JP5967357B2 - Iron-based amorphous alloy ribbon - Google Patents
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- JP5967357B2 JP5967357B2 JP2012078770A JP2012078770A JP5967357B2 JP 5967357 B2 JP5967357 B2 JP 5967357B2 JP 2012078770 A JP2012078770 A JP 2012078770A JP 2012078770 A JP2012078770 A JP 2012078770A JP 5967357 B2 JP5967357 B2 JP 5967357B2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 110
- 229910052742 iron Inorganic materials 0.000 title claims description 49
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 33
- 230000003746 surface roughness Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000007712 rapid solidification Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910006639 Si—Mn Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005315 distribution function Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Description
本発明は、巻きトランスや積みトランス等に使用される鉄心の材料に用いて好適な鉄系非晶質合金薄帯に関するものである。 The present invention relates to an iron-based amorphous alloy ribbon suitable for use as a material for an iron core used in a winding transformer or a stacking transformer.
小型のトランスやリアクトル等の鉄心材料として、Ｆｅ−Ｂ−Ｓｉ系の非晶質合金薄帯が使用されることが多くなってきている。上記合金薄帯としては、例えば、特許文献１〜３には、Ｆｅをベースにして、ＢやＳｉ等を添加した鉄系合金の溶湯を、高速回転する冷却ロールの外周面に射出して急冷凝固させた、厚さが数十μｍの非晶質合金薄帯が開示されている。 Fe-B-Si amorphous alloy ribbons are increasingly used as iron core materials such as small transformers and reactors. As the alloy ribbon, for example, in Patent Documents 1 to 3, an iron-based alloy melt based on Fe and added with B, Si, or the like is injected into the outer peripheral surface of a cooling roll that rotates at high speed to be rapidly cooled A solidified amorphous alloy ribbon having a thickness of several tens of μm is disclosed.
しかし、上記Ｆｅ−Ｂ−Ｓｉ系の非晶質合金薄帯は、高価なＢを多量に含有させる必要があり、原料コストの点からは不利であり、Ｂを別の金属で代替することが検討されている。例えば、特許文献４および特許文献５には、上記合金系において、高価なＢを低減し、Ｍｎを添加した鉄系非晶質合金が開示されている。 However, the Fe—B—Si-based amorphous alloy ribbon needs to contain a large amount of expensive B, which is disadvantageous in terms of raw material cost, and it is possible to substitute B with another metal. It is being considered. For example, Patent Document 4 and Patent Document 5 disclose an iron-based amorphous alloy in which expensive B is reduced and Mn is added in the above alloy system.
しかしながら、Ｂの一部をＭｎで代替した合金系は、Ｍｎ添加によって磁気特性が低下するという問題点を抱えており、上記特許文献４および５でも、この点についての検討がなされている。しかし、例えば、特許文献５に開示された非晶質合金は、鉄損Ｗ１３／５０（磁束密度１．３Ｔ、励磁周波数５０Ｈｚでの鉄損）の値が最小でも０．１２Ｗ／ｋｇ程度であり、Ｍｎをほとんど含有しない合金系の鉄損値（０．１０Ｗ／ｋｇ）よりも劣っており、十分なレベルまで改善されていない。 However, an alloy system in which a part of B is replaced with Mn has a problem that magnetic properties are deteriorated by the addition of Mn. Patent Documents 4 and 5 have also been studied on this point. However, for example, the amorphous alloy disclosed in Patent Document 5 has an iron loss W 13/50 (iron loss at a magnetic flux density of 1.3 T and an excitation frequency of 50 Hz) of at least about 0.12 W / kg. Yes, it is inferior to the iron loss value (0.10 W / kg) of an alloy system that hardly contains Mn, and has not been improved to a sufficient level.
一方、近年、エネルギーロスのさらなる低減が要求されるようになってきており、上述した特許文献４および５に開示された鉄系非晶質合金では、近年における低損失化に対する要求を十分に満足させることができなくなってきている。 On the other hand, in recent years, further reduction in energy loss has been demanded, and the iron-based amorphous alloys disclosed in Patent Documents 4 and 5 described above sufficiently satisfy the recent demand for low loss. It is becoming impossible to let you.
本発明は、従来技術が抱える上記問題点に鑑みてなされたものであり、その目的は、Ｆｅ−Ｂ−Ｓｉ−Ｍｎ系で、鉄損特性に優れる非晶質合金薄帯を提供することにある。 The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide an amorphous alloy ribbon that is Fe-B-Si-Mn and excellent in iron loss characteristics. is there.
発明者らは、上記課題を解決するために鋭意検討を重ねた。その結果、Ｆｅ−Ｂ−Ｓｉ系にＭｎを添加した成分系の鉄系非晶質合金薄帯において、薄帯の表面性状を適正化することで、Ｍｎ添加による磁気特性の劣化を軽減することができ、従来よりも低鉄損の鉄系非晶質合金薄帯を得ることができることを見出し、本発明を開発するに至った。 Inventors repeated earnest examination in order to solve the said subject. As a result, in the iron-based amorphous alloy ribbon with a component system in which Mn is added to the Fe-B-Si system, the deterioration of magnetic properties due to the addition of Mn can be reduced by optimizing the surface properties of the ribbon. Thus, the present inventors have found that an iron-based amorphous alloy ribbon having a lower iron loss than before can be obtained and the present invention has been developed.
すなわち、本発明は、
化学式：ＦｅｘＢｙＳｉｚＭｎａ
（ここで、ｘ：７５〜８７ａｔ％、ｙ：６〜１５ａｔ％、ｚ：７〜１７ａｔ％、ａ：０．２〜３ａｔ％）
で表される成分組成からなり、冷却ロールと接した面における表面粗さ曲線のスキューネス（Ｒｓｋ）が−１以下である鉄系非晶質合金薄帯である。
That is, the present invention
Formula: Fe x B y Si z Mn a
(Where x: 75 to 87 at%, y: 6 to 15 at%, z: 7 to 17 at%, a: 0.2 to 3 at%)
Is an iron-based amorphous alloy ribbon having a surface roughness curve skewness (Rsk) of −1 or less on the surface in contact with the cooling roll.
本発明の鉄系非晶質合金薄帯は、上記成分組成に加えてさらに、Ｎｉ：０．５ａｔ％以下、Ｃｒ：１．０ａｔ％以下、Ｃ：２．０ａｔ％以下、Ｐ：１．０ａｔ％以下およびＣｕ：２．０ａｔ％以下のうちから選ばれる１種または２種以上を含有することを特徴とする。 In addition to the above component composition, the iron-based amorphous alloy ribbon of the present invention further includes Ni: 0.5 at% or less, Cr: 1.0 at% or less, C: 2.0 at% or less, P: 1.0 at % Or less and Cu: 2.0 at% or less selected from one or more selected from 2.0 at% or less.
本発明によれば、鉄損特性に優れかつ鉄系非晶質合金薄帯を安価に提供することができるので、小型の変圧器やモーター、リアクトル等の鉄心に用いて好適に材料を提供することができる。 According to the present invention, an iron-based amorphous alloy ribbon having excellent iron loss characteristics can be provided at low cost. Therefore, a material is suitably provided for use in iron cores such as small transformers, motors, and reactors. be able to.
まず、本発明を開発する契機となった実験について説明する。
Ｆｅ：８０．５ａｔ％、Ｂ：８．２ａｔ％、Ｓｉ：１０ａｔ％およびＭｎ：１．３ａｔ％からなる成分組成からなる合金溶湯を、高速回転している単ロール式のＣｕロール外周面に射出し、厚みが２５μｍ、幅が７０ｍｍの鉄系非晶質合金薄帯を作製した。この際、Ｃｕロールの表面性状や表面温度および溶湯射出時の雰囲気を種々に変更した。
次いで、上記のようにして得た合金薄帯からサンプルを採取し、４００℃で１時間の磁場中焼鈍を施した後、磁気特性および薄帯の表面性状を調査した。なお、磁場中焼鈍時の磁界の強さは１．２ＭＡ／ｍとした。
磁気特性については、ＪＩＳ Ｃ２５５０に記載の方法で鉄損Ｗ１３／５０を測定した。
また、表面性状については、ＪＩＳ Ｂ０６３３：２００１に記載の方法で、ＪＩＳ Ｂ０６０１：２００１に規定された算術平均粗さＲａおよび粗さ曲線のスキューネスＲｓｋを測定した。なお、単ロール法の場合、薄帯表面には、Ｃｕロールに接した面（ロール面）と、その反対側のＣｕロールと接しなかった面（自由面）とがあるが、製造条件による変化が大きいロール面側を調査し、測定方向は幅方向とした（以後、断りのない限り、同様とする。）。
First, an experiment that triggered the development of the present invention will be described.
A molten alloy having a composition of Fe: 80.5 at%, B: 8.2 at%, Si: 10 at% and Mn: 1.3 at% is injected onto the outer peripheral surface of a single-roll Cu roll rotating at high speed. Then, an iron-based amorphous alloy ribbon having a thickness of 25 μm and a width of 70 mm was produced. At this time, the surface properties and surface temperature of the Cu roll and the atmosphere at the time of molten metal injection were variously changed.
Next, a sample was taken from the alloy ribbon obtained as described above, and after annealing in a magnetic field at 400 ° C. for 1 hour, the magnetic properties and the surface properties of the ribbon were investigated. Note that the strength of the magnetic field during annealing in the magnetic field was 1.2 MA / m.
The magnetic characteristics were measured iron loss W 13/50 in the manner described in JIS C2550.
Regarding the surface properties, the arithmetic average roughness Ra and the skewness Rsk of the roughness curve defined in JIS B0601: 2001 were measured by the method described in JIS B0633: 2001. In the case of the single roll method, the surface of the ribbon has a surface in contact with the Cu roll (roll surface) and a surface not in contact with the opposite Cu roll (free surface). The roll surface side with a large diameter was investigated, and the measurement direction was the width direction (the same shall apply hereinafter unless otherwise specified).
図１は、上記測定結果について、薄帯の表面粗さＲａと鉄損Ｗ１３／５０との関係を示したものである。この図から、表面粗さＲａが小さいほど鉄損が低くなる傾向が認められるが、Ｒａが小さくても鉄損が高い例や、Ｒａが１．４μｍを超えても低鉄損である例があり、明確ではない。 FIG. 1 shows the relationship between the surface roughness Ra of the ribbon and the iron loss W 13/50 for the above measurement results. From this figure, it is recognized that the iron loss tends to be lower as the surface roughness Ra is smaller. However, there are examples in which the iron loss is high even if Ra is small, and in which the iron loss is low even if Ra exceeds 1.4 μm. Yes, not clear.
これに対して、図２は、粗さ曲線のスキューネスＲｓｋと鉄損との関係を示したものであり、Ｒｓｋと鉄損とはよい相関があり、Ｒｓｋが小さいほど鉄損が低くなること、特に、スキューネスＲｓｋが０未満では、鉄損が安定して低く、さらに、−１以下では、より鉄損が低減していることがわかる。 On the other hand, FIG. 2 shows the relationship between the skewness Rsk of the roughness curve and the iron loss, and there is a good correlation between Rsk and the iron loss, and the smaller the Rsk, the lower the iron loss. In particular, when the skewness Rsk is less than 0, the iron loss is stably low, and when the skewness Rsk is −1 or less, the iron loss is further reduced.
粗さ曲線のスキューネスＲｓｋが小さいほど、鉄損が低くなる理由については、まだ十分に明らかとなっていないが、発明者らは、次のように考えている。
粗さ曲線のスキューネスＲｓｋは、粗さ曲線の確率密度関数の非対象性の尺度、簡単に言えば、粗さ曲線の山と谷の高さ分布の非対象性を評価するパラメータであり、スキューネスが小さいとは、薄帯表面の粗さ曲線における山を凸、谷を凹とすると、図３（ａ）に示すように、粗さ曲線が凸側に偏って存在し、表面が滑らかであることを示している。したがって、Ｒｓｋが小さいときは、薄帯表面まで密に非晶質合金が存在するので、励磁されたときには薄帯の表面には磁束が多くに流れて、磁気特性が向上する。逆に、スキューネスＲｓｋが大きいとは、図３（ｂ）に示すように、粗さ曲線の凸部が先鋭化し、凸部同士が離間していることを示している。したがって、Ｒｓｋが大きいときは、薄帯表面の非晶質合金の密度が低く、励磁されたときに表面に流れる磁束が少なくなり、磁気特性が低下する。
The reason why the iron loss decreases as the skewness Rsk of the roughness curve decreases is not yet fully clarified, but the inventors consider as follows.
The skewness Rsk of the roughness curve is a parameter for evaluating the non-objectivity of the probability distribution function of the roughness curve, simply speaking, the non-objectivity of the height distribution of the peaks and valleys of the roughness curve. Is small, when the peaks in the roughness curve of the ribbon surface are convex and the valleys are concave, as shown in FIG. 3 (a), the roughness curve is biased toward the convex side and the surface is smooth. It is shown that. Therefore, when Rsk is small, an amorphous alloy is densely present up to the surface of the ribbon, and when excited, a large amount of magnetic flux flows on the surface of the ribbon to improve the magnetic characteristics. Conversely, the fact that the skewness Rsk is large indicates that the convex portions of the roughness curve are sharpened and the convex portions are separated from each other as shown in FIG. Therefore, when Rsk is large, the density of the amorphous alloy on the surface of the ribbon is low, the magnetic flux flowing on the surface when excited is reduced, and the magnetic properties are deteriorated.
発明者らは、上記の結果から、Ｆｅ−Ｂ−Ｓｉ系にＭｎを添加した成分系でも、合金薄帯の表面性状を適正化することで、Ｍｎ添加による磁気特性の劣化を抑制し、鉄損特性に優れる鉄系非晶質合金を得ることができることを見出し、本発明を開発するに至った。 From the above results, the inventors have suppressed the deterioration of the magnetic properties due to the addition of Mn by optimizing the surface properties of the alloy ribbon even in the component system in which Mn is added to the Fe—B—Si system. It has been found that an iron-based amorphous alloy having excellent loss characteristics can be obtained, and the present invention has been developed.
次の、本発明の鉄系非晶質合金の成分組成について説明する。
本発明の鉄系非晶質合金は、ＦｅｘＢｙＳｉｚＭｎａ（ここで、ｘ，ｙ，ｚおよびａは、各元素のａｔ％を示す。）の化学式で表される成分組成を有するものであることが必要である。以下、具体的に説明する。
Next, the component composition of the iron-based amorphous alloy of the present invention will be described.
Iron-based amorphous alloy of the present invention, (wherein, x, y, z and a are. Indicating the at% of each element) Fe x B y Si z Mn a component composition represented by the chemical formula It is necessary to have. This will be specifically described below.
Ｆｅ：７５〜８７ａｔ％
Ｆｅは、本発明の鉄系非晶質合金のベース成分であり、７５ａｔ％未満では、磁束密度が低くなり過ぎ、一方、８７ａｔ％を超えると、鉄損特性が低下する。よって、Ｆｅは７５〜８７ａｔ％の範囲とする。好ましく８０〜８３ａｔ％の範囲である。
Fe: 75-87 at%
Fe is a base component of the iron-based amorphous alloy of the present invention, and if it is less than 75 at%, the magnetic flux density becomes too low, while if it exceeds 87 at%, the iron loss characteristic is lowered. Therefore, Fe is made into the range of 75-87 at%. Preferably it is the range of 80-83 at%.
Ｂ：６〜１５ａｔ％
Ｂは、非晶質化するために必要な元素であり、６ａｔ％未満では、合金が非晶質化しなくなる。一方、１５ａｔ％を超えると、磁束密度が低下するだけでなく、原料コストも増大する。よって、Ｂは６〜１５ａｔ％の範囲とする。好ましくは７〜９ａｔ％の範囲である。
B: 6-15 at%
B is an element necessary for making amorphous, and if it is less than 6 at%, the alloy does not become amorphous. On the other hand, if it exceeds 15 at%, not only the magnetic flux density is lowered but also the raw material cost is increased. Therefore, B is in the range of 6 to 15 at%. Preferably it is the range of 7-9 at%.
Ｓｉ：７〜１７ａｔ％
Ｓｉは、鉄損の低減と非晶質化に必要な元素であり、７ａｔ％未満では、合金が非晶質化しなくなる。一方、１７ａｔ％を超えると、磁束密度が大きく低下する。よって、Ｓｉは７〜１７ａｔ％の範囲とする。好ましくは７〜１１ａｔ％の範囲である。
Si: 7 to 17 at%
Si is an element necessary for reduction of iron loss and amorphization. When the content is less than 7 at%, the alloy does not become amorphous. On the other hand, if it exceeds 17 at%, the magnetic flux density is greatly reduced. Therefore, Si is set to a range of 7 to 17 at%. Preferably it is the range of 7-11 at%.
Ｍｎ：０．２〜３ａｔ％
Ｍｎは、高価なＢの代替元素であるとともに、表層酸化膜を改質し、良質の絶縁皮膜を形成する効果があることから、本発明では０．２ａｔ％以上を添加する。一方、３ａｔ％を超える添加は、磁束密度の低下をもたらす。よって、Ｍｎは０．２〜３ａｔ％の範囲とする。好ましくは０．５〜２ａｔ％の範囲である。
Mn: 0.2-3at%
Mn is an expensive substitute element for B, and has the effect of modifying the surface oxide film and forming a high-quality insulating film. Therefore, in the present invention, 0.2 at% or more is added. On the other hand, addition exceeding 3 at% brings about a decrease in magnetic flux density. Therefore, Mn is in the range of 0.2 to 3 at%. Preferably it is the range of 0.5-2 at%.
また、本発明の鉄系非晶質合金は、鉄損を低減することを目的として、上記基本成分組成に対し、内数で、すなわち合金全体に対して、Ｎｉ:０．５ａｔ％以下、Ｃｒ：１ａｔ％以下、Ｃ：２ａｔ％以下、Ｐ：１ａｔ％以下およびＣｕ：２．０ａｔ％以下のうちから選ばれる１種または２種以上を含有することができる。ただし、これら値を超える添加は、磁束密度の大幅な低下をもたらすので好ましくない。
なお、上記成分以外の残部は、不可避的不純物である。
Further, the iron-based amorphous alloy of the present invention is Ni: 0.5 at% or less, Cr: 1 at% or less, C: 2 at% or less, P: 1 at% or less, and Cu: 2.0 at% or less can be contained. However, addition exceeding these values is not preferable because it causes a significant decrease in magnetic flux density.
In addition, the remainder other than the said component is an unavoidable impurity.
次に、本発明の鉄系非晶質合金薄帯の表面性状について説明する。
本発明の鉄系非晶質合金薄帯は、前述したように、磁気特性、特に鉄損特性を向上する観点から、急冷ロールと接した面（ロール面）側の表面における粗さ曲線のスキューネスＲｓｋが０未満であることが必要である。好ましくは−１以下である。
Next, the surface properties of the iron-based amorphous alloy ribbon of the present invention will be described.
As described above, the iron-based amorphous alloy ribbon of the present invention has a roughness curve skewness on the surface (roll surface) side in contact with the quenching roll from the viewpoint of improving magnetic properties, particularly iron loss properties. Rsk needs to be less than 0. Preferably it is -1 or less.
なお、本発明が、ロール面側の表面における粗さ曲線のスキューネスＲｓｋを管理し、自由面側のＲｓｋを管理しない理由は、一般に、自由面側のＲｓｋは条件によらず０に近いこと、また、ロール面側のＲｓｋは、冷却ロールの表面粗さや急冷凝固条件によって大きく変動するため、自由面側よりも厳格に管理する必要があるからである。 The reason why the present invention manages the skewness Rsk of the roughness curve on the surface on the roll surface side and does not manage the Rsk on the free surface side is that the Rsk on the free surface side is generally close to 0 regardless of conditions, Further, the Rsk on the roll surface side largely varies depending on the surface roughness of the cooling roll and the rapid solidification conditions, and therefore, it is necessary to manage it more strictly than on the free surface side.
次に、本発明の鉄系非晶質合金薄帯の製造方法について説明する。
本発明の鉄系非晶質合金薄帯は、上記成分組成に調整した合金の溶湯を、急速冷却して凝固させることで得られる。上記急冷方法としては、水冷された高速で回転しているＣｕ製あるいはＣｕ合金製のロール外周面に溶湯を射出し、急冷凝固させて非晶質化する一般的な薄帯製造方法を用いることができる。
Next, a method for producing the iron-based amorphous alloy ribbon of the present invention will be described.
The iron-based amorphous alloy ribbon of the present invention can be obtained by rapidly cooling and solidifying a molten alloy prepared to have the above component composition. As the rapid cooling method, use a general ribbon manufacturing method in which a molten metal is injected to the outer peripheral surface of a Cu or Cu alloy roll that is rotating at high speed that is water-cooled, and then rapidly solidified. Can do.
上記方法は、ロールの数によって単ロール法と双ロール法に分けられるが、何れを用いてもよい。なお、本発明では、薄帯表面の粗さ曲線のスキューネスＲｓｋを管理しているが、単ロール法を用いる場合はロールと接する面側のみ、双ロール法を用いる場合は両面のＲｓｋを管理する必要がある。 Although the said method is divided into a single roll method and a twin roll method according to the number of rolls, any may be used. In the present invention, the skewness Rsk of the surface roughness curve of the ribbon is managed. However, when the single roll method is used, only the side in contact with the roll is managed, and when the twin roll method is used, the Rsk of both sides is managed. There is a need.
また、上記急冷凝固させる際の条件として、雰囲気ガスは、薄帯の表面酸化による脆化を防止するため、ＣＯ２やＡｒ、Ｎ２等の非酸化性雰囲気とするのが好ましく、さらに、溶湯に混入した微量の酸素Ｏによる酸化を抑制する観点から、Ｈ２を０．５ｖｏｌ％以上含有させた還元性雰囲気とするのがより好ましい。
また、薄帯表面のスキューネスＲｓｋを低減する観点からは、Ｈ２を０．５ｖｏｌ％以上含んだＣＯ２ガスやＡｒガスを溶湯がロールに接触する箇所に向けて噴射するのが効果的であるが、本発明では、スキューネスＲｓｋを０未満に低減できるなら、雰囲気ガスや噴射ガスを特に限定するものではない。
Further, as a condition for the rapid solidification, the atmospheric gas is preferably a non-oxidizing atmosphere such as CO 2 , Ar, N 2 or the like in order to prevent embrittlement due to surface oxidation of the ribbon. from the viewpoint of suppressing oxidation by oxygen O traces mixed in, and more preferably a reducing atmosphere which contains of H 2 than 0.5 vol%.
Also, from the viewpoint of reducing the skewness Rsk on the surface of the ribbon, it is effective to inject CO 2 gas or Ar gas containing 0.5 vol% or more of H 2 toward the location where the molten metal contacts the roll. However, in the present invention, the atmosphere gas and the injection gas are not particularly limited as long as the skewness Rsk can be reduced to less than 0.
また、急冷凝固させる急冷ロールの表面粗さは、薄帯表面のスキューネスＲｓｋを低減する観点から、小さいほど好ましく、具体的には、算術平均粗さＲａで１０μｍ以下とするのが好ましい。さらに、１μｍ以下とすることがより好ましい。 Further, the surface roughness of the rapid cooling roll for rapid solidification is preferably as small as possible from the viewpoint of reducing the skewness Rsk on the surface of the ribbon, and specifically, the arithmetic average roughness Ra is preferably 10 μm or less. Furthermore, it is more preferable to set it as 1 micrometer or less.
また、薄帯表面のスキューネスＲｓｋを低減するためには、急冷凝固させる際の急冷ロールの表面に、８００℃程度に加熱した雰囲気ガスを熱風として吹き付け、ロールの表面温度と溶湯との温度差を少なくすることも有効である。その理由は、温度差に起因したＲｓｋの上昇を抑えるためである。 In addition, in order to reduce the skewness Rsk on the surface of the ribbon, an atmospheric gas heated to about 800 ° C. is blown as hot air on the surface of the quenching roll during rapid solidification, and the temperature difference between the roll surface temperature and the molten metal is increased. Reducing it is also effective. The reason is to suppress an increase in Rsk due to the temperature difference.
急冷ロール表面で急冷凝固させた薄帯は、その後、ロール表面から剥離し、コイル状に巻き取るのが好ましい。なお、磁性特性の向上を図るため、磁場中焼鈍を施したのち、コイル状に巻き取ってもよい。磁場中焼鈍の処理条件としては、５００ｋＡ／ｍ以上の磁場中において、２５０〜５５０℃の温度範囲で１０秒〜２時間程度の熱処理を施すのが好ましい。処理温度が２５０℃未満では、薄帯内部の歪を解消することができないため磁気特性向上効果が小さく、一方、５５０℃を超えると、結晶化が起こって磁気特性が低下するからである。その後、薄帯間同士の絶縁性を確保するため、絶縁皮膜を被成して製品とするのが好ましい。 The ribbon that has been rapidly solidified on the surface of the quench roll is preferably peeled off from the roll surface and wound into a coil. In addition, in order to improve a magnetic characteristic, after performing annealing in a magnetic field, you may wind up in a coil form. As processing conditions for annealing in a magnetic field, it is preferable to perform a heat treatment for about 10 seconds to 2 hours in a temperature range of 250 to 550 ° C. in a magnetic field of 500 kA / m or more. This is because if the treatment temperature is less than 250 ° C., the distortion inside the ribbon cannot be eliminated and the effect of improving the magnetic properties is small. Thereafter, in order to ensure insulation between the ribbons, it is preferable to form a product by depositing an insulating film.
Ｆｅ８１．２Ｂ８．３Ｓｉ９Ｍｎ１．５の成分組成を有する鉄系合金の溶湯を、高速回転するＣｕロールの外周面に射出（単ロール法）して、厚みが２５μｍ、幅が１００ｍｍの非晶質合金薄帯を作製した。このとき、Ｃｕロールの表面粗さＲａ、射出時の雰囲気ガスを表１に示したように種々に変化させた。また、表１に示した一部の例では、溶湯がＣｕロールに接触する直前のロール表面に８００℃に加熱した１ｖｏｌ％Ｈ２＋９９ｖｏｌ％ＣＯ２の熱風を吹き付けた。 A molten iron-based alloy having a component composition of Fe 81.2 B 8.3 Si 9 Mn 1.5 is injected onto the outer peripheral surface of a Cu roll rotating at high speed (single roll method). The thickness is 25 μm and the width is A 100 mm amorphous alloy ribbon was prepared. At this time, the surface roughness Ra of the Cu roll and the atmosphere gas at the time of injection were variously changed as shown in Table 1. In some examples shown in Table 1, hot air of 1 vol% H 2 +99 vol% CO 2 heated to 800 ° C. was blown onto the roll surface immediately before the molten metal contacted the Cu roll.
斯くして得られた薄帯に、２ＭＡ／ｍの磁場中で３８０℃×１時間の磁場中焼鈍を施した後、表面性状を評価するため、薄帯のロール面側の粗さ曲線のスキューネスＲｓｋを、ＪＩＳ Ｂ０６３３：２００１に記載の方法で測定し、また、磁気特性を評価するため、ＪＩＳ Ｃ２５５０に記載の方法で鉄損Ｗ１３／５０を測定した、それらの結果を表１中に併記した。この結果から、スキューネスＲｓｋが−１以下である本発明例の合金薄帯は、いずれも良好な鉄損特性を有していることがわかる。
The thin ribbon thus obtained was subjected to annealing in a magnetic field of 380 ° C. for 1 hour in a magnetic field of 2 MA / m, and then the skewness of the roughness curve on the roll surface side of the ribbon to evaluate the surface properties. the Rsk, JIS B0633: as measured by the method described in 2001, also in order to evaluate the magnetic properties were measured iron loss W 13/50 in the manner described in JIS C2550, also shown the results in Table 1 did. From this result, the alloy ribbon of the present invention examples skewness Rsk is -1 or less, it can be seen that both have a good good iron loss properties.
表２に示した種々の成分組成を有する鉄系合金の溶湯を、高速回転するＣｕロールの外周面上に射出し（単ロール法）、厚みが２５μｍ、幅が１５０ｍｍの非晶質合金薄帯を作製した。この際、薄帯ロール面側の粗さ曲線のスキューネスＲｓｋの低減を目的として、Ｃｕロールの表面粗さＲａを０．１５μｍに低減し、溶湯射出時の雰囲気を３ｖｏｌ％Ｈ２＋９７ｖｏｌ％ＣＯ２ガス雰囲気とした。また、全ての条件で、溶湯がＣｕロールに接触する直前のロール表面に８００℃に加熱した３ｖｏｌ％Ｈ２＋９７ｖｏｌ％ＣＯ２ガスの熱風を吹き付けた。 An amorphous alloy ribbon having a thickness of 25 μm and a width of 150 mm is injected on the outer peripheral surface of a Cu roll that rotates at high speed (single roll method). Was made. At this time, in order to reduce the skewness Rsk of the roughness curve on the ribbon roll surface side, the surface roughness Ra of the Cu roll is reduced to 0.15 μm, and the atmosphere at the time of molten metal injection is 3 vol% H 2 +97 vol% CO 2. A gas atmosphere was used. Moreover, in all conditions, the melt was blown with hot air of 3vol% H 2 + 97vol% CO 2 gas heated to 800 ° C. on the roll surface immediately prior to contact with the Cu roll.
斯くして得られた非晶質合金薄帯に、５ＭＡ／ｍの磁場中で３８０℃×１時間の磁場中焼鈍を施した後、実施例１と同様にして、薄帯表面の粗さ曲線のスキューネスＲｓｋを測定した。その結果、Ｒｓｋはいずれも−１．４２〜−１．６３の範囲内にあった。また、実施例１と同様にして、鉄損Ｗ１３/５０を測定し、その結果を表２に併記した。表２から、本発明の成分組成を満たす非晶質合金薄帯は、いずれも優れた鉄損特性を有していることがわかる。 The amorphous alloy ribbon thus obtained was annealed in a magnetic field of 380 ° C. for 1 hour in a magnetic field of 5 MA / m and then subjected to a roughness curve of the ribbon surface in the same manner as in Example 1. The skewness Rsk was measured. As a result, all Rsk values were within the range of -1.42 to -1.63. Further, in the same manner as in Example 1, the iron loss W 13/50 was measured, and the results are also shown in Table 2. From Table 2, it can be seen that the amorphous alloy ribbon satisfying the composition of the present invention has excellent iron loss characteristics.
Claims (2)
（ここで、ｘ：７５〜８７ａｔ％、ｙ：６〜１５ａｔ％、ｚ：７〜１７ａｔ％、ａ：０．２〜３ａｔ％）
で表される成分組成からなり、
冷却ロールと接した面における表面粗さ曲線のスキューネス（Ｒｓｋ）が−１以下である鉄系非晶質合金薄帯。 Formula: Fe x B y Si z Mn a
(Where x: 75 to 87 at%, y: 6 to 15 at%, z: 7 to 17 at%, a: 0.2 to 3 at%)
The component composition represented by
An iron-based amorphous alloy ribbon in which the skewness (Rsk) of the surface roughness curve on the surface in contact with the cooling roll is −1 or less .
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