JPH07310149A - Ferrous amorphous alloy thin strip - Google Patents

Ferrous amorphous alloy thin strip

Info

Publication number
JPH07310149A
JPH07310149A JP6098574A JP9857494A JPH07310149A JP H07310149 A JPH07310149 A JP H07310149A JP 6098574 A JP6098574 A JP 6098574A JP 9857494 A JP9857494 A JP 9857494A JP H07310149 A JPH07310149 A JP H07310149A
Authority
JP
Japan
Prior art keywords
ribbon
cooling rate
thin strip
amorphous alloy
sec
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Withdrawn
Application number
JP6098574A
Other languages
Japanese (ja)
Inventor
Toshio Yamada
田 利 男 山
Hiroaki Sakamoto
本 広 明 坂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority to JP6098574A priority Critical patent/JPH07310149A/en
Publication of JPH07310149A publication Critical patent/JPH07310149A/en
Withdrawn legal-status Critical Current

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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni

Landscapes

  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Continuous Casting (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

PURPOSE:To produce a ferrous amorphous alloy thin strip easily treatable and shoving good mechanical properties and magnetic properties even in the case of a producing condition in which the cooling rate is small. CONSTITUTION:This amorphous alloy thin strip is the one produced by a single roll method in such a manner that the average cooling rate in which the temp. of the free surface of the thin strip lies in 500 to 200 deg.C is regulated to range of 10<2>K to 10<3>K/sec. The compsn. of the alloy is constituted of (Fe Si B C)100-xSn; where, by atom, (x) satisfies 0.003 to 1.096, and 70<=a<=86%, 1<=b<=19%, 7<=c<=20%, 0<=d<=4% and a+b+c+d=100% are regulated. Thus, the thin strip good in magnetic properties and mechanical properties can easily be produced. Moreover, since the obtd. ferrous amorphous alloy thin strip shows good characteristics, it is applicable to various uses including the iron core material for a power transformer.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、電力トランス、高周波
トランスなどの鉄心に用いられるＦｅ基非晶質合金薄帯
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Fe-based amorphous alloy ribbon used for iron cores of power transformers, high frequency transformers and the like.

【０００２】[0002]

【従来の技術】非晶質合金薄帯の工業的な用途として、
電力トランスの鉄心などが挙げられるが、薄帯の板厚を
大きくすることは巻き回数や、積層枚数を減らすことに
なり、薄帯の工業材料としての発展に効果的である。し
かしながら、板厚を厚くすることによって薄帯の冷却速
度が低下するため、良好な磁気特性および機械的特性を
得ることが困難であった。これは冷却速度の低下によっ
て薄帯が結晶化するためであり、薄帯の良好な特性を保
持するためには、冷却速度を大きくする工夫や結晶化を
抑える方法が必要であった。2. Description of the Related Art As an industrial application of an amorphous alloy ribbon,
Examples of the cores of power transformers include increasing the thickness of the thin strip, which reduces the number of windings and the number of laminated layers, and is effective in developing the thin strip as an industrial material. However, it is difficult to obtain good magnetic properties and mechanical properties because the cooling rate of the ribbon decreases by increasing the plate thickness. This is because the ribbon is crystallized due to the decrease in the cooling rate, and in order to maintain the good characteristics of the ribbon, it was necessary to devise a method for increasing the cooling rate or to suppress the crystallization.

【０００３】本発明者らは、薄帯の冷却速度を大きくす
る方法として、特開昭６０−２５５２４３号公報におい
て、多重スリット法を提案している。この方法によれば
板厚が５０μｍ以上、板幅が２０ｍｍ以上で磁気特性に
優れ、かつ強靭な薄帯が得られる。さらに、特開昭６１
−２１２４４９号公報および特願平０５−２４８０６８
号公報においては、薄帯が冷却基板から剥離するときの
温度を制御し、冷却速度を１０3 ℃／秒以上とすること
によって、靭性の高いＦｅ基非晶質合金薄帯が得られる
ことを提案している。The inventors of the present invention have proposed a multiple slit method in Japanese Patent Laid-Open No. 60-255243 as a method for increasing the cooling rate of the ribbon. According to this method, a thin ribbon having a plate thickness of 50 μm or more and a plate width of 20 mm or more, excellent magnetic properties and being tough can be obtained. Furthermore, JP-A-61
-212449 and Japanese Patent Application No. 05-248068
In the publication, it is disclosed that a Fe-based amorphous alloy ribbon with high toughness can be obtained by controlling the temperature at which the ribbon strips from the cooling substrate and controlling the cooling rate to 10 3 ° C / sec or more. is suggesting.

【０００４】一方、薄帯の結晶化を抑制する方法とし
て、本発明者らは、Ｓｎを添加することにより、Ｓｎが
薄帯の表面に富化して薄帯の表面結晶化を抑制すること
を見い出した。そして、特願平３−１０１６６０号、特
願平３−１９０３９２号、特願平３−１９０３９３号、
および特願平５−０７４１４５号において既に提案して
いる。On the other hand, as a method of suppressing the crystallization of the ribbon, the present inventors added Sn to enrich the surface of the ribbon and suppress the surface crystallization of the ribbon. I found it. And Japanese Patent Application No. 3-101660, Japanese Patent Application No. 3-190392, Japanese Patent Application No. 3-190393,
And it has already been proposed in Japanese Patent Application No. 5-074145.

【０００５】上述のように、本発明者らは、Ｓｎが表面
富化することにより、薄帯の表面結晶化を抑制する効果
があることを見い出したが、実施例などに報告されてい
る冷却装置はいずれも１０3 ℃／秒以上であり、それよ
りも小さい冷却速度の場合にＳｎの結晶化抑制効果が確
認された報告はなされていない。従来技術においては、
冷却速度を高める方法や、表面の結晶化を抑制する方法
について種々開示されているが、高度な製造技術や複雑
な装置構造が必要とされており、またいずれも冷却速度
が１０3 ℃／秒以上であることを条件としていた。As described above, the present inventors have found that the surface enrichment of Sn has the effect of suppressing the surface crystallization of the ribbon, but the cooling reported in the Examples and the like. All the devices have a temperature of 10 3 ° C / sec or more, and no report has been made that the crystallization-suppressing effect of Sn was confirmed when the cooling rate was lower than that. In the prior art,
Various methods of increasing the cooling rate and suppressing the crystallization of the surface have been disclosed, but advanced manufacturing techniques and complicated device structures are required, and all of them have a cooling rate of 10 3 ° C / sec. It was a condition that it was above.

【０００６】[0006]

【発明が解決しようとする課題】工業的にみた場合、容
易に、しかも形状の安定した薄帯が安価で得られること
が望ましい。例えば、多重スリットにおけるスリット数
は少ない方がよく、また、冷却ロールは安価な材質のも
のを使用し、ロール径を小さくする等が考えられる。こ
の様な場合、冷却速度は悪くなる方向に働き、結晶化に
よって磁気特性や機械的性質が劣化する等の問題が生じ
ていた。From an industrial point of view, it is desirable that a ribbon having a stable shape can be easily obtained at a low cost. For example, it is preferable that the number of slits in the multiple slits is small, and that the cooling roll is made of an inexpensive material and the roll diameter is reduced. In such a case, the cooling rate tends to deteriorate, and there has been a problem that the crystallization causes deterioration of magnetic properties and mechanical properties.

【０００７】本発明は、冷却速度が１０3 ℃／秒以下の
小さい製造条件の場合においても、取扱いが容易であ
り、良好な機械的性質および磁気的性質を示すＦｅ基非
晶質合金薄帯を提供することを目的とするものである。According to the present invention, the Fe-based amorphous alloy ribbon which is easy to handle and has good mechanical and magnetic properties even under a small manufacturing condition of a cooling rate of 10 3 ° C / sec or less. It is intended to provide.

【０００８】[0008]

【課題を解決するための手段】本発明は、以下の事項を
その要旨とするものである。薄帯の自由表面の温度が５
００℃から２００℃の範囲で平均冷却速度が１０2Ｋ／
秒以上、１０3 Ｋ／秒以下の範囲で単ロール法によって
製造される非晶質合金薄帯であり、合金組成が下記の条
件を満足しており、優れた機械的性質および磁気的性質
を有することを特徴とするＦｅ基非晶質合金薄帯。 （ＦｅａＳｉｂＢｃＣｄ）１００−ｘＳｎｘ ただし、原子％で、７０％≦ａ≦８６％、 １％≦ｂ≦１９％、 ７％≦ｃ≦２０％、 ０％≦ｄ≦ ４％、 ０．００３％≦ｘ≦１．０％ ａ＋ｂ＋ｃ＋ｄ＝１００％SUMMARY OF THE INVENTION The present invention has the following features. The temperature of the free surface of the ribbon is 5
An average cooling rate of 10 2 K / in the range of 00 ° C to 200 ° C
It is an amorphous alloy ribbon manufactured by the single roll method in the range of not less than 10 seconds and not more than 10 3 K / second, and the alloy composition satisfies the following conditions, and has excellent mechanical properties and magnetic properties. An Fe-based amorphous alloy ribbon having. (Fe a Si b B c C d ) 100-x Sn x However, in atomic%, 70% ≦ a ≦ 86%, 1% ≦ b ≦ 19%, 7% ≦ c ≦ 20%, 0% ≦ d ≦ 4%, 0.003% ≦ x ≦ 1.0% a + b + c + d = 100%

【０００９】以下に、本発明を詳細に説明する。まず、
冷却速度を制御する温度域を上記範囲に限定した理由に
ついて述べる。本発明は、溶湯が凝固した後のガラス遷
移温度以下における薄帯の冷却速度が小さい場合に効果
を発揮する。本来、冷却速度を制御すべき温度域の上限
はガラス遷移温度とすべきであるが、このガラス遷移温
度は合金組成によって異なるのみならず、非晶質合金で
は正確にこの遷移温度を求めることが困難な場合が多
い。そこで、冷却速度を制御する温度域の上限を５００
℃とした。また、下限が２００℃より大きい場合は、薄
帯の中に部分的に冷却条件の異なる領域が存在し、特性
値にバラツキが生じる。したがって、冷却速度を制御す
る温度域を５００℃から２００℃とした。The present invention will be described in detail below. First,
The reason why the temperature range for controlling the cooling rate is limited to the above range will be described. The present invention is effective when the cooling rate of the ribbon at the glass transition temperature or less after the molten metal is solidified is small. Originally, the upper limit of the temperature range in which the cooling rate should be controlled should be the glass transition temperature, but this glass transition temperature differs not only with the alloy composition, but with amorphous alloys, it is possible to accurately determine this transition temperature. Often difficult. Therefore, the upper limit of the temperature range for controlling the cooling rate is set to 500
℃ was made. When the lower limit is higher than 200 ° C., there are regions in the ribbon that have different cooling conditions, and the characteristic values vary. Therefore, the temperature range for controlling the cooling rate is set to 500 ° C to 200 ° C.

【００１０】次に、薄帯の冷却速度を限定した理由につ
いて述べる。冷却速度が１０3 Ｋ／秒以上の場合につい
ては、従来法にて磁気特性および機械的特性の良好な薄
帯が得られる。本発明において１０3 Ｋ／秒以下の冷却
速度で製造された薄帯は、Ｓｎ添加によって磁気特性お
よび機械的性質が著しく改善できることを見い出した。
一方、１０2 Ｋ／秒未満の冷却速度において非晶質薄帯
を製造することが不可能であることは、経験的に明かで
ある。したがって、冷却速度の下限を１０2 Ｋ／秒以上
とした。Next, the reason for limiting the cooling rate of the ribbon will be described. When the cooling rate is 10 3 K / sec or more, a ribbon having good magnetic properties and mechanical properties can be obtained by the conventional method. In the present invention, it has been found that ribbons manufactured at a cooling rate of 10 3 K / sec or less can significantly improve magnetic properties and mechanical properties by adding Sn.
On the other hand, it is empirically clear that it is impossible to produce an amorphous ribbon at a cooling rate of less than 10 2 K / sec. Therefore, the lower limit of the cooling rate is set to 10 2 K / sec or more.

【００１１】鋳造中の薄帯の冷却速度は、例えば、特開
昭５６−６４１１４号公報に開示されている接触式の温
度計による方法で測温できる。この方法を用いることに
よって、５００℃〜２００℃の間の平均冷却速度を求め
ることができる。The cooling rate of the ribbon during casting can be measured by, for example, a method using a contact type thermometer disclosed in Japanese Patent Laid-Open No. 56-64114. By using this method, the average cooling rate between 500 ° C and 200 ° C can be determined.

【００１２】Ｓｎの添加量、および基本組成の配合比を
限定した理由について述べる。なお、以下特に断らない
限り全て原子％を意味している。Ｓｎ：本発明の合金を
構成する最も重要な元素であるＳｎは、表面に富化する
ことによって薄帯表面の結晶化を抑制する効果を示すも
のであるが、添加量０．００３％未満では十分な効果が
得られない。また、１．０％を超えた量を添加しても、
効果の向上は見られない。したがって、Ｓｎの添加量は
０．００３％以上、１．０％以下とした。The reason for limiting the addition amount of Sn and the compounding ratio of the basic composition will be described. In the following, all atomic percentages are meant unless otherwise specified. Sn: Sn, which is the most important element constituting the alloy of the present invention, has the effect of suppressing crystallization of the ribbon surface by enriching the surface, but if the addition amount is less than 0.003% Not enough effect. Also, even if the amount added exceeds 1.0%,
The effect is not improved. Therefore, the addition amount of Sn is set to 0.003% or more and 1.0% or less.

【００１３】ＦｅａＢｉｂＢｃＣｄ：基本組成ＦｅａＢ
ｉｂＢｃＣｄにおける、ａ，ｂ，ｃ，ｄを限定する理由
を述べる。ａは、実用的なレベルとして１．６Ｔ（テス
ラ）以上の高い飽和磁束密度が得られることを条件に、
７０％以上、８６％以下とした。ａが前記の範囲の下限
７０％をはずれると、１．６Ｔ以上の飽和磁束密度を達
成することが困難となり、一方、上限８６％を超えると
非晶質の形成が困難になり磁気特性のバラツキが大きく
なるからである。Fe a Bi b B c C d : Basic composition Fe a B
The reason for limiting a, b, c, d in i b B c C d will be described. a is a condition that a high saturation magnetic flux density of 1.6 T (tesla) or more is obtained as a practical level,
70% or more and 86% or less. If a deviates from the lower limit of 70% of the above range, it becomes difficult to achieve a saturation magnetic flux density of 1.6 T or more, while if it exceeds the upper limit of 86%, it becomes difficult to form an amorphous material and variations in magnetic properties occur. Because it becomes larger.

【００１４】ＳｉとＢ：これらの元素は非晶質形成能お
よび熱的安定性を向上させるために加える。本発明にお
いては、ｂは１％以上、１９％以下、ｃは７％以上、２
０％以下である。ｂが１％未満、あるいはｃが７％未満
では非晶質相が安定に形成されず、一方、ｂが１９％、
ｃが２０％を超えても原料コストが高くなるだけで、非
晶質形成能、熱的安定性の向上が認められない。従っ
て、ｂは１％以上、１９％以下、ｃは７％以上、２０％
以下の範囲に限定した。Si and B: These elements are added to improve the amorphous forming ability and the thermal stability. In the present invention, b is 1% or more and 19% or less, and c is 7% or more, 2
It is 0% or less. If b is less than 1% or c is less than 7%, an amorphous phase is not stably formed, while b is 19%,
Even if c exceeds 20%, the raw material cost only increases, and no improvement in amorphous forming ability and thermal stability is observed. Therefore, b is 1% or more and 19% or less, c is 7% or more and 20%
It is limited to the following range.

【００１５】Ｃ：炭素は非晶質薄帯の製造性向上に必要
な元素である。本発明においてはＣが含まれていなくて
も効果を得ることができるが、より効果を得るためには
Ｃを含有することが望ましい。Ｃを含有させることによ
り、冷却基板材質として良く用いられるＣｕなどとの濡
れ性が向上して性状の良い薄帯を形成することができ
る。Ｃは０．０１％程度の少量でも加わることによっ
て、冷却基板との濡れ性の改善効果を示す。しかし、４
％を超えると熱的安定性が低下するとともに薄帯表面層
が結晶化しやすくなる。従って、Ｃの範囲ｄは、０％以
上、４％以下に規定した。C: Carbon is an element necessary for improving the productivity of the amorphous ribbon. In the present invention, the effect can be obtained even if C is not contained, but it is desirable to contain C in order to obtain more effect. By containing C, the wettability with Cu or the like, which is often used as a material for the cooling substrate, is improved, and a thin strip with good properties can be formed. By adding C even in a small amount of about 0.01%, the effect of improving the wettability with the cooling substrate is exhibited. But 4
%, The thermal stability is lowered and the ribbon surface layer is easily crystallized. Therefore, the range d of C is defined to be 0% or more and 4% or less.

【００１６】従来、板厚が６０μｍ以上で磁気特性や機
械的特性の良好な薄帯を得るには、多重ノズルを用いる
しかなかった。これは板厚の増加による冷却速度の低下
を抑制するための方法である。得ようとする板厚が大き
くなるに従い、スリットの多重度も増し、３重、４重の
ノズルを使用しなければならなかった。しかし、本発明
によって、単一ノズルによっても板厚６０μｍ以上で特
性の良好な薄帯が得られるようになった。多重ノズルを
使用するには高度な製造技術を要するばかりでなく、ス
リットの加工精度も重要である。したがって、スリット
の多重度が小さい方が製造は容易になり、単一スリット
で製造できることが望ましい。また、スリットの多重度
を小さくする方向の効果ばかりでなく、多重スリットの
場合において、個々の多重度の板厚限界を大きくする効
果もある。Conventionally, in order to obtain a thin strip having a plate thickness of 60 μm or more and having good magnetic properties and mechanical properties, only a multiple nozzle has been used. This is a method for suppressing a decrease in cooling rate due to an increase in plate thickness. As the plate thickness to be obtained increased, the multiplicity of slits also increased, and triple or quadruple nozzles had to be used. However, according to the present invention, even with a single nozzle, it is possible to obtain a thin strip having a good plate thickness of 60 μm or more. In order to use multiple nozzles, not only sophisticated manufacturing technology is required, but also slit processing accuracy is important. Therefore, the smaller the multiplicity of the slits, the easier the manufacturing is, and it is desirable that the slits can be manufactured. Further, not only the effect of decreasing the multiplicity of the slits but also the effect of increasing the plate thickness limit of each multiplicity in the case of the multi-slits.

【００１７】冷却速度に影響を与えるものとして、ロー
ルの材質がある。通常は冷却性能を高めるために、熱伝
達率の高いＣｕ製のロールを用いる。しかし、Ｃｕより
も熱伝達率の小さい材質のロールを使用した場合、冷却
速度は必然的に小さくなる。例えば、Ｆｅ製のロールは
熱伝達率がＣｕの１／５以下である。この様に熱伝達率
の低下による冷却速度の低下が生じた場合においても、
特性の良好な薄帯を得ることができる。The material of the roll has an effect on the cooling rate. Usually, a roll made of Cu having a high heat transfer coefficient is used in order to enhance the cooling performance. However, when a roll made of a material having a heat transfer coefficient smaller than that of Cu is used, the cooling rate is inevitably low. For example, a roll made of Fe has a heat transfer coefficient of 1/5 or less that of Cu. In this way, even when the cooling rate decreases due to the decrease in heat transfer coefficient,
It is possible to obtain a ribbon having good characteristics.

【００１８】従来、１０3 Ｋ／秒以上の冷却速度を得る
ためには、製造条件において、ロールの周速を早めてい
る。この場合、パドル（湯溜まり）が不安定になり、薄
帯の表面性状が悪くなったり、板厚の変動が生じたりす
る。また、薄帯の鋳造同時巻取りが困難になるなどの問
題がある。したがって、工業的に見た場合、冷却速度は
小さくなるが、周速は遅い方が良い。本発明はこの様な
場合における、冷却速度の低下に対しても、効果を発揮
する。Conventionally, in order to obtain a cooling rate of 10 3 K / sec or more, the peripheral speed of the roll is increased under the manufacturing conditions. In this case, the paddle (pouring pool) becomes unstable, the surface quality of the ribbon becomes poor, and the plate thickness varies. Further, there is a problem that it becomes difficult to simultaneously wind a thin strip by casting. Therefore, from an industrial point of view, the cooling rate is low, but the peripheral speed is preferably low. The present invention exerts an effect even with respect to a decrease in cooling rate in such a case.

【００１９】また、冷却速度を高めるために、ロールを
水冷構造にするなども行われているが、本発明を用いれ
ば、ロールにこの様な効果で、複雑な機構を持たせる必
要がなくなり、設備コストを低く抑えることができる。Further, in order to increase the cooling rate, the roll is made to have a water cooling structure, etc., but according to the present invention, it is not necessary to provide the roll with a complicated mechanism due to such an effect. The equipment cost can be kept low.

【００２０】次に、本発明の実施態様について述べる。
まず、Ｆｅ，Ｓｉ，Ｂ，Ｃ，Ｓｎが上述した所定の組成
範囲（Ｃは０もしくは０．０１原子％以上）となるよう
に配合した原料あるいは母合金を溶解し、通常の単ロー
ル急冷法など片面冷却法を用いて非晶質の急冷薄帯とす
る。冷却基板の材質は、Ｃｕ，Ｆｅおよびその他の合金
製のいずれかでも良い。Next, embodiments of the present invention will be described.
First, a raw material or a master alloy compounded so that Fe, Si, B, C, and Sn are in the above-described predetermined composition range (C is 0 or 0.01 atomic% or more) is melted, and a normal single roll quenching method is used. A single-sided cooling method is used to form an amorphous quenched ribbon. The material of the cooling substrate may be any of Cu, Fe and other alloys.

【００２１】この時使用するノズルは単一のスリットノ
ズル、あるいは多重スリットノズルを用いることができ
る。ここで単一ノズルとは、基板の移動方向に測った幅
が、０．２ｍｍ以上、１．０ｍｍ以下の細長いスリット
状開口部をひとつもつノズルで、薄帯の板厚が主に４０
μｍ以下のときに用いられる。また、多重スリットノズ
ルは、スリット状開口部を基板の移動方向に所定の間隔
に配列したノズルで、主に４５μｍ以上の厚肉材料の製
造に用いられる。なお、鋳造する雰囲気は、大気中、不
活性ガス中、真空中のいずれかでもよい。The nozzle used at this time may be a single slit nozzle or a multiple slit nozzle. Here, the single nozzle is a nozzle having one elongated slit-shaped opening whose width measured in the moving direction of the substrate is 0.2 mm or more and 1.0 mm or less, and the thin plate thickness is mainly 40
Used when μm or less. The multi-slit nozzle is a nozzle in which slit-shaped openings are arranged at a predetermined interval in the moving direction of the substrate, and is mainly used for manufacturing thick materials of 45 μm or more. The atmosphere for casting may be any of air, inert gas, and vacuum.

【００２２】[0022]

【実施例】以下、本発明を実施例に基づいてさらに説明
する。実施例１ 合金組成が（Ｆｅ８０．５Ｓｉ６．５Ｂ１２Ｃ１）
１００−ｘＳｎｘで、ｘが０〜１．０原子％の範囲で変
化させて配合した合金を、単ロール法を用いて幅２５ｍ
ｍの急冷薄帯にそれぞれ作製した。使用したノズルは、
２重スリットノズル（幅０．９ｍｍ、長さ２５ｍｍ、間
隔１ｍｍ）である。このノズルから６００ｒｐｍで回転
する直径５８０ｍｍのＣｕ合金製冷却ロールの上に溶湯
を噴出した。得られた薄帯の板厚は、およそ７５μｍで
ある。この薄帯の冷却速度は、８×１０2 Ｋ／秒以上で
ある。冷却速度は、薄帯の自由表面の温度の５００℃か
ら２００℃の範囲の平均冷却速度である。EXAMPLES The present invention will be further described below based on examples. Example 1 The alloy composition is (Fe 80.5 Si 6.5 B 12 C 1 ).
An alloy prepared by mixing 100-x Sn x with x varied in the range of 0 to 1.0 atomic% and having a width of 25 m using a single roll method.
Each of them was made into a quenched ribbon of m. The nozzle used is
It is a double slit nozzle (width 0.9 mm, length 25 mm, interval 1 mm). From this nozzle, the molten metal was jetted onto a cooling roll made of Cu alloy having a diameter of 580 mm rotating at 600 rpm. The plate thickness of the obtained ribbon is about 75 μm. The cooling rate of this ribbon is 8 × 10 2 K / sec or more. The cooling rate is an average cooling rate in the range of 500 ° C. to 200 ° C. of the temperature of the free surface of the ribbon.

【００２３】この薄帯を３６０℃で１時間、窒素雰囲気
中で磁場焼鈍し、磁気特性を測定した。１．３Ｔ，５０
Ｈｚにおける鉄損値は、比較材が６．０Ｗ／ｋｇ以上で
あるのに対し、本発明材は０．２Ｗ／ｋｇ以下の良好な
特性を示した。This ribbon was magnetically annealed at 360 ° C. for 1 hour in a nitrogen atmosphere, and its magnetic characteristics were measured. 1.3T, 50
The iron loss value at Hz was 6.0 W / kg or more for the comparative material, while the invention material exhibited good characteristics of 0.2 W / kg or less.

【００２４】また、これらの薄帯の非晶質性を調べるた
めに、薄帯の自由面をＸ線回折法によって解析したとこ
ろ、比較材は結晶化していることを示す大きなピークが
見られるのに対し、Ｓｎを添加した本発明の材料は結晶
化を示すピークが認められなかった。これらの結果か
ら、通常では結晶化してしまい磁気的性質が著しく劣化
するような小さな冷却速度の場合でも、Ｓｎを添加する
ことにより表面の結晶化を抑制し、磁気的性質を向上さ
せることがわかる。Further, in order to investigate the amorphousness of these ribbons, the free surface of the ribbons was analyzed by X-ray diffraction method, and a large peak showing that the comparative material was crystallized was found. On the other hand, in the material of the present invention to which Sn was added, no peak indicating crystallization was observed. From these results, it is understood that the addition of Sn suppresses the crystallization of the surface and improves the magnetic properties even at a small cooling rate at which crystallization usually occurs and the magnetic properties are significantly deteriorated. .

【００２５】実施例２ 合金組成が（Ｆｅ７８Ｓｉ１０Ｂ１０Ｃ２）１００−ｘ
Ｓｎｘで、ｘが０〜１．０原子％の範囲で変化させて配
合したそれぞれの合金を、単ロール法を用いて幅２５ｍ
ｍの急冷薄帯に作製した。使用したノズルは、単一スリ
ットノズル（幅０．８ｍｍ、長さ２５ｍｍ）である。こ
のノズルから５００ｒｐｍで回転する直径５８０ｍｍの
Ｆｅ製冷却ロールの上に溶湯を噴出した。得られた薄帯
の板厚は、およそ４５μｍである。この薄帯の冷却速度
は、７×１０2 Ｋ／秒以上である。冷却速度は、薄帯の
自由表面の温度の５００℃から２００℃の範囲の平均冷
却速度である。 Example 2 The alloy composition is (Fe 78 Si 10 B 10 C 2 ) 100-x.
Sn x , alloys mixed by changing x in the range of 0 to 1.0 atomic% were prepared using a single roll method to obtain a width of 25 m.
It was made into a quenched ribbon of m. The nozzle used is a single slit nozzle (width 0.8 mm, length 25 mm). From this nozzle, the molten metal was jetted onto a Fe-made cooling roll having a diameter of 580 mm which was rotated at 500 rpm. The plate thickness of the obtained ribbon is about 45 μm. The cooling rate of this ribbon is 7 × 10 2 K / sec or more. The cooling rate is an average cooling rate in the range of 500 ° C. to 200 ° C. of the temperature of the free surface of the ribbon.

【００２６】各薄帯について１８０度密着曲げ試験を行
った。評価は破壊時の薄帯の曲げ直径で行った。比較材
は３０ｍｍ以上の曲げ径で破壊したのに対し、本発明材
は６ｍｍ以下の直径まで破壊しなかった。この結果から
明らかなように、Ｓｎを添加することによって曲げ破壊
特性が大幅に改善されることがわかる。A 180-degree contact bending test was performed on each thin strip. The evaluation was performed by the bending diameter of the ribbon at the time of breaking. The comparative material fractured at a bending diameter of 30 mm or more, whereas the inventive material did not fracture to a diameter of 6 mm or less. As is clear from this result, it is understood that the bending fracture characteristics are significantly improved by adding Sn.

【００２７】実施例１および実施例２より明らかなよう
に、本発明は、鋳造中の薄帯の冷却温度が１０2 Ｋ／秒
以上、１０3 Ｋ／秒以下と小さな場合においても、薄帯
表面の結晶化を抑制することにより磁気特性および靭性
などの劣化を防ぐ効果を示すものである。As is clear from Examples 1 and 2, the present invention enables the thin ribbon to be cooled even when the cooling temperature of the thin ribbon during casting is as small as 10 2 K / sec or more and 10 3 K / sec or less. By suppressing the crystallization of the surface, it has the effect of preventing the deterioration of the magnetic properties and toughness.

【００２８】[0028]

【発明の効果】本発明によって、従来にない冷却速度の
小さい領域においても、高度な製造技術や複雑な装置を
用いることなく、磁気特性および機械的特性の良好な薄
帯を、容易に製造することができる。また、本発明で得
られたＦｅ基非晶質合金薄帯は、板厚が厚く、広幅の材
料であっても、良好な特性を示すことから、電力トラン
スの鉄心材をはじめとする種々の用途に使用でき、応用
範囲を拡大することが可能となる。According to the present invention, a ribbon having good magnetic properties and mechanical properties can be easily manufactured without using a high-level manufacturing technique or a complicated device even in an area where the cooling rate is unprecedented. be able to. In addition, the Fe-based amorphous alloy ribbon obtained in the present invention exhibits good characteristics even if it is a thick plate and has a wide width, so that it can be used in various materials including iron core materials for power transformers. It can be used for various purposes and the range of applications can be expanded.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】薄帯の自由表面の温度が５００℃から２０
０℃の範囲で平均冷却速度が１０2Ｋ／秒以上、１０3
Ｋ／秒以下の範囲で単ロール法によって製造される非晶
質合金薄帯であり、合金組成が下記の条件を満足してお
り、優れた機械的性質および磁気的性質を有することを
特徴とするＦｅ基非晶質合金薄帯。 （ＦｅａＳｉｂＢｃＣｄ）１００−ｘＳｎｘ ただし、原子％で、７０％≦ａ≦８６％、 １％≦ｂ≦１９％、 ７％≦ｃ≦２０％、 ０％≦ｄ≦ ４％、 ０．００３％≦ｘ≦１．０％ ａ＋ｂ＋ｃ＋ｄ＝１００％1. The temperature of the free surface of the ribbon ranges from 500.degree. C. to 20.
The average cooling rate is 10 2 K / sec or more in the range of 0 ° C and 10 3
An amorphous alloy ribbon produced by a single roll method in a range of K / sec or less, characterized in that the alloy composition satisfies the following conditions and has excellent mechanical properties and magnetic properties. Fe-based amorphous alloy ribbon. (Fe a Si b B c C d ) 100-x Sn x However, in atomic%, 70% ≦ a ≦ 86%, 1% ≦ b ≦ 19%, 7% ≦ c ≦ 20%, 0% ≦ d ≦ 4%, 0.003% ≦ x ≦ 1.0% a + b + c + d = 100%
JP6098574A 1994-05-12 1994-05-12 Ferrous amorphous alloy thin strip Withdrawn JPH07310149A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6098574A JPH07310149A (en) 1994-05-12 1994-05-12 Ferrous amorphous alloy thin strip

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6098574A JPH07310149A (en) 1994-05-12 1994-05-12 Ferrous amorphous alloy thin strip

Publications (1)

Publication Number Publication Date
JPH07310149A true JPH07310149A (en) 1995-11-28

Family

ID=14223448

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6098574A Withdrawn JPH07310149A (en) 1994-05-12 1994-05-12 Ferrous amorphous alloy thin strip

Country Status (1)

Country Link
JP (1) JPH07310149A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002012576A1 (en) * 2000-08-07 2002-02-14 Tanaka Kikinzoku Kogyo K.K. Noble-metal-based amorphous alloys
WO2009107561A1 (en) * 2008-02-25 2009-09-03 新日本製鐵株式會社 Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
JP2009195967A (en) * 2008-02-25 2009-09-03 Shun Sato Apparatus and method for manufacturing amorphous alloy foil strip
JP2010099682A (en) * 2008-10-22 2010-05-06 Shun Sato Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
JP2010099683A (en) * 2008-10-22 2010-05-06 Shun Sato Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
JP2018070998A (en) * 2009-11-19 2018-05-10 イドロ−ケベックＨｙｄｒｏ−Ｑｕｅｂｅｃ System and method for treating amorphous alloy ribbon

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002012576A1 (en) * 2000-08-07 2002-02-14 Tanaka Kikinzoku Kogyo K.K. Noble-metal-based amorphous alloys
US6749698B2 (en) 2000-08-07 2004-06-15 Tanaka Kikinzoku Kogyo K.K. Precious metal based amorphous alloys
WO2009107561A1 (en) * 2008-02-25 2009-09-03 新日本製鐵株式會社 Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
JP2009195967A (en) * 2008-02-25 2009-09-03 Shun Sato Apparatus and method for manufacturing amorphous alloy foil strip
US8327917B2 (en) 2008-02-25 2012-12-11 Nippon Steel Corporation Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
US8602086B2 (en) 2008-02-25 2013-12-10 Nippon Steel & Sumitomo Metal Corporation Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
JP2010099682A (en) * 2008-10-22 2010-05-06 Shun Sato Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
JP2010099683A (en) * 2008-10-22 2010-05-06 Shun Sato Apparatus for producing amorphous alloy foil strip and method for producing amorphous alloy foil strip
JP2018070998A (en) * 2009-11-19 2018-05-10 イドロ−ケベックＨｙｄｒｏ−Ｑｕｅｂｅｃ System and method for treating amorphous alloy ribbon

Similar Documents

Publication Publication Date Title
JP4402960B2 (en) Fe-based amorphous alloy ribbon with excellent soft magnetic properties, iron core produced using the same, and master alloy for producing rapidly solidified ribbon used therefor
US7425239B2 (en) Fe-based amorphous alloy ribbon
KR100447090B1 (en) Fe-based amorphous alloy thin strip and core produced using the same
US5593518A (en) Amorphous Fe-B-Si-C alloys having soft magnetic characteristics useful in low frequency applications
JP3342767B2 (en) Fe-based soft magnetic alloy
EP0072893B1 (en) Metallic glasses having a combination of high permeability, low coercivity, low ac core loss, low exciting power and high thermal stability
JP2008231534A5 (en)
JP2550449B2 (en) Amorphous alloy ribbon for transformer core with high magnetic flux density
JP2778719B2 (en) Iron-based amorphous magnetic alloy containing cobalt
JPH07310149A (en) Ferrous amorphous alloy thin strip
JP3434844B2 (en) Low iron loss, high magnetic flux density amorphous alloy
JP4037989B2 (en) Fe-based amorphous alloy ribbon with ultrathin oxide layer
JPH08283919A (en) Iron-base amorphous alloy foil and its production
JP2588450B2 (en) Amorphous alloy ribbon with improved crystallization resistance of surface layer and method for producing the same
US5456770A (en) Amorphous magnetic alloy with high magnetic flux density
JP2812574B2 (en) Low frequency transformer
JPH06287721A (en) Amorphous alloy thin strip enhanced in crystallization resistance on surface
JP3208051B2 (en) Iron-based amorphous alloy with excellent thermal stability
JPH05222494A (en) Amorphous alloy sheet steel for transformer iron core having high magnetic flux density
JP2812569B2 (en) Low frequency transformer
JPH11131199A (en) Soft magnetic glass alloy
JP2002285304A (en) Fe BASED AMORPHOUS ALLOY THIN STRIP HAVING HIGH MAGNETIC FLUX DENSITY
JP2000144347A (en) Iron base soft magnetic alloy and control of magnetostriction therein
JPH04362162A (en) Amorphous alloy thin strip having crystallized layer at inside of sheet thickness and excellent in magnetic property
JPH05132744A (en) Production of amorphous alloy strip having high saturation magnetic flux density and amorphous alloy iron core

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 20010731