JP7371108B2 - Rare earth diffusion magnet manufacturing method and rare earth diffusion magnet - Google Patents
Rare earth diffusion magnet manufacturing method and rare earth diffusion magnet Download PDFInfo
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Description
本発明は、希土類磁石の製造に関し、特に、希土類拡散磁石の製造方法と希土類拡散磁石に関する。 The present invention relates to the production of rare earth magnets, and particularly to a method for producing rare earth diffused magnets and a rare earth diffused magnet.
焼結ＮｄＦｅＢ磁石は優れた磁気特性を持ち、電子情報、自動車工業、医療機器、エネルギー交通等の多くの分野で広く使用されている。近年、風力発電、省エネ家電、新エネルギー自動車など、省エネや環境保護の分野で新たな用途がある。結晶粒界拡散の方法で、重希土類元素を磁石の結晶粒界と主相結晶粒のエッジ領域に拡散させる。これにより、残留磁気と磁気エネルギー積を著しく低下させずに、磁石の異方性磁場を増加させるという目的を達成できる。 Sintered NdFeB magnets have excellent magnetic properties and are widely used in many fields such as electronic information, automobile industry, medical equipment, energy transportation, etc. In recent years, new applications have emerged in the fields of energy conservation and environmental protection, such as wind power generation, energy-saving home appliances, and new energy vehicles. Using the grain boundary diffusion method, heavy rare earth elements are diffused into the grain boundaries and edge regions of the main phase grains of the magnet. Thereby, the objective of increasing the anisotropic magnetic field of the magnet can be achieved without significantly reducing the residual magnetism and magnetic energy product.
既存の希土類磁石の製造方法は、連続パス式マグネトロンスパッタリング装置を使用して、磁石の表面にＤｙ、Ｔｂなどの重希土類金属をスパッタリングし、スパッタリング層の厚さおよび均一性を効果的に制御し、結晶粒界拡散技術による磁石の迅速かつ連続的な作製を実現することができる。しかしながら、この方法は、スパッタリング中にＤｙ／Ｔｂターゲットを迅速に消費し、重希土類は高価であり、それは磁石の製造コストを増加させる。 The existing rare earth magnet manufacturing method uses a continuous pass magnetron sputtering device to sputter heavy rare earth metals such as Dy and Tb onto the surface of the magnet, effectively controlling the thickness and uniformity of the sputtered layer. , it is possible to realize rapid and continuous production of magnets using grain boundary diffusion technology. However, this method quickly consumes the Dy/Tb target during sputtering, and heavy rare earths are expensive, which increases the manufacturing cost of the magnet.
別の方法では、複合ターゲット材の化学気相成長により、結晶粒界拡散の希土類永久磁石材料を製造する。複合ターゲット材の堆積、中高温処理、および低温時効処理により、磁石の保磁力は明らかに改善され、残留磁気と磁気エネルギー積は基本的に減少しない。複合ターゲット材は磁石の性能を向上させることができるが、発明者は、複合ターゲットの拡散過程で磁石の内部に元々存在している軽希土類元素が濃度の差により表面に拡散し、磁石の表面に希土類リッチ層を形成していることを発見した。このような希土類リッチ層は酸化しやすく、磁石の耐食性を劣化させる。 Another method produces grain boundary diffused rare earth permanent magnet materials by chemical vapor deposition of composite target materials. Through the deposition of composite target material, medium-high temperature treatment, and low-temperature aging treatment, the coercive force of the magnet is obviously improved, and the residual magnetism and magnetic energy product are basically not reduced. Composite target materials can improve the performance of magnets, but the inventor believes that during the diffusion process of composite targets, the light rare earth elements that originally exist inside the magnets diffuse to the surface due to the difference in concentration, causing the surface of the magnet to It was discovered that a rare earth-rich layer was formed in the area. Such a rare earth rich layer is easily oxidized and deteriorates the corrosion resistance of the magnet.
上記の問題を解決するために、本発明は、希土類拡散磁石の製造方法と希土類拡散磁石を提供し、スパッタリングめっき層中のＲＬの含有量を制御し、得られた希土類拡散磁石は、高い総合磁気特性と優れた耐食性を有する。 In order to solve the above problems, the present invention provides a method for manufacturing a rare earth diffused magnet and a rare earth diffused magnet, controls the content of RL in the sputtering plating layer, and the obtained rare earth diffused magnet has a high overall It has magnetic properties and excellent corrosion resistance.
本発明の実施形態は以下のステップを含む、希土類拡散磁石の製造方法を提供する：
ステップＡ．第一ターゲット材を基材にスパッタリングし、前記基材の表面に第一めっき層を形成し、前記第一ターゲット材の組成は、質量パーセントでＲＨx－ＲＬｙ－Ｍｚである。ただし、ＲＨがＤｙ、Ｔｂ、またはＨｏの１つ以上であり、ＲＨはＤｙまたはＴｂの少なくとも１つを含み、ＲＬはＮｄ、Ｐｒ、Ｃｅ、Ｌａ、およびＹの１つ以上であり、ＲＬはＮｄまたはＰｒの少なくとも１つを含み、ＭはＣｏ、Ｃｕ、Ｇａ、Ａｇ、ＳｎまたはＡｌの少なくとも１つの元素であり、ｙは２２～２８ｗｔ％であり、ｚは０～２０ｗｔ％であり、ｘは（１００－ｙ－ｚ）ｗｔ％であり、前記基材は希土類磁石であるステップと、
ステップＢ．スパッタリングされた基材に拡散処理を行い、希土類拡散磁石を得るステップ。
Embodiments of the present invention provide a method of manufacturing a rare earth diffused magnet, including the following steps:
Step A. A first target material is sputtered onto a substrate to form a first plating layer on the surface of the substrate, and the composition of the first target material is RH x -RL y -M z in mass percent. However, RH is one or more of Dy, Tb, or Ho, RH includes at least one of Dy or Tb, RL is one or more of Nd, Pr, Ce, La, and Y, and RL is Contains at least one of Nd or Pr, M is at least one element of Co, Cu, Ga, Ag, Sn or Al, y is 22 to 28 wt%, z is 0 to 20 wt%, x is (100-yz)wt%, and the base material is a rare earth magnet;
Step B. A step of performing a diffusion treatment on the sputtered base material to obtain a rare earth diffused magnet.
好ましくは、前記希土類拡散磁石の製造方法において、ｙは２５～２８ｗｔ％であり、ｚは０～１２ｗｔ％である。 Preferably, in the method for manufacturing a rare earth diffused magnet, y is 25 to 28 wt%, and z is 0 to 12 wt%.
前記希土類拡散磁石の製造方法において、前記第一めっき層の厚さは２～２０μｍである。 In the method for manufacturing a rare earth diffused magnet, the first plating layer has a thickness of 2 to 20 μm.
前記希土類拡散磁石の製造方法の前記ステップＡでは、第一ターゲット材がスパッタリングされた後、第二ターゲット材をスパッタリングして、前記第一めっき層上に第二めっき層を形成し、前記第二ターゲット材の組成はＣｒ、Ｔｉ、Ｗ、Ｍｏ、Ｓｉ、Ａｌ２Ｏ３またはＺｒＯ２の少なくとも１つである。 In step A of the method for manufacturing a rare earth diffused magnet, after the first target material is sputtered, a second target material is sputtered to form a second plating layer on the first plating layer, and the second plating layer is formed on the first plating layer. The composition of the target material is at least one of Cr, Ti, W, Mo, Si, Al2O3 , or ZrO2 .
本発明の好ましい実態形態として、前記第二めっき層の厚さは０．１～６μｍである。 In a preferred embodiment of the present invention, the second plating layer has a thickness of 0.1 to 6 μm.
上記の希土類拡散磁石の製造方法では、前記ステップＡの前に、さらに前記基材の製造を含み、前記基材の製造は、原材料の溶解と急速な凝固によって合金フレークが作られること、前記合金フレークに対して水素破砕およびジェットミル処理を行い、合金粉末を得ること、前記合金粉末を磁場でプレスしてプレス成形体を得ること、前記プレス成形体を焼結炉に送って焼結させて焼結磁石を得ること、および前記焼結磁石をスライス加工して前記基材を得ることを含む。 The above method for manufacturing a rare earth diffused magnet further includes manufacturing the base material before the step A, and the manufacturing of the base material includes forming alloy flakes by melting and rapid solidification of raw materials, and forming the alloy flakes by melting and rapidly solidifying raw materials. The flakes are subjected to hydrogen crushing and jet mill treatment to obtain an alloy powder, the alloy powder is pressed in a magnetic field to obtain a press molded body, and the press molded body is sent to a sintering furnace to be sintered. The method includes obtaining a sintered magnet, and slicing the sintered magnet to obtain the base material.
上記の希土類拡散磁石の製造方法において、前記合金フレークの厚さは０．１５～０．５ｍｍである。 In the above method for manufacturing a rare earth diffused magnet, the thickness of the alloy flakes is 0.15 to 0.5 mm.
上記の希土類拡散磁石の製造方法では、前記基材の厚さは１～１０ｍｍである。 In the above method for producing a rare earth diffused magnet, the thickness of the base material is 1 to 10 mm.
上記の希土類拡散磁石の製造方法において、前記拡散処理は、一次熱処理：８００～１０００℃で２～１８時間の保温と、二次熱処理：４５０℃～６００℃で３～８時間の保温とを含む。 In the above method for producing a rare earth diffused magnet, the diffusion treatment includes primary heat treatment: keeping warm at 800 to 1000°C for 2 to 18 hours, and secondary heat treatment: keeping warm at 450 to 600°C for 3 to 8 hours. .
本発明はまた、前記希土類拡散磁石の製造方法で作成された希土類拡散磁石を提供する。 The present invention also provides a rare earth diffused magnet manufactured by the method for manufacturing a rare earth diffused magnet.
本発明の希土類拡散磁石の製造方法およびに希土類拡散磁石において、めっき層中のＲＬ元素の含有量は、基材中のＲＬ元素の含有量に近く、拡散する際に、重希土類元素が基材中に入るが、基材内のＲＬ元素は表面に濃化されないため、希土類拡散磁石の表面に希土類リッチ層は形成されず、希土類拡散磁石の耐食性が改善される。 In the rare earth diffused magnet manufacturing method and rare earth diffused magnet of the present invention, the content of the RL element in the plating layer is close to the content of the RL element in the base material, and when diffusing, the heavy rare earth element is transferred to the base material. However, since the RL elements in the base material are not concentrated on the surface, a rare earth rich layer is not formed on the surface of the rare earth diffused magnet, and the corrosion resistance of the rare earth diffused magnet is improved.
以下、本発明の実施形態およびその各利点をよりよく理解できるように、添付の図面および実施例と結合して本発明を実施するための形態をより詳細に説明する。しかしながら、以下に記載される特定の実施形態および実施例は本発明を説明するものにすぎず、本発明を限定するものではない。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to provide a better understanding of embodiments of the present invention and their respective advantages, modes for carrying out the present invention will now be described in more detail in conjunction with the accompanying drawings and examples. However, the specific embodiments and examples described below are merely illustrative of the invention and are not intended to limit the invention.
本発明で言及される「接続」は、他に明確に指定または限定されない限り、広い意味で理解されるべきであり、それは、直接接続されるか、または中間体を介して接続され得る。なお、本発明の説明において、「上」、「下」、「前」、「後」、「左」、「右」、「上端」、「下端」などによって示される方位または位置関係は、添付図面に基づいて示される方位または位置関係である。これは、参照されるデバイスまたは素子が特定の方位を有する必要があることや、特定の方位で構築および操作される必要があることを示したり暗示したりするのではなく、本発明を説明し、説明を単純化するための便宜に過ぎない。このため、これらの記載を本発明の限定として理解すべきではない。 The "connection" referred to in the present invention is to be understood in a broad sense, unless explicitly specified or limited otherwise, and it can be directly connected or connected via an intermediate. In the description of the present invention, directions or positional relationships indicated by "top", "bottom", "front", "rear", "left", "right", "upper end", "lower end", etc. This is the orientation or positional relationship shown based on the drawing. This is not intended to indicate or imply that the referenced devices or elements must have any particular orientation or be constructed or operated in any particular orientation, but rather are intended to illustrate the invention. , is merely a convenience to simplify the explanation. Therefore, these descriptions should not be construed as limitations on the invention.
図１に示すように、本発明の実施形態に係る希土類拡散磁石は、基材１上にスパッタリングしてめっき層を形成し、その後、スパッタリングされた基材に対して拡散処理を行うことにより得られる。前記の基材は希土類磁石である。スパッタリングする際に、基材は第一ターゲット材の下を通過して、基材の表面上に第一めっき層２１を形成する。必要に応じて、第一ターゲット材の後に第二ターゲット材を設けて、基材が第一ターゲット材を通過した後、第二ターゲット材をスパッタリングして、第一めっき層２１上に第二めっき層２２を形成してもよい。第二めっき層２２は、希土類拡散磁石の性能をさらに向上させることができる。基材の一つの表面のスパッタリングが完了した後、その後の熱拡散処理を行ってもよく、必要に応じて基材を裏返し、別の表面にスパッタリングした後に熱拡散処理を行ってもよい。一般に、基材のスパッタリングされる２つの表面は相互に反対側になり、スパッタリングされる表面は、基材の磁化方向に垂直な表面である。
As shown in FIG. 1, the rare earth diffused magnet according to the embodiment of the present invention can be obtained by forming a plating layer on a
本発明の実施形態における上記の希土類拡散磁石の製造方法は、基材の製造プロセスを含み得る。基材の製造は、
Ｓ１、基材の組成に応じて原材料を配合し、原材料の溶解と急速凝固によって合金フレークを作成し、好ましくは、合金フレークの厚さは、その後の処理を容易にするために０．１５～０．５ｍｍであるように制御されるステップ、
Ｓ２、合金フレークを水素破砕し、好ましくは、５４０℃で６時間脱水素を行い、脱水素後の水素含有量を１２００ｐｐｍにして、中程度に破砕した粉末を得て、中程度に破砕した粉末をジェットミルに入れて細粉を製造し、Ｄ５０＝４．０μｍの合金粉末を得るステップ、
Ｓ３、合金粉末を磁場内で、好ましくは磁場強度１．８Ｔでプレスして、プレス成形体を得るステップ、
Ｓ４、プレス成形体を焼結炉に入れて焼結し、好ましくは、焼結温度が１０００℃であり、保温時間が６ｈであり、焼結磁石を得るステップ、
Ｓ５、焼結磁石の表面を酸洗いして脱脂し、次にスライス加工して基材を得るステップを含む。
基材の厚みは１～１０ｍｍであることが好ましい。
The above method for manufacturing a rare earth diffused magnet in an embodiment of the present invention may include a process for manufacturing a base material. The production of the base material is
S1, blend the raw materials according to the composition of the base material, and create alloy flakes by melting and rapid solidification of the raw materials, preferably the thickness of the alloy flakes is 0.15 ~ 0.15 to facilitate subsequent processing. a step controlled to be 0.5 mm;
S2, hydrogen crush the alloy flakes, preferably perform dehydrogenation at 540 ° C. for 6 hours, and make the hydrogen content after dehydrogenation 1200 ppm to obtain a moderately crushed powder; into a jet mill to produce fine powder to obtain an alloy powder with D50=4.0 μm;
S3, pressing the alloy powder in a magnetic field, preferably at a magnetic field strength of 1.8T to obtain a pressed body;
S4, placing the press molded body in a sintering furnace and sintering it, preferably at a sintering temperature of 1000°C and a heat retention time of 6 hours to obtain a sintered magnet;
S5, including the step of pickling the surface of the sintered magnet to degrease it, and then slicing it to obtain a base material.
The thickness of the base material is preferably 1 to 10 mm.
基材が得られた後、基材に対して後続処理を実行して、希土類拡散磁石を得た。具体的なステップは次のとおりである。 After the substrate was obtained, subsequent processing was performed on the substrate to obtain a rare earth diffused magnet. The specific steps are as follows.
ステップＡ．基材に対してスパッタリングする。好ましくは、スパッタリング条件は次のとおりである。温度が１００～２００℃であり、単位面積当たりの堆積圧力はアルゴンガス条件で１～３０Ｐａとし、スパッタリングゾーンを通過する基材の速度が０．０１～１．０ｍ／ｓであり、スパッタリングのターゲット材と基材の上面との垂直距離は１０～２００ｍｍである。 Step A. Sputter onto the base material. Preferably, the sputtering conditions are as follows. The temperature is 100 to 200°C, the deposition pressure per unit area is 1 to 30 Pa under argon gas conditions, the speed of the substrate passing through the sputtering zone is 0.01 to 1.0 m/s, and the sputtering target is The vertical distance between the material and the top surface of the substrate is 10 to 200 mm.
基材は第一ターゲット材の下を通過し、第一ターゲット材のスパッタリングを実行して、第一めっき層が基材の表面に形成される。第一ターゲット材の組成は質量パーセントでＲＨx－ＲＬｙ－Ｍｚである。ただし、ＲＨがＤｙ、Ｔｂ、またはＨｏの１つ以上であり、ＲＨはＤｙまたはＴｂの少なくとも１つを含み、ＲＬはＮｄ、Ｐｒ、Ｃｅ、Ｌａ、およびＹの１つ以上であり、ＲＬはＮｄまたはＰｒの少なくとも１つを含み、ＭはＣｏ、Ｃｕ、Ｇａ、Ａｇ、ＳｎまたはＡｌの少なくとも１つの元素であり、ｙは２２～２８ｗｔ％であり、ｚは０～２０ｗｔ％であり、ｘは（１００－ｙ－ｚ）ｗｔ％であり、基材は希土類磁石である。この実施形態では、ｚは０であってもよい、すなわち、第一ターゲット材はＭを含まない。 The substrate passes under the first target material, and the first target material is sputtered to form a first plating layer on the surface of the substrate. The composition of the first target material is RH x -RL y -M z in mass percent. However, RH is one or more of Dy, Tb, or Ho, RH includes at least one of Dy or Tb, RL is one or more of Nd, Pr, Ce, La, and Y, and RL is Contains at least one of Nd or Pr, M is at least one element of Co, Cu, Ga, Ag, Sn or Al, y is 22 to 28 wt%, z is 0 to 20 wt%, x is (100-yz)wt%, and the base material is a rare earth magnet. In this embodiment, z may be 0, ie, the first target material does not contain M.
ステップＢ．スパッタリングされた基材に拡散処理を行い、希土類拡散磁石を得る。好ましくは、拡散処理は、一次熱処理：８００℃～１０００℃で２～１８時間の保温、二次熱処理：４５０℃～６００℃で３～８時間の保温を含む。 Step B. A diffusion treatment is performed on the sputtered base material to obtain a rare earth diffused magnet. Preferably, the diffusion treatment includes a primary heat treatment: incubation at 800°C to 1000°C for 2 to 18 hours, and a secondary heat treatment: incubation at 450°C to 600°C for 3 to 8 hours.
基材の表面に重希土類めっき層をスパッタリングした後、拡散源である重希土類めっき層について高温で拡散処理を行い、拡散源中の希土類を基材の結晶粒界相と主相へ拡散させる。拡散過程では、めっき層中のＲＨ元素が結晶粒界に沿って拡散し、主相中のＲＬ元素が置換され、主相の結晶粒の周りにコアシェル構造が形成される。主相の中でＲＬ元素が置換された後、主相の結晶粒界に拡散した。基材の表層の希土類と濃度勾配が形成されると、結晶粒界相の中のＲＬ元素が基材の表面へ拡散する。この実施形態では、拡散源中のＲＬ元素の含有量は、基材の内部のＲＬ元素に比較的近い。拡散する際に、拡散源中の重希土類は、基材の内部との濃度の差が依然として存在しているので、基材の内部に拡散し続ける。拡散源中のＲＬ元素の濃度と基材の内部の濃度との差が小さいため、基材内の軽希土類元素が表面に拡散して希土類リッチ層を形成する駆動力が抑制されたので、基材の表面に希土類リッチ層は形成されない。これにより、希土類拡散磁石の耐食性が向上する。ターゲット材に含まれるＲＬ元素の含有量が多すぎると、重希土類の濃度が低下して、最終的な磁石の固有保磁力Ｈｃｊの改善が十分ではない。また、ＲＬ元素の含有量が少なすぎると、基材内のＲＬ元素の表面濃化を抑制するのに十分ではない。ターゲット材は、少量のＣｕまたはＡｌまたはＣｏを含んでもよく、ＲＨ元素の金属原子の拡散をさらに加速し、それによって磁石の保磁力を増加させる。基材の組成に応じて、めっき層中のＲＬ元素の含有量は基材中ＲＬ元素の含有量よりも少ないように、めっき層の組成を適切に調整することができる。 After sputtering a heavy rare earth plating layer on the surface of the base material, a diffusion treatment is performed on the heavy rare earth plating layer, which is a diffusion source, at a high temperature, and the rare earth in the diffusion source is diffused into the grain boundary phase and main phase of the base material. In the diffusion process, the RH element in the plating layer diffuses along the grain boundaries, replaces the RL element in the main phase, and forms a core-shell structure around the crystal grains of the main phase. After the RL element was substituted in the main phase, it diffused into the grain boundaries of the main phase. When a concentration gradient is formed with the rare earth in the surface layer of the base material, the RL element in the grain boundary phase diffuses to the surface of the base material. In this embodiment, the content of RL elements in the diffusion source is relatively close to the RL elements inside the substrate. During diffusion, the heavy rare earths in the diffusion source continue to diffuse into the interior of the substrate because a concentration difference with the interior of the substrate still exists. Since the difference between the concentration of the RL element in the diffusion source and the concentration inside the base material was small, the driving force for the light rare earth elements in the base material to diffuse to the surface and form a rare earth rich layer was suppressed. No rare earth rich layer is formed on the surface of the material. This improves the corrosion resistance of the rare earth diffused magnet. If the content of the RL element contained in the target material is too large, the concentration of heavy rare earth elements will decrease, and the final specific coercive force Hcj of the magnet will not be sufficiently improved. Moreover, if the content of the RL element is too small, it will not be sufficient to suppress surface concentration of the RL element within the base material. The target material may contain a small amount of Cu or Al or Co, further accelerating the diffusion of the metal atoms of the RH element, thereby increasing the coercive force of the magnet. Depending on the composition of the base material, the composition of the plating layer can be appropriately adjusted so that the content of the RL element in the plating layer is less than the content of the RL element in the base material.
好ましくは、前記希土類拡散磁石の製造方法において、第一ターゲット材のｙは２５～２８ｗｔ％であり、ｚは０～１２ｗｔ％である。 Preferably, in the method for manufacturing a rare earth diffused magnet, y of the first target material is 25 to 28 wt%, and z is 0 to 12 wt%.
好ましくは、前記第一メッキ層の厚さは２～２０μｍである。第一めっき層の厚さが薄すぎると、固有保磁力Ｈｃｊの増加に影響を与えているが、第一めっき層の厚さが厚すぎると、ターゲット材が無駄になる。 Preferably, the first plating layer has a thickness of 2 to 20 μm. If the thickness of the first plating layer is too thin, this will affect the increase in the intrinsic coercive force Hcj, but if the thickness of the first plating layer is too thick, the target material will be wasted.
上記のステップＡにおいて、第一ターゲット材がスパッタリングされた後、基材に対して第二ターゲット材がスパッタリングされて、第一めっき層上に第二めっき層を形成する。第二ターゲット材の組成は、Ｃｒ、Ｔｉ、Ｗ、Ｍｏ、Ｓｉ、Ａｌ２Ｏ３またはＺｒＯ２の少なくとも１つである。 In step A above, after the first target material is sputtered, the second target material is sputtered onto the base material to form a second plating layer on the first plating layer. The composition of the second target material is at least one of Cr, Ti, W, Mo, Si, Al2O3 , or ZrO2 .
第二めっき層は、希土類拡散磁石の耐食性をさらに高めることができ、かつ第二めっき層の被覆により、第一めっき層における希土類元素は、拡散処理を行う際に、揮発による損失が少なくなり、それによって希土類拡散磁石の性能がさらに向上する。好ましい実施形態として、第二めっき層の厚さは０．１～６μｍである。 The second plating layer can further improve the corrosion resistance of the rare earth diffusion magnet, and due to the coating with the second plating layer, the loss of rare earth elements in the first plating layer due to volatilization is reduced during diffusion treatment. This further improves the performance of the rare earth diffused magnet. In a preferred embodiment, the thickness of the second plating layer is 0.1 to 6 μm.
（実施例１－１）
希土類拡散磁石の製造プロセスは以下のとおりである。
(Example 1-1)
The manufacturing process of the rare earth diffused magnet is as follows.
１．原材料の配合
基材Ｃ１および第一ターゲット材の組成質量比に従って、それぞれ原材料を配合する。
1. Mixing of raw materials Raw materials are mixed according to the composition mass ratio of the base material C1 and the first target material.
基材Ｃ１の組成はＮｄ２２．５Ｐｒ６．９Ｄｙ２．６Ｃｏ１．０Ｃｕ０．１Ｇａ０．１２Ａｌ０．３Ｂ０．９８Ｆｅｂａｌである。 The composition of the base material C1 is Nd 22.5 Pr 6.9 Dy 2.6 Co 1.0 Cu 0.1 Ga 0.12 Al 0.3 B 0.98 Fe bal .
第一ターゲット材の組成はＴｂ６８Ｎｄ２３Ｐｒ４Ａｌ５である。 The composition of the first target material is Tb 68 Nd 23 Pr 4 Al 5 .
２．溶解
基材Ｃ１の原材料は、溶解され、急速に凝固されて、合金フレークの薄いストリップになり、そのキャスト温度は１３８０℃であり、合金フレークの厚さは０．２～０．５ｍｍに制御される。
2. Melting The raw material of the substrate C1 is melted and rapidly solidified into thin strips of alloy flakes, the casting temperature of which is 1380 °C, and the thickness of the alloy flakes is controlled to be 0.2-0.5 mm. Ru.
第一ターゲット材の原材料を真空溶解炉に入れて真空溶解させる。溶解温度は１０５０℃、溶解時間は１５分、合金インゴットにキャストして、鍛造、熱間圧延、冷間圧延および機械的加工をした後、第一ターゲット材を形成する。 The raw material for the first target material is placed in a vacuum melting furnace and melted in vacuum. The melting temperature is 1050° C., the melting time is 15 minutes, and the alloy ingot is cast and subjected to forging, hot rolling, cold rolling and mechanical processing to form the first target material.
３．基材の作製
３１．基材Ｃ１の合金フレークを水素破砕し、５４０℃で６時間脱水素を行い、脱水素後の水素含有量を１２００ｐｐｍにして、合金を中程度に破砕した粉末を得る。中程度に破砕した粉末をジェットミルに入れて、細粉を製造し、Ｄ５０＝４．０μｍの合金粉末を得る。
3. Preparation of base material 31. The alloy flakes of the base material C1 are subjected to hydrogen crushing and dehydrogenation is performed at 540° C. for 6 hours, and the hydrogen content after dehydrogenation is set to 1200 ppm to obtain a powder in which the alloy is crushed to a medium degree. The medium crushed powder is put into a jet mill to produce fine powder, and an alloy powder with D50=4.0 μm is obtained.
３２．合金粉末は、磁場内で、好ましく１．８Ｔの磁場強度で、プレスされて、プレス成形体を得て、プレス成形体の密度は４．３ｇ／ｃｍ３である。 32. The alloy powder is pressed in a magnetic field, preferably at a field strength of 1.8 T, to obtain a pressed body, the density of which is 4.3 g/cm 3 .
３３．プレス成形体を焼結炉に入れて焼結し、焼結温度は１０００℃、保温時間は６ｈであり、焼結磁石を得る。焼結磁石の密度は７．５６ｇ／ｃｍ３である。 33. The press-formed body is placed in a sintering furnace and sintered at a sintering temperature of 1000° C. and a heat retention time of 6 hours to obtain a sintered magnet. The density of the sintered magnet is 7.56 g/ cm3 .
３４．焼結磁石の表面を酸洗いして油を除去し、次にスライス加工して３０×１７×５ｍｍの基材Ｃ１を得る。 34. The surface of the sintered magnet is pickled to remove oil, and then sliced to obtain a base material C1 of 30 x 17 x 5 mm.
４．基材に対してスパッタリングする
スパッタリングはメッキ室内で行われ、ターゲット材が第一ターゲット材であり、基材Ｃ１が第一ターゲット材の下を通過して、基材の表面に第一めっき層を形成する。第一めっき層の厚さは８μｍである。
4. Sputtering is performed on the base material Sputtering is performed in a plating chamber, the target material is the first target material, and the base material C1 passes under the first target material to form the first plating layer on the surface of the base material. Form. The thickness of the first plating layer is 8 μm.
５．スパッタリングされた後の基材Ｃ１に対して拡散処理を行い、このプロセスは８００℃で１８時間保温した後、焼戻し時効処理を５００℃で４時間行い、希土類拡散磁石を得る。 5. A diffusion treatment is performed on the sputtered base material C1, and after this process is kept at 800° C. for 18 hours, a tempering aging treatment is performed at 500° C. for 4 hours to obtain a rare earth diffused magnet.
希土類拡散磁石の磁気性能試験および耐食性試験を実施する。本実施例の希土類拡散磁石の性能を表１に示す。 Conduct magnetic performance tests and corrosion resistance tests on rare earth diffused magnets. Table 1 shows the performance of the rare earth diffused magnet of this example.
表１における基材サンプル１は、めっき層のスパッタリングと拡散処理を行っていない基材Ｃ１のサンプルであり、２段階の焼き戻し時効熱処理を経た後に製造されたものである。その中で、焼き戻しプロセスは次のとおりである。一次焼き戻しプロセスは９２０℃で２時間の保温であり、二次焼戻しプロセスは５００℃で４時間の保温である。
耐食性試験の条件：サンプルをＰＣＴエージングテストボックスに入れ、条件を２ａｔｍ、１２０℃、１００％ＲＨに９６時間設定し、耐食性試験を実施する。 Corrosion resistance test conditions: A sample is placed in a PCT aging test box, the conditions are set to 2 atm, 120°C, and 100% RH for 96 hours, and a corrosion resistance test is conducted.
減量率＝（サンプルの初期重量－ＰＣＴ実験後のサンプルの重量）／サンプルの表面積。 Weight loss rate=(initial weight of sample−weight of sample after PCT experiment)/surface area of sample.
（実施例１－２）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材はＴｂ７０Ｎｄ２５Ａｌ５であり、めっき層の厚さは８μｍである。
(Example 1-2)
This example is basically the same as Example 1 except that the sputtering target material is different, but the sputtering target material is Tb 70 Nd 25 Al 5 , and the thickness of the plating layer is 8 μm.
（実施例１－３）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材の組成はＴｂ７０Ｎｄ２５Ｇａ５であり、基材Ｃ１の表面でのそのスパッタリング厚さは８μｍである。
(Example 1-3)
It is basically the same as Example 1 except that the sputtering target material is different, but the composition of the sputtering target material is Tb 70 Nd 25 Ga 5 , and its sputtering thickness on the surface of the base material C1 is 8 μm.
（実施例１－４）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材の組成はＴｂ７０Ｎｄ２５Ｃｕ５であり、基材Ｃ１の表面でのそのスパッタリング厚さは８μｍである。
(Example 1-4)
It is basically the same as Example 1 except that the sputtering target material is different, but the composition of the sputtering target material is Tb 70 Nd 25 Cu 5 , and its sputtering thickness on the surface of the base material C1 is 8 μm.
（実施例１－５）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材の組成はＴｂ７０Ｎｄ２５Ａｇ５であり、基材Ｃ１の表面でのそのスパッタリング厚さは８μｍである。
(Example 1-5)
It is basically the same as Example 1 except that the sputtering target material is different, but the composition of the sputtering target material is Tb 70 Nd 25 Ag 5 , and its sputtering thickness on the surface of the base material C1 is 8 μm.
（実施例１－６）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材の組成はＴｂ７０Ｎｄ２２Ｃｅ３Ａｌ５であり、基材Ｃ１の表面でのそのスパッタリング厚さは８μｍである。
(Example 1-6)
It is basically the same as Example 1 except that the sputtering target material is different, but the composition of the sputtering target material is Tb 70 Nd 22 Ce 3 Al 5 , and its sputtering on the surface of the base material C1 The thickness is 8 μm.
（実施例１－７）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材の組成はＴｂ７０Ｎｄ２２Ｌａ３Ａｌ５であり、基材Ｃ１の表面でのそのスパッタリング厚さは８μｍである。
(Example 1-7)
It is basically the same as Example 1 except that the sputtering target material is different, but the composition of the sputtering target material is Tb 70 Nd 22 La 3 Al 5 , and its sputtering on the surface of the base material C1 The thickness is 8 μm.
（比較例１）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じである。スパッタリングのターゲット材は純金属Ｔｂターゲットであり、Ｔｂめっき層の厚さは８μｍである。
(Comparative example 1)
This example is basically the same as Example 1 except that the sputtering target material is different. The sputtering target material was a pure metal Tb target, and the thickness of the Tb plating layer was 8 μm.
（比較例２）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材の組成はＴｂ８０Ｎｄ１５Ａｌ５であり、基材Ｃ１の表面でのそのスパッタリング厚さは８μｍである。
(Comparative example 2)
It is basically the same as Example 1 except that the sputtering target material is different, but the composition of the sputtering target material is Tb 80 Nd 15 Al 5 , and its sputtering thickness on the surface of the base material C1 is 8 μm.
（比較例３）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例１と同じであるが、スパッタリングのターゲット材の組成はＴｂ５５Ｎｄ４０Ａｌ５であり、基材Ｃ１の表面でのそのスパッタリング厚さは８μｍである。
(Comparative example 3)
It is basically the same as Example 1 except that the sputtering target material is different, but the composition of the sputtering target material is Tb 55 Nd 40 Al 5 , and its sputtering thickness on the surface of the base material C1 is 8 μm.
表１において「Ｂｒ」とは残留磁気であり、「Ｈｃｊ」とは固有保磁力であり、（ＢＨ）ｍａｘとは最大磁気エネルギー積であり、「Ｈｋ／Ｈｃｊ」とは角型度である。 In Table 1, "Br" is residual magnetism, "Hcj" is intrinsic coercive force, (BH)max is maximum magnetic energy product, and "Hk/Hcj" is squareness.
比較からわかるように、実施例１－１から１－７、比較例１、比較例２、および比較例３で製造された希土類拡散磁石は、基材サンプル１と比較して、Ｈｃｊが大幅に増加され、Ｂｒがわずかに減少した。耐食性の試験結果によれば、実施例１－１から１－７の希土類拡散磁石の耐食性は、比較例１、比較例２、比較例３で作製した希土類拡散磁石の耐食性よりも高い。実施例１－１から実施例１－７の耐食性と、基材サンプル１の耐食性が近い。これからわかるように、実施例１－１から１－７の希土類拡散磁石には、スパッタリングおよび拡散処理が施されているものの、耐食性が低下していないのに対して、比較例１、２および３の希土類拡散磁石の耐食性は大幅に低下した。
As can be seen from the comparison, the rare earth diffused magnets manufactured in Examples 1-1 to 1-7, Comparative Example 1, Comparative Example 2, and Comparative Example 3 have significantly higher Hcj than
（実施例２）
基本的に実施例１のプロセスと同じであるが、次の点が異なる。
(Example 2)
The process is basically the same as that of Example 1, but differs in the following points.
この実施例の基材Ｃ２の組成はＮｄ３１Ｄｙ０．５Ｃｏ１．２Ｃｕ０．１６Ａｌ０．４Ｂ０．９８Ｆｅｂａｌである。 The composition of the base material C2 of this example is Nd 31 Dy 0.5 Co 1.2 Cu 0.16 Al 0.4 B 0.98 Fe bal .
第一ターゲット材の組成はＴｂ６５Ｐｒ２５Ａｌ１０である。 The composition of the first target material is Tb 65 Pr 25 Al 10 .
スパッタリングされた第一めっき層の厚さは６μｍである。 The thickness of the sputtered first plating layer is 6 μm.
スパッタリング後の拡散処理は、一次熱処理：１０００℃で２時間の保温、二次熱処理：６００℃で３時間の保温を含んだ。 The diffusion treatment after sputtering included primary heat treatment: keeping warm at 1000°C for 2 hours, and secondary heat treatment: keeping warm at 600°C for 3 hours.
実施例２の希土類拡散磁石の性能および耐食性試験の結果を表２に示す。 Table 2 shows the performance and corrosion resistance test results of the rare earth diffused magnet of Example 2.
表２における基材サンプル２は、めっき層のスパッタリングと拡散処理を行っていない基材Ｃ２のサンプルであり、２段階の焼き戻し時効熱処理を経た後に調製されたものである。この焼き戻しプロセスは次のとおりである。一次焼き戻しプロセスは１０００℃で２時間の保温であり、二次焼戻しプロセスは６００℃で３時間の保温である。 Base material sample 2 in Table 2 is a sample of base material C2 without sputtering and diffusion treatment of the plating layer, and was prepared after undergoing two-stage tempering and aging heat treatment. This tempering process is as follows. The primary tempering process is kept at 1000°C for 2 hours, and the secondary tempering process is kept at 600°C for 3 hours.
（実施例３）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例２と同じであるが、スパッタリングのターゲット材の組成はＤｙ６５Ｐｒ２５Ｓｎ１０であり、基材Ｃ２の表面でのそのスパッタリング厚さは６μｍである。
(Example 3)
It is basically the same as Example 2 except that the sputtering target material is different, but the composition of the sputtering target material is Dy 65 Pr 25 Sn 10 , and its sputtering thickness on the surface of the base material C2 is 6 μm.
（実施例４）
スパッタリングのターゲット材が異なることを除いて、基本的に実施例２と同じであるが、スパッタリングのターゲット材の組成はＤｙ３５Ｔｂ２５Ｐｒ２５Ｃｕ１５であり、基材Ｃ２の表面でのそのスパッタリング厚さは６μｍである。
(Example 4)
It is basically the same as Example 2 except that the sputtering target material is different, but the composition of the sputtering target material is Dy 35 Tb 25 Pr 25 Cu 15 , and its sputtering on the surface of the base material C2 The thickness is 6 μm.
（実施例５）
スパッタリングのターゲット材が異なることを除いて、実施例２と基本的に同じであり、スパッタリングのターゲット材の組成はＴｂ６０Ｈｏ８Ｐｒ２２Ａｌ１０であり、基材Ｃ２の表面でのそのスパッタリング厚さは６μｍである。
(Example 5)
It is basically the same as Example 2 except that the sputtering target material is different, and the composition of the sputtering target material is Tb 60 Ho 8 Pr 22 Al 10 , and its sputtering thickness on the surface of the base material C2 is The diameter is 6 μm.
（実施例６）
スパッタリングのターゲット材が異なることを除いて、実施例２と基本的に同じであり、スパッタリンのグターゲット材の組成はＴｂ６６Ｐｒ２０Ｙ２Ｃｏ１２であり、基材Ｃ２の表面でのそのスパッタリング厚さは６μｍである。
(Example 6)
It is basically the same as Example 2 except that the sputtering target material is different, and the composition of the sputtering target material is Tb 66 Pr 20 Y 2 Co 12 . The sputtering thickness is 6 μm.
（実施例７）
スパッタリングのターゲット材が異なることを除いて、実施例２と基本的に同じであり、スパッタリングのターゲット材の組成はＴｂ６３Ｐｒ２７Ａｌ１０であり、基材Ｃ２の表面でのそのスパッタリング厚さは６μｍである。
(Example 7)
It is basically the same as Example 2 except that the sputtering target material is different, and the composition of the sputtering target material is Tb 63 Pr 27 Al 10 , and its sputtering thickness on the surface of the base material C2 is It is 6 μm.
表２から、本発明の希土類拡散磁石は、基材と比較して耐食性がわずかに変化していたことが分かる。本発明のターゲット材でスパッタリングした後、作製された希土類拡散磁石の耐食性は大幅に改善されている。実際のニーズに応じて、第一めっき層の厚さを２μｍに減らすことができる。 From Table 2, it can be seen that the corrosion resistance of the rare earth diffused magnet of the present invention was slightly changed compared to the base material. After sputtering with the target material of the present invention, the corrosion resistance of the prepared rare earth diffused magnet is significantly improved. According to actual needs, the thickness of the first plating layer can be reduced to 2 μm.
（実施例８～１５）
基材Ｃ２を使用して、組成はＮｄ３１Ｄｙ０．５Ｃｏ１．２Ｃｕ０．１６Ａｌ０．４Ｂ０．９８Ｆｅｂａｌである。
(Examples 8 to 15)
Using base material C2, the composition is Nd 31 Dy 0.5 Co 1.2 Cu 0.16 Al 0.4 B 0.98 Fe bal .
基材Ｃ２の製造プロセスは、実施例１と同様である。第一ターゲット材および第二ターゲット材の製造プロセスは、実施例１における第一ターゲット材の製造プロセスと同じである。 The manufacturing process for the base material C2 is the same as in Example 1. The manufacturing process of the first target material and the second target material is the same as the manufacturing process of the first target material in Example 1.
基材Ｃ２に対してスパッタリングする時に、まず、第一ターゲット材のスパッタリングが行われ、基材Ｃ２の表面に第一めっき層が形成され、次に第二ターゲット材がスパッタリングされ、第二めっき層が第一めっき層の表面に形成される。第一めっき層と第二めっき層の厚さを表３に示す載されている。 When sputtering the base material C2, first, a first target material is sputtered to form a first plating layer on the surface of the base material C2, and then a second target material is sputtered to form a second plating layer. is formed on the surface of the first plating layer. The thicknesses of the first plating layer and the second plating layer are shown in Table 3.
スパッタリングされた後の基材Ｃ２は拡散処理される。拡散処理は一次熱処理：９２０℃で６時間の保温、二次熱処理：４５０℃で８時間の保温を含んだ。 The base material C2 after being sputtered is subjected to a diffusion treatment. The diffusion treatment included a primary heat treatment: incubation at 920°C for 6 hours, and a secondary heat treatment: incubation at 450°C for 8 hours.
実施例８～１５のめっき層の組成、磁気特性および耐食性の試験結果を表３に示す。 Table 3 shows the composition, magnetic properties, and corrosion resistance test results of the plating layers of Examples 8 to 15.
表３における基材サンプル３は、めっき層のスパッタリングと拡散処理を行っていない基材Ｃ２のサンプルであり、２段階の焼き戻し時効熱処理を経た後に製造されたものである。この焼き戻しプロセスは次のとおりである。一次焼き戻しプロセスは９２０℃で４時間の保温であり、二次焼戻しプロセスは４５０℃で８時間の保温である。 Base material sample 3 in Table 3 is a sample of base material C2 without sputtering and diffusion treatment of the plating layer, and was manufactured after undergoing two-stage tempering and aging heat treatment. This tempering process is as follows. The primary tempering process is kept at 920°C for 4 hours, and the secondary tempering process is kept at 450°C for 8 hours.
塩水噴霧試験：試験サンプルを塩水噴霧試験箱に入れて、連続噴霧環境での腐食を行った。噴霧溶液の液体は５％ＮａＣｌ溶液であり、ＰＨ＝７．１であり、温度２５℃で、２４時間ごとにサンプルに錆の斑点があるかどうかを観察する。 Salt spray test: The test sample was placed in a salt spray test box to undergo corrosion in a continuous spray environment. The liquid of the spray solution is a 5% NaCl solution, pH=7.1, and the temperature is 25° C. The samples are observed every 24 hours for rust spots.
高温高圧実験：試験サンプルを高温高圧実験ボックスに入れ、実験温度は１２０±３℃、蒸気圧は０．２０ＭＰａ、実験は２８８時間を行った後にサンプルを取り出し、超音波洗浄を使用して腐食生成物を除去し、腐食前後の重量差を記録する。最後に、減量をサンプルの表面積で割って、基材の減量パラメーターとして単位表面積あたりの減量を計算する。 High-temperature and high-pressure experiment: put the test sample into a high-temperature and high-pressure experiment box, the experiment temperature is 120 ± 3 ° C, the vapor pressure is 0.20 MPa, the experiment is carried out for 288 hours, and then the sample is taken out and ultrasonic cleaning is used to investigate the corrosion generation. Remove the object and record the difference in weight before and after corrosion. Finally, the weight loss per unit surface area is calculated as the substrate weight loss parameter by dividing the weight loss by the surface area of the sample.
第一めっき層のみがスパッタリングされた希土類拡散磁石と比較して、第二めっき層がスパッタリングされた後、希土類拡散磁石の耐塩水噴霧試験の時間数が増加し、減量試験の減量率が低下し、その耐食性はさらに改善される。同時に、第二めっき層がスパッタリングされた磁石は、第一めっき層のみがスパッタリングされた磁石よりも、Ｈｃｊがわずかに向上した。 Compared with the rare earth diffused magnet in which only the first plating layer was sputtered, the time of the salt water spray resistance test of the rare earth diffused magnet increased after the second plating layer was sputtered, and the weight loss rate in the weight loss test decreased. , its corrosion resistance is further improved. At the same time, the magnet with the second plating layer sputtered had slightly improved Hcj than the magnet with only the first plating layer sputtered.
なお、添付の図面を参照して記載された上記の様々な実施例は、本発明を説明するためのものに過ぎず、本発明の範囲を限定するものではない。当業者は、本発明の思想および範囲から逸脱することなく、本発明に対してなされた修正または同等の置換が、すべて本発明の範囲内に含まれるべきであると理解すべきである。さらに、文脈で別段の指示がない限り、単数形で表示される単語には複数形が含まれ、その逆も同様である。さらに、特に明記しない限り、任意の実施例の全部または一部を、他の任意の実施例の全部または一部と組み合わせて使用することができる。 The various embodiments described above with reference to the accompanying drawings are merely for explaining the present invention, and do not limit the scope of the present invention. Those skilled in the art should understand that all modifications or equivalent substitutions made to the present invention without departing from the spirit and scope of the invention are to be included within the scope of the invention. Further, unless the context dictates otherwise, words appearing in the singular include the plural and vice versa. Further, unless otherwise specified, all or a portion of any embodiment may be used in combination with all or a portion of any other embodiment.
Claims (9)
ステップＢ．スパッタリングされた基材に対して拡散処理を行い、希土類拡散磁石を得るステップとを
含むことを特徴とする希土類拡散磁石の製造方法。 Step A. A first target material is sputtered onto a base material to form a first plating layer on the surface of the base material, and the composition of the first target material is RH x -RL y -M z in mass percent, provided that: RH is one or more of Dy, Tb, or Ho, RH includes at least one of Dy or Tb, RL is one or more of Nd, Pr, Ce, La, and Y, and RL is Nd or M is at least one element of Co, Cu, Ga, Ag, Sn or Al, y is 25 to 28 wt%, z is 0 to 20 wt%, and x is ( 100-y-z) wt%, and the substrate is a sintered NdFeB magnet;
Step B. A method for manufacturing a rare earth diffused magnet, comprising the step of performing a diffusion treatment on a sputtered base material to obtain a rare earth diffused magnet.
原材料の溶解と急速な凝固により、合金フレークが作られること、
前記合金フレークに対して水素破砕およびジェットミル処理を行って、合金粉末を得ること、
前記合金粉末を磁場でプレスしてプレス成形体を得ること、
前記プレス成形体を焼結炉に入れて焼結し、焼結磁石を得ること、および
前記焼結磁石をスライス加工して、前記基材を得ることを含むことを特徴とする、請求項１に記載の希土類拡散磁石の製造方法。 Before said step A, the manufacturing of said substrate further comprises: producing alloy flakes by melting and rapid solidification of raw materials;
performing hydrogen crushing and jet milling on the alloy flakes to obtain alloy powder;
pressing the alloy powder in a magnetic field to obtain a press molded body;
Claim 1 characterized by comprising: placing the press molded body in a sintering furnace and sintering it to obtain a sintered magnet; and slicing the sintered magnet to obtain the base material. A method for manufacturing a rare earth diffused magnet described in .
一次熱処理：８００～１０００℃で２～１８時間の保温
二次熱処理：４５０～６００℃で３～８時間の保温 The method for manufacturing a rare earth diffused magnet according to claim 1, wherein the diffusion treatment includes the following primary heat treatment and secondary heat treatment.
Primary heat treatment: Insulation at 800-1000℃ for 2-18 hours Secondary heat treatment: Insulation at 450-600℃ for 3-8 hours
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| CN114783751A (en) * | 2022-03-31 | 2022-07-22 | 山西师范大学 | Grain boundary diffusion process of high-performance sintered neodymium-iron-boron magnet |
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| WO2020155113A1 (en) | 2020-08-06 |
| CN111524670A (en) | 2020-08-11 |
| JP2022516380A (en) | 2022-02-25 |
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