JP2008045214A - Powder for producing sintered rare earth magnet alloy - Google Patents
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本発明は、磁気特性の優れた焼結希土類磁石合金を安定して製造する方法に関する。 The present invention relates to a method for stably producing a sintered rare earth magnet alloy having excellent magnetic properties.
Ｒ−Ｂ−（Ｃｏ）−Ｆｅ系の焼結希土類磁石合金（Ｒは希土類元素の１種または２種以上を表す）や特許第２７８９３６４号等に提案されたＲ−Ｂ−Ｃ−（Ｃｏ）−Ｆｅ系の焼結希土類磁石合金が汎用されている。このような焼結希土類磁石合金は，一般に，粗合金の溶製，鋳造，粉砕（破砕，粗粉砕，微粉砕），粉体の成形，焼結の各工程を経て製造されている。
前記の製造工程のうち，焼結に供される粉体の諸特性が焼結製品の磁気特性に大きく影響を与えることがわかった。すなわち，鋳塊を破砕し，粗粉砕し，さらに微粉砕して焼結用の粉体を製造する場合，その粉体特性によって得られる焼結製品の磁気特性が変化することがわかった。 Of the manufacturing processes described above, it was found that the characteristics of the powder subjected to sintering greatly affect the magnetic characteristics of the sintered product. In other words, it was found that when the ingot was crushed, coarsely pulverized, and then finely pulverized to produce a powder for sintering, the magnetic properties of the sintered product obtained depend on the powder characteristics.
したがって，本発明の課題は，かかる焼結希土類磁石合金の製造にさいして，鋳造品から焼結用粉体を製造するさいに最も適切な製造条件を見いだし，磁気特性の優れた焼結希土類磁石合金を安定して製造することにある。 Therefore, the object of the present invention is to find the most suitable production conditions for producing a sintered powder from a cast product, and to produce a sintered rare earth magnet having excellent magnetic properties. It is to produce an alloy stably.
本発明によれば，粗合金の溶湯を溶製し，この溶湯を合金塊に鋳造し，この合金塊を粗粉砕したあと更に微粉砕し，得られた粉末を用いて圧粉成形し，この成形品を焼結して，下記の成分組成を有する焼結希土類磁石合金を製造する方法において，前記の微粉砕を２回以上実施することを特徴とする焼結希土類磁石合金の製造法を提供する。
〔焼結希土類磁石合金の成分組成〕
Ｃ：２０ at.％以下（０ at.％を含む）
Ｂ：０.５〜１５ at.％，
Ｃｏ：４０ at.％以下（０ at.％を含む），
Ｒ：１０〜３０ at.％，
ただし，Ｒは希土類元素の少なくとも一種を表す，
残部：Ｆｅおよび不可避的不純物。
According to the present invention, a melt of a crude alloy is melted, the melt is cast into an alloy lump, the alloy lump is coarsely pulverized and further finely pulverized, and the obtained powder is compacted and formed. In a method for producing a sintered rare earth magnet alloy having the following component composition by sintering a molded article, a method for producing a sintered rare earth magnet alloy is provided, wherein the fine pulverization is performed twice or more. To do.
[Component composition of sintered rare earth magnet alloy]
C: 20 at.% Or less (including 0 at.%)
B: 0.5-15 at.%,
Co: 40 at.% Or less (including 0 at.%),
R: 10-30 at.%,
Where R represents at least one rare earth element,
The balance: Fe and inevitable impurities.
この製法に従って２回以上の微粉砕で得られる粉末としては，平均粒径が２〜３μｍで且つ粒径が７μｍ以上の粒子が存在する体積割合が７容積％以下であるのがよい。また，２回以上の微粉砕のうち少なくとも１回は振動ボールミルを用い，振動ボールミルだけで微粉砕を行う場合には，各回とも条件を変えて行うのがよい。 As a powder obtained by pulverization twice or more according to this production method, the volume ratio of particles having an average particle diameter of 2 to 3 μm and a particle diameter of 7 μm or more is preferably 7% by volume or less. In addition, when at least one of the two or more fine pulverizations is performed using a vibration ball mill and fine pulverization is performed only with the vibration ball mill, it is preferable to change the conditions at each time.
本発明の製造法によると，磁気特性の優れた焼結希土類磁石合金を安定して製造することができる。 According to the manufacturing method of the present invention, a sintered rare earth magnet alloy having excellent magnetic properties can be manufactured stably.
本発明が対象とする焼結希土類磁石合金は，原子比百分率（at.%）で，Ｃ：２０ at.％以下（０ at.％を含む），好ましくは０.５〜２０ at.％以下，Ｂ：０.５〜１５at.%，好ましくは２ at.％未満，Ｃｏ：４０at.%以下（０at.%を含む），Ｒ：８〜３０ at.％，好ましくは１０〜２０at.%（Ｒは希土類元素の少なくとも一種），残部：Ｆｅおよび不可避的不純物からなる成分組成を有するものである。 The sintered rare earth magnet alloy targeted by the present invention has an atomic percentage (at.%) Of C: 20 at.% Or less (including 0 at.%), Preferably 0.5 to 20 at.% Or less. , B: 0.5-15 at.%, Preferably less than 2 at.%, Co: 40 at.% Or less (including 0 at.%), R: 8-30 at.%, Preferably 10-20 at.% ( R has at least one kind of rare earth element), the balance: Fe and a component composition consisting of unavoidable impurities.
この焼結希土類磁石合金は，溶解，鋳造，粉砕，成形，焼結という一連の工程で焼結磁石とする。具体的には，合金組成となるように秤量した各成分の原料（Ｃの一部または全部は除く）を真空溶解炉で１６００℃以上で溶解し，水冷鋳型に急冷鋳造する。得られた鋳塊を好ましくは６００℃以上でＡｒ雰囲気中で熱処理したあと，ジョークラッシャー等で粗粉砕する。得られた粗粉を微粉砕する。これらの粉砕工程は好ましくはＡｒ雰囲気中で行う。ついで，得られた粉体を所定の形状に圧粉成形し，これを焼結する。 This sintered rare earth magnet alloy is made into a sintered magnet through a series of processes of melting, casting, crushing, molding and sintering. Specifically, raw materials of each component (excluding part or all of C) weighed so as to have an alloy composition are melted at 1600 ° C. or higher in a vacuum melting furnace, and then rapidly cast into a water-cooled mold. The obtained ingot is preferably heat-treated in an Ar atmosphere at 600 ° C. or higher and then roughly pulverized with a jaw crusher or the like. The obtained coarse powder is pulverized. These grinding steps are preferably performed in an Ar atmosphere. Next, the obtained powder is compacted into a predetermined shape and sintered.
微粉砕の工程では，振動ボールミル，ジェットミルなどを使用して少なくとも２回以上実施するが，少なくとも１回は振動ボールミルを用いて行う。微粉砕を行う前に，Ｃ原料の一部または全部として，カーボンブラックまたは潤滑剤（脂肪族炭化水素系潤滑剤，高級脂肪族アルコール系潤滑剤，高級脂肪酸系潤滑剤，脂肪酸アマイド系潤滑剤，金属石鹸および脂肪族エステルの群から選ばれる少なくとも１種の潤滑剤）を粗粉に配合しておくのがよい。すなわち，このような潤滑剤を，微粉砕工程の前の合金，または微粉砕工程の途中の合金，とくに振動ボールミルを用いた微粉砕では振動ボールミルによる微粉砕を行う前の合金に対して，Ｃ原料の一部または全部として配合して微粉砕するのがよい。なぜなら，振動ボールミルは，ドラム内に装填された合金粉に振動を付与しながら内装されたボールによって合金粉の粉砕が行われるものであり，ここに潤滑剤が存在すると，合金粉が潤滑効果で粒度分布の狭い均一粒径のものに粉砕されながら各粒子表面には均一に潤滑剤が被着した状態のものが得られる。潤滑剤のうち，特に好ましいのは，パラフィン，ポリアクリル酸塩系ポリマー，ポリエチレンオキサイド，ポリオキシエチレンモノステアレート，ステアリン酸，エチレンビスステアリルアマイド，オレフィンアマイドなどが挙げられる。 The fine pulverization step is performed at least twice using a vibration ball mill, a jet mill or the like, but at least once using a vibration ball mill. Before pulverizing, carbon black or lubricant (aliphatic hydrocarbon lubricant, higher aliphatic alcohol lubricant, higher fatty acid lubricant, fatty acid amide lubricant, It is preferable to add at least one lubricant selected from the group of metal soaps and aliphatic esters to the coarse powder. That is, such a lubricant is applied to an alloy before the fine pulverization process or an alloy in the middle of the fine pulverization process, particularly an alloy before fine pulverization by the vibration ball mill in the fine pulverization using the vibration ball mill. It is good to mix and pulverize as a part or all of the raw material. This is because the vibration ball mill pulverizes the alloy powder with balls that are internally provided with vibrations applied to the alloy powder loaded in the drum. While being pulverized to have a uniform particle size with a narrow particle size distribution, the surface of each particle is uniformly coated with a lubricant. Among the lubricants, paraffin, polyacrylate polymer, polyethylene oxide, polyoxyethylene monostearate, stearic acid, ethylene bisstearyl amide, olefin amide and the like are particularly preferable.
本発明者らの数多くの試験によると，微粉砕工程に振動ボールミルのみを用いた場合は，一回の処理では，安定した品質の粉体が得られないことがわかった。すなわち，振動ボールミルによる制御可能な粉砕条件として，振幅，振動数，粉砕時間などの運転条件と，ボール径，ボール充填率，ボール／粉体の重量比（Ｂ／Ｐと呼ばれる）などの装填条件が代表的なものであるが，これらの条件を如何様に設定して粉砕しても，一回の粉砕処理では所望の粉体特性を得るには限界があり，必ずしも磁石製品としての磁気特性を最良にする粉体特性を持つ粉体が得られるとは限らないことがわかった。 According to a number of tests conducted by the present inventors, it was found that when only a vibrating ball mill was used in the pulverization process, a stable quality powder could not be obtained by a single treatment. That is, as controllable grinding conditions by a vibrating ball mill, operating conditions such as amplitude, frequency, grinding time, and loading conditions such as ball diameter, ball filling rate, and ball / powder weight ratio (referred to as B / P) However, no matter how these conditions are set and pulverized, there is a limit to obtaining the desired powder characteristics in a single pulverization process. It has been found that it is not always possible to obtain a powder having the best powder characteristics.
これは，粉砕過程において，粉末の状態は粉砕の進行に従って変化してゆくのに対し，振動ボールミルの場合には，ボール径，ボール充填率，Ｂ／Ｐなどは固定されたままであるため，その時々の粉末の状態に対して常に適正な条件を維持することが出来ないためであると考えられる。 This is because in the pulverization process, the powder state changes as the pulverization progresses, whereas in the case of a vibrating ball mill, the ball diameter, ball filling rate, B / P, etc. remain fixed. This is probably because the proper conditions cannot always be maintained for the state of the powder.
本発明によれば，微粉砕工程において，条件を変えて少なくとも２回の微粉砕を行うと，そして少なくともその１回は振動ボールミルで行うと，適正な粉体特性を有する希土類磁石合金粉末が得られることが明らかとなった。 According to the present invention, when pulverization is performed at least twice under different conditions in the pulverization step, and at least one of the pulverization is performed by a vibration ball mill, a rare earth magnet alloy powder having appropriate powder characteristics can be obtained. It became clear that
より具体的には，前記のように粗粉砕された粗粉に対し，本発明の一つの態様として，振動ボールミルだけで複数回の微粉砕を行う場合には，前記のようにカーボンブラックおよび／または潤滑剤をＣ原料の一部または全部となるように適量配合したうえ，振動ボールミルで第１回目の粉砕を行う。そのさい，粉砕条件として，振幅，振動数，粉砕時間，ボール径，ボール充填率，Ｂ／Ｐを設定し（粉砕対象の合金組成や粗粉の特性に応じた値に設定する），所望の粉体特性が得られるようにする。第１回目の粉砕条件と得られる粉体特性の関係は，合金組成や粗粉の状態に応じて行った数多くの経験値（メモリ値）から予測することができ，このメモリ値を参考にして第１回目の粉砕条件を設定する。ついで，第１回目の粉砕で得られた粉体を，同じく振動ボールミルを用いて，新たに粉砕条件を設定して，第２回目の粉砕を行って，所望の粉体特性が得られるようにする。この場合も，予め行った経験値を参考にして粉砕条件を設定する。第２回目の粉砕で所望特性を得ることが困難な場合には，第３回目の粉砕，さらには第４回目の粉砕と繰り返しながら所望の粉体特性が得られるまで振動ボールミルによる粉砕を実施する。 More specifically, as one embodiment of the present invention, when coarsely pulverized a plurality of times with only a vibration ball mill, the coarsely pulverized powder as described above is carbon black and / or as described above. Alternatively, an appropriate amount of a lubricant is blended so as to be a part or all of the C raw material, and the first pulverization is performed by a vibration ball mill. At that time, as pulverization conditions, amplitude, frequency, pulverization time, ball diameter, ball filling rate, B / P are set (set to values according to the alloy composition to be pulverized and characteristics of the coarse powder), and desired Ensure that powder characteristics are obtained. The relationship between the first pulverization condition and the obtained powder characteristics can be predicted from a large number of experience values (memory values) according to the alloy composition and the state of the coarse powder. Set the first grinding conditions. Next, the powder obtained in the first pulverization is set using the same vibration ball mill, and new pulverization conditions are set, and then the second pulverization is performed so that desired powder characteristics can be obtained. To do. In this case as well, the pulverization conditions are set with reference to the experience values obtained in advance. If it is difficult to obtain the desired characteristics by the second crushing, crushing by the vibration ball mill is performed until the desired powder characteristics are obtained while repeating the third crushing and further the fourth crushing. .
また，本発明の他の態様として，振動ボールミルと他の粉砕機例えばジェットミルとを組み合わせて複数回の微粉砕を行う場合には，どちらを先行させてもよいが，実際には，他の粉砕機で第１回目の微粉砕を行ない，次いで振動ボールミルによる第２回目若しくはそれ以降の微粉砕を行うのが好ましい。潤滑剤の配合については，各微粉砕ごとに分配して各微粉砕の前に添加することができ，最終の粉砕までに全量が配合されるようにすればよい。 As another aspect of the present invention, when a vibrating ball mill and another pulverizer such as a jet mill are combined to perform fine pulverization a plurality of times, whichever may be preceded, It is preferable that the first pulverization is performed by a pulverizer, and then the second pulverization by a vibration ball mill or the subsequent pulverization is performed. As for the blending of the lubricant, it can be distributed for each pulverization and added before each pulverization, and the entire amount may be blended before the final pulverization.
焼結希土類磁石合金は，特定組成の比較的大きな磁性結晶粒が各種の成分からなる非磁性相を介して接合した特殊な金属組織を有するものであるが，このような特殊な金属組織を有する焼結希土類磁石合金の磁気特性は，焼結前の粉体特性に大きく影響を受ける。本発明者らの経験よると，焼結前の粉末が，平均粒径２〜３μｍで且つ粒径が７μｍ以上の粒子が存在する体積割合が７容積％以下である場合に，最も良好な磁気特性を示すことを見い出した。 Sintered rare earth magnet alloys have a special metal structure in which relatively large magnetic crystal grains of a specific composition are joined via a nonmagnetic phase composed of various components. The magnetic properties of sintered rare earth magnet alloys are greatly affected by the powder properties before sintering. According to the experiences of the present inventors, the best magnetic properties are obtained when the powder before sintering has an average particle size of 2 to 3 μm and a volume ratio of particles having a particle size of 7 μm or more is 7% by volume or less. Found to show characteristics.
したがって，微粉砕工程での粉砕のさいに，各段階での粉砕条件を適正に設定して，最終的に平均粒径２〜３μｍで且つ粒径が７μｍ以上の粒子が存在する体積割合が７容積％以下の粉体が得られるように粉砕処理するのがよい。平均粒径が２μｍ未満になると，粉末の活性化が著しくなって酸化の影響を受けやすくなり，磁気特性の低下を招く原因となる。他方，平均粒径が３μｍを超えると，磁気製品において高い保磁力が得られなくなる。また，粗粒の割合が少ないことも肝要であり，７μｍ以上の粒子が存在する体積割合が７容積％を超えると，平均粒径が適正であっても，保磁力が低下するようになるので好ましくはない。 Therefore, when pulverizing in the fine pulverization step, pulverization conditions at each stage are set appropriately, and the volume ratio in which particles having an average particle diameter of 2 to 3 μm and a particle diameter of 7 μm or more are finally present is 7 It is preferable to pulverize so as to obtain a powder having a volume% or less. If the average particle size is less than 2 μm, the activation of the powder becomes remarkable and it is easily affected by oxidation, which causes a decrease in magnetic properties. On the other hand, when the average particle size exceeds 3 μm, a high coercive force cannot be obtained in the magnetic product. It is also important that the ratio of coarse particles is small. If the volume ratio in which particles of 7 μm or more exist exceeds 7% by volume, the coercive force decreases even if the average particle size is appropriate. It is not preferable.
なお，この粉砕時に前記のような潤滑剤を使用すると，潤滑剤で粒子表面が被覆されて流動性が良好となり，所望の形状（例えばロッド状）に磁場中で圧粉成形するさいの配向性および成形性が良くなる。粉体の成形にあたっては，成形圧１〜５ｔ／ｃｍ2，外部磁場１０ＫＯe 以上が適切である。 If a lubricant such as that described above is used during the pulverization, the particle surface is coated with the lubricant to improve fluidity, and orientation when compacting into a desired shape (for example, a rod shape) in a magnetic field. And the moldability is improved. In forming the powder, a forming pressure of 1 to 5 t / cm 2 and an external magnetic field of 10 KOe or more are appropriate.
ついで，この成形体を焼結処理に供するが，焼結条件としては例えば真空中または不活性ガス中１０００〜１２００℃の温度で焼結処理する。そのさい該潤滑剤は分解・蒸発し，焼成残渣としてのＣ（炭素）が，磁性結晶粒やその周囲の非磁性相に合金成分として含有されることになる。焼結温度から急冷，もしくは急冷と徐冷を組合せて，焼結終了後は１０℃／分以上の温度で冷却することにより，さらには，徐冷と急冷を組み合わせて，焼結終了後 0.5〜２０℃/ 分の速度で冷却し温度が６００から１０５０に達した後，直ちに急冷することにより, 磁性結晶粒の周囲の非磁性相を均質且つ強固なものとすることができる。 Next, this compact is subjected to a sintering process. As a sintering condition, for example, the sintering process is performed at a temperature of 1000 to 1200 ° C. in vacuum or in an inert gas. At that time, the lubricant decomposes and evaporates, and C (carbon) as a firing residue is contained as an alloy component in the magnetic crystal grains and the surrounding nonmagnetic phase. Rapid cooling from the sintering temperature, or a combination of rapid cooling and slow cooling, cooling at a temperature of 10 ° C / min or higher after the sintering is completed, and further combining slow cooling and rapid cooling, 0.5 to By cooling at a rate of 20 ° C./min and the temperature reaches 600 to 1050 and immediately quenching, the nonmagnetic phase around the magnetic crystal grains can be made homogeneous and strong.
得られた焼結体は，さらに４００〜１１００℃，好ましくは５００〜１０５０℃の温度で0 .5〜２４時間の後熱処理を施すことにより，磁気特性を改善できることがある。その場合は最終熱処理温度が４００℃未満では磁気特性を改善する効果は小さく，また１１００℃を超えると焼結を伴うようになり，磁性結晶粒が粗大化してＢｒおよびｉＨc が低下する。また該温度域での保持時間は0.5 時間未満では磁気特性を改善する効果は小さくまた２４時間を超えてもその効果は小さい。 The obtained sintered body may be further subjected to post-heat treatment at a temperature of 400 to 1100 ° C., preferably 500 to 1050 ° C. for 0.5 to 24 hours, so that the magnetic properties may be improved. In that case, if the final heat treatment temperature is less than 400 ° C., the effect of improving the magnetic properties is small, and if it exceeds 1100 ° C., sintering is accompanied, and the magnetic crystal grains become coarse and Br and iHc decrease. Further, if the holding time in the temperature range is less than 0.5 hours, the effect of improving the magnetic properties is small, and if it exceeds 24 hours, the effect is small.
このようにして耐酸化性に優れたＲ−Ｂ−Ｃ−（Ｃｏ）−Ｆｅ系の焼結希土類磁石合金を製造できるが，本発明で対象とする合金の成分組成を限定する理由の概要は次のとおりである。
まず本発明合金を構成する必須元素のＲは希土類元素であって，これらは，Y,La, Ce, Nd, Pr, Tb, Dy, Ho, Er, Sm, Gd, Eu, Pm, Tm, Yb 及び Lu のうちの一種または二種以上である。二種以上の混合物であるミッシュメタル，ジジム等も原料とすることができる。ここでＲを１０〜３０at.%とするのは，この範囲内でＢｒが実用上非常に優れるためである。
Thus, an R—B—C— (Co) —Fe-based sintered rare earth magnet alloy having excellent oxidation resistance can be produced. The outline of the reason for limiting the component composition of the target alloy in the present invention is as follows. It is as follows.
First, R as an essential element constituting the alloy of the present invention is a rare earth element, and these are Y, La, Ce, Nd, Pr, Tb, Dy, Ho, Er, Sm, Gd, Eu, Pm, Tm, Yb. And one or more of Lu. Misch metal, didymium, etc., which are a mixture of two or more, can also be used as raw materials. Here, the reason why R is 10 to 30 at.% Is that Br is very excellent in practical use within this range.
Ｂ（ボロン）は，この系統の希土類磁石合金において磁性結晶粒を形成するための必須の元素であり，Ｂ＝０.５〜１５at.%の範囲で含有させる。Ｂを２at.%より多く含有する合金であっても，Ｃを適切に含有する結果，その合金組織は耐酸化性に優れたものとなるが，場合によってはＣ量を増加することによって，Ｂを２ at.％未満の範囲で含有させることもできる。磁石合金中のＣ含有量は２０at.%以下とする。２０at.%を超えるとＢｒの低下が著しくなる。 B (boron) is an essential element for forming magnetic crystal grains in this series of rare earth magnet alloys, and is contained in a range of B = 0.5 to 15 at.%. Even if an alloy contains more than 2 at.% Of B, as a result of appropriately containing C, the alloy structure becomes excellent in oxidation resistance, but in some cases, by increasing the amount of C, B May be contained in a range of less than 2 at.%. The C content in the magnet alloy is 20 at.% Or less. If it exceeds 20 at.%, The reduction of Br becomes remarkable.
Ｃｏは，この系統の焼結磁石合金のキュリー点を上昇させ，また耐酸化性の向上にも寄与する。本発明の対象とする磁石合金においてもＣｏを含有させることができ，この場合には４０at.%までとする。これ以上を配合してもコスト高になる割にはその効果は飽和する。 Co raises the Curie point of this series of sintered magnet alloys and contributes to the improvement of oxidation resistance. Co can also be contained in the magnet alloy which is the subject of the present invention, and in this case, it is limited to 40 at.%. Even if it mixes more than this, the effect is saturated for the cost increase.
〔実施例１〕
原料として純度99.9％の電解鉄，ボロン含有量19.3％のフェロボロン合金，純度99.5% のカーボンブラック, および純度 98.5% (不純物として他の希土類金属を含有する) のネオジム金属を使用し，組成比として 13Nd-2.5Dy-72.5Fe-9Co-2B-1Cとなるように計量，配合し，高周波誘導炉で真空中で溶解した後，水冷銅鋳型中に鋳込み，合金塊を得た。
[Example 1]
Using 99.9% purity electrolytic iron, boron content 19.3% ferroboron alloy, purity 99.5% carbon black, and purity 98.5% (containing other rare earth metals as impurities) as raw materials. Weighed and blended to 13Nd-2.5Dy-72.5Fe-9Co-2B-1C, melted in a high-frequency induction furnace in vacuum, and then cast into a water-cooled copper mold to obtain an alloy lump.
この合金塊をジョークラッシャーで破砕し，さらにアルゴンガス中でディスクミルを用いて粗砕した。得られた粗砕粉にＣ原料として潤滑剤（ステアリン酸を使用）を混合添加した。潤滑剤の添加量は，その潤滑剤中に含まれるＣ量によって，粗砕粉の組成比が 12.6Nd-2.4Dy-70.3Fe-8.7Co-1.9B-4.1Cとなるような量とした。 This alloy lump was crushed with a jaw crusher and further crushed using a disk mill in argon gas. A lubricant (using stearic acid) was mixed and added as a C raw material to the obtained coarsely pulverized powder. The amount of lubricant added was such that the composition ratio of the coarsely crushed powder was 12.6Nd-2.4Dy-70.3Fe-8.7Co-1.9B-4.1C depending on the amount of C contained in the lubricant.
潤滑剤を混合添加した粗砕粉を振動ボールミルを用いて, 表１に示す粉砕条件で第１回目の粉砕を行い，得られた粉体を同じく振動ボールミルを用いて，表1に示す粉砕条件で第２回目の粉砕を行った。第２回目の粉砕によって，平均粒径２.４２μｍ，７μｍ以上の粒子が存在する体積割合が３.１５容積％の粉体が得られた。粒度分布の測定はレーザー回折式粒度分布計によった。 The coarsely pulverized powder to which the lubricant was added and mixed was pulverized for the first time using the vibration ball mill under the pulverization conditions shown in Table 1, and the obtained powder was also pulverized under the conditions shown in Table 1 using the vibration ball mill. Then, the second pulverization was performed. By the second pulverization, a powder having an average particle size of 2.42 μm and a volume ratio of 3.15% by volume containing particles of 7 μm or more was obtained. The particle size distribution was measured by a laser diffraction particle size distribution meter.
この合金微粉末を１０kOe の磁界中１ton/cm2 の圧力で成形し，その成形体を，真空中１０５０℃に２時間保持した後，急冷し焼結希土類磁石合金を得た。得られた焼結希土類磁石合金についてＶＳＭにより測定した磁気特性を表１に併記した。 This alloy fine powder was molded in a magnetic field of 10 kOe at a pressure of 1 ton / cm 2 , and the compact was held at 1050 ° C. for 2 hours in a vacuum and then rapidly cooled to obtain a sintered rare earth magnet alloy. The magnetic properties measured by VSM for the obtained sintered rare earth magnet alloy are also shown in Table 1.
〔実施例２〕
振動ボールミルでの第２回目の粉砕時間を変えた以外は，実施例１を繰り返した。表１にそれらの粉砕条件と，得られた粉体の粉体特性，および得られた焼結希土類磁石合金の磁気特性を併記した。
[Example 2]
Example 1 was repeated except that the second grinding time in the vibrating ball mill was changed. Table 1 shows the grinding conditions, the powder characteristics of the obtained powder, and the magnetic characteristics of the obtained sintered rare earth magnet alloy.
〔比較例１〕
振動ボールミルでの粉砕を１回だけで行った以外は，実施例１を繰り返した。表１にその粉砕条件と，得られた粉体の粉体特性，および得られた焼結希土類磁石合金の磁気特性を併記した。
[Comparative Example 1]
Example 1 was repeated except that the grinding with a vibrating ball mill was performed only once. Table 1 shows the grinding conditions, the powder characteristics of the obtained powder, and the magnetic characteristics of the obtained sintered rare earth magnet alloy.
〔比較例２〕
振動ボールミルでの粉砕時間を変えた以外は比較例１を繰り返した。表１にその粉砕条件と，得られた粉体の粉体特性，および得られた焼結希土類磁石合金の磁気特性を併記した。
[Comparative Example 2]
Comparative Example 1 was repeated except that the pulverization time in the vibration ball mill was changed. Table 1 shows the grinding conditions, the powder characteristics of the obtained powder, and the magnetic characteristics of the obtained sintered rare earth magnet alloy.
〔実施例３〕
ジェットミル（栗本鐵工所製のＫＪ−５０型）を用いて表２に示す条件で第１回目の粉砕を行い，得られた粉砕を実施例１と同じ振動ボールミルを用いて表２に示す条件で第２回目の粉砕を行った以外は，実施例１を繰り返した。得られた粉体の粉体特性，および得られた焼結希土類磁石合金の磁気特性を表２に併記した。
Example 3
The first pulverization was performed using a jet mill (KJ-50 model manufactured by Kurimoto Steel Works) under the conditions shown in Table 2, and the obtained pulverization is shown in Table 2 using the same vibration ball mill as in Example 1. Example 1 was repeated except that the second pulverization was performed under the conditions. Table 2 shows the powder characteristics of the obtained powder and the magnetic characteristics of the obtained sintered rare earth magnet alloy.
表１の結果から明らかのように，粉砕工程で１回だけの粉砕を行った比較例のものに比べ，複数回の粉砕を行った実施例の焼結希土類磁石合金では，保磁力が高くなっており，ＢＨｍａｘも高くなっていることがわかる。また，表２の結果から，他の粉砕機と振動ボールミルとを組み合わせて複数回の微粉砕を行った場合でも保磁力とＢＨmax が高くなっていることがわかる。 As is clear from the results in Table 1, the coercive force is higher in the sintered rare earth magnet alloy of the example in which the pulverization was performed several times than in the comparative example in which the pulverization process was performed only once. It can be seen that BHmax is also high. In addition, it can be seen from the results in Table 2 that the coercive force and BHmax are high even when the pulverization is performed a plurality of times by combining another pulverizer and a vibration ball mill.
Claims (2)
〔粉末の成分組成〕
Ｃ：０.５〜２０ ａｔ．％以下、
Ｂ：２ ａｔ．％未満（０ ａｔ．％を含まず）、
Ｒ：１０〜３０ ａｔ．％、
ただし、Ｒは希土類元素の少なくとも一種を表す、
Ｃｏ：４０ ａｔ．％以下（０ ａｔ．％を含む）、
残部：Ｆｅおよび不可避的不純物。 The volume ratio in which particles having the following component composition and an average particle diameter of 2 to 3 μm and a particle diameter of 7 μm or more are 7% by volume or less, and each particle surface is an aliphatic hydrocarbon lubricant, Sintered rare earth magnet comprising powder coated with at least one lubricant selected from the group of higher aliphatic alcohol lubricants, higher fatty acid lubricants, fatty acid amide lubricants, metal soaps and aliphatic esters Powder for alloy production.
[Component composition of powder]
C: 0.5-20 at. %Less than,
B: 2 at. % (Excluding 0 at.%),
R: 10-30 at. %,
Where R represents at least one rare earth element,
Co: 40 at. % Or less (including 0 at.%),
The balance: Fe and inevitable impurities.
〔粉末の成分組成〕
Ｃ：０.５〜２０ ａｔ．％以下、
Ｂ：２ ａｔ．％未満（０ ａｔ．％を含まず）、
Ｒ：１０〜３０ ａｔ．％、
ただし、Ｒは希土類元素の少なくとも一種を表す、
Ｃｏ：４０ ａｔ．％以下（０ ａｔ．％を含む）、
残部：Ｆｅおよび不可避的不純物。 The volume ratio in which particles having the following component composition and an average particle diameter of 2 to 3 μm and a particle diameter of 7 μm or more are 7% by volume or less, and the surface of each particle is paraffin and a polyacrylate polymer. A powder for producing a sintered rare earth magnet alloy comprising a powder coated with at least one lubricant selected from the group consisting of polyethylene oxide, polyoxyethylene monostearate, stearic acid, ethylene bisstearyl amide, and olefin amide.
[Component composition of powder]
C: 0.5-20 at. %Less than,
B: 2 at. % (Excluding 0 at.%),
R: 10-30 at. %,
Where R represents at least one rare earth element,
Co: 40 at. % Or less (including 0 at.%),
The balance: Fe and inevitable impurities.
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| CN102784920A (en) * | 2012-07-19 | 2012-11-21 | 河北工程大学 | Method for preparing rare earth permanent-magnet alloy nanosheet-shaped powder |
| CN109465094A (en) * | 2018-11-06 | 2019-03-15 | 西南科技大学 | Preparation method of fine iron powder based on red mud extract |
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