JP5537534B2 - Fe-based nanocrystalline alloy powder and manufacturing method thereof, and dust core and manufacturing method thereof - Google Patents
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本発明は、良好な磁気特性を有する圧粉磁心とその製造方法並びに当該圧粉磁心製造に適するＦｅ基ナノ結晶合金粉末とその製造方法に関する。 The present invention relates to a dust core having good magnetic properties, a method for producing the same, an Fe-based nanocrystalline alloy powder suitable for producing the dust core, and a method for producing the same.
Ｆｅ基ナノ結晶合金は、高飽和磁束密度と低磁歪の両立が可能な軟磁性材料である。このＦｅ基ナノ結晶合金は、概略、非晶質相を主相とする合金に対して熱処理を施すことによって得ることができる。 The Fe-based nanocrystalline alloy is a soft magnetic material that can achieve both high saturation magnetic flux density and low magnetostriction. This Fe-based nanocrystalline alloy can be roughly obtained by heat-treating an alloy having an amorphous phase as a main phase.
特許文献１には、Ｆｅ基ナノ結晶合金粉末を用いた圧粉磁心が開示されている。従来の圧粉磁心は、特許文献１の実施例に示されているように、非晶質相を主相とする合金粉末とバインダとを混合し、加圧成型した後、硬化することにより製造されていた。即ち、従来、ナノ結晶相の析出と圧粉磁心の硬化とを同一熱処理により行っていた。 Patent Document 1 discloses a dust core using an Fe-based nanocrystalline alloy powder. As shown in the example of Patent Document 1, a conventional dust core is manufactured by mixing an alloy powder having a main phase of an amorphous phase and a binder, press molding, and then curing. It had been. That is, conventionally, precipitation of the nanocrystalline phase and hardening of the powder magnetic core have been performed by the same heat treatment.
なお、特許文献２及び特許文献３には、熱処理時における結晶粒の粒成長を抑制するために出発原料となる合金にＮｂやＺｒなどの金属元素を含有する技術について開示されている。 Patent Documents 2 and 3 disclose a technique in which a metal element such as Nb or Zr is contained in an alloy as a starting material in order to suppress grain growth of crystal grains during heat treatment.
特許文献１の実施例の方法により製造すると、良好な磁気特性を有する圧粉磁心が得られない場合がある。 If it manufactures by the method of the Example of patent document 1, the dust core which has a favorable magnetic characteristic may not be obtained.
そこで、本発明は、良好な磁気特性を有する圧粉磁心の製造に用いることのできる粉末及び粉末の製造方法、並びにそれを用いて製造される圧粉磁心及び圧粉磁心の製造方法を提供することを目的とする。 Therefore, the present invention provides a powder that can be used for the production of a dust core having good magnetic properties, a method for producing the powder, a dust core produced using the powder, and a method for producing the dust core. For the purpose.
本発明の発明者らは、非晶質相を主相とする合金を熱処理してナノ結晶相を析出させようとする際、相変態に伴うエネルギー放出が起こり、合金が自己発熱してしまうことを見出した。 When the inventors of the present invention attempt to heat-treat an alloy having an amorphous phase as a main phase to precipitate a nanocrystalline phase, energy release accompanying phase transformation occurs and the alloy self-heats. I found.
前述したように、特許文献１の方法においては、ナノ結晶相の析出と圧粉磁心の硬化とを同一熱処理により行っていることから、合金が相変態時に自己発熱してしまうと硬化の際には設定温度よりも高い温度となってしまう場合がある。このような予期せぬ熱処理温度の上昇は、例えば、結晶粒の粗大化や化合物相の生成を生じさせ、圧粉磁心の磁気特性の低下を招く恐れがある。 As described above, in the method of Patent Document 1, since precipitation of the nanocrystalline phase and hardening of the powder magnetic core are performed by the same heat treatment, if the alloy self-heats during the phase transformation, May become higher than the set temperature. Such an unexpected increase in the heat treatment temperature may cause, for example, coarsening of crystal grains and generation of a compound phase, leading to a decrease in magnetic properties of the dust core.
そこで、本発明の発明者らは、ナノ結晶相の析出に係る熱処理と圧粉磁心の硬化とを敢えて分けることにより、熱処理温度の制御を意図したとおりに行えるようにし、特に、ナノ結晶相の析出に係る熱処理に際しては、結晶粒の粗大化や化合物相の生成の抑制を図れるように処理内容を設定することとした。具体的には、本発明は以下に掲げる手段を提供する。 Therefore, the inventors of the present invention dare to separate the heat treatment relating to the precipitation of the nanocrystalline phase and the hardening of the powder magnetic core so that the heat treatment temperature can be controlled as intended, and in particular, the nanocrystalline phase. In the heat treatment related to the precipitation, the content of the treatment was set so as to suppress the coarsening of the crystal grains and the generation of the compound phase. Specifically, the present invention provides the following means.
即ち、本発明は、第１のＦｅ基ナノ結晶合金粉末の製造方法として、
非晶質相を主相とする合金粉末を作製する粉末作製工程と、作製した前記合金粉末に対して所定の熱処理を行う熱処理工程とを備えるＦｅ基ナノ結晶合金粉末の製造方法であって、
前記合金粉末は、所定の温度で熱処理した場合におけるＤＳＣ曲線の発熱ピークを２つ以上有するものであり、
前記所定の熱処理は、第１結晶化開始温度（Ｔｘ１）と第１結晶化終了温度（Ｔｚ１）の間の温度範囲の７０％を少なくとも含む加熱範囲であって第２結晶化開始温度（Ｔｘ２）までは達しない加熱範囲に亘って前記合金粉末を毎分３０℃以上の昇温速度にて加熱してＦｅ基ナノ結晶合金粉末を得るものであり、
前記第１結晶化開始温度は、前記ＤＳＣ曲線のベースラインから最も低温側の前記発熱ピークである第１ピークに至るまでの第１立ち上がり部のうちの最も正の傾きの大きい点を通る接線である第１上昇接線と前記ベースラインとの交点にて定まるものであり、
前記第１結晶化終了温度は、前記第１ピークから前記ベースラインに至るまでの第１立ち下がり部のうちの最も負の傾きの大きい点を通る接線である第１下降接線と前記ベースラインとの交点にて定まるものであり、
前記第２結晶化開始温度は、前記ベースラインから前記第１ピークの次の前記発熱ピークである第２ピークに至るまでの第２立ち上がり部のうちの最も正の傾きの大きい点を通る接線である第２上昇接線と前記ベースラインとの交点にて定まるものである
Ｆｅ基ナノ結晶合金粉末の製造方法を提供する。
That is, the present invention provides a method for producing the first Fe-based nanocrystalline alloy powder,
A method for producing an Fe-based nanocrystalline alloy powder comprising a powder production step of producing an alloy powder having an amorphous phase as a main phase, and a heat treatment step of performing a predetermined heat treatment on the produced alloy powder,
The alloy powder has two or more exothermic peaks of the DSC curve when heat-treated at a predetermined temperature,
The predetermined heat treatment is a heating range including at least 70% of a temperature range between the first crystallization start temperature (Tx1) and the first crystallization end temperature (Tz1), and the second crystallization start temperature (Tx2). The alloy powder is heated at a temperature increase rate of 30 ° C./min or more over a heating range that does not reach until a Fe-based nanocrystalline alloy powder is obtained,
The first crystallization start temperature is a tangent line passing through a point having the largest positive slope in the first rising portion from the baseline of the DSC curve to the first peak which is the exothermic peak on the lowest temperature side. It is determined at the intersection of a certain first rising tangent and the baseline,
The first crystallization end temperature is a first descending tangent that is a tangent passing through a point having the largest negative slope of the first falling portion from the first peak to the base line, and the base line. Is determined at the intersection of
The second crystallization start temperature is a tangent line passing through a point having the largest positive slope in the second rising portion from the base line to the second peak which is the exothermic peak next to the first peak. Provided is a method for producing an Fe-based nanocrystalline alloy powder that is determined at an intersection between a second rising tangent and the base line.
また、本発明は、第２のＦｅ基ナノ結晶合金粉末の製造方法として、第１のＦｅ基ナノ結晶合金粉末の製造方法であって、
前記加熱範囲は、前記第１結晶化開始温度と第１結晶化終了温度の間の温度範囲の７０％以上１００％以下である
Ｆｅ基ナノ結晶合金粉末の製造方法を提供する。
Further, the present invention is a method for producing the first Fe-based nanocrystalline alloy powder as a method for producing the second Fe-based nanocrystalline alloy powder,
The heating range provides a method for producing an Fe-based nanocrystalline alloy powder that is 70% to 100% of a temperature range between the first crystallization start temperature and the first crystallization end temperature.
また、本発明は、第３のＦｅ基ナノ結晶合金粉末の製造方法として、第１又は第２のＦｅ基ナノ結晶合金粉末の製造方法であって、
前記昇温速度は、毎分３００℃以下である
Ｆｅ基ナノ結晶合金粉末の製造方法を提供する。
Further, the present invention is a method for producing the first or second Fe-based nanocrystalline alloy powder as the third Fe-based nanocrystalline alloy powder,
The temperature increase rate provides a method for producing an Fe-based nanocrystalline alloy powder that is 300 ° C. or less per minute.
また、本発明は、第４のＦｅ基ナノ結晶合金粉末の製造方法として、第１乃至第３のいずれかのＦｅ基ナノ結晶合金粉末の製造方法であって、
前記合金粉末の前記第１結晶化開始温度と前記第２結晶化開始温度との差ΔＴは、７０℃以上３００℃以下である
Ｆｅ基ナノ結晶合金粉末の製造方法を提供する。
Further, the present invention is a method for producing any one of the first to third Fe-based nanocrystalline alloy powders as a fourth Fe-based nanocrystalline alloy powder producing method,
A difference ΔT between the first crystallization start temperature and the second crystallization start temperature of the alloy powder provides a method for producing an Fe-based nanocrystalline alloy powder that is 70 ° C. or higher and 300 ° C. or lower.
また、本発明は、第５のＦｅ基ナノ結晶合金粉末の製造方法として、第１乃至第４のいずれかのＦｅ基ナノ結晶合金粉末の製造方法であって、
前記合金粉末は、組成式ＦｅａＢｂＳｉｃＰｘＣｙＣｕｚ（但し、７９≦ａ≦８４ａｔ％、５≦ｂ≦１３ａｔ％、０≦ｃ≦８ａｔ％、１≦ｘ≦１０ａｔ％、０≦ｙ≦５ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦１．２）で表わされる
Ｆｅ基ナノ結晶合金粉末の製造方法を提供する。
Further, the present invention is a method for producing any one of the first to fourth Fe-based nanocrystalline alloy powders as a fifth Fe-based nanocrystalline alloy powder producing method,
The alloy powder composition formula Fe a B b Si c P x C y Cu z ( where, 79 ≦ a ≦ 84at%, 5 ≦ b ≦ 13at%, 0 ≦ c ≦ 8at%, 1 ≦ x ≦ 10at%, A method for producing an Fe-based nanocrystalline alloy powder represented by 0 ≦ y ≦ 5 at%, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 1.2) is provided.
また、本発明は、第６のＦｅ基ナノ結晶合金粉末の製造方法として、第５のＦｅ基ナノ結晶合金粉末の製造方法であって、
Ｆｅの一部をＴｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa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Ｆｅ基ナノ結晶合金において、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素は組成全体の３ａｔ％以下であり、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素とＦｅとの合計は前記ａについての条件７９≦ａ≦８４ａｔ％を満たす
Ｆｅ基ナノ結晶合金粉末の製造方法を提供する。
Further, the present invention provides a fifth Fe-based nanocrystalline alloy powder manufacturing method as a sixth Fe-based nanocrystalline alloy powder manufacturing method,
Part of Fe is Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V In a Fe-based nanocrystalline alloy substituted with one or more elements of Mg, Ca and rare earth elements, Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, One or more elements of Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca, and rare earth elements are 3 at% or less of the entire composition, and Ti, Zr, Hf Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca and 1 of rare earth elements The total of more than one kind of elements and Fe satisfies the condition 79 ≦ a ≦ 84 at% for the a. To provide a process for the preparation of nanocrystalline alloy powder.
更に、本発明は、第７のＦｅ基ナノ結晶合金粉末の製造方法として、第１乃至第６のいずれかのＦｅ基ナノ結晶合金粉末の製造方法であって、
前記粉末作製工程において、前記合金粉末は、ガスアトマイズ法又は水アトマイズ法により作製される
Ｆｅ基ナノ結晶合金粉末の製造方法を提供する。
Furthermore, the present invention provides a method for producing any one of the first to sixth Fe-based nanocrystalline alloy powders as a seventh method for producing a Fe-based nanocrystalline alloy powder,
In the powder production step, the alloy powder provides a method for producing an Fe-based nanocrystalline alloy powder produced by a gas atomization method or a water atomization method.
また、本発明は、第１乃至第７のいずれかの製造方法により製造されたＦｅ基ナノ結晶合金粉末とバインダとを混合して混合物を得る工程と、前記混合物を加圧成型して圧粉体を得る工程と、前記圧粉体を硬化して圧粉磁心を得る工程とを備える圧粉磁心の製造方法を提供する。 The present invention also includes a step of mixing an Fe-based nanocrystalline alloy powder produced by any one of the first to seventh production methods and a binder to obtain a mixture, and pressure-molding the mixture by pressure molding Provided is a method of manufacturing a dust core comprising a step of obtaining a body and a step of curing the powder compact to obtain a dust core.
また、本発明は、第１のＦｅ基ナノ結晶合金粉末として、
組成式ＦｅａＢｂＳｉｃＰｘＣｙＣｕｚ（但し、７９≦ａ≦８４ａｔ％、５≦ｂ≦１３ａｔ％、０≦ｃ≦８ａｔ％、１≦ｘ≦１０ａｔ％、０≦ｙ≦５ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦１．２）で表わされるＦｅ基ナノ結晶合金粉末であって、
当該Ｆｅ基ナノ結晶合金粉末の内部に析出したｂｃｃＦｅ結晶の平均結晶粒径が３０ｎｍ以下である
Ｆｅ基ナノ結晶合金粉末を提供する。
Further, the present invention provides a first Fe-based nanocrystalline alloy powder,
Composition formula Fe a B b Si c P x C y Cu z ( where, 79 ≦ a ≦ 84at%, 5 ≦ b ≦ 13at%, 0 ≦ c ≦ 8at%, 1 ≦ x ≦ 10at%, 0 ≦ y ≦ 5at %, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 1.2) Fe-based nanocrystalline alloy powder,
Provided is an Fe-based nanocrystalline alloy powder in which the average crystal grain size of bccFe crystals precipitated inside the Fe-based nanocrystalline alloy powder is 30 nm or less.
また、本発明は、第２のＦｅ基ナノ結晶合金粉末として、第１のＦｅ基ナノ結晶合金粉末であって、
Ｆｅの一部をＴｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa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Ｆｅ基ナノ結晶合金において、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素は組成全体の３ａｔ％以下であり、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素とＦｅとの合計は前記ａについての条件７９≦ａ≦８４ａｔ％を満たす
Ｆｅ基ナノ結晶合金粉末を提供する。
Further, the present invention is a first Fe-based nanocrystalline alloy powder as the second Fe-based nanocrystalline alloy powder,
Part of Fe is Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V In a Fe-based nanocrystalline alloy substituted with one or more elements of Mg, Ca and rare earth elements, Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, One or more elements of Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca, and rare earth elements are 3 at% or less of the entire composition, and Ti, Zr, Hf Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca and 1 of rare earth elements The total of more than one kind of elements and Fe satisfies the condition 79 ≦ a ≦ 84 at% for the a. Providing nanocrystalline alloy powder.
また、本発明は、第３のＦｅ基ナノ結晶合金粉末として、
組成式ＦｅａＢｂＳｉｃＰｘＣｙＣｕｚ（但し、７９≦ａ≦８４ａｔ％、５≦ｂ≦１３ａｔ％、０≦ｃ≦８ａｔ％、１≦ｘ≦１０ａｔ％、０≦ｙ≦５ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦１．２）で表わされるＦｅ基ナノ結晶合金粉末であって、
飽和磁歪定数が１８×１０-６以下である
Ｆｅ基ナノ結晶合金粉末を提供する。
The present invention also provides a third Fe-based nanocrystalline alloy powder.
Composition formula Fe a B b Si c P x C y Cu z ( where, 79 ≦ a ≦ 84at%, 5 ≦ b ≦ 13at%, 0 ≦ c ≦ 8at%, 1 ≦ x ≦ 10at%, 0 ≦ y ≦ 5at %, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 1.2) Fe-based nanocrystalline alloy powder,
Provided is an Fe-based nanocrystalline alloy powder having a saturation magnetostriction constant of 18 × 10 −6 or less.
また、本発明は、第４のＦｅ基ナノ結晶合金粉末として、第３のＦｅ基ナノ結晶合金粉末であって、
Ｆｅの一部をＴｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa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Ｆｅ基ナノ結晶合金において、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素は組成全体の３ａｔ％以下であり、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素とＦｅとの合計は前記ａについての条件７９≦ａ≦８４ａｔ％を満たす
Ｆｅ基ナノ結晶合金粉末を提供する。
Further, the present invention is a third Fe-based nanocrystalline alloy powder as the fourth Fe-based nanocrystalline alloy powder,
Part of Fe is Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V In a Fe-based nanocrystalline alloy substituted with one or more elements of Mg, Ca and rare earth elements, Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, One or more elements of Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca, and rare earth elements are 3 at% or less of the entire composition, and Ti, Zr, Hf Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca and 1 of rare earth elements The total of more than one kind of elements and Fe satisfies the condition 79 ≦ a ≦ 84 at% for the a. Providing nanocrystalline alloy powder.
更に、本発明は、第１乃至第４のいずれかのＦｅ基ナノ結晶合金粉末とバインダとを混合したものを加圧成型した後、熱処理して得られる圧粉磁心を提供する。 Furthermore, the present invention provides a dust core obtained by heat-molding a mixture of any one of the first to fourth Fe-based nanocrystalline alloy powders and a binder, followed by heat treatment.
本発明によれば、ナノ結晶相の析出に係る熱処理と圧粉磁心の硬化とを分けた上で、ナノ結晶相の析出に係る熱処理を行う際に、第２結晶化開始温度に至る前に昇温速度を下げることとしたため、高磁化のｂｃｃＦｅからなる３０ｎｍ以下の微細なナノ結晶が析出したナノ結晶合金粉末（即ち、結晶粒の粗大化や化合物相の生成の抑制された良好なナノ結晶合金粉末）を得ることができる。 According to the present invention, the heat treatment related to the precipitation of the nanocrystalline phase and the hardening of the powder magnetic core are separated, and the heat treatment related to the precipitation of the nanocrystalline phase is performed before reaching the second crystallization start temperature. Nanocrystal alloy powder with fine nanocrystals of 30 nm or less consisting of highly magnetized bccFe precipitated (ie, good nanocrystals with suppressed coarsening of crystal grains and formation of compound phase) Alloy powder).
また、上述したような良好なナノ結晶合金粉末を用いて圧粉磁心を製造することとしたため、ナノ結晶合金粉末の特性に不確定要素が少なくなり、優れた軟磁気特性と高飽和磁束密度とを有する圧粉磁心を得ることができる。特に、飽和磁歪定数が１８×１０-６以下である（即ち、ゼロに近い）ナノ結晶合金粉末を用いて圧粉磁心を製造する場合には、成型やバインダの硬化に伴って粉末内部に発生する応力歪みを低減させることができるため、更に優れた軟磁気特性を有する圧粉磁心を得ることができる。 In addition, since the powder magnetic core is manufactured using the excellent nanocrystalline alloy powder as described above, there are fewer uncertainties in the characteristics of the nanocrystalline alloy powder, and excellent soft magnetic characteristics and high saturation magnetic flux density A powder magnetic core having the following can be obtained. In particular, when a powder magnetic core is produced using a nanocrystalline alloy powder having a saturation magnetostriction constant of 18 × 10 −6 or less (that is, close to zero), it is generated inside the powder as the molding and binder are hardened. Therefore, a dust core having further excellent soft magnetic properties can be obtained.
特に、上述したような組成式で表わされる合金から製造された場合には、優れた軟磁気特性と１．６０Ｔを超える高飽和磁束密度を有するＦｅ基ナノ結晶合金粉末を得ることができる。また、当該組成式の合金は、ＮｂやＺｒを含有しなくともナノ結晶化が可能なものであることから、原料価格を低減することが可能である。更に、合金粉末を熱処理していることから、圧粉磁心作製前に粉末に錆が生じてしまうといった事態を抑制することができる。 In particular, when manufactured from an alloy represented by the composition formula as described above, an Fe-based nanocrystalline alloy powder having excellent soft magnetic properties and a high saturation magnetic flux density exceeding 1.60 T can be obtained. In addition, since the alloy having the composition formula can be nanocrystallized without containing Nb or Zr, the raw material cost can be reduced. Furthermore, since the alloy powder is heat-treated, it is possible to suppress a situation in which rust is generated on the powder before the dust core is produced.
本発明の実施の形態による圧粉磁心の製造方法は、図１に示されるように、概略、３つの工程：即ち、非晶質相を主相とする合金粉末（非晶質性合金粉末）を作製する粉末作製工程Ｐ１と；非晶質性合金粉末を熱処理してＦｅ基ナノ結晶合金粉末を作製する熱処理工程Ｐ２と；Ｆｅ基ナノ結晶合金粉末を用いて圧粉磁心を作製する磁心作製工程Ｐ３とを備えている。 As shown in FIG. 1, the method for manufacturing a dust core according to an embodiment of the present invention is roughly divided into three steps: an alloy powder having an amorphous phase as a main phase (amorphous alloy powder). A powder preparation step P1 for producing a heat treatment step P2 for producing a Fe-based nanocrystalline alloy powder by heat-treating an amorphous alloy powder; and a magnetic core production for producing a dust core using the Fe-based nanocrystalline alloy powder And a process P3.
粉末作製工程Ｐ１においては、例えば、溶湯を細かく粉末化するアトマイズ法を用いて所望とする合金粉末を得ることができる。詳しくは、Ｆｅや半金属元素等の原料を秤量した後、溶解して合金溶湯を生成する。この合金溶湯をノズルから排出して出来た合金溶湯の流れに冷却媒体を衝突させて、合金溶湯を微細化すると共に急冷し、非晶質性合金粉末を得る。ここで、冷却媒体についての限定は特にはない。従って、例えば、アルゴンなどの不活性ガスや窒素及び空気などの各種気体を用いるガスアトマイズ法や、高圧の水を用いる水アトマイズ法を採用することができる。加えて、高速回転する金属ロールや金属板に合金溶湯を衝突させることにより粉末化することとしても良い。更には、微細化と急冷とに異なる媒体を用いて実施しても良い。 In the powder production process P1, for example, a desired alloy powder can be obtained by using an atomizing method in which a molten metal is finely powdered. Specifically, after raw materials such as Fe and metalloid elements are weighed, they are melted to form a molten alloy. A cooling medium is made to collide with the flow of the molten alloy produced by discharging the molten alloy from the nozzle, and the molten alloy is refined and rapidly cooled to obtain amorphous alloy powder. Here, there is no particular limitation on the cooling medium. Therefore, for example, a gas atomizing method using an inert gas such as argon or various gases such as nitrogen and air, or a water atomizing method using high-pressure water can be employed. In addition, it is good also as pulverizing by making a molten alloy collide with the metal roll and metal plate which rotate at high speed. Further, different media may be used for miniaturization and rapid cooling.
熱処理工程Ｐ２においては、概略、加熱範囲に注意して、以下に詳述するように所定の加熱範囲のみについて毎分３０℃以上の昇温速度にて非晶質性合金粉末に対する熱処理を施す。 In the heat treatment step P2, the amorphous alloy powder is subjected to heat treatment at a rate of temperature increase of 30 ° C./min or more only in a predetermined heating range as described in detail below, paying attention to the heating range.
熱処理工程Ｐ２において処理対象となる非晶質性合金粉末は、図２に示されるように、所定の昇温速度となるように加熱し続けた場合に、発熱ピーク（１１，１５）を２つ以上有するようなＤＳＣ（示差走査熱量分析：Differential scanning calorimetry）曲線１０を得られるようなものである。以下、２つの発熱ピークのうち、最も低温側の発熱ピークを第１ピーク１１といい、第１ピーク１１の次の発熱ピークを第２ピーク１５という。また、ＤＳＣ曲線１０のベースライン２０から第１ピーク１１に至るまでの第１立ち上がり部１２のうちの最も正の傾きの大きい点を通る接線である第１上昇接線３２とベースライン２０との交点にて定まる温度を第１結晶化開始温度Ｔｘ１とし、第１ピーク１１からベースライン２１に至るまでの第１立ち下がり部１３のうちの最も負の傾きの大きい点を通る接線である第１下降接線３４とベースライン２１との交点にて定まる温度を第１結晶化終了温度Ｔｚ１とする。同様に、ベースライン２２から第２ピーク１５に至るまでの第２立ち上がり部１６のうちの最も正の傾きの大きい点を通る接線である第２上昇接線４２とベースライン２２との交点にて定まる温度を第２結晶化開始温度Ｔｘ２とし、第２ピーク１５からベースライン２３に至るまでの第２立ち下がり部１７のうちの最も負の傾きの大きい点を通る接線である第２下降接線４４とベースライン２３との交点にて定まる温度を第２結晶化終了温度とする。
As shown in FIG. 2, the amorphous alloy powder to be treated in the heat treatment step P2 has two exothermic peaks (11, 15) when it is continuously heated to a predetermined temperature rise rate. The DSC (Differential Scanning Calorimetry) curve 10 as described above can be obtained. Hereinafter, of the two exothermic peaks, the exothermic peak on the lowest temperature side is referred to as the first peak 11, and the exothermic peak next to the first peak 11 is referred to as the
第１ピーク１１で示される発熱反応は、合金粉末に最初の結晶化（第１結晶化）が生じた際の発熱反応であり、第２ピーク１５で示される発熱反応は、合金粉末に２回目の結晶化（第２結晶化）が生じた際の発熱反応である。第１結晶化によって析出するのは、主として、軟磁性を担うｂｃｃＦｅ（αＦｅ，Ｆｅ−Ｓｉ）であり、第２結晶化によって析出するのは、主として、磁気特性を劣化させるＦｅ−ＢやＦｅ−Ｐなどである。従って、第１結晶化のみを促進すれば、優れた磁気特性を有するＦｅ基ナノ結晶合金粉末を製造することができる。
The exothermic reaction shown by the first peak 11 is an exothermic reaction when the first crystallization (first crystallization) occurs in the alloy powder, and the exothermic reaction shown by the
そのため、本実施の形態においては、第１結晶化開始温度（Ｔｘ１）と第１結晶化終了温度（Ｔｚ１）の間の温度範囲の７０％を少なくとも含む加熱範囲であって第２結晶化開始温度（Ｔｘ２）までは達しない加熱範囲を所定の加熱範囲とする。ここで、所定の加熱範囲を第１結晶化開始温度と第１結晶化終了温度の間の少なくとも７０％以上としたのは、加熱範囲が７０％未満の場合には、結晶粒の生成及び成長が不十分となり、製造されたＦｅ基ナノ結晶合金粉末の保磁力が劣化してしまうためである。なお、第２結晶化の抑制を確実なものとするため、所定の加熱範囲は、第１結晶化開始温度と第１結晶化終了温度の間の温度範囲の７０％以上１００％以下とするのが好ましい。 Therefore, in the present embodiment, the second crystallization start temperature is a heating range including at least 70% of the temperature range between the first crystallization start temperature (Tx1) and the first crystallization end temperature (Tz1). A heating range that does not reach (Tx2) is defined as a predetermined heating range. Here, the predetermined heating range is set to at least 70% or more between the first crystallization start temperature and the first crystallization end temperature when the heating range is less than 70%. This is because the coercive force of the produced Fe-based nanocrystalline alloy powder deteriorates. In order to ensure the suppression of the second crystallization, the predetermined heating range is 70% to 100% of the temperature range between the first crystallization start temperature and the first crystallization end temperature. Is preferred.
また、第１結晶化のみを促進すると共に第２結晶化を抑制することにより、ｂｃｃＦｅの結晶のみを安定して析出させるためには広いΔＴ（＝Ｔｘ２−Ｔｘ１）を有していることが必要とされる。このため、本実施の形態においては、ΔＴが７０℃以上３００℃以下であることが好ましい。 Further, it is necessary to have a wide ΔT (= Tx2−Tx1) in order to precipitate only bccFe crystals stably by promoting only the first crystallization and suppressing the second crystallization. It is said. For this reason, in this Embodiment, it is preferable that (DELTA) T is 70 to 300 degreeC.
本実施の形態による熱処理工程Ｐ２において、所定の加熱範囲における昇温速度は毎分３０℃以上である。かかる昇温速度とするのは、昇温速度が毎分３０℃より遅いと、結晶粒が粗大化し、製造されたＦｅ基ナノ結晶合金の保磁力が劣化してしまうためである。なお、低保磁力特性のＦｅ基ナノ結晶合金粉末を安定的に得るためには、昇温速度は、毎分３００℃以下であることが望ましい。 In the heat treatment step P2 according to the present embodiment, the rate of temperature increase in a predetermined heating range is 30 ° C. or more per minute. The reason for this temperature increase rate is that if the temperature increase rate is slower than 30 ° C. per minute, the crystal grains become coarse and the coercivity of the produced Fe-based nanocrystalline alloy deteriorates. In order to stably obtain an Fe-based nanocrystalline alloy powder having low coercive force characteristics, it is desirable that the rate of temperature increase be 300 ° C. or less per minute.
毎分３０℃以上で昇温させる熱処理方法としては、例えば、赤外線加熱や高周波加熱など急速昇温が可能な装置を用いた熱処理方法や、結晶化以下の温度で余熱した試料を第１結晶化の発熱反応以上の温度の炉に入れる熱処理方法が考えられる。しかしながら、本発明は、これらに限定されたものではない。 As a heat treatment method for raising the temperature at 30 ° C. or more per minute, for example, a heat treatment method using an apparatus capable of rapid temperature rise such as infrared heating or high-frequency heating, or a first crystallization of a sample preheated at a temperature below crystallization A heat treatment method in which the temperature is higher than the exothermic reaction in the furnace can be considered. However, the present invention is not limited to these.
なお、Ｆｅ基ナノ結晶合金粉末の出発原料たる非晶質性合金粉末として適切なものは、組成式ＦｅａＢｂＳｉｃＰｘＣｙＣｕｚ（但し、７９≦ａ≦８４ａｔ％、５≦ｂ≦１３ａｔ％、０≦ｃ≦８ａｔ％、１≦ｘ≦１０ａｔ％、０≦ｙ≦５ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦１．２）で表わされる組成を有するものであり、従って、製造されるＦｅ基ナノ結晶合金も同様の組成を有している。 Incidentally, appropriate as raw materials serving amorphous alloy powder starting Fe-based nanocrystalline alloy powder composition formula Fe a B b Si c P x C y Cu z ( where, 79 ≦ a ≦ 84at%, 5 ≦ b ≦ 13 at%, 0 ≦ c ≦ 8 at%, 1 ≦ x ≦ 10 at%, 0 ≦ y ≦ 5 at%, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 1.2) Therefore, the produced Fe-based nanocrystalline alloy has a similar composition.
上記Ｆｅ基ナノ結晶合金粉末において、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８４ａｔ％より多いと、液体急冷条件下における非晶質相の形成が困難になり、アトマイズにより作製した合金粉末において、結晶相の割合が増加してしまう。即ち、Ｆｅの割合が８４ａｔ％より多いと、均質なナノ結晶組織が得られず、合金粉末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、８４ａｔ％以下であるのが望ましい。特に１．６０Ｔ以上の飽和磁束密度が必要とされる場合、Ｆｅの割合が８０ａｔ％以上であることが好ましい。 In the Fe-based nanocrystalline alloy powder, 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 84 at%, it becomes difficult to form an amorphous phase under a liquid quenching condition, and the proportion of the crystalline phase increases in the alloy powder produced by atomization. That is, when the proportion of Fe is more than 84 at%, a homogeneous nanocrystalline structure cannot be obtained, and the alloy powder has deteriorated soft magnetic properties. Accordingly, the Fe ratio is desirably 79 at% or more and 84 at% or less. In particular, when a saturation magnetic flux density of 1.60 T or more is required, the ratio of Fe is preferably 80 at% or more.
上記Ｆｅ基ナノ結晶合金粉末において、Ｂ元素は非晶質相の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非晶質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、合金粉末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粉末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 Fe-based nanocrystalline alloy powder, the B element is an essential element responsible for forming an amorphous phase. When the proportion 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 powder 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 powder needs to have a low melting point for mass production, the ratio of B is preferably 10 at% or less.
上記Ｆｅ基ナノ結晶合金粉末において、Ｓｉ元素は非晶質相の形成を担う元素であり、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の割合が８ａｔ％よりも多いと、非晶質形成能が低下し、更に軟磁気特性が劣化する。従って、Ｓｉの割合は、８ａｔ％以下であることが望ましく、更に５ａｔ％以下が好ましい。 In the Fe-based nanocrystalline alloy powder, the Si element is an element responsible for forming an amorphous phase, and contributes to the stabilization of the nanocrystal in the nanocrystallization. When the Si ratio is more than 8 at%, the amorphous forming ability is lowered and the soft magnetic characteristics are further deteriorated. Therefore, the Si ratio is desirably 8 at% or less, and more preferably 5 at% or less.
上記Ｆｅ基ナノ結晶合金粉末において、Ｐ元素は非晶質相の形成を担う必須元素であり、アトマイズにおいては、合金溶湯の融点低下により粘性を低減し、球状の粉末を作製しやすくする効果を有している。Ｐの割合が１ａｔ％より少ないと、液体急冷条件下における非晶質相の形成が困難になる。Ｐの割合が１０ａｔ％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、１０ａｔ％以下であることが望ましい。 In the Fe-based nanocrystalline alloy powder, the P element is an essential element responsible for the formation of an amorphous phase. Atomization has the effect of reducing the viscosity by lowering the melting point of the molten alloy and making it easier to produce a spherical powder. Have. 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 10 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 10 at% or less.
上記Ｆｅ基ナノ結晶合金粉末において、Ｃ元素は非晶質相の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、非晶質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 Fe-based nanocrystalline alloy powder, element C is an element responsible for forming an amorphous phase. In this embodiment, by using a combination of B element, Si element, P element, and C element, compared with the case where only one of them is used, the amorphous forming ability and the stability of nanocrystals are improved. Trying to increase. 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Ｆｅ基ナノ結晶合金粉末において、Ｃｕ元素はナノ結晶化に寄与する必須元素である。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、非晶質相が不均質になり、熱処理によって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、特に合金粉末の酸化及び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 Fe-based nanocrystalline alloy powder, Cu element is an essential element contributing to nanocrystallization. When the ratio of Cu is less than 0.4 at%, nanocrystallization becomes difficult. When the proportion of Cu is more than 1.4 at%, the amorphous phase becomes inhomogeneous, a uniform nanocrystal structure cannot be obtained by heat treatment, and the soft magnetic properties deteriorate. Therefore, it is desirable that the Cu content be 0.4 at% or more and 1.4 at% or less, and considering the oxidation of the alloy powder and the grain growth into the nanocrystal, the Cu ratio is 0.6 at% or more, 1 .3 at% or less is preferable.
Ｐ原子とＣｕ原子との間には強い引力がある。従って、合金粉末が特定の比率の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、ナノ結晶が析出する際にｂｃｃＦｅ結晶は微細構造を有するようになる。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、従って合金粉末は優れた軟磁気特性を有せない。なお、特定の比率（ｚ／ｘ）は、合金粉末の酸化を考慮すると、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 powder contains a specific ratio of P element and Cu element, a cluster having a size of 10 nm or less is formed, and when the nanocrystal is precipitated by the nanosize cluster, the bccFe crystal has a fine structure. Will have. 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 therefore the alloy powder cannot have excellent soft magnetic properties. Note that the specific ratio (z / x) is preferably 0.08 or more and 0.8 or less in consideration of oxidation of the alloy powder.
ここで、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の一部をＴｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa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。但し、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素は組成全体の３ａｔ％以下であり、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素とＦｅとの合計はＦｅの割合ａについての条件７９≦ａ≦８４ａｔ％を満たすものとする。 Here, in order to improve the corrosion resistance and adjust the electric resistance, a part of Fe is Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni in a range where the saturation magnetic flux density does not significantly decrease. Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca, and rare earth elements may be substituted with one or more elements. However, Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, One or more elements of Ca and rare earth elements are 3 at% or less of the entire composition, and Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S , Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca, and the total of one or more of the rare earth elements and Fe satisfy the condition 79 ≦ a ≦ 84 at% for the ratio a of Fe. Shall be satisfied.
特許文献１等の従来技術のように磁心の形態に成型した後にナノ結晶化を図るのではなく、上述したように粉末の形態のままナノ結晶化を図る場合であっても、相変態に伴う合金の自己発熱は生じる。しかし、粉末は比表面積が大きいことから、放熱特性に優れており、従って、自己発熱が結果物たるＦｅ基ナノ結晶合金粉末の磁気特性に与える影響は極めて限られたものとなる。本実施の形態においては、このように安定して良好な磁気特性を有するＦｅ基ナノ結晶合金粉末を熱処理工程Ｐ２にて得た後、そのＦｅ基ナノ結晶合金粉末を用いて磁心作製工程Ｐ３にて圧粉磁心を作製する。 Even if nanocrystallization is not attempted after molding into a magnetic core form as in the prior art of Patent Document 1 or the like, it is accompanied by phase transformation even when nanocrystallization is attempted in the form of powder as described above. Self-heating of the alloy occurs. However, since the powder has a large specific surface area, the powder is excellent in heat dissipation characteristics. Therefore, the influence of self-heating on the magnetic characteristics of the resultant Fe-based nanocrystalline alloy powder is extremely limited. In the present embodiment, after the Fe-based nanocrystalline alloy powder having stable and good magnetic properties is obtained in the heat treatment step P2, the Fe-based nanocrystalline alloy powder is used for the magnetic core manufacturing step P3. To prepare a dust core.
具体的には、まず、Ｆｅ基ナノ結晶合金粉末を樹脂などのバインダと混合・造粒して造粒粉を得る。次いで、金型を用いて造粒粉を加圧成型して圧粉体を得る。その後、圧粉体を硬化して圧粉磁心を得る。このようにして得られた圧粉磁心に含まれるＦｅ基ナノ結晶合金粉末は、熱処理条件が適切にコントロールされていることから、結晶の粗大化や不要な化合物の生成の抑制されたものであり、従って、圧粉磁心も優れた軟磁気特性と高飽和磁束密度を有するものとなる。尚、飽和磁歪定数がゼロに近い（例えば、１８×１０-６以下の）ナノ結晶合金粉末を用いることにより、成型やバインダの硬化に伴って発生する応力歪みが少ない圧粉磁心の製造が可能であるが、このような歪みを除去するために、結晶粒の粗大化が起こらない範囲において、熱処理を行っても良い。 Specifically, first, an Fe-based nanocrystalline alloy powder is mixed and granulated with a binder such as a resin to obtain a granulated powder. Next, the granulated powder is pressure-molded using a mold to obtain a green compact. Thereafter, the green compact is cured to obtain a powder magnetic core. The Fe-based nanocrystalline alloy powder contained in the dust core obtained in this way is one in which the coarsening of crystals and the generation of unnecessary compounds are suppressed because the heat treatment conditions are appropriately controlled. Therefore, the dust core also has excellent soft magnetic characteristics and high saturation magnetic flux density. By using a nanocrystalline alloy powder with a saturation magnetostriction constant close to zero (for example, 18 × 10 −6 or less), it is possible to produce a dust core with less stress strain generated by molding and binder hardening. However, in order to remove such distortion, heat treatment may be performed as long as the crystal grains are not coarsened.
以下、実施例を挙げ、上述した本発明の実施の形態によるＦｅ基ナノ結晶合金粉末及びその製造方法並びにそのＦｅ基ナノ結晶合金粉末を含む圧粉磁心及びその製造方法について、複数の実施例を参照にしながら具体的に説明する。 Hereinafter, examples will be described, and a plurality of examples of the Fe-based nanocrystalline alloy powder and the manufacturing method thereof, and the dust core including the Fe-based nanocrystalline alloy powder and the manufacturing method thereof according to the embodiment of the present invention described above will be described. A specific description will be given with reference.
Ｆｅ、Ｆｅ−Ｓｉ、Ｆｅ−Ｂ、Ｆｅ−Ｐ、Ｃｕからなる原料をＦｅ８３．３Ｓｉ４Ｂ８Ｐ４Ｃｕ０．７の合金組成になるように秤量し、高周波溶解にて溶解した。その後、溶解した合金溶湯を窒素雰囲気中において水アトマイズ法にて処理し、平均粒径４５μｍの合金粉末を作製した。結晶化に伴う発熱反応は示差走査型熱量分析計（ＤＳＣ）を用いて表１に示す熱処理条件と同じ昇温速度にて評価した。粉末の非晶質性を評価するに当たり、「アモルファス度」という評価基準を用いた。ここで、「アモルファス度」とは、Ｘ線回折装置（ＸＲＤ）にて非晶質であることが確認されている同じ合金組成の薄帯における発熱量を基準にして、ｂｃｃＦｅ（αＦｅ，Ｆｅ−Ｓｉ）の析出に伴う単位重量あたりの発熱量を百分率で表したものである。具体的には、ＤＳＣにより測定した第１ピークの発熱量と、同じ合金組成を有する厚さ約２０μｍ、幅１ｍｍの薄帯における第１ピークの発熱量とを比較して上述した「アモルファス度」を求めることにより、粉末の非晶質性を評価した。結晶粒径は、表１に示した熱処理条件にてナノ結晶化熱処理を施した後に、ＸＲＤを用いてｂｃｃＦｅ（αＦｅ，Ｆｅ−Ｓｉ）のメインピークを測定し、Ｓｃｈｅｒｒｅｒの式により算出した。 The raw material consisting of Fe, Fe-Si, Fe-B, Fe-P, and Cu was weighed so as to have an alloy composition of Fe 83.3 Si 4 B 8 P 4 Cu 0.7 and dissolved by high-frequency dissolution. Thereafter, the molten alloy melt was treated by a water atomization method in a nitrogen atmosphere to produce an alloy powder having an average particle size of 45 μm. The exothermic reaction accompanying crystallization was evaluated using a differential scanning calorimeter (DSC) at the same heating rate as the heat treatment conditions shown in Table 1. In evaluating the amorphous nature of the powder, an evaluation standard called “amorphous degree” was used. Here, the “amorphous degree” refers to bccFe (αFe, Fe−−) based on the calorific value of a ribbon having the same alloy composition that is confirmed to be amorphous by an X-ray diffractometer (XRD). The calorific value per unit weight accompanying the precipitation of Si) is expressed as a percentage. Specifically, the “amorphous degree” described above by comparing the calorific value of the first peak measured by DSC with the calorific value of the first peak in a ribbon having the same alloy composition and a thickness of about 20 μm and a width of 1 mm. Was determined to evaluate the amorphous nature of the powder. The crystal grain size was calculated by Scherrer's equation after performing nanocrystallization heat treatment under the heat treatment conditions shown in Table 1, measuring the main peak of bccFe (αFe, Fe-Si) using XRD.
表１から理解されるように、粉末作製工程Ｐ１により作製されたＦｅ８３．３Ｓｉ４Ｂ８Ｐ４Ｃｕ０．７の合金組成を有する粉末は、アモルファス度が７０％であり、非晶質相を主相としていることがわかる。実施例１〜３のＦｅ基ナノ結晶合金粉末は、熱処理工程Ｐ２において、第１結晶化開始温度と第１結晶化終了温度の間の少なくとも７０％以上の加熱範囲に亘って、毎分３０℃以上の昇温速度にて加熱したことから、結晶粒径３０ｎｍ以下の微細組織を有している。一方、比較例１のＦｅ基ナノ結晶合金粉末は、熱処理工程Ｐ２における昇温速度が毎分３０℃未満のため、結晶粒径は３０ｎｍより大きく、すなわち結晶の粗大化が確認されている。 As understood from Table 1, the powder having the alloy composition of Fe 83.3 Si 4 B 8 P 4 Cu 0.7 produced by the powder production process P1 has an amorphous degree of 70% and is amorphous. It can be seen that the phase is the main phase. In the heat treatment step P2, the Fe-based nanocrystalline alloy powders of Examples 1 to 3 have a heating range of 30 ° C./min over a heating range of at least 70% between the first crystallization start temperature and the first crystallization end temperature. Since it heated at the above temperature increase rate, it has a fine structure with a crystal grain size of 30 nm or less. On the other hand, the Fe-based nanocrystalline alloy powder of Comparative Example 1 has a crystal grain size larger than 30 nm because the rate of temperature increase in the heat treatment step P2 is less than 30 ° C. per minute, that is, the crystal is coarsened.
Ｆｅ、Ｆｅ−Ｓｉ、Ｆｅ−Ｂ、Ｆｅ−Ｐ、Ｃｕからなる原料を表２に示す合金組成になるように秤量し、高周波溶解にて溶解した。その後、溶解した合金溶湯を窒素雰囲気中において水アトマイズ法にて処理し、平均粒径４５μｍ程度の合金粉末を作製した。結晶化に伴う発熱反応は示差走査型熱量分析計（ＤＳＣ）を用いて、毎分４０℃の昇温速度にて評価した。粉末の非晶質性は、ＤＳＣにより測定した第１ピークの発熱量と、同じ合金組成を有する厚さ約２０μｍ、幅１ｍｍの薄帯における第１ピークの発熱量とを比較して得られる「アモルファス度」により評価した。飽和磁束密度は、合金粉末に、赤外線加熱装置を用いて毎分４０℃の昇温速度にて加熱し、表２に示した熱処理条件にてナノ結晶化熱処理を施した後に、振動試料型磁力計（ＶＳＭ）を用いて１５００ｋＡ／ｍの磁場にて測定した。評価結果を表２に示す。 Raw materials composed of Fe, Fe-Si, Fe-B, Fe-P, and Cu were weighed so as to have the alloy composition shown in Table 2, and dissolved by high-frequency dissolution. Thereafter, the molten alloy melt was treated by a water atomization method in a nitrogen atmosphere to produce an alloy powder having an average particle size of about 45 μm. The exothermic reaction accompanying crystallization was evaluated using a differential scanning calorimeter (DSC) at a heating rate of 40 ° C. per minute. The amorphousness of the powder can be obtained by comparing the calorific value of the first peak measured by DSC with the calorific value of the first peak in a thin strip having the same alloy composition and a thickness of about 20 μm and a width of 1 mm. Evaluation was based on “amorphous degree”. The saturation magnetic flux density is determined by heating the alloy powder at a heating rate of 40 ° C. per minute using an infrared heating device and performing nanocrystallization heat treatment under the heat treatment conditions shown in Table 2, and then vibrating sample type magnetic force. Measurement was performed using a meter (VSM) in a magnetic field of 1500 kA / m. The evaluation results are shown in Table 2.
表２から理解されるように、実施例４〜１１のＦｅ基ナノ結晶合金粉末は、Ｆｅ量が７９≦ａ≦８４ａｔ％の範囲にあることから、アモルファス度７０％以上の非晶質相を主相とする合金粉末を得ることができ、ナノ結晶化後の飽和磁束密度についても１．６１Ｔ以上の高い飽和磁束密度を得ることができている。一方、比較例２のＦｅ基ナノ結晶合金粉末は、Ｆｅ量が８４．８ａｔ％であるため、急冷により得られた合金粉末のアモルファス度は１０％であり、非晶質相を主相とする合金粉末を得られていないことがわかる。 As can be seen from Table 2, the Fe-based nanocrystalline alloy powders of Examples 4 to 11 had an amorphous phase with an amorphous degree of 70% or more because the Fe amount was in the range of 79 ≦ a ≦ 84 at%. An alloy powder as a main phase can be obtained, and a high saturation magnetic flux density of 1.61 T or more can be obtained for the saturation magnetic flux density after nanocrystallization. On the other hand, since the Fe-based nanocrystalline alloy powder of Comparative Example 2 has an Fe amount of 84.8 at%, the amorphous degree of the alloy powder obtained by rapid cooling is 10%, and the amorphous phase is the main phase. It turns out that the alloy powder is not obtained.
続いて、実施例１２及び１３として、実施例５及び７のＦｅ基ナノ結晶合金粉末を用いて圧粉磁心を作製し、電磁気特性を評価した。比較例３及び４として、実施例５及び７と同じ合金組成であり、熱処理工程Ｐ２を施していない、非晶質相を主相とする合金粉末を用いて圧粉体を作製し、その後、ナノ結晶化のための熱処理を施した場合の電磁気特性を評価した。また、比較例５として、比較例２のＦｅ基ナノ結晶合金粉末（粉末作製工程Ｐ１で作製された合金粉末が非晶質相を主相としないＦｅ基ナノ結晶合金粉末）を用いて圧粉磁心を作製し、電磁気特性を評価した。以下に、本実施例による磁心作製工程Ｐ３，即ち、圧粉磁心の作製方法について示す。 Subsequently, as Examples 12 and 13, dust cores were prepared using the Fe-based nanocrystalline alloy powders of Examples 5 and 7, and the electromagnetic characteristics were evaluated. As Comparative Examples 3 and 4, a green compact was produced using an alloy powder having the same alloy composition as in Examples 5 and 7 and not subjected to the heat treatment step P2, and having an amorphous phase as a main phase. The electromagnetic properties when heat treatment for nanocrystallization was performed were evaluated. Further, as Comparative Example 5, the Fe-based nanocrystalline alloy powder of Comparative Example 2 (Fe-based nanocrystalline alloy powder in which the alloy powder produced in the powder production step P1 does not have an amorphous phase as a main phase) is compacted. A magnetic core was fabricated and the electromagnetic characteristics were evaluated. Hereinafter, a magnetic core manufacturing process P3 according to this embodiment, that is, a method for manufacturing a dust core will be described.
まず、合金粉末と合金粉末に対して重量比で４％となる熱硬化性バインダを混合し、５００μｍのメッシュを通して造粒した。造粒粉２．５ｇを金型に入れ、油圧式自動プレス機により圧力７３５ＭＰａにて成型し、外径１３ｍｍ−内径８ｍｍの円筒形状の圧粉体を作製した。バインダが硬化する温度に設定した恒温槽内に圧粉体を保持して、バインダを硬化させ、圧粉磁心を得た。比較例３及び４においては、バインダを硬化させた後、赤外線加熱装置を用いて、４７５℃まで毎分４０℃の昇温速度となるように加熱し、４７５℃にて１０分間保持した後、空冷し、圧粉磁心を得た。電磁気特性については、周波数２０ｋＨｚにおける初透磁率μｉと周波数２０ｋＨｚ−磁束密度１００ｍＴにおけるコアロスＰｃｖを測定し、評価した。なお、初透磁率μｉはインピーダンスアナライザを用いて測定し、コアロスＰｃｖはＢ−Ｈアナライザを用いて測定した。評価結果を表３に示す。 First, a thermosetting binder having a weight ratio of 4% with respect to the alloy powder and the alloy powder was mixed and granulated through a 500 μm mesh. The granulated powder (2.5 g) was put in a mold and molded by a hydraulic automatic press at a pressure of 735 MPa to produce a cylindrical green compact having an outer diameter of 13 mm and an inner diameter of 8 mm. The green compact was held in a thermostat set to a temperature at which the binder was cured, and the binder was cured to obtain a powder magnetic core. In Comparative Examples 3 and 4, after curing the binder, using an infrared heating device, it was heated to 475 ° C. at a rate of 40 ° C. per minute and held at 475 ° C. for 10 minutes, Air-cooled to obtain a dust core. The electromagnetic characteristics were evaluated by measuring the initial permeability μi at a frequency of 20 kHz and the core loss Pcv at a frequency of 20 kHz-magnetic flux density of 100 mT. The initial permeability μi was measured using an impedance analyzer, and the core loss Pcv was measured using a BH analyzer. The evaluation results are shown in Table 3.
表３から理解されるように、実施例１２及び１３の圧粉磁心は、比較例３及び４に示す圧粉体を作製した後にナノ結晶化熱処理を施した磁心に対して、高い初透磁率μｉと低いコアロスＰｃｖを示しており、優れた軟磁気特性を得ることができている。また、比較例５の圧粉磁心は、実施例１２及び１３と比較して、十分な軟磁気特性が得られておらず、これは、粉末作製工程Ｐ１において、作製された合金粉末のアモルファス度が１０％であり、非晶質相を主相とする合金粉末が得られていないためである。 As can be seen from Table 3, the powder magnetic cores of Examples 12 and 13 have a higher initial magnetic permeability than the magnetic cores that were subjected to nanocrystallization heat treatment after the green compacts shown in Comparative Examples 3 and 4 were produced. μi and a low core loss Pcv are shown, and excellent soft magnetic properties can be obtained. Further, the powder magnetic core of Comparative Example 5 did not have sufficient soft magnetic properties as compared with Examples 12 and 13, which was due to the amorphous degree of the alloy powder produced in the powder production process P1. This is because an alloy powder whose main phase is an amorphous phase is not obtained.
図３は、実施例１２と比較例３に示す圧粉磁心のＸＲＤパターンである。図３を参照すると、実施例１２のナノ結晶合金粉末より作製した圧粉磁心の結晶相はｂｃｃＦｅ（αＦｅ，Ｆｅ−Ｓｉ）のみであるが、比較例３に示す圧粉磁心においては、ｂｃｃＦｅ（αＦｅ，Ｆｅ−Ｓｉ）に加えて、Ｆｅ−Ｂ系化合物が生成していることが確認できる。また、実施例１２のＦｅ基ナノ結晶合金粉末のＸＲＤパターンより、Ｓｃｈｅｒｒｅｒの式を用いて算出した結晶粒径は２４ｎｍであり、本実施の形態において、３０ｎｍ以下の微結晶を析出できていることがわかった。このように、本発明の実施例によるＦｅ基ナノ結晶合金粉末を用いた磁心は、化合物の生成が防がれており、且つ、優れた軟磁気特性と高飽和磁束密度を有するものであることが理解される。 FIG. 3 is an XRD pattern of the dust core shown in Example 12 and Comparative Example 3. Referring to FIG. 3, the crystalline phase of the powder magnetic core produced from the nanocrystalline alloy powder of Example 12 is only bccFe (αFe, Fe—Si), but in the powder magnetic core shown in Comparative Example 3, bccFe ( In addition to (αFe, Fe—Si), it can be confirmed that an Fe—B-based compound is formed. Further, from the XRD pattern of the Fe-based nanocrystalline alloy powder of Example 12, the crystal grain size calculated using Scherrer's formula is 24 nm, and in this embodiment, microcrystals of 30 nm or less can be precipitated. I understood. As described above, the magnetic core using the Fe-based nanocrystalline alloy powder according to the example of the present invention has a compound that is prevented from being formed and has excellent soft magnetic characteristics and high saturation magnetic flux density. Is understood.
Ｆｅ、Ｆｅ−Ｓｉ、Ｆｅ−Ｂ、Ｆｅ−Ｐ、Ｃｕからなる原料を表４に示す合金組成になるように秤量し、高周波溶解にて溶解した。その後、溶解した合金溶湯を窒素雰囲気中において水アトマイズ法にて処理し、平均粒径４５μｍ程度の合金粉末を作製した。合金粉末を、赤外線加熱装置を用いて毎分４０℃の昇温速度にて加熱し、表４に示した熱処理条件にてナノ結晶化熱処理を施した。熱処理した合金粉末と合金粉末に対して重量比で２％となる熱硬化性バインダとを混合し、５００μｍのメッシュを通して造粒した。造粒粉２．５ｇを金型に入れ、油圧式自動プレス機により圧力７３５ＭＰａにて成型し、外径１３ｍｍ−内径８ｍｍの円筒形状の圧粉体を作製した。バインダが硬化する温度に設定した恒温槽内に圧粉体を保持して、バインダを硬化させ、圧粉磁心を得た。飽和磁歪定数は、各合金粉末と同じ合金組成を有する厚さ約２０μｍ、幅４ｍｍ、長さ１５ｍｍの薄帯に対して、各合金粉末と同じ熱処理条件にて熱処理を施した後に、歪みゲージを貼り付け、無磁場の状態に２００ｋＡ／ｍの磁場を印可した際の歪みゲージの抵抗値の変化によって測定した。尚、コアロスＰｃｖは、Ｂ−Ｈアナライザを用いて、周波数２０ｋＨｚ−磁束密度１００ｍＴにおいて測定した。評価結果を表４に示す。 Raw materials composed of Fe, Fe-Si, Fe-B, Fe-P, and Cu were weighed so as to have the alloy composition shown in Table 4, and dissolved by high-frequency dissolution. Thereafter, the molten alloy melt was treated by a water atomization method in a nitrogen atmosphere to produce an alloy powder having an average particle size of about 45 μm. The alloy powder was heated at a temperature increase rate of 40 ° C. per minute using an infrared heating device, and subjected to nanocrystallization heat treatment under the heat treatment conditions shown in Table 4. The heat-treated alloy powder and a thermosetting binder having a weight ratio of 2% with respect to the alloy powder were mixed and granulated through a 500 μm mesh. The granulated powder (2.5 g) was put in a mold and molded by a hydraulic automatic press at a pressure of 735 MPa to produce a cylindrical green compact having an outer diameter of 13 mm and an inner diameter of 8 mm. The green compact was held in a thermostat set to a temperature at which the binder was cured, and the binder was cured to obtain a powder magnetic core. The saturation magnetostriction constant is determined by applying a strain gauge to a thin ribbon having a thickness of about 20 μm, a width of 4 mm, and a length of 15 mm having the same alloy composition as each alloy powder, after performing heat treatment under the same heat treatment conditions as each alloy powder. The measurement was performed by changing the resistance value of the strain gauge when a magnetic field of 200 kA / m was applied in the state of pasting and no magnetic field. The core loss Pcv was measured at a frequency of 20 kHz and a magnetic flux density of 100 mT using a BH analyzer. The evaluation results are shown in Table 4.
表４から理解されるように、圧粉磁心のコアロスＰｃｖは、飽和磁歪定数が小さい合金粉末を用いて製造された方が低くなる傾向を示している。具体的には、飽和磁歪定数が１８×１０-６より大きなＦｅ基合金粉末を用いて製造されている比較例６〜１１の圧粉磁心は、６００ｋＷ／ｍ３以上のコアロスＰｃｖを有している。一方、実施例１４〜１６の圧粉磁心は、飽和磁歪定数が１８×１０-６以下のＦｅ基ナノ結晶合金粉末を用いて製造されていることから、６００ｋＷ／ｍ３未満の低いコアロスＰｃｖを有しており、優れた軟磁気特性を得られることがわかる。 As understood from Table 4, the core loss Pcv of the dust core shows a tendency to be lower when manufactured using an alloy powder having a small saturation magnetostriction constant. Specifically, the dust cores of Comparative Examples 6 to 11 manufactured using Fe-based alloy powder having a saturation magnetostriction constant larger than 18 × 10 −6 have a core loss Pcv of 600 kW / m 3 or more. Yes. On the other hand, since the dust cores of Examples 14 to 16 are manufactured using Fe-based nanocrystalline alloy powder having a saturation magnetostriction constant of 18 × 10 −6 or less, a low core loss Pcv of less than 600 kW / m 3 is obtained. It can be seen that excellent soft magnetic properties can be obtained.
以上、具体的な例を掲げて本発明について説明してきたが、本発明は上述した実施の形態や実施例に限定されるものではない。例えば、粉末の平均粒径や粒度分布の相違は問題なく、粉末形状についても、球状のみならず、凹凸を有する不規則形状や多孔質であっても構わない。また、粒子表面が平滑でも粗くても構わないし、粒子表面に酸化膜や合金組成に含まれる特定の元素が偏析していても可能である。また、熱処理工程において、本加熱の前に予備加熱を行う、昇温速度を途中で変更する等の多段階加熱とすることも可能であり、保持時間の長さについても自由に変更することもできる。更に、圧粉磁心を作製する際のバインダも変更可能であり、バインダ量は合金粉末の比表面積に応じて適宜増減することができ、バインダの種類についても有機系・無機系を問わない。また、熱硬化性ではなく、紫外線硬化型等の結着剤を使用することも可能である。 Although the present invention has been described with specific examples, the present invention is not limited to the above-described embodiments and examples. For example, there is no problem in the difference in the average particle size and particle size distribution of the powder, and the powder shape may be not only spherical but also irregular or porous with irregularities. Further, the particle surface may be smooth or rough, and it is possible even if a specific element contained in the oxide film or alloy composition is segregated on the particle surface. Also, in the heat treatment step, it is possible to perform multi-step heating such as preheating before the main heating, changing the heating rate in the middle, and the length of the holding time can be freely changed. it can. Furthermore, the binder at the time of producing the dust core can be changed, the amount of the binder can be appropriately increased or decreased according to the specific surface area of the alloy powder, and the type of the binder is not limited to organic or inorganic. Further, it is possible to use a binder such as an ultraviolet curing type instead of thermosetting.
上述した実施の形態では、本発明のＦｅ基ナノ結晶合金粉末が圧粉磁心の磁心材料に適用可能である旨を説明したが、当該Ｆｅ基ナノ結晶合金粉末は他の磁性部品に利用することができる。 In the embodiment described above, it has been explained that the Fe-based nanocrystalline alloy powder of the present invention can be applied to a magnetic core material of a dust core, but the Fe-based nanocrystalline alloy powder should be used for other magnetic parts. Can do.
Ｐ１ 粉末作製工程
Ｐ２ 熱処理工程
Ｐ３ 磁心作製工程
１０ ＤＳＣ曲線
１１ 第１ピーク
１２ 第１立ち上がり部
１３ 第１立ち下がり部
１５ 第２ピーク
１６ 第２立ち上がり部
１７ 第２立ち下がり部
２０〜２３ ベースライン
３２ 第１上昇接線
３４ 第１下降接線
４２ 第２上昇接線
４４ 第２下降接線
Ｔｘ１ 第１結晶化開始温度
Ｔｚ１ 第１結晶化終了温度
Ｔｘ２ 第２結晶化開始温度
P1 powder preparation process P2 heat treatment process P3 magnetic
Claims (6)
前記合金粉末は、所定の昇温速度となるように加熱し続けた場合におけるＤＳＣ曲線の発熱ピークを２つ以上有するものであり、
前記所定の熱処理は、第１結晶化開始温度（Ｔｘ１）と第１結晶化終了温度（Ｔｚ１）の間の温度範囲の７０％を少なくとも含む加熱範囲であって第２結晶化開始温度（Ｔｘ２）までは達しない加熱範囲に亘って前記合金粉末を毎分３０℃以上の昇温速度にて所定温度に達するまで加熱した後に前記所定温度にて所定時間の保持を行ってＦｅ基ナノ結晶合金粉末を得るものであり、
前記第１結晶化開始温度は、前記ＤＳＣ曲線のベースラインから最も低温側の前記発熱ピークである第１ピークに至るまでの第１立ち上がり部のうちの最も正の傾きの大きい点を通る接線である第１上昇接線と前記ベースラインとの交点にて定まるものであり、
前記第１結晶化終了温度は、前記第１ピークから前記ベースラインに至るまでの第１立ち下がり部のうちの最も負の傾きの大きい点を通る接線である第１下降接線と前記ベースラインとの交点にて定まるものであり、
前記第２結晶化開始温度は、前記ベースラインから前記第１ピークの次の前記発熱ピークである第２ピークに至るまでの第２立ち上がり部のうちの最も正の傾きの大きい点を通る接線である第２上昇接線と前記ベースラインとの交点にて定まるものであり、
前記合金粉末は、組成式Ｆｅ ａ Ｂ ｂ Ｓｉ ｃ Ｐ ｘ Ｃ ｙ Ｃｕ ｚ （但し、７９≦ａ≦８４ａｔ％、５≦ｂ≦１３ａｔ％、０≦ｃ≦８ａｔ％、１≦ｘ≦１０ａｔ％、０≦ｙ≦５ａｔ％、０．４≦ｚ≦１．４ａｔ％、及び０．０８≦ｚ／ｘ≦１．２）で表わされ、
前記第１ピークは、軟磁性を担う結晶が析出される際のピークであり、前記第２ピークは、磁気特性を劣化させる結晶が析出される際のピークであり、
前記硬化処理工程においては、前記第１結晶化開始温度以上の温度での熱処理を行わない
圧粉磁心の製造方法。 A powder production process for producing an alloy powder having an amorphous phase as a main phase, a heat treatment process for producing an Fe-based nanocrystalline alloy powder by subjecting the produced alloy powder to a predetermined heat treatment, and the produced Fe A step of mixing a base nanocrystalline alloy powder and a binder to obtain a mixture, a step of pressure-molding the mixture to obtain a green compact, and a curing treatment step of curing the green compact to obtain a dust core. A method of manufacturing a dust core comprising :
The alloy powder has two or more DSC curve exothermic peaks when it is continuously heated to have a predetermined rate of temperature increase,
The predetermined heat treatment is a heating range including at least 70% of a temperature range between the first crystallization start temperature (Tx1) and the first crystallization end temperature (Tz1), and the second crystallization start temperature (Tx2). Fe-based nanocrystalline alloy by heating the alloy powder over a heating range that does not reach until a predetermined temperature is reached at a heating rate of 30 ° C. or more per minute , and holding for a predetermined time at the predetermined temperature To obtain powder,
The first crystallization start temperature is a tangent line passing through a point having the largest positive slope in the first rising portion from the baseline of the DSC curve to the first peak which is the exothermic peak on the lowest temperature side. It is determined at the intersection of a certain first rising tangent and the baseline,
The first crystallization end temperature is a first descending tangent that is a tangent passing through a point having the largest negative slope of the first falling portion from the first peak to the base line, and the base line. Is determined at the intersection of
The second crystallization start temperature is a tangent line passing through a point having the largest positive slope in the second rising portion from the base line to the second peak which is the exothermic peak next to the first peak. all SANYO determined at certain second rising tangent intersection of the baseline,
The alloy powder composition formula Fe a B b Si c P x C y Cu z ( where, 79 ≦ a ≦ 84at%, 5 ≦ b ≦ 13at%, 0 ≦ c ≦ 8at%, 1 ≦ x ≦ 10at%, 0 ≦ y ≦ 5 at%, 0.4 ≦ z ≦ 1.4 at%, and 0.08 ≦ z / x ≦ 1.2),
The first peak is a peak when a crystal bearing soft magnetism is precipitated, and the second peak is a peak when a crystal deteriorating magnetic properties is precipitated,
In the curing treatment step, no heat treatment is performed at a temperature equal to or higher than the first crystallization start temperature.
Manufacturing method of a dust core .
前記加熱範囲は、前記第１結晶化開始温度と第１結晶化終了温度の間の温度範囲の７０％以上１００％以下である
圧粉磁心の製造方法。 It is a manufacturing method of the dust core according to claim 1,
The heating range is 70% or more and 100% or less of a temperature range between the first crystallization start temperature and the first crystallization end temperature.
Manufacturing method of a dust core .
前記昇温速度は、毎分３００℃以下である
圧粉磁心の製造方法。 It is a manufacturing method of the dust core according to claim 1 or 2,
The heating rate is 300 ° C. or less per minute.
Manufacturing method of a dust core .
前記合金粉末の前記第１結晶化開始温度と前記第２結晶化開始温度との差ΔＴは、７０℃以上３００℃以下である
圧粉磁心の製造方法。 A method of manufacturing a dust core according to any one of claims 1 to 3,
The difference ΔT between the first crystallization start temperature and the second crystallization start temperature of the alloy powder is 70 ° C. or more and 300 ° C. or less.
Manufacturing method of a dust core .
Ｆｅの一部をＴｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa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Ｆｅ基ナノ結晶合金において、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素は組成全体の３ａｔ％以下であり、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗ、Ｃｒ、Ｃｏ、Ｎｉ、Ａｌ、Ｍｎ、Ａｇ、Ｚｎ、Ｓ、Ｓｎ、Ａｓ、Ｓｂ、Ｂｉ、Ｙ、Ｎ、Ｏ、Ｖ、Ｍｇ、Ｃa及び希土類元素のうち１種類以上の元素とＦｅとの合計は前記ａについての条件７９≦ａ≦８４ａｔ％を満たす
圧粉磁心の製造方法。 A method of manufacturing a dust core according to any one of claims 1 to 4 ,
Part of Fe is Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V In a Fe-based nanocrystalline alloy substituted with one or more elements of Mg, Ca and rare earth elements, Ti, Zr, Hf, Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, One or more elements of Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca, and rare earth elements are 3 at% or less of the entire composition, and Ti, Zr, Hf Nb, Ta, Mo, W, Cr, Co, Ni, Al, Mn, Ag, Zn, S, Sn, As, Sb, Bi, Y, N, O, V, Mg, Ca and 1 of rare earth elements The total of more than one kind of elements and Fe satisfies the condition 79 ≦ a ≦ 84 at% for the a.
Manufacturing method of a dust core .
前記粉末作製工程において、前記合金粉末は、ガスアトマイズ法又は水アトマイズ法により作製される
圧粉磁心の製造方法。 A method of manufacturing a dust core according to any one of claims 1 to 5 ,
In the powder production step, the alloy powder is produced by a gas atomization method or a water atomization method.
Manufacturing method of a dust core .
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