JP2000309860A - Fe-BASE AMORPHOUS ALLOY RIBBON WITH EXTRA THIN OXIDE LAYER - Google Patents
Fe-BASE AMORPHOUS ALLOY RIBBON WITH EXTRA THIN OXIDE LAYERInfo
- Publication number
- JP2000309860A JP2000309860A JP11117698A JP11769899A JP2000309860A JP 2000309860 A JP2000309860 A JP 2000309860A JP 11117698 A JP11117698 A JP 11117698A JP 11769899 A JP11769899 A JP 11769899A JP 2000309860 A JP2000309860 A JP 2000309860A
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- Prior art keywords
- ribbon
- oxide layer
- amorphous alloy
- layer
- thickness
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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
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- 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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電力トランス用な
どの鉄心材に用いられる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 an iron core material for a power transformer or the like.
【０００２】[0002]
【従来の技術】非晶質合金薄帯は、合金を溶融状態から
急冷することによって得られる。薄帯を製造する方法と
しては、遠心急冷法、単ロール法、双ロール法、等が知
られている。これらの方法は、高速回転する金属製ドラ
ムの内周面または外周面に溶融金属をオリフィス等から
噴出させることによって、急速に溶融金属を凝固させて
薄帯や線材を製造するものである。さらに、合金組成を
適正に選ぶことによって、磁気的性質、機械的性質、あ
るいは耐食性に優れた非晶質合金薄帯を得ることができ
る。2. Description of the Related Art An amorphous alloy ribbon is obtained by rapidly cooling an alloy from a molten state. As a method for producing a ribbon, a centrifugal quenching method, a single roll method, a twin roll method, and the like are known. In these methods, a molten metal is ejected from an orifice or the like onto the inner or outer peripheral surface of a metal drum rotating at a high speed, thereby rapidly solidifying the molten metal to produce a ribbon or a wire. Furthermore, by properly selecting the alloy composition, an amorphous alloy ribbon excellent in magnetic properties, mechanical properties, or corrosion resistance can be obtained.
【０００３】この非晶質合金薄帯は、その優れた特性か
ら多くの用途において工業用材料として有望視されてい
る。その中でも、電力トランスや高周波トランスなどの
鉄心材料の用途としては、鉄損が低く、かつ、飽和磁束
密度および透磁率が高いこと、等の理由からFe系非晶質
合金薄帯、例えば、Fe-Si-B 系などが採用されている。[0003] This amorphous alloy ribbon is regarded as a promising industrial material in many applications because of its excellent properties. Among them, applications of iron core materials such as power transformers and high-frequency transformers include low iron loss, and high saturation magnetic flux density and high magnetic permeability. -Si-B type is adopted.
【０００４】非晶質合金薄帯を鉄心材料として用いる場
合、磁気特性向上を目的に薄帯表面に皮膜を形成する方
法が数多く開示されている。例えば、薄帯に酸化物など
の絶縁皮膜を形成する方法がある。絶縁皮膜は非晶質合
金薄帯を巻き回したり積層して作られるトランス磁心に
おいて、層間の絶縁性を高め、渡り磁束によって生じる
渦電流損失を減少させる効果を持つ。例えば、特開平６
−３４６２１９号公報においては、薄帯の熱処理工程で
20％以上の酸素を導入して薄帯表面に数10〜100 nmの酸
化膜を付けてトロイダルコアにした時の層間の絶縁性を
高めて透磁率を改善する方法が開示されている。また、
薄帯中にCr、Nb、Tiなどの4A、5A、6A族の元素、特にCr
を含有すると、それらの元素を含む酸化膜が生成され、
透磁率の高い薄帯が得られることが述べられている。し
かし、改善された磁気特性は、４MHz や10MHz の高周波
領域のものであり、数10Hz程度の低周波領域での磁気特
性は十分に改善されたとは言えない。[0004] When an amorphous alloy ribbon is used as an iron core material, many methods for forming a film on the surface of the ribbon have been disclosed for the purpose of improving magnetic properties. For example, there is a method of forming an insulating film such as an oxide on a ribbon. In a transformer core made by winding or laminating an amorphous alloy ribbon, the insulating film has the effect of increasing the insulation between the layers and reducing the eddy current loss caused by the crossover magnetic flux. For example, Japanese Unexamined Patent Publication
In the publication No. 346219, the heat treatment process of the ribbon
There is disclosed a method for improving the magnetic permeability by increasing the insulating properties between layers when a toroidal core is formed by introducing an oxide film of several tens to 100 nm on the surface of a ribbon by introducing 20% or more of oxygen. Also,
Group 4A, 5A, 6A elements such as Cr, Nb, Ti, etc., especially Cr
Contains, an oxide film containing those elements is generated,
It is stated that a ribbon having a high magnetic permeability can be obtained. However, the improved magnetic characteristics are in the high-frequency range of 4 MHz or 10 MHz, and the magnetic characteristics in the low-frequency range of about several tens Hz cannot be said to have been sufficiently improved.
【０００５】他に、薄帯表面での皮膜形成により、薄帯
に圧縮応力を付与して鉄損などを改善する方法がある。
特開昭６１−２５０１６２号公報において、熱処理を不
活性ガスと酸素の混合雰囲気中で行い、20nm〜300nm の
酸化皮膜層を形成する方法が開示されている。皮膜が薄
帯面内方向に圧縮応力を与えて鉄損改善を図っている。
50kHz での鉄損は改善されているものの、数10Hz程度の
低周波領域での磁気特性は十分に改善されたとは言えな
い。In addition, there is a method of improving the core loss by applying a compressive stress to the ribbon by forming a film on the surface of the ribbon.
JP-A-61-250162 discloses a method in which a heat treatment is performed in a mixed atmosphere of an inert gas and oxygen to form an oxide film layer having a thickness of 20 nm to 300 nm. The coating applies compressive stress in the in-plane direction of the ribbon to improve iron loss.
Although the iron loss at 50 kHz is improved, the magnetic properties in the low frequency range of several tens of Hz are not sufficiently improved.
【０００６】[0006]
【発明が解決しようとする課題】上述のごとく、従来技
術として、薄帯の鉄損を改善する目的で薄帯表面に酸化
層を形成させた薄帯はあるものの、鉄損が十分に改善さ
れたとは言えない。また、表面酸化層の構造や薄帯中の
As、Sb、Bi、Se、Te、Ｐ、Ｓなどの微量元素が薄帯の表
面酸化層に及ぼす効果を記述したものもない。As described above, as a prior art, although there is a ribbon in which an oxide layer is formed on the surface of the ribbon for the purpose of improving the iron loss of the ribbon, the iron loss is sufficiently improved. I can't say that. In addition, the structure of the surface oxide layer and the
None describes the effects of trace elements such as As, Sb, Bi, Se, Te, P, and S on the surface oxide layer of the ribbon.
【０００７】本発明は、極薄酸化層、および、該酸化層
と非晶質母相との界面近傍に、As、Sb、Bi、Se、Teの少
なくとも1 種以上の元素を含む偏析層を形成させること
によって、鉄損を低減させた、低鉄損Fe基非晶質合金を
提供することを目的とするものである。The present invention provides an ultra-thin oxide layer and a segregation layer containing at least one element of As, Sb, Bi, Se, and Te near the interface between the oxide layer and the amorphous matrix. An object of the present invention is to provide a low iron loss Fe-based amorphous alloy having reduced iron loss by being formed.
【０００８】[0008]
【課題を解決するための手段】本発明の要旨とするとこ
ろは以下の通りである。 （１）移動する冷却基板上に、スロット状の開口部を有
する注湯ノズルを介して溶融金属を噴出し、急冷凝固さ
せて得られる急冷金属薄帯であって、少なくとも片側の
薄帯表面に極薄酸化層を有し、さらに該酸化層と非晶質
母相との界面近傍に、As、Sb、Bi、Se、Teの少なくとも
１種以上の元素を含む偏析層を有することを特徴とする
Fe基非晶質合金薄帯。The gist of the present invention is as follows. (1) A rapidly quenched metal ribbon obtained by jetting molten metal onto a moving cooling substrate through a pouring nozzle having a slot-shaped opening and rapidly quenching and solidifying the molten metal. It has an ultrathin oxide layer, and further has a segregation layer containing at least one or more elements of As, Sb, Bi, Se, and Te near the interface between the oxide layer and the amorphous matrix. Do
Fe-based amorphous alloy ribbon.
【０００９】（２）移動する冷却基板上に、スロット状
の開口部を有する注湯ノズルを介して溶融金属を噴出
し、急冷凝固させて得られる急冷金属薄帯であって、少
なくとも片側の薄帯表面に極薄酸化層を有し、さらに該
酸化層と非晶質母相との界面近傍に、As、Sb、Bi、Se、
Teの少なくとも１種以上の元素を含み、さらに、Ｐおよ
びＳの少なくとも１種以上の元素を含む偏析層を有する
ことを特徴とするFe基非晶質合金薄帯。(2) A quenched metal ribbon obtained by jetting molten metal onto a moving cooling substrate through a pouring nozzle having a slot-shaped opening and rapidly solidifying the molten metal, wherein at least one side of the quenched metal ribbon is thinned. It has an ultra-thin oxide layer on the band surface, and further, near the interface between the oxide layer and the amorphous matrix, As, Sb, Bi, Se,
An Fe-based amorphous alloy ribbon comprising at least one element of Te and a segregation layer containing at least one element of P and S.
【００１０】（３）少なくとも冷却基板に接触しない側
の薄帯表面に極薄酸化層と偏析層を有することを特徴と
する（１）または（２）記載のFe基非晶質合金薄帯。 （４）偏析層の厚みが0.2nm 以上であることを特徴とす
る（１）、（２）または（３）記載のFe基非晶質合金薄
帯。 （５）極薄酸化層がFe系、Si系、B 系あるいはそれらの
複合体から構成されることを特徴とする（１）、
（２）、（３）または（４）記載のFe基非晶質合金薄
帯。(3) The Fe-based amorphous alloy ribbon according to (1) or (2), which has an ultrathin oxide layer and a segregation layer on at least the surface of the ribbon that is not in contact with the cooling substrate. (4) The Fe-based amorphous alloy ribbon according to (1), (2) or (3), wherein the thickness of the segregation layer is 0.2 nm or more. (5) The ultra-thin oxide layer is composed of Fe-based, Si-based, B-based or a composite thereof.
The Fe-based amorphous alloy ribbon according to (2), (3) or (4).
【００１１】（６）薄帯の板厚が10μm 以上、100 μm
以下であることを特徴とする（１）、（２）、（３）、
（４）または（５）記載のFe基非晶質合金薄帯。(6) The thickness of the ribbon is 10 μm or more and 100 μm or more.
(1), (2), (3),
The Fe-based amorphous alloy ribbon according to (4) or (5).
【００１２】[0012]
【発明の実施の形態】本発明の特徴とするところは、極
薄酸化層、および、該酸化層と非晶質母相との界面近傍
に、As、Sb、Bi、Se、Teの少なくとも１種以上の元素を
含む偏析層を有する薄帯構造、または、極薄酸化層、お
よび、該酸化層と非晶質母相との界面近傍に、As、Sb、
Bi、Se、Teの少なくとも１種以上の元素を含み、さら
に、P 、S の少なくとも1 種以上の元素を含む偏析層を
有する薄帯構造をFe基非晶質合金薄帯に形成させるとこ
ろにある。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is characterized in that at least one of As, Sb, Bi, Se, and Te is formed near an interface between an ultrathin oxide layer and an amorphous matrix. A ribbon structure having a segregation layer containing at least one kind of element, or an ultrathin oxide layer, and near the interface between the oxide layer and the amorphous matrix, As, Sb,
In forming a ribbon structure having a segregation layer containing at least one element of Bi, Se, and Te and further containing at least one element of P and S in an Fe-based amorphous alloy ribbon. is there.
【００１３】本発明者らは、非晶質合金薄帯を大気中で
鋳造する過程において薄帯表面に形成される極めて薄い
酸化層が鉄損に影響を及ぼすことを明らかにし、それに
基づいて、極薄酸化層を有する低鉄損Fe基非晶質合金薄
帯を出願した（特願平１０−１２２７３５）。特願平１
０−１２２７３５号では、少なくとも片側の表面に厚さ
5nm から20nmの極薄酸化層を持つFe非晶質合金薄帯、お
よび、極薄酸化層とその極薄酸化層の下部にP およびS
の少なくとも1 種を含む偏析層を有するFe基非晶質合金
薄帯が低鉄損を示すことが開示されている。The present inventors have clarified that an extremely thin oxide layer formed on the surface of a ribbon in the process of casting an amorphous alloy ribbon in the atmosphere affects iron loss. We filed a low iron loss Fe-based amorphous alloy ribbon having an extremely thin oxide layer (Japanese Patent Application No. 10-122735). Japanese Patent Application No. 1
No. 0-122735, a thickness is provided on at least one surface.
Fe amorphous alloy ribbon with an ultrathin oxide layer of 5 to 20 nm, and P and S below the ultrathin oxide layer and the ultrathin oxide layer
It is disclosed that an Fe-based amorphous alloy ribbon having a segregation layer containing at least one of the following exhibits low iron loss.
【００１４】本発明者らは、鉄損低減に効果を持つ元素
を探索的に鋭意検討した結果、As、Sb、Bi、Se、Teを含
有する偏析層を、薄帯表面の極薄酸化層と非晶質母相の
界面近傍に形成させることにより、非晶質合金薄帯の鉄
損を低減できることを見出し、本発明を完成するに至っ
たのである。本発明のFe基非晶質合金薄帯は、少なくと
も片側の薄帯表面に極薄酸化層を有し、さらに、その酸
化層と非晶質母相との界面近傍に、As、Sb、Bi、Se、Te
の少なくとも１種以上の元素を含む偏析層を有する。偏
析層は、極薄酸化層と非晶質母相との界面の酸化層側に
あってもよいし、非晶質母相側にあってもよい。また、
界面の両側にあってもよい。The present inventors have conducted intensive studies on elements that have an effect on reducing iron loss. As a result, the segregation layer containing As, Sb, Bi, Se, and Te was changed to an ultrathin oxide layer on the surface of the ribbon. The present inventors have found that the iron loss of the amorphous alloy ribbon can be reduced by forming it near the interface between the amorphous matrix and the amorphous matrix, and have completed the present invention. The Fe-based amorphous alloy ribbon of the present invention has an ultrathin oxide layer on at least one side of the ribbon surface, and further, near the interface between the oxide layer and the amorphous matrix, As, Sb, Bi. , Se, Te
Having a segregation layer containing at least one or more of the following elements. The segregation layer may be on the oxide layer side of the interface between the ultrathin oxide layer and the amorphous matrix, or may be on the amorphous matrix phase. Also,
It may be on both sides of the interface.
【００１５】薄帯表面に極薄酸化層を形成させるのは非
晶質合金薄帯に張力を付与するためである。非晶質合金
薄帯に張力を付与することにより磁区細分化が起こり、
鉄損が低減すると考えられる。酸化層が厚くなるほど非
晶質母相に大きな張力がかかるため、鉄損が低減する傾
向にある。しかし、酸化層が厚くなりすぎると鉄損低減
効果がなくなってしまう。これは、酸化層が厚くなりす
ぎると、酸化層と非晶質母相の密着性が悪くなり、張力
が伝わりにくくなるのではないかと考えられる。したが
って、極薄酸化層の厚みは5nm 以上20nm以下が好まし
い。酸化層が5nm未満では鉄損低減効果が小さく、ま
た、酸化層が20nmを超えても、それ以上の鉄損低減効果
が認められないからである。The reason for forming the ultrathin oxide layer on the surface of the ribbon is to apply tension to the amorphous alloy ribbon. Magnetic domain refinement occurs by applying tension to the amorphous alloy ribbon,
It is considered that iron loss is reduced. The thicker the oxide layer, the greater the tension applied to the amorphous matrix, which tends to reduce iron loss. However, if the oxide layer is too thick, the effect of reducing iron loss is lost. This is thought to be because if the oxide layer is too thick, the adhesion between the oxide layer and the amorphous matrix deteriorates, and the tension is hardly transmitted. Therefore, the thickness of the ultrathin oxide layer is preferably 5 nm or more and 20 nm or less. If the oxide layer is less than 5 nm, the effect of reducing iron loss is small, and if the oxide layer exceeds 20 nm, no further effect of reducing iron loss is observed.
【００１６】As、Sb、Bi、Se、Teの少なくとも１種以上
の元素を含有した偏析層の効果は、その偏析層が存在す
ることにより、表面酸化層が厚くなることである。ま
た、偏析層が存在することにより、極薄酸化層の厚みが
均一となる効果もある。これらの効果により、偏析層を
有しない場合と比べて鉄損低減効果は大きくなる。As、
Sb、Bi、Se、Teの少なくとも１種以上の元素に加えて、
P およびS の少なくとも1 種以上の元素を含む場合、さ
らに鉄損低減効果が得られる。The effect of the segregation layer containing at least one element of As, Sb, Bi, Se and Te is that the presence of the segregation layer increases the thickness of the surface oxide layer. In addition, the presence of the segregation layer also has the effect of making the thickness of the ultrathin oxide layer uniform. Due to these effects, the iron loss reduction effect is greater than when no segregation layer is provided. As,
In addition to at least one element of Sb, Bi, Se, and Te,
When at least one element of P and S is contained, the effect of reducing iron loss is further obtained.
【００１７】偏析層の厚みは、0.2 nm以上が好ましい。
0.2 nm未満では鉄損低減の効果が小さいからである。ま
た、15nm超の厚みになってもそれ以上の鉄損低減効果が
見られないので、15nm以下が好ましい。さらに好ましく
は、10nm以下である。極薄酸化層と偏析層は、必ずしも
薄帯の両面に存在しなくてもよく、少なくとも薄帯のど
ちらかの面に存在すれば鉄損低減の効果が得られる。例
えば、薄帯の両面に形成されている極薄酸化層と偏析層
を化学エッチング等によって両面とも除去した場合、鉄
損低減効果はなくなる。除去した面に2nm 程度の自然酸
化膜が形成されるが、これは鉄損低減に寄与しない。し
かし、片面の酸化層および偏析層のみを除去し、もう片
面の酸化層および偏析層を残した場合、酸化層および偏
析層が両面にある場合には及ばないものの鉄損低減効果
を示す。冷却基板に接触する面にはエアーポケットがあ
り極薄酸化層が均一になりにくいことから、少なくとも
冷却基板に接触しない面に極薄酸化層があれば良い。The thickness of the segregation layer is preferably at least 0.2 nm.
If the thickness is less than 0.2 nm, the effect of reducing iron loss is small. Further, even if the thickness exceeds 15 nm, no further effect of reducing iron loss is observed, so that the thickness is preferably 15 nm or less. More preferably, it is 10 nm or less. The ultra-thin oxide layer and the segregation layer do not necessarily need to be present on both sides of the ribbon, and if at least on either side of the ribbon, the effect of reducing iron loss can be obtained. For example, when the ultrathin oxide layer and the segregation layer formed on both sides of the ribbon are removed by chemical etching or the like, the effect of reducing iron loss is lost. A native oxide film of about 2 nm is formed on the removed surface, but this does not contribute to reducing iron loss. However, when only the oxide layer and the segregation layer on one side are removed and the oxide layer and the segregation layer on the other side are left, the effect of reducing iron loss is shown, which is inferior to the case where the oxide layer and the segregation layer are on both sides. Since there is an air pocket on the surface in contact with the cooling substrate and the ultrathin oxide layer is difficult to be uniform, it is sufficient that at least the surface not in contact with the cooling substrate has the ultrathin oxide layer.
【００１８】本発明で好ましい薄帯の板厚は、10μm 以
上100 μm 以下である。板厚が10μm 未満では、薄帯を
安定して製造するのが困難なことがあり、また、板厚が
100μm を超える場合も薄帯を安定して製造することが
難しく、さらに、薄帯が脆くなりやすい。板厚が10μｍ
以上70μｍ以下の場合、薄帯の鋳造がより安定化するた
め、さらに好ましい。薄帯幅は特に制限されないが、20
mm以上が好ましい。The preferred thickness of the ribbon in the present invention is 10 μm or more and 100 μm or less. If the sheet thickness is less than 10 μm, it may be difficult to stably manufacture the ribbon, and if the sheet thickness is
Even when the thickness exceeds 100 μm, it is difficult to stably produce the ribbon, and the ribbon tends to become brittle. Plate thickness is 10μm
When the thickness is 70 μm or less, the casting of the ribbon is more stabilized, and therefore, it is more preferable. The width of the ribbon is not particularly limited, but may be 20
mm or more is preferable.
【００１９】本発明の薄帯の望ましい組成は、Fea Sib
Ｂc Ｃd 、ただし、ａ、ｂ、ｃおよびｄは原子％で、70
≦ａ≦86、１≦ｂ≦19、７≦ｃ≦20、0.02≦ｄ≦４、ａ
＋ｂ＋ｃ＋ｄ＝100 、さらに重量％で0.0003％以上0.15
％以下のAs、Sb、Bi、Se、Teの少なくとも１種以上の元
素を含むものである。これらの元素の含有量が0.0003％
未満では0.2nm 以上の厚さを持つ偏析層を形成しにくい
ため、鉄損低減の効果が小さく、0.15％超では、薄帯が
脆くなるなどの作用が起きやすくなるからである。さら
に好ましくは、重量％で0.0003％以上0.15％以下のAs、
Sb、Bi、Se、Teの少なくとも１種以上の元素を含み、さ
らに、重量％で0.0003％以上0.1 ％以下のP およびＳの
少なくとも1 種以上の元素を含むことによって、さらに
鉄損が低減できる。0.0003％未満ではP およびS を含む
効果が小さく、0.10％を超えて含有してもそれ以上の鉄
損低減効果はない。また、As、Sb、Bi、Se、Teの少なく
とも１種または2 種以上、および、P およびＳの少なく
とも1 種の添加元素の合計含有重量％は、0.15％以下が
好ましい。0.15% を超えると薄帯が脆くなるなどの作用
が起きやすくなるからである。The preferred composition of the ribbon of the present invention is Fe a Si b
B c C d , where a, b, c and d are at.
≤a≤86, 1≤b≤19, 7≤c≤20, 0.02≤d≤4, a
+ B + c + d = 100, 0.0003% or more by weight and 0.15%
% Or less of at least one element of As, Sb, Bi, Se, and Te. 0.0003% of the content of these elements
If it is less than 0.2 nm, it is difficult to form a segregation layer having a thickness of 0.2 nm or more, so that the effect of reducing iron loss is small. If it is more than 0.15%, an action such as brittleness of the ribbon is likely to occur. More preferably, 0.0003% or more and 0.15% or less of As by weight,
Iron loss can be further reduced by containing at least one or more elements of Sb, Bi, Se, and Te, and further containing at least one or more elements of P and S in 0.0003 to 0.1% by weight. . If it is less than 0.0003%, the effect containing P and S is small, and if it exceeds 0.10%, there is no further effect of reducing iron loss. The total content by weight of at least one or two or more of As, Sb, Bi, Se and Te, and at least one of P and S is preferably 0.15% or less. If it exceeds 0.15%, effects such as brittleness of the ribbon will easily occur.
【００２０】薄帯を鉄心に使用する場合、鉄心の飽和磁
束密度は1.5 Ｔ以上の高い値にする必要がある。そのた
めにはFeの含有量を70原子％以上にしなければならな
い。また、Feの含有量が86原子％超になると非晶質の形
成が困難になって良好な薄帯特性が得られなくなる。し
たがって、Feを70原子％以上86原子％以下にする。Siお
よびＢは非晶質形成能および熱安定性を向上させるため
のものである。Siが１原子％未満、Ｂが７原子％未満で
は非晶質が安定して形成されず、一方、Siが19原子％
超、Ｂが20原子％超としても原料コストが高くなるだけ
で、非晶質形成能および熱的安定性の向上は認められな
い。したがって、Siは１原子％以上19原子％以下、Ｂは
７原子％以上20原子％以下が好ましい。Ｃは薄帯の鋳造
性向上に効果がある元素である。Ｃを含有させることに
よって、溶湯と冷却基板の濡性が向上して良好な薄帯を
形成することができる。0.02原子％未満ではこの効果が
得られない。また、Ｃを４原子％超としてもこの効果の
向上は認められない。したがって、Ｃを0.02原子％以上
４原子％以下にした。さらなる磁気特性の安定化をはか
るには、Feを77原子％以上83原子％以下、Siを２原子％
以上９原子％以下、Ｂを11原子％以上17原子％以下にす
るのが好ましい。さらに、Feを80原子％超82原子％以
下、Siを２原子％以上５原子％未満、Ｂを14原子％以
上、16原子％以下、Ｃを0.02原子％以上、４原子％以下
の範囲では、特に極薄酸化層および偏析層による鉄損低
減効果が大きい。When a thin ribbon is used for the iron core, the saturation magnetic flux density of the iron core needs to be a high value of 1.5 T or more. For this purpose, the content of Fe must be 70 atomic% or more. On the other hand, if the Fe content exceeds 86 atomic%, it becomes difficult to form an amorphous phase, and good ribbon properties cannot be obtained. Therefore, Fe is set to 70 atomic% or more and 86 atomic% or less. Si and B are for improving the ability to form an amorphous phase and the thermal stability. If Si is less than 1 atomic% and B is less than 7 atomic%, amorphous is not formed stably, while Si is 19 atomic%.
Even if the content of B exceeds 20 atomic%, only the raw material cost is increased, and no improvement in the ability to form an amorphous phase and thermal stability is observed. Therefore, it is preferable that Si is 1 atomic% or more and 19 atomic% or less, and B is 7 atomic% or more and 20 atomic% or less. C is an element effective for improving the castability of the ribbon. By containing C, the wettability between the molten metal and the cooling substrate is improved, and a good ribbon can be formed. If less than 0.02 atomic%, this effect cannot be obtained. Further, even if C exceeds 4 atomic%, no improvement in this effect is observed. Therefore, C is set to 0.02 atomic% or more and 4 atomic% or less. In order to further stabilize the magnetic properties, 77 atomic% or more and 83 atomic% or less of Fe and 2 atomic% of Si
It is preferable that the content of B is not less than 9 atomic% and the content of B is not less than 11 atomic% and not more than 17 atomic%. Further, if Fe is more than 80 atomic% and 82 atomic% or less, Si is 2 atomic% or more and less than 5 atomic%, B is 14 atomic% or more and 16 atomic% or less, and C is 0.02 atomic% or more and 4 atomic% or less. In particular, an extremely thin oxide layer and a segregation layer have a large iron loss reducing effect.
【００２１】好ましい極薄酸化層は、Fe系、Si系、Ｂ系
の酸化物、あるいは、それらの複合酸化物を主体とした
極薄酸化層である。これらの極薄酸化物が、薄帯表面に
形成されることによって、非晶質合金薄帯に最適な張力
を生じるものと考えられる。中でも、Fe系の酸化物を主
体とすることがより好ましい。本発明の薄帯は、例えば
Fe80.5Si6.5 Ｂ12Ｃ1 （原子％）、あるいは、Fe80.5Si
2.5 Ｂ16Ｃ1 （原子％）に、As、Sb、Bi、Se、Teの少な
くとも1 種以上の元素、および、P 、S の少なくとも1
種以上の元素を添加した組成の合金溶湯を雰囲気制御が
可能なチャンバーを持つ単ロール装置を用い、チャンバ
ー内の酸素濃度を制御することによって製造することが
できる。添加元素の量および酸素濃度を制御することに
よって、極薄酸化層および偏析層の厚みを好適範囲に制
御でき、鉄損を低減した非晶質合金薄帯が得られる。ま
た、大気鋳造装置で、薄帯の板厚と剥離温度を制御する
方法も用いることができる。この方法では、添加元素の
量および剥離温度の制御によって、極薄酸化層および偏
析層の厚みを好適範囲に制御でき、鉄損を低減した非晶
質合金薄帯が得られる。あるいは、ロール上のパドル近
傍の雰囲気を制御することによっても製造することがで
きる。A preferred ultrathin oxide layer is an ultrathin oxide layer mainly composed of an Fe-based, Si-based, or B-based oxide, or a composite oxide thereof. It is considered that the formation of these ultra-thin oxides on the surface of the ribbon causes an optimum tension in the amorphous alloy ribbon. Among them, it is more preferable to mainly use an Fe-based oxide. The ribbon of the present invention is, for example,
Fe 80.5 Si 6.5 B 12 C 1 (atomic%) or Fe 80.5 Si
To 2.5 B 16 C 1 (atomic%), As, Sb, Bi , Se, at least one element of Te, and, P, at least one of S
A molten alloy having a composition to which more than one element is added can be manufactured by controlling the oxygen concentration in the chamber using a single-roll apparatus having a chamber capable of controlling the atmosphere. By controlling the amount of the added element and the oxygen concentration, the thickness of the ultra-thin oxide layer and the segregation layer can be controlled in a suitable range, and an amorphous alloy ribbon with reduced iron loss can be obtained. In addition, a method of controlling the thickness of the ribbon and the peeling temperature with an atmospheric casting apparatus can also be used. In this method, the thickness of the ultrathin oxide layer and the thickness of the segregation layer can be controlled to a suitable range by controlling the amount of the added element and the peeling temperature, and an amorphous alloy ribbon with reduced iron loss can be obtained. Alternatively, it can be manufactured by controlling the atmosphere near the paddle on the roll.
【００２２】本発明の薄帯は、単ロール装置だけでな
く、双ロール装置、ドラムの内壁を使う遠心急冷装置、
エンドレスタイプのベルトを使う装置によっても製造す
ることができる。薄帯の組成は、通常の化学分析等の方
法で測定可能である。また、極薄酸化層および偏析層の
厚みは、GDS （グロー放電発光分光法）、XPS 、AES な
どの表面解析方法を用いて測定した各元素の深さ方向の
濃度プロファイルから計測できる。The ribbon of the present invention can be used not only in a single roll device but also in a twin roll device, a centrifugal quenching device using the inner wall of a drum,
It can also be manufactured by a device using an endless type belt. The composition of the ribbon can be measured by a method such as ordinary chemical analysis. The thickness of the ultrathin oxide layer and the segregation layer can be measured from the concentration profile in the depth direction of each element measured using a surface analysis method such as GDS (glow discharge emission spectroscopy), XPS, and AES.
【００２３】[0023]
【実施例】以下の実施例に基づき、本発明をさらに説明
する。 （実施例１）母材は合金組成が原子％でFe80.5Si2.5B16
C1に配合されたものを用いた。添加元素M は、As、Sb、
Bi、Se、Teの各元素を単独あるいは複合して添加した。
この原料を外径が600mm のCu製冷却ロールを持つ単ロー
ル装置を用い、大気中で薄帯の製造を行った。薄帯の剥
離位置を変えることにより薄帯の剥離温度を制御して、
極薄酸化層および偏析層の厚みを制御した。薄帯の板厚
は約25μm 、板幅は25mmである。得られた薄帯中の添加
元素の含有量は、化学分析を用いて行った。得られた薄
帯の極薄酸化層および偏析層の厚みをGDS で調べた。そ
の1 例（薄帯No. ８）を図１に示す。ただし、各元素の
感度係数は異なっている。酸素ピークと重なる位置にF
e、Si、B のピークが観察されることから、Fe系、Si
系、B 系の酸化物を含む極薄酸化層であることがわか
る。さらに、酸素ピークの強度が急激に低下している位
置にSeのピークが観察される。このことは、極薄酸化層
と非晶質層との界面近傍に添加元素の偏析層が存在して
いることを示している。本発明で選択した添加元素As、
Sb、Bi、Se、Teは、各元素を単独あるいは複合して添加
した場合において、すべてこの極薄酸化層と非晶質母相
との界面近傍に偏析していた。The present invention will be further described with reference to the following examples. (Example 1) The base material has an alloy composition of atomic% and Fe 80.5 Si 2.5 B 16
It was used formulated in C 1. The additive element M is As, Sb,
Each element of Bi, Se, and Te was added alone or in combination.
Using this material, a ribbon was manufactured in the atmosphere using a single roll device having a cooling roll made of Cu having an outer diameter of 600 mm. By controlling the stripping temperature of the ribbon by changing the stripping position of the ribbon,
The thickness of the ultra-thin oxide layer and the segregation layer was controlled. The thickness of the ribbon is about 25 μm and the width is 25 mm. The content of the additional element in the obtained ribbon was determined using chemical analysis. The thickness of the ultra-thin oxide layer and segregation layer of the obtained ribbon was examined by GDS. One example (thin ribbon No. 8) is shown in FIG. However, the sensitivity coefficients of each element are different. F at the position overlapping the oxygen peak
Since e, Si, and B peaks are observed, Fe-based, Si-
It can be seen that the oxide layer is an ultra-thin oxide layer containing a B-based oxide. Further, a Se peak is observed at a position where the intensity of the oxygen peak sharply decreases. This indicates that a segregation layer of the additive element exists near the interface between the ultrathin oxide layer and the amorphous layer. Additive element As selected in the present invention,
Sb, Bi, Se, and Te were all segregated near the interface between the ultrathin oxide layer and the amorphous matrix when each element was added alone or in combination.
【００２４】極薄酸化層および偏析層の厚みは、図２で
示したようにGDS のピークの半値幅を用いた。これらの
薄帯を360 ℃で1 時間、窒素雰囲気中で磁場中焼鈍した
後、SST （Single Strip Tester ）を用いて、磁束密度
1.3T、周波数50Hzでの鉄損W13/50を測定した。極薄酸化
層の厚みは焼鈍の前後でほとんど変化がなかった。結果
を表１に示す。As the thickness of the ultrathin oxide layer and the segregation layer, the half width of the GDS peak was used as shown in FIG. After annealing these ribbons in a magnetic field at 360 ° C for 1 hour in a nitrogen atmosphere, the magnetic flux density was measured using SST (Single Strip Tester).
The iron loss W13 / 50 at 1.3T, frequency 50Hz was measured. The thickness of the ultra-thin oxide layer hardly changed before and after annealing. Table 1 shows the results.
【００２５】添加元素を用いた場合、酸化層厚が厚くな
り、鉄損が低下していることがわかる。特に、酸化層厚
が5nm 以上の薄帯（No．4-15）の鉄損は、0.120W/kg 以
下の良好な値を示す。しかし、No.15 の薄帯が示すよう
に、添加元素の薄帯中の合計含有量が重量% で0.15% を
超えると薄帯が脆化することがある。It can be seen that when an additive element is used, the thickness of the oxide layer is increased and the iron loss is reduced. In particular, the iron loss of a ribbon (No. 4-15) having an oxide layer thickness of 5 nm or more shows a good value of 0.120 W / kg or less. However, as indicated by the ribbon of No. 15, when the total content of the additive elements in the ribbon exceeds 0.15% by weight, the ribbon may be embrittled.
【００２６】[0026]
【表１】 [Table 1]
【００２７】（実施例２）母材は実施例１と同じく、合
金組成が原子％でFe80.5Si2.5B16C1に配合されたものを
用いた。添加元素M は、As、Sb、Bi、Se、TeおよびP 、
S の各元素を複合して添加した。実施例1 と同様に、外
径が600mm のCu製冷却ロールを持つ単ロール装置を用
い、大気中で薄帯の製造を行った。薄帯の剥離位置を変
えることにより薄帯の剥離温度を制御して、極薄酸化層
および偏析層の厚みを制御した。薄帯の板厚は約25μm
、板幅は25mmである。得られた薄帯中の添加元素の含
有量は、化学分析を用いて行った。得られた薄帯の極薄
酸化層および偏析層の厚みをGDSで調べた。厚みの評価
方法は実施例1 と同じである。(Example 2) As in Example 1, a base material having an alloy composition of atomic% and mixed with Fe 80.5 Si 2.5 B 16 C 1 was used. The additive element M is As, Sb, Bi, Se, Te and P,
Each element of S was added in combination. In the same manner as in Example 1, a ribbon was manufactured in the air using a single roll device having a cooling roll made of Cu having an outer diameter of 600 mm. The thickness of the ultrathin oxide layer and the segregation layer was controlled by controlling the stripping temperature of the ribbon by changing the stripping position of the ribbon. The thickness of the ribbon is about 25μm
, The board width is 25mm. The content of the additional element in the obtained ribbon was determined using chemical analysis. The thickness of the ultrathin oxide layer and segregation layer of the obtained ribbon was examined by GDS. The method for evaluating the thickness is the same as in Example 1.
【００２８】これらの薄帯を360 ℃で1 時間、窒素雰囲
気中で磁場中焼鈍した後、実施例１と同様にSST （Sing
le Strip Tester ）で鉄損W13/50を測定した。極薄酸化
層の厚みは焼鈍の前後でほとんど変化がなかった。結果
を表２に示す。As、Sb、Bi、Se、Teに加えて、P 、S を
添加した場合（薄帯No.16-23）は、P、S を加えない場
合（実施例１：薄帯No.5-12 ）と比較して、酸化層厚が
厚くなり、さらに鉄損が低下していることがわかる。薄
帯No.24 の例が示すように、添加元素の含有量の合計が
重量% で0.15% を超えると薄帯が脆化することがある。After annealing these ribbons in a magnetic field at 360 ° C. for 1 hour in a nitrogen atmosphere, SST (Singing) was performed in the same manner as in Example 1.
le Strip Tester) to measure iron loss W13 / 50. The thickness of the ultra-thin oxide layer hardly changed before and after annealing. Table 2 shows the results. When P and S are added in addition to As, Sb, Bi, Se and Te (thin strip No. 16-23), when P and S are not added (Example 1: thin strip No. 5-12) ), The thickness of the oxide layer is increased, and the iron loss is further reduced. As shown in the example of ribbon No. 24, when the total content of the added elements exceeds 0.15% by weight, the ribbon may be embrittled.
【００２９】[0029]
【表２】 [Table 2]
【００３０】（実施例３）実施例１および２で得た薄帯
をエッチングして表面層を落としたことによる影響を調
べた。焼鈍後の薄帯を、化学エッチングで両面あるいは
片面の表面酸化層を落とした。片面のみを落とす場合
は、残す面をマスクしてエッチングを行った。落とした
エッチング量は、片面につき約0.2 μm である。その
後、SST で鉄損を評価し、GDS で極薄酸化層の厚さおよ
び偏析層の厚さを評価した。鉄損および厚みの評価方法
は実施例1 と同じである。その結果を表３に示す。Example 3 The effects of dropping the surface layer by etching the ribbons obtained in Examples 1 and 2 were examined. The annealed ribbon was subjected to chemical etching to remove a surface oxide layer on both surfaces or one surface. When only one side was dropped, etching was performed with the remaining side being masked. The amount of etching dropped is about 0.2 μm per side. After that, iron loss was evaluated by SST, and the thickness of ultra-thin oxide layer and segregation layer were evaluated by GDS. The methods for evaluating iron loss and thickness are the same as in Example 1. Table 3 shows the results.
【００３１】薄帯No.8-c、23-cからわかるように、両面
をエッチングして極薄酸化層および偏析層を除去した場
合、エッチング後に、2nm 程度の自然酸化層が形成され
ているが鉄損W13/50が0.140W/kg 台と悪い値を示す。つ
まり、2nm 程度の自然酸化層は鉄損低減に寄与しないと
言える。これに対し、F 面（冷却基板に接触しない面）
およびR 面（冷却基板に接触している面）のどちらかに
極薄酸化層および偏析層がある場合は、両面にある場合
には及ばないものの、W13/50が0.120W/kg 以下の良い値
を示す。したがって、極薄酸化層および偏析層は、どち
らか片面にあればよいということがわかる。F 面とR 面
での比較では、極薄酸化層および偏析層がF 面にある方
が優れた値を示している。As can be seen from the ribbons No. 8-c and 23-c, when the ultrathin oxide layer and the segregation layer were removed by etching both sides, a natural oxide layer of about 2 nm was formed after the etching. Shows a bad value of iron loss W13 / 50 on the order of 0.140 W / kg. In other words, it can be said that a natural oxide layer of about 2 nm does not contribute to the reduction of iron loss. On the other hand, the F surface (the surface that does not contact the cooling substrate)
If there is an ultra-thin oxide layer or segregation layer on one of the surfaces and the R surface (the surface that is in contact with the cooling substrate), W13 / 50 is better than 0.120 W / kg, although it is not as good as on both surfaces Indicates a value. Therefore, it is understood that the ultra-thin oxide layer and the segregation layer only have to be on one side. In the comparison between the F plane and the R plane, excellent values are shown when the ultrathin oxide layer and the segregation layer are present on the F plane.
【００３２】[0032]
【表３】 [Table 3]
【００３３】（実施例４）母材は、実施例１と同じ物を
用いた。この母材に添加元素Seを重量％で0.02%加え
て、雰囲気制御可能なチャンバー内に外径300mm のCu製
冷却ロールを持つ単ロール装置を用い、チャンバー内の
酸素濃度を少量づつ変化させ、種々の厚さの極薄酸化層
および偏析層を持つ薄帯を製造した。薄帯の板厚は約25
μm 、板幅は25mmである。得られた薄帯中のSeの含有量
は、化学分析を用いて行った結果、添加量とほぼ同じで
あった。酸化層および偏析層の厚さは、GDS より求め
た。厚みの評価方法は実施例1 と同じである。実施例1
と同様に、これらの薄帯を熱処理した後、SST により鉄
損W13/50を測定した。その結果を、表４に示す。Example 4 The same base material as in Example 1 was used. 0.02% by weight of the added element Se is added to this base material, and the oxygen concentration in the chamber is changed little by little using a single roll device having a Cu cooling roll having an outer diameter of 300 mm in an atmosphere controllable chamber. Strips with various thicknesses of ultra-thin oxide and segregation layers were produced. The thickness of the ribbon is about 25
μm and the board width is 25 mm. The content of Se in the obtained ribbon was almost the same as the addition amount as a result of performing the analysis using chemical analysis. The thicknesses of the oxide layer and the segregation layer were determined by GDS. The method for evaluating the thickness is the same as in Example 1. Example 1
After heat treatment of these ribbons, the iron loss W13 / 50 was measured by SST. Table 4 shows the results.
【００３４】本実施例のすべての薄帯の鉄損W13/50は0.
130W/kg 以下の良い値を示しているが、極薄酸化層の厚
さを5nm 以上20nm以下、および、偏析層を0.2nm 以上15
nm以下の好適範囲に制御した薄帯（No.26 −36）は、鉄
損W13/50が0.120W/kg 以下の特に優れた値が得られてい
ることがわかる。No.37 の薄帯のように、偏析層の厚み
が15nmを超えても更なる鉄損低減効果は認められない。
また、No.38-40の薄帯のように、酸化層を20nmを超えて
厚くしても更なる鉄損低減効果は認められない。The iron loss W13 / 50 of all the ribbons in the present embodiment is 0.3.
It shows a good value of 130 W / kg or less, but the thickness of the ultra-thin oxide layer is 5 nm or more and 20 nm or less, and the segregation layer is
It can be seen that the ribbon (No. 26-36) controlled to a preferable range of nm or less has a particularly excellent iron loss W13 / 50 of 0.120 W / kg or less. Like the ribbon of No. 37, even if the thickness of the segregation layer exceeds 15 nm, no further iron loss reduction effect is observed.
Further, even when the thickness of the oxide layer exceeds 20 nm as in the case of the ribbon of No. 38-40, no further effect of reducing iron loss is recognized.
【００３５】[0035]
【表４】 [Table 4]
【００３６】（実施例５）実施例４と同じ原料を用い
て、外径600mm のCu製冷却ロールを持つ単ロール装置を
用い、大気中で薄帯の製造を行った。シングルおよびマ
ルチスロットを用いて種々の板厚を薄帯を製造した。製
造の際、薄帯の剥離位置を変えて薄帯の剥離温度を変え
ることで極薄酸化層及び偏析層の厚みを制御した。薄帯
の板幅は25mmである。得られた薄帯中の添加元素の含有
量は、化学分析を用いて行った。得られた薄帯の極薄酸
化層と偏析層の厚さはGDS で評価した。厚みの評価方法
は実施例1 と同じである。また、得られた薄帯を実施例
１と同じ条件で熱処理を行い、その後、SST で鉄損を評
価した。その結果を表５に示す。Example 5 Using the same raw material as in Example 4, a ribbon was manufactured in the air using a single roll device having a cooling roll made of Cu and having an outer diameter of 600 mm. Strips of various thicknesses were produced using single and multi-slots. During production, the thickness of the ultrathin oxide layer and the segregation layer were controlled by changing the stripping position of the ribbon and changing the stripping temperature of the ribbon. The width of the strip is 25 mm. The content of the additional element in the obtained ribbon was determined using chemical analysis. The thickness of the ultra-thin oxide layer and segregation layer of the obtained ribbon was evaluated by GDS. The method for evaluating the thickness is the same as in Example 1. Further, the obtained ribbon was subjected to a heat treatment under the same conditions as in Example 1, and thereafter, iron loss was evaluated by SST. Table 5 shows the results.
【００３７】本実施例のすべての薄帯の鉄損W13/50は0.
130W/kg 以下の良い値を示しているが、極薄酸化層の厚
さを5nm 以上20nm以下、および、偏析層を0.2nm 以上15
nm以下の好適範囲に制御した薄帯（No.42 −53）は、鉄
損W13/50が0.120W/kg 以下の特に優れた値が得られてい
ることがわかる。また、板厚が10μm 以上100 μm 以下
の薄帯は安定して製造することができた。薄帯No.41 の
板厚8 μm の場合は穴が無数にあき、薄帯No.53 の板厚
105 μm の場合は安定製造ができなかった。The iron loss W13 / 50 of all the ribbons in the present embodiment is 0.3.
It shows a good value of 130 W / kg or less, but the thickness of the ultra-thin oxide layer is 5 nm or more and 20 nm or less, and the segregation layer is
It can be seen that the ribbon (No. 42-53) controlled to a preferable range of nm or less has a particularly excellent value of iron loss W13 / 50 of 0.120 W / kg or less. In addition, a ribbon having a thickness of 10 μm or more and 100 μm or less could be manufactured stably. When the strip No. 41 has a thickness of 8 μm, holes are innumerable, and the strip No. 53 has a thickness of
In the case of 105 μm, stable production was not possible.
【００３８】[0038]
【表５】 [Table 5]
【００３９】[0039]
【発明の効果】極薄酸化層、および、該極薄酸化層と非
晶質母相近傍に、As、Sb、Bi、Se、Teの少なくとも1 種
以上、あるいは、これらの元素にさらにP およびS の少
なくとも1 種以上の元素を含む偏析層を有する本発明の
Fe基非晶質合金薄帯を、電力トランスなどの鉄心材料と
して用いることによって、鉄損が低減したトランスを得
ることが可能となる。According to the present invention, at least one or more of As, Sb, Bi, Se, and Te, or at least one of P and The present invention having a segregation layer containing at least one element of S
By using the Fe-based amorphous alloy ribbon as an iron core material such as a power transformer, it is possible to obtain a transformer with reduced iron loss.
【図１】GDS （グロー放電発光分光法）を用いて得た薄
帯自由面の深さ方向の元素濃度プロファイルの1 例。FIG. 1 is an example of an element concentration profile in a depth direction of a free surface of a ribbon obtained by using GDS (glow discharge emission spectroscopy).
【図２】GDS を用いて得た元素プロファイルから極薄酸
化層および偏析層の厚みの計測方法を示す略図。FIG. 2 is a schematic diagram showing a method for measuring the thickness of an ultrathin oxide layer and a segregation layer from an element profile obtained by using GDS.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山田 利男 神奈川県川崎市中原区井田３−35−１ 新 日本製鐵株式会社技術開発本部内 Ｆターム(参考） 5E041 AA19 BC01 BD00 BD03 CA02 HB07 NN06 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Yamada 3-35-1 Ida, Nakahara-ku, Kawasaki-shi, Kanagawa F-term in the Technology Development Division of Nippon Steel Corporation (reference) 5E041 AA19 BC01 BD00 BD03 CA02 HB07 NN06
Claims (6)
口部を有する注湯ノズルを介して溶融金属を噴出し、急
冷凝固させて得られる急冷金属薄帯であって、少なくと
も片側の薄帯表面に極薄酸化層を有し、さらに該酸化層
と非晶質母相との界面近傍に、As、Sb、Bi、Se、Teの少
なくとも１種以上の元素を含む偏析層を有することを特
徴とするFe基非晶質合金薄帯。1. A quenched metal ribbon obtained by jetting molten metal onto a moving cooling substrate through a pouring nozzle having a slot-shaped opening and rapidly solidifying the molten metal. It has an ultrathin oxide layer on the surface, and further has a segregation layer containing at least one or more elements of As, Sb, Bi, Se, and Te in the vicinity of the interface between the oxide layer and the amorphous matrix. Fe-based amorphous alloy ribbon.
口部を有する注湯ノズルを介して溶融金属を噴出し、急
冷凝固させて得られる急冷金属薄帯であって、少なくと
も片側の薄帯表面に極薄酸化層を有し、さらに該酸化層
と非晶質母相との界面近傍に、As、Sb、Bi、Se、Teの少
なくとも１種以上の元素を含み、さらに、ＰおよびＳの
少なくとも１種以上の元素を含む偏析層を有することを
特徴とするFe基非晶質合金薄帯。2. A rapidly quenched metal ribbon obtained by jetting molten metal onto a moving cooling substrate through a pouring nozzle having a slot-shaped opening and rapidly solidifying the molten metal, wherein at least one side of the ribbon is quenched. An ultrathin oxide layer on the surface, and further containing at least one or more elements of As, Sb, Bi, Se, and Te near the interface between the oxide layer and the amorphous matrix; An Fe-based amorphous alloy ribbon having a segregation layer containing at least one or more of the following elements.
帯表面に極薄酸化層と偏析層を有することを特徴とする
請求項１または２記載のFe基非晶質合金薄帯。3. The Fe-based amorphous alloy ribbon according to claim 1, further comprising an ultrathin oxide layer and a segregation layer on at least the surface of the ribbon that does not contact the cooling substrate.
特徴とする請求項１、２または３記載のFe基非晶質合金
薄帯。4. The Fe-based amorphous alloy ribbon according to claim 1, wherein the thickness of the segregation layer is 0.2 nm or more.
それらの複合体から構成されることを特徴とする請求項
１、２、３または４記載のFe基非晶質合金薄帯。5. The Fe-based amorphous alloy thin film according to claim 1, wherein the ultra-thin oxide layer is made of Fe-based, Si-based, B-based or a composite thereof. band.
であることを特徴とする請求項１、２、３、４または５
記載のFe基非晶質合金薄帯。6. The ribbon according to claim 1, wherein the thickness of the ribbon is 10 μm or more and 100 μm or less.
The described Fe-based amorphous alloy ribbon.
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|---|---|---|---|
| JP11769899A JP4037988B2 (en) | 1999-04-26 | 1999-04-26 | Fe-based amorphous alloy ribbon with ultrathin oxide layer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11769899A JP4037988B2 (en) | 1999-04-26 | 1999-04-26 | Fe-based amorphous alloy ribbon with ultrathin oxide layer |
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| Publication Number | Publication Date |
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| JP2000309860A true JP2000309860A (en) | 2000-11-07 |
| JP4037988B2 JP4037988B2 (en) | 2008-01-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7282103B2 (en) | 2002-04-05 | 2007-10-16 | Nippon Steel Corporation | Iron-base amorphous alloy thin strip excellent in soft magnetic properties, iron core manufactured by using said thin strip, and mother alloy for producing rapidly cooled and solidified thin strip |
| CN103695813A (en) * | 2013-12-19 | 2014-04-02 | 南京信息工程大学 | Amorphous alloy material with high saturation magnetization and preparation method thereof |
-
1999
- 1999-04-26 JP JP11769899A patent/JP4037988B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7282103B2 (en) | 2002-04-05 | 2007-10-16 | Nippon Steel Corporation | Iron-base amorphous alloy thin strip excellent in soft magnetic properties, iron core manufactured by using said thin strip, and mother alloy for producing rapidly cooled and solidified thin strip |
| CN103695813A (en) * | 2013-12-19 | 2014-04-02 | 南京信息工程大学 | Amorphous alloy material with high saturation magnetization and preparation method thereof |
| CN103695813B (en) * | 2013-12-19 | 2015-08-19 | 南京信息工程大学 | A kind of high saturation and magnetic intensity amorphous alloy material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP4037988B2 (en) | 2008-01-23 |
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