JP5916983B2 - Alloy composition, Fe-based nanocrystalline alloy and method for producing the same, and magnetic component - Google Patents
Alloy composition, Fe-based nanocrystalline alloy and method for producing the same, and magnetic component Download PDFInfo
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Description
本発明は、トランスやインダクタ、モータの磁芯などの使用に好適である、Ｆｅ基ナノ結晶合金及びその製造方法に関する。 The present invention relates to an Fe-based nanocrystalline alloy suitable for use in transformers, inductors, motor cores, and the like, and a method for producing the same.
ナノ結晶合金を得る際にＮｂ等の非磁性金属元素を用いると飽和磁束密度が低下してしまうという問題が生じる。Ｆｅ量を増加させ、Ｎｂ等の非磁性金属元素の量を減らすこととすると、飽和磁束密度を増加させることはできるが、結晶粒は粗大となるという他の問題が生じる。かかる問題をクリアするＦｅ基ナノ結晶合金としては、例えば特許文献１に開示されているものがある。また、工業化に際しＦｅ−Ｓｉ、Ｆｅ−Ｂ、Ｆｅ−Ｐ、Ｆｅ−Ｎｂなど低価格の工業原料を使用すると、そこに含有されるＡｌやＴｉ、Ｍｎなどの不純物が靭性やナノ結晶の形成に多大な影響を与え、軟磁気特性が劣化し更に特性のバラツキが大きくなる。そこで不純物量を規定し低価格の工業原料を選択できるものとして特許文献２が開示されている。 When a non-magnetic metal element such as Nb is used when obtaining a nanocrystalline alloy, there arises a problem that the saturation magnetic flux density is lowered. If the amount of Fe is increased and the amount of nonmagnetic metal elements such as Nb is decreased, the saturation magnetic flux density can be increased, but another problem that the crystal grains become coarse occurs. As an Fe-based nanocrystalline alloy that clears such a problem, there is one disclosed in Patent Document 1, for example. In addition, when industrial materials such as Fe-Si, Fe-B, Fe-P, and Fe-Nb are used at the time of industrialization, impurities such as Al, Ti, and Mn contained therein are used for toughness and formation of nanocrystals. A great influence is exerted, the soft magnetic characteristics are deteriorated, and the variation in characteristics is further increased. Therefore, Patent Document 2 discloses that the amount of impurities can be defined and low-cost industrial raw materials can be selected.
しかしながら、特許文献１のＦｅ基ナノ結晶合金は１４×１０−６といった大きい磁歪を有し、且つ、低い透磁率を有している。また急冷状態で多量に結晶を析出させるため、特許文献１のＦｅ基ナノ結晶合金は靭性に乏しい。また特許文献２のＦｅ基ナノ結晶合金についてＰの含有量が０．００１〜０．５重量％の範囲で好ましいとされ、実施例についても低Ｐ組成にて記述があるのみであり、その許容不純物量も狭い範囲である。また両者とも実施例として１３〜１６ａｔ％程度の多量のＢを含有する高融点組成となっている。 However, the Fe-based nanocrystalline alloy of Patent Document 1 has a large magnetostriction of 14 × 10 −6 and a low magnetic permeability. Further, since a large amount of crystals are precipitated in the rapidly cooled state, the Fe-based nanocrystalline alloy of Patent Document 1 has poor toughness. In addition, the Fe-based nanocrystalline alloy of Patent Document 2 is considered to be preferable when the P content is in the range of 0.001 to 0.5% by weight, and the examples are only described with a low P composition. The amount of impurities is also in a narrow range. Moreover, both have a high melting point composition containing a large amount of B of about 13 to 16 at% as an example.
そこで、本発明は不純物の多い工業原料を用いても安定に製造することが可能であり、高Ｆｅ組成で高飽和磁束密度を有し且つ低い保磁力、高い透磁率を有するＦｅ基ナノ結晶合金とそれを製造する方法とを提供することを目的とする。 Therefore, the present invention can be stably manufactured even using industrial materials with many impurities, and has a high Fe composition, a high saturation magnetic flux density, a low coercive force, and a high magnetic permeability. And a method of manufacturing the same.
本発明の発明者は、鋭意検討の結果、Ｐを必須とした特定の合金組成物を所定の不純物量範囲の収まるように工業原料の品質を選定することで高い飽和磁束密度を有し且つ低い保磁力、高い透磁率を有するＦｅ基ナノ結晶合金を得るための出発原料として用いることができることを見出した。ここで特定の合金組成物は、所定の組成式で表され、主相としてアモルファス相を有しており、且つ、優れた靭性を有している。特定の合金組成物を熱処理すると、ｂｃｃＦｅ相からなるナノ結晶を析出させることができる。この磁化の高いｂｃｃＦｅからなるナノ結晶を析出させることで高い飽和磁束密度が可能になる。また負の磁歪であるナノ結晶相と正の磁歪である残留アモルファス相の相殺によりＦｅ基ナノ結晶合金の飽和磁歪を大幅に低減することができる。この低減された飽和磁歪は、低い保磁力と高い透磁率をもたらす。このように、特定の合金組成物は、高い飽和磁束密度を有し且つ低い保磁力Ｈｃと高い透磁率を有するＦｅ基ナノ結晶合金を得るための出発原料として有益な材料である。 As a result of intensive studies, the inventors of the present invention have a high saturation magnetic flux density by selecting a quality of an industrial raw material so that a specific alloy composition in which P is essential is contained within a predetermined impurity amount range, and low. It has been found that it can be used as a starting material for obtaining an Fe-based nanocrystalline alloy having a coercive force and a high magnetic permeability. Here, the specific alloy composition is represented by a predetermined composition formula, has an amorphous phase as a main phase, and has excellent toughness. When a specific alloy composition is heat-treated, nanocrystals composed of a bccFe phase can be precipitated. A high saturation magnetic flux density can be obtained by depositing nanocrystals made of bccFe having high magnetization. Further, the saturation magnetostriction of the Fe-based nanocrystalline alloy can be greatly reduced by offsetting the nanocrystalline phase that is negative magnetostriction and the residual amorphous phase that is positive magnetostriction. This reduced saturation magnetostriction results in low coercivity and high permeability. Thus, the specific alloy composition is a material useful as a starting material for obtaining an Fe-based nanocrystalline alloy having a high saturation magnetic flux density and a low coercive force Hc and a high magnetic permeability.
本発明によれば、第１の合金組成物として、組成式ＦｅａＢｂＳｉｃＰｘＣｙＣｕｚの合金組成物であって、７９≦ａ≦８６ａｔ％、５≦ｂ≦１３ａｔ％、０＜ｃ≦８ａｔ％、１≦ｘ≦８ａｔ％、０≦ｙ≦５ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦１．２である合金組成物において、不純物としてＡｌ，Ｔｉ，Ｍｎ，Ｓ，Ｏ，Ｎを０≦Ａｌ≦０．３質量％、０≦Ｔｉ≦０．３質量％、０≦Ｍｎ≦１．０質量％、０≦Ｓ≦０．３質量％、０．００１≦Ｏ≦０．３質量％、Ｎ≦０．１質量％である合金組成物が得られる。 According to the present invention, as the first alloy composition, an alloy composition of the formula Fe a B b Si c P x C y Cu z, 79 ≦ a ≦ 86at%, 5 ≦ b ≦ 13at%, In an alloy composition where 0 <c ≦ 8 at%, 1 ≦ x ≦ 8 at%, 0 ≦ y ≦ 5 at%, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 1.2 Al, Ti, Mn, S, O, N as impurities are 0 ≦ Al ≦ 0.3 mass%, 0 ≦ Ti ≦ 0.3 mass%, 0 ≦ Mn ≦ 1.0 mass%, 0 ≦ S ≦ 0 An alloy composition in which 0.3 mass%, 0.001 ≦ O ≦ 0.3 mass%, and N ≦ 0.1 mass% is obtained.
また、本発明によれば、第２の合金組成物として、第１の合金組成物であって、８１≦ａ≦８６ａｔ％、６≦ｂ≦１０ａｔ％、１≦ｃ≦６ａｔ％、２≦ｘ≦５ａｔ％、０≦ｙ≦４ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦１．２である合金組成物が得られる。 According to the present invention, as the second alloy composition, the first alloy composition is 81 ≦ a ≦ 86 at%, 6 ≦ b ≦ 10 at%, 1 ≦ c ≦ 6 at%, 2 ≦ x. An alloy composition is obtained with ≦ 5 at%, 0 ≦ y ≦ 4 at%, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 1.2.
また、本発明によれば、第３の合金組成物として、第２の合金組成物であって、０≦ｙ≦３ａｔ％、０．６≦ｚ≦１．３ａｔ％及び０．０８≦ｚ／ｘ≦０．８である合金組成物が得られる。 Further, according to the present invention, the third alloy composition is a second alloy composition, wherein 0 ≦ y ≦ 3 at%, 0.6 ≦ z ≦ 1.3 at%, and 0.08 ≦ z / An alloy composition with x ≦ 0.8 is obtained.
また、本発明によれば、第４の合金組成物として、第１乃至第３の合金組成物のいずれかであって、Ｆｅの３ａｔ％以下を、Ｚｒ，Ｈｆ，Ｎｂ，Ｔａ，Ｍｏ，Ｗ，Ｃｒ，Ｃｏ，Ｎｉ，Ａｇ，Ｚｎ，Ｓｎ，Ａｓ，Ｓｂ，Ｂｉ，Ｙ及び希土類元素のうち、１種類以上の元素で置換してなる合金組成物が得られる。 According to the present invention, as the fourth alloy composition, any one of the first to third alloy compositions, wherein 3 at% or less of Fe is contained in Zr, Hf, Nb, Ta, Mo, W , Cr, Co, Ni, Ag, Zn, Sn, As, Sb, Bi, Y and an alloy composition obtained by substituting one or more elements among rare earth elements can be obtained.
また、本発明によれば、第５の合金組成物として、第１乃至第４の合金組成物のいずれかであって、前記不純物として、Ａｌ，Ｔｉ，Ｍｎ，Ｓ，Ｏ，Ｎを０＜Ａｌ≦０．１質量％、０＜Ｔｉ≦０．０５質量％、０＜Ｍｎ≦０．５質量％、０＜Ｓ≦０．１質量％、０．００１≦Ｏ≦０．１質量％、０＜Ｎ≦０．０１質量％含有する合金組成物が得られる。 According to the present invention, as the fifth alloy composition, any one of the first to fourth alloy compositions, wherein Al, Ti, Mn, S, O, and N are set as 0 < Al ≦ 0.1% by mass, 0 <Ti ≦ 0.05% by mass, 0 <Mn ≦ 0.5% by mass, 0 <S ≦ 0.1% by mass, 0.001 ≦ O ≦ 0.1% by mass, An alloy composition containing 0 <N ≦ 0.01% by mass is obtained.
また、本発明によれば、第６の合金組成物として、第５の合金組成物であって、前記不純物として、Ａｌ，Ｔｉ，Ｍｎ，Ｓ，Ｏ，Ｎを０.０００４≦Ａｌ≦０．１質量％、０．０００３≦Ｔｉ≦０．０５質量％、０．００１≦Ｍｎ≦０．５質量％、０．０００３≦Ｓ≦０．１質量％、０．０１≦Ｏ≦０．１質量％、０．０００４≦Ｎ≦０．０１質量％含有する合金組成物が得られる。 According to the present invention, the sixth alloy composition is a fifth alloy composition, and Al, Ti, Mn, S, O, and N are used as the impurities, and 0.0004 ≦ Al ≦ 0. 1% by mass, 0.0003 ≦ Ti ≦ 0.05% by mass, 0.001 ≦ Mn ≦ 0.5% by mass, 0.0003 ≦ S ≦ 0.1% by mass, 0.01 ≦ O ≦ 0.1% by mass %, 0.0004 ≦ N ≦ 0.01% by mass is obtained.
また、本発明によれば、第７の合金組成物として、第１乃至第６の合金組成物のいずれかであって、連続薄帯形状を有する合金組成物が得られる。 According to the present invention, as the seventh alloy composition, an alloy composition having any one of the first to sixth alloy compositions and having a continuous ribbon shape can be obtained.
また、本発明によれば、第８の合金組成物として、第７の合金組成物であって、１８０度曲げ試験時において密着曲げ可能である合金組成物が得られる。 Further, according to the present invention, as the eighth alloy composition, an alloy composition that is a seventh alloy composition and can be tightly bent in a 180-degree bending test is obtained.
また、本発明によれば、第９の合金組成物として、第１乃至第６の合金組成物のいずれかであって、粉末形状を有する合金組成物が得られる。 In addition, according to the present invention, as the ninth alloy composition, an alloy composition having any one of the first to sixth alloy compositions and having a powder shape can be obtained.
また、本発明によれば、第１０の合金組成物として、第１乃至第９の合金組成物のいずれかであって、差（ΔＴ＝Ｔｘ２−Ｔｘ１）が１００℃〜２００℃である第１結晶化開始温度（Ｔｘ１）と第２結晶化開始温度（Ｔｘ２）を有する合金組成物が得られる。 According to the invention, as the tenth alloy composition, any one of the first to ninth alloy compositions, wherein the difference (ΔT = T x2 −T x1 ) is 100 ° C. to 200 ° C. An alloy composition having a first crystallization start temperature (T x1 ) and a second crystallization start temperature (T x2 ) is obtained.
また、本発明によれば、第１１の合金組成物として、第１乃至第１０の合金組成物のいずれかであって、非晶質と該非晶質中に存在する初期微結晶とからなるナノヘテロ構造であって前記初期微結晶の平均粒径が０．３〜１０ｎｍであるナノヘテロ構造を有する合金組成物が得られる。 Further, according to the present invention, as the eleventh alloy composition, any one of the first to tenth alloy compositions, which is a nanoheterogene composed of amorphous and initial microcrystals present in the amorphous. An alloy composition having a structure and a nano-heterostructure in which the initial crystallite has an average particle size of 0.3 to 10 nm is obtained.
また、本発明によれば、磁性部品として、第１乃至第１１の合金組成物のいずれかを用いて構成された磁性部品が得られる。 In addition, according to the present invention, a magnetic component configured using any one of the first to eleventh alloy compositions can be obtained as the magnetic component.
また、本発明によれば、磁性部品として、第１乃至第１１の合金組成物のいずれかを用意するステップと、処理温度が当該合金組成物の（結晶化開始温度−５０℃）以上であるという条件の下で前記合金組成物を熱処理するステップを含む、Ｆｅ基ナノ結晶合金の製造方法が得られる。 According to the present invention, the step of preparing any one of the first to eleventh alloy compositions as the magnetic component, and the processing temperature is equal to or higher than the crystallization start temperature (-50 ° C.) of the alloy composition. A method for producing an Fe-based nanocrystalline alloy is provided, which includes a step of heat-treating the alloy composition under the conditions described above.
また、本発明によれば、第１のＦｅ基ナノ結晶合金として、前記製造方法により製造された１０，０００以上の透磁率と１．６５Ｔ以上の飽和磁束密度を有するＦｅ基ナノ結晶合金が得られる。 In addition, according to the present invention, as the first Fe-based nanocrystalline alloy, an Fe-based nanocrystalline alloy having a magnetic permeability of 10,000 or more and a saturation magnetic flux density of 1.65 T or more manufactured by the above manufacturing method is obtained. It is done.
また、本発明によれば、第２のＦｅ基ナノ結晶合金として、第１のＦｅ基ナノ結晶合金であって、平均粒径が５〜２５ｎｍであるＦｅ基ナノ結晶合金が得られる。 Further, according to the present invention, as the second Fe-based nanocrystalline alloy, an Fe-based nanocrystalline alloy having an average particle diameter of 5 to 25 nm can be obtained.
また、本発明によれば、第３のＦｅ基ナノ結晶合金として、第１又は第２のＦｅ基ナノ結晶合金であって、１０×１０−６以下の飽和磁歪を有するＦｅ基ナノ結晶合金が得られる。 Further, according to the present invention, as the third Fe-based nanocrystalline alloy, an Fe-based nanocrystalline alloy which is the first or second Fe-based nanocrystalline alloy and has a saturation magnetostriction of 10 × 10 −6 or less. can get.
更に、本発明によれば、第１乃至第３のＦｅ基ナノ結晶合金のいずれかを用いて構成された磁性部品が得られる。 Furthermore, according to the present invention, a magnetic component configured using any one of the first to third Fe-based nanocrystalline alloys can be obtained.
上記いずれかの合金組成物を出発原料として用いて製造されたＦｅ基ナノ結晶合金は、安価で、飽和磁歪が低く、更に高い飽和磁束密度を有し且つ低い保磁力、高い透磁率を有している。 An Fe-based nanocrystalline alloy produced using any one of the above alloy compositions as a starting material is inexpensive, has a low saturation magnetostriction, has a high saturation magnetic flux density, and has a low coercive force and a high magnetic permeability. ing.
本発明の実施の形態による合金組成物は、Ｆｅ基ナノ結晶合金の出発原料として好適であり、組成式ＦｅａＢｂＳｉｃＰｘＣｙＣｕｚを主成分とするものである。ここで、本実施の形態による合金組成物は、ａ，ｂ，ｃ，ｘ，ｙ，ｚ及びｚ／ｘについて、７９≦ａ≦８６ａｔ％、５≦ｂ≦１３ａｔ％、０＜ｃ≦８ａｔ％、１≦ｘ≦８ａｔ％、０≦ｙ≦５ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦０．８を満たし、且つ、不純物としてＡｌ，Ｔｉ，Ｍｎ，Ｓ，Ｏ，Ｎを０≦Ａｌ≦０．３質量％、０≦Ｔｉ≦０．３質量％、０≦Ｍｎ≦１．０質量％、０≦Ｓ≦０．３質量％、０．００１≦Ｏ≦０．３質量％、０≦Ｎ≦０．１質量％だけ含有している。なお、ｂ、ｃ、ｘについては、次の条件を満たすことが好ましい：６≦ｂ≦１０；１≦ｃ≦６；及び２≦ｘ≦５。また、ｙ、ｚ、ｚ／ｘについて次の条件を満たすことが好ましい：０≦ｙ≦３ａｔ％；０．６≦ｚ≦１．３ａｔ％；及び０．０８≦ｚ／ｘ≦０．８。なお、Ｆｅの３ａｔ％以下を、Ｚｒ，Ｈｆ，Ｎｂ，Ｔａ，Ｍｏ，Ｗ，Ｃｒ，Ｃｏ，Ｎｉ，Ａｇ，Ｚｎ，Ｓｎ，Ａｓ，Ｓｂ，Ｂｉ，Ｙ及び希土類元素のうち、１種類以上の元素で置換しても良い。また不純物量は０＜Ａｌ≦０．１質量％、０＜Ｔｉ≦０．０５質量％、０＜Ｍｎ≦０．５質量％、０＜Ｓ≦０．１質量％、０．００１≦Ｏ≦０．３質量％、０＜Ｎ≦０．１質量％の条件を満たすことが好ましい。更に０．０００４≦Ａｌ≦０．１質量％、０．０００３≦Ｔｉ≦０．０５質量％、０．００１≦Ｍｎ≦０．５質量％、０．０００３≦Ｓ≦０．１質量％、０．０１≦Ｏ≦０．３質量％、０.０００４≦Ｎ≦０．０１質量％の条件を満たすことが好ましい。 Alloy composition according to an embodiment of the present invention is suitable as starting materials for the Fe-based nanocrystalline alloys, as a primary component, a composition formula Fe a B b Si c P x C y Cu z. Here, the alloy composition according to the present embodiment has 79 ≦ a ≦ 86 at%, 5 ≦ b ≦ 13 at%, and 0 <c ≦ 8 at% with respect to a, b, c, x, y, z, and z / x. 1 ≦ x ≦ 8 at%, 0 ≦ y ≦ 5 at%, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 0.8 and Al, Ti, Mn as impurities , S, O, N 0 ≦ Al ≦ 0.3 mass%, 0 ≦ Ti ≦ 0.3 mass%, 0 ≦ Mn ≦ 1.0 mass%, 0 ≦ S ≦ 0.3 mass%, 0.001 ≦ O ≦ 0.3 mass%, 0 ≦ N ≦ 0.1 mass% is contained. Note that b, c, and x preferably satisfy the following conditions: 6 ≦ b ≦ 10; 1 ≦ c ≦ 6; and 2 ≦ x ≦ 5. Moreover, it is preferable that the following conditions are satisfied for y, z, and z / x: 0 ≦ y ≦ 3 at%; 0.6 ≦ z ≦ 1.3 at%; and 0.08 ≦ z / x ≦ 0.8. Note that 3 at% or less of Fe is at least one of Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Ag, Zn, Sn, As, Sb, Bi, Y and rare earth elements. You may substitute with an element. Further, the amount of impurities is 0 <Al ≦ 0.1% by mass, 0 <Ti ≦ 0.05% by mass, 0 <Mn ≦ 0.5% by mass, 0 <S ≦ 0.1% by mass, 0.001 ≦ O ≦ It is preferable to satisfy the conditions of 0.3% by mass and 0 <N ≦ 0.1% by mass. Further, 0.0004 ≦ Al ≦ 0.1 mass%, 0.0003 ≦ Ti ≦ 0.05 mass%, 0.001 ≦ Mn ≦ 0.5 mass%, 0.0003 ≦ S ≦ 0.1 mass%, 0 It is preferable to satisfy the conditions of .01 ≦ O ≦ 0.3 mass% and 0.0004 ≦ N ≦ 0.01 mass%.
上記合金組成物において、Ｆｅ元素は主元素であり、磁性を担う必須元素である。飽和磁束密度の向上及び原料価格の低減のため、Ｆｅの割合が多いことが基本的には好ましい。Ｆｅの割合が７９ａｔ％より少ないと、望ましい飽和磁束密度が得られない。Ｆｅの割合が８６ａｔ％より多いと、液体急冷条件下におけるアモルファス相の形成が困難になり、結晶粒径がばらついたり、粗大化したりする。即ち、Ｆｅの割合が８６ａｔ％より多いと、均質なナノ結晶組織が得られず、合金組成物は劣化した軟磁気特性を有することとなる。従って、Ｆｅの割合は、７９ａｔ％以上、８６ａｔ％以下であるのが望ましい。特に１．７Ｔ以上の飽和磁束密度が必要とされる場合、Ｆｅの割合が８１ａｔ％以上であることが好ましい。 In the above alloy composition, the Fe element is a main element and an essential element responsible for magnetism. In order to improve the saturation magnetic flux density and reduce the raw material price, it is basically preferable that the ratio of Fe is large. If the Fe ratio is less than 79 at%, a desired saturation magnetic flux density cannot be obtained. When the proportion of Fe is more than 86 at%, formation of an amorphous phase under liquid quenching conditions becomes difficult, and the crystal grain size varies or becomes coarse. That is, when the proportion of Fe is more than 86 at%, a homogeneous nanocrystalline structure cannot be obtained, and the alloy composition has deteriorated soft magnetic properties. Accordingly, the Fe ratio is desirably 79 at% or more and 86 at% or less. In particular, when a saturation magnetic flux density of 1.7 T or more is required, the proportion of Fe is preferably 81 at% or more.
上記合金組成物において、Ｂ元素はアモルファス相形成を担う必須元素である。Ｂの割合が５ａｔ％より少ないと、液体急冷条件下におけるアモルファス相の形成が困難になる。Ｂの割合が１３ａｔ％より多いと、ΔＴが減少し、均質なナノ結晶組織を得ることができず、合金組成物は劣化した軟磁気特性を有することとなる。従って、Ｂの割合は、５ａｔ％以上、１３ａｔ％以下であることが望ましい。特に量産化のため合金組成物が低い融点を有する必要がある場合、Ｂの割合が１０ａｔ％以下であることが好ましい。 In the above alloy composition, the B element is an essential element for forming an amorphous phase. When the ratio of B is less than 5 at%, it becomes difficult to form an amorphous phase under liquid quenching conditions. If the ratio of B is more than 13 at%, ΔT decreases, a homogeneous nanocrystalline structure cannot be obtained, and the alloy composition has deteriorated soft magnetic properties. Therefore, the ratio of B is desirably 5 at% or more and 13 at% or less. In particular, when the alloy composition needs to have a low melting point for mass production, the ratio of B is preferably 10 at% or less.
上記合金組成物において、Ｓｉ元素はアモルファス形成を担う必須元素であり、ナノ結晶化にあたってはナノ結晶の安定化に寄与する。Ｓｉを含まないと、アモルファス相形成能が低下し、更に均質なナノ結晶組織が得られず、その結果、軟磁気特性が劣化する。Ｓｉの割合が８ａｔ％よりも多いと、飽和磁束密度とアモルファス相形成能が低下し、更に軟磁気特性が劣化する。従って、Ｓｉの割合は、８ａｔ％以下（０を含まない）であることが望ましい。特にＳｉの割合が２ａｔ％以上であると、アモルファス相形成能が改善され連続薄帯を安定して作製でき、また、ΔＴが増加することで均質なナノ結晶を得ることができる。 In the above alloy composition, Si element is an essential element responsible for amorphous formation, and contributes to stabilization of nanocrystals in nanocrystallization. If Si is not contained, the ability to form an amorphous phase is lowered, and a more uniform nanocrystal structure cannot be obtained. As a result, soft magnetic properties are deteriorated. When the proportion of Si is more than 8 at%, the saturation magnetic flux density and the amorphous phase forming ability are lowered, and the soft magnetic characteristics are further deteriorated. Accordingly, the Si ratio is desirably 8 at% or less (not including 0). In particular, when the proportion of Si is 2 at% or more, the amorphous phase forming ability is improved, a continuous ribbon can be stably produced, and a homogeneous nanocrystal can be obtained by increasing ΔT.
上記合金組成物において、Ｐ元素はアモルファス形成を担う必須元素である。本実施の形態においては、Ｂ元素、Ｓｉ元素及びＰ元素の組み合わせを用いることで、いずれか一つしか用いない場合と比較して、アモルファス相形成能やナノ結晶の安定性を高めることとしている。Ｐの割合が１ａｔ％より少ないと、液体急冷条件下におけるアモルファス相の形成が困難になる。Ｐの割合が８ａｔ％より多いと、飽和磁束密度が低下し軟磁気特性が劣化する。従って、Ｐの割合は、１ａｔ％以上、８ａｔ％以下であることが望ましい。特にＰの割合が２ａｔ％以上、５ａｔ％以下であると、アモルファス相形成能が向上し、連続薄帯を安定して作製することができる。 In the alloy composition, the P element is an essential element responsible for amorphous formation. In the present embodiment, by using a combination of B element, Si element, and P element, the amorphous phase forming ability and the stability of nanocrystals are improved as compared with the case where only one of them is used. . When the proportion of P is less than 1 at%, it becomes difficult to form an amorphous phase under liquid quenching conditions. When the ratio of P is more than 8 at%, the saturation magnetic flux density is lowered and the soft magnetic characteristics are deteriorated. Therefore, the ratio of P is desirably 1 at% or more and 8 at% or less. In particular, when the ratio of P is 2 at% or more and 5 at% or less, the amorphous phase forming ability is improved, and a continuous ribbon can be stably produced.
上記合金組成物において、Ｃ元素はアモルファス形成を担う元素である。本実施の形態においては、Ｂ元素、Ｓｉ元素、Ｐ元素、Ｃ元素の組み合わせを用いることで、いずれか一つしか用いない場合と比較して、アモルファス相形成能やナノ結晶の安定性を高めることとしている。また、Ｃは安価であるため、Ｃの添加により他の半金属量が低減され、総材料コストが低減される。但し、Ｃの割合が５ａｔ％を超えると、合金組成物が脆化し、軟磁気特性の劣化が生じるという問題がある。従って、Ｃの割合は、５ａｔ％以下が望ましい。特にＣの割合が３ａｔ％以下であると、溶解時におけるＣの蒸発に起因した組成のばらつきを抑えることができる。 In the above alloy composition, the C element is an element responsible for amorphous formation. In this embodiment, by using a combination of B element, Si element, P element, and C element, the amorphous phase forming ability and the stability of nanocrystals are improved as compared with the case where only one of them is used. I am going to do that. Moreover, since C is inexpensive, the amount of other metalloids is reduced by adding C, and the total material cost is reduced. However, when the proportion of C exceeds 5 at%, there is a problem that the alloy composition becomes brittle and soft magnetic properties are deteriorated. Therefore, the C ratio is desirably 5 at% or less. In particular, when the proportion of C is 3 at% or less, it is possible to suppress variation in composition due to evaporation of C during dissolution.
上記合金組成物において、Ｃｕ元素はナノ結晶化に寄与する必須元素である。ここで、Ｓｉ元素、Ｂ元素及びＰ元素とＣｕ元素との組み合わせ又はＳｉ元素、Ｂ元素、Ｐ元素及びＣ元素とＣｕ元素との組み合わせがナノ結晶化に寄与することは、本発明前には知られていなかった点に着目すべきである。また、Ｃｕ元素は基本的に高価であり、Ｆｅの割合が８１ａｔ％以上である場合には、合金組成物の脆化や酸化を生じさせやすい点に注意すべきである。なお、Ｃｕの割合が０．４ａｔ％より少ないと、ナノ結晶化が困難になる。Ｃｕの割合が１．４ａｔ％より多いと、アモルファス相からなる前駆体が不均質になり、そのためＦｅ基ナノ結晶合金の形成の際に均質なナノ結晶組織が得られず、軟磁気特性が劣化する。従って、Ｃｕの割合は、０．４ａｔ％以上、１．４ａｔ％以下であることが望ましく、特に合金組成物の脆化や酸化、またはナノ結晶への粒成長を考慮するとＣｕの割合は０．６ａｔ％以上、１．３ａｔ％以下であることが好ましい。 In the alloy composition, Cu element is an essential element contributing to nanocrystallization. Here, the combination of Si element, B element, P element and Cu element or the combination of Si element, B element, P element, C element and Cu element contributes to nanocrystallization before the present invention. It should be noted that it was not known. Also, it should be noted that Cu element is basically expensive, and when the proportion of Fe is 81 at% or more, the alloy composition is likely to be embrittled or oxidized. If the Cu content is less than 0.4 at%, nanocrystallization becomes difficult. When the Cu content is higher than 1.4 at%, the precursor composed of the amorphous phase becomes inhomogeneous, so that a homogeneous nanocrystalline structure cannot be obtained when forming the Fe-based nanocrystalline alloy, and the soft magnetic properties deteriorate. To do. Accordingly, the Cu ratio is desirably 0.4 at% or more and 1.4 at% or less. In particular, considering the embrittlement or oxidation of the alloy composition, or the grain growth into the nanocrystal, the Cu ratio is set to 0. It is preferably 6 at% or more and 1.3 at% or less.
Ｐ原子とＣｕ原子との間には強い引力がある。従って、合金組成物が特定の比率のＰ元素とＣｕ元素とを含んでいると、１０ｎｍ以下のサイズのクラスターが形成され、このナノサイズのクラスターによってＦｅ基ナノ結晶合金の形成の際にｂｃｃＦｅ結晶は微細構造を有するようになる。より具体的には、本実施の形態によるＦｅ基ナノ結晶合金は平均粒径が２５ｎｍ以下であるｂｃｃＦｅ結晶を含んでいる。本実施の形態において、Ｐの割合（ｘ）とＣｕの割合（ｚ）との特定の比率（ｚ／ｘ）は、０．０８以上、１．２以下である。この範囲以外では、均質なナノ結晶組織が得られず、従って合金組成物は優れた軟磁気特性を有せない。なお、特定の比率（ｚ／ｘ）は、合金組成物の脆化及び酸化を考慮すると、０．０８以上０．８以下であることが好ましい。 There is a strong attractive force between P atoms and Cu atoms. Therefore, when the alloy composition contains a specific ratio of P element and Cu element, a cluster having a size of 10 nm or less is formed, and this nano-sized cluster forms a bccFe crystal when forming an Fe-based nanocrystalline alloy. Has a fine structure. More specifically, the Fe-based nanocrystalline alloy according to the present embodiment includes bccFe crystals having an average particle size of 25 nm or less. In the present embodiment, the specific ratio (z / x) of the ratio (x) of P and the ratio (z) of Cu is 0.08 or more and 1.2 or less. Outside this range, a homogeneous nanocrystalline structure cannot be obtained, and thus the alloy composition cannot have excellent soft magnetic properties. The specific ratio (z / x) is preferably 0.08 or more and 0.8 or less in consideration of embrittlement and oxidation of the alloy composition.
上記合金組成物において、Ａｌは工業原料を用いることで混入する不純物である。このＡｌの割合が０．３質量％より多いと大気中において液体急冷下におけるアモルファス相の形成が困難になり、熱処理後にも粗大な結晶が析出し、軟磁気特性は大幅に劣化する。従って、Ａｌの割合は０．３質量％以下であることが望ましい。特にＡｌの割合が０．１０質量％以下の場合、液体急冷下にて溶湯粘性の上昇を抑制することにより大気中でも表面平滑で変色の無い薄帯を安定的に作製できる。更にＡｌはまた結晶の粗大化を抑制でき均質なナノ組織を得ることができることで軟磁気特性の向上が見込める。下限に関しては、原料として高純度の試薬を用いるとＡｌの混入は抑制され安定な薄帯及び磁気特性を得ることができるが原料コストが高くなる。これに対して、Ａｌを０．０００４質量％以上含むこととすると、磁気特性に悪影響がない一方で、低価格の工業原料を用いることができる。特に本組成においてはＡｌを微量含有させることにより溶湯の粘性が向上し、表面が平滑な薄帯を安定的に作製することができる。 In the above alloy composition, Al is an impurity mixed by using industrial raw materials. When the Al content is more than 0.3% by mass, it becomes difficult to form an amorphous phase in the atmosphere under liquid quenching, and coarse crystals are precipitated even after the heat treatment, so that the soft magnetic properties are greatly deteriorated. Therefore, the Al ratio is desirably 0.3% by mass or less. In particular, when the Al content is 0.10% by mass or less, a thin ribbon having a smooth surface and no discoloration can be stably produced even in the atmosphere by suppressing an increase in the viscosity of the melt under liquid quenching. Furthermore, Al can also suppress the coarsening of the crystal and can obtain a homogeneous nanostructure, so that it is possible to improve soft magnetic properties. Regarding the lower limit, when a high-purity reagent is used as a raw material, mixing of Al can be suppressed and a stable ribbon and magnetic properties can be obtained, but the raw material cost becomes high. On the other hand, if Al is contained at 0.0004 mass% or more, low-priced industrial raw materials can be used while there is no adverse effect on the magnetic properties. In particular, in the present composition, by containing a small amount of Al, the viscosity of the molten metal is improved, and a ribbon having a smooth surface can be stably produced.
上記合金組成物において、Ｔｉは工業原料を用いることで混入する不純物である。このＴｉの割合が０．３質量％より多いと大気中において液体急冷下におけるアモルファス相の形成が困難になり、熱処理後にも粗大な結晶が析出し、軟磁気特性は大幅に劣化する。従って、Ｔｉの割合は０．３質量％以下であることが望ましい。特にＴｉの割合が０．０５質量％以下の場合、液体急冷下にて溶湯粘性の上昇を抑制することにより大気中でも表面平滑で変色の無い薄帯を安定的に作製できる。更にＴｉはまた結晶の粗大化を抑制でき均質なナノ組織を得ることができることで軟磁気特性の向上が見込める。下限に関しては、高純度の試薬を用いるとＴｉの混入は抑制され安定な薄帯及び磁気特性を得ることができるが原料コストが高くなる。これに対して、Ｔｉを０．０００３質量％以上含むこととすると、磁気特性には悪影響がない一方で、低価格の工業原料を用いることができる。特に本組成においてはＴｉを微量含有させることにより溶湯の粘性が向上し、表面が平滑な薄帯を安定的に作製することができる。 In the above alloy composition, Ti is an impurity mixed by using industrial raw materials. If the Ti content is more than 0.3% by mass, it becomes difficult to form an amorphous phase in the atmosphere under liquid quenching, coarse crystals are precipitated even after heat treatment, and the soft magnetic properties are greatly deteriorated. Therefore, the Ti ratio is desirably 0.3% by mass or less. In particular, when the proportion of Ti is 0.05% by mass or less, a thin ribbon having a smooth surface and no discoloration can be stably produced even in the atmosphere by suppressing an increase in melt viscosity under liquid quenching. Furthermore, Ti can also suppress the coarsening of the crystal and can obtain a homogeneous nanostructure, so that it can be expected to improve soft magnetic properties. Regarding the lower limit, when a high-purity reagent is used, mixing of Ti can be suppressed and a stable ribbon and magnetic properties can be obtained, but the raw material cost increases. On the other hand, if Ti is contained in an amount of 0.0003 mass% or more, low-priced industrial raw materials can be used while the magnetic properties are not adversely affected. In particular, in this composition, by adding a small amount of Ti, the viscosity of the molten metal is improved, and a ribbon having a smooth surface can be stably produced.
上記合金組成物において、Ｍｎは工業原料を用いることで混入する不可避不純物である。このＭｎの割合が１．０質量％より多いと飽和磁束密度が低下する。従って、Ｍｎの割合は１．０質量％以下であることが望ましい。特にＭｎの割合は１．７Ｔ以上の飽和磁束密度を得ることができる０．５質量％以下であることが好ましい。下限に関しては、原料として高純度の試薬を用いると混入は抑制され安定な薄帯及び磁気特性を得ることができるが原料コストが高くなる。これに対して、Ｍｎを０．００１質量％以上含むこととすると、磁気特性には悪影響がない一方で、低価格の工業原料を用いることができる。更に、Ｍｎはアモルファス形成能を向上させる効果があり０．０１質量％以上含まれても良い。また結晶の粗大化を抑制でき均質なナノ組織を得ることができることで軟磁気特性の向上が見込める。 In the above alloy composition, Mn is an unavoidable impurity mixed by using industrial raw materials. When the ratio of Mn is more than 1.0% by mass, the saturation magnetic flux density is lowered. Accordingly, the Mn ratio is desirably 1.0% by mass or less. In particular, the ratio of Mn is preferably 0.5% by mass or less so that a saturation magnetic flux density of 1.7 T or more can be obtained. Regarding the lower limit, when a high-purity reagent is used as a raw material, mixing is suppressed and a stable ribbon and magnetic properties can be obtained, but the raw material cost increases. On the other hand, if Mn is contained in an amount of 0.001% by mass or more, low-priced industrial raw materials can be used while the magnetic properties are not adversely affected. Furthermore, Mn has an effect of improving the amorphous forming ability and may be contained in an amount of 0.01% by mass or more. In addition, it is possible to improve soft magnetic properties by suppressing the coarsening of crystals and obtaining a homogeneous nanostructure.
上記合金組成物において、Ｓは工業原料を用いることで混入する不純物である。このＳの割合が０．３質量％より多いと靭性が低下し、また熱的安定性の低下から、ナノ結晶化後の軟磁気特性も劣化する。従って、Ｓの割合は０．３質量％以下であることが望ましい。特にＳの割合が０．１質量％以下の場合、軟磁気特性の良好で磁気特性のバラツキの小さい薄帯を得ることができる。下限に関しては、原料として高純度の試薬を用いると混入は抑制され安定な薄帯及び磁気特性を得ることができるが原料コストが高くなる。これに対して、Ｓが上記質量％以下含まれることを許容することとすると、磁気特性には悪影響がない一方で、低価格の工業原料を用いることができる。このＳには融点の低減、溶融状態での粘性の低減させる効果がある。更には、Ｓを０．０００３質量％以上含ませると、アトマイズによる粉末の作製において粉末の球状化を促進させる効果がある。そのためアトマイズにて粉末を作製する場合は０．０００３質量％以上含まれていることが好ましい。 In the above alloy composition, S is an impurity mixed by using industrial raw materials. If the S content is more than 0.3% by mass, the toughness is lowered, and the soft magnetic properties after nanocrystallization are also deteriorated due to the decrease in thermal stability. Accordingly, the S ratio is desirably 0.3% by mass or less. In particular, when the proportion of S is 0.1% by mass or less, a ribbon having good soft magnetic characteristics and small variations in magnetic characteristics can be obtained. Regarding the lower limit, when a high-purity reagent is used as a raw material, mixing is suppressed and a stable ribbon and magnetic properties can be obtained, but the raw material cost increases. In contrast, if S is allowed to be contained in the mass% or less, low-cost industrial raw materials can be used while the magnetic properties are not adversely affected. This S has the effect of reducing the melting point and the viscosity in the molten state. Furthermore, when 0.0003 mass% or more of S is contained, there is an effect of promoting the spheroidization of the powder in the production of the powder by atomization. Therefore, when producing powder by atomization, it is preferable that 0.0003 mass% or more is contained.
上記合金組成物において、Ｏは溶解時、熱処理時又は工業原料を用いることで混入する不可避不純物である。単ロール液体急冷法などにより薄帯を作製するには雰囲気を制御できるチャンバー中で製造すると酸化や変色が抑制され、更に薄帯表面を平滑にすることができるが製造コストが高くなる。本実施の形態においては大気中若しくは急冷部に窒素やアルゴン、炭酸ガスなどの不活性、還元ガスをフローさせＯが０．０１質量％以上含有する製造方法においても表面状態が平滑な薄帯を連続的作製でき、更に安定な磁気特性を得ることができることから大幅な製造コストの低減が可能になる。更に水アトマイズ法やガスアトマイズ法などによる粉末作製においても同様であり、Ｏが０．０１質量％以上含有する製造方法においても表面状態が良好で球状の成形性に優れ、安定な磁気特性を得ることができることから大幅な製造コストの低減が可能になる。更に絶縁性を上げ周波数特性を向上させるために酸化雰囲気中で熱処理を施し表面に酸化被膜を形成させることも可能である。また本実施の形態においては、Ｏの割合が０．３質量％より多いと表面が変色し磁気特性が劣化すると同時に占積率や成形性が低下する。従って、Ｏの割合は０．３質量％以下であることが望ましい。特に薄帯形状の合金組成物の場合はＯの磁気特性に与える影響が大きく０．１質量％以下であることが好ましい。 In the above alloy composition, O is an unavoidable impurity mixed during melting, heat treatment, or use of industrial raw materials. In order to produce a ribbon by a single roll liquid quenching method or the like, if it is produced in a chamber in which the atmosphere can be controlled, oxidation and discoloration are suppressed, and the ribbon surface can be smoothed, but the production cost is increased. In the present embodiment, a thin ribbon having a smooth surface state is produced even in a manufacturing method in which an inert or reducing gas such as nitrogen, argon or carbon dioxide gas is flowed in the atmosphere or a quenching portion and O is contained in an amount of 0.01% by mass or more. Since it can be continuously manufactured and more stable magnetic characteristics can be obtained, the manufacturing cost can be greatly reduced. Furthermore, the same applies to powder production by water atomization method or gas atomization method, etc. Even in the production method containing 0.01% by mass or more of O, the surface state is good, the spherical formability is excellent, and stable magnetic properties are obtained. Therefore, the manufacturing cost can be greatly reduced. Further, in order to improve insulation and improve frequency characteristics, it is possible to heat-treat in an oxidizing atmosphere to form an oxide film on the surface. In the present embodiment, when the proportion of O is more than 0.3% by mass, the surface is discolored and the magnetic properties are deteriorated, and at the same time, the space factor and formability are lowered. Therefore, the O ratio is desirably 0.3% by mass or less. Particularly in the case of a ribbon-shaped alloy composition, the influence on the magnetic properties of O is large, and it is preferably 0.1% by mass or less.
上記合金組成物において、Ｎは溶解時、熱処理時又は工業原料を用いることで混入する不純物である。単ロール液体急冷法などにより薄帯を作製する際、大気中若しくは急冷部に窒素やアルゴン、炭酸ガスなどの不活性、還元ガスをフローさせＮが０．０００４質量％以上含有する製造方法においても表面状態が平滑な薄帯を連続的作製でき、更にナノ結晶化の熱処理時においても真空中でなくＮガスフロー中で熱処理を施しても安定な磁気特性を得ることができることから大幅な製造コストの低減が可能になる。また本実施の形態においては、Ｎの割合が０．１質量％より多いと軟磁気特性が劣化する。従って、Ｎの割合は０．１質量％以下であることが望ましい。 In the above alloy composition, N is an impurity mixed during melting, heat treatment, or using industrial raw materials. In the production method in which a thin ribbon is produced by a single roll liquid quenching method or the like, an inert or reducing gas such as nitrogen, argon or carbon dioxide gas is flowed into the atmosphere or the quenching portion to contain N in an amount of 0.0004% by mass or more. A thin ribbon with a smooth surface can be produced continuously, and stable magnetic properties can be obtained even when heat treatment is performed in N gas flow instead of in vacuum during heat treatment for nanocrystallization. Can be reduced. In this embodiment, if the proportion of N is more than 0.1% by mass, the soft magnetic characteristics deteriorate. Therefore, the N ratio is preferably 0.1% by mass or less.
本実施の形態における合金組成物は、様々な形状を有することができる。例えば、合金組成物は、連続薄帯形状を有していてもよいし、粉末形状を有していてよい。連続薄帯形状の合金組成物は、Ｆｅ基アモルファス薄帯などの製造に使用されている単ロール製造装置や双ロール製造装置のような従来の装置を使用して形成することができる。粉末形状の合金組成物は水アトマイズ法やガスアトマイズ法によって作製してもよいし、薄帯の合金組成物を粉砕することで作製してもよい。また薄帯や粉末などの合金組成物はアルゴンや窒素などの不活性雰囲気中又は真空中で製造することが出来るが大気中でも問題なく作製することもできる。またアルゴンや窒素などのガスをフローさせて製造することも可能である。 The alloy composition in the present embodiment can have various shapes. For example, the alloy composition may have a continuous ribbon shape or a powder shape. The continuous ribbon-shaped alloy composition can be formed using a conventional apparatus such as a single roll manufacturing apparatus or a twin roll manufacturing apparatus used for manufacturing an Fe-based amorphous ribbon. The alloy composition in powder form may be produced by a water atomizing method or a gas atomizing method, or may be produced by pulverizing a ribbon-like alloy composition. An alloy composition such as a ribbon or powder can be produced in an inert atmosphere such as argon or nitrogen or in a vacuum, but can also be produced without any problem in the air. It is also possible to manufacture by flowing a gas such as argon or nitrogen.
特に、高い靭性への要求を考慮すると、連続薄帯形状の合金組成物は熱処理前の状態において１８０°曲げ試験の際に密着曲げ可能であることが好ましい。ここで、１８０°曲げ試験とは、靭性を評価するための試験であり、曲げ角度が１８０°であり内側半径が零となるように試料を曲げるものである。即ち、１８０°曲げ試験によれば、試料は密着曲げされる（○）か破断される（×）。後述する評価においては、長さ３ｃｍの薄帯試料をその中心において折り曲げて密着曲げできたか（○）破断したか（×）をチェックした。 In particular, considering the demand for high toughness, it is preferable that the continuous ribbon-shaped alloy composition can be tightly bent in a 180 ° bending test in a state before heat treatment. Here, the 180 ° bending test is a test for evaluating toughness, and the sample is bent so that the bending angle is 180 ° and the inner radius is zero. That is, according to the 180 ° bending test, the sample is bent tightly (◯) or broken (×). In the evaluation described later, it was checked whether a 3 cm long strip sample was bent at its center and bent tightly (◯) or broken (×).
本実施の形態による合金組成物を成形して、巻磁芯、積層磁芯、圧粉磁芯などの磁気コアを形成することができる。また、その磁気コアを用いて、トランス、インダクタ、モータや発電機などの部品を提供することができる。 The alloy composition according to the present embodiment can be molded to form a magnetic core such as a wound magnetic core, a laminated magnetic core, or a dust core. Moreover, components, such as a transformer, an inductor, a motor, and a generator, can be provided using the magnetic core.
本実施の形態による合金組成物は主相としてアモルファス相を有している。従って、本実施の形態による合金組成物をＡｒガス雰囲気のような不活性雰囲気中で熱処理すると、２回以上結晶化される。最初に結晶化が開始した温度を第１結晶化開始温度（Ｔｘ１）とし、２回目の結晶化が開始した温度を第２結晶化開始温度（Ｔｘ２）とする。また、第１結晶化開始温度（Ｔｘ１）と第２結晶化開始温度（Ｔｘ２）の間の温度差をΔＴ＝Ｔｘ２−Ｔｘ１とする。単に「結晶化開始温度」といった場合、第１結晶化開始温度（Ｔｘ１）を意味する。なお、これら結晶化温度は、例えば、示差走査熱量分析（ＤＳＣ）装置を用い、４０℃／分程度の昇温速度で熱分析を行うことで評価可能である。 The alloy composition according to the present embodiment has an amorphous phase as a main phase. Therefore, when the alloy composition according to the present embodiment is heat-treated in an inert atmosphere such as an Ar gas atmosphere, it is crystallized twice or more. The temperature at which crystallization starts first is the first crystallization start temperature (T x1 ), and the temperature at which the second crystallization starts is the second crystallization start temperature (T x2 ). In addition, a temperature difference between the first crystallization start temperature (T x1 ) and the second crystallization start temperature (T x2 ) is ΔT = T x2 −T x1 . When simply referred to as “crystallization start temperature”, it means the first crystallization start temperature (T x1 ). In addition, these crystallization temperatures can be evaluated by performing thermal analysis at a temperature increase rate of about 40 ° C./min using, for example, a differential scanning calorimetry (DSC) apparatus.
本実施の形態による合金組成物を（結晶化開始温度（即ち、第１結晶化開始温度）−５０℃）以上で熱処理をすると、本実施の形態によるＦｅ基ナノ結晶合金を得ることができる。また磁気特性を劣化させる要因であるＦｅ−Ｂ等の化合物相を抑制させるため第２結晶化温度以下で熱処理する必要がある。Ｆｅ基ナノ結晶合金形成の際に均質なナノ結晶組織を得るためには、合金組成物の第１結晶化開始温度（Ｔｘ１）と第２結晶化開始温度（Ｔｘ２）の差ΔＴが１００℃以上２００℃以下であることが好ましい。また熱処理は通常アルゴンや窒素などの不活性雰囲気中で行うが真空中や酸化雰囲気中で行っても良い。また磁気特性制御をするため応力下や磁場中により誘導磁気異方性を付加し熱処理することも可能である。 When the alloy composition according to the present embodiment is heat-treated at (crystallization start temperature (ie, first crystallization start temperature) −50 ° C.) or higher, the Fe-based nanocrystalline alloy according to the present embodiment can be obtained. Further, it is necessary to perform heat treatment at a temperature equal to or lower than the second crystallization temperature in order to suppress a compound phase such as Fe-B, which is a factor for deteriorating magnetic characteristics. In order to obtain a homogeneous nanocrystalline structure during the formation of the Fe-based nanocrystalline alloy, the difference ΔT between the first crystallization start temperature (T x1 ) and the second crystallization start temperature (T x2 ) of the alloy composition is 100 It is preferable that it is 200 degreeC or more. The heat treatment is usually performed in an inert atmosphere such as argon or nitrogen, but may be performed in a vacuum or an oxidizing atmosphere. Further, in order to control the magnetic properties, it is also possible to perform heat treatment by adding induced magnetic anisotropy under stress or in a magnetic field.
このようにして得られた本実施の形態によるＦｅ基ナノ結晶合金は、１０，０００以上の高い透磁率と１．６５Ｔ以上の高い飽和磁束密度を有する。特に、Ｐの割合（ｘ）とＣｕの割合（ｚ）並びに特定の比率（ｚ／ｘ）や熱処理条件を選択することにより、ナノ結晶の量を制御して飽和磁歪を低減することができる。軟磁気特性の劣化を避けるため、飽和磁歪は１０×１０−６以下であることが望ましく、更に、２０，０００以上の高透磁率を得るため、飽和磁歪は５×１０−６以下であることが好ましい。また低損失の材料のために保磁力は２０Ａ／ｍ以下であることが望ましい。 The Fe-based nanocrystalline alloy according to the present embodiment thus obtained has a high magnetic permeability of 10,000 or higher and a high saturation magnetic flux density of 1.65 T or higher. In particular, by selecting the ratio of P (x), the ratio of Cu (z), the specific ratio (z / x), and the heat treatment conditions, the amount of nanocrystals can be controlled to reduce saturation magnetostriction. The saturation magnetostriction is desirably 10 × 10 −6 or less in order to avoid the deterioration of the soft magnetic characteristics, and the saturation magnetostriction is 5 × 10 −6 or less in order to obtain a high permeability of 20,000 or more. Is preferred. Moreover, it is desirable that the coercive force is 20 A / m or less for a low loss material.
本実施の形態によるＦｅ基ナノ結晶合金を用いて安価な磁気コアを形成することができる。また、その磁気コアを用いて、トランス、インダクタ、モータや発電機などの部品を構成することができる。また磁気コアには本実施の形態による薄帯を用いた巻磁芯や積層磁芯、また粉末を用いた圧粉磁芯などを適用することができる。 An inexpensive magnetic core can be formed using the Fe-based nanocrystalline alloy according to the present embodiment. Moreover, components, such as a transformer, an inductor, a motor, and a generator, can be comprised using the magnetic core. The magnetic core may be a wound magnetic core using a ribbon according to the present embodiment, a laminated magnetic core, or a powder magnetic core using powder.
以下、本発明の実施の形態について、複数の複数の実施例を参照しながら更に詳細に説明する。 Hereinafter, embodiments of the present invention will be described in more detail with reference to a plurality of examples.
（実施例１〜１８及び比較例１〜４）
原料を下記の表１に掲げられた本発明の実施例１〜１８及び比較例１〜３の主成分組成となるように秤量し、高周波加熱装置により溶解した。実施例１は純度が99.95%以上Ｆｅ、クリスタルＳｉ、クリスタルＢ、Ｆｅ３Ｐ、Ｃｕの高純度の原料を用い、実施例２〜１８はＦｅ、Ｆｅ−Ｓｉ、Ｆｅ−Ｂ、Ｆｅ−Ｐ、Ｃｕで種々の純度の安価な工業原料を用いた。その後、溶解した合金組成物を大気中において単ロール液体急冷法にて処理し、厚さ２０〜２５μｍ、幅約１５ｍｍ、長さ約１０ｍの連続薄帯を作製した。また比較例４として、厚み２５μｍの市販のＦｅアモルファス薄帯を使用した。
(Examples 1-18 and Comparative Examples 1-4)
The raw materials were weighed so as to have the main component compositions of Examples 1 to 18 and Comparative Examples 1 to 3 of the present invention listed in Table 1 below, and dissolved by a high frequency heating apparatus. Example 1 uses 99,95% or more of high purity raw materials of Fe, crystal Si, crystal B, Fe3P, and Cu. Examples 2 to 18 are made of Fe, Fe-Si, Fe-B, Fe-P, and Cu. Inexpensive industrial raw materials of various purity were used. Then, the melted alloy composition was processed in the atmosphere by a single roll liquid quenching method to produce a continuous ribbon having a thickness of 20 to 25 μm, a width of about 15 mm, and a length of about 10 m. As Comparative Example 4, a commercially available Fe amorphous ribbon having a thickness of 25 μm was used.
これら連続薄帯の合金組成物における相の同定はＸ線回折法にて行った。それらの第１結晶化開始温度及び第２結晶化開始温度は、示差走査型熱量分析計（ＤＳＣ）を用いて評価した。更に、表２に記載の熱処理条件の下で、実施例１〜１８及び比較例１〜４の合金組成物を熱処理した。熱処理された合金組成物の夫々の飽和磁束密度Ｂｓは振動試料型磁力計（ＶＭＳ）を用いて８００ｋＡ／ｍの磁場にて測定した。各合金組成物の保磁力Ｈｃは直流ＢＨトレーサーを用い２〜４ｋＡ／ｍの磁場にて測定し、また損失Ｐｃｍは交流ＢＨトレーサーを用い５０Ｈｚの周波数にて測定した。測定結果を表２に示す。 The phases in these continuous ribbon alloy compositions were identified by the X-ray diffraction method. The first crystallization start temperature and the second crystallization start temperature were evaluated using a differential scanning calorimeter (DSC). Furthermore, the alloy compositions of Examples 1 to 18 and Comparative Examples 1 to 4 were heat-treated under the heat treatment conditions described in Table 2. The saturation magnetic flux density Bs of each heat-treated alloy composition was measured in a magnetic field of 800 kA / m using a vibrating sample magnetometer (VMS). The coercive force Hc of each alloy composition was measured in a magnetic field of 2 to 4 kA / m using a DC BH tracer, and the loss Pcm was measured at a frequency of 50 Hz using an AC BH tracer. The measurement results are shown in Table 2.
表２から理解されるように、実施例１〜１８の合金組成物はすべて急冷処理後の状態においてアモルファス相を主相とするものであり、また、１８０°曲げ試験で密着曲げできることが確認できた。 As can be seen from Table 2, all of the alloy compositions of Examples 1 to 18 have an amorphous phase as the main phase in the state after the rapid cooling treatment, and it can be confirmed that they can be tightly bent by a 180 ° bending test. It was.
また、表２から理解されるように、熱処理後の実施例１〜１８の合金組成物は良好なナノ結晶組織を得ることができ、従って、１．６５Ｔ以上の高い飽和磁束密度Ｂｓと２０Ａ／ｍ以下の低い保磁力Ｈｃを得ることができた。一方、比較例１の合金組成物はＡｌ量が多いため、薄帯を製造した時に結晶相が主相となり連続薄帯を作製できない。また比較例２、３はＰが含まれていないため主相が結晶相となり、熱処理後も均質なナノ組織が形成できず保磁力Ｈｃは著しく劣化する。また実施例３の合金組成物の融点は１０５７℃と低く液体急冷条件下におけるアモルファス相の形成が容易であるのに対し、比較例２や３の合金組成物の融点は１１７６℃、１１７４℃と非常に高いためアモルファス相の形成が容易でないものと考えられる。また比較例４はＦｅＳｉＢからなるアモルファス薄帯であり、Ｃｕが含まれていないため熱処理後において、約５０ｎｍの粗大な結晶が析出し保磁力Ｈｃは著しく劣化する。 Further, as understood from Table 2, the alloy compositions of Examples 1 to 18 after the heat treatment can obtain a good nanocrystalline structure, and accordingly, a high saturation magnetic flux density Bs of 1.65 T or more and 20 A / A low coercive force Hc of m or less could be obtained. On the other hand, since the alloy composition of Comparative Example 1 has a large amount of Al, when a ribbon is produced, the crystalline phase becomes the main phase and a continuous ribbon cannot be produced. In Comparative Examples 2 and 3, since P is not contained, the main phase becomes a crystalline phase, and a uniform nanostructure cannot be formed even after heat treatment, and the coercive force Hc is significantly deteriorated. Further, the melting point of the alloy composition of Example 3 is as low as 1057 ° C. and the amorphous phase can be easily formed under the liquid quenching condition, whereas the melting points of the alloy compositions of Comparative Examples 2 and 3 are 1176 ° C. and 1174 ° C. It is considered that formation of an amorphous phase is not easy because it is very high. Further, Comparative Example 4 is an amorphous ribbon made of FeSiB and does not contain Cu, so that after heat treatment, coarse crystals of about 50 nm are precipitated and the coercive force Hc is remarkably deteriorated.
図１は透過型電子顕微鏡(ＴＥＭ)を用いて観察した実施例２(熱処理後)の微細組織である。図１から平均結晶粒径が１４ｎｍのｂｃｃＦｅからなる均質なナノ結晶から形成されていることが分かる。また他の熱処理後の実施例についても直径２５ｎｍ以下のナノ結晶組織からなることを確認している。このようにｂｃｃＦｅからなる微細なナノ結晶を形成することで高飽和磁束密度Ｂｓと低保磁力Ｈｃの両立が可能になり、磁歪も１０×１０−６以下に低減できる。 FIG. 1 is a microstructure of Example 2 (after heat treatment) observed using a transmission electron microscope (TEM). It can be seen from FIG. 1 that the film is formed from homogeneous nanocrystals composed of bccFe having an average crystal grain size of 14 nm. In addition, it has been confirmed that the examples after other heat treatments are composed of nanocrystalline structures having a diameter of 25 nm or less. By forming fine nanocrystals made of bccFe in this way, both high saturation magnetic flux density Bs and low coercive force Hc can be achieved, and magnetostriction can be reduced to 10 × 10 −6 or less.
また、表２から理解されるように、実施例１〜１８の合金組成物の結晶化開始温度差ΔＴ（＝Ｔｘ２−Ｔｘ１）は１００℃以上ある。かかる合金組成物を最高到達熱処理温度が第１結晶化開始温度（Ｔｘ１）−５０℃以上、第２結晶化開始温度（Ｔｘ２）以下の間になるような条件で熱処理すると、表１及び表２に示されるように良好な軟磁気特性（保磁力Ｈｃ）を得ることができる。 Moreover, as understood from Table 2, the crystallization start temperature difference ΔT (= T x2 −T x1 ) of the alloy compositions of Examples 1 to 18 is 100 ° C. or higher. When such an alloy composition is heat-treated under conditions such that the highest ultimate heat treatment temperature is not less than the first crystallization start temperature (T x1 ) −50 ° C. and not more than the second crystallization start temperature (T x2 ), Table 1 and As shown in Table 2, good soft magnetic characteristics (coercive force Hc) can be obtained.
また、表１及び表２より本実施の形態の合金組成物は、不純物量をＡｌ：０．３質量％以下、Ｔｉ：０．３質量％以下、Ｓ：０．３質量％以下、Ｍｎ：１．０質量％以下、Ｏ：０．３質量％以下、Ｎ：０．１質量％以下にすることで、１．６５Ｔ以上の高い飽和磁束密度Ｂｓと２０Ａ／ｍ以下の低い保磁力Ｈｃを得ることができる。更にＡｌ、Ｔｉ、Ｍｎはナノ結晶形成のおり、粗大な結晶粒抑制に効果があり、実施例３、４、１１、１２、１５から分かるように、低保磁力Ｈｃ化が可能なＡｌ：０．１質量％以下、Ｔｉ：０．０５質量％以下、Ｍｎ：１．０質量％以下の範囲が好ましい。またＭｎ添加は飽和磁束密度を低下させるため、飽和磁束密度Ｂｓが１．７Ｔ以上になる０．５質量％以下が好ましい。またＳは０．１質量％以下の範囲で磁気特性の変化は小さく、０．１質量％以下が好ましい。更に安価な工業原料を用いた実施例２〜１８から分かるように、低Ｈｃ化が可能で、均質な薄帯を連続的に得られ、コスト低減が可能な、Ａｌ：０．０００４質量％以上、Ｔｉ：０．０００３質量％以上、Ｍｎ：０．００１質量％以上、Ｓ：０．０００３質量％以上、Ｏ：０．０１質量％以上、Ｎ：０．０００４質量％以上の範囲が好ましい。 From Tables 1 and 2, the alloy composition of the present embodiment has an impurity amount of Al: 0.3% by mass or less, Ti: 0.3% by mass or less, S: 0.3% by mass or less, Mn: By setting 1.0 mass% or less, O: 0.3 mass% or less, and N: 0.1 mass% or less, a high saturation magnetic flux density Bs of 1.65 T or more and a low coercive force Hc of 20 A / m or less are obtained. Can be obtained. Further, Al, Ti, and Mn are nanocrystal-forming, and are effective in suppressing coarse crystal grains. As can be seen from Examples 3, 4, 11, 12, and 15, Al: 0 that enables low coercive force Hc. The range of 0.1 mass% or less, Ti: 0.05 mass% or less, and Mn: 1.0 mass% or less is preferable. Further, since addition of Mn lowers the saturation magnetic flux density, 0.5 mass% or less at which the saturation magnetic flux density Bs becomes 1.7 T or more is preferable. Further, S has a small change in magnetic properties in the range of 0.1% by mass or less, and preferably 0.1% by mass or less. Furthermore, as can be seen from Examples 2 to 18 using inexpensive industrial raw materials, it is possible to reduce Hc, to obtain a uniform ribbon continuously, and to reduce costs. Al: 0.0004 mass% or more Ti: 0.0003 mass% or more, Mn: 0.001 mass% or more, S: 0.0003 mass% or more, O: 0.01 mass% or more, N: 0.0004 mass% or more are preferable.
また、図２より実施例３は従来材料である電磁鋼板やＦｅアモルファスなどと比較して
高飽和磁束密度Ｂｓまで損失が非常に低いことが分かる。
In addition, it can be seen from FIG. 2 that the loss in Example 3 is very low to a high saturation magnetic flux density Bs as compared with the conventional steel sheet and Fe amorphous.
（実施例１９及び比較例５、６）
Ｆｅ，Ｓｉ，Ｂ，Ｐ，Ｃｕの原料を合金組成Ｆｅ８３．３Ｂ８Ｓｉ４Ｐ４Ｃｕ０．７となるように秤量し、高周波誘導溶解処理により溶解して母合金を作製した。この母合金を水アトマイズ法にて処理し実施例１９の粉末を得た。更に得られた粉末とエポキシ樹脂をエポキシ樹脂が４．５重量％となるように混合した。混合物をメッシュサイズ５００μｍのふるいにかけ、粒径が５００μｍ以下の造粒粉末を得た。次いで、外径１３ｍｍ内径８ｍｍの金型を用いて面圧７，０００ｋｇｆ／ｃｍ２の条件下で造粒粉末を成形し、高さ５ｍｍのトロイダル形状の成形体を作製した。このようにして作製された成形体を窒素雰囲気中で１５０℃×２時間の条件にて硬化処理した。更に、成形体及び粉末をＡｒ雰囲気中で３５０℃×１０分の条件にて熱処理した。
(Example 19 and Comparative Examples 5 and 6)
The raw materials of Fe, Si, B, P, and Cu were weighed so as to have an alloy composition of Fe 83.3 B 8 Si 4 P 4 Cu 0.7, and melted by high-frequency induction melting treatment to produce a master alloy. This mother alloy was processed by the water atomization method to obtain the powder of Example 19. Furthermore, the obtained powder and an epoxy resin were mixed so that an epoxy resin might be 4.5 weight%. The mixture was passed through a sieve having a mesh size of 500 μm to obtain a granulated powder having a particle size of 500 μm or less. Next, the granulated powder was molded using a mold having an outer diameter of 13 mm and an inner diameter of 8 mm under the condition of a surface pressure of 7,000 kgf / cm 2 to prepare a toroidal shaped molded body having a height of 5 mm. The molded body thus produced was cured in a nitrogen atmosphere at 150 ° C. for 2 hours. Furthermore, the compact and the powder were heat-treated in an Ar atmosphere at 350 ° C. for 10 minutes.
Ｆｅアモルファス合金及びＦｅ−Ｓｉ−Ｃｒ合金を水アトマイズ法にて処理し、比較例５及び６の粉末を得た。比較例５及び６の粉末は２０μｍの平均粒径を有していた。これらの粉末を実施例１９と同様に処理した。念のため、実施例１９並びに比較例５及び６の組成について表３にリストする。 The Fe amorphous alloy and the Fe—Si—Cr alloy were treated by the water atomization method to obtain powders of Comparative Examples 5 and 6. The powders of Comparative Examples 5 and 6 had an average particle size of 20 μm. These powders were treated as in Example 19. As a precaution, the compositions of Example 19 and Comparative Examples 5 and 6 are listed in Table 3.
熱処理された粉末の飽和磁束密度Ｂｓは振動試料型磁力計（ＶＭＳ）を用いて８００ｋＡ／ｍの磁場にて測定した。熱処理された成形体の鉄損は交流ＢＨアナライザーを用いて３００ｋＨｚ−５０ｍＴの励磁条件で測定した。測定結果を表４に示す。 The saturation magnetic flux density Bs of the heat-treated powder was measured in a magnetic field of 800 kA / m using a vibrating sample magnetometer (VMS). The iron loss of the heat-treated molded body was measured under an excitation condition of 300 kHz-50 mT using an AC BH analyzer. Table 4 shows the measurement results.
表４から理解されるように、実施例１９の合金組成物は、熱処理後において、２５ｎｍ以下の平均粒径のナノ結晶を有し、比較例５（Ｆｅアモルファス）や比較例６（Ｆｅ−Ｓｉ−Ｃｒ）と比較して、高い飽和磁束密度Ｂｓと低い鉄損Ｐｃｖを有している。従って、これを用いると、小型且つ高効率の磁性部品を提供することができる。 As can be seen from Table 4, the alloy composition of Example 19 has nanocrystals having an average particle size of 25 nm or less after heat treatment, and Comparative Example 5 (Fe amorphous) and Comparative Example 6 (Fe-Si). Compared with -Cr), it has a high saturation magnetic flux density Bs and a low iron loss Pcv. Therefore, when this is used, a small and highly efficient magnetic component can be provided.
以上、説明したように、本発明による靭性のある合金組成物を出発原料とすれば、安価で優れた軟磁気特性を有するＦｅ基ナノ結晶合金を得ることができる。 As described above, when the tough alloy composition according to the present invention is used as a starting material, an Fe-based nanocrystalline alloy having low-cost and excellent soft magnetic properties can be obtained.
なお、耐食性の改善や電気抵抗の調整などのため、飽和磁束密度の著しい低下が生じない範囲でＦｅの３ａｔ％以下を、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ａｇ、Ｚｎ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ及び希土類元素のうち、１種類以上の元素で置換してもよい。 In order to improve the corrosion resistance and adjust the electrical resistance, 3 at% or less of Fe is reduced within a range in which the saturation magnetic flux density does not significantly decrease. Zr, Hf, Nb, Ta, Mo, W, Cr, Ag, Zn, You may substitute by 1 or more types of elements among Sn, As, Sb, Bi, Y, and rare earth elements.
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