JPS63254703A - Manufacture of rare earth permanent magnet with excellent anti-oxidation - Google Patents
Manufacture of rare earth permanent magnet with excellent anti-oxidationInfo
- Publication number
- JPS63254703A JPS63254703A JP62087917A JP8791787A JPS63254703A JP S63254703 A JPS63254703 A JP S63254703A JP 62087917 A JP62087917 A JP 62087917A JP 8791787 A JP8791787 A JP 8791787A JP S63254703 A JPS63254703 A JP S63254703A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- rare earth
- alloy powder
- phase
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000002910 rare earth metals Chemical class 0.000 title claims description 8
- 230000003064 anti-oxidating effect Effects 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 60
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052745 lead Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical group 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract 4
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004663 powder metallurgy Methods 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 27
- 230000007797 corrosion Effects 0.000 abstract description 27
- 239000012071 phase Substances 0.000 abstract description 26
- 229910017086 Fe-M Inorganic materials 0.000 abstract description 18
- 239000006104 solid solution Substances 0.000 abstract description 14
- 239000007791 liquid phase Substances 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000002075 main ingredient Substances 0.000 abstract 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910017489 Cu I Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
- C22C1/0441—Alloys based on intermetallic compounds of the type rare earth - Co, Ni
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
- B22F9/008—Rapid solidification processing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はＮｄ２Ｆｅ１４Ｂ系磁石で代表される希土類（
Ｒ）と遷移金属ｅｒ）とＢとからなるＲ２Ｔ１４Ｂ系金
属間化合物磁石の中で、特にＲ−Ｆｅ−８を主成分とす
る永久磁石に係わシ、その耐酸化性及び磁石特性を改善
したＲ−Ｆｅ−Ｂ系磁石に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention uses rare earth (
Among R2T14B intermetallic compound magnets consisting of R), transition metal er), and B, the oxidation resistance and magnetic properties of permanent magnets, especially those whose main component is R-Fe-8, have been improved. This relates to an R-Fe-B magnet.
Ｎｄ−Ｆｅ−Ｂ系磁石で代表されるＲ−Ｆｅ−Ｂ系磁石
は、従来より普及しているＳｍ−Ｃｏ系合金永久磁石に
比べ。R-Fe-B magnets, typified by Nd-Fe-B magnets, are compared to Sm-Co alloy permanent magnets, which have been widely used in the past.
高い磁石を有するため、その用途が拡大しつつある。Due to its high magnetism, its applications are expanding.
しかしながら、 Ｒ−Ｆｅ−Ｂ系磁石合金はその金属組
織中に、大気中において極めて酸化し易いＲ−Ｆｅ固溶
体相を含有しているため、磁気回路等の装置に組込だ場
合に、Ｓｍ−Ｃｏ系磁石に比べ磁石の酸化による特性劣
化及びバラツキが大きく、また磁石より発生した酸化物
の飛散による周辺部品への汚染を引き起こすという欠点
を有する。However, since the R-Fe-B magnet alloy contains an R-Fe solid solution phase in its metal structure, which is extremely easily oxidized in the atmosphere, when it is incorporated into devices such as magnetic circuits, Sm- Compared to Co-based magnets, these magnets suffer from greater deterioration and variation in characteristics due to oxidation of the magnet, and also have the disadvantage of causing contamination of peripheral parts due to scattering of oxides generated from the magnet.
これら耐食性の改善に関する文献として、特開昭６０−
５４４０６号（Ｊ、Ｐ、Ａ）や特開昭６０−６３９０３
号等が挙げられる。これら文献では、磁石体表面にメッ
キ、化成皮膜等の耐酸化性皮膜を形成し、その耐食性向
上を図ることを目的としている。As a literature regarding improvement of these corrosion resistance, JP-A-60-
No. 54406 (J, P, A) and JP-A-60-63903
For example, the number etc. These documents aim to improve the corrosion resistance of the magnet by forming an oxidation-resistant film such as plating or chemical conversion film on the surface of the magnet.
しかし、これらの耐酸化性皮膜は、その工程中において
多量の水及び水溶液を使用するため、処理工程中に、磁
石のＲ−Ｆｅ固溶体相が酸化することにより、皮膜形成
後、内部より酸化が進行しふくれ又は皮膜の剥離等を生
じてしまうため、耐食性の改善としては適していない。However, since these oxidation-resistant coatings use large amounts of water and aqueous solutions during the process, the R-Fe solid solution phase of the magnet is oxidized during the treatment process, which causes oxidation to occur from within after the coating is formed. This progresses and causes blistering or peeling of the film, so it is not suitable for improving corrosion resistance.
また、水を使用しない方法として、エポキシ等の耐酸化
性樹脂コーティングまたは、最近、普及してきたスパッ
タ。In addition, methods that do not use water include oxidation-resistant resin coating such as epoxy, or sputtering, which has recently become popular.
蒸着、イオンシレーティング等の方法によるｋｌ、Ｎｉ
等の金属皮膜を形成させ、耐食性改善を図る乾式メッキ
等の方法もある。しかしながら、これら水を未使用のク
ーリング（ｃｏｏｌｉｎｇ）においても、長期使用によ
る皮膜の劣化、使用中又は製品検査および装置への紹み
込みなどの取扱い時に、微小なカケ等により磁石表面が
大気と接した場合、この部分より磁石組織中のＲ−Ｆｅ
固溶体が時間と共に著しく酸化し、磁石内部全体に広が
っていくため。Kl, Ni by methods such as vapor deposition and ion silating
There are also methods such as dry plating that form a metal film such as , etc. to improve corrosion resistance. However, even when unused water is used for cooling, the film may deteriorate due to long-term use, and the surface of the magnet may come into contact with the atmosphere due to minute chips, etc. during use or during handling such as product inspection or introduction into equipment. In this case, R-Fe in the magnet structure is removed from this part.
This is because the solid solution oxidizes significantly over time and spreads throughout the interior of the magnet.
耐食性改善の方策としては適していない。It is not suitable as a measure to improve corrosion resistance.
〔発明が解決しようとする問題点３
以上述べたように、いずれの従来の耐食性改善方法にお
いても、磁石中に極度に酸化し易いＲ−Ｆｅ固溶体が存
在するため上記した各方策が有する本来の耐食性を水系
磁石に付寄することは極めて困難であった。[Problem to be Solved by the Invention 3] As mentioned above, in any of the conventional methods for improving corrosion resistance, the inherent problems of each of the above-mentioned measures are It has been extremely difficult to impart corrosion resistance to water-based magnets.
すなわち９本系磁石においてはこのＲ−Ｆ ｅ固溶体相
の耐食性を根本的に改善しなければ、充分な耐食性を得
ることは不可能である。That is, in a nine-piece magnet, it is impossible to obtain sufficient corrosion resistance unless the corrosion resistance of this R-Fe solid solution phase is fundamentally improved.
この方策として１本系磁石合金にＮｉ ＋Ｃｕ 、ｓ＠
、ｐｂ等を添加する。ことにより２本系磁石合論の耐食
性を向上させ先に述べた各種耐食性皮膜を水系磁石にク
ーリング（ｃｏｏｌｉｎｇ）することにより上記欠点を
解決することも可能であるが、従来の方法では磁石合金
インゴット作製時に、これら元素を添加して溶解したイ
ンゴットを使用するため、 Ｒ−Ｆｅ固溶体のみならず
１本系磁石の磁性相であるＮｄ２Ｆｅ１４Ｂ相へも、こ
れら元素が一様に拡散してしまい磁石特性を著しく劣化
させてしまうため、対策としては適していない。As a measure for this purpose, Ni + Cu, s@
, pb, etc. Although it is possible to solve the above drawbacks by improving the corrosion resistance of the two-piece magnet and cooling the water-based magnet with the various corrosion-resistant coatings described above, the conventional method uses a magnet alloy ingot. Since an ingot with these elements added and melted is used during manufacturing, these elements diffuse uniformly not only into the R-Fe solid solution but also into the Nd2Fe14B phase, which is the magnetic phase of the single-piece magnet, resulting in poor magnetic properties. It is not suitable as a countermeasure as it significantly deteriorates the
そこで１本発明はこれらの問題点を解決するものであり
、 Ｒ−Ｆｅ−Ｍ 、 Ｒ−Ｆｅ −Ｍ−Ｂ （Ｍは
Ｃｏ、Ｎｉ ＋Ｃｕ＋Ｐｔｌ＋異
Ｓ−の一種以上）液体急冷合金粉末及び薄帯（アモルフ
ァス及び微結晶）より得られる合金粉末と。Therefore, the present invention solves these problems, and provides R-Fe-M, R-Fe-M-B (M is one or more of Co, Ni + Cu + Ptl + different S-) liquid quenched alloy powder and ribbon. (amorphous and microcrystalline) and alloy powder obtained from.
従来より製造されている主にＮｄ ２Ｆｅ １４Ｂ固固
相分相より成る＋ ｎｇｏ を粉末を混合、成形した圧
粉体を従来通シの方法で焼結することにより著しく耐食
性が向上し磁石特性の劣化の度合が、極めて小さい磁石
を得ることができるものである。By sintering conventionally produced green compacts, which are made by mixing powder of Nd 2Fe 14B solid-solid phase separated + ngo powder and molding it, the corrosion resistance is significantly improved and the magnetic properties are improved. It is possible to obtain a magnet with an extremely small degree of deterioration.
そこで２本発明によれば、 Ｒ，Ｆｅ、Ｂを主成分とす
るＲ２Ｔ１４Ｂ系合金磁石（ここで、ＲはＹを含む希土
類元素、Ｔは遷移金属を示す。）を粉末冶金法にて製造
する方法において、Ｒ２Ｔ１４Ｂ相結晶質合金粉末にＲ
−Ｆｅ−Ｍ又はＲ−Ｆｅ−Ｍ−Ｂ （ＭはＣｏ、ｈｌ
、Ｃｕ、Ｐｂ、Ｓ、ｐの一種以上）液体急冷合金粉末又
は薄帯（アモルファス及び微結晶）よ！ｌｌ得られる合
金粉末を５〜３０ ｖｏｔｓ含有する粉末成形体を焼結
することを特徴とする希土類永久磁石の製造方法が得ら
れる。Therefore, according to the present invention, an R2T14B alloy magnet containing R, Fe, and B as main components (here, R is a rare earth element containing Y, and T is a transition metal) is manufactured by a powder metallurgy method. In the method, R2T14B phase crystalline alloy powder is
-Fe-M or R-Fe-M-B (M is Co, hl
, Cu, Pb, S, p) liquid quenched alloy powder or ribbon (amorphous and microcrystalline)! A method for producing a rare earth permanent magnet is obtained, which is characterized by sintering a powder compact containing 5 to 30 vots of the obtained alloy powder.
尚、好ましくはＭ （Ｃｏ ＋Ｎｉ ｒ Ｃｕ ＋ Ｐ
ｂ ＋ Ｓｍ ）より一種を選択する場合は、 Ｃｏ
： １０〜５０ｗｔ％Ｎｉ、Ｃｕ：１０〜４０ ｗｔ％
Ｐｂ ： １０〜２５ ｗｔ％ｓ９ ： １０〜１５
ｗｔ％とする。In addition, preferably M (Co + Ni r Cu + P
When selecting one type from b + Sm), Co
: 10-50 wt% Ni, Cu: 10-40 wt%
Pb: 10-25 wt%s9: 10-15
Let it be wt%.
またＭ （Ｃｏ、Ｎｉ、Ｃｕ＋Ｐｂ＋Ｓｍ ）より二種
以上の元素を選択する場合は、これら元素の総含有量が
１０〜５５ ｗｔチとする。In addition, when selecting two or more elements from M (Co, Ni, Cu+Pb+Sm), the total content of these elements is set to 10 to 55 wt.
ここで本発明は。Here, the present invention.
１）焼結時に液相の核となり、また、液相の主成分とな
るＲ−Ｆｅ−Ｂ粉末のみにＮｉ＋Ｃｕ、Ｐｂ等の元素を
添加したＲ−Ｆｅ−Ｍ又はＲ−Ｆｅ−Ｍ−Ｂ （Ｍ＝
Ｃｏ 、Ｎｉ 、Ｃｕ 。1) R-Fe-M or R-Fe-M-B in which elements such as Ni+Cu and Pb are added only to R-Fe-B powder, which becomes the nucleus of the liquid phase during sintering and is the main component of the liquid phase. (M=
Co, Ni, Cu.
Ｐｂ ＋ Ｓｍの１種以上）を用いることにより、焼結
体中のＲ−Ｆｅ固溶体相を耐食性の向上したＲ−Ｆｅ−
Ｍ固溶体にさせる。また、更にメブキ、化成被膜等の持
つ本来の耐食性を水系磁石に付与する。(Pb + Sm), the R-Fe solid solution phase in the sintered body is transformed into R-Fe- with improved corrosion resistance.
M to form a solid solution. Furthermore, it imparts to the water-based magnet the inherent corrosion resistance that is inherent in coatings, chemical conversion coatings, and the like.
２）上記Ｒ−Ｆｅ−Ｍ又はＲ−Ｆｅ−Ｍ−Ｂ （Ｍ＝Ｃ
ｏ、Ｎｉ ＋Ｃｕ、Ｐｂ＋＋Ｊ （７）一種以上）を用
いることにより、焼結体の゛磁性相（Ｒ２Ｆｅ１４Ｂ相
）の界面付近のみにＣｕ ＋ Ｐ ｂ ｒ Ｎｌ ｙＳ
？を分布させ、磁性相のＢｒの低下を極力弁えるの２点
を目的としている。2) The above R-Fe-M or R-Fe-M-B (M=C
By using Ni+Cu, Pb++J (7) or more, Cu+PbrNlyS is formed only near the interface of the magnetic phase (R2Fe14B phase) of the sintered body.
? The two objectives are to distribute Br in the magnetic phase and to minimize the reduction in Br in the magnetic phase.
すなわち１本発明によれば、焼結時に液相の核となり、
液相の主成分となる粉末にＲ−Ｆｅ−Ｂよりも耐食性の
向上したＲ−Ｆｅ−Ｍ、Ｒ−Ｆｅ −Ｍ−Ｂ （Ｍ＝＝
Ｃｏ＋Ｎ１ｔＣｕ、Ｐｂ、Ｓ？の一種以上）粉末を用い
ているだめ焼結後得られた焼結体組織中のＲ−Ｆｅ固溶
体は、Ｒ−（Ｆｅ−Ｍ）固溶体となっており、耐食性が
向上しているだめに１本発明の目的の第一項が達成され
る。That is, according to the present invention, the liquid phase becomes the core during sintering,
The main component of the liquid phase is R-Fe-M, R-Fe-M-B (M==
Co+N1tCu, Pb, S? The R-Fe solid solution in the structure of the sintered body obtained after sintering using powder (one or more types of powder) becomes an R-(Fe-M) solid solution, and the corrosion resistance is improved. The first object of the invention is achieved.
又、焼結時に液相の核となシ、液相の主成分となる粉末
のみにＣＯ＋ Ｎｌ ＊ Ｃｕ等を添加しておシ、焼結
時に主に固相となる粉末には、これら元素を添加してい
ないため２両粉末を混合、成形した圧粉体を焼結するこ
とにより、哲られた焼結体の金属組織において、磁性相
（Ｒ２Ｆｅ１４Ｂ相）の界面付近及びＲ−Ｆｅ固溶体相
のみに、 Ｃｕ、Ｎｉ、Ｐｂ、Ｓｌ１等のＢｒを低下せ
しめる元素を濃縮させることが可能となる。In addition, CO + Nl * Cu, etc. are added only to the powder that becomes the nucleus of the liquid phase and the main component of the liquid phase during sintering, and these elements are added to the powder that becomes the main component of the liquid phase during sintering. By mixing the two powders and sintering the molded green compact, the metallographic structure of the sintered compact is formed near the interface of the magnetic phase (R2Fe14B phase) and the R-Fe solid solution phase. This makes it possible to concentrate elements that reduce Br, such as Cu, Ni, Pb, and Sl1.
すなわち、 Ｒ２Ｆｅ１４Ｂ相の持つ高い飽和磁化の低
減を極力弁えた焼結体組織が得られるため本発明の目的
の第２項が達成される。That is, a sintered body structure is obtained in which the high saturation magnetization of the R2Fe14B phase is reduced as much as possible, so that the second object of the present invention is achieved.
本発明において、焼結時液相の核となシ、生成分となる
Ｒ−Ｆｅ−Ｍ 、 Ｒ−Ｆｅ −Ｍ−Ｂ （Ｍ ＝ Ｃ
ｏ 、Ｎｉ 、Ｃｕ 、Ｐｂ 。In the present invention, R-Fe-M, R-Fe-M-B (M = C
o, Ni, Cu, Pb.
ＳＰの一種以上）粉末を、液体急冷合金粉末又は。one or more types of SP) powder, liquid quenched alloy powder or
薄帯（アモルファス及び微結晶）より得られる合金粉末
としたのは＋ Ｒ−Ｆ ｅ −Ｍ ＋ Ｒ−Ｆ ｅ−Ｍ
−Ｂインゴットは被粉砕性に劣るため、粉砕した粉末の
粒度分布が広くなったり、焼結時に、液相の核となるＲ
−Ｆｅ−Ｍ固溶体相粉末と固相であるＲ２Ｆｅ１４Ｂ相
粉末との均一混合ができないため、焼結体組織が不均一
となり磁石特性の劣化をもたらすため本発明の目的の第
２項の効果を低減させてしまう。The alloy powder obtained from the ribbon (amorphous and microcrystalline) is + R-Fe-M + R-Fe-M
- Since the B ingot has poor crushability, the particle size distribution of the crushed powder becomes wide, and during sintering, R becomes the core of the liquid phase.
-Since the Fe-M solid solution phase powder and the solid R2Fe14B phase powder cannot be mixed uniformly, the structure of the sintered body becomes non-uniform, resulting in deterioration of magnetic properties, which reduces the effect of the second objective of the present invention. I'll let you.
それ故＋ Ｒ−Ｆ ｅ −Ｍ ＋ Ｒ−Ｆ ｅ −Ｍ−
Ｂ粉末は、被粉砕性の高い液体急冷合金粉末、又は薄帯
（アモルファス及び微結晶）より得られる合金粉末とす
る必要がある。Therefore + R-F e -M + R-F e -M-
Powder B needs to be a liquid quenched alloy powder with high pulverizability, or an alloy powder obtained from a ribbon (amorphous or microcrystalline).
本発明において、液体急冷合金粉末又は薄帯（アモルフ
ァス及び微結晶）より成るＲ−Ｆｅ−Ｍ又はＲ−Ｆｅ−
Ｍ−Ｂ粉末のＭ （Ｃｏ、Ｎｉ 、Ｃｕ１４’、Ｐｂ
）値を１０ｗｔ％以上としたのは、これよりも低いＭ値
では。In the present invention, R-Fe-M or R-Fe-
M-B powder M (Co, Ni, Cu14', Pb
) value was set to 10 wt% or more for M values lower than this.
本発明の特徴とするＲ−Ｆｅ固溶体相の耐食性向上が不
充分であるためである。又Ｃｏ≦５０ ｗｔ％ ＋ Ｎ
ｔ ＋ Ｃｕ≦４０ ｗｔ％、ｐｂ≦２５ ｗｔ％ 、
ｓ、９≦１５ｗｔ％及びこれら元素の複合添加におい
てその上限を５５ ｗｔ％としたのは、これよりも多い
Ｍ値では、磁性結晶粒内に存在するＣｕ、Ｐｂ１４値が
多くなり過ぎたり、また。This is because the improvement in corrosion resistance of the R-Fe solid solution phase, which is a feature of the present invention, is insufficient. Also, Co≦50 wt% + N
t + Cu≦40 wt%, pb≦25 wt%,
The reason why we set the upper limit to 55 wt% for s, 9≦15 wt% and composite addition of these elements is because if the M value is higher than this, the Cu and Pb14 values present in the magnetic crystal grains may become too large, or .
Ｎｉ、Ｃｏにおいては焼結体内に磁石のＩＨＣを劣化さ
せるラーフェス（Ｌａｖｅｓ）相の量が多くなり過ぎる
ことによる磁石特性の劣化を生ずるためである。又。This is because in the case of Ni and Co, the amount of Laves phase which deteriorates the IHC of the magnet becomes too large in the sintered body, resulting in deterioration of the magnetic properties. or.
これら液体急冷合金粉末及び薄帯（アモルファス及び微
結晶）より成る粉末の添加量を１０〜３゜ｖｏｊ％とじ
たのは１０ ｖｏｔ％より少ない領域では耐食性向上が
得られず、 ３０ ｖｏＬ％を越えた領域で肚記同様磁
石特性の劣化が著しく本発明の目的にそわないだめであ
る。The addition amount of these powders consisting of liquid quenched alloy powder and ribbon (amorphous and microcrystalline) was limited to 10 to 3° voj%, because corrosion resistance cannot be improved if it is less than 10 voj%, and if it exceeds 30 voj%. In the above range, as in the case of Wuji, the magnetic properties deteriorate significantly, which is unsuitable for the purpose of the present invention.
本発明によれば、従来法で得られるインゴットを粉砕し
て得られたＲ２Ｆｅ１４Ｂ相を主相とし焼結時に主に固
相となる粉末に焼結時主に液相となるＲ−Ｆｅ−Ｍ又は
Ｒ−Ｆｅ−Ｍ−Ｂ （Ｍ＝ Ｃｏ 、Ｎｉ 、Ｃｕ 、
Ｐｂ 、 Ｓｆの一種以上）原料粉末を液体急冷合金粉
末又は薄帯（アモルファス及び微結晶）より得た後、こ
れら粉末を混合・成形した圧粉体を従来と同様の方法で
焼結することにより、従来よりも耐食性に優れた。しか
も、磁石特性の優れた焼結体が得られ実用上非常に有益
である。According to the present invention, the R2Fe14B phase obtained by crushing an ingot obtained by the conventional method is the main phase, and the R-Fe-M powder becomes mainly a solid phase during sintering. or R-Fe-M-B (M=Co, Ni, Cu,
After obtaining the raw material powder from liquid quenched alloy powder or ribbon (amorphous and microcrystalline) (Pb, Sf), by mixing and molding these powders and sintering the green compact in the same manner as before. , superior corrosion resistance than conventional products. Moreover, a sintered body with excellent magnetic properties can be obtained, which is very useful in practice.
〈実施例−１〉
純度９９ ｗｔ％以上のＮｄ−Ｆｅ−Ｂを用いアルゴン
雰囲気中にて高周波加熱により２６．７ Ｎｄ−１，Ｏ
Ｂ−Ｆｅｂａｌ（、ｔ％）の組成を有するＲ２Ｆｅ１４
Ｂ相ｉｎｇｏｔを得てさらにディスクミルを用いて、粗
粉砕した。そしてこの粉末をＩ材とした。<Example-1> Nd-Fe-B with a purity of 99 wt% or more was heated to 26.7 Nd-1,O by high-frequency heating in an argon atmosphere.
R2Fe14 with the composition of B-Febal (, t%)
A phase B ingot was obtained and further coarsely ground using a disc mill. This powder was used as material I.
次に上記同等のＮｄ ｒ Ｆ ｅ ＋ Ｂ ｒ Ｎｒ
＋ Ｃｕ Ｉ Ｃｏ １４ ） Ｐ ｂを用いて、 ６
ＯＮｄ−１，ＯＢ−１０Ｃｏ 、 ５５Ｎｄ−１，０Ｂ
−２９Ｃｏ 。Next, the above equivalent Nd r Fe + B r Nr
+ Cu I Co 14 ) P b using 6
ONd-1, OB-10Co, 55Nd-1, 0B
-29Co.
５ＯＮｄ−１，０Ｂ−４０Ｃｏ１４３Ｎｄ−１，０Ｂ−
５０Ｃｏ、６ＯＮｄ−１，０Ｂ−１ＯＮｉ 、 ５７Ｎ
ｄ−１，０Ｂ−１８Ｎｉ 、 ５ＯＮｄ−１，ＯＢ−４
ＯＮｉ 、６ＯＮｄ−１，０Ｂ−１０Ｃｕ 、６ＯＮｄ
−１，ＯＢ−２１Ｃｕ １４５Ｎｄ１．０Ｂ−３９Ｃｕ
、６ＯＮｄ−１，０Ｂ−１０Ｐｂ、６ＯＮｄ−１，０
Ｂｙ１７Ｐｂ、６ＯＮｄ−１，０Ｂ−２５Ｐｂ 、 ６
ＯＮｄ−１，０Ｂ−１０８整、６ＯＮ入−１，０Ｂ−１
５８ｐ、（いずれもｗｔ％ ＋ Ｆ ｅはｂａｌａｎｃ
ｅ ）の組成を有する１５種類のアモルファスリデン細
片を単ロール法にて得だ。そしてこれらアモルファスリ
、ｙン細片を粗粉砕して得られた１５種類の粗粉末を■
材とした。そして、この１５種類の■材に対して■材を
おのおの加え３０ Ｎｄ−１，ＯＢ−（Ｆｅ−Ｍ） ｂ
ａｌ（Ｍ” Ｎｒ ＋ Ｃｏ ＋ Ｃｕ ＋ Ｓ９ ＋
Ｐｂ ）の秤量組成を有する１５種類の粗粉末を得た
。これら１５種の粗粉末をが一ルミルを用いて平均粒径
３〜５μｍに微粉砕した。5ONd-1,0B-40Co143Nd-1,0B-
50Co, 6ONd-1, 0B-1ONi, 57N
d-1,0B-18Ni, 5ONd-1,OB-4
ONi, 6ONd-1, 0B-10Cu, 6ONd
-1, OB-21Cu 145Nd1.0B-39Cu
, 6ONd-1,0B-10Pb, 6ONd-1,0
By17Pb, 6ONd-1,0B-25Pb, 6
ONd-1,0B-108 set, 6ON included-1,0B-1
58p, (both wt% + Fe is balanc
Fifteen types of amorphous elidene strips having the composition shown in e) were obtained by a single roll method. Then, 15 types of coarse powder obtained by coarsely crushing these amorphous pieces were
It was used as a material. Then, to each of these 15 types of ■materials, we added ■materials to 30 Nd-1, OB-(Fe-M) b
al(M” Nr + Co + Cu + S9 +
Fifteen kinds of coarse powders with a weighed composition of Pb) were obtained. These 15 kinds of coarse powders were pulverized to an average particle size of 3 to 5 μm using a lumen mill.
次に得られた微粉末を２０ ｋｏｅの磁場中、１．０ｔ
ｏｎ／ｃｍ”の圧力で成形し圧粉体を得た。これら圧粉
体を１０００〜１２００℃でＯ〜２ｈｒＡｒ中焼結した
。Next, the obtained fine powder was heated at 1.0 t in a 20 koe magnetic field.
A green compact was obtained by compacting at a pressure of 1000 to 1200° C. in Ar for 0 to 2 hours.
その後１４００〜８００℃で０．５〜１０ ｈｒ加熱し
た後急冷した。又比較材として３０Ｎｄ−１，ＯＢ −
Ｆｅｂａｌ（ｗｔ％）の組成を有するインゴットを上記
と同様にして得た。その後上記と同様粗粉砕、微粉砕磁
場中成形。Thereafter, it was heated at 1400 to 800°C for 0.5 to 10 hr, and then rapidly cooled. Also, as a comparison material, 30Nd-1, OB −
An ingot having a composition of Febal (wt%) was obtained in the same manner as above. After that, it is coarsely crushed and finely crushed and formed in a magnetic field as above.
焼結、熱処理を行い焼結体を得た。そしてこれら焼結体
を１０ｗ＊Ｘ １０ｗＸ ８ｍに加工した後、 Ｃｕ下
皿メッキとした電解Ｎｉメッキ及びフロメート処理を施
こした。そしてこれらの膜厚を測定したところ３〜２０
μｍであったこれら試験片の磁石特性及び６０℃×９０
チ湿度試験を３００ ｈｒ施こし耐食性試験を行った結
果を第−表に示す。Sintering and heat treatment were performed to obtain a sintered body. After processing these sintered bodies into a size of 10w*×10w×8m, electrolytic Ni plating with Cu under plate plating and furomate treatment were performed. The thickness of these films was measured and was 3 to 20.
The magnetic properties of these test pieces and 60℃×90
A humidity test was conducted for 300 hours and a corrosion resistance test was conducted, and the results are shown in Table 1.
第−表より本発明による試験片はいずれも比較例の試験
片に比べ耐食性を示し、又磁石特性の面でも永久磁石と
して優れた磁石特性を示すことがわかる。From Table 1, it can be seen that all the test pieces according to the present invention exhibit better corrosion resistance than the test pieces of the comparative examples, and also exhibit excellent magnetic properties as permanent magnets in terms of magnetic properties.
以下余日
〈実施例−２〉
実施例−１と同等の純度のＮｄ −Ｆｅ−Ｂ−Ｎｉ −
Ｃｏ −Ｃｕ−Ｐｂ−８ｒｙｐを用いて６ＯＮｄ−１，
０Ｂ−２０Ｃｏ−１０Ｃｕ 。The remaining days <Example-2> Nd-Fe-B-Ni- with the same purity as Example-1
6ONd-1 using Co-Cu-Pb-8ryp,
0B-20Co-10Cu.
４ＯＮｄ−１，０Ｂ−５０Ｃｏ−５ＳｖＰ、６ＯＮｄ−
１，０Ｂ−５ＳＰ５Ｐｂ。4ONd-1, 0B-50Co-5SvP, 6ONd-
1,0B-5SP5Pb.
５ＯＮｄ１．０Ｂ−２０Ｃｕ−１０Ｐｂ 、 ５ＯＮｄ
−１，０Ｂ−１０Ｃｕ−１，０Ｂ−１０Ｃｏ−５８＠−
６Ｃｕ 、５ＯＮｄ−１，０Ｂ−１５Ｎｉ−６Ｃｕ −
３Ｐｂ （いずれもＦｅ−ｂａｌ 、ｗｔチ）の組成を
有するアモルファスＩＪ 、ｙン細片をＡｒ中中口ロー
ル法て得た。そしてこれらアモルファスリボン細片を粗
粉砕し得られた粗粉末を■材とした。次にこれら１０種
類の■材おのおのに実施例−１で得られたＩ材のｉ ｎ
ｇｏ を粉末を加え３ ＯＮｄ −１，ＯＢ −（Ｆｅ
−Ｍ）ｂａｔ （Ｍ＝ Ｃｏ 。5ONd1.0B-20Cu-10Pb, 5ONd
-1,0B-10Cu-1,0B-10Co-58@-
6Cu, 5ONd-1,0B-15Ni-6Cu −
An amorphous IJ, Yin strip having a composition of 3Pb (both Fe-bal and wt) was obtained using an Ar medium roll method. Then, these amorphous ribbon pieces were coarsely pulverized, and the resulting coarse powder was used as material (2). Next, for each of these 10 types of material I, in
3 ONd −1,OB −(Fe
-M) bat (M=Co.
ｌル
Ｎｉ 、Ｃｕ １４．Ｐｂの一種以上）ｗｔ％の組成を
有する１０゜種類の粗粉末を得た。さらにこれら１０種
類の粗粉末を実施例−１と同様にして微粉砕、磁場中′
成形、焼結、熱処理、加工を耐食性メッキ及び化成処理
を行い試験片（１０ＸＩ ＯＸ８ ）を得た。次にこれ
ら試験片に実施例１と同様６０℃×９０チ極温恒湿試験
を行った。第２表にこれら試験片の磁石特性及び恒温恒
湿試験結果実施例−１の比較材の結果を示す。l Ni, Cu 14. 10° types of coarse powders having a composition of (at least one type of Pb) wt% were obtained. Furthermore, these 10 kinds of coarse powders were finely pulverized in the same manner as in Example-1, and then placed in a magnetic field.
A test piece (10XI OX8) was obtained by molding, sintering, heat treatment, and processing, followed by corrosion-resistant plating and chemical conversion treatment. Next, these test pieces were subjected to an extreme temperature and humidity test at 60° C. x 90 times in the same manner as in Example 1. Table 2 shows the magnetic properties of these test pieces and the constant temperature and humidity test results for the comparative material of Example-1.
第２表より本発明による磁石試験片は、いずれも比較材
に比べ耐食性に優れ、又磁石特性の面でも永久磁石とし
て優れた磁石特性を示している。Table 2 shows that all of the magnet test pieces according to the present invention have superior corrosion resistance compared to comparative materials, and exhibit excellent magnetic properties as permanent magnets in terms of magnetic properties.
以下余日
〈実施例−３〉
実施例−１で得られた焼結体のうち、６０Ｎｄ−１，Ｏ
Ｂ −２１Ｃｕ−Ｆｅｂａｌ 、 ６ＯＮｄ−１，０Ｂ
−１７Ｐｂ−Ｆｅｂａｌ （ｗｔ４）及び実施例２で得
られた焼結体のうち６ＯＮｄ −１，ＯＢ −１０Ｃｕ
−２ＯＮｉ−Ｆｅｂａｌ、６ＯＮｄ−１，０Ｂ−１０Ｃ
ｏ−５８＄−６Ｃｕ７Ｆｅｂａｌ （ｗｔ％）を加えて
得られた焼結体について。The remaining days will be discussed below.Example-3 Among the sintered bodies obtained in Example-1, 60Nd-1,O
B-21Cu-Febal, 6ONd-1,0B
-17Pb-Febal (wt4) and 6ONd -1, OB -10Cu of the sintered bodies obtained in Example 2
-2ONi-Febal, 6ONd-1,0B-10C
Regarding the sintered body obtained by adding o-58$-6Cu7Febal (wt%).
Ｅ、Ｄ、Ｘを用いて各元素の濃度分布を調査するためＮ
ｄ ２Ｆ ｅ １４Ｂ相界面付近より粒子内へ２μｍ間
隔にてスポット分析を行った。その結果をおのおの第３
表〜第６表に示す。N to investigate the concentration distribution of each element using E, D, and
Spot analysis was performed at 2 μm intervals into the particles from near the d 2F e 14B phase interface. The results are shown in the third column.
Shown in Tables to Table 6.
第３′”〜第６表よ’） Ｃｏ ｒ Ｃｕ ＋ Ｎｌ
ｒ Ｐ ｂ ｐ ＳＲの元素がＮｄ２Ｆｅ１４Ｂ粒子界
面付近に濃縮していることがわかる。3'''~Table 6') Cor Cu + Nl
It can be seen that the r P b p SR element is concentrated near the Nd2Fe14B particle interface.
以下ｆ−日
第３表 ６ＯＮｄ−１，０Ｂ−２１Ｃｕ−Ｆｅｂａ １
第４表 ６ＯＮｄ−１，０Ｂ−１７，０Ｐｂ−Ｆｅｂａ
ｌ第５表 ６ＯＮｄ−１，０Ｂ−１０Ｃｕ−２ＯＮｉ−
Ｆｅｂａｌ第６表 ６ＯＮｄ−１，ＯＢ−１０１０Ｃｏ
−５４−６Ｃｕ−Ｆｅｂａｌ（％）
ここで２表を簡単に説明する。Below is f-day Table 3 6ONd-1,0B-21Cu-Feba 1
Table 4 6ONd-1,0B-17,0Pb-Feba
lTable 5 6ONd-1,0B-10Cu-2ONi-
Febal Table 6 6ONd-1, OB-1010Co
-54-6Cu-Febal (%) Table 2 will be briefly explained here.
第１表は実施例１におけるアモルファスＮｄ−Ｆｅ−Ｂ
−Ｍ （Ｍ ＝Ｃｏ ＋ Ｎｉｒ Ｃｕ ｒ Ｐ ｂ
＋ Ｓ￥１の一種）を混合して得られた焼結体の磁石特
性及びこれら焼結体に電解Ｎｉメッキ及び亜鉛クロメー
ト処理を施した試料の６０℃Ｘ９０チ湿度試験（３００
ｈｒ ）結果を示したものである。Table 1 shows the amorphous Nd-Fe-B in Example 1.
−M (M = Co + Nir Cur P b
60°C x 90° humidity test (300°C
hr) The results are shown.
第２表は実施例２におけるアモルファスＮｄ−Ｆｅ−Ｂ
−Ｍ （Ｍ ＝ Ｃｏ＋Ｎｉ 、Ｃｕ、Ｐｂ、Ｓ９の
二種以上）を混合して得られた焼結体の磁石特性及びこ
れら焼結体に電解Ｎｉメッキ、亜鉛クロメート処理を施
した試料の６０℃×９０％湿度試験（３００ｈｒ）結果
を示したものである。Table 2 shows the amorphous Nd-Fe-B in Example 2.
Magnetic properties of sintered bodies obtained by mixing -M (M = two or more of Co+Ni, Cu, Pb, and S9) and samples subjected to electrolytic Ni plating and zinc chromate treatment on these sintered bodies at 60°C ×90% humidity test (300 hr) results are shown.
第３表は実施例３における６ＯＮｄ−１，０Ｂ−２１Ｃ
ｕ−Ｆｅｂａｌ （ｗｔ％）のアモルファス粉末を混合
して得られた焼結体のＥ、Ｄ、Ｘスポット分析結果であ
る。Table 3 shows 6ONd-1,0B-21C in Example 3.
These are the E, D, and X spot analysis results of a sintered body obtained by mixing u-Febal (wt%) amorphous powder.
第４表、第５表、第６表はおのおの実施例３における６
ＯＮｄ１．０Ｂ−１７Ｐｂ−Ｆｅｂａｌ、６ＯＮｄ−１
，０Ｂ−１１０Ｃｕ−２ＯＮｊ−Ｆｅｂａｌ 、 ６Ｏ
Ｎｄ−１，０Ｂ−１０Ｃｏ−５４−６Ｃｕ−Ｆｅｂａｌ
アモルファス粉末をおのおの加えて得られた焼結体のＥ
、Ｄ、Ｘスポット分析結果である。Tables 4, 5, and 6 are 6 in Example 3, respectively.
ONd1.0B-17Pb-Febal, 6ONd-1
,0B-110Cu-2ONj-Febal, 6O
Nd-1,0B-10Co-54-6Cu-Febal
E of the sintered body obtained by adding each amorphous powder
, D, X spot analysis results.
以上の実施例で示される如（、Ｎｄ−Ｆｅ−Ｂ系磁石を
粉末冶金法により製造する場合において、従来の製法で
得られる結晶性Ｎｄ２Ｆｅ１４Ｂ相を主相とするインゴ
ット粉末に焼結時に主に液相となる原料粉末であるＲ−
Ｆｅ−Ｍ又はＲ−Ｆｅ−Ｂ−Ｍ粉末を非晶質合金又は微
結晶合金より待た後、これら粉末を混合成形した圧粉体
を焼結することにより従来よりも耐酸化性を向上させる
ことができ、 Ｎｉ等の耐酸化性メッキ、化成被膜等の
持つ本来の耐食性を付与することが可能となる。また、
特に液相成分と固相成分とを混合した成形体を焼結して
いるため。As shown in the above examples (in the case of manufacturing Nd-Fe-B magnets by powder metallurgy), ingot powder having the crystalline Nd2Fe14B phase obtained by the conventional manufacturing method as the main phase is mainly used during sintering. R-, which is the raw material powder that becomes the liquid phase
After Fe-M or R-Fe-B-M powder is added to the amorphous alloy or microcrystalline alloy, the oxidation resistance is improved more than before by sintering a compact formed by mixing and molding these powders. This makes it possible to provide the inherent corrosion resistance of oxidation-resistant plating such as Ni, chemical conversion coating, etc. Also,
Especially since a molded body containing a mixture of a liquid phase component and a solid phase component is sintered.
Ｎｄ２Ｆｅ１４Ｂ相界面付近にのみ、耐食性を向上させ
磁石特性を劣化させるＮｉ 、Ｃｕ ＋ Ｐｂ ＋ ｓ
ｌ等の元素を濃縮させた金属組織を有する焼結体が得ら
れ、磁石特性の劣化が小さり、シかも耐酸化性に優れた
焼結体磁石を得ることができる。Ni, Cu + Pb + s, which improve corrosion resistance and deteriorate magnetic properties only near the Nd2Fe14B phase interface
A sintered body having a metal structure in which elements such as 1 are concentrated can be obtained, and a sintered body magnet with less deterioration of magnetic properties and excellent oxidation resistance can be obtained.
以上Ｎｄ−Ｆｅ−Ｂについてのみ述べたが、Ｙを含めた
希土類元素（Ｒ）−Ｆｅ−Ｂ系合金についても同様の効
果が期待できることは容易に推察できるところである。Although only Nd-Fe-B has been described above, it can be easily inferred that similar effects can be expected for rare earth element (R)-Fe-B alloys including Y as well.
Claims (3)
系合金磁石（ここで、ＲはＹを含む希土類元素、Ｔは遷
移金属を示す。）を粉末冶金法にて製造する方法におい
て、Ｒ＿２Ｔ＿１＿４Ｂ相結晶質合金粉末にＲ−Ｆｅ−
Ｍ又はＲ−Ｆｅ−Ｍ−Ｂ（ＭはＣｏ、Ｎｉ、Ｃｕ、Ｐｂ
、Ｓｎの一種以上）液体急冷合金粉末又は薄帯（アモル
ファス及び微結晶）より得られる合金粉末を５〜３０ｖ
ｏｌ％含有する粉末成形体を焼結することを特徴とする
耐酸化性に優れた希土類永久磁石の製造方法。(1) R_2T_1_4B whose main components are R, Fe, and B
In a method for producing a R_2T_1_4B phase crystalline alloy powder (herein, R is a rare earth element containing Y, and T is a transition metal) by a powder metallurgy method, R-Fe-
M or R-Fe-M-B (M is Co, Ni, Cu, Pb
, one or more types of Sn) liquid quenched alloy powder or alloy powder obtained from ribbon (amorphous and microcrystalline) at 5 to 30V.
1. A method for producing a rare earth permanent magnet with excellent oxidation resistance, which comprises sintering a powder compact containing ol%.
法において、前記Ｍ（Ｃｏ、Ｎｉ、Ｃｕ、Ｐｂ、Ｓｎ）
より一種を選択する場合は、Ｃｏ：１０〜５０ｗｔ％Ｎ
ｉ、Ｃｕ：１０〜４０ｗｔ％Ｐｂ：１０〜２５ｗｔ％
Ｓｎ：１０〜１５ｗｔ％とすることを特徴とする耐酸化
性に優れた希土類永久磁石の製造方法。(2) In the method for manufacturing a rare earth magnet according to claim 1, the M (Co, Ni, Cu, Pb, Sn)
When selecting one type, Co: 10-50wt%N
i, Cu: 10-40 wt% Pb: 10-25 wt%
A method for producing a rare earth permanent magnet with excellent oxidation resistance, characterized in that Sn: 10 to 15 wt%.
法において、前記Ｍ（Ｃｏ、Ｎｉ、Ｃｕ、Ｐｂ、Ｓｎ）
より二種以上の元素を選択する場合は、これら元素の総
含有量が１０〜５５ｗｔ％であることを特徴とする耐酸
化性に優れた希土類永久磁石の製造方法。(3) In the method for manufacturing a rare earth magnet according to claim 4, the M (Co, Ni, Cu, Pb, Sn)
A method for producing a rare earth permanent magnet with excellent oxidation resistance, characterized in that when two or more elements are selected, the total content of these elements is 10 to 55 wt%.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62087917A JP2700643B2 (en) | 1987-04-11 | 1987-04-11 | Manufacturing method of rare earth permanent magnet with excellent oxidation resistance |
| EP87113557A EP0261579B1 (en) | 1986-09-16 | 1987-09-16 | A method for producing a rare earth metal-iron-boron permanent magnet by use of a rapidly-quenched alloy powder |
| DE8787113557T DE3783413T2 (en) | 1986-09-16 | 1987-09-16 | METHOD FOR PRODUCING A RARE-EARTH IRON BOR PERMANENT MAGNET WITH THE AID OF A QUARKED ALLOY POWDER. |
| US07/336,207 US4898625A (en) | 1986-09-16 | 1989-04-11 | Method for producing a rare earth metal-iron-boron permanent magnet by use of a rapidly-quenched alloy powder |
| US07/438,724 US5011552A (en) | 1986-09-16 | 1989-11-17 | Method for producing a rare earth metal-iron-boron permanent magnet by use of a rapidly-quenched alloy powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62087917A JP2700643B2 (en) | 1987-04-11 | 1987-04-11 | Manufacturing method of rare earth permanent magnet with excellent oxidation resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63254703A true JPS63254703A (en) | 1988-10-21 |
| JP2700643B2 JP2700643B2 (en) | 1998-01-21 |
Family
ID=13928273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62087917A Expired - Fee Related JP2700643B2 (en) | 1986-09-16 | 1987-04-11 | Manufacturing method of rare earth permanent magnet with excellent oxidation resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2700643B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991006107A1 (en) * | 1989-10-12 | 1991-05-02 | Kawasaki Steel Corporation | Corrosion-resistant, rare earth-transition metal magnet and method of production thereof |
| WO2012032961A1 (en) * | 2010-09-06 | 2012-03-15 | ダイハツ工業株式会社 | Magnetic material and method for producing same |
| JP2012062541A (en) * | 2010-09-17 | 2012-03-29 | Daihatsu Motor Co Ltd | Method for manufacturing magnetic material |
| JP2012080073A (en) * | 2010-09-06 | 2012-04-19 | Daihatsu Motor Co Ltd | Magnetic material |
| WO2012124387A1 (en) * | 2011-03-16 | 2012-09-20 | ダイハツ工業株式会社 | Magnetic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6393841A (en) * | 1986-10-04 | 1988-04-25 | Shin Etsu Chem Co Ltd | Rare-earth permanent magnet alloy |
| JPS63127505A (en) * | 1986-11-17 | 1988-05-31 | Taiyo Yuden Co Ltd | Magnet and manufacture thereof |
| JPS63127504A (en) * | 1986-11-17 | 1988-05-31 | Taiyo Yuden Co Ltd | Magnet and manufacture thereof |
-
1987
- 1987-04-11 JP JP62087917A patent/JP2700643B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6393841A (en) * | 1986-10-04 | 1988-04-25 | Shin Etsu Chem Co Ltd | Rare-earth permanent magnet alloy |
| JPS63127505A (en) * | 1986-11-17 | 1988-05-31 | Taiyo Yuden Co Ltd | Magnet and manufacture thereof |
| JPS63127504A (en) * | 1986-11-17 | 1988-05-31 | Taiyo Yuden Co Ltd | Magnet and manufacture thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991006107A1 (en) * | 1989-10-12 | 1991-05-02 | Kawasaki Steel Corporation | Corrosion-resistant, rare earth-transition metal magnet and method of production thereof |
| WO2012032961A1 (en) * | 2010-09-06 | 2012-03-15 | ダイハツ工業株式会社 | Magnetic material and method for producing same |
| JP2012080073A (en) * | 2010-09-06 | 2012-04-19 | Daihatsu Motor Co Ltd | Magnetic material |
| JP2012062541A (en) * | 2010-09-17 | 2012-03-29 | Daihatsu Motor Co Ltd | Method for manufacturing magnetic material |
| WO2012124387A1 (en) * | 2011-03-16 | 2012-09-20 | ダイハツ工業株式会社 | Magnetic material |
| JP6033768B2 (en) * | 2011-03-16 | 2016-11-30 | ダイハツ工業株式会社 | Manufacturing method of magnetic material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2700643B2 (en) | 1998-01-21 |
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