JP2022050132A - Fe ALLOY, Fe ALLOY THIN STRIP, Fe AMORPHOUS ALLOY AND Fe AMORPHOUS ALLOY THIN STRIP - Google Patents
Fe ALLOY, Fe ALLOY THIN STRIP, Fe AMORPHOUS ALLOY AND Fe AMORPHOUS ALLOY THIN STRIP Download PDFInfo
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本発明は、Ｆｅ系合金、Ｆｅ系合金薄帯、Ｆｅ系非晶質合金及びＦｅ系非晶質合金薄帯に関する。 The present invention relates to Fe-based alloys, Fe-based alloy strips, Fe-based amorphous alloys and Fe-based amorphous alloy strips.
ここでいう非晶質とは、非特許文献１に記載されているように『アモルファスは、「無定形」、「非晶質」などと訳されているが、定義は「物質を構成する原子の配置が結晶様の長周期規則性をもたないもの」』である（非特許文献１）。一般に、融液の急冷、電着、蒸着、スパッタリングなどの製法により製作される。 As described in Non-Patent Document 1, "amorphous" as used herein is translated as "amorphous", "amorphous", etc., but the definition is "atoms constituting a substance". The arrangement of the above does not have a crystal-like long-period regularity "" (Non-Patent Document 1). Generally, it is manufactured by a manufacturing method such as quenching of a melt, electrodeposition, thin film deposition, or sputtering.
合金を溶融状態から急冷することによって、連続的に薄帯や線を製造する方法として、遠心急冷法、単ロ－ル法、双ロ－ル法等が知られている。これらの方法は、高速回転する金属製ドラムの内周面または外周面に溶融金属をオリフィス等から噴出させることによって、急速に溶融金属を凝固させて薄帯や線を製造するものである。また、合金組成を適正に選ぶことによって、液体金属に類似した非晶質合金を得ることができ、磁気的性質あるいは機械的性質に優れた材料を製造することができる。 As a method for continuously producing a thin band or a wire by quenching the alloy from a molten state, a centrifugal quenching method, a single roll method, a double roll method and the like are known. In these methods, molten metal is rapidly solidified by ejecting molten metal from an orifice or the like onto the inner peripheral surface or the outer peripheral surface of a metal drum rotating at high speed to produce a thin band or a wire. Further, by appropriately selecting the alloy composition, an amorphous alloy similar to a liquid metal can be obtained, and a material having excellent magnetic or mechanical properties can be produced.
特許文献１、２では、急冷凝固により得られた非晶質合金に熱処理を施し、結晶化させることで良好な磁気特性を有した微細結晶合金が得られることを報告している。これらの微細結晶合金は透磁率が高い、磁歪が低い、保磁力が低いなどの特徴を有しており、各種トランス、チョークコイル、ノイズ対策部品などに用いることができる。 Patent Documents 1 and 2 report that a fine crystalline alloy having good magnetic properties can be obtained by subjecting an amorphous alloy obtained by quenching solidification to heat treatment and crystallizing it. These fine crystal alloys have features such as high magnetic permeability, low magnetostriction, and low coercive force, and can be used for various transformers, choke coils, noise suppression components, and the like.
微細結晶材料の組織と磁気特性には相関が見られ、例えば、非特許文献２ではＦｅの結晶粒径Ｄと保磁力Ｈｃの関係について、結晶粒径Ｄを小さくしていった場合、結晶粒径Ｄが６００Å（６０ｎｍ）より大きい領域ではＨｃは結晶粒径Ｄの低下に伴い結晶粒径Ｄに反比例して大きくなるが、６００Å（６０ｎｍ）より小さい領域ではＨｃは結晶粒径の６乗（Ｄ６）に比例して急激に小さくなることを報告している。また、特許文献２では、Ｆｅ基軟磁性合金において優れた軟磁気特性を示すために好ましい平均粒径は５００Å（５０ｎｍ）以下であり、より好ましくは２００Å（２０ｎｍ）である、との報告もなされている。 A correlation is found between the structure of the fine crystal material and the magnetic properties. For example, in Non-Patent Document 2, regarding the relationship between the crystal grain size D of Fe and the coercive force Hc, when the crystal grain size D is reduced, the crystal grains are reduced. In the region where the diameter D is larger than 600 Å (60 nm), Hc increases in inverse proportion to the crystal grain size D as the crystal grain size D decreases, but in the region smaller than 600 Å (60 nm), Hc is the sixth power of the crystal grain size ( It is reported that it decreases sharply in proportion to D6 ). Further, Patent Document 2 also reports that the average particle size of the Fe-based soft magnetic alloy is preferably 500 Å (50 nm) or less, and more preferably 200 Å (20 nm) in order to exhibit excellent soft magnetic properties. ing.
近年、特許文献３では、微細結晶の核を有する初期超微細結晶合金を熱処理することで、磁気特性とハンドリング性が両立したナノ結晶軟磁性合金を得る手法が報告されている。 In recent years, Patent Document 3 reports a method of obtaining a nanocrystal soft magnetic alloy having both magnetic properties and handleability by heat-treating an initial ultrafine crystal alloy having fine crystal nuclei.
微細結晶合金からなる薄帯は、単ロール法や双ロール法などの急冷凝固プロセスで一旦非晶質からなる薄帯を作製し、その後熱処理によって製造されていた。しかしながら、この熱処理時に、まれに、結晶粒が部分的あるいは広域に渡って粗大化することが生じていた。また、熱処理前の非晶質状態で加工性が悪い場合には、最終製品の形状に加工する際に割れが生じて歩留りが低下するなどの問題が生じていた。 The thin band made of a fine crystalline alloy was manufactured by once forming an amorphous thin band by a quenching solidification process such as a single roll method or a bi-roll method, and then by heat treatment. However, during this heat treatment, in rare cases, the crystal grains were partially or over a wide area of coarsening. Further, when the workability is poor in the amorphous state before the heat treatment, there is a problem that cracks occur when processing into the shape of the final product and the yield is lowered.
本発明は、上記事情に鑑みてなされたものであり、優れた軟磁気特性を有するＦｅ系合金およびＦｅ系合金薄帯を提供することを課題とする。また、本発明は、優れた軟磁気特性を有するＦｅ系合金の素材となる、加工性に優れたＦｅ系非晶質合金およびＦｅ系非晶質合金薄帯を提供することを課題とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an Fe-based alloy and a Fe-based alloy strip having excellent soft magnetic properties. Another object of the present invention is to provide an Fe-based amorphous alloy having excellent processability and a Fe-based amorphous alloy strip, which are materials for Fe-based alloys having excellent soft magnetic properties.
本発明は、上記課題を解決するためになされたものであり、その要旨は、以下のとおりである。 The present invention has been made to solve the above problems, and the gist thereof is as follows.
［１］ 組成式がＦｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦５、０＜ｄ≦３、０．１＜ｅ≦３、１．１＜ｃ＋ｅ＜６を満たし、
Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上であることを特徴とする、Ｆｅ系合金。
［２］ 組成式がＦｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦５、０＜ｄ≦３、１＜ｅ≦３、２＜ｃ＋ｅ＜６を満たし、Ｆｅは７９原子％未満であり、
Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上であることを特徴とする、Ｆｅ系合金。
［３］ 組成式がＦｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦３、０＜ｄ≦３、２＜ｅ≦３、３＜ｃ＋ｅ＜６を満たし、Ｆｅは７９原子％未満であり、
Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上であることを特徴とする、Ｆｅ系合金。
［４］ 金属組織が平均粒径６０ｎｍ以下の微細結晶組織からなることを特徴とする、［１］乃至［３］の何れか一項に記載のＦｅ系合金。
［５］ 前記金属組織が熱処理前の非晶質組織からなる段階での、Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下であり、
前記金属組織が熱処理後の前記微細結晶組織からなる段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が、前記非晶質組織からなる熱処理前の段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅に対して、１／３０以上、１／３以下であることを特徴とする、［１］乃至［４］の何れか一項に記載のＦｅ系合金。
［６］前記熱処理が、昇温速度：５℃／分以上１００℃／分以下、均熱温度が、示差走査熱量測定法により測定した第一発熱部ピーク温度（Ｔｐ１）以上第二発熱部ピーク温度（Ｔｐ２）以下、均熱時間が０．５時間以上６時間以下の熱処理であることを特徴とする［５］に記載のＦｅ系合金。
［７］ ［１］乃至［６］の何れか一項に記載のＦｅ系合金からなるＦｅ系合金薄帯。
［８］ 組成式がＦｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦５、０＜ｄ≦３、０．１＜ｅ≦３、１．１＜ｃ＋ｅ＜６を満たし、
金属組織が非晶質組織からなり、
Ｘ源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下であることを特徴とする、Ｆｅ系非晶質合金。
［９］ 組成式がＦｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦５、０＜ｄ≦３、１＜ｅ≦３、２＜ｃ＋ｅ＜６を満たし、Ｆｅは７９原子％未満であり、
金属組織が非晶質組織からなり、
Ｘ源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下であることを特徴とする、Ｆｅ系非晶質合金。
［１０］ 組成式がＦｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦３、０＜ｄ≦３、２＜ｅ≦３、３＜ｃ＋ｅ＜６を満たし、Ｆｅは７９原子％未満であり、
金属組織が非晶質組織からなり、
Ｘ源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下であることを特徴とする、Ｆｅ系非晶質合金。
［１１］ 熱処理により前記金属組織を平均粒径６０ｎｍ以下の微細結晶組織にした場合のｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が、前記金属組織が前記非晶質組織からなる場合のｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅に対して、１／３０以上、１／３以下の範囲であることを特徴とする［８］乃至［１０］の何れか一項に記載のＦｅ系非晶質合金。
［１２］ 熱処理により前記金属組織を平均粒径６０ｎｍ以下の微細結晶組織にした場合のｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上であることを特徴とする［１１］に記載のＦｅ系非晶質合金。
［１３］ 前記熱処理が、昇温速度：５℃／分以上１００℃／分以下、均熱温度が、示差走査熱量測定法により測定した第一発熱部ピーク温度（Ｔｐ１）以上第二発熱部ピーク温度（Ｔｐ２）以下、均熱時間が０．５時間以上６時間以下の熱処理であることを特徴とする［１１］または［１２］に記載のＦｅ系非晶質合金。
［１４］ ［８］乃至［１３］の何れか一項に記載のＦｅ系非晶質合金からなるＦｅ系非晶質合金薄帯。
［１５］ 曲げ破壊直径が１ｍｍ以下であることを特徴とする［１４］に記載のＦｅ系非晶質合金薄帯。
[1] The composition formula is represented by Fe 100-ab-c-e B a Si b X c Cu d Z e , and the balance is composed of impurity elements, where X in the composition formula is Nb. One or more elements selected from the group of Ti, Zr, Hf, V, Ta, Cr, Mo, W, Z is one or two selected from the group of C, N, P, S. These elements are the above elements, and the composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 0.1. Satisfy <e≤3, 1.1 <c + e <6,
An Fe-based alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X-ray source is 0.25 deg or more.
[2] The composition formula is represented by Fe 100-ab-c-e B a Si b X c Cu d Z e , and the balance is composed of impurity elements, except that X in the above composition formula is Nb. One or more elements selected from the group of Ti, Zr, Hf, V, Ta, Cr, Mo, W, Z is one or two selected from the group of C, N, P, S. These elements are the above elements, and the composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 1 <e. ≤3, 2 <c + e <6, Fe is less than 79 atomic%,
An Fe-based alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X-ray source is 0.25 deg or more.
[3] The composition formula is represented by Fe 100-ab-c-e B a Si b X c Cu d Z e , and the balance is composed of impurity elements, where X in the above composition formula is Nb. One or more elements selected from the group of Ti, Zr, Hf, V, Ta, Cr, Mo, W, Z is one or two selected from the group of C, N, P, S. These elements are the above elements, and the composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 3, 0 <d ≦ 3, 2 <e. ≤3, 3 <c + e <6, Fe is less than 79 atomic%,
An Fe-based alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X-ray source is 0.25 deg or more.
[4] The Fe-based alloy according to any one of [1] to [3], wherein the metal structure is composed of a fine crystal structure having an average particle size of 60 nm or less.
[5] Half-value width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co-Kα rays as an X-ray source at the stage where the metal structure is composed of an amorphous structure before heat treatment. Is 6 deg or more and 8 deg or less,
The half-value width of the diffraction peak of the (110) plane of bcc-Fe at the stage where the metal structure is composed of the fine crystal structure after heat treatment is the (1) of bcc-Fe at the stage before heat treatment having the amorphous structure. 110) The Fe-based alloy according to any one of [1] to [4], which is 1/30 or more and 1/3 or less with respect to the half-value width of the diffraction peak on the surface.
[6] The heat treatment has a heating rate of 5 ° C./min or more and 100 ° C./min or less, and the soaking temperature is the peak temperature of the first heat generating portion (Tp1) or more measured by the differential scanning calorimetry method. The Fe-based alloy according to [5], which is a heat treatment having a temperature (Tp2) or less and a soaking time of 0.5 hours or more and 6 hours or less.
[7] An Fe-based alloy strip made of the Fe-based alloy according to any one of [1] to [6].
[8] The composition formula is represented by Fe 100-ab-c-e B a Si b X c Cu d Ze, and the balance is composed of impurity elements, where X in the composition formula is Nb. One or more elements selected from the group of Ti, Zr, Hf, V, Ta, Cr, Mo, W, Z is one or two selected from the group of C, N, P, S. These elements are the above elements, and the composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 0.1. Satisfy <e≤3, 1.1 <c + e <6,
The metal structure consists of an amorphous structure,
An Fe-based amorphous alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X source is 6 deg or more and 8 deg or less.
[9] The composition formula is represented by Fe 100-ab-c-e B a Si b X c Cu d Ze, and the balance is composed of impurity elements, where X in the composition formula is Nb. One or more elements selected from the group of Ti, Zr, Hf, V, Ta, Cr, Mo, W, Z is one or two selected from the group of C, N, P, S. These elements are the above elements, and the composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 1 <e. ≤3, 2 <c + e <6, Fe is less than 79 atomic%,
The metal structure consists of an amorphous structure,
An Fe-based amorphous alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X source is 6 deg or more and 8 deg or less.
[10] The composition formula is represented by Fe 100-ab-c-e B a Si b X c Cu d Z e , and the balance is composed of impurity elements, except that X in the above composition formula is Nb. One or more elements selected from the group of Ti, Zr, Hf, V, Ta, Cr, Mo, W, Z is one or two selected from the group of C, N, P, S. These elements are the above elements, and the composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 3, 0 <d ≦ 3, 2 <e. ≤3, 3 <c + e <6, Fe is less than 79 atomic%,
The metal structure consists of an amorphous structure,
An Fe-based amorphous alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X source is 6 deg or more and 8 deg or less.
[11] When the half-value width of the diffraction peak of the (110) plane of bcc-Fe when the metal structure is made into a fine crystal structure having an average particle size of 60 nm or less by heat treatment is the case where the metal structure is composed of the amorphous structure. In any one of [8] to [10], the range is 1/30 or more and 1/3 or less with respect to the half-value width of the diffraction peak of the (110) plane of bcc-Fe. The Fe-based amorphous alloy described.
[12] The half-value width of the diffraction peak on the (110) plane of bcc-Fe when the metal structure is made into a fine crystal structure having an average particle size of 60 nm or less by heat treatment is 0.25 deg or more [11]. ] The Fe-based amorphous alloy described in.
[13] The heat treatment is performed at a heating rate of 5 ° C./min or more and 100 ° C./min or less, and the soaking temperature is equal to or higher than the peak temperature (T p1 ) of the first heat generating portion measured by the differential scanning calorimetry method. The Fe-based amorphous alloy according to [11] or [12], which is a heat treatment having a peak temperature (T p2 ) or less and a soaking time of 0.5 hours or more and 6 hours or less.
[14] A Fe-based amorphous alloy ribbon made of the Fe-based amorphous alloy according to any one of [8] to [13].
[15] The Fe-based amorphous alloy strip according to [14], wherein the bending fracture diameter is 1 mm or less.
本発明によれば、優れた軟磁気特性を有するＦｅ系合金およびその薄帯を提供できる。また、本発明によれば、優れた軟磁気特性を有し、かつ、トランス等の製品に実際的に適用可能なＦｅ系合金およびその薄帯を提供できる。また、本発明によれば、優れた軟磁気特性を有するＦｅ系合金の素材となる、加工性に優れたＦｅ系非晶質合金およびその薄帯を提供できる。 According to the present invention, it is possible to provide an Fe-based alloy having excellent soft magnetic properties and a strip thereof. Further, according to the present invention, it is possible to provide an Fe-based alloy having excellent soft magnetic properties and practically applicable to products such as transformers and a thin band thereof. Further, according to the present invention, it is possible to provide an Fe-based amorphous alloy having excellent processability and a thin band thereof, which is a material for the Fe-based alloy having excellent soft magnetic properties.
本発明者らは、非晶質合金を熱処理することによって微細結晶組織を有する微細結晶合金を製造するにあたり、元素Ｘ（Ｎｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ）および元素Ｚ（Ｃ、Ｎ、Ｐ、Ｓ）の熱処理における微細結晶を生み出す役割について初めて明らかにし、その成果からこれら元素の最適な添加量を明確にすることで、本発明を提案するに至った。また、Ｘ線回折パターンから求めた新たな評価指数によって微細結晶合金を特定することで、微細結晶合金の軟磁気特性をより高めることを知見するに至った。 In producing a fine crystalline alloy having a fine crystalline structure by heat-treating an amorphous alloy, the present inventors have elements X (Nb, Ti, Zr, Hf, V, Ta, Cr, Mo, W) and The present invention has been proposed by clarifying for the first time the role of producing fine crystals in the heat treatment of the element Z (C, N, P, S) and clarifying the optimum addition amount of these elements from the results. In addition, it has been found that the soft magnetic properties of the fine crystal alloy can be further enhanced by specifying the fine crystal alloy by a new evaluation index obtained from the X-ray diffraction pattern.
従来から、Ｆｅ－Ｓｉ－Ｂ系非晶質合金を熱処理すると、結晶化が発現することが知られている。その結晶化の過程は２つのステップで進行するとされている。最初の第１のステップでは、熱処理温度の上昇に伴って初期結晶（α―Ｆｅ）が生成する。次の第２のステップでは、更なる熱処理温度の上昇に伴い、不連続に初期結晶が結晶成長を起こし、最終的にはボロン化合物も析出して結晶化が終了に至る。ここで、非晶質合金中に僅かにＣｕを含有させると、第１ステップで多くの微細な結晶が生成する。さらに、ＣｕとともにＮｂなどの元素を非晶質合金に含有させると、結晶の微細化がさらに進行するとされている。つまり、ＣｕやＮｂなどの元素の添加は、微細結晶を生む効果を有していることが知られている。そして、微細な結晶合金を得るためには、第２ステップまでに至らないように、熱処理温度を制御する必要がある。第２ステップまで至ると折角微細に析出した結晶を粗大化させてしまうからである。 Conventionally, it has been known that crystallization occurs when a Fe—Si—B amorphous alloy is heat-treated. The crystallization process is said to proceed in two steps. In the first first step, initial crystals (α-Fe) are formed as the heat treatment temperature rises. In the next second step, as the heat treatment temperature rises further, the initial crystals grow discontinuously, and finally the boron compound also precipitates to complete the crystallization. Here, if a small amount of Cu is contained in the amorphous alloy, many fine crystals are generated in the first step. Further, it is said that when an element such as Nb is contained in the amorphous alloy together with Cu, the crystal refinement is further promoted. That is, it is known that the addition of elements such as Cu and Nb has the effect of producing fine crystals. Then, in order to obtain a fine crystalline alloy, it is necessary to control the heat treatment temperature so as not to reach the second step. This is because when the second step is reached, the finely precipitated crystals are coarsened.
そこで、Ｃｕ及びＮｂを含有させたＦｅ－Ｓｉ－Ｂ－Ｃｕ－Ｎｂ系の微細結晶合金は、一旦非晶質合金を形成させたのち、第１ステップと第２ステップの間の温度で熱処理することが必須とされていた。ところが、先に述べたように、工業的に熱処理する際に、時々結晶粒が部分的あるいは広域に渡って粗大化することが生じていた。その原因は、工業的に量産する熱処理炉では炉内の温度分布が大きく、炉内温度が目的とする制御温度より高くなるところが炉内や製品内で発生し、第２ステップが起きる温度まで炉内温度が上昇する箇所があったためと考えられる。 Therefore, the Fe—Si—B—Cu—Nb-based fine crystalline alloy containing Cu and Nb is once formed into an amorphous alloy and then heat-treated at a temperature between the first step and the second step. Was required. However, as described above, during the industrial heat treatment, the crystal grains sometimes coarsen partially or over a wide area. The cause is that in an industrially mass-produced heat treatment furnace, the temperature distribution in the furnace is large, and the temperature inside the furnace becomes higher than the target controlled temperature in the furnace or in the product, and the temperature reaches the temperature at which the second step occurs. It is probable that there was a place where the internal temperature rose.
そこで、本発明者らは、第１ステップと第２ステップの温度差を大きくすることで、工業的規模の熱処理炉における炉内温度差を乗り越えて、すべての炉内位置において、第１ステップと第２ステップの間の温度の範囲内で非晶質合金を熱処理できるようになると考え、鋭意研究を進めた。その結果、非晶質合金からなる薄帯に、Ｎｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの１種または２種以上を最適な範囲で予め含有させることで、熱処理中の第１ステップと第２ステップとの間の温度差を広げることができることを見出した。つまり、安定して微細結晶粒合金およびその薄帯を得ることが可能であることを明らかにした。 Therefore, the present inventors overcome the temperature difference in the furnace in the heat treatment furnace of an industrial scale by increasing the temperature difference between the first step and the second step, and set the first step at all the positions in the furnace. We thought that it would be possible to heat-treat the amorphous alloy within the temperature range during the second step, and proceeded with diligent research. As a result, the thin band made of an amorphous alloy is preliminarily contained with one or more of Nb, Ti, Zr, Hf, V, Ta, Cr, Mo, and W in an optimum range during heat treatment. It was found that the temperature difference between the first step and the second step of the above can be widened. In other words, it was clarified that it is possible to stably obtain fine grain alloys and their thin bands.
また、微細結晶合金は一般に、非晶質合金の状態で切断、積層、巻回などの工程を経て所定の形状に加工した後に、熱処理を行うことで微細結晶化させている。従って、非晶質合金の状態で加工性が低い場合には、最終製品の製造歩留りの低下が生じる場合がある。そこで、本発明者らは、Ｃ、Ｎ、Ｐ、Ｓの１種または２種以上を適量含有させることで、アモルファス形成能を向上させ、加工性に優れる非晶質合金を安定的に製造できることを見出した。 Further, the fine crystal alloy is generally processed into a predetermined shape through steps such as cutting, laminating, and winding in the state of an amorphous alloy, and then subjected to heat treatment to be finely crystallized. Therefore, if the processability is low in the state of an amorphous alloy, the production yield of the final product may decrease. Therefore, the present inventors can improve the amorphous forming ability and stably produce an amorphous alloy having excellent processability by containing one or more of C, N, P, and S in an appropriate amount. I found.
さらに、本発明者らは、製造した微細結晶合金および薄帯についてＸ線回折にて評価し、Ｘ線回折像での新たな評価指数を導入することで本発見を明確化することに成功し、本発明を提案するに至った。 Furthermore, the present inventors have succeeded in clarifying the present discovery by evaluating the produced fine crystal alloy and the ribbon by X-ray diffraction and introducing a new evaluation index in the X-ray diffraction image. , Have come to propose the present invention.
すなわち、本発明に係るＦｅ系合金およびその薄帯は、Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおいて、金属組織が熱処理後の微細結晶組織からなる段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が、非晶質組織からなる熱処理前の段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅に対して、１／３０以上、１／３以下であることがより好ましい。Ｘ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅の熱処理前後の比（以下、半値幅比という場合がある）をこの範囲内とすることで、工業的に熱処理して微細結晶合金、薄帯を製造する際に生じていた結晶粒の部分的あるいは広域に渡っての粗大化を阻止できることが判明し、この従来生じていた問題を解消することが可能となった。 That is, the Fe-based alloy and its thin band according to the present invention are bcc-Fe at the stage where the metal structure is composed of a fine crystal structure after heat treatment in an X-ray diffraction pattern using Co—Kα rays as an X-ray source. The half-value width of the diffraction peak on the (110) plane is 1/30 or more, 1/3 of the half-value width of the diffraction peak on the (110) plane of bcc-Fe in the stage before the heat treatment consisting of an amorphous structure. The following is more preferable. By setting the ratio of the half-value width of the diffraction peak of the (110) plane of bcc-Fe before and after the heat treatment (hereinafter, may be referred to as the half-value width ratio) in the X-ray diffraction pattern within this range, the heat treatment is performed industrially. It has been found that it is possible to prevent the partial or wide-area coarsening of crystal grains that has occurred during the production of fine crystal alloys and ribbons, and it has become possible to solve this conventional problem.
ここで、半値幅比が１／３０以上にすることで、部分的もしくは広域で粗大結晶粒が生じるおそれがなく、１／３以下とすることで微細結晶組織を金属組織のほぼ全域で生成することができる。よって、好ましい微細結晶粒組織を得るためには、この指標範囲を１／３０以上１／３以下とする必要がある。 Here, when the half width ratio is 1/30 or more, there is no possibility that coarse crystal grains are partially or over a wide area, and when it is 1/3 or less, a fine crystal structure is generated in almost the entire metal structure. be able to. Therefore, in order to obtain a preferable fine crystal grain structure, it is necessary to set this index range to 1/30 or more and 1/3 or less.
従前まで、Ｆｅ系合金の軟磁気特性を高めるために、微細結晶組織の平均結晶粒径をナノメートルオーダーのサイズに制御していたが、本発明者らは、軟磁気特性をより安定して発現させるためには結晶粒径の制御だけでは十分ではなく、結晶粒の部分的あるいは広域に渡る粗大化を防止する必要があることを見出した。そして鋭意検討したところ、結晶粒の部分的あるいは広域に渡る粗大化の指標として、上記の半値幅比によって合金を規定することを知見したのである。Ｆｅ系合金においてナノメートル程度の微細結晶粒の部分的な粗大化を直接検知することは容易ではない。このように、本発明は、その構造または特性を直接できないか、おおよそ実際的ではない事情があるため、半値幅比で発明を特定することとしている。 Previously, in order to improve the soft magnetic properties of Fe-based alloys, the average crystal grain size of the fine crystal structure was controlled to a size on the order of nanometers, but the present inventors have made the soft magnetic properties more stable. It was found that it is not enough to control the crystal grain size for the expression, but it is necessary to prevent the coarsening of the crystal grains partially or over a wide area. As a result of diligent studies, it was found that the alloy is defined by the above half width ratio as an index of partial or widespread coarsening of crystal grains. It is not easy to directly detect the partial coarsening of fine crystal grains of about nanometers in Fe-based alloys. As described above, since the structure or property of the present invention cannot be directly determined or there are circumstances that are not practical, the invention is specified by the full width at half maximum ratio.
また、金属組織が非晶質組織からなる段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上であれば、加工性に優れる非晶質合金であり、歩留りよく所定の形状に加工することができる。この半値幅に特に上限はないが、８ｄｅｇが上限と考えられる。 Further, if the half-value width of the diffraction peak of the (110) plane of bcc-Fe at the stage where the metal structure is composed of an amorphous structure is 6 deg or more, it is an amorphous alloy having excellent processability, and the yield is good. It can be processed into a shape. There is no particular upper limit to this half-value width, but 8 deg is considered to be the upper limit.
本発明によれば、Ｆｅ－Ｓｉ－Ｂ系非晶質合金に、Ｃｕを含有させるとともに、Ｎｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの１種または２種以上を、最適な範囲で予め含有させて、結晶化の第１ステップと第２ステップの間の温度で熱処理することで、半値幅比を１／３０以上１／３以下の範囲とすることが可能となった。また、Ｃ、Ｎ、Ｐ、Ｓの１種または２種以上を適量含有させることで、熱処理前の非晶質状態でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅を６ｄｅｇ以上とすることで、加工性を向上させることが可能となった。 According to the present invention, a Fe—Si—B-based amorphous alloy contains Cu, and one or more of Nb, Ti, Zr, Hf, V, Ta, Cr, Mo, and W are added. By preliminarily containing it in the optimum range and heat-treating it at a temperature between the first step and the second step of crystallization, it is possible to set the half-price width ratio to the range of 1/30 or more and 1/3 or less. rice field. Further, by containing one or more of C, N, P, and S in an appropriate amount, the half width of the diffraction peak of the (110) plane of bcc-Fe in the amorphous state before the heat treatment is set to 6 deg or more. By doing so, it became possible to improve the workability.
以下、本発明に係るＦｅ系合金及びＦｅ系非晶質合金について詳細に説明する。 Hereinafter, the Fe-based alloy and the Fe-based amorphous alloy according to the present invention will be described in detail.
（Ｆｅ系合金及びＦｅ系非晶質合金の組成）
本実施形態のＦｅ系非晶質合金及びＦｅ系合金は、Ｆｅ、Ｂ、Ｓｉ、Ｘ、Ｃｕ及びＺ（但し、ＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの１種または２種以上の元素、ＺはＣ、Ｎ、Ｐ、Ｓの１種または２種以上の元素）を含有する合金において、非晶質状態での加工性が悪化する問題と、熱処理工程での結晶粒が部分的あるいは広域に渡って粗大化する問題を、以下の組成式（Ｉ）とすることで解消したことにある。好ましくは組成式（ＩＩ）がよく、更に好ましくは組成式（ＩＩＩ）がよい。
(Composition of Fe-based alloy and Fe-based amorphous alloy)
The Fe-based amorphous alloy and Fe-based alloy of the present embodiment are Fe , B, Si, X, Cu and Z (where X is Nb, Ti, Zr, Hf, V, Ta, Cr, Mo and W. In alloys containing one or more elements, Z is one or more elements of C, N, P, S), the problem of deterioration of processability in the amorphous state and the heat treatment step The problem that the crystal grains in the above are partially or over a wide area of coarsening is solved by using the following composition formula (I). The composition formula (II) is preferable, and the composition formula (III) is more preferable.
組成式（Ｉ）：
Ｆｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦５、０＜ｄ≦３、０．１＜ｅ≦３、１．１＜ｃ＋ｅ＜６を満たす。
Composition formula (I):
Fe 100-ab-c-d-e B a Si b X c Cu d Z e and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr, Hf, One or more elements selected from the group V, Ta, Cr, Mo, W, Z is one or more elements selected from the group C, N, P, S. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 0.1 <e ≦ 3, 1 .1 <c + e <6 is satisfied.
組成式（ＩＩ）：
Ｆｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦５、０＜ｄ≦３、１＜ｅ≦３、２＜ｃ＋ｅ＜６を満たし、Ｆｅは７９原子％未満である。
Composition formula (II):
Fe 100-ab-c-d-e B a Si b X c Cu d Z e and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr, Hf, One or more elements selected from the group V, Ta, Cr, Mo, W, Z is one or more elements selected from the group C, N, P, S. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 1 <e ≦ 3, 2 <c + e. <6 is satisfied, and Fe is less than 79 atomic%.
組成式（ＩＩＩ）：
Ｆｅ１００－ａ－ｂ－ｃ－ｄ－ｅＢａＳｉｂＸｃＣｕｄＺｅで表されるとともに残部が不純物元素からなり、但し、前記組成式におけるＸはＮｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの群から選択される一種または２種以上の元素であり、ＺはＣ、Ｎ、Ｐ、Ｓの群から選択される一種または２種以上の元素であり、組成比ａ、ｂ、ｃ、ｄ、ｅはそれぞれ原子％で、４≦ａ≦２０、５≦ｂ≦２０、１≦ｃ≦３、０＜ｄ≦３、２＜ｅ≦３、３＜ｃ＋ｅ＜６を満たし、Ｆｅは７９原子％未満である。
Composition formula (III):
Fe 100-ab-c-d-e B a Si b X c Cu d Z e and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr, Hf, One or more elements selected from the group V, Ta, Cr, Mo, W, Z is one or more elements selected from the group C, N, P, S. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 3, 0 <d ≦ 3, 2 <e ≦ 3, 3 <c + e. <6 is satisfied, and Fe is less than 79 atomic%.
Ｂは、非晶質形成能を高める元素であり、Ｂの組成比ａは原子％で４≦ａ≦２０である。Ｂの組成比ａが４原子％未満では非晶質形成能が劣化するため好ましくなく、２０原子％を超えると飽和磁束密度の低下を招くため好ましくない。よってＢの組成比ａは４≦ａ≦２０とする。より好ましいａの範囲は５≦ａ≦１０であり、更に好ましいａの範囲は５≦ａ≦８である。 B is an element that enhances the ability to form an amorphous substance, and the composition ratio a of B is 4 ≦ a ≦ 20 in atomic%. If the composition ratio a of B is less than 4 atomic%, the amorphous forming ability is deteriorated, which is not preferable, and if it exceeds 20 atomic%, the saturation magnetic flux density is lowered, which is not preferable. Therefore, the composition ratio a of B is 4 ≦ a ≦ 20. The more preferable range of a is 5 ≦ a ≦ 10, and the more preferable range of a is 5 ≦ a ≦ 8.
Ｓｉは、非晶質形成能を高める元素であり、Ｓｉの組成比ｂは原子％で５≦b≦２０である。Ｓｉは、合金表面に酸化物として偏析することで、磁心などとして積層させて使用する際に層間絶縁を向上させる効果もある。Ｓｉが５原子％未満では非晶質形成能が不十分になる。Ｓｉの組成比ｂが２０原子％を超えると飽和磁束密度の低下を招くため好ましくない。よって、Ｓｉの組成比ｂは原子％で５≦ｂ≦２０とする。より好ましい組成比ｂの範囲は８≦ｂ≦１６であり、更に好ましい組成比ｂの範囲は１２≦ｂ≦１６であり、更には１２．５≦ｂ≦１５．５でもよい。 Si is an element that enhances the ability to form an amorphous substance, and the composition ratio b of Si is 5 ≦ b ≦ 20 in atomic%. Si segregates on the surface of the alloy as an oxide, which also has the effect of improving interlayer insulation when laminated and used as a magnetic core or the like. If Si is less than 5 atomic%, the amorphous forming ability becomes insufficient. If the composition ratio b of Si exceeds 20 atomic%, the saturation magnetic flux density is lowered, which is not preferable. Therefore, the composition ratio b of Si is 5 ≦ b ≦ 20 in atomic%. The range of the more preferable composition ratio b is 8 ≦ b ≦ 16, the range of the more preferable composition ratio b is 12 ≦ b ≦ 16, and further, 12.5 ≦ b ≦ 15.5 may be used.
Ｘ元素は、Ｎｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの１種または２種以上の元素である。Ｘ元素は、熱処理中の第１ステップと第２ステップとの間の温度差を広げる効果があり、工業的規模の熱処理炉でも安定して微細結晶粒合金およびその薄帯を得ることができる。Ｎｂ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの１種または２種以上がより好ましく、Ｎｂ、Ｖ、Ｗ、Ｃｒの１種または２種以上が更に好ましい。 The element X is one or more of Nb, Ti, Zr, Hf, V, Ta, Cr, Mo, and W. The element X has an effect of widening the temperature difference between the first step and the second step during the heat treatment, and a fine crystal grain alloy and a thin band thereof can be stably obtained even in an industrial scale heat treatment furnace. One or more of Nb, V, Ta, Cr, Mo, and W are more preferable, and one or more of Nb, V, W, and Cr are even more preferable.
Ｘ元素の組成比ｃは原子％で１≦ｃ≦５である。Ｘ元素を含有させることで、熱処理中の第１ステップと第２ステップとの間の温度差を広げる効果が得られるが、１原子％以上含有させることが十分な効果が得られるため好ましい。Ｘ元素の組成比ｃが５原子％を超えると、飽和磁束密度の低下を招くため好ましくない。更に好ましいＸ元素の組成比ｃは１≦ｃ≦４であり、より好ましくは１≦ｃ≦３である。 The composition ratio c of the X element is 1 ≦ c ≦ 5 in atomic%. By containing the X element, the effect of widening the temperature difference between the first step and the second step during the heat treatment can be obtained, but it is preferable to contain 1 atomic% or more because a sufficient effect can be obtained. If the composition ratio c of the X element exceeds 5 atomic%, the saturation magnetic flux density is lowered, which is not preferable. A more preferable composition ratio c of the X element is 1 ≦ c ≦ 4, and more preferably 1 ≦ c ≦ 3.
Ｃｕは、微細結晶化の際に核形成の起点として作用し、微細な結晶粒を均一に形成する効果を有する。Ｃｕの組成比ｄは０＜ｄ≦３である。微細結晶化のためにはＣｕは必須であるが、３原子％を超えると非晶質形成能が低下し、連続的な非晶質合金薄帯の製造が困難となる。より好ましいＣｕの組成比ｄは０＜ｄ≦２であり、更に好ましくは０．５＜ｄ≦１である。 Cu acts as a starting point for nucleation during fine crystallization and has the effect of uniformly forming fine crystal grains. The composition ratio d of Cu is 0 <d ≦ 3. Cu is indispensable for fine crystallization, but if it exceeds 3 atomic%, the amorphous forming ability is lowered, and it becomes difficult to produce a continuous amorphous alloy strip. The more preferable composition ratio d of Cu is 0 <d ≦ 2, and more preferably 0.5 <d ≦ 1.
Ｚ元素は、Ｃ、Ｎ、Ｐ、Ｓの１種または２種以上の元素である。これらのＺ元素は、アモルファス形成能を向上させる効果があり、また、非晶質状態での加工性を改善することができる。特に、Ｃ、Ｐの１種以上が好ましい。Ｚ元素の組成比ｅは０．１＜ｅ≦３とする。Ｚ元素の組成比ｅが３原子％を超えると、飽和磁束密度の低下を招くため好ましくない。また、Ｚ元素の組成比ｅが０．１原子％以下ではアモルファス形成能が十分ではない。より好ましいＺ元素の組成比ｅは１＜ｅ≦３であり、更に、より好ましいＺ元素の組成比ｅは２＜ｅ≦３である。 The Z element is one or more of C, N, P, and S. These Z elements have the effect of improving the amorphous forming ability, and can also improve the processability in the amorphous state. In particular, one or more of C and P are preferable. The composition ratio e of the Z element is 0.1 <e ≦ 3. If the composition ratio e of the Z element exceeds 3 atomic%, the saturation magnetic flux density is lowered, which is not preferable. Further, when the composition ratio e of the Z element is 0.1 atomic% or less, the amorphous forming ability is not sufficient. The more preferable composition ratio e of the Z element is 1 <e ≦ 3, and the more preferable composition ratio e of the Z element is 2 <e ≦ 3.
上述のように、Ｘ元素（Ｎｂ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｃｒ、Ｍｏ、Ｗの１種または２種以上）は、熱処理中の第１ステップと第２ステップとの間の温度差を広げる効果があり、また、Ｚ元素（Ｃ、Ｎ、Ｐ、Ｓの１種以上）は、アモルファス形成能を向上させる効果があり加工性を改善することができるが、本発明者らが鋭意研究を重ねた結果、Ｘ元素の組成比ｃとＺ元素の組成比ｅの和（ｃ＋ｅ）を調整することで、これらの効果を両立できることを見出した。具体的にはＸ元素とＺ元素の和を、１．１＜ｃ＋ｅ＜６、より好ましくは２＜ｃ＋ｅ＜６、さらに好ましくは３＜ｃ＋ｅ＜６とするとよい。 As mentioned above, the element X (one or more of Nb, Ti, Zr, Hf, V, Ta, Cr, Mo, W) is the temperature between the first step and the second step during the heat treatment. The Z element (one or more of C, N, P, and S) has the effect of widening the difference, and has the effect of improving the amorphous forming ability and can improve the workability. As a result of diligent research, it was found that these effects can be achieved at the same time by adjusting the sum (c + e) of the composition ratio c of the X element and the composition ratio e of the Z element. Specifically, the sum of the X element and the Z element may be 1.1 <c + e <6, more preferably 2 <c + e <6, and even more preferably 3 <c + e <6.
本発明に係るＦｅ系非晶質合金またはＦｅ系合金における残部は、Ｆｅ及び不純物元素である。Ｆｅは、より好ましくは７９原子％以下がよい。Ｆｅの含有量を制限することで、他の添加元素の含有量を相対的に高めることができ、軟磁気特性及び加工性を一層高めることができる。特に、アモルファス形成能が向上して鋳造性が向上することで、急冷法によって安定的に鋳造を行うことができる。 The balance in the Fe-based amorphous alloy or Fe-based alloy according to the present invention is Fe and impurity elements. Fe is more preferably 79 atomic% or less. By limiting the content of Fe, the content of other additive elements can be relatively increased, and the soft magnetic properties and processability can be further improved. In particular, since the amorphous forming ability is improved and the castability is improved, stable casting can be performed by the quenching method.
また、本発明に係るＦｅ系非晶質合金またはＦｅ系合金は、鉄鋼材料に含まれる不純物を不純物元素として含んでいてもよい。例えば、Ｃ、Ｎ、Ｐ、Ｓ、Ｏ等を不純物として含有してもよい。Ｃ、Ｐ、ＳはＺ元素として上記の所定量の範囲で含有してもよく、不純物元素として微量を含有してもよい。 Further, the Fe-based amorphous alloy or Fe-based alloy according to the present invention may contain impurities contained in the steel material as an impurity element. For example, C, N, P, S, O and the like may be contained as impurities. C, P, and S may be contained as the Z element in the above-mentioned predetermined amount range, or may be contained in a trace amount as the impurity element.
（Ｆｅ系非晶質合金の金属組織）
次に、Ｆｅ系非晶質合金の金属組織について説明する。
Ｆｅ系非晶質合金の金属組織は、非晶質組織である。金属組織の一部に結晶組織があると、その後の熱処理において粗大な結晶粒組織が形成されるおそれがある。従って金属組織の全体が非晶質組織である必要がある。
(Metal structure of Fe-based amorphous alloy)
Next, the metal structure of the Fe-based amorphous alloy will be described.
The metal structure of the Fe-based amorphous alloy is an amorphous structure. If there is a crystal structure in a part of the metal structure, a coarse crystal grain structure may be formed in the subsequent heat treatment. Therefore, the entire metal structure needs to be an amorphous structure.
また、Ｆｅ系非晶質合金は、Ｘ源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下とする。半値幅が６ｄｅｇ未満では、Ｆｅ系非晶質合金の加工性を向上できない。一方、金属組織が非晶質であるので、半値幅の上限は特に規定する必要はないが、あえて上限を規定するならば、８ｄｅｇ以下とすれば十分である。 Further, in the Fe-based amorphous alloy, the half width of the diffraction peak of the (110) plane of bcc—Fe in the X-ray diffraction pattern using Co—Kα rays as the X source is set to 6 deg or more and 8 deg or less. If the half width is less than 6 deg, the processability of the Fe-based amorphous alloy cannot be improved. On the other hand, since the metal structure is amorphous, it is not necessary to specify the upper limit of the half width in particular, but if the upper limit is intentionally specified, it is sufficient to set it to 8 deg or less.
また、本実施形態のＦｅ系非晶質合金は、厚さ１０μｍ以上１００μｍ以下、板幅が１０ｍｍ以上の薄帯であってもよい。 Further, the Fe-based amorphous alloy of the present embodiment may be a thin band having a thickness of 10 μm or more and 100 μm or less and a plate width of 10 mm or more.
Ｆｅ系非晶質合金からなる薄帯は、曲げ破壊直径が２ｍｍ以下であることが好ましく、１ｍｍ以下であることがより好ましい。上記組成式（ＩＩＩ）の場合に、１ｍｍ以下の曲げ破壊直径が得られやすく、上記組成式（Ｉ）または（ＩＩ）の場合に２ｍｍ以下の曲げ破壊直径が得られやすい。曲げ破壊半径は、ＪＩＳ Ｚ ２２４８：２００６の金属材料曲げ試験方法に準拠し、曲げ試験機にＦｅ系非晶質合金からなる薄帯を設置し、密着するまで試験片の両端を互いに押し合い、破断した際の試験片の直径（曲げ破壊直径）を測定する。 The thin band made of an Fe-based amorphous alloy preferably has a bending fracture diameter of 2 mm or less, and more preferably 1 mm or less. In the case of the composition formula (III), a bending fracture diameter of 1 mm or less can be easily obtained, and in the case of the composition formula (I) or (II), a bending fracture diameter of 2 mm or less can be easily obtained. The bending fracture radius conforms to the metal material bending test method of JIS Z 2248: 2006, a thin band made of Fe-based amorphous alloy is installed in the bending tester, and both ends of the test piece are pressed against each other until they are in close contact with each other to break. The diameter of the test piece (bending fracture diameter) at the time of the test piece is measured.
本実施形態に係るＦｅ系非晶質合金からなる薄帯は、曲げ破壊直径が小さく、加工性に優れる。そのため、トランス、チョークコイル、ノイズ対策品等を製造する際に、Ｆｅ系非晶質合金からなる薄帯を破損させることなく、これら製品の部品素材として組み込むことができる。そして、適切な条件で熱処理を行うことで、軟磁気特性に優れたＦｅ系合金を備えたトランス等の製品を製造することが可能になる。 The thin band made of the Fe-based amorphous alloy according to the present embodiment has a small bending fracture diameter and is excellent in workability. Therefore, when manufacturing a transformer, a choke coil, a noise suppression product, or the like, it can be incorporated as a component material of these products without damaging the thin band made of the Fe-based amorphous alloy. Then, by performing the heat treatment under appropriate conditions, it becomes possible to manufacture a product such as a transformer equipped with an Fe-based alloy having excellent soft magnetic properties.
（Ｆｅ系合金の金属組織）
次に、Ｆｅ系合金の金属組織について説明する。なお、本実施形態のＦｅ系合金の金属組織は、本実施形態のＦｅ系非晶質合金を熱処理することによって得ることができる。
(Metal structure of Fe-based alloy)
Next, the metal structure of the Fe-based alloy will be described. The metal structure of the Fe-based alloy of the present embodiment can be obtained by heat-treating the Fe-based amorphous alloy of the present embodiment.
本実施形態のＦｅ系合金は、Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおける、ｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上である。好ましくは０．４ｄｅｇ以上である。後述するシェラーの式より平均結晶粒径を求めると、半値幅が０．２５ｄｅｇ以上の場合は平均結晶粒径が６０ｎｍ以下、半値幅が０．４ｄｅｇ以上の場合は平均結晶粒径が３０ｎｍ以下となる。このような半値幅を有するＦｅ系合金は、優れた軟磁気特性を示すものとなる。 In the Fe-based alloy of the present embodiment, the half width of the diffraction peak of the (110) plane of bcc—Fe in the X-ray diffraction pattern using Co—Kα rays as the X-ray source is 0.25 deg or more. It is preferably 0.4 deg or more. When the average crystal grain size is calculated from the Scherrer formula described later, the average crystal grain size is 60 nm or less when the half width is 0.25 deg or more, and the average crystal grain size is 30 nm or less when the half width is 0.4 deg or more. Become. An Fe-based alloy having such a half-value width exhibits excellent soft magnetic properties.
Ｆｅ系非晶質合金の金属組織は、結晶粒径が６０ｎｍ以下の微細結晶組織であることが好ましい。より好適には３０ｎｍ以下の微細結晶組織が好ましい。このような微細結晶組織とすることで、Ｆｅ系合金は優れた軟磁気特性を示す。 The metal structure of the Fe-based amorphous alloy is preferably a fine crystal structure having a crystal grain size of 60 nm or less. More preferably, a fine crystal structure of 30 nm or less is preferable. With such a fine crystal structure, the Fe-based alloy exhibits excellent soft magnetic properties.
また、本実施形態のＦｅ系合金は、上記の組成式（Ｉ）～（ＩＩＩ）のいずれか組成を備えているため、６０ｎｍ以下の結晶粒径を得るための熱処理の均熱温度の上限及び下限の幅が５０℃以上と広くなる。これにより、熱処理装置内の温度バラつきの影響による不良品の発生率が低下し、製品歩留まりを向上させることができる。 Further, since the Fe-based alloy of the present embodiment has any of the above composition formulas (I) to (III), the upper limit of the soaking temperature of the heat treatment for obtaining a crystal grain size of 60 nm or less and the upper limit of the soaking temperature The width of the lower limit becomes as wide as 50 ° C. or higher. As a result, the rate of occurrence of defective products due to the influence of temperature variation in the heat treatment apparatus is reduced, and the product yield can be improved.
また、Ｆｅ系合金は、Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおける、金属組織が熱処理後の微細結晶組織からなる段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が、非晶質組織からなる熱処理前の段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅に対して、１／３０以上、１／３以下であることが好ましい。Ｘ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅の熱処理前後の比（半値幅比）をこの範囲とすることで、工業的に熱処理して微細結晶合金、薄帯を製造する際に生じていた結晶粒の部分的あるいは広域に渡っての粗大化を阻止できる。 Further, the Fe-based alloy has a diffraction peak on the (110) plane of bcc-Fe at the stage where the metal structure is composed of a fine crystal structure after heat treatment in an X-ray diffraction pattern using Co—Kα rays as an X-ray source. The half-price width is preferably 1/30 or more and 1/3 or less with respect to the half-price width of the diffraction peak of the (110) plane of bcc-Fe in the stage before the heat treatment having an amorphous structure. By setting the ratio (half-value width ratio) of the half-value width of the diffraction peak of the (110) plane of bcc-Fe in the X-ray diffraction pattern before and after the heat treatment in this range, the fine crystal alloy and the thin band are industrially heat-treated. It is possible to prevent the partial or wide-area coarsening of crystal grains generated during production.
また、本実施形態のＦｅ系合金は、厚さ１０μｍ以上１００μｍ以下、板幅が１０ｍｍ以上の薄帯であってもよい。 Further, the Fe-based alloy of the present embodiment may be a thin band having a thickness of 10 μm or more and 100 μm or less and a plate width of 10 mm or more.
本実施形態のＦｅ系非晶質合金及びＦｅ系合金におけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅は、これらの合金に対してＸ線回折測定を行ってＸ線回折パターンを得ることにより、求めることができる。Ｘ線回折測定のＸ線源はＣｏ－Ｋα（波長λ＝１．７９０２Å）とし、スキャン範囲は２θ＝１０ｄｅｇ以上１２０ｄｅｇ以下とする。Ｘ線回折パターンからｂｃｃ－Ｆｅの（１１０）面の回折ピークを特定し、その回折ピークの半値幅を求めればよい。 The half-value width of the diffraction peak of the (110) plane of bcc—Fe in the Fe-based amorphous alloy and the Fe-based alloy of the present embodiment is obtained by performing X-ray diffraction measurement on these alloys to obtain an X-ray diffraction pattern. By doing so, it can be obtained. The X-ray source for X-ray diffraction measurement is Co—Kα (wavelength λ = 1.7902 Å), and the scan range is 2θ = 10 deg or more and 120 deg or less. The diffraction peak on the (110) plane of bcc-Fe may be specified from the X-ray diffraction pattern, and the half width of the diffraction peak may be obtained.
また、Ｆｅ系合金の金属組織の平均結晶粒径は、ｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅を、シェラーの式に導入することで、求めることができる。シェラーの式は下記式で表される。シェラーの式におけるＫはシェラー定数（０．９４）であり、λはＸ線源の波長（１．７９０２Å）であり、βは回折ピークの半値幅であり、θは（１１０）面の回折ピークの回折角であり、Ｄが平均結晶粒径である。なお、回折ピークから測定される半値幅には測定機器によるピーク拡がりを含むことから、半値幅からピーク拡がり（０．０７ｄｅｇ）を減算した値を半値幅βとして使用する。 Further, the average crystal grain size of the metal structure of the Fe-based alloy can be obtained by introducing the half width of the diffraction peak of the (110) plane of bcc—Fe into Scheller's equation. Scherrer's equation is expressed by the following equation. In Scheller's equation, K is the Scherrer constant (0.94), λ is the wavelength of the X-ray source (1.7902 Å), β is the half width of the diffraction peak, and θ is the diffraction peak on the (110) plane. Diffraction angle, where D is the average crystal grain size. Since the half-value width measured from the diffraction peak includes the peak width by the measuring device, the value obtained by subtracting the peak width (0.07 deg) from the half-value width is used as the half-value width β.
Ｄ＝Ｋλ／βｃｏｓθ …（シェラーの式） D = Kλ / βcosθ… (Scherrer's equation)
更に、半値幅比を求める際の熱処理条件は、昇温速度：５～１００℃／分、均熱温度：第一発熱部ピーク温度（Ｔｐ１）以上、第二発熱部ピーク温度（Ｔｐ２）以下、均熱時間：０．５～６時間の範囲とする。このような熱処理条件の範囲内であれば、Ｆｅ系合金のｂｃｃ－Ｆｅの半値幅はほぼ一定の値となるので、半値幅を測定する際の熱処理条件は上記の範囲において任意に選択すればよい。そして、上記の範囲内において熱処理を実施した場合に、半値幅比及び熱処理後のＦｅの（１１０）面の半値幅が上記の範囲に含まれればよい。 Further, the heat treatment conditions for obtaining the full width at half maximum are: temperature rise rate: 5 to 100 ° C./min, soaking temperature: first heat generating part peak temperature (T p1 ) or higher, second heat generating part peak temperature (T p2 ). Hereinafter, the soaking time is in the range of 0.5 to 6 hours. Within the range of such heat treatment conditions, the half-value width of bcc-Fe of the Fe-based alloy is almost constant. Therefore, the heat treatment conditions for measuring the half-value width can be arbitrarily selected in the above range. good. Then, when the heat treatment is performed within the above range, the half width ratio and the half width of the (110) plane of Fe after the heat treatment may be included in the above range.
次に、本実施形態のＦｅ系非晶質合金及びＦｅ系合金の製造方法について説明する。 Next, the Fe-based amorphous alloy and the method for producing the Fe-based alloy of the present embodiment will be described.
本実施形態のＦｅ系非晶質合金は、上記の組成式から成る合金溶湯を急冷することによって製造できる。また、本実施形態のＦｅ系合金は、Ｆｅ系非晶質合金を適切な条件下で熱処理を行うことにより製造できる。 The Fe-based amorphous alloy of the present embodiment can be produced by quenching the molten alloy having the above composition formula. Further, the Fe-based alloy of the present embodiment can be produced by heat-treating the Fe-based amorphous alloy under appropriate conditions.
本実施形態では、単ロ－ル法、双ロ－ル法によって薄帯の形態で非晶質合金を得ることができる。これらのロール法に用いるロールは金属製であり、ロールを高速回転させ、ロール表面またはロール内面に合金溶湯を衝突させることで合金の急冷凝固が可能である。単ロ－ル装置には、ドラムの内壁を使う遠心急冷装置、エンドレスタイプのベルトを使う装置、およびこれらの改良型である補助ロールやロール表面温度制御装置を付属させたもの、減圧下あるいは真空中、または不活性ガス中での鋳造装置も含まれる。 In the present embodiment, the amorphous alloy can be obtained in the form of a thin band by the single roll method and the double roll method. The rolls used in these roll methods are made of metal, and the alloy can be rapidly cooled and solidified by rotating the roll at high speed and causing the molten alloy to collide with the surface of the roll or the inner surface of the roll. The single roll device includes a centrifugal quenching device that uses the inner wall of the drum, a device that uses an endless type belt, and an auxiliary roll or roll surface temperature control device that is an improved version of these, under reduced pressure or vacuum. Casting equipment in medium or in inert gas is also included.
薄帯の板厚、板幅などの寸法は特に限定しないが、薄帯の板厚は、例えば、１０μｍ以上１００μｍ以下が好ましい。また、板幅は１０ｍｍ以上が好ましい。 The dimensions such as the plate thickness and the plate width of the thin band are not particularly limited, but the plate thickness of the thin band is preferably, for example, 10 μm or more and 100 μm or less. Further, the plate width is preferably 10 mm or more.
なお、本実施形態のＦｅ系非晶質合金は、薄帯の他に粉末状とすることも可能である。その場合、上述の組成の合金溶湯を満たしたるつぼのノズルから回転するロールあるいは冷却用の水などの液体の中に高速で合金溶湯あるいは合金溶湯の液滴を噴出して急冷凝固する方法を採用することができ、薄帯を裁断、破砕して粉末状とすることも可能である。 The Fe-based amorphous alloy of the present embodiment can be in the form of powder in addition to the thin band. In that case, a method is adopted in which droplets of the alloy molten metal or the alloy molten metal are ejected at high speed into a liquid such as a rotating roll or cooling water from a nozzle of a crucible filled with the alloy molten metal having the above composition to quench and solidify. It is also possible to cut and crush the crucible into a powder.
次に、熱処理条件について説明する。
均熱温度に到達する前に結晶化が開始する場合があることから、昇温速度は早い方がよく、５℃／分以上、好ましくは１０℃／分以上とする。昇温速度を５℃／分以上にすることで、平均粒径６０ｎｍ以下の均一な微細結晶組織を形成させることができる。昇温速度は高いほど好ましいが、熱処理装置内の温度分布を均一にするには、昇温速度を１００℃／分以下にするとよい。
Next, the heat treatment conditions will be described.
Since crystallization may start before the soaking temperature is reached, the rate of temperature rise is preferably 5 ° C./min or higher, preferably 10 ° C./min or higher. By setting the temperature rise rate to 5 ° C./min or higher, a uniform fine crystal structure having an average particle size of 60 nm or less can be formed. The higher the temperature rise rate, the more preferable, but in order to make the temperature distribution in the heat treatment apparatus uniform, the temperature rise rate should be 100 ° C./min or less.
均熱温度は、示差走査熱量測定法により測定した第一発熱部ピーク温度（Ｔｐ１）以上、第二発熱部ピーク温度（Ｔｐ２）以下とする。示差走査熱量測定の際の昇温速度は１０℃～４０℃／分の範囲内であれば一定のピーク温度を求めることができる。実際上には１０℃／分とする。第一発熱部ピーク温度（Ｔｐ１）は、昇温開始後にＤＳＣ曲線に最初に観察された発熱ピークのピーク温度とする。また、第二発熱部ピーク温度（Ｔｐ２）は、第一発熱部ピーク温度（Ｔｐ１）よりも高い温度域において、第一発熱部ピーク温度（Ｔｐ１）の発熱ピークの次に現れた発熱ピークのピーク温度とする。Ｆｅ系非晶質合金に対して、Ｔｐ１以上Ｔｐ２以下の均熱温度で熱処理を行うことで、結晶粒が部分的あるいは広域に渡って粗大化する問題を解消することができ、安定してＦｅ系合金を得ることができる。また、本実施形態に係る組成式を満たす合金であれば、Ｔｐ１とＴｐ２の温度差を５０℃以上にすることができる。 The soaking temperature shall be equal to or higher than the peak temperature of the first heat generating portion (T p1 ) and lower than the peak temperature of the second heat generating portion (T p2 ) measured by the differential scanning calorimetry method. If the rate of temperature rise in the differential scanning calorimetry is within the range of 10 ° C. to 40 ° C./min, a constant peak temperature can be obtained. Practically, it is set to 10 ° C./min. The peak temperature of the first exothermic part (T p1 ) is the peak temperature of the exothermic peak first observed on the DSC curve after the start of temperature rise. Further, the second heat generation part peak temperature (T p2 ) is the heat generation that appears next to the heat generation peak of the first heat generation part peak temperature (T p1 ) in a temperature range higher than the first heat generation part peak temperature (T p1 ). Let it be the peak temperature of the peak. By heat-treating the Fe-based amorphous alloy at a soaking temperature of T p1 or more and T p2 or less, it is possible to solve the problem that the crystal grains are partially or over a wide area and become stable. Fe-based alloys can be obtained. Further, the temperature difference between T p1 and T p2 can be set to 50 ° C. or higher as long as the alloy satisfies the composition formula according to the present embodiment.
均熱時間は、０．５時間以上６時間以下の範囲が好ましい。均熱時間を０．５時間以上にすることで、金属組織全体に微細結晶組織を形成させることができる。また、均熱時間を６時間以下とすることで、微細結晶粒の粗大化を防止できる。 The soaking time is preferably in the range of 0.5 hours or more and 6 hours or less. By setting the soaking time to 0.5 hours or more, a fine crystal structure can be formed in the entire metal structure. Further, by setting the soaking time to 6 hours or less, coarsening of fine crystal grains can be prevented.
熱処理装置は、電気加熱炉、赤外ランプ加熱炉、レーザーでの加熱装置などがあるが、いずれの装置でもＦｅ系合金を得ることができる。熱処理は大気中、真空中、不活性ガス（Ａｒ、窒素、Ｈｅなど）中、水蒸気中で行うことができるが、特に不活性ガス中で行うことが好ましい。 The heat treatment apparatus includes an electric heating furnace, an infrared lamp heating furnace, a laser heating apparatus, and the like, and any of the apparatus can obtain an Fe-based alloy. The heat treatment can be carried out in the atmosphere, in vacuum, in an inert gas (Ar, nitrogen, He, etc.) or in steam, but is particularly preferably carried out in the inert gas.
また、本実施形態では、Ｆｅ系非晶質合金を熱処理することによりＦｅ系合金を製造する際の、結晶粒径が６０ｎｍ以下となる均熱温度範囲の上下限の温度差が５０℃以上、好ましくは６０℃以上、より好ましくは８０℃以上になる。均熱温度範囲の温度差が５０℃以上になることで、工業的規模の熱処理炉における炉内温度差を乗り越えて、すべての炉内位置において、第１ステップと第２ステップの間の温度の範囲内で非晶質合金を熱処理した場合に、粒径６０ｎｍ以下の結晶粒を持つＦｅ系合金を安定して製造できるようになる。 Further, in the present embodiment, when the Fe-based alloy is produced by heat-treating the Fe-based amorphous alloy, the temperature difference between the upper and lower limits of the soaking temperature range in which the crystal grain size is 60 nm or less is 50 ° C. or more. The temperature is preferably 60 ° C. or higher, more preferably 80 ° C. or higher. By setting the temperature difference in the soaking temperature range to 50 ° C. or higher, the temperature difference between the first step and the second step can be overcome at all the furnace positions, overcoming the temperature difference in the heat treatment furnace of an industrial scale. When the amorphous alloy is heat-treated within the range, an Fe-based alloy having crystal grains having a particle size of 60 nm or less can be stably produced.
以下、実施例について説明する。
表１に示す各種成分の合金をアルゴン雰囲気中で溶解し、単ロ－ル装置で急冷して鋳造することにより、Ｆｅ系非晶質合金の薄帯を作製した。鋳造雰囲気は大気中であった。なお、用いた単ロ－ル装置は、直径３００ｍｍの銅合金製冷却ロ－ルと、試料溶解用の高周波電源と、先端にスロットノズルが付いている石英ルツボ等とから構成される。本実験では、長さ１０ｍｍ、幅０．６ｍｍのスロットノズルを使用した。冷却ロ－ルの周速は２４ｍ／秒とした。結果として、得られた薄帯の板厚は約２０μｍであり、板幅はスロットノズルの長さに依存するので１０ｍｍであり、長さはおよそ１００ｍであった。
Hereinafter, examples will be described.
Alloys of various components shown in Table 1 were melted in an argon atmosphere, rapidly cooled by a single roll device, and cast to prepare a thin band of Fe-based amorphous alloy. The casting atmosphere was in the atmosphere. The single roll device used is composed of a copper alloy cooling roll having a diameter of 300 mm, a high frequency power supply for melting the sample, a quartz crucible having a slot nozzle at the tip, and the like. In this experiment, a slot nozzle having a length of 10 mm and a width of 0.6 mm was used. The peripheral speed of the cooling roll was set to 24 m / sec. As a result, the plate thickness of the obtained thin band was about 20 μm, the plate width was 10 mm because it depends on the length of the slot nozzle, and the length was about 100 m.
得られた非晶質合金について、示差走査熱量測定法により、第一発熱部ピーク温度（Ｔｐ１）及び第二発熱部ピーク温度（Ｔｐ２）を測定した。示差走査熱量測定の昇温速度は１０℃／分とした。第一発熱部ピーク温度（Ｔｐ１）は、昇温開始後にＤＳＣ曲線に最初に観察された発熱ピークのピーク温度とした。また、第二発熱部ピーク温度（Ｔｐ２）は、第一発熱部ピーク温度（Ｔｐ１）よりも高い温度域において、第一発熱部ピーク温度（Ｔｐ１）の発熱ピークの次に現れた発熱ピークのピーク温度とした。 With respect to the obtained amorphous alloy, the peak temperature of the first heat generating portion (T p1 ) and the peak temperature of the second heat generating portion (T p2 ) were measured by the differential scanning calorimetry method. The rate of temperature rise in the differential scanning calorimetry was 10 ° C./min. The peak temperature of the first exothermic part (T p1 ) was defined as the peak temperature of the exothermic peak first observed on the DSC curve after the start of temperature rise. Further, the second heat generation part peak temperature (T p2 ) is the heat generation that appears next to the heat generation peak of the first heat generation part peak temperature (T p1 ) in a temperature range higher than the first heat generation part peak temperature (T p1 ). The peak temperature was used as the peak temperature.
そして、非晶質合金に対して表１に示す条件で熱処理を行って、微細結晶組織を形成させることにより、Ｆｅ系合金を製造した。均熱温度は、第一発熱部ピーク温度（Ｔｐ１）以上、第二発熱部ピーク温度（Ｔｐ２）以下の範囲内とした。表１に、第一発熱部ピーク温度（Ｔｐ１）と第二発熱部ピーク温度（Ｔｐ２）を併せて示す。 Then, the amorphous alloy was heat-treated under the conditions shown in Table 1 to form a fine crystal structure to produce an Fe-based alloy. The soaking temperature was set within the range of the peak temperature of the first heat generating portion (T p1 ) or higher and the peak temperature of the second heat generating portion (T p2 ) or less. Table 1 also shows the peak temperature of the first heat generating portion (T p1 ) and the peak temperature of the second heat generating portion (T p2 ).
得られたＦｅ系非晶質合金及びＦｅ系合金に対して、Ｘ線回折測定を行ってＸ線回折パターンを得た。そして、それぞれの合金について、Ｘ線回折パターン上のＦｅの（１１０）面の回折ピークの半値幅を測定した。また熱処理前のＦｅ系非晶質合金のＦｅの（１１０）面の回折ピークの半値幅と、Ｆｅ系合金のＦｅの（１１０）面の回折ピークの半値幅とから、半値幅比を求めた。Ｘ線回折測定のＸ線源はＣｏ－Ｋα（波長λ＝１．７９０２Å）とし、スキャン範囲は２θ＝１０ｄｅｇ以上１２０ｄｅｇ以下とした。Ｘ線回折パターンからｂｃｃ－Ｆｅの（１１０）面の回折ピークを特定し、その回折ピークの半値幅を求めた。結果を表２に示す。 The obtained Fe-based amorphous alloy and Fe-based alloy were subjected to X-ray diffraction measurement to obtain an X-ray diffraction pattern. Then, for each alloy, the half width of the diffraction peak of the (110) plane of Fe on the X-ray diffraction pattern was measured. Further, the half width ratio was obtained from the half width of the diffraction peak of the Fe (110) plane of the Fe-based amorphous alloy before the heat treatment and the half width of the diffraction peak of the Fe (110) plane of the Fe-based alloy. .. The X-ray source for the X-ray diffraction measurement was Co—Kα (wavelength λ = 1.7902 Å), and the scan range was 2θ = 10 deg or more and 120 deg or less. The diffraction peak on the (110) plane of bcc-Fe was identified from the X-ray diffraction pattern, and the half width of the diffraction peak was determined. The results are shown in Table 2.
また、Ｆｅ系合金のＦｅの（１１０）面の回折ピークの半値幅から、Ｆｅ系合金の金属組織の平均結晶粒径を求めた。平均結晶粒径は、ｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅を、シェラーの式に導入することで、求めた。シェラーの式は下記式で表される。シェラーの式におけるＫはシェラー定数（０．９４）であり、λはＸ線源の波長（１．７９０２Å）であり、βは回折ピークの半値幅であり、θは（１１０）面の回折ピークの回折角であり、Ｄが平均結晶粒径である。なお、回折ピークから測定される半値幅には測定機器によるピーク拡がりを含むことから、半値幅からピーク拡がり（０．０７ｄｅｇ）を減算した値を半値幅βとして使用した。結果を表２に示す。 Further, the average crystal grain size of the metal structure of the Fe-based alloy was obtained from the half width of the diffraction peak of the Fe (110) plane of the Fe-based alloy. The average crystal grain size was determined by introducing the half width of the diffraction peak on the (110) plane of bcc-Fe into Scheller's equation. Scherrer's equation is expressed by the following equation. In Scheller's equation, K is the Scherrer constant (0.94), λ is the wavelength of the X-ray source (1.7902 Å), β is the half width of the diffraction peak, and θ is the diffraction peak on the (110) plane. Diffraction angle, where D is the average crystal grain size. Since the half-value width measured from the diffraction peak includes the peak width by the measuring device, the value obtained by subtracting the peak width (0.07 deg) from the half-value width was used as the half-value width β. The results are shown in Table 2.
Ｄ＝Ｋλ／βｃｏｓθ …（シェラーの式） D = Kλ / βcosθ… (Scherrer's equation)
また、結晶粒径が６０ｎｍ以下となる均熱温度範囲を次のようにして求めた。単ロ－ル装置で急冷して鋳造したＦｅ系非晶質合金薄帯から１０ｍｍ×１０ｍｍの試料を作製し、試料を昇温速度１０℃／分、保持温度は第一発熱部ピーク温度（Ｔｐ１）から第二発熱部ピーク温度（Ｔｐ２）まで１０℃刻みとし、窒素雰囲気中で熱処理を行った。熱処理後の試料について、Ｘ線回折測定を行ってＸ線回折パターンから半値幅を測定し、シェラーの式から平均結晶粒径を求め、結晶粒径が６０ｎｍ以下となる均熱温度範囲を求めた。 Further, the soaking temperature range in which the crystal grain size is 60 nm or less was determined as follows. A sample of 10 mm × 10 mm was prepared from the Fe-based amorphous alloy strip cast by quenching with a single roll device, the temperature rise rate of the sample was 10 ° C./min, and the holding temperature was the peak temperature of the first heat generating part (T). The heat treatment was performed in a nitrogen atmosphere in increments of 10 ° C. from p1 ) to the peak temperature of the second heat generating portion (T p2 ). For the sample after heat treatment, X-ray diffraction measurement was performed, the half width was measured from the X-ray diffraction pattern, the average crystal grain size was obtained from Scherrer's equation, and the soaking temperature range in which the crystal grain size was 60 nm or less was obtained. ..
Ｆｅ系合金の薄帯から、内径１５ｍｍ、外径２０ｍｍ、幅１０ｍｍのトロイダルコアを作製し、直流磁気特性を評価した。最大磁場８００Ａ／ｍで測定した初透磁率および保磁力Ｈｃ、磁場を大きくした際に飽和した磁束密度（飽和磁束密度）を表３に示す。初透磁率が５００００以上、保磁力Ｈｃが１．０Ａ／ｍ以下、飽和磁束密度は１．０Ｔ以上の場合に、軟磁気特性が優れるとして合格とした。 A toroidal core having an inner diameter of 15 mm, an outer diameter of 20 mm, and a width of 10 mm was prepared from a thin band of Fe-based alloy, and the DC magnetic characteristics were evaluated. Table 3 shows the initial magnetic permeability and coercive force Hc measured at a maximum magnetic field of 800 A / m, and the magnetic flux density saturated when the magnetic field is increased (saturated magnetic flux density). When the initial magnetic permeability was 50,000 or more, the coercive force Hc was 1.0 A / m or less, and the saturation magnetic flux density was 1.0 T or more, the soft magnetic characteristics were judged to be excellent and passed.
更に、Ｆｅ系非晶質合金について、曲げ破壊直径を測定した。曲げ破壊半径は、ＪＩＳ Ｚ ２２４８：２００６の属材料曲げ試験方法に準拠し、曲げ試験機にＦｅ系非晶質合金からなる薄帯を設置し、破断した際の曲げ破壊直径を測定した。結果を表３に示す。 Further, the bending fracture diameter of the Fe-based amorphous alloy was measured. The bending fracture radius was based on the JIS Z 2248: 2006 genus material bending test method, a thin band made of Fe-based amorphous alloy was installed in the bending tester, and the bending fracture diameter at the time of fracture was measured. The results are shown in Table 3.
表１～表３に示すように、実施例１～８のＦｅ系非晶質合金は、曲げ破壊半径が１ｍｍ以下となり、密着曲げを行うことが可能で加工性に優れていた。また、軟磁気特性に優れたＦｅ系合金の素材として利用できるものであった。
また、表１～表３に示すように、実施例１～８のＦｅ系合金は、初透磁率及び飽和磁束密度が高く、保磁力が低く、軟磁気特性に優れていた。
As shown in Tables 1 to 3, the Fe-based amorphous alloys of Examples 1 to 8 had a bending fracture radius of 1 mm or less, were capable of close contact bending, and were excellent in workability. Further, it can be used as a material for Fe-based alloys having excellent soft magnetic properties.
Further, as shown in Tables 1 to 3, the Fe-based alloys of Examples 1 to 8 had high initial magnetic permeability and saturation magnetic flux density, low coercive force, and were excellent in soft magnetic properties.
比較例１および比較例２は、Ｘ元素の組成比が本発明の範囲から外れたため、急冷後のＦｅ系非晶質合金を熱処理した後のＦｅ（１１０）面のピークの半値幅が０．２５ｄｅｇ未満になり、金属組織が粗大結晶組織となり、軟磁気特性が十分ではなかった。このため、比較例１及び比較例２のＦｅ系非晶質合金は、軟磁気特性に優れたＦｅ系合金の素材として利用できるものではなかった。 In Comparative Example 1 and Comparative Example 2, since the composition ratio of the element X was out of the range of the present invention, the half-value width of the peak of the Fe (110) plane after the heat treatment of the Fe-based amorphous alloy after quenching was 0. It became less than 25 deg, the metal structure became a coarse crystal structure, and the soft magnetic properties were not sufficient. Therefore, the Fe-based amorphous alloys of Comparative Example 1 and Comparative Example 2 could not be used as a material for Fe-based alloys having excellent soft magnetic properties.
比較例３および比較例４は、Ｚ元素の組成比が本発明の範囲から外れていたため、熱処理前のＦｅ系非晶質合金のＦｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ．未満で、曲げ破壊半径が１ｍｍ超となり、加工性が低下した。従って、比較例３及び比較例４のＦｅ系合金を、トランス、チョークコイル、ノイズ対策品等への適用を試みたとしても、素材であるＦｅ系非晶質合金の加工性が低いために、これらトランス等の製品の製造時の歩留まりが大幅に低下すると予測された。よって、比較例３及び比較例４のＦｅ系合金は、実用的なものとはいえなかった。 In Comparative Example 3 and Comparative Example 4, since the composition ratio of the Z element was out of the range of the present invention, the half width of the diffraction peak of the Fe (110) plane of the Fe-based amorphous alloy before the heat treatment was 6 deg. If it is less than, the bending fracture radius becomes more than 1 mm, and the workability is deteriorated. Therefore, even if the Fe-based alloys of Comparative Example 3 and Comparative Example 4 are applied to transformers, choke coils, noise suppression products, etc., the workability of the Fe-based amorphous alloy as a material is low. It was predicted that the yield at the time of manufacturing products such as these transformers would be significantly reduced. Therefore, the Fe-based alloys of Comparative Example 3 and Comparative Example 4 could not be said to be practical.
比較例５は、Ｂの組成比ａが４原子％未満であり、非晶質形成能が不十分であったため、単ロ－ル装置で急冷して鋳造した薄帯のＸ線回折測定の結果、Ｆｅの（１１０）面の回折ピークが明確に存在していた。急冷後の薄帯の金属組織は粗大な結晶組織となり、非晶質合金を得ることができなかった。そのため、示差走査熱量測定法によるピーク温度の測定や、熱処理による微細結晶化、熱処理後の磁気特性評価を行うことができないため、表１～表３の欄中に「－」と記載した。従って、比較例５の急冷後の合金は、Ｆｅ系合金の素材として利用できるものではなかった。 In Comparative Example 5, since the composition ratio a of B was less than 4 atomic% and the amorphous forming ability was insufficient, the result of X-ray diffraction measurement of the thin band cast by quenching with a single roll device was performed. , The diffraction peak of the (110) plane of Fe was clearly present. The thin metal structure after quenching became a coarse crystal structure, and an amorphous alloy could not be obtained. Therefore, since it is not possible to measure the peak temperature by the differential scanning calorimetry method, perform fine crystallization by heat treatment, and evaluate the magnetic characteristics after heat treatment, "-" is described in the columns of Tables 1 to 3. Therefore, the alloy after quenching in Comparative Example 5 could not be used as a material for Fe-based alloys.
比較例６は、Ｂの組成比ａが２０原子％を超えており、熱処理後の合金の飽和磁束密度が１．０Ｔ未満となり、軟磁気特性が十分ではなかった。このため、比較例６のＦｅ系非晶質合金は、軟磁気特性に優れたＦｅ系合金の素材として利用できるものではなく、また、比較例６のＦｅ系合金は軟磁気特性が十分でなかった。 In Comparative Example 6, the composition ratio a of B exceeded 20 atomic%, the saturation magnetic flux density of the alloy after the heat treatment was less than 1.0 T, and the soft magnetic characteristics were not sufficient. Therefore, the Fe-based amorphous alloy of Comparative Example 6 cannot be used as a material for the Fe-based alloy having excellent soft magnetic properties, and the Fe-based alloy of Comparative Example 6 does not have sufficient soft magnetic properties. rice field.
比較例７は、Ｓｉの組成比ｂが５原子％未満であり、単ロ－ル装置で急冷して鋳造した薄帯のＸ線回折測定の結果、Ｆｅの（１１０）面の回折ピークが明確に存在していた。急冷後の薄帯の金属組織は粗大な結晶組織となり、非晶質合金を得ることができなかった。そのため、示差走査熱量測定法によるピーク温度の測定や、熱処理による微細結晶化、熱処理後の磁気特性評価を行うことができないため、表１～表３の欄中に「－」と記載した。従って、比較例７の急冷後の合金は、Ｆｅ系合金の素材として利用できるものではなかった。 In Comparative Example 7, the composition ratio b of Si is less than 5 atomic%, and as a result of X-ray diffraction measurement of a thin band cast by quenching with a single roll device, the diffraction peak of the (110) plane of Fe is clear. Was present in. The thin metal structure after quenching became a coarse crystal structure, and an amorphous alloy could not be obtained. Therefore, since it is not possible to measure the peak temperature by the differential scanning calorimetry method, perform fine crystallization by heat treatment, and evaluate the magnetic characteristics after heat treatment, "-" is described in the columns of Tables 1 to 3. Therefore, the alloy after quenching in Comparative Example 7 could not be used as a material for Fe-based alloys.
比較例８は、Ｓｉの組成比ａが２０原子％を超えており、熱処理後の合金の飽和磁束密度が１．０Ｔ未満となり、軟磁気特性が十分ではなかった。このため、比較例８のＦｅ系非晶質合金は、軟磁気特性に優れたＦｅ系合金の素材として利用できるものではなく、また、比較例８のＦｅ系合金は軟磁気特性が十分でなかった。 In Comparative Example 8, the composition ratio a of Si exceeded 20 atomic%, the saturation magnetic flux density of the alloy after the heat treatment was less than 1.0 T, and the soft magnetic characteristics were not sufficient. Therefore, the Fe-based amorphous alloy of Comparative Example 8 cannot be used as a material for the Fe-based alloy having excellent soft magnetic properties, and the Fe-based alloy of Comparative Example 8 does not have sufficient soft magnetic properties. rice field.
比較例９は、Ｃｕを含まない例であり、これを素材とするＦｅ系合金の平均結晶粒径が６０ｎｍを超えてしまい、軟磁気特性が十分ではなかったため、軟磁気特性に優れたＦｅ系合金の素材として利用できるものではなかった。 Comparative Example 9 is an example in which Cu is not contained, and the average crystal grain size of the Fe-based alloy using this as a material exceeds 60 nm, and the soft magnetic property is not sufficient. Therefore, the Fe-based alloy having excellent soft magnetic property is obtained. It could not be used as a material for alloys.
比較例１０は、Ｃｕの組成比ｄが３原子％を超えており、単ロ－ル装置で急冷して鋳造した薄帯のＸ線回折測定の結果、Ｆｅの（１１０）面の回折ピークが明確に存在していた。急冷後の薄帯の金属組織は粗大な結晶組織となり、非晶質合金を得ることができなかった。そのため、示差走査熱量測定法によるピーク温度の測定や、熱処理による微細結晶化、熱処理後の磁気特性評価を行うことができないため、表１～表３の欄中に「－」と記載した。従って、比較例１０の急冷後の合金は、Ｆｅ系合金の素材として利用できるものではなかった。 In Comparative Example 10, the composition ratio d of Cu exceeds 3 atomic%, and as a result of X-ray diffraction measurement of a thin band cast by quenching with a single roll device, the diffraction peak of the (110) plane of Fe is found. It clearly existed. The thin metal structure after quenching became a coarse crystal structure, and an amorphous alloy could not be obtained. Therefore, since it is not possible to measure the peak temperature by the differential scanning calorimetry method, perform fine crystallization by heat treatment, and evaluate the magnetic characteristics after heat treatment, "-" is described in the columns of Tables 1 to 3. Therefore, the alloy after quenching in Comparative Example 10 could not be used as a material for Fe-based alloys.
Claims (15)
Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上であることを特徴とする、Ｆｅ系合金。 The composition formula is represented by Fe 100-ab-c-d-e B a Si b X c Cu d Ze and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr. , Hf, V, Ta, Cr, Mo, W, one or more elements selected from the group, Z is one or more elements selected from the C, N, P, S group. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 0.1 <e ≦. Satisfy 3, 1.1 <c + e <6,
An Fe-based alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X-ray source is 0.25 deg or more.
Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上であることを特徴とする、Ｆｅ系合金。 The composition formula is represented by Fe 100-ab-c-d-e B a Si b X c Cu d Ze and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr. , Hf, V, Ta, Cr, Mo, W, one or more elements selected from the group, Z is one or more elements selected from the C, N, P, S group. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 1 <e ≦ 3, Satisfying 2 <c + e <6, Fe is less than 79 atomic%,
An Fe-based alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X-ray source is 0.25 deg or more.
Ｘ線源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が０．２５ｄｅｇ以上であることを特徴とする、Ｆｅ系合金。 The composition formula is represented by Fe 100-ab-c-d-e B a Si b X c Cu d Ze and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr. , Hf, V, Ta, Cr, Mo, W, one or more elements selected from the group, Z is one or more elements selected from the C, N, P, S group. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 3, 0 <d ≦ 3, 2 <e ≦ 3, Satisfying 3 <c + e <6, Fe is less than 79 atomic%,
An Fe-based alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X-ray source is 0.25 deg or more.
前記金属組織が熱処理後の前記微細結晶組織からなる段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が、前記非晶質組織からなる熱処理前の段階でのｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅に対して、１／３０以上、１／３以下であることを特徴とする、請求項１乃至請求項４の何れか一項に記載のＦｅ系合金。 The half width of the diffraction peak of the (110) plane of bcc-Fe in the X-ray diffraction pattern using Co-Kα rays as the X-ray source at the stage where the metal structure is composed of an amorphous structure before heat treatment is 6 deg or more. 8 deg or less,
The half-value width of the diffraction peak of the (110) plane of bcc-Fe at the stage where the metal structure is composed of the fine crystal structure after heat treatment is the (1) of bcc-Fe at the stage before heat treatment having the amorphous structure. 110) The Fe-based alloy according to any one of claims 1 to 4, which is 1/30 or more and 1/3 or less with respect to the half-value width of the diffraction peak on the surface.
金属組織が非晶質組織からなり、
Ｘ源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下であることを特徴とする、Ｆｅ系非晶質合金。 The composition formula is represented by Fe 100-ab-c-d-e B a Si b X c Cu d Ze and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr. , Hf, V, Ta, Cr, Mo, W, one or more elements selected from the group, Z is one or more elements selected from the C, N, P, S group. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 0.1 <e ≦. Satisfy 3, 1.1 <c + e <6,
The metal structure consists of an amorphous structure,
An Fe-based amorphous alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X source is 6 deg or more and 8 deg or less.
金属組織が非晶質組織からなり、
Ｘ源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下であることを特徴とする、Ｆｅ系非晶質合金。 The composition formula is represented by Fe 100-ab-c-d-e B a Si b X c Cu d Ze and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr. , Hf, V, Ta, Cr, Mo, W, one or more elements selected from the group, Z is one or more elements selected from the C, N, P, S group. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 5, 0 <d ≦ 3, 1 <e ≦ 3, Satisfying 2 <c + e <6, Fe is less than 79 atomic%,
The metal structure consists of an amorphous structure,
An Fe-based amorphous alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X source is 6 deg or more and 8 deg or less.
金属組織が非晶質組織からなり、
Ｘ源としてＣｏ－Ｋα線を用いたＸ線回折パターンにおけるｂｃｃ－Ｆｅの（１１０）面の回折ピークの半値幅が６ｄｅｇ以上８ｄｅｇ以下であることを特徴とする、Ｆｅ系非晶質合金。 The composition formula is represented by Fe 100-ab-c-d-e B a Si b X c Cu d Ze and the balance is composed of impurity elements, where X in the composition formula is Nb, Ti, Zr. , Hf, V, Ta, Cr, Mo, W, one or more elements selected from the group, Z is one or more elements selected from the C, N, P, S group. The composition ratios a, b, c, d, and e are atomic%, respectively, and 4 ≦ a ≦ 20, 5 ≦ b ≦ 20, 1 ≦ c ≦ 3, 0 <d ≦ 3, 2 <e ≦ 3, Satisfying 3 <c + e <6, Fe is less than 79 atomic%,
The metal structure consists of an amorphous structure,
An Fe-based amorphous alloy characterized in that the half width of the diffraction peak of the (110) plane of bcc-Fe in an X-ray diffraction pattern using Co—Kα rays as an X source is 6 deg or more and 8 deg or less.
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