CN104269238A - High-performance sintered neodymium-iron-boron magnet and preparation method - Google Patents
High-performance sintered neodymium-iron-boron magnet and preparation method Download PDFInfo
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Abstract
一种高性能烧结钕铁硼磁体,包括85~97wt%主相合金RExFe余MzBy和3~15wt%晶界富稀土相合金RESNJFe余,主相合金中的REx为轻稀土元素Nd和Pr中的一种或二种,晶界富稀土相合金中的RES包含Nd、Dy、Tb中的一种或一种以上,且至少包含重稀土元素Dy和Tb的一种或二种,制备方法包括:按主相合金与晶界富稀土相合金的成分组成分别进行配料、熔炼、铸片、氢破碎,将经氢破碎筛选的晶界富稀土相合金粉末进行气流磨成2.5~3.5μm的细粉,将经气流磨后的晶界富稀土与主相合金氢破粉末按比例混合,再进行气流磨成2.8~3.0μm粉末,然后称重入模、磁场取向压制成型,再将保压静置生坯入真空炉烧结。本发明可将重稀土Dy、Tb分布到主相合金的晶界上制备成本更低的高性能磁体。
A high-performance sintered NdFeB magnet, including 85-97wt% main phase alloy RE x Fe residual M z B y and 3-15 wt% grain boundary rare earth-rich phase alloy RE S N J Fe residual , RE in the main phase alloy x is one or two of light rare earth elements Nd and Pr, RE S in grain boundary rare earth rich phase alloy contains one or more of Nd, Dy, Tb, and at least contains heavy rare earth elements Dy and Tb One or two of them, the preparation method includes: according to the composition of the main phase alloy and the grain boundary rare earth phase alloy, respectively batching, smelting, casting, hydrogen crushing, and the grain boundary rare earth phase alloy powder screened by hydrogen crushing Airflow milling into 2.5-3.5μm fine powder, mixing the jet-milled grain boundary-rich rare earth with the main phase alloy hydrogen powder in proportion, and then airflow grinding into 2.8-3.0μm powder, and then weighing into the mold, Magnetic field orientation press molding, and then sintering the green compact in a vacuum furnace. The invention can distribute the heavy rare earths Dy and Tb to the grain boundary of the main phase alloy to prepare a high-performance magnet with lower cost.
Description
技术领域 technical field
本发明涉及一种高性能烧结磁体和制备方法。 The invention relates to a high-performance sintered magnet and a preparation method.
背景技术 Background technique
自1983年烧结Nd-Fe-B问世以来,由于其优异的磁性能而广泛地应用IT、医疗、新能源、航天航空等领域。烧结Nd-Fe-B磁体一般由Nd2Fe14B基体相、晶界富Nd相及Nd1+εFe4B4富硼相组成。其中,晶界富Nd相在起到液相烧结加速致密作用的同时,其成分、结构及分布也对磁体性能有重要影响。烧结钕铁硼磁体的矫顽力机制为形核机制,其易在晶界处形成反磁化畴而降低磁体矫顽力。研究表明,如果能将Dy、Tb等重稀土元素扩散到晶界,提高晶界的各向异性,则磁体矫顽力能有大幅度提升,同时磁体剩磁反应强度Br下降很少,并且可以有效减少Dy的添加量。针对这种情况,国内外的科研机构和相关的企业都纷纷开展渗Dy、Tb技术的研究。但是,渗Dy技术在产业化应用上还存在许多问题,比如:扩散深度有限不适合大尺寸产品;批量生产时性能可控性差,产品稳定性和一致性不好;晶界扩散的专业设备还不成熟,需要进一步的研究。因此,目前国内企业制备烧结钕铁硼磁体还是采用常规的制备方法:单合金法或一般的双合金法。采用常规的制备方法无法有效地利用重稀土元素,同时晶界可控性差,制备高性能磁体不仅需要更高的成本,同时难以制备超高性能磁体。 Since the advent of sintered Nd-Fe-B in 1983, it has been widely used in IT, medical, new energy, aerospace and other fields due to its excellent magnetic properties. Sintered Nd-Fe-B magnets generally consist of Nd 2 Fe 14 B matrix phase, grain boundary Nd-rich phase and Nd 1+ε Fe 4 B 4 boron-rich phase. Among them, the grain boundary Nd-rich phase plays a role in accelerating the densification of liquid phase sintering, and its composition, structure and distribution also have an important impact on the performance of the magnet. The coercive force mechanism of sintered NdFeB magnets is a nucleation mechanism, which is easy to form reverse magnetization domains at the grain boundaries and reduce the coercive force of the magnet. Studies have shown that if the heavy rare earth elements such as Dy and Tb can be diffused to the grain boundary and the anisotropy of the grain boundary can be improved, the coercive force of the magnet can be greatly improved, and the remanence Br of the magnet can be reduced very little, and can Effectively reduce the amount of Dy added. In response to this situation, domestic and foreign scientific research institutions and related enterprises have carried out research on infiltration Dy and Tb technology. However, there are still many problems in the industrial application of infiltration Dy technology, such as: limited diffusion depth is not suitable for large-scale products; poor performance controllability in mass production, poor product stability and consistency; professional equipment for grain boundary diffusion Immature and needs further research. Therefore, at present, domestic enterprises still use conventional preparation methods to prepare sintered NdFeB magnets: single alloy method or general double alloy method. Conventional preparation methods cannot effectively utilize heavy rare earth elements, and at the same time, the controllability of grain boundaries is poor. The preparation of high-performance magnets not only requires higher costs, but it is also difficult to prepare ultra-high-performance magnets.
发明内容 Contents of the invention
本发明提供了一种高性能磁体和高性能磁体的制备方法。采用本发明方法不仅能更好地将Dy、Tb元素分布到晶界,获得低成本高性能磁体,且无须改动原有生产设备进行产业化生产,而且还能够制备超高性能的磁体。 The invention provides a high-performance magnet and a preparation method of the high-performance magnet. The method of the invention can not only better distribute Dy and Tb elements to grain boundaries, obtain low-cost high-performance magnets, and do not need to modify original production equipment for industrial production, but also can prepare ultra-high-performance magnets.
本发明的技术方案是: 一种高性能烧结钕铁硼磁体,其特征包括85~97wt%主相合金RExFe余MzBy和3~15wt%晶界富稀土相合金 RESNJFe余,其中: The technical solution of the present invention is: a high-performance sintered NdFeB magnet, which is characterized by comprising 85-97wt% main phase alloy RE x Fe remaining M z B y and 3-15wt% grain boundary rare earth-rich phase alloy RE S N J The remainder of Fe, of which:
主相合金成分中的REx为轻稀土元素Nd和Pr中的一种或二种,REx为28~29wt%,Mz为添加金属元素Ga、Cu、Al、Co中的一种或一种以上,Mz为0.2~2wt%, B元素By为0.95~1.02wt%,余量为Fe; RE x in the main phase alloy composition is one or two of light rare earth elements Nd and Pr, RE x is 28 to 29 wt%, and M z is one or one of the added metal elements Ga, Cu, Al, Co More than one species, M z is 0.2-2wt%, B element By is 0.95-1.02wt%, and the balance is Fe;
晶界富稀土相合金成分中的RES包含Nd、Dy、Tb中的一种或一种以上,且至少包含重稀土元素Dy和Tb的一种或二种,RES为40~80 wt%,且(Dy+Tb)的比例为15%~RES,NJ为添加金属元素Ga、Cu、Al、Co、Nb、Zr中的一种或一种以上,NJ为4~10 wt%,余量为Fe。 RE S in the grain boundary rare earth-rich phase alloy composition contains one or more of Nd, Dy, and Tb, and at least one or two of heavy rare earth elements Dy and Tb, and RE S is 40 to 80 wt% , and the proportion of (Dy+Tb) is 15%~ RES , N J is one or more of the added metal elements Ga, Cu, Al, Co, Nb, Zr, N J is 4~10 wt%, and the rest The amount is Fe.
高性能烧结钕铁硼磁体的制备方法,包括以下步骤: A method for preparing a high-performance sintered NdFeB magnet, comprising the following steps:
1)、按照主相合金的成分配比进行配料称重,放入真空中频熔炼炉中熔炼,采用速凝工艺铸片,设置铜辊转速1.5~2.0m/s,浇铸温度1420~1430℃,制得主相合金铸片;主相合金铸片进行氢破碎,控制破碎粉末的氧含量≤400PPm; 1) According to the composition ratio of the main phase alloy, the ingredients are weighed, put into a vacuum intermediate frequency melting furnace for melting, and the casting is cast by the quick-setting process. The main phase alloy casting sheet is obtained; the main phase alloy casting sheet is subjected to hydrogen crushing, and the oxygen content of the crushed powder is controlled to be ≤400PPm;
2)、按照晶界富稀土相合金的成分配比进行配料称重,放入真空中频熔炼炉中熔炼,采用常规速凝工艺铸片,设置铜辊转速1.2~1.5m/s,浇铸温度1440℃~1450℃,制得晶界富稀土相合金铸片;将晶界富稀土合金铸片进行氢破碎,筛选氢破粉末粒度中≤380μm的粉末; 2) According to the composition ratio of rare earth-rich phase alloy at the grain boundary, the batching and weighing are carried out, put into the vacuum intermediate frequency melting furnace for melting, adopt the conventional quick-setting process to cast the sheet, set the copper roller speed to 1.2-1.5m/s, and the casting temperature to 1440 ℃~1450℃, to prepare the grain boundary rare earth-rich phase alloy cast piece; carry out hydrogen crushing on the grain boundary rare earth-rich alloy cast piece, and screen the powder with a particle size of ≤380μm in the hydrogen broken powder;
3)、将经氢破筛选的晶界富稀土相合金粉末在惰性气体气氛下进行气流磨,氧含量控制在5 PPm以下,气流磨后的细粉粒度控制在2.5~3.5μm; 3) The grain boundary rare earth-rich phase alloy powder screened by hydrogen blasting is jet milled under an inert gas atmosphere, the oxygen content is controlled below 5 PPm, and the particle size of the fine powder after jet milling is controlled at 2.5-3.5 μm;
4)、将经气流磨后的晶界富稀土相合金细粉和主相合金氢破粉末按比例混合,其中晶界富稀土相合金细粉添加比例为3wt%~15wt%,将混合的粉末在惰性气体气氛下再进行气流磨,控制磨室氧含量≤10 PPm,粉末粒度2.8~3.0μm; 4) Mix the grain boundary rare earth-rich phase alloy fine powder and the main phase alloy hydrogen broken powder in proportion after jet milling, and the addition ratio of the grain boundary rare earth Jet milling is carried out under an inert gas atmosphere, and the oxygen content in the milling chamber is controlled to be ≤10 ppm, and the powder particle size is 2.8-3.0 μm;
5)、将均匀混合粉末称重,填入成型模具内,加≥2.0T磁场取向压制成型,生坯抽真空封装后,放入压力机中加压150~200Mpa,保压静置1~3分钟; 5) Weigh the uniformly mixed powder, fill it into the forming mold, add ≥ 2.0T magnetic field orientation and press molding, after the green body is vacuum-packed, put it into the press and pressurize 150-200Mpa, keep the pressure and let it stand for 1-3 minute;
6)、将经保压静置后的生坯,放入真空度≤4.0×10-2Pa的真空烧结炉内,在1020℃~1060℃的温度下烧结3.5~5.5h后,在450℃~600℃进行4~6h时效处理,从烧结炉中取出制成的钕铁硼磁体。 6) Put the green body that has been kept under pressure into a vacuum sintering furnace with a vacuum degree of ≤4.0×10 -2 Pa, sinter at a temperature of 1020°C to 1060°C for 3.5 to 5.5 hours, and then sinter at a temperature of 450°C ~600°C for 4~6h aging treatment, take out the finished NdFeB magnet from the sintering furnace.
上述中,主相合金中的RE选择Nd、Pr,不添加Dy、Tb等重稀土是为保证其不扩散进主相内部,x选择28~29wt%则是因为主相合金成分必须接近钕铁硼主相成分;主相合金由于稀土含量低易在熔炼过程中产生软磁性相a-Fe,通过添加M元素以抑制熔炼中a-Fe的生成;B添加量过高则导致Nd1+εFe4B4相比例过高而降低主相比例,从而影响磁体性能; In the above, Nd and Pr are selected for RE in the main phase alloy, and heavy rare earths such as Dy and Tb are not added to ensure that they do not diffuse into the main phase. X is selected to be 28-29wt% because the composition of the main phase alloy must be close to NdFe The main phase composition of boron; the main phase alloy is easy to produce soft magnetic phase a-Fe during the smelting process due to the low rare earth content, and the formation of a-Fe during smelting can be suppressed by adding M element; too high B addition will lead to Nd 1+ε The proportion of Fe 4 B 4 phase is too high to reduce the proportion of the main phase, thus affecting the performance of the magnet;
上述中,晶界富稀土相合金中必须添加大比例的重稀土元素,是因为本发明目的就是为了将Dy、Tb等重稀土元素更好地分布在边界;而N元素的添加则是能在磁体晶界形成晶界相,细化主相晶粒; In the above, a large proportion of heavy rare earth elements must be added to the grain boundary rare earth-rich phase alloy, because the purpose of the present invention is to better distribute heavy rare earth elements such as Dy and Tb on the boundary; The grain boundary of the magnet forms a grain boundary phase and refines the grains of the main phase;
晶界富稀土相细粉如添加比例<3wt%,则导致磁体晶界相过少,性能恶化;如添加比例>15wt%,则导致晶界相过多而出现大量的晶界相团聚的情况导致性能下降。 If the grain boundary rare earth-rich phase fine powder is added in a ratio of <3wt%, it will lead to too little grain boundary phase of the magnet, and the performance will deteriorate; if the addition ratio is >15wt%, it will cause too much grain boundary phase and a large amount of grain boundary phase agglomeration lead to performance degradation.
上述中,主相合金只经过一次磨粉,晶界富稀土相合金则等于经过两次磨粉;采用该方法的好处在于:即进一步细化晶界富稀土相粉末粒度,使其更有效的包裹主合金相,又可以防止对晶界富稀土相单独两次磨粉时存在粉末氧化的风险;而且通过气流磨过程能使粉末混合的更均匀。 Among the above, the main phase alloy is only ground once, and the grain boundary rare earth-rich phase alloy is equal to two grinding times; the advantage of adopting this method is that it further refines the particle size of the grain boundary rare earth-rich phase powder to make it more effective. Encapsulation of the main alloy phase can prevent the risk of powder oxidation when the grain boundary rare earth-rich phase is milled separately twice; moreover, the powder can be mixed more uniformly through the jet milling process.
采用本方法制备磁体1)相同成分的情况下,可以在更低的烧结温度下获得致密磁体,因而可以控制磁体因高温烧结而出现的晶粒异常长大情况;2)更有效地将重稀土Dy、Tb分布到晶界而制备成本更低的高性能磁体;3)可以制备得到超高性能磁体。4)本发明可以在现有生产线上产业化,无须特殊的重稀土晶界扩散装备。 Using this method to prepare magnets 1) In the case of the same composition, a dense magnet can be obtained at a lower sintering temperature, so the abnormal grain growth of the magnet due to high temperature sintering can be controlled; 2) The heavy rare earth can be more effectively Dy and Tb are distributed to the grain boundaries to prepare low-cost high-performance magnets; 3) ultra-high-performance magnets can be prepared. 4) The present invention can be industrialized on the existing production line without special heavy rare earth grain boundary diffusion equipment.
专利附图patent drawings
以下3个图是本发明制备的磁体中重稀土元素的分布,测试方法为EMPA; The following 3 figures are the distribution of heavy rare earth elements in the magnet prepared by the present invention, and the test method is EMPA;
图1是磁体微观组织结构图片,图中白色是磁体晶界富稀土相,黑色是主相; Figure 1 is a picture of the microstructure of the magnet. In the figure, the white is the rare earth-rich phase at the grain boundary of the magnet, and the black is the main phase;
图2是对应图1的重稀土元素Dy的分布情况,主要分布在晶界; Figure 2 is the distribution of the heavy rare earth element Dy corresponding to Figure 1, mainly distributed in the grain boundary;
图3是对应图1的重稀土元素Tb的分布情况,主要分布在晶界。 Fig. 3 is the distribution of the heavy rare earth element Tb corresponding to Fig. 1, which is mainly distributed in the grain boundary.
注:图2和图3右边颜色变化的标尺表示对应的元素在图1中各区域的分布丰度,分布的多少与标尺中的数值对应。 Note: The color-changing scale on the right side of Figure 2 and Figure 3 indicates the distribution abundance of the corresponding element in each area in Figure 1, and the distribution corresponds to the value in the scale.
具体实施方式 Detailed ways
实施例1:Example 1:
1)主相合金按 Nd29.0Co1.0Ga0.2B1.0Fe余(wt%)的配比进行配料熔炼,采用速凝技术铸片,铜辊转速为1.5m/s,浇注温度为1430℃;铸片进行氢破碎,破碎的粉末氧含量控制≤400PPm; 1) The main phase alloy is smelted according to the proportion of Nd 29.0 Co 1.0 Ga 0.2 B 1.0 Fe (wt%), and the cast sheet is cast by quick-setting technology, the copper roll speed is 1.5m/s, and the pouring temperature is 1430°C; The tablets are crushed by hydrogen, and the oxygen content of the crushed powder is controlled to be ≤400PPm;
2)晶界富稀土相合金按Nd25Dy15Cu2.0Al2.0Co3.0Fe余(wt%)的配比配料熔炼,采用速凝技术铸片,铜辊转速1.2m/s,浇铸温度为1450℃;铸片氢破,氢破粉末在Ar保护环境中(O2≤10PPm)进行过筛,筛孔为40目,筛选出粒度≤380μm的富稀土相氢破粉末; 2) The grain boundary rare earth-rich phase alloy is smelted according to the proportion of Nd 25 Dy 15 Cu 2.0 Al 2.0 Co 3.0 Fe (wt%), and the cast piece is cast by the rapid solidification technology, the copper roll speed is 1.2m/s, and the casting temperature is 1450 ℃; casting sheet hydrogen crushing, the hydrogen crushing powder is sieved in an Ar protection environment (O 2 ≤10PPm), the sieve opening is 40 mesh, and the rare earth-rich phase hydrogen crushing powder with a particle size of ≤380 μm is screened;
3)将经氢破筛选的晶界富稀土相合金粉末在Ar气体气氛下进行气流磨,控制磨室氧含量≤5PPm,粉末粒度3~3.5μm; 3) The grain boundary rare earth-rich phase alloy powder screened by hydrogen blasting is jet-milled in an Ar gas atmosphere, and the oxygen content in the milling chamber is controlled to be ≤5PPm, and the particle size of the powder is 3-3.5μm;
4)将经气流磨后的晶界富稀土相合金粉末与主相合金的氢破粉末混合(即将上述的1)和2)进行混合),晶界富稀土相合金粉末添加比例为8wt%,主相合金粉末为92 wt%。混合后的合金粉末组成含量为:Nd28.68Dy1.20Co1.16Cu0.16Al0.16Ga0.18B0.92Fe余(wt%)。将混合的粉末在Ar气气氛下再进行气流磨,控制磨室氧含量≤10PPm,粉末粒度3.0μm; 4) Mix the jet-milled grain boundary rare earth-rich phase alloy powder with the hydrogen-breaking powder of the main phase alloy (that is, mix the above 1) and 2), and the addition ratio of the grain boundary rare earth-rich phase alloy powder is 8wt%, The main phase alloy powder is 92 wt%. The composition content of the mixed alloy powder is: Nd 28.68 Dy 1.20 Co 1.16 Cu 0.16 Al 0.16 Ga 0.18 B 0.92 Fe (wt%). Jet mill the mixed powder under Ar gas atmosphere, control the oxygen content in the mill chamber to be ≤10PPm, and the powder particle size to be 3.0μm;
5)将均匀混合粉末填入模具内,加2.0T磁场取向压制成型,生坯真空封装后放入压力机中,加压220Mpa,油冷等静压1min; 5) Fill the uniformly mixed powder into the mold, add 2.0T magnetic field orientation and press molding, vacuum seal the green body and put it into the press, pressurize at 220Mpa, and oil-cool isostatic pressing for 1min;
6)等静压后的坯料在≤4.0×10-2Pa的真空炉中进行烧结和时效,烧结温度为1020℃~1060℃,烧结时间为3.5h;时效工艺:500℃×4h。时效结束制备得到烧结NdFeB磁体。 6) The blank after isostatic pressing is sintered and aged in a vacuum furnace of ≤4.0×10 -2 Pa, the sintering temperature is 1020℃~1060℃, and the sintering time is 3.5h; aging process: 500℃×4h. After aging, sintered NdFeB magnets were obtained.
比较例1A:Comparative Example 1A:
1) 采用常规制备方法,成分为Nd28.68Dy1.2Co1.16Cu0.16Al0.16Ga0.18B0.92Fe余(即实施例1中混合后合金粉末的成分),采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using conventional preparation methods, the composition is Nd 28.68 Dy 1.2 Co 1.16 Cu 0.16 Al 0.16 Ga 0.18 B 0.92 Fe ( that is, the composition of the mixed alloy powder in Example 1), using conventional rapid-setting technology: copper roll speed 1.2~ 1.5m/s, casting temperature 1440℃~1460℃; cast sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2) 氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the fine powder particle size to 3.0-3.5 μm;
3) 将经气流磨的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the air-milled powder into the mold, shape it in a magnetic field of 2.0T, and vacuum-pack the green body. The packaged blank is subjected to oil-cooled isostatic pressing at 200-250MPa for 1-3 minutes;
4) 等静压后的坯料在≤4.0×10-2Pa真空条件下进行烧结和时效,烧结温度1020℃~1060℃,烧结时间3.5h;时效工艺,500℃×4h。时效结束后制备得到烧结NdFeB磁体。 4) The blank after isostatic pressing is sintered and aged under the vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1020℃~1060℃, the sintering time is 3.5h; the aging process is 500℃×4h. After aging, the sintered NdFeB magnet was prepared.
比较例1B:Comparative Example 1B:
1)采用常规制备方法,成分为Nd28Dy1.6Co1.2Cu0.2Al0.2Ga0.2B0.95Fe余采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) The conventional preparation method is adopted, the composition is Nd 28 Dy 1.6 Co 1.2 Cu 0.2 Al 0.2 Ga 0.2 B 0.95 Fe, and the conventional quick-setting technology is adopted: the copper roller speed is 1.2-1.5m/s, the casting temperature is 1440℃~1460℃; Hydrogen flakes, hydrogen powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the particle size of the fine powder to 3.0-3.5 μm;
3)将气流磨后的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet-milled powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is oil-cooled and isostatically pressed at 200-250MPa for 1-3 minutes;
4)等静压坯料在≤4.0×10-2Pa真空条件下在烧结1045℃×3.5h;时效工艺,500℃×4h。时效结束后制备得到烧结NdFeB磁体。 4) The isostatic pressing blank is sintered at 1045°C for 3.5h under the vacuum condition of ≤4.0×10 -2 Pa; aging process, 500°C×4h. After aging, the sintered NdFeB magnet was prepared.
表1A 不同烧结温度密度对比表 Table 1A Density comparison table at different sintering temperatures
从上述对比表可以看到,采用本发明方法在1020℃~1050℃的烧结温度下制得的钕铁硼磁钢,其密度要明显大于采用常规方法制得的磁钢。在1060℃的烧结温度下制得的钕铁硼磁钢虽然致密度相同,但采用传统方法制得的钕铁硼磁钢晶粒异常长大,影响磁体性能。因此,采用本发明,在相同成分的情况下,可以在更低的烧结温度下获得致密磁体,因而可以控制磁体因高温烧结而出现的晶粒异常长大情况。 It can be seen from the comparison table above that the density of NdFeB magnets prepared by the method of the present invention at a sintering temperature of 1020° C. to 1050° C. is significantly higher than that of magnets prepared by conventional methods. Although the NdFeB magnets produced at the sintering temperature of 1060°C have the same density, the grains of the NdFeB magnets produced by the traditional method grow abnormally, which affects the performance of the magnet. Therefore, with the present invention, under the condition of the same composition, a dense magnet can be obtained at a lower sintering temperature, so that the abnormal grain growth of the magnet due to high temperature sintering can be controlled.
表1B 磁性能和Dy含量对比表 Table 1B Comparison table of magnetic properties and Dy content
从上述对比表可以看到,采用本发明方法和常规方法制得磁性能相近的钕铁硼磁钢,其重稀土Dy的含量下降了0.4wt%,降低了成本。因此,本方法能够制备成本更低的高性能磁体。 It can be seen from the comparison table above that the NdFeB magnets with similar magnetic properties obtained by the method of the present invention and the conventional method have a 0.4wt% reduction in the content of heavy rare earth Dy, which reduces the cost. Therefore, the present method enables the preparation of lower-cost high-performance magnets.
实施例2:Example 2:
1)主相合金按照 Nd28.5Fe余Cu0.2Ga0.2B1.0(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速为1.8m/s,浇注温度为1425℃;铸片进行氢破碎,破碎的粉末氧含量控制≤400PPm; 1) The main phase alloy is smelted according to the ratio of Nd 28.5 Fe to Cu 0.2 Ga 0.2 B 1.0 (wt%), and the cast sheet is cast by quick-setting technology, the copper roll speed is 1.8m/s, and the pouring temperature is 1425°C; Hydrogen crushing is carried out, and the oxygen content of the crushed powder is controlled to be ≤400PPm;
2)晶界富稀土相合金按照Nd45Dy25Tb10Nb1.0Al2.0Co3.0Fe余(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速1.2m/s,浇铸温度为1450℃;铸片氢破,氢破粉末在Ar保护环境中(O2≤10PPm)进行过筛,筛孔为40目,筛选出粒度≤380μm的富稀土相氢破粉末; 2) Rare-earth-rich phase alloys at grain boundaries were smelted according to the ratio of Nd 45 Dy 25 Tb 10 Nb 1.0 Al 2.0 Co 3.0 Fe (wt%), and the casting was cast using rapid solidification technology. The copper roll speed was 1.2m/s, and the casting temperature was The temperature is 1450°C; cast hydrogen powder, the hydrogen powder is sieved in an Ar protection environment (O 2 ≤10PPm), the sieve is 40 mesh, and the rare earth-rich phase hydrogen powder with a particle size of ≤380μm is screened;
3)将经氢破筛选的晶界富稀土相合金粉末在Ar气体气氛中进行气流磨,控制磨室氧含量≤5PPm,粉末粒度3.0~3.5μm; 3) The grain boundary rare earth-rich phase alloy powder screened by hydrogen breaking is jet-milled in an Ar gas atmosphere, and the oxygen content in the milling chamber is controlled to be ≤5PPm, and the powder particle size is 3.0-3.5μm;
4)将经气流磨后的晶界富稀土相合金粉末与主相合金氢破粉末混合(即将上述的1)和2)进行混合),晶界富稀土相合金添加比例为5wt%,主相合金为95 wt%;混合后的合金粉末的组成含量为:Nd29.33Dy1.25Tb0.50Co0.50Cu0.19Al0.10Ga0.19Nb0.05B0.95Fe余(wt%),将混合的合金粉末在Ar气体气氛下再进行气流磨,控制磨室氧含量≤10PPm,粉末粒度2.8~3.0μm; 4) Mix the grain boundary rare earth-rich phase alloy powder after jet milling with the main phase alloy hydrogen powder (that is, mix the above 1) and 2), the addition ratio of the grain boundary rare earth phase alloy is 5wt%, the main phase The alloy is 95 wt%; the composition content of the mixed alloy powder is: Nd 29.33 Dy 1.25 Tb 0.50 Co 0.50 Cu 0.19 Al 0.10 Ga 0.19 Nb 0.05 B 0.95 Fe (wt%), the mixed alloy powder in the Ar gas atmosphere Then carry out jet milling, control the oxygen content in the milling chamber ≤10PPm, and the powder particle size is 2.8~3.0μm;
5)将均匀混合后的粉末放入模具内加2.0T磁场取向压制成型,生坯真空封装后放入压力机中,加压220MPa,油冷等静压1min; 5) Put the uniformly mixed powder into the mold and apply 2.0T magnetic field orientation to press molding. After the green body is vacuum packaged, put it into the press, pressurize at 220MPa, and oil-cool isostatic pressing for 1min;
6)等静压后的坯料在≤4.0×10-2Pa的真空条件下进行烧结和时效,烧结温度为1020℃~1050℃,烧结时间为4.5h;时效工艺:480℃×4h。时效结束制备得到烧结NdFeB磁体。 6) The blank after isostatic pressing is sintered and aged under the vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1020℃~1050℃, and the sintering time is 4.5h; aging process: 480℃×4h. After aging, sintered NdFeB magnets were obtained.
比较例2A:Comparative Example 2A:
1)采用常规制备方法,成分为Nd29.33Dy1.25Tb0.5Co0.5Cu0.19Al0.1Ga0.19Nb0.05B0.95Fe余(wt%)(即实施例2中混合后合金粉末的成分);采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using a conventional preparation method, the composition is Nd 29.33 Dy 1.25 Tb 0.5 Co 0.5 Cu 0.19 Al 0.1 Ga 0.19 Nb 0.05 B 0.95 Fe (wt%) (that is, the composition of the mixed alloy powder in Example 2); Coagulation technology: Copper roller speed 1.2~1.5m/s, casting temperature 1440℃~1460℃; cast sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the particle size of the fine powder to 3.0-3.5 μm;
3)将气流磨后的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet-milled powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is oil-cooled and isostatically pressed at 200-250MPa for 1-3 minutes;
4)等静压坯料在≤4.0×10-2Pa真空条件下在进行烧结和时效,烧结温度1020℃~1050℃,烧结时间4.5h;时效工艺,480℃×4h。时效结束后制备得到烧结NdFeB磁体。 4) The isostatic pressing blank is sintered and aged under the vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1020℃~1050℃, the sintering time is 4.5h; the aging process is 480℃×4h. After aging, the sintered NdFeB magnet was prepared.
比较例2B:Comparative Example 2B:
1)采用常规制备方法,成分为Nd29.5Dy1.8Tb0.5Co0.5Cu0.19Al0.10Ga0.19Nb0.05B0.95Fe余(wt%);采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using conventional preparation methods, the composition is Nd 29.5 Dy 1.8 Tb 0.5 Co 0.5 Cu 0.19 Al 0.10 Ga 0.19 Nb 0.05 B 0.95 Fe (wt%); using conventional quick-setting technology: copper roller speed 1.2 ~ 1.5m/s, Casting temperature is 1440℃~1460℃; casting sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled, and the fine powder particle size is 3.0-3.5 μm;
3)将气流磨粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet mill powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is subjected to oil-cooled isostatic pressing at 200-250MPa for 1-3 minutes;
等静压坯料在≤4.0×10-2Pa真空条件下在烧结1040℃×4.5h;时效工艺,480℃×4h。时效结束后制备得到烧结NdFeB磁体。 The isostatic pressing blank is sintered at 1040°C for 4.5h under the vacuum condition of ≤4.0×10 -2 Pa; the aging process is 480°C for 4h. After aging, the sintered NdFeB magnet was prepared.
表2A 不同烧结温度密度对比表 Table 2A Density comparison table at different sintering temperatures
从上述对比表可以看到,采用本发明方法在1020℃~1040℃的烧结温度下制得的钕铁硼磁钢,其密度要大于采用常规方法制得的磁钢。在1050℃的烧结温度下制得的钕铁硼磁钢虽然致密度相同,但采用常规方法制得的钕铁硼磁钢晶粒异常长大,影响磁体性能。因此,采用本发明,在相同成分的情况下,可以在更低的烧结温度下获得致密磁体,因而可以控制磁体因高温烧结而出现的晶粒异常长大情况。 It can be seen from the comparison table above that the density of NdFeB magnets prepared by the method of the present invention at a sintering temperature of 1020° C. to 1040° C. is higher than that of magnets prepared by conventional methods. Although the NdFeB magnets produced at the sintering temperature of 1050°C have the same density, the grains of the NdFeB magnets produced by conventional methods grow abnormally, which affects the performance of the magnets. Therefore, with the present invention, under the condition of the same composition, a dense magnet can be obtained at a lower sintering temperature, so that the abnormal grain growth of the magnet due to high temperature sintering can be controlled.
表2B 磁性能和Dy含量对比表 Table 2B Comparison table of magnetic properties and Dy content
从上述对比表可以看到,采用本发明方法和常规方法制得磁性能相近的钕铁硼磁钢,其重稀土Dy的含量下降了0.55%,降低了成本。因此,本方法能够制备成本更低的高性能磁体。 It can be seen from the comparison table above that the NdFeB magnets with similar magnetic properties are produced by the method of the present invention and the conventional method, and the content of the heavy rare earth Dy is reduced by 0.55%, which reduces the cost. Therefore, the present method enables the preparation of lower-cost high-performance magnets.
实施例3:Example 3:
1)主相合金按照 Pr7Nd21Fe余Al0.2Co1.0B1.0(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速为2.0m/s,浇注温度为1425℃;铸片进行氢破碎,破碎的粉末氧含量控制≤400PPm; 1) The main phase alloy is smelted according to the proportion of Pr 7 Nd 21 Fe remaining Al 0.2 Co 1.0 B 1.0 (wt%), using the quick-setting technology to cast the sheet, the copper roll speed is 2.0m/s, and the pouring temperature is 1425°C; The casting is crushed by hydrogen, and the oxygen content of the crushed powder is controlled to be ≤400PPm;
2)晶界富稀土相合金按照Nd30Dy20Zr1.0Ga2Cu2Fe余(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速1.4m/s,浇铸温度为1450℃;铸片氢破,氢破粉末在Ar保护环境中(O2≤10PPm)进行过筛,筛孔为40目,筛选出粒度≤380μm的富稀土相氢破粉末; 2) The grain boundary rare earth-rich phase alloy is smelted according to the ratio of Nd 30 Dy 20 Zr 1.0 Ga 2 Cu 2 Fe (wt%), and the casting is cast using the rapid solidification technology. The copper roll speed is 1.4m/s, and the casting temperature is 1450 ℃; casting sheet hydrogen crushing, the hydrogen crushing powder is sieved in an Ar protection environment (O 2 ≤10PPm), the sieve opening is 40 mesh, and the rare earth-rich phase hydrogen crushing powder with a particle size of ≤380 μm is screened;
3)将经氢破筛选的晶界富稀土相合金粉末在Ar气体气氛下进行气流磨,控制磨室氧含量≤5PPm,粉末粒度3.0μm; 3) The grain boundary rare earth-rich phase alloy powder screened by hydrogen blasting is jet-milled in an Ar gas atmosphere, and the oxygen content in the milling chamber is controlled to be ≤5PPm, and the particle size of the powder is 3.0μm;
4)将经气流磨后的晶界富稀土相合金粉末与主相合金氢破粉末混合(即将上述的1)和2)进行混合),富稀土相合金粉末添加比例为15wt%,主相合金为85 wt%;混合后的合金粉末组成含量为:Nd22.35Pr5.95Dy3.0Co0.85Cu0.3Al0.17Ga0.3Zr0.15B0.85Fe余(wt%)。在Ar气体气氛下将混合的合金粉末再进行气流磨,控制磨室氧含量≤10PPm,粉末粒度2.8μm; 4) Mix the grain boundary rare earth-rich phase alloy powder after jet milling with the main phase alloy hydrogen breaking powder (that is, mix the above 1) and 2), the addition ratio of the rare earth-rich phase alloy powder is 15wt%, and the main phase alloy is 85 wt%; the mixed alloy powder composition content is: Nd 22.35 Pr 5.95 Dy 3.0 Co 0.85 Cu 0.3 Al 0.17 Ga 0.3 Zr 0.15 B 0.85 Fe (wt%). Under the Ar gas atmosphere, the mixed alloy powder is jet milled again, and the oxygen content in the milling chamber is controlled to be ≤10PPm, and the powder particle size is 2.8μm;
5)将均匀混合后的粉末填入模具内加2.0T磁场取向压制成型,生坯真空封装后放入压力机中,加压220MPa,油冷等静压1min; 5) Fill the uniformly mixed powder into the mold and apply 2.0T magnetic field orientation to press molding. After the green body is vacuum packaged, put it into the press, pressurize at 220MPa, and oil-cool isostatic pressing for 1min;
6)等静压后的坯料在≤4.0×10-2Pa的真空条件下进行烧结和时效,烧结温度为1020℃~1050℃,烧结时间为4.5h;时效工艺:520℃×4h。时效结束制备得到烧结NdFeB磁体。 6) The blank after isostatic pressing is sintered and aged under the vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1020℃~1050℃, and the sintering time is 4.5h; aging process: 520℃×4h. After aging, sintered NdFeB magnets were obtained.
比较例3A:Comparative Example 3A:
1)采用常规制备方法,成分为Nd22.35Pr5.95Dy3.0Co0.85Cu0.3Al0.17Ga0.3Zr0.15B0.85Fe余(wt.%)(即实施例3中混合后合金粉末的成分);采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using a conventional preparation method, the composition is Nd 22.35 Pr 5.95 Dy 3.0 Co 0.85 Cu 0.3 Al 0.17 Ga 0.3 Zr 0.15 B 0.85 Fe (wt.%) (that is, the composition of the mixed alloy powder in Example 3); Accelerated setting technology: copper roll speed 1.2~1.5m/s, casting temperature 1440℃~1460℃; cast sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the particle size of the fine powder to 3.0-3.5 μm;
3)将气流磨后的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet-milled powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is oil-cooled and isostatically pressed at 200-250MPa for 1-3 minutes;
4)等静压坯料在≤4.0×10-2Pa真空条件下进行烧结和时效,烧结温度在1020℃~1050℃,烧结时间4.5h;时效工艺,520℃×4h。时效结束后制备得到烧结NdFeB磁体。 4) The isostatic pressing billet is sintered and aged under the vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1020℃~1050℃, and the sintering time is 4.5h; the aging process is 520℃×4h. After aging, the sintered NdFeB magnet was prepared.
比较例3B:Comparative Example 3B:
1)采用常规制备方法,成分为Nd22.4Pr5.6Dy4.0Co1.0Cu0.3Al0.2Ga0.3Zr0.15B0.85Fe余(wt.%);采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using conventional preparation methods, the composition is Nd 22.4 Pr 5.6 Dy 4.0 Co 1.0 Cu 0.3 Al 0.2 Ga 0.3 Zr 0.15 B 0.85 Fe (wt.%); using conventional quick-setting technology: copper roller speed 1.2 ~ 1.5m/s , the casting temperature is 1440℃~1460℃; cast sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the particle size of the fine powder to 3.0-3.5 μm;
3)将气流磨后的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet-milled powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is oil-cooled and isostatically pressed at 200-250MPa for 1-3 minutes;
等静压坯料在≤4.0×10-2Pa真空条件下在烧结1045℃×3.5h;时效工艺,480℃×4h。时效结束后制备得到烧结NdFeB磁体。 The isostatic pressing blank is sintered at 1045°C for 3.5h under the vacuum condition of ≤4.0×10 -2 Pa; the aging process is at 480°C for 4h. After aging, the sintered NdFeB magnet was prepared.
表3A 不同烧结温度密度对比表 Table 3A Density comparison table at different sintering temperatures
从上述对比表可以看到,采用本发明方法在1020℃~1050℃的烧结温度下制得的钕铁硼磁钢,其密度要大于采用常规方法制得的磁钢。因此,采用本发明,在相同成分的情况下,可以在更低的烧结温度下获得致密磁体,因而可以控制磁体因高温烧结而出现的晶粒异常长大情况。 It can be seen from the comparison table above that the density of NdFeB magnets prepared by the method of the present invention at a sintering temperature of 1020° C. to 1050° C. is higher than that of magnets prepared by conventional methods. Therefore, with the present invention, under the condition of the same composition, a dense magnet can be obtained at a lower sintering temperature, so that the abnormal grain growth of the magnet due to high temperature sintering can be controlled.
表3B 磁性能和Dy含量对比表 Table 3B Magnetic properties and Dy content comparison table
从上述对比表可以看到,采用本发明方法和常规方法制得磁性能相近的钕铁硼磁钢,其重稀土Dy的含量下降了0.5%,降低了成本。因此,本方法能够制备成本更低的高性能磁体。 It can be seen from the comparison table above that the NdFeB magnets with similar magnetic properties are produced by the method of the present invention and the conventional method, and the content of the heavy rare earth Dy is reduced by 0.5%, which reduces the cost. Therefore, the present method enables the preparation of lower-cost high-performance magnets.
实施例4:Example 4:
1)主相合金按照 Nd28.5Fe余Co1.0B1.0(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速为1.8m/s,浇注温度为1420℃;铸片进行氢破碎,破碎的粉末氧含量控制≤400PPm; 1) The main phase alloy is smelted according to the ratio of Nd 28.5 Fe to Co 1.0 B 1.0 (wt%), using the rapid solidification technology to cast the sheet, the copper roll speed is 1.8m/s, and the pouring temperature is 1420°C; Broken, crushed powder oxygen content control ≤ 400PPm;
2)晶界富稀土相合金按照Nd35Dy20Nb1.0Ga2Cu2Fe余(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速1.5m/s,浇铸温度为1450℃;铸片氢破,氢破粉末在Ar保护环境中(O2≤10PPm)进行过筛,筛孔为40目,筛选出粒度≤380μm的富稀土相氢破粉末; 2) The grain boundary rare earth-rich phase alloy is smelted according to the ratio of Nd 35 Dy 20 Nb 1.0 Ga 2 Cu 2 Fe (wt%), and the casting is cast by quick-setting technology, the copper roll speed is 1.5m/s, and the casting temperature is 1450 ℃; casting sheet hydrogen crushing, the hydrogen crushing powder is sieved in an Ar protection environment (O 2 ≤10PPm), the sieve opening is 40 mesh, and the rare earth-rich phase hydrogen crushing powder with a particle size of ≤380 μm is screened;
3)将经氢破筛选的晶界富稀土相合金粉末在Ar气体气氛下进行气流磨,控制磨室O2≤5PPm,粉末粒度3.0μm; 3) The grain boundary rare-earth-rich phase alloy powder screened by hydrogen blasting is jet-milled in an Ar gas atmosphere, and the O 2 in the milling chamber is controlled to be ≤5PPm, and the particle size of the powder is 3.0μm;
4)将经气流磨后的晶界富稀土相合金粉末与主相合金氢破粉末混合(即将上述的1)和2)进行混合),富稀土相合金粉末添加比例为3wt%,主相合金为97wt%;混合后的合金粉末组成含量为:Nd28.83Dy1.00Co0.95Cu0.10Ga0.10Nb0.05B0.95Fe余(wt%),在Ar气体气氛下将混合的合金粉末再进行气流磨,控制磨室氧含量≤10PPm,粉末粒度2.8μm; 4) Mix the grain boundary rare earth-rich phase alloy powder after jet milling with the main phase alloy hydrogen breaking powder (that is, mix the above 1) and 2), the addition ratio of the rare earth-rich phase alloy powder is 3wt%, and the main phase alloy is 97wt%; the mixed alloy powder composition content is: Nd 28.83 Dy 1.00 Co 0.95 Cu 0.10 Ga 0.10 Nb 0.05 B 0.95 Fe (wt%), the mixed alloy powder is then jet milled under the Ar gas atmosphere to control Oxygen content in the mill chamber ≤10PPm, powder particle size 2.8μm;
5)将均匀混合后的粉末填入模具内加2.0T磁场取向压制成型,生坯真空封装后放入压力机中,加压220MPa,油冷等静压3min; 5) Fill the uniformly mixed powder into the mold and apply 2.0T magnetic field orientation to press molding. After the green body is vacuum-packaged, put it into the press, pressurize at 220MPa, and press oil-cooled isostatically for 3 minutes;
6)等静压后的坯料在≤4.0×10-2Pa的真空条件下进行烧结和时效,烧结温度为1045℃,烧结时间为5.5h;时效工艺:485℃×4h。时效结束制备得到烧结NdFeB磁体,磁体具有超高剩磁和磁能积,性能如下表4。 6) The blank after isostatic pressing is sintered and aged under the vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1045°C, and the sintering time is 5.5h; aging process: 485°C×4h. After aging, a sintered NdFeB magnet was prepared. The magnet has ultra-high remanence and magnetic energy product, and its performance is shown in Table 4.
表4 磁体性能表 Table 4 Magnet performance table
比较例4Comparative example 4
1)采用常规制备方法,成分为Nd28.83Dy1.0Co0.95Cu0.1Ga0.1Nb0.05B0.95Fe余(wt%);采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using conventional preparation methods, the composition is Nd 28.83 Dy 1.0 Co 0.95 Cu 0.1 Ga 0.1 Nb 0.05 B 0.95 Fe (wt%); using conventional quick-setting technology: copper roller speed 1.2-1.5m/s, casting temperature 1440°C ~1460℃; cast sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the particle size of the fine powder to 3.0-3.5 μm;
3)将气流磨后的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet-milled powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is oil-cooled and isostatically pressed at 200-250MPa for 1-3 minutes;
等静压坯料在≤4.0×10-2Pa真空条件下在烧结1045℃×3.5h;时效工艺,480℃×4h。时效结束后制备得到烧结NdFeB磁体。该磁体难以烧结致密,磁体密度不到7.0g/cm3,没有磁性能。 The isostatic pressing blank is sintered at 1045°C for 3.5h under the vacuum condition of ≤4.0×10 -2 Pa; the aging process is at 480°C for 4h. After aging, the sintered NdFeB magnet was prepared. The magnet is difficult to be sintered densely, the density of the magnet is less than 7.0g/cm 3 , and it has no magnetic performance.
通过上述对比可以看出,采用相同配方,通过本发明方法可制得具有超高剩磁和磁能积的磁体,而采用常规方法,则制备的钕铁硼磁体没有磁性能。原因在于:制备超高剩磁和磁能积磁体,必须保证磁体成分中稀土含量接近主相成分含量(26.8wt%)以获得高比例的主相,而晶界富稀土相含量较少。采用常规制备方法,晶界富稀土相自由分布,会出现分布不均的情况,因而导致烧结过程中液相烧结不充分,磁体密度低下。而采用本发明,晶界富稀土相能非常均匀分布在晶界,从而提升了烧结致密行为,即使在晶界富稀土相比例较少的情况下也能获得高致密磁体。因此,采用本发明方法可以制得同时具有高剩磁和高磁能积的超高磁性能磁体。 It can be seen from the above comparison that with the same formula, a magnet with ultra-high remanence and magnetic energy product can be produced by the method of the present invention, while the NdFeB magnet prepared by the conventional method has no magnetic properties. The reason is: to prepare ultra-high remanence and energy product magnets, it is necessary to ensure that the rare earth content in the magnet composition is close to the main phase composition content (26.8wt%) to obtain a high proportion of the main phase, while the grain boundary rare earth-rich phase content is less. With the conventional preparation method, the rare earth-rich phase at the grain boundary is freely distributed, and the distribution will be uneven, which leads to insufficient liquid phase sintering during the sintering process and low magnet density. However, with the present invention, the rare earth-rich phase at the grain boundary can be very uniformly distributed in the grain boundary, thereby improving the sintering compact behavior, and a high-density magnet can be obtained even when the ratio of the rare earth-rich phase at the grain boundary is small. Therefore, the method of the present invention can be used to prepare an ultra-high magnetic performance magnet with both high remanence and high magnetic energy product.
实施例5:Example 5:
1)主相合金按照 Nd28.5Fe余Co1.0B1.0(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速为1.8m/s,浇注温度为1420℃;铸片进行氢破碎,破碎的粉末氧含量控制≤400PPm; 1) The main phase alloy is smelted according to the ratio of Nd 28.5 Fe to Co 1.0 B 1.0 (wt%), using the rapid solidification technology to cast the sheet, the copper roll speed is 1.8m/s, and the pouring temperature is 1420°C; Broken, crushed powder oxygen content control ≤ 400PPm;
2)晶界富稀土相合金按照Dy25Tb20Co2.0Ga2.0Cu2.0Al4.0Fe余(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速1.3m/s,浇铸温度为1445℃;铸片氢破,氢破粉末在Ar保护环境中(O2≤10PPm)进行过筛,筛孔为40目,筛选出粒度≤380μm的富稀土相合金氢破粉末; 2) The grain boundary rare earth-rich phase alloy is smelted according to the proportion of Dy 25 Tb 20 Co 2.0 Ga 2.0 Cu 2.0 Al 4.0 Fe (wt%), using the rapid solidification technology to cast the sheet, the copper roll speed is 1.3m/s, and the casting temperature is The temperature is 1445°C; the cast hydrogen powder is sieved in an Ar protection environment (O 2 ≤10PPm), the sieve hole is 40 mesh, and the rare earth-rich phase alloy hydrogen powder with a particle size of ≤380 μm is screened;
3)将经氢破筛选的晶界富稀土相合金粉末在Ar气体保护下进行气流磨,磨室O2≤5PPm,粉末粒度3.5μm; 3) The grain boundary rare-earth-rich phase alloy powder screened by hydrogen blasting is jet-milled under the protection of Ar gas, the O 2 in the milling chamber is ≤5PPm, and the particle size of the powder is 3.5μm;
4)将经气流磨后的晶界富稀土相合金粉末与主相合金氢破粉末混合(即将上述的1)和2)进行混合),富稀土相合金粉末添加比例为10wt%,主相合金为90wt%;混合后的合金粉末组成含量为:Nd25.65Dy2.50Tb2.00Co1.10Cu0.20Ga0.20Al0.40B0.95Fe余(wt%),在Ar气体气氛下将混合的合金粉末再进行气流磨,控制磨室氧含量≤10PPm,粉末粒度3.0μm; 4) Mix the grain boundary rare earth-rich phase alloy powder after jet milling with the main phase alloy hydrogen breaking powder (that is, mix the above 1) and 2), the addition ratio of the rare earth-rich phase alloy powder is 10wt%, and the main phase alloy 90wt%; the composition of the alloy powder after mixing is: Nd 25.65 Dy 2.50 Tb 2.00 Co 1.10 Cu 0.20 Ga 0.20 Al 0.40 B 0.95 Fe (wt%), the mixed alloy powder is jet milled under the Ar gas atmosphere , control the oxygen content in the mill room ≤ 10PPm, powder particle size 3.0μm;
5)将均匀混合后的粉末填入模具内加2.0T磁场取向压制成型,生坯真空封装后放入压力机中,加压220MPa,油冷等静压2min; 5) Fill the uniformly mixed powder into the mold and apply 2.0T magnetic field orientation to press molding. After the green body is vacuum packaged, put it into the press, pressurize at 220MPa, and press oil-cooled isostatically for 2 minutes;
6)等静压后的坯料在≤4.0×10-2Pa的真空条件下进行烧结和时效,烧结温度为1045℃,烧结时间为3.5h;时效工艺:485℃×4h。时效结束制备得到烧结NdFeB磁体,磁体具有高剩磁和高矫顽力,性能如下表5。 6) The blank after isostatic pressing is sintered and aged under a vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1045°C, and the sintering time is 3.5h; aging process: 485°C×4h. After aging, a sintered NdFeB magnet was prepared. The magnet has high remanence and high coercive force, and its performance is shown in Table 5.
比较例5Comparative Example 5
1)采用常规制备方法,成分为Nd25.65Dy2.5Tb2.0Co1.1Cu0.2Ga0.2Al0.4B0.95Fe余(wt%);采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using conventional preparation methods, the composition is Nd 25.65 Dy 2.5 Tb 2.0 Co 1.1 Cu 0.2 Ga 0.2 Al 0.4 B 0.95 Fe (wt%); using conventional quick-setting technology: copper roller speed 1.2-1.5m/s, casting temperature 1440℃~1460℃; cast sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the particle size of the fine powder to 3.0-3.5 μm;
3)将气流磨后的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet-milled powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is oil-cooled and isostatically pressed at 200-250MPa for 1-3 minutes;
等静压坯料在≤4.0×10-2Pa真空条件下在烧结1045℃×3.5h;时效工艺,480℃×4h。时效结束后制备得到烧结NdFeB磁体。磁体性能见表5 The isostatic pressing blank is sintered at 1045°C for 3.5h under the vacuum condition of ≤4.0×10 -2 Pa; the aging process is at 480°C for 4h. After aging, the sintered NdFeB magnet was prepared. The magnet properties are shown in Table 5
表5 磁体性能对比表 Table 5 Magnet performance comparison table
从上述对比表中可以看出,采用相同的材料配方通过本发明方法制得的钕铁硼磁体相比于常规方法制得的钕铁硼磁体,其剩磁提高了0.15kGs,矫顽力提高了2.3kOe。采用常规制备方法,由于Dy、Tb重稀土元素更多进入到主相中,因此,如通过添加重稀土来提高磁体矫顽力,则会牺牲剩磁;如果通过提高主相比例来提高剩磁,那矫顽力水平就要下降。所以,本实施例的配方,如果采用常规方法要制备矫顽力水平达到20.5kOe的磁体,则必须在配料中增加重稀土Dy或Tb的含量,而Dy或Tb的增加会导致剩磁下降,剩磁达不到13.75kGs的水平,无法制得既有高剩磁又有高矫顽力的磁体。采用本发明,由于Dy、Tb重稀土能均匀分布在晶界,很少进入主相,因此可制得同时具有高剩磁和高矫顽力的超高磁性能的磁体。 As can be seen from the above comparison table, the NdFeB magnets prepared by the method of the present invention using the same material formula have an increased remanence of 0.15kGs and a higher coercive force than the NdFeB magnets prepared by the conventional method. 2.3kOe. With the conventional preparation method, since Dy and Tb heavy rare earth elements enter into the main phase more, if the coercive force of the magnet is increased by adding heavy rare earth, the remanence will be sacrificed; if the remanence is increased by increasing the proportion of the main phase , the coercive force level will drop. Therefore, for the formulation of this example, if the conventional method is used to prepare a magnet with a coercive force level of 20.5kOe, the content of heavy rare earth Dy or Tb must be increased in the ingredients, and the increase of Dy or Tb will lead to a decrease in remanence. The remanence can't reach the level of 13.75kGs, and it is impossible to make a magnet with both high remanence and high coercive force. With the present invention, since Dy and Tb heavy rare earths can be evenly distributed in the grain boundaries and rarely enter the main phase, a magnet with ultra-high magnetic properties with high remanence and high coercive force can be produced.
实施例6:Embodiment 6:
1)主相合金按照 Nd29.0Fe余Co1.0B1.0(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速为1.8m/s,浇注温度为1420℃;铸片进行氢破碎,破碎的粉末氧含量控制≤400PPm; 1) The main phase alloy is smelted according to the ratio of Nd 29.0 Fe to Co 1.0 B 1.0 (wt%), using the rapid solidification technology to cast the sheet, the copper roll speed is 1.8m/s, and the pouring temperature is 1420°C; Broken, crushed powder oxygen content control ≤ 400PPm;
2)晶界富稀土相合金按照Dy20Tb30Co3.0Ga2.0Cu2.0Al4.0Fe余(wt%)配比进行配料熔炼,采用速凝技术铸片,铜辊转速1.3m/s,浇铸温度为1445℃;铸片氢破,氢破粉末在Ar保护环境中(O2≤10PPm)进行过筛,筛孔为40目,筛选出粒度≤380μm的富稀土相氢破粉末; 2) The grain boundary rare earth-rich phase alloy is smelted according to the proportion of Dy 20 Tb 30 Co 3.0 Ga 2.0 Cu 2.0 Al 4.0 Fe (wt%), using the rapid solidification technology to cast the sheet, the copper roll speed is 1.3m/s, and the casting temperature is The temperature is 1445°C; the cast hydrogen powder is sieved in an Ar protection environment (O 2 ≤10PPm), and the sieve opening is 40 mesh, and the rare earth-rich phase hydrogen powder with a particle size of ≤380 μm is screened;
3)将经氢破筛选的晶界富稀土相合金粉末在Ar气体保护下进行气流磨,控制磨室O2≤5PPm,粉末粒度3.5μm; 3) The grain boundary rare-earth-rich phase alloy powder screened by hydrogen blasting is jet milled under the protection of Ar gas, and the O 2 in the milling chamber is controlled to be ≤5PPm, and the particle size of the powder is 3.5μm;
4)将经气流磨后的晶界富稀土相合金粉末与主相合金氢破粉末混合(即将上述的1)和2)进行混合),富稀土相合金粉末添加比例为12wt%,主相合金为88wt%;混合后的合金粉末组成含量为:Nd25.52Dy2.40Tb3.60Co1.24Cu0.24Ga0.24Al0.48B0.88Fe余(wt%),在Ar气体气氛下将混合的合金粉末再进行气流磨,控制磨室氧含量≤10PPm,粉末粒度3.0μm; 4) Mix the grain boundary rare earth-rich phase alloy powder after jet milling with the main phase alloy hydrogen breaking powder (that is, mix the above 1) and 2), the addition ratio of the rare earth-rich phase alloy powder is 12wt%, and the main phase alloy 88wt%; the composition of the alloy powder after mixing is: Nd 25.52 Dy 2.40 Tb 3.60 Co 1.24 Cu 0.24 Ga 0.24 Al 0.48 B 0.88 Fe (wt%), the mixed alloy powder is jet milled under the Ar gas atmosphere , control the oxygen content in the mill room ≤ 10PPm, powder particle size 3.0μm;
5)将均匀混合后的粉末填入模具内加2.0T磁场取向压制成型,生坯真空封装后放入压力机中,加压220MPa,油冷等静压3min; 5) Fill the uniformly mixed powder into the mold and apply 2.0T magnetic field orientation to press molding. After the green body is vacuum-packaged, put it into the press, pressurize at 220MPa, and press oil-cooled isostatically for 3 minutes;
6)等静压后的坯料在≤4.0×10-2Pa的真空条件下进行烧结和时效,烧结温度为1045℃,烧结时间为3.5h;时效工艺:485℃×4h。时效结束制备得到烧结NdFeB磁体,磁体具有高剩磁和超高矫顽力,性能如下表6。磁体组织结构如图1所示,Dy的分布如图2,Tb的分布如图3所示。 6) The blank after isostatic pressing is sintered and aged under a vacuum condition of ≤4.0×10 -2 Pa, the sintering temperature is 1045°C, and the sintering time is 3.5h; aging process: 485°C×4h. After aging, a sintered NdFeB magnet was prepared. The magnet has high remanence and ultra-high coercive force, and its performance is shown in Table 6. The structure of the magnet is shown in Figure 1, the distribution of Dy is shown in Figure 2, and the distribution of Tb is shown in Figure 3.
比较例6Comparative example 6
1)采用常规制备方法,成分为Nd25.52Dy2.40Tb3.60Co1.24Cu0.24Ga0.24Al0.48B0.88Fe余(wt.%);采用常规速凝技术:铜辊转速1.2~1.5m/s,浇铸温度1440℃~1460℃;铸片氢破,氢破粉末O2≤800PPm,H2≤800PPm; 1) Using conventional preparation methods, the composition is Nd 25.52 Dy 2.40 Tb 3.60 Co 1.24 Cu 0.24 Ga 0.24 Al 0.48 B 0.88 Fe (wt.%); using conventional quick-setting technology: copper roller speed 1.2 ~ 1.5m/s, casting Temperature 1440℃~1460℃; cast sheet hydrogen broken, hydrogen broken powder O 2 ≤800PPm, H 2 ≤800PPm;
2)氢破粉末进行气流磨,控制细粉粒度3.0~3.5μm; 2) The hydrogen broken powder is jet milled to control the particle size of the fine powder to 3.0-3.5 μm;
3)将气流磨后的粉末装入模具,在2.0T的磁场中成型,成型生坯真空封装,封装后的坯料在200~250MPa进行油冷等静压1~3min; 3) Put the jet-milled powder into the mold, shape it in a 2.0T magnetic field, and vacuum-pack the formed green body. The packaged blank is oil-cooled and isostatically pressed at 200-250MPa for 1-3 minutes;
等静压坯料在≤4.0×10-2Pa真空条件下在烧结1045℃×3.5h;时效工艺,480℃×4h。时效结束后制备得到烧结NdFeB磁体。磁体性能见表6。 The isostatic pressing blank is sintered at 1045°C for 3.5h under the vacuum condition of ≤4.0×10 -2 Pa; the aging process is at 480°C for 4h. After aging, the sintered NdFeB magnet was prepared. The magnet properties are shown in Table 6.
表6 磁体性能对比表 Table 6 Magnet performance comparison table
从上述对比表中可以看出,采用相同的材料配方,通过本发明方法制得的钕铁硼磁体相比于普通方法制得的钕铁硼磁体,其剩磁提高了0.25kGs,矫顽力提高了2.5kOe。采用常规制备方法,由于Dy、Tb重稀土元素更多进入到主相中,因此,如通过添加重稀土来提高磁体矫顽力,则会牺牲剩磁;如果通过提高主相比例来提高剩磁,那矫顽力水平就要下降。所以,本实施例的配方,如果采用普通方法要制备矫顽力水平达到30.5kOe的磁体,则必须在配料中增加重稀土Dy或Tb的含量,而Dy或Tb的增加,则会导致剩磁下降,达不到12.85kGs的水平,无法制得既有高剩磁又有高矫顽力的磁体。采用本发明方法可制得同时具有高剩磁和高矫顽力的超高磁性能的磁体。 As can be seen from the above comparison table, using the same material formula, the NdFeB magnets prepared by the method of the present invention have a remanence of 0.25kGs and a coercive force of Increased by 2.5kOe. With the conventional preparation method, since Dy and Tb heavy rare earth elements enter into the main phase more, if the coercive force of the magnet is increased by adding heavy rare earth, the remanence will be sacrificed; if the remanence is increased by increasing the proportion of the main phase , the coercive force level will drop. Therefore, for the formulation of this example, if a magnet with a coercive force level of 30.5kOe is to be prepared by a common method, the content of heavy rare earth Dy or Tb must be increased in the ingredients, and the increase of Dy or Tb will lead to remanence Decrease, the level of 12.85kGs cannot be reached, and it is impossible to make a magnet with both high remanence and high coercive force. The method of the invention can be used to prepare a magnet with high remanence and high coercive force and ultra-high magnetic performance.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001006911A (en) * | 1999-06-21 | 2001-01-12 | Shin Etsu Chem Co Ltd | Manufacturing method of rare earth permanent magnet |
CN101325109A (en) * | 2008-04-08 | 2008-12-17 | 浙江大学 | High-strength and toughness sintered NdFeB magnet with grain boundary phase reconstruction and its preparation method |
CN103065787A (en) * | 2012-12-26 | 2013-04-24 | 宁波韵升股份有限公司 | Method for preparing sintered neodymium-iron-boron magnet |
CN103506626A (en) * | 2013-10-22 | 2014-01-15 | 宁波科田磁业有限公司 | Manufacturing method for improving sintered NdFeB magnet coercive force |
CN103827988A (en) * | 2011-09-30 | 2014-05-28 | 日东电工株式会社 | Permanent magnet and method for manufacturing permanent magnet |
CN103915232A (en) * | 2013-01-07 | 2014-07-09 | 昭和电工株式会社 | R-T-B rare earth sintered magnet, alloy for R-T-B rare earth sintered magnet, and method of manufacturing the same |
-
2014
- 2014-09-30 CN CN201410519324.6A patent/CN104269238B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001006911A (en) * | 1999-06-21 | 2001-01-12 | Shin Etsu Chem Co Ltd | Manufacturing method of rare earth permanent magnet |
CN101325109A (en) * | 2008-04-08 | 2008-12-17 | 浙江大学 | High-strength and toughness sintered NdFeB magnet with grain boundary phase reconstruction and its preparation method |
CN103827988A (en) * | 2011-09-30 | 2014-05-28 | 日东电工株式会社 | Permanent magnet and method for manufacturing permanent magnet |
CN103065787A (en) * | 2012-12-26 | 2013-04-24 | 宁波韵升股份有限公司 | Method for preparing sintered neodymium-iron-boron magnet |
CN103915232A (en) * | 2013-01-07 | 2014-07-09 | 昭和电工株式会社 | R-T-B rare earth sintered magnet, alloy for R-T-B rare earth sintered magnet, and method of manufacturing the same |
CN103506626A (en) * | 2013-10-22 | 2014-01-15 | 宁波科田磁业有限公司 | Manufacturing method for improving sintered NdFeB magnet coercive force |
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