JP2562316B2 - Method for producing soft magnetic amorphous alloy powder having high saturation magnetic flux density - Google Patents
Method for producing soft magnetic amorphous alloy powder having high saturation magnetic flux densityInfo
- Publication number
- JP2562316B2 JP2562316B2 JP62074487A JP7448787A JP2562316B2 JP 2562316 B2 JP2562316 B2 JP 2562316B2 JP 62074487 A JP62074487 A JP 62074487A JP 7448787 A JP7448787 A JP 7448787A JP 2562316 B2 JP2562316 B2 JP 2562316B2
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- Prior art keywords
- amorphous alloy
- powder
- flux density
- alloy powder
- magnetic flux
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Links
- 239000000843 powder Substances 0.000 title claims description 71
- 230000005291 magnetic effect Effects 0.000 title claims description 45
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 42
- 230000004907 flux Effects 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000005551 mechanical alloying Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 9
- 229910000531 Co alloy Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010953 base metal Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 32
- 229910045601 alloy Inorganic materials 0.000 description 20
- 239000000956 alloy Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000010791 quenching Methods 0.000 description 10
- 230000000171 quenching effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005280 amorphization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003302 ferromagnetic material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910020641 Co Zr Inorganic materials 0.000 description 1
- 229910020517 Co—Ti Inorganic materials 0.000 description 1
- 229910020520 Co—Zr Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明はメカニカルアロイング法により、高飽和磁
束密度をもつ軟質磁性材料として最適なCoリツチCo合金
系のアモルフアス合金粉末の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a method for producing an amorphous alloy powder of Co-rich, a Co alloy, which is optimal as a soft magnetic material having a high saturation magnetic flux density, by a mechanical alloying method. is there.
アモルフアス合金は、結晶化されていないか、あるい
は長範囲の規則度のない原子配列の金属であり、化学
的，磁気的，電気的および機械的に優れた特性を有して
おり、近年その応用分野が急速に拡大しつつある。Amorphous alloys are metals that are not crystallized or have a long range of non-ordered atomic arrangement, and have excellent chemical, magnetic, electrical and mechanical properties. The field is expanding rapidly.
特にアモルフアス合金の微細粉末は、表面の高活性や
垂直磁気異方性から、特異な性能を創り出したり、また
適当な結合剤を用いての成型，加圧焼結法，衝撃圧着法
等を採用することにより、所望の形状のものを容易に製
造することができるので、アモルフアス合金の応用分野
を大巾に拡大するものとして重視されている。In particular, fine powder of amorphous alloy creates unique performance due to high surface activity and perpendicular magnetic anisotropy, and adopts molding using a suitable binder, pressure sintering method, impact pressure bonding method, etc. By doing so, it is possible to easily produce a desired shape, and therefore, it is regarded as important for greatly expanding the application field of amorphous alloys.
従来、アモルフアス合金の粉末を製造する方法として
は、スパツタ法，真空蒸着法等のように金属ガスを急冷
する気相急冷法，超音波ガス噴霧法，双ロール法等の熔
融金属を急冷する液体急冷法、そして水素吸蔵法のよう
に固体金属から出発する固相反応法等の方法があるが、
液体急冷法が一般的な製造方法である。Conventionally, as a method for producing powder of an amorphous alloy, a vapor phase quenching method for quenching a metal gas such as a sputtering method or a vacuum deposition method, an ultrasonic gas atomization method, a liquid for rapidly quenching a molten metal such as a twin roll method. There are methods such as quenching method and solid-state reaction method starting from solid metal such as hydrogen absorption method.
The liquid quenching method is a general manufacturing method.
しかし、液体急冷法の場合は、20μｍ以下の微細で均
一な構造をもつ粉末状のアモルフアス合金を大量に得る
ことができない。However, in the case of the liquid quenching method, it is not possible to obtain a large amount of powdery amorphous amorphous alloy having a fine and uniform structure of 20 μm or less.
また、スパツタ法では、微細な粉末を得ることができ
るが、一度にはきわめて少量しか生産することができな
いため量産には適しない。Further, although the sputter method can obtain fine powder, it is not suitable for mass production because it can produce a very small amount at a time.
最近、固体状態の金属からメカニカルアロイング法に
より直接アモルフアス合金を大量に製造する新しい固相
反応プロセス技術が発表されている〔昭和61年11月４
日，日本複合材料学会発行「第11回複合材料シンポジウ
ム講演要旨集」メカニカルアロイング法によるアモルフ
アス複合粒子の作製（第41〜第44頁）参照。〕 〔発明が解決しようとする問題点〕 前記液体急冷法や気相急冷法の場合は、アモルフアス
化が可能な合金組成範囲が狭いので、合金組成のコント
ロールが難しいという問題がある。Recently, a new solid-state reaction process technology for mass-producing amorphous alloy directly from solid state metal by mechanical alloying method has been announced [November 61, 1986]
See Japan, Japan Society for Composite Materials, "11th Composite Materials Symposium Abstracts", Preparation of Amorphous Composite Particles by Mechanical Alloying Method (Pages 41 to 44). [Problems to be Solved by the Invention] In the case of the liquid quenching method or the vapor quenching method, there is a problem that it is difficult to control the alloy composition because the alloy composition range in which amorphous formation is possible is narrow.
またメカニカルアロイング法により直接Co系のアモル
フアス合金を製造する場合、CoとZrまたはTiとを１対１
（原子量比）付近の組成にすると、得られたアモルフア
ス合金の磁気特性がほとんど無く特に飽和磁束密度は高
くても1000ガウス（Ｇ）以下である。When directly manufacturing a Co-based amorphous alloy by mechanical alloying, Co and Zr or Ti are in a one-to-one relationship.
When the composition is in the vicinity of (atomic weight ratio), the obtained amorphous alloy has almost no magnetic properties, and particularly the saturation magnetic flux density is 1000 Gauss (G) or less even if it is high.
一方、高飽和磁性体であることが期待されるCoリツチ
Co合金については、固相反応法の一種である原子単位の
層間物質のイオンミキシングにより製造することが試み
られているが、Coが60％以上でのアモルフアス化をする
ことは未だ成功していない。また高飽和磁束密度をもつ
CoリツチCo合金系のアモルフアス合金粉末をメカニカル
アロイング法により製造する方法も未だ開発されていな
い。On the other hand, a Co latch that is expected to be a highly saturated magnetic substance.
Co alloys have been attempted to be produced by ion mixing of interatomic substances of atomic unit, which is a kind of solid-phase reaction method, but Co has not yet succeeded in amorphization at 60% or more. . Also has a high saturation magnetic flux density
Co Litchi A method for producing amorphous alloy powder of a Co alloy system by a mechanical alloying method has not been developed yet.
さらにまた、高濃度CoのCoZr系やCoTi系などの遷移金
属−遷移金属系アモルフアス合金粉末を従来の製造技術
の主流をなしている液体急冷法により製造することが考
えられるが、この場合は、高融点金属で酸化性の著しい
ZrやTiを基本組成に含むため、連続的に大量の粉末を一
工程で製造することは極めて困難であり、しかもアモル
フアス化できる範囲が著しく狭いという問題がある。Furthermore, it is conceivable to produce transition metal such as CoZr system and CoTi system with high concentration Co by a liquid quenching method, which is a mainstream of conventional production techniques, and transition metal-amorphous alloy powder, but in this case, High melting point metal with remarkable oxidizability
Since Zr and Ti are contained in the basic composition, it is extremely difficult to continuously produce a large amount of powder in one step, and there is a problem that the range in which amorphization is possible is extremely narrow.
この発明は、メカニカルアロイング法により、高飽和
磁束密度をもつCoリツチCoリツチCo合金系の軟質磁性ア
モルフアス合金粉末を容易に大量に生産性高く製造でき
る方法を提供することを目的とするものであつて、この
発明の要旨とするところは、Coからなるベース金属粉末
をZrまたはTiからなるIV a族の金属粉末を配合し、かつ
IV a族の金属粉末の原子量％を１〜35％にすると共に、
各金属粉末の合計原子量％を100％に設定し、前記各金
属粉末からなる原料粉末を、衝撃式ミルを用いて外部か
ら加熱することなくメカニカルアロイング法により処理
して、CoリツチCo合金系の高飽和磁束密度をもつ軟質磁
性アモルフアス合金粉末を得ることを特徴とする高飽和
磁束密度をもつ軟質磁性アモルフアス合金粉末の製造方
法にある。The present invention aims to provide a method capable of easily producing a large amount of a soft magnetic amorphous alloy powder of Co-rich, Co-rich, and Co-alloy system having a high saturation magnetic flux density by a mechanical alloying method with high productivity. Now, the gist of the present invention is that a base metal powder made of Co is mixed with a group IVa metal powder made of Zr or Ti, and
The atomic weight% of the IVa group metal powder is set to 1 to 35%, and
The total atomic weight% of each metal powder is set to 100%, the raw material powder consisting of each metal powder is processed by a mechanical alloying method using an impact mill without external heating, and a Co-Ritch Co alloy system is used. The method for producing a soft magnetic amorphous alloy powder having a high saturation magnetic flux density is characterized by obtaining a soft magnetic amorphous amorphous alloy powder having a high saturation magnetic flux density.
なおメカニカルアロイング法によるアモルフアス合金
化のメカニズムは推定の域をでないが、衝撃式ミル例え
ばボールミルを使用してメカニカルアロイングを実施す
る場合、複数種の金属粒子がボールとボールとの間に挾
まれて打撃される際に、一方の金属粒子が他方の金属粒
子中に叩き込まれて合金化される作用と金属粒子の粉砕
作用とが繰り返して行なわれるためであると推定され
る。The mechanism of amorphous alloying by the mechanical alloying method is within the range of estimation, but when mechanical alloying is performed using an impact mill such as a ball mill, multiple types of metal particles are sandwiched between the balls. It is presumed that this is because, when the metal particles are hit by being hit, the metal particles are hammered into the other metal particles to be alloyed and the metal particles are crushed repeatedly.
次にこの発明の実施例について詳細に説明する。 Next, embodiments of the present invention will be described in detail.
実施例１ 平均粒径５μｍのCo粉末および平均粒径20μｍのZr粉
末を、Co80Zr20,Co85Zr15,Co90Zr10の原子量割合になる
ように精秤して混合し、得られた３種類の混合粉末を、
それぞれ第１図に示す鋼球撹拌型の衝撃式ミル（商品
名：アトライタ）１の容器２内に収容し、かつ容器２内
の上部に不活性ガスからなるシールガスを供給し、アジ
テータ３を300RPMの回転速度で25時間回転させ、メカニ
カルアロイング法により合金化とアモルフアス化とを行
なつた。Example 1 Co powder having an average particle diameter of 5 μm and Zr powder having an average particle diameter of 20 μm were precisely weighed and mixed so that the atomic weight ratios of Co80Zr20, Co85Zr15, and Co90Zr10 were mixed, and the obtained three kinds of mixed powders were mixed,
Each of them is housed in a container 2 of a steel ball stirring type impact mill (trade name: Attritor) 1 shown in FIG. 1, and a seal gas composed of an inert gas is supplied to the upper part of the container 2 to set an agitator 3. The alloy was alloyed and amorphized by the mechanical alloying method while rotating at a rotation speed of 300 RPM for 25 hours.
この実施例の方法によつて得られた３種類のCoZr系ア
モルフアス合金粉末のＸ線デイフラクトメータによる回
折図形を第２図に示す。第２図のＸ線回折図形には、通
常の金属結晶特有のシヤープなピークは全く見られず、
アモルフアス合金特有のハーロパターン（ブロードなピ
ーク）のみであり、異種金属粉末の混合状態から一挙に
アモルフアス化した合金粉末が得られたことがわかる。FIG. 2 shows the diffraction patterns of the three types of CoZr-based amorphous alloy powders obtained by the method of this example by an X-ray diffractometer. In the X-ray diffraction pattern of FIG. 2, no sharp peaks peculiar to ordinary metal crystals are seen,
It is only the halo pattern (broad peak) peculiar to the amorphous alloy, and it can be seen that the alloy powder converted into amorphous alloy powder was obtained all at once from the mixed state of the different metal powders.
また第３図には、この実施例の方法により得られる３
種類のCoZr系アモルフアス合金粉末を、超音波分散後に
光散乱法〔マイクロトラツク（商品名）の使用による〕
により測定したときの粒度分布を示している。第３図の
場合、何れの組成も対数正規分布を示しており、その平
均粒径は約10〜30μｍの間にある。In addition, FIG. 3 shows that 3 obtained by the method of this embodiment.
Ultrasonic dispersion of various types of CoZr-based amorphous alloy powders followed by light scattering method [by using Microtrack (trade name)]
3 shows the particle size distribution measured by. In the case of FIG. 3, all compositions show a logarithmic normal distribution, and the average particle size is between about 10 and 30 μm.
第４図には、この実施例の方法により得られたCo90Zr
10のアモルフアス合金粉末を振動磁束計（VSM）により
測定した磁束密度Ｂと磁場の強さＨとの関係カーブすな
わちＢ−Ｈループカーブを示している。FIG. 4 shows Co90Zr obtained by the method of this example.
The relationship curve of the magnetic flux density B measured by the vibrating magnetometer (VSM) and the strength H of the magnetic field, that is, the BH loop curve, is shown.
また第５図には、この実施例の方法により得られるCo
Zr系アモルフアス合金粉末の飽和磁化密度とZr濃度（原
子量％）との関係を表わしている。さらに表１には、こ
の実施例の方法により得られた３種類のCoZr系アモルフ
アス合金粉末の固体密度，平均粒径，結晶化温度，飽和
磁束密度および保磁力を示している。Further, in FIG. 5, Co obtained by the method of this embodiment is shown.
It shows the relationship between the saturation magnetization density and the Zr concentration (atomic weight%) of Zr-based amorphous alloy powder. Further, Table 1 shows the solid density, average particle size, crystallization temperature, saturation magnetic flux density and coercive force of the three types of CoZr-based amorphous alloy powders obtained by the method of this example.
第４図から、この実施例の方法により得られたCo濃度
の高いCoZr系アモルフアス合金粉末は、スムースなＢ−
Ｈカーブを示しており強磁性体であることがわかる。From FIG. 4, it can be seen that the CoZr-based amorphous alloy powder having a high Co concentration obtained by the method of this example has a smooth B-
An H curve is shown, which shows that it is a ferromagnetic material.
またVSMにより求めた飽和磁束密度はCo濃度（原子量
％）が高くなるにしたがつて増大し、Co90Zr10のアモル
フアス合金粉末の場合は、13400ガウス（Ｇ）の高い値
が得られる。保磁力は、アモルフアス合金製造時には11
エルステツド（Oe）であるが、390℃において30エルス
テツド（Oe）の回転磁界の中で熱処理を行なうと、保磁
力が1.5エルステツド（Oe）にまで回復し、経時変化が
著しく小さい良好な軟磁気特性を示す。The saturation magnetic flux density determined by VSM increases as the Co concentration (atomic weight%) increases, and in the case of the amorphous alloy powder of Co90Zr10, a high value of 13400 gauss (G) is obtained. The coercive force is 11 when manufacturing amorphous alloys.
Although it is an Elsted (Oe), when it is heat-treated at 390 ° C in a rotating magnetic field of 30 Elsted (Oe), the coercive force recovers to 1.5 Elsted (Oe), and the soft magnetic characteristics are excellent with little change over time. Indicates.
したがつて、前述のCoZr系アモルフアス合金粉末は高
飽和磁束密度をもつ軟磁性粉末材料とし用途展開するこ
とができる。例えば合金粉末として電磁クラツチ用，磁
気研磨用などに適用できる。またホツトプレスやHIP
（熱間静水圧プレス）法などによる圧粉成形磁性体とし
ては、磁気ヘツドコア，トランスや磁気センサーなど多
彩な用途が考えられる。Therefore, the above-mentioned CoZr-based amorphous alloy powder can be used as a soft magnetic powder material having a high saturation magnetic flux density and can be used for various purposes. For example, as an alloy powder, it can be applied to electromagnetic clutches and magnetic polishing. Also hot press and HIP
Various applications such as magnetic head cores, transformers, and magnetic sensors can be considered as the powder compact magnetic material produced by the (hot isostatic pressing) method.
なおCoとZrの原子量％をCo95Zr5に設定した場合も、
前述の場合と同様に高飽和磁束密度をもつ軟質磁性アモ
ルフアス合金粉末が得られる。Even when the atomic weight% of Co and Zr is set to Co95Zr5,
Soft magnetic amorphous alloy powder having a high saturation magnetic flux density can be obtained as in the case described above.
実施例２ 平均粒径５μｍのCo粉末および平均粒径20μｍのTi粉
末を、Co80Ti20の原子量割合になるように精秤して混合
し、得られた混合粉末を、実施例１の場合と同一の衝撃
式ミル１の容器２内に収容し、アジテータ３を300RPMの
回転速度で50時間回転させ、メカニカルアロイング法に
より合金化とアモルフアス化とを行なつた。Example 2 Co powder having an average particle size of 5 μm and Ti powder having an average particle size of 20 μm were precisely weighed and mixed so as to have an atomic weight ratio of Co80Ti20, and the resulting mixed powder was the same as in Example 1. It was housed in a container 2 of an impact mill 1, the agitator 3 was rotated at a rotation speed of 300 RPM for 50 hours, and alloying and amorphization were performed by a mechanical alloying method.
この実施例の方法によつて得られたCoTi系アモルフア
ス合金粉末のＸ線デイフラクトメータによる回折図形を
第６図に示す。第６図のＸ線回折図形には、通常の金属
結晶特有のシヤープなピークは全く見られず、アモルフ
アス合金特有のハーロパターンのみであり、異種金属粉
末の混合状態から一挙にアモルフアス合金粉末が得られ
たことがわかる。FIG. 6 shows the diffraction pattern of the CoTi-based amorphous alloy powder obtained by the method of this example, measured by an X-ray diffractometer. In the X-ray diffraction pattern of FIG. 6, there are no sharp peaks peculiar to ordinary metal crystals, and only the Haro pattern peculiar to amorphous alloys is obtained. It can be seen that it was obtained.
この実施例の方法によつて得られたCoTi系アモルフア
ス合金粉末を実施例１の場合と同様に振動磁束計（VS
M）により測定したところ、得られたＢ−Ｈループカー
ブはスムーズであり、前記CoTi系アモルフアス合金粉末
が強磁性体であることがわかる。また実施例１の場合と
同一条件に設定した加熱下の回転磁界中で、前記CoTi系
アモルフアス合金粉末を熱処理を施したところ、良好な
軟磁性特性を示した。The CoTi-based amorphous alloy powder obtained by the method of this example was applied to the oscillating magnetometer (VS
As a result of measurement by M), the obtained BH loop curve is smooth, and it can be seen that the CoTi-based amorphous alloy powder is a ferromagnetic material. When the CoTi-based amorphous alloy powder was heat-treated in a rotating magnetic field under heating set under the same conditions as in Example 1, good soft magnetic characteristics were exhibited.
なおこの発明による高飽和磁束密度をもつ軟質磁性材
料であるCoリツチ合金系のアモルフアス合金を得るに
は、前記実施例に記載したCo−Zr系やCo−Ti系だけでな
く、同じIV a族のHfを使用してもはば同等の特性を得ら
れる。Incidentally, in order to obtain an amorphous alloy of a Co-rich alloy system which is a soft magnetic material having a high saturation magnetic flux density according to the present invention, not only the Co-Zr system and the Co-Ti system described in the above examples but also the same IVa group The same characteristics can be obtained by using Hf.
この発明を実施する場合、衝撃式ミルとしては、前記
アトライタに代えて、ボールミル，ポツトミル，チュー
ブミル，バイブロミル等を使用してもよく、またタワー
ミル，媒体（メデイア）撹拌型ミル等のように、容器と
その中に装入されているボールやロツド等の衝撃用媒体
（メデイア）とから成り立つており、容器を回転または
振動させるか、容器中の媒体を撹拌棒，撹拌翼，撹拌デ
イスク等により撹拌あるいは振動させることにより、媒
体相互間または容器と媒体との間で、粉体に強い衝撃力
または圧縮，剪断力等を与える型式のものを使用しても
よい。When carrying out the present invention, as the impact type mill, a ball mill, a pot mill, a tube mill, a vibro mill or the like may be used instead of the attritor, and a tower mill, a medium (media) stirring type mill or the like, It consists of a container and an impact medium (media) such as balls and rods loaded in the container. The container is rotated or vibrated, or the medium in the container is stirred by a stirring rod, stirring blade, stirring disk, or the like. You may use the type which gives a strong impact force or compression, shearing force, etc. to a powder between mediums or between a container and a medium by stirring or vibrating.
またこれらの衝撃式ミルによるアモルフアス合金化の
ための処理時間，容器またはアジテータの回転数や振動
数，衝撃用媒体であるボールやロツド等の材質や大きさ
や量等の条件は、合金組成，原料金属粒径や処理機器の
特性を加味して最適値を選定すればよく、前記実施例に
限定されるものではない。The conditions such as the processing time for alloying alloys with these impact mills, the number of revolutions and frequencies of the container or agitator, and the material, size and amount of impact medium such as balls and rods depend on the alloy composition and the raw material. The optimum value may be selected in consideration of the metal particle size and the characteristics of the processing equipment and is not limited to the above-mentioned embodiment.
この発明を実施する場合、CoとZrまたはTi等のIV a族
の金属とからなる結晶合金粉末におけるIV a族の金属粉
末の原子量％を１〜35％にすると共に、各金属粉末の合
計原子量％を100％に設定し、前記結晶合金粉末からな
る原料粉末を、衝撃式ミルを用いて外部から加熱するこ
となくメカニカルアロイング法により処理して、高濃度
Co合金系の高飽和磁束密度をもつ軟質磁性アモルフアス
合金粉末を製造してもよい。When carrying out the present invention, the atomic weight% of the group IVa metal powder in the crystal alloy powder consisting of Co and the group IVa metal such as Zr or Ti is set to 1 to 35%, and the total atomic weight of each metal powder is % Was set to 100%, and the raw material powder consisting of the crystalline alloy powder was treated by a mechanical alloying method without external heating using an impact mill to obtain a high concentration.
A soft magnetic amorphous alloy powder having a high saturation magnetic flux density of a Co alloy system may be manufactured.
前記Co,Zr,Tiの単独の金属粉末またはそれらの結晶合
金粉末の粒径は約7mm以下，好ましくは約0.1μｍから各
1mmが望ましい。原料粒径が約7mmよりも大きいと、アモ
ルフアス合金化作用が発揮される前に粒子の粉砕作用が
行なわれるので、その分だけ製造時間が長くかかる。ま
た原料粒径が0.1μｍよりも小さいと、比表面積が大き
く汚染されやすいし、一般的に原料の価格が高くなるの
で不経済である。The particle size of the above Co, Zr, and Ti single metal powders or their crystal alloy powders is about 7 mm or less, preferably about 0.1 μm.
1mm is preferable. If the raw material particle size is larger than about 7 mm, the particles are crushed before the amorphous alloying effect is exerted, so that the production time becomes longer accordingly. If the particle size of the raw material is smaller than 0.1 μm, the specific surface area is large and the material is easily polluted, and the raw material is generally expensive, which is uneconomical.
原料組成中のZrやTiの原子量％は、前述した範囲に設
定する必要がある。ZrおよびTiの原子量％が１原子量％
よりも少ないと、アモルフアス合金化が難かしくなり、
またZrおよびTiの原子量％が35原子量％を越えると、飽
和磁束密度が最高でも1000ガウス以下であり、約4000ガ
ウス以上の高飽和磁束密度をもつ軟質磁性アモルフアス
合金粉末を製造することができない。The atomic weight% of Zr or Ti in the raw material composition needs to be set within the range described above. The atomic weight% of Zr and Ti is 1 atomic weight%
If it is less than the above, it becomes difficult to form an amorphous alloy,
When the atomic weight% of Zr and Ti exceeds 35 atomic%, the saturation magnetic flux density is 1000 gauss or less at the maximum, and it is not possible to produce a soft magnetic amorphous alloy powder having a high saturation magnetic flux density of about 4000 gauss or more.
この発明によれば、Coからなるベース金属粉末にZrま
たはTiからなるIV a族の金属粉末を配合し、かつIV a族
の金属粉末の原子量％を１〜35％にすると共に、各金属
粉末の合計原子量％を100％に設定し、前記各金属粉末
からなる原料粉末を、衝撃式ミルを用いて外部から加熱
することなくメカニカルアロイング法により処理し、異
種金属粉末の混合物をそのまま固体状態で合金化すると
共にアモルフアス化するので、高飽和磁束密度をもつCo
系軟質磁性アモルフアス合金粉末を、容易にかつ大量
に，生産性高く製造することができ、特に高濃度Coをベ
ースにした遷移金属−遷移金属系アモルフアス合金であ
るので、遷移金属−半金属系アモルフアス合金に比べ
て、高飽和磁束密度，高透磁率，高結晶化温度を有し、
かつ耐摩耗性や耐食性に優れており、さらにこの発明の
場合は、従来の液体急冷法に比べてアモルフアス化が容
易な合金組成範囲が広いので、合金組成コントロールが
容易であり、かつ均一なアモルフアス構造と経時変化の
極めて小さい特性をもつアモルフアス合金粉末を得るこ
とができる。またこの発明により得られるアモルフアス
合金は、薄膜や薄いテープではなく微細な粉末であるの
で、合金粉末のままでも利用でき、かつ種々の形に一体
成形加工することもでき、そのため最終製品の大きさと
形状の範囲を広くできる等の効果が得られる。According to this invention, a group IVa metal powder made of Zr or Ti is mixed with a base metal powder made of Co, and the atomic weight% of the group IVa metal powder is set to 1 to 35%. The total atomic weight% of is set to 100%, and the raw material powder consisting of each of the metal powders is processed by a mechanical alloying method without external heating using an impact mill, and the mixture of different metal powders is in a solid state as it is. Since it alloys with and becomes amorphous, Co with high saturation magnetic flux density
A soft magnetic amorphous amorphous alloy powder can be produced easily and in a large amount with high productivity. In particular, since it is a transition metal-transition metal amorphous alloy based on high concentration Co, a transition metal-semimetal amorphous amorphous powder is used. Compared with alloy, it has high saturation magnetic flux density, high permeability, high crystallization temperature,
And excellent in wear resistance and corrosion resistance, further, in the case of the present invention, since the alloy composition range that is easily amorphized compared to the conventional liquid quenching method is wide, alloy composition control is easy, and a uniform amorphous It is possible to obtain an amorphous alloy powder having a structure and characteristics of which the change with time is extremely small. Further, since the amorphous alloy obtained by the present invention is not a thin film or a thin tape but a fine powder, it can be used as an alloy powder as it is and can be integrally molded into various shapes, and therefore, the size of the final product and The effect that the range of the shape can be widened can be obtained.
第１図は衝撃式ミルの一例を示す縦断側面図、第２図は
この発明の第１実施例の方法により得られたCoZr系アモ
ルフアス合金粉末のＸ線のデイフラクトメータによる回
折図形を示す図、第３図は前記アモルフアス合金粉末の
粒度分布を示す図、第４図はCo90Zr10アモルフアス合金
粉末の未処理及び熱処理物を振動磁束計により測定して
得た磁束密度と磁場の強さとの関係を示すＢ−Ｈループ
図、第５図は前記アモルフアス合金粉末の飽和磁束密度
とZr濃度との関係を示す図である。第６図は第２実施例
の方法により得られたアモルフアス合金粉末のＸ線のデ
イフラクトメータよる回折図形を示す図である。 図において、１は衝撃式ミル、２は容器、３はアジテー
タである。FIG. 1 is a longitudinal side view showing an example of an impact mill, and FIG. 2 is a diagram showing an X-ray diffraction pattern of a CoZr-based amorphous alloy powder obtained by the method of the first embodiment of the present invention by a diffractometer. Fig. 3 shows the particle size distribution of the amorphous alloy powder, and Fig. 4 shows the relationship between the magnetic flux density and the magnetic field strength obtained by measuring the untreated and heat-treated Co90Zr10 amorphous alloy powder with a vibrating magnetometer. FIG. 5 is a B-H loop diagram, and FIG. 5 is a diagram showing a relationship between the saturation magnetic flux density and the Zr concentration of the amorphous alloy powder. FIG. 6 is a view showing an X-ray diffraction pattern of an amorphous alloy powder obtained by the method of the second embodiment by an X-ray diffractometer. In the figure, 1 is an impact mill, 2 is a container, and 3 is an agitator.
Claims (1)
らなるIV a族の金属粉末を配合し、かつIV a族の金属粉
末の原子量％を１〜35％にすると共に、各金属粉末の合
計原子量％を100％に設定し、前記各金属粉末からなる
原料粉末を、衝撃式ミルを用いて外部から加熱すること
なくメカニカルアロイング法により処理して、Coリツチ
Co合金系の高飽和磁束密度をもつ軟質磁性アモルフアス
合金粉末を得ることを特徴とする高飽和磁束密度をもつ
軟質磁性アモルフアス合金粉末の製造方法。1. A base metal powder made of Co is blended with a group IVa metal powder made of Zr or Ti, and the atomic weight% of the group IVa metal powder is adjusted to 1 to 35%. The total atomic weight% is set to 100%, and the raw material powder consisting of each of the metal powders is processed by a mechanical alloying method using an impact mill without external heating, and a Co-rich
A method for producing a soft magnetic amorphous alloy powder having a high saturation magnetic flux density, which comprises obtaining a soft magnetic amorphous alloy powder having a high saturation magnetic flux density of a Co alloy system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62074487A JP2562316B2 (en) | 1987-03-30 | 1987-03-30 | Method for producing soft magnetic amorphous alloy powder having high saturation magnetic flux density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62074487A JP2562316B2 (en) | 1987-03-30 | 1987-03-30 | Method for producing soft magnetic amorphous alloy powder having high saturation magnetic flux density |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63241102A JPS63241102A (en) | 1988-10-06 |
| JP2562316B2 true JP2562316B2 (en) | 1996-12-11 |
Family
ID=13548694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62074487A Expired - Lifetime JP2562316B2 (en) | 1987-03-30 | 1987-03-30 | Method for producing soft magnetic amorphous alloy powder having high saturation magnetic flux density |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2562316B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111979B (en) * | 2016-08-31 | 2018-03-09 | 广东省钢铁研究所 | A kind of automatic annealing device of magnetically soft alloy powder decomposed ammonia |
-
1987
- 1987-03-30 JP JP62074487A patent/JP2562316B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63241102A (en) | 1988-10-06 |
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