JPH08111306A - Nd-fe-b based magnet powder for bonded magnet excellent in corrosion resistance, bonded magnet and production of magnet powder - Google Patents
Nd-fe-b based magnet powder for bonded magnet excellent in corrosion resistance, bonded magnet and production of magnet powderInfo
- Publication number
- JPH08111306A JPH08111306A JP6270460A JP27046094A JPH08111306A JP H08111306 A JPH08111306 A JP H08111306A JP 6270460 A JP6270460 A JP 6270460A JP 27046094 A JP27046094 A JP 27046094A JP H08111306 A JPH08111306 A JP H08111306A
- Authority
- JP
- Japan
- Prior art keywords
- magnet
- magnet powder
- bonded
- powder
- 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.)
- Withdrawn
Links
Classifications
-
- 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
- H01F1/0578—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 bonded together
-
- 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
- H01F1/0572—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 with a protective layer
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、耐食性に優れたボン
ド磁石用Ｎｄ−Ｆｅ−Ｂ系磁石粉末、この磁石粉末で作
製したＮｄ−Ｆｅ−Ｂ系ボンド磁石、およびボンド磁石
用Ｎｄ−Ｆｅ−Ｂ系磁石粉末の製造方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Nd-Fe-B system magnet powder for a bond magnet having excellent corrosion resistance, an Nd-Fe-B system bond magnet produced from this magnet powder, and an Nd-Fe-for a bond magnet. The present invention relates to a method for producing B-based magnet powder.
【０００２】[0002]
【従来の技術】一般に、Ｎｄ−Ｆｅ−Ｂ系磁石粉末を樹
脂バインダーで結合して所定の寸法形状に成形したＮｄ
−Ｆｅ−Ｂ系ボンド磁石は比較的安価で高い磁気特性を
有するとともに、寸法精度が高く、薄肉で複雑な形状の
磁石に容易に製造できるところから、電気電子機器に広
く使用されている。2. Description of the Related Art In general, Nd-Fe-B magnet powder is bound with a resin binder and molded into a predetermined size and shape.
The -Fe-B based bonded magnet is widely used in electric and electronic devices because it is relatively inexpensive and has high magnetic properties, has high dimensional accuracy, and can be easily manufactured into a magnet having a thin wall and a complicated shape.
【０００３】しかしながら、一般にＮｄ−Ｆｅ−Ｂ系磁
石粉末は酸化しやすく、このため多湿高温環境下で保存
することができないのは勿論のこと、このＮｄ−Ｆｅ−
Ｂ系磁石粉末を樹脂バインダーで結合したボンド磁石を
上記多湿高温環境下で使用しても酸化し、磁気特性が大
幅に低下することは避けられなかった。However, in general, Nd-Fe-B type magnet powder is easily oxidized and therefore cannot be stored in a high humidity and high temperature environment.
Even if the bonded magnet in which the B-based magnet powder was bonded with the resin binder was used in the above-mentioned high-humidity and high-temperature environment, it was unavoidable that it was oxidized and the magnetic characteristics were significantly lowered.
【０００４】この対策として、Ｎｄ−Ｆｅ−Ｂ系磁石粉
末表面にポリオレフィン、ポリスチレン等の高分子保護
皮膜を形成し、耐食性の改善を図ることが提案されてい
る（特開平４−２５７２０２号公報参照）。As a countermeasure against this, it has been proposed to form a polymer protective film of polyolefin, polystyrene or the like on the surface of the Nd-Fe-B magnet powder to improve the corrosion resistance (see JP-A-4-257202). ).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記高
分子保護皮膜は、（ａ） １００℃程度の比較的低温で
熱劣化を起こして急速に防食性を失うため、多湿、高温
の環境下での使用に限界がある、（ｂ） Ｏ2 やＨ2 Ｏ
に対するバリヤー性が十分でないために、通常１０μｍ
以上の厚膜とする必要があるが、このような厚膜にする
と実効的なボンド磁石中での磁石粉末の体積分率が下が
り、ボンド磁石の磁気特性を低下させる、などの課題が
あった。However, the above-mentioned polymer protective film (a) undergoes thermal deterioration at a relatively low temperature of about 100 ° C. and rapidly loses its anticorrosion property. Limited use, (b) O 2 and H 2 O
Since the barrier property against
Although it is necessary to use the thick film as described above, such a thick film has a problem that the volume fraction of the magnet powder in the effective bonded magnet is lowered and the magnetic characteristics of the bonded magnet are deteriorated. .
【０００６】[0006]
【発明が解決しようとする課題】そこで、本発明者等
は、かかる課題を解決するべく研究を行った結果、
（イ） 二酸化ケイ素（以下、ＳｉＯ2 で示す）皮膜
は、Ｎｄ−Ｆｅ−Ｂ系ボンド磁石の使用温度範囲内の高
温環境下でも物性に変化がなく、したがって高温環境下
における防食性の低下はない、（ロ） ＳｉＯ2 皮膜
は、高分子皮膜に比べてＯ2 やＨ2 Ｏに対するバリヤー
性が高く、またＮｄ−Ｆｅ−Ｂ系磁石粉末に対する密着
性もよく、従って、Ｎｄ−Ｆｅ−Ｂ系磁石粉末に対する
保護皮膜としては高分子皮膜よりも薄くすることがで
き、このＳｉＯ2 皮膜を形成した磁石粉末を用いて作製
したボンド磁石は高分子皮膜を形成した磁石粉末を用い
て作製したボンド磁石に比べて磁石粉末の体積分率を向
上させることができるので、ボンド磁石の磁気特性を向
上させることができる、などの研究結果が得られたので
ある。Therefore, as a result of the research conducted by the present inventors to solve these problems,
(A) The physical properties of the silicon dioxide (hereinafter referred to as SiO 2 ) film do not change even in a high temperature environment within the operating temperature range of the Nd-Fe-B based bonded magnet, and therefore the corrosion resistance does not deteriorate in the high temperature environment. (B) The SiO 2 film has a higher barrier property against O 2 and H 2 O than the polymer film, and also has good adhesion to the Nd-Fe-B magnet powder, and therefore Nd-Fe-B. The protective coating for the system magnet powder can be made thinner than the polymer coating, and the bond magnet produced using this SiO 2 coating-formed magnet powder is the bond produced using the polymer-coated magnet powder. Research results have been obtained such that the volume fraction of the magnet powder can be improved as compared with the magnet, and thus the magnetic characteristics of the bonded magnet can be improved.
【０００７】この発明は、かかる研究結果に基づいてな
されたものであって、（１） Ｎｄ−Ｆｅ−Ｂ系磁石粉
末の表面にＳｉＯ2 保護皮膜が形成されている耐食性に
優れたボンド磁石用Ｎｄ−Ｆｅ−Ｂ系磁石粉末、およ
び、（２） 上記（１）の磁石粉末を樹脂バインダーで
結合したボンド磁石、に特徴を有するものである。The present invention has been made on the basis of such research results, and (1) For bonded magnets having an excellent corrosion resistance in which a SiO 2 protective film is formed on the surface of Nd-Fe-B system magnet powder. The present invention is characterized by Nd-Fe-B based magnet powder and (2) a bonded magnet in which the magnet powder of (1) above is bonded with a resin binder.
【０００８】上記Ｎｄ−Ｆｅ−Ｂ系磁石粉末の表面に形
成されるＳｉＯ2 保護皮膜は、連続した緻密な膜である
ために、平均膜厚は０．１〜２μｍの範囲内にあれば十
分である。Since the SiO 2 protective film formed on the surface of the Nd-Fe-B magnet powder is a continuous and dense film, it is sufficient that the average film thickness is within the range of 0.1 to 2 μm. Is.
【０００９】したがって、この発明は、（３） Ｎｄ−
Ｆｅ−Ｂ系磁石粉末の表面に、平均膜厚：０．１〜２μ
ｍのＳｉＯ2 保護皮膜が形成されている耐食性に優れた
ボンド磁石用Ｎｄ−Ｆｅ−Ｂ系磁石粉末にも特徴を有す
るものである。Therefore, the present invention provides (3) Nd-
On the surface of the Fe-B magnet powder, average film thickness: 0.1 to 2 μ
The Nd—Fe—B based magnet powder for bonded magnets, which has a SiO 2 protective film of m and is excellent in corrosion resistance, is also characterized.
【００１０】この発明の耐食性に優れたボンド磁石用Ｎ
ｄ−Ｆｅ−Ｂ系磁石粉末のＳｉＯ2保護皮膜は、下記の
方法で形成する。The N for bonded magnets according to the present invention having excellent corrosion resistance
The SiO 2 protective film of the d-Fe-B magnet powder is formed by the following method.
【００１１】（Ｉ） エチルシリケートを用いたゾル・
ゲル反応によるＳｉＯ2 保護皮膜の形成方法。(I) A sol containing ethyl silicate
Method for forming SiO 2 protective film by gel reaction.
【００１２】先ず、Ｓｉ（ＯＣ2 Ｈ5 ）4 （テトラエチ
ルオルトシリケート）のアルコール溶液に加水分解反応
の触媒として少量の酸を添加したのち、撹拌し放置する
と化１に示される加水分解が起きる。First, a small amount of acid is added to an alcohol solution of Si (OC 2 H 5 ) 4 (tetraethyl orthosilicate) as a catalyst for a hydrolysis reaction, and then the mixture is stirred and left to stand to cause the hydrolysis shown in Chemical formula 1.
【００１３】[0013]
【化１】 Embedded image
【００１４】この加水分解が起きた溶液をさらにアルコ
ールで希釈する。この希釈された溶液濃度はＳｉＯ2 換
算で０．１〜５wt％となるように希釈することが好まし
い。その理由は、溶液中のＳｉＯ2 換算濃度が０．１wt
％未満では連続した皮膜の形成が困難であり、またＳｉ
Ｏ2 換算濃度が５wt％を越えると皮膜の厚さが２μｍよ
りも厚くなり、磁性体の体積分率が下がり、ボンド磁石
の磁気特性が落ちるとともに、それ以降の工程の加熱処
理時に皮膜に割れが入り、かえって耐食性改善効果が減
少するからである。The solution in which the hydrolysis has occurred is further diluted with alcohol. The diluted solution concentration is preferably diluted to 0.1 to 5 wt% in terms of SiO 2 . The reason is that the concentration of SiO 2 in the solution is 0.1 wt.
%, It is difficult to form a continuous film.
When the concentration converted to O 2 exceeds 5 wt%, the thickness of the coating becomes thicker than 2 μm, the volume fraction of the magnetic material decreases, the magnetic properties of the bonded magnet deteriorate, and the coating cracks during the heat treatment in the subsequent steps. This is because the corrosion resistance is reduced and the effect of improving corrosion resistance is reduced.
【００１５】このようにして作成した溶液に、Ｎｄ−Ｆ
ｅ−Ｂ系磁石粉末を浸漬し、ろ別後室温で撹拌しながら
乾燥すると、磁石粉末の表面にＳｉ（ＯＨ）4 モノマー
の皮膜が一様に形成され、このＳｉ（ＯＨ）4 モノマー
皮膜が形成された磁石粉末を加熱するとＳｉ（ＯＨ）4
モノマーが縮合反応し、磁石粉末の表面に緻密で連続し
たＳｉＯ2 皮膜が形成される。The solution thus prepared was added with Nd-F.
When the e-B magnet powder is dipped, filtered and dried at room temperature with stirring, a film of Si (OH) 4 monomer is uniformly formed on the surface of the magnet powder, and this Si (OH) 4 monomer film is formed. When the formed magnetic powder is heated, Si (OH) 4
The monomer undergoes a condensation reaction to form a dense and continuous SiO 2 film on the surface of the magnet powder.
【００１６】上記Ｓｉ（ＯＨ）4 モノマーに縮合反応を
起こさせる加熱雰囲気は、真空またはＡｒ，Ｎ2 などの
不活性ガス雰囲気が好ましく、その加熱温度は８０〜５
００℃が好ましい。縮合反応を促進するためには８０℃
以上の温度が必要であり、また磁石粉末の金属組織変化
が起こらないためには５００℃以下であることが望まし
い。The heating atmosphere for causing the condensation reaction of the Si (OH) 4 monomer is preferably vacuum or an atmosphere of an inert gas such as Ar or N 2 , and the heating temperature is 80 to 5.
00 ° C is preferred. 80 ° C to accelerate the condensation reaction
The above temperature is required, and it is preferably 500 ° C. or lower so that the metal structure of the magnet powder does not change.
【００１７】（ＩＩ） プラズマ化学蒸着法によるＳｉ
Ｏ2 皮膜の形成方法。(II) Si by plasma enhanced chemical vapor deposition
Method of forming O 2 film.
【００１８】真空容器内に原料ガスとして水素化シリコ
ンガス、アルキルシラン、アルコキシシラン鎖状ポリシ
ロキサン、環状ポリシロキサンなどのＳｉ源のガスと、
Ｏ2，Ｎ2 Ｏなどの酸素源のガスを導入し、真空ポンプ
により容器内の圧力を一定に保持しながら、電極に高周
波電力を加えて放電を起こさせてプラズマを発生させ、
その化学反応により磁石粉末表面にＳｉＯ2 皮膜を形成
する。磁石粉末表面に均一にＳｉＯ2 皮膜を形成させる
ためには、蒸着中は磁石粉末を常に転動または流動させ
る必要があり、そのための各種装置を使用する。この方
法により磁石粉末表面に形成されるＳｉＯ2 皮膜の平均
膜厚も０．１〜２μｍの範囲内にあることが好ましい。Si source gas such as silicon hydride gas, alkylsilane, alkoxysilane chain polysiloxane and cyclic polysiloxane as raw material gas in a vacuum container,
Gas of oxygen source such as O 2 and N 2 O is introduced, and while maintaining a constant pressure in the container by a vacuum pump, high frequency power is applied to the electrodes to cause discharge to generate plasma,
The chemical reaction forms a SiO 2 film on the surface of the magnet powder. In order to uniformly form a SiO 2 film on the surface of the magnet powder, it is necessary to constantly roll or flow the magnet powder during vapor deposition, and various devices for that purpose are used. The average film thickness of the SiO 2 film formed on the surface of the magnet powder by this method is also preferably within the range of 0.1 to 2 μm.
【００１９】したがって、この発明は、（４） エチル
シリケートを用いたゾル・ゲル反応により、またはプラ
ズマ化学蒸着法により、Ｎｄ−Ｆｅ−Ｂ系磁石粉末表面
に二酸化ケイ素の保護皮膜を形成する耐食性に優れたボ
ンド磁石用Ｎｄ−Ｆｅ−Ｂ系磁石粉末の製造方法に特徴
を有するものである。Therefore, the present invention provides (4) corrosion resistance for forming a protective film of silicon dioxide on the surface of Nd-Fe-B based magnet powder by a sol-gel reaction using ethyl silicate or by a plasma chemical vapor deposition method. It is characterized by an excellent method for producing Nd-Fe-B magnet powder for bonded magnets.
【００２０】この発明のＳｉＯ2 皮膜を形成するための
Ｎｄ−Ｆｅ−Ｂ系磁石粉末は、粉砕磁石粉末、液体急冷
法による等方性磁石粉末、水素処理による異方性磁石粉
末のいずれの粉末でもよいが、特に耐食性が劣る粉砕磁
石粉末または水素処理磁石粉末に適用すると効果があ
る。The Nd-Fe-B system magnet powder for forming the SiO 2 film of the present invention is any one of ground magnet powder, isotropic magnet powder by liquid quenching method, and anisotropic magnet powder by hydrogen treatment. However, it is particularly effective when applied to pulverized magnet powder or hydrogen-treated magnet powder having poor corrosion resistance.
【００２１】上記（Ｉ）および（ＩＩ）の方法で得られ
たこの発明のＳｉＯ2 皮膜を有するＮｄ−Ｆｅ−Ｂ系磁
石粉末をナイロン、ポリブチレンテレフタレート、ポリ
フェニレンサルファイドなどの熱可塑性樹脂と混合し、
この混合物を射出成形または押出成形してボンド磁石を
作製することができる。The Nd-Fe-B magnet powder having the SiO 2 coating of the present invention obtained by the above methods (I) and (II) is mixed with a thermoplastic resin such as nylon, polybutylene terephthalate or polyphenylene sulfide. ,
The mixture can be injection molded or extruded to make a bonded magnet.
【００２２】また、この発明のＳｉＯ2 皮膜を有するＮ
ｄ−Ｆｅ−Ｂ系磁石粉末はニトリルブチルゴムなどの合
成ゴムと混合し、これをロール法により成形して可撓性
ゴム磁石を作製することができる。Further, N having the SiO 2 coating of the present invention
The d-Fe-B magnet powder can be mixed with a synthetic rubber such as nitrile butyl rubber and molded by a roll method to prepare a flexible rubber magnet.
【００２３】さらに、この発明のＳｉＯ2 皮膜を有する
Ｎｄ−Ｆｅ−Ｂ系磁石粉末をエポキシ、ビスマレイミド
トリアジンなどの熱硬化性樹脂と混合し、これを圧縮成
形してボンド磁石を作製することもできる。Further, the Nd-Fe-B magnet powder having the SiO 2 coating of the present invention may be mixed with a thermosetting resin such as epoxy or bismaleimide triazine, and this may be compression molded to prepare a bonded magnet. it can.
【００２４】[0024]
【実施例】プラズマアーク溶解してＮｄ：１２．６at
％、Ｃｏ：１１．６at％、Ｂ：６．０at％、Ｇａ：１．
０at％、Ｆｅ：残部からなる組成のインゴットを作製
し、このインゴットにＡｒ雰囲気中、温度：１１２０
℃、２０時間保持したのちＡｒガスで急冷の均質化焼鈍
を施し、この均質化焼鈍したインゴットをジョークラッ
シャにより１０mm角以下に粗粉砕し、この粗粉砕したも
のを真空炉に装入し、真空炉内の雰囲気を１気圧のＨ2
フロー雰囲気とし、真空炉内の温度を８３０℃まで昇温
し、同温度で３時間保持したのち真空排気を行い、１×
１０-2Torrの真空度となるまで脱水素を行なったのち直
ちにＡｒガスにより急冷し、ブラウンミルにより粉砕
し、平均粒度：約１００μｍのＮｄ−Ｆｅ−Ｂ系磁石粉
末を作製した。[Example] Plasma arc melting and Nd: 12.6 at
%, Co: 11.6 at%, B: 6.0 at%, Ga: 1.
An ingot having a composition of 0 at% and Fe: balance was prepared, and this ingot was heated in an Ar atmosphere at a temperature of 1120.
After holding at ℃ for 20 hours, homogenized annealing is performed by quenching with Ar gas, the homogenized annealed ingot is roughly crushed into 10 mm square or less by a jaw crusher, and the roughly crushed one is put into a vacuum furnace and vacuumed. The atmosphere in the furnace is set to 1 atm of H 2
In a flow atmosphere, the temperature inside the vacuum furnace is raised to 830 ° C., and the temperature is maintained for 3 hours, then vacuum exhaust is performed and 1 ×
After dehydrogenation to a vacuum of 10 -2 Torr, it was immediately quenched with Ar gas and pulverized with a brown mill to prepare Nd-Fe-B magnet powder having an average particle size of about 100 μm.
【００２５】実施例１ テトラエチルオルトシリケート（以下、ＴＥＯＳと記
す）をイソプロピルアルコールで溶解し、４０．９wt％
ＴＥＯＳアルコール溶液を作製し、この４０．９wt％Ｔ
ＥＯＳアルコール溶液に対して、触媒として０．３wt％
硝酸水溶液を７．１wt％添加し撹拌したのち２４時間放
置した。Example 1 Tetraethyl orthosilicate (hereinafter referred to as TEOS) was dissolved in isopropyl alcohol to obtain 40.9% by weight.
A TEOS alcohol solution was prepared and this 40.9 wt% T
0.3 wt% as a catalyst for EOS alcohol solution
After adding 7.1 wt% of nitric acid aqueous solution and stirring, the mixture was left standing for 24 hours.
【００２６】このようにして得られた溶液をイソプロピ
ルアルコールで２１倍に希釈し、ＳｉＯ2 換算で０．５
wt％の表面処理溶液を作製した。The solution thus obtained was diluted 21-fold with isopropyl alcohol, and converted to 0.5 in terms of SiO 2.
A wt% surface treatment solution was prepared.
【００２７】上記平均粒度：約１００μｍのＮｄ−Ｆｅ
−Ｂ系磁石粉末を上記表面処理溶液に浸漬し、ろ別した
のち室温で撹拌しながら乾燥し、上記Ｎｄ−Ｆｅ−Ｂ系
磁石粉末表面にＳｉ（ＯＨ）4 皮膜を形成し、ついで２
×１０-5Torrの真空雰囲気中、温度：２５０℃で１時間
加熱し、ＳｉＯ2 平均膜厚：１μｍの本発明磁石粉末１
を作製した。The above average particle size: Nd-Fe of about 100 μm
The -B magnet powder was immersed in the surface treatment solution, filtered, and dried at room temperature with stirring to form a Si (OH) 4 film on the surface of the Nd-Fe-B magnet powder, and then 2
In a vacuum atmosphere of × 10 -5 Torr, the magnet powder 1 of the present invention having a SiO 2 average film thickness of 1 μm was heated at a temperature of 250 ° C. for 1 hour.
Was produced.
【００２８】この本発明磁石粉末１に対して２．５wt％
のビスマレイミドトリアジン樹脂を添加し混合したの
ち、配向磁界１５ＫＯｅを圧縮方向と平行に印加しなが
ら圧力：６ton ／cm2 で常温圧縮成形して直径：１０m
m、高さ：７mmの成形体を作製し、この成形体をＡｒ気
流中、温度：１５０℃、３０分保持の条件で樹脂硬化さ
せ、本発明ボンド磁石１を作製した。2.5 wt% with respect to the magnet powder 1 of the present invention
After adding and mixing the bismaleimide triazine resin of No. 1, while applying an orientation magnetic field of 15 KOe parallel to the compression direction, press-mold at room temperature at a pressure of 6 ton / cm 2 and a diameter of 10 m.
A molded body having m and a height of 7 mm was prepared, and the molded body was resin-cured under the conditions of a temperature of 150 ° C. and a holding time of 30 minutes in Ar gas flow to manufacture the bonded magnet 1 of the present invention.
【００２９】実施例２ 上記Ｎｄ−Ｆｅ−Ｂ系磁石粉末を真空容器内に設置され
た回転羽根方式の撹拌機により転動しながら、真空容器
内にヘキサメチルジシロキサンガスとＮ2 Ｏガスを同時
に各々５０cc／min の流量で導入し、２４．５ＭＨｚの
高周波プラズマにより投入電力：３００Ｗで放電を行
い、３０分間蒸着を行ない、ＳｉＯ2 皮膜の平均厚さが
１μｍの本発明磁石粉末２を作製した。Example 2 Hexamethyldisiloxane gas and N 2 O gas were introduced into the vacuum container while rolling the Nd-Fe-B magnet powder by means of a rotary blade type agitator installed in the vacuum container. At the same time, each was introduced at a flow rate of 50 cc / min, discharged with a high-frequency plasma of 24.5 MHz at an input power of 300 W, and vapor-deposited for 30 minutes to prepare a magnet powder 2 of the present invention having an average SiO 2 film thickness of 1 μm. did.
【００３０】この本発明磁石粉末２を用い、実施例１と
同様にして本発明ボンド磁石２を作製した。Using this magnet powder 2 of the present invention, a bonded magnet 2 of the present invention was produced in the same manner as in Example 1.
【００３１】従来例１〜３ ポリエチレン、ポリプロピレン、ポリスチレンをそれぞ
れキシレンに溶解させて樹脂濃度を調整し、溶液の粘度
を５００センチポイズに調整した。これら各種溶液に上
記Ｎｄ−Ｆｅ−Ｂ系磁石粉末を浸漬した後、ろ別して緩
やかに撹拌しながらブロワーで乾燥し、平均膜厚：１５
μｍのポリエチレン皮膜を形成した従来磁石粉末１、平
均膜厚：１５μｍのポリプロピレン皮膜を形成した従来
磁石粉末２および平均膜厚：１５μｍのポリスチレン皮
膜を形成した従来磁石粉末３をそれぞれ作製した。さら
にこれら従来磁石粉末１，２および３を用い、実施例１
と同様にして、それぞれ従来ボンド磁石１，２および３
を作製した。Conventional Examples 1 to 3 Polyethylene, polypropylene and polystyrene were each dissolved in xylene to adjust the resin concentration, and the viscosity of the solution was adjusted to 500 centipoise. After immersing the Nd-Fe-B magnet powder in these various solutions, it was filtered and dried with a blower while gently stirring, and the average film thickness: 15
A conventional magnet powder 1 having a polyethylene film having a thickness of μm, a conventional magnet powder 2 having a polypropylene film having an average film thickness of 15 μm, and a conventional magnet powder 3 having a polystyrene film having an average film thickness of 15 μm were prepared. Furthermore, using these conventional magnet powders 1, 2 and 3, Example 1
Similarly to the conventional bonded magnets 1, 2 and 3 respectively.
Was produced.
【００３２】上記実施例１〜２および従来例１〜３で得
られた本発明磁石粉末１〜２および従来磁石粉末１〜３
をそれぞれ１０ｇ秤量し、この本発明磁石粉末１〜２お
よび従来磁石粉末１〜３を大気中、温度：６５℃、温
度：９５％の多湿高温雰囲気に５００時間保持し、再び
重量を測定し、その差を酸化量として求め、表１に示し
た。The magnet powders 1 and 2 of the present invention and the conventional magnet powders 1 to 3 obtained in Examples 1 to 2 and Conventional Examples 1 to 3 above.
Were weighed 10 g each, and the present magnet powders 1 and 2 and conventional magnet powders 1 to 3 were held in the atmosphere in a humid and high temperature atmosphere of temperature: 65 ° C. and temperature: 95% for 500 hours, and the weight was measured again. The difference was determined as the amount of oxidation and is shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】表１に示される結果から、平均膜厚１μｍ
のＳｉＯ2 皮膜を形成した本発明磁石粉末１〜２は、平
均膜厚：１５μｍのポリエチレン、ポリプロピレン、ポ
リスチレン皮膜をそれぞれ形成した従来磁石粉末１〜３
に比べて重量差が少ないところから耐食性に優れている
ことがわかる。From the results shown in Table 1, the average film thickness is 1 μm.
The magnetic powders 1 to 2 of the present invention having the SiO 2 coating formed are conventional magnet powders 1 to 3 each having a polyethylene, polypropylene and polystyrene coating having an average film thickness of 15 μm.
It can be seen that the corrosion resistance is excellent from the point where the difference in weight is small compared to.
【００３５】さらに、本発明ボンド磁石１〜２および従
来ボンド磁石１〜３について５０ＫＯｅのパルス着磁を
施したのち、オープンフラックスを磁束計を用いて引き
抜き法により測定し、また磁気特性をＢＨカーブトレー
サを用いて最大印加磁界２０ＫＯｅで測定し、その結果
を表２に示した。Further, after applying 50 KOe pulse magnetization to the bonded magnets 1 to 2 of the present invention and the conventional bonded magnets 1 to 3, the open flux was measured by a drawing method using a magnetometer, and the magnetic characteristics were measured by a BH curve. The measurement was performed at a maximum applied magnetic field of 20 KOe using a tracer, and the results are shown in Table 2.
【００３６】これら測定が終ったのち再び５０ＫＯｅの
パルス着磁を施したこれらボンド磁石を８０℃、９５％
ＲＨに保った恒温恒湿槽に装入し、５００時間保持した
のち取り出して外観の発錆状態を観察し、さらにオープ
ンフラックスを測定し、恒温恒湿槽装入前後の減少率を
求めてその結果を表２に示し、耐食性の評価を行った。
さらに本発明ボンド磁石１〜２および従来ボンド磁石１
〜３について、１３０℃に保持された恒温槽に装入し、
５００時間保持したのち取り出して恒温槽装入前後のオ
ープンフラックスを測定し、その減少率を求めてその結
果を表２に示し、耐熱性の評価を行った。After these measurements were completed, the bonded magnets pulse-magnetized at 50 KOe were again applied at 80 ° C. and 95%.
It was charged in a thermo-hygrostat kept at RH, kept for 500 hours, taken out, and observed for rust appearance, and the open flux was measured to determine the decrease rate before and after the thermo-humidity bath was charged. The results are shown in Table 2 and the corrosion resistance was evaluated.
Further, the bonded magnets 1 to 2 of the present invention and the conventional bonded magnet 1
About ~ 3, charged into a constant temperature bath maintained at 130 ℃,
After holding for 500 hours, it was taken out and the open flux before and after charging in a constant temperature bath was measured, the reduction rate was calculated, and the results are shown in Table 2 to evaluate the heat resistance.
【００３７】[0037]
【表２】 [Table 2]
【００３８】表２に示される結果から、本発明磁石粉末
１〜２で作製された本発明ボンド磁石１〜２はいずれも
従来磁石粉末１〜３で作製された従来ボンド磁石１〜３
に比べて耐食耐熱性に優れていることがわかる。From the results shown in Table 2, all of the bonded magnets 1 and 2 of the present invention made of the magnet powders 1 and 2 of the present invention are conventional bonded magnets 1 to 3 made of the conventional magnet powders 1 to 3, respectively.
It can be seen that the corrosion resistance is superior to that of
【００３９】[0039]
【発明の効果】上述のように、この発明の製造方法で作
製したＳｉＯ2 皮膜を有するこの発明のボンド磁石用Ｎ
ｄ−Ｆｅ−Ｂ系磁石粉末は、従来の高分子皮膜を有する
Ｎｄ−Ｆｅ−Ｂ系磁石粉末よりも磁気特性および耐食耐
熱性に優れたボンド磁石を製造することができ、電気電
子産業の発展に大いに貢献しうるものである。As described above, the N for bonded magnet of the present invention having the SiO 2 film produced by the manufacturing method of the present invention is as described above.
The d-Fe-B magnet powder can manufacture a bonded magnet having magnetic properties and corrosion resistance superior to those of the conventional Nd-Fe-B magnet powder having a polymer coating. Can greatly contribute to.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｆ 1/053 1/08 Ｈ０１Ｆ 1/08 Ａ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location H01F 1/053 1/08 H01F 1/08 A
Claims (4)
化ケイ素の保護皮膜が形成されていることを特徴とする
耐食性に優れたボンド磁石用Ｎｄ−Ｆｅ−Ｂ系磁石粉
末。1. A Nd-Fe-B based magnet powder for bonded magnets having excellent corrosion resistance, characterized in that a protective film of silicon dioxide is formed on the surface of the Nd-Fe-B based magnet powder.
ーで結合したことを特徴とするボンド磁石。2. A bonded magnet, wherein the magnet powder according to claim 1 is bonded with a resin binder.
応によりＮｄ−Ｆｅ−Ｂ系磁石粉末表面に二酸化ケイ素
の保護皮膜を形成することを特徴とする耐食性に優れた
ボンド磁石用Ｎｄ−Ｆｅ−Ｂ系磁石粉末の製造方法。3. A Nd-Fe-B for bonded magnet excellent in corrosion resistance, characterized in that a protective film of silicon dioxide is formed on the surface of an Nd-Fe-B based magnet powder by a sol-gel reaction using ethyl silicate. Method for producing a base magnet powder.
Ｂ系磁石粉末表面に二酸化ケイ素の保護皮膜を形成する
ことを特徴とする耐食性に優れたボンド磁石用Ｎｄ−Ｆ
ｅ−Ｂ系磁石粉末の製造方法。4. Nd-Fe- by a plasma chemical vapor deposition method.
Nd-F for bonded magnet excellent in corrosion resistance, characterized by forming a protective film of silicon dioxide on the surface of B-based magnet powder
Method for producing e-B magnet powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6270460A JPH08111306A (en) | 1994-10-07 | 1994-10-07 | Nd-fe-b based magnet powder for bonded magnet excellent in corrosion resistance, bonded magnet and production of magnet powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6270460A JPH08111306A (en) | 1994-10-07 | 1994-10-07 | Nd-fe-b based magnet powder for bonded magnet excellent in corrosion resistance, bonded magnet and production of magnet powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08111306A true JPH08111306A (en) | 1996-04-30 |
Family
ID=17486608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6270460A Withdrawn JPH08111306A (en) | 1994-10-07 | 1994-10-07 | Nd-fe-b based magnet powder for bonded magnet excellent in corrosion resistance, bonded magnet and production of magnet powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08111306A (en) |
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| WO2003088279A1 (en) * | 2002-04-09 | 2003-10-23 | The Electrodyne Company, Inc. | Bonded permanent magnets |
| WO2010090229A1 (en) | 2009-02-03 | 2010-08-12 | 戸田工業株式会社 | Surface treated rare earth magnetic powder, bonded magnet resin composition that includes the rare earth magnetic powder, and bonded magnet |
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-
1994
- 1994-10-07 JP JP6270460A patent/JPH08111306A/en not_active Withdrawn
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| JP2002367820A (en) * | 2001-06-12 | 2002-12-20 | Japan Science & Technology Corp | Rare-earth bonded magnet recycling waste magnet material |
| WO2003088279A1 (en) * | 2002-04-09 | 2003-10-23 | The Electrodyne Company, Inc. | Bonded permanent magnets |
| US6707361B2 (en) | 2002-04-09 | 2004-03-16 | The Electrodyne Company, Inc. | Bonded permanent magnets |
| WO2010090229A1 (en) | 2009-02-03 | 2010-08-12 | 戸田工業株式会社 | Surface treated rare earth magnetic powder, bonded magnet resin composition that includes the rare earth magnetic powder, and bonded magnet |
| EP2497094A1 (en) * | 2009-11-05 | 2012-09-12 | Robert Bosch GmbH | Method for producing a magnet, magnet, and electric machine |
| US20120319807A1 (en) * | 2009-11-05 | 2012-12-20 | Robert Bosch Gmbh | Method for producing a magnet, magnet and electric machine |
| JP2011216659A (en) * | 2010-03-31 | 2011-10-27 | Nitto Denko Corp | R-Fe-B BASED PERMANENT MAGNET |
| CN104919546A (en) * | 2012-11-14 | 2015-09-16 | 大众汽车有限公司 | Method for producing a permanent magnet and permanent magnet |
| US10312019B2 (en) | 2012-11-14 | 2019-06-04 | Volkswagen Aktiengesellschaft | Method for producing a permanent magnet and permanent magnet |
| DE102013213494A1 (en) * | 2013-07-10 | 2015-01-29 | Volkswagen Aktiengesellschaft | Method for producing a permanent magnet and permanent magnet and electric machine with such a permanent magnet |
| JP2020050904A (en) * | 2018-09-26 | 2020-04-02 | 日亜化学工業株式会社 | Magnetic powders and method for producing same |
| US11424055B2 (en) | 2018-09-26 | 2022-08-23 | Nichia Corporation | Magnetic powder and preparation method thereof |
| US11710586B2 (en) | 2018-09-26 | 2023-07-25 | Nichia Corporation | Magnetic powder |
| JP2021055133A (en) * | 2019-09-27 | 2021-04-08 | 日亜化学工業株式会社 | Manufacturing method of magnetic powder |
| US11594352B2 (en) | 2019-09-27 | 2023-02-28 | Nichia Corporation | Method of producing magnetic powder |
| CN112002512A (en) * | 2020-10-29 | 2020-11-27 | 宁波合力磁材技术有限公司 | Anti-corrosion sintered neodymium iron boron magnetic material and preparation process thereof |
| CN112002512B (en) * | 2020-10-29 | 2021-03-02 | 宁波合力磁材技术有限公司 | Anti-corrosion sintered neodymium iron boron magnetic material and preparation process thereof |
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