁材料。③Spray casting: using the conventional metal melt rapid quenching method, re-melting the Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 master alloy ingot obtained in step ② to obtain a master alloy melt; melting the master alloy The body is sprayed onto a copper wheel with a rotational speed of 25m/s to obtain a Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 quenched alloy strip with a width of 1-2mm and a thickness of 25-30μm. The quenched alloy strip is NdFeB nano-two-phase composite permanent magnet material.
本实施例中，在步骤③的喷铸工艺中，可采用带有喷铸装置的铸造炉，Fe81Nd10Co2Nb1B5.8P0.2母合金铸锭在铸造炉中重新熔化后，利用铸造炉中的喷铸装置，将母合金熔体喷射到铜轮上。In this embodiment, in the spray casting process of step ③, a casting furnace with a spray casting device can be used. After the Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 master alloy ingot is re-melted in the casting furnace, A spray casting device in a casting furnace that sprays a master alloy melt onto a copper wheel.
对本实施例的Fe81Nd10Co2Nb1B5.8P0.2快淬合金带材进行检测，其磁滞回线(VSM)如图1所示，X射线衍射图(XRD)如图2所示。The Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 quick-quenching alloy strip of this embodiment is detected, and its hysteresis loop (VSM) is shown in Figure 1, and the X-ray diffraction pattern (XRD) is shown in Figure 2 .
分析图1可知，本实施例的Fe81Nd10Co2Nb1B5.8P0.2快淬合金带材具有明显的剩磁效应，而且磁滞回线表现为单一永磁性能，这反映了该快淬合金带材内软磁相和硬磁相之间产生较强的交换耦合作用，从而使该成分快淬带材具有优异的磁性能：Hcj＝502kA/m，Br＝1.14T，(BH)max＝155kJ/m3。其硬磁性能明显优于Fe81Nd10Co2Nb1B6的合金条带，如表1所示。Analysis of Figure 1 shows that the Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 quenched alloy strip in this embodiment has obvious remanence effect, and the hysteresis loop shows a single permanent magnetic property, which reflects the fast A strong exchange coupling effect occurs between the soft magnetic phase and the hard magnetic phase in the quenched alloy strip, so that the quenched strip of this composition has excellent magnetic properties: H cj =502kA/m, B r =1.14T, ( BH) max = 155 kJ/m 3 . Its hard magnetic properties are obviously better than those of Fe 81 Nd 10 Co 2 Nb 1 B 6 alloy strips, as shown in Table 1.
分析图2可知，本实施例的Fe81Nd10Co2Nb1B5.8P0.2快淬合金带材其衍射峰为多峰，表明快淬合金带材已结晶，而且通过衍射峰标定发现主要析出相为Nd2Fe14B硬磁相和α-Fe软磁相，证明该快淬合金带材为NdFeB纳米双相复合永磁材料，且相比Fe81Nd10Co2Nb1B6合金成分，增加微量的P元素后的快淬合金带材晶化度有一定的提升，同时软磁相的比例和尺寸有一定的增大，这也是造成Bs和Br提高的主要原因。根据谢乐公式得出两相的晶粒尺寸在15-35nm范围内，这个尺寸接近于交换耦合模型的理论尺寸，从而有利于材料磁性能的提高。Analysis of Figure 2 shows that the Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 quenching alloy strip of this example has multiple peaks in its diffraction peaks, indicating that the quenching alloy strip has crystallized, and it is found that the main precipitation is through the calibration of the diffraction peaks The phases are Nd 2 Fe 14 B hard magnetic phase and α-Fe soft magnetic phase, which proves that the quenched alloy strip is a NdFeB nano-dual phase composite permanent magnet material, and compared with Fe 81 Nd 10 Co 2 Nb 1 B 6 alloy composition , the crystallinity of the quick-quenching alloy strip after adding a trace amount of P element has a certain increase, and at the same time the proportion and size of the soft magnetic phase have a certain increase, which is also the main reason for the increase of B s and B r . According to the Scherrer formula, the grain size of the two phases is in the range of 15-35nm, which is close to the theoretical size of the exchange coupling model, which is conducive to the improvement of the magnetic properties of the material.
综上所述，本实施例通过微量添加0.2％的P元素所制备的Fe81Nd10Co2Nb1B5.8P0.2快淬合金带材较对比例具有更加优异的微观结构和良好的磁性能。In summary, the Fe 81 Nd 10 Co 2 Nb 1 B 5.8 P 0.2 quenching alloy strip prepared by adding a small amount of 0.2% P element in this example has a more excellent microstructure and good magnetic properties than the comparative example .
实施例三：一种NdFeB纳米双相复合永磁材料，其成分及含量用公式表示为Fe81Nd10Co2Nb1B5.5P0.5。Embodiment 3: A NdFeB nano-two-phase composite permanent magnet material, the composition and content of which are expressed by the formula Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 .
本实施例中，Fe、Nd、Co、Nb、B和P元素的纯度为99.9％(重量百分比)以上。In this embodiment, the purity of Fe, Nd, Co, Nb, B and P elements is above 99.9% (weight percentage).
本实施例的Fe81Nd10Co2Nb1B5.9P0.1的制备方法，具体包括以下步骤：The preparation method of Fe 81 Nd 10 Co 2 Nb 1 B 5.9 P 0.1 in this embodiment specifically includes the following steps:
①配比原材料：将原料纯度为99.9％(重量百分比)以上的Fe、Nd、Co、Nb、B和P六种组分按原子比为81：10：2：1：5.5：0.5配好；① Proportioning of raw materials: the six components of Fe, Nd, Co, Nb, B and P with a raw material purity of more than 99.9% (weight percent) are prepared according to the atomic ratio of 81:10:2:1:5.5:0.5;
②制备母合金铸锭：将原材料放入电弧炉中，在钛吸附的氩气气氛下反复熔炼4次以上，混合均匀，冷却后得到Fe81Nd10Co2Nb1B5.5P0.5母合金铸锭；②Preparation of master alloy ingots: Put the raw materials into an electric arc furnace, and repeatedly smelt them for more than 4 times under the argon atmosphere adsorbed by titanium, mix them evenly, and obtain Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 master alloy castings after cooling ingot;
③喷铸：使用常规的金属熔体快淬的方法，将步骤②制得的Fe81Nd10Co2Nb1B5.5P0.5母合金铸锭重新熔化，得到母合金熔体；将母合金熔体喷射到转速为25m/s的铜轮上，得到宽为1-2mm，厚25-30μm的Fe81Nd10Co2Nb1B5.5P0.5快淬合金带材，该快淬合金带材为NdFeB纳米双相复合永磁材料。③Spray casting: using the conventional metal melt rapid quenching method, re-melting the Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 master alloy ingot obtained in step ② to obtain a master alloy melt; melting the master alloy The body is sprayed onto a copper wheel with a rotational speed of 25m/s to obtain a Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 quenched alloy strip with a width of 1-2mm and a thickness of 25-30μm. The quenched alloy strip is NdFeB nano-two-phase composite permanent magnet material.
本实施例中，在步骤③的喷铸工艺中，可采用带有喷铸装置的铸造炉，Fe81Nd10Co2Nb1B5.5P0.5母合金铸锭在铸造炉中重新熔化后，利用铸造炉中的喷铸装置，将母合金熔体喷射到铜轮上。In this embodiment, in the spray casting process of step ③, a casting furnace with a spray casting device can be used. After the Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 master alloy ingot is re-melted in the casting furnace, A spray casting device in a casting furnace that sprays a master alloy melt onto a copper wheel.
对本实施例的Fe81Nd10Co2Nb1B5.5P0.5快淬合金带材进行检测，其磁滞回线(VSM)如图1所示，X射线衍射图(XRD)如图2所示。The Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 quick-quenching alloy strip of this embodiment is detected, and its hysteresis loop (VSM) is shown in Figure 1, and the X-ray diffraction pattern (XRD) is shown in Figure 2 .
分析图1可知，本实施例的Fe81Nd10Co2Nb1B5.5P0.5快淬合金带材具有明显的剩磁效应，而且磁滞回线表现为单一永磁性能，这反映了该快淬合金带材内软磁相和硬磁相之间产生较强的交换耦合作用，从而使该成分快淬合金带材具有优异的磁性能：Hcj＝605kA/m，Br＝1.03T，(BH)max＝135kJ/m3。其硬磁性能明显优于Fe81Nd10Co2Nb1B6的合金条带，但相比于添加0.1％和0.2％P元素的快淬合金带材性能有所下降，如表1所示。Analysis of Figure 1 shows that the Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 quenched alloy strip in this embodiment has obvious remanence effect, and the hysteresis loop shows a single permanent magnetic property, which reflects the fast A strong exchange coupling effect occurs between the soft magnetic phase and the hard magnetic phase in the quenched alloy strip, so that the quenched alloy strip of this composition has excellent magnetic properties: H cj = 605kA/m, B r = 1.03T, (BH) max = 135 kJ/m 3 . Its hard magnetic properties are significantly better than those of Fe 81 Nd 10 Co 2 Nb 1 B 6 alloy strips, but compared with those of the quenched alloy strips with 0.1% and 0.2% P elements, the properties are lower, as shown in Table 1 .
分析图2可知，本实施例的Fe81Nd10Co2Nb1B5.5P0.5快淬合金带材其衍射峰为多峰，表明快淬合金带材已结晶，而且通过衍射峰标定发现主要析出相为Nd2Fe14B硬磁相和α-Fe软磁相，证明该快淬合金带材为NdFeB纳米双相复合永磁材料，且相比Fe81Nd10Co2Nb1B6合金成分，增加微量的P元素后的快淬合金带材晶化度有一定的提升，同时软磁相的比例和尺寸有一定的增大，这也是造成Bs和Br提高的主要原因。根据谢乐公式得出两相的晶粒尺寸在15-35nm范围内，这个尺寸接近于交换耦合模型的理论尺寸，从而有利于材料磁性能的提高。但是，添加过量的P元素会使晶粒尺寸变大，导致磁性能下降。Analysis of Figure 2 shows that the Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 quenching alloy strip of this example has multiple peaks in its diffraction peaks, indicating that the quenching alloy strip has crystallized, and it is found that the main precipitation is through the calibration of the diffraction peaks The phases are Nd 2 Fe 14 B hard magnetic phase and α-Fe soft magnetic phase, which proves that the quenched alloy strip is a NdFeB nano-dual phase composite permanent magnet material, and compared with Fe 81 Nd 10 Co 2 Nb 1 B 6 alloy composition , the crystallinity of the quick-quenching alloy strip after adding a trace amount of P element has a certain increase, and at the same time the proportion and size of the soft magnetic phase have a certain increase, which is also the main reason for the increase of B s and B r . According to the Scherrer formula, the grain size of the two phases is in the range of 15-35nm, which is close to the theoretical size of the exchange coupling model, which is conducive to the improvement of the magnetic properties of the material. However, adding an excessive amount of P element will increase the grain size, resulting in a decrease in magnetic properties.
综上所述，本实施例通过微量添加0.5％的P元素所制备的Fe81Nd10Co2Nb1B5.5P0.5快淬合金带材较对比例具有更加优异的微观结构和良好的磁性能。In summary, the Fe 81 Nd 10 Co 2 Nb 1 B 5.5 P 0.5 quenching alloy strip prepared by adding a small amount of 0.5% P element in this example has a more excellent microstructure and good magnetic properties than the comparative example .
实施例四：一种NdFeB纳米双相复合永磁材料，其成分及含量用公式表示为Fe82Nd11Nb1B5.8P0.2。Embodiment 4: A NdFeB nano-two-phase composite permanent magnet material, the composition and content of which are expressed by the formula Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 .
本实施例中，Fe、Nd、Nb、B和P元素的纯度为99.9％(重量百分比)以上。In this embodiment, the purity of Fe, Nd, Nb, B and P elements is above 99.9% (weight percentage).
本实施例的Fe82Nd11Nb1B5.8P0.2的制备方法，具体包括以下步骤：The preparation method of Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 in this embodiment specifically includes the following steps:
①配比原材料：将原料纯度为99.9％(重量百分比)以上的Fe、Nd、Nb、B和P五种组分按原子比为82：11：1：5.8：0.2配好；① Proportioning of raw materials: the five components of Fe, Nd, Nb, B and P with a raw material purity of more than 99.9% (weight percentage) are prepared according to the atomic ratio of 82:11:1:5.8:0.2;
②制备母合金铸锭：将原材料放入电弧炉中，在钛吸附的氩气气氛下反复熔炼4次以上，混合均匀，冷却后得到Fe82Nd11Nb1B5.8P0.2母合金铸锭；②Preparation of master alloy ingots: put the raw materials into an electric arc furnace, repeatedly smelt them for more than 4 times under the argon atmosphere adsorbed by titanium, mix them evenly, and obtain Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 master alloy ingots after cooling;
③喷铸：使用常规的金属熔体快淬的方法，将步骤②制得的Fe82Nd11Nb1B5.8P0.2母合金铸锭重新熔化，得到母合金熔体；将母合金熔体喷射到转速为25m/s的铜轮上，得到宽为1-2mm，厚25-30μm的Fe82Nd11Nb1B5.8P0.2快淬合金带材，该快淬合金带材为NdFeB纳米双相复合永磁材料。③Spray casting: use the conventional metal melt rapid quenching method to re-melt the Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 master alloy ingot obtained in step ② to obtain the master alloy melt; spray the master alloy melt On a copper wheel with a rotating speed of 25m/s, a Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 quick-quenching alloy strip with a width of 1-2mm and a thickness of 25-30μm is obtained. The quick-quenching alloy strip is NdFeB nano-duplex Composite permanent magnet materials.
本实施例中，在步骤③的喷铸工艺中，可采用带有喷铸装置的铸造炉，Fe82Nd11Nb1B5.8P0.2母合金铸锭在铸造炉中重新熔化后，利用铸造炉中的喷铸装置，将母合金熔体喷射到铜轮上。In this embodiment, in the spray casting process of step ③, a casting furnace with a spray casting device can be used. After the Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 master alloy ingot is re-melted in the casting furnace, the In the spray casting device, the master alloy melt is sprayed onto the copper wheel.
对本实施例的Fe82Nd11Nb1B5.8P0.2快淬合金带材进行检测，其磁滞回线(VSM)如图1所示。The Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 quenched alloy strip of this embodiment was tested, and its hysteresis loop (VSM) is shown in FIG. 1 .
分析图1可知，本实施例的Fe82Nd11Nb1B5.8P0.2快淬合金带材具有明显的剩磁效应，而且磁滞回线表现为单一永磁性能，这反映了该快淬合金带材内软磁相和硬磁相之间产生较强的交换耦合作用，从而使该成分快淬合金带材具有优异的磁性能：Hcj＝627kA/m，Br＝1.08T，(BH)max＝161kJ/m3。其硬磁性能明显优于Fe81Nd10Co2Nb1B6的合金条带，如表1所示。Analysis of Figure 1 shows that the Fe 82 Nd 11 Nb 1 B 5.8 P 0.2 fast-quenching alloy strip in this example has obvious remanence effect, and the hysteresis loop shows a single permanent magnetic property, which reflects that the fast-quenching alloy Strong exchange coupling occurs between the soft magnetic phase and the hard magnetic phase in the strip, so that the quenched alloy strip of this composition has excellent magnetic properties: H cj =627kA/m, B r =1.08T, (BH ) max = 161 kJ/m 3 . Its hard magnetic properties are obviously better than those of Fe 81 Nd 10 Co 2 Nb 1 B 6 alloy strips, as shown in Table 1.
可见，本实施例通过调整P元素的种类和含量可以进一步改善NdFeB纳米双相复合永磁材料的磁性能。It can be seen that in this embodiment, the magnetic properties of the NdFeB nano-two-phase composite permanent magnet material can be further improved by adjusting the type and content of the P element.
本发明的实施例一至实施例四及对比例的NdFeB纳米双相复合永磁材料的磁性能参数表如下表1所示。The magnetic performance parameters of the NdFeB nano-two-phase composite permanent magnet materials of Embodiment 1 to Embodiment 4 of the present invention and comparative examples are shown in Table 1 below.
表1第一组成分合金快淬条带的磁性能参数值表Table 1 The magnetic property parameter value table of the first component alloy quenching strip
综上所述，本发明通过微量添加P元素进一步改善了NdFeB纳米双相复合永磁材料的微观结构和硬磁性能，而且在一定的成分调整范围内，其性能和结构比较稳定。In summary, the present invention further improves the microstructure and hard magnetic properties of the NdFeB nano-two-phase composite permanent magnet material by adding a small amount of P element, and its performance and structure are relatively stable within a certain range of composition adjustment.
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| CN103858190A (en) * | 2011-10-11 | 2014-06-11 | 丰田自动车株式会社 | Manufacturing method for magnetic powder for forming sintered body of rare-earth magnet precursor |
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