JP2022008547A - Si-CONTAINING Fe-BASED ALLOY POWDER PROVIDED WITH SiO2-CONTAINING COATING FILM AND MANUFACTURING METHOD THEREOF - Google Patents

Si-CONTAINING Fe-BASED ALLOY POWDER PROVIDED WITH SiO2-CONTAINING COATING FILM AND MANUFACTURING METHOD THEREOF Download PDF

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JP2022008547A
JP2022008547A JP2021156138A JP2021156138A JP2022008547A JP 2022008547 A JP2022008547 A JP 2022008547A JP 2021156138 A JP2021156138 A JP 2021156138A JP 2021156138 A JP2021156138 A JP 2021156138A JP 2022008547 A JP2022008547 A JP 2022008547A
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based alloy
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phosphoric acid
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敏郎 佐藤
Toshiro Sato
誠 曽根原
Makoto Sonehara
佳奈子 杉村
Kanako Sugimura
直希 藪
Naoki Yabu
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Shinshu University NUC
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Abstract

PROBLEM TO BE SOLVED: To provide a metal magnetic powder having an insulating film which is more stable in film thickness than conventional and has high insulation and is inexpensive.
SOLUTION: A manufacturing method of a Si-containing Fe-based alloy powder provided with a SiO2-containing coating includes preparing a Si-containing Fe-based alloy powder, obtaining a Si-containing Fe-based alloy powder including an Fe-O-Si-P based coating film by immersing the Si-containing Fe-based alloy powder in an aqueous phosphoric acid solution, and taking out the Si-containing Fe-based alloy powder from the aqueous phosphoric acid solution and drying the Si-containing Fe-based alloy powder, and obtaining a Si-containing Fe-based alloy powder provided with a SiO2-containing coating on the surface by immersing a Si-containing Fe-based alloy powder including an Fe-O-Si-P based coating film in an aqueous hydrochloric acid solution, and taking out the Si-containing Fe-based alloy powder from the hydrochloric acid aqueous solution and drying the Si-containing Fe-based alloy powder.
SELECTED DRAWING: Figure 8
COPYRIGHT: (C)2022,JPO&INPIT

Description

本開示は、ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉及びその製造方法に関する。 The present disclosure relates to a Si-containing Fe-based alloy powder having a SiO 2 -containing film and a method for producing the same.

従来、パワー半導体としてＳｉ半導体が主に用いられているが、これに代えて、オン抵抗が低くスイッチング速度が速く且つ高温で動作可能なＳｉＣまたはＧａＮパワー半導体の利用が検討されている。ＳｉＣまたはＧａＮパワー半導体を用いることで、ＡＣアダプタ、ＶＲＭ（電圧レギュレータモジュール）、サーバー電源等のＤＣ－ＤＣコンバータのスイッチング周波数を数ＭＨｚ～数十ＭＨｚに高周波化することができる。ＤＣ－ＤＣコンバータのスイッチング周波数の高周波化とともに、高周波数領域に対応可能なトランスやインダクタ等の受動部品の開発が進められているが、高周波数領域で低損失な磁性材料の開発は遅れているのが現状である。 Conventionally, Si semiconductors are mainly used as power semiconductors, but instead of these, the use of SiC or GaN power semiconductors having low on-resistance, high switching speed, and operation at high temperatures is being studied. By using SiC or GaN power semiconductors, the switching frequency of DC-DC converters such as AC adapters, VRMs (voltage regulator modules), and server power supplies can be increased to several MHz to several tens of MHz. With the increase in the switching frequency of DC-DC converters, the development of passive components such as transformers and inductors that can handle high frequency regions is underway, but the development of low-loss magnetic materials in the high frequency region has been delayed. is the current situation.

トランスやインダクタ等の磁気部品には軟磁性材料が用いられているが、図４８に示すように、１ＭＨｚを超えるような高周波数領域で十分に対応可能な磁性材料がない。例えば、水アトマイズ法やガスアトマイズ法で作製される軟磁性金属粉末を用いたダストコアはハイブリッド自動車や電気自動車のパワートレーン系のＤＣ－ＤＣコンバータに用いられているが、数１００ｋＨｚ以下の周波数領域で用いられており、１ＭＨｚ以上の高周波数領域には対応しない。Ｍｎ－Ｚｎ系フェライトは絶縁型ＤＣ－ＤＣコンバータのメイントランスに用いられ、微結晶化や焼結条件の改良により２ＭＨｚ程度まで利用できるように改良が進んでいるが、これ以上の周波数では残留損失の急増により使用は困難になる。また、Ｎｉ－Ｚｎ系フェライトは、１ＭＨｚ以上の周波数領域に対応し通信用に多くの実績があるものの、大振幅励磁される高周波電力変換用としての性能は必ずしも十分ではない。そのため、現状では、Ｓｉパワー半導体を用いた数十ｋＨｚ～数百ｋＨｚスイッチングのＤＣ－ＤＣコンバータが大半を占めており、ＳｉＣやＧａＮパワー半導体デバイスの特徴を活かした小型軽量で高効率の高周波スイッチングＤＣ－ＤＣコンバータを実現し、普及させるためには高周波低損失の軟磁性材料とそれを用いたインダクタやトランスの開発が急務となっている。 Soft magnetic materials are used for magnetic parts such as transformers and inductors, but as shown in FIG. 48, there is no magnetic material that can sufficiently cope with a high frequency region exceeding 1 MHz. For example, a dust core using a soft magnetic metal powder produced by a water atomization method or a gas atomization method is used in a power train DC-DC converter of a hybrid vehicle or an electric vehicle, but is used in a frequency range of several hundred kHz or less. It does not correspond to the high frequency region of 1 MHz or more. Mn-Zn-based ferrite is used in the main transformer of an isolated DC-DC converter, and is being improved so that it can be used up to about 2 MHz by microcrystallization and improvement of sintering conditions, but residual loss is progressing at frequencies higher than this. It becomes difficult to use due to the rapid increase in the number of. Further, although Ni—Zn-based ferrite corresponds to a frequency domain of 1 MHz or more and has many achievements for communication, its performance for high-frequency power conversion that is excited by a large amplitude is not always sufficient. Therefore, at present, most DC-DC converters that use Si power semiconductors for switching from several tens of kHz to several hundreds of kHz are compact, lightweight, and highly efficient high-frequency switching that takes advantage of the characteristics of SiC and GaN power semiconductor devices. In order to realize and popularize DC-DC converters, there is an urgent need to develop high-frequency, low-loss soft magnetic materials and inductors and transformers using them.

一方、金属軟磁性粉末をバインダとともに高圧プレス成型して作製されるダストコア技術をベースに１０μｍ以下の微細な金属磁性粉末を用いて樹脂と複合化したコンポジット磁性材料の開発が進められており、超微細な金属磁性粉末を採用することで１ＭＨｚ以上の周波数でも損失の少ない軟磁性材料を実現できる。この際、金属磁性粉末内部にうず電流を閉じ込めて微細粉末の効果を発揮させるには、粉末表面の絶縁皮膜処理が必要になる。 On the other hand, based on the dust core technology produced by high-pressure press molding of soft metallic powder with a binder, the development of a composite magnetic material that is composited with a resin using fine metallic magnetic powder of 10 μm or less is underway. By adopting fine metallic magnetic powder, it is possible to realize a soft magnetic material with little loss even at a frequency of 1 MHz or higher. At this time, in order to confine the eddy current inside the metallic magnetic powder and exert the effect of the fine powder, it is necessary to treat the insulating film on the surface of the powder.

絶縁皮膜によってうず電流を金属磁性粉末に閉じ込めた場合のコンポジット磁性材料のうず電流損は、下記の式（１）：
Ｗe＝Ｋ（πｄＢmｆ）2／２０ρ（Ｗ／ｍ3） （１）
（式中、Ｋは複合材料中の金属磁性粉末の充填率、ｄは、金属磁性粉末の粒子径、Ｂmは最大磁束密度、ｆは周波数、ρは金属磁性粉末の電気抵抗率である）で算出される。 The eddy current loss of the composite magnetic material when the eddy current is confined in the metallic magnetic powder by the insulating film is calculated by the following formula (1):
W e = K (π dB m f) 2 /20ρ (W / m 3 ) (1)
(In the formula, K is the filling rate of the metal magnetic powder in the composite material, d is the particle size of the metal magnetic powder, B m is the maximum magnetic flux density, f is the frequency, and ρ is the electrical resistivity of the metal magnetic powder). It is calculated by.

式（１）から分かるように、うず電流損は、粉末粒子径の二乗に比例し、磁性粉末の電気抵抗率ρに反比例する。そのため、１０μｍ以下の範囲の粒径が小さい磁性粉末を用いること、及び電気抵抗率の高い磁性粉末の採用がコンポジット磁性材料のうず電流損の低減に有効である。 As can be seen from the equation (1), the eddy current loss is proportional to the square of the powder particle size and inversely proportional to the electrical resistivity ρ of the magnetic powder. Therefore, it is effective to use a magnetic powder having a small particle size in the range of 10 μm or less and to use a magnetic powder having a high electrical resistivity to reduce the vortex current loss of the composite magnetic material.

金属磁性粉末を用いた場合は、表面に絶縁皮膜を形成し、うず電流が磁性粒子内のみを流れるようにする必要がある。絶縁皮膜を形成する方法として、アンモニアを触媒として用いてＴＥＯＳ（有機シラン）を加水分解して磁性金属粒子の表面にＳｉＯ2被膜を形成することが提案されている（非特許文献１）。また、酸素を含む雰囲気中で加熱することによって磁性金属粒子の表面を酸化して、磁性金属粒子の表面に酸化膜を形成する方法が提案されている（非特許文献２）。 When a metallic magnetic powder is used, it is necessary to form an insulating film on the surface so that the eddy current flows only in the magnetic particles. As a method for forming an insulating film, it has been proposed to hydrolyze TEOS (organic silane) using ammonia as a catalyst to form a SiO 2 film on the surface of magnetic metal particles (Non-Patent Document 1). Further, a method has been proposed in which the surface of magnetic metal particles is oxidized by heating in an atmosphere containing oxygen to form an oxide film on the surface of the magnetic metal particles (Non-Patent Document 2).

杉村佳奈子 他、鉄系メタルコンポジット鉄心材料用カルボニル鉄粉の高抵抗被膜形成に関する基礎検討、平成２７年日本磁気学会学術講演会、１１ａＢ－２（２０１５）Kanako Sugimura et al., Basic study on formation of high resistance film formation of carbonyl iron powder for iron-based metal composite iron core material, 2015 Academic Lecture Meeting of the Magnetic Society of Japan, 11aB-2 (2015) 杉村佳奈子 他、鉄系メタルコンポジット鉄心材料用アモルファス合金粉の酸化被膜形成に関する基礎検討、平成２８年日本電気学会Ａ部門大会、５－Ｂ－ｐ２－２、ｐｐ．２８（２０１６）Kanako Sugimura et al., Basic study on forming an oxide film of amorphous alloy powder for iron-based metal composite iron core materials, 2016 IEEJ A Division Conference, 5-B-p2-2, pp. 28 (2016)

しかしながら、従来の水アトマイズ法やガスアトマイズ法で１０μｍ以下、特にサブミクロン～数ミクロン範囲の粒径が小さい金属磁性体粒子を安定して製造することは難しい。また、粒径が小さい金属磁性体粒子を用いても、磁性粉末の充填率を高めるために金属磁性体粒子同士が接触すると磁性体粒子をまたぐうず電流が発生し、コンポジット磁性材料全体をうず電流が流れることによって大きなうず電流損が発生し、高周波特性が低下する。そのため、磁性体粒子の粒径が小さい意味がなくなってしまう。 However, it is difficult to stably produce metal magnetic particles having a small particle size of 10 μm or less, particularly in the submicron to several micron range, by the conventional water atomization method or gas atomization method. Even if metal magnetic particles with a small particle size are used, when the metal magnetic particles come into contact with each other in order to increase the filling rate of the magnetic powder, an eddy current is generated across the magnetic particles, and an eddy current is generated in the entire composite magnetic material. A large eddy current loss occurs due to the flow of magnetism, and the high frequency characteristics deteriorate. Therefore, it is meaningless that the particle size of the magnetic particles is small.

非特許文献１に開示の方法は、単に、金属磁性体粒子の表面に化学反応でＳｉＯ2被膜をコーティングするものであるが、高価なＴＥＯＳ（有機シラン）を利用しなくてはならないこと、及び粉末表面に外部からＳｉＯ2被膜を形成するために粉末表面の凹凸に左右されて均一な厚みでコーティングすることが難しく、薄くコーティングすると金属磁性体粒子が露出する箇所が発生し、金属磁性体粒子の露出を防止しようとするとコーティングの平均厚みが大きくなってしまうという欠点を有する。非特許文献２に開示の方法では、酸化膜の抵抗が不十分であるため金属磁性粉末の高抵抗化が難しく、酸化膜の膜厚制御も難しい。 The method disclosed in Non-Patent Document 1 simply coats the surface of metallic magnetic particles with a SiO 2 film by a chemical reaction, but it must use expensive TEOS (organic silane), and Since a SiO 2 film is formed on the surface of the powder from the outside, it is difficult to coat it with a uniform thickness due to the unevenness of the surface of the powder. It has the disadvantage that the average thickness of the coating increases when trying to prevent the exposure of the particles. In the method disclosed in Non-Patent Document 2, since the resistance of the oxide film is insufficient, it is difficult to increase the resistance of the metal magnetic powder, and it is also difficult to control the film thickness of the oxide film.

そのため、従来よりも膜厚が安定しており絶縁性が高く安価な絶縁皮膜を有する金属磁性粉末が求められている。 Therefore, there is a demand for a metal magnetic powder having a stable film thickness, high insulating properties, and an inexpensive insulating film as compared with the conventional case.

本発明者は、金属磁性体粒子の表面に高抵抗被膜を形成する新規の方法を見出した。Ｓｉ含有Ｆｅ基合金粒子の表面を化学反応で表面修飾を行い、表面にＳｉＯ2含有被膜を形成する方法である。 The present inventor has found a novel method for forming a high resistance film on the surface of metallic magnetic particles. This is a method in which the surface of Si-containing Fe-based alloy particles is surface-modified by a chemical reaction to form a SiO 2 -containing film on the surface.

本開示は、Ｓｉ含有Ｆｅ基合金粉を準備すること、
前記Ｓｉ含有Ｆｅ基合金粉をリン酸水溶液に浸漬し、前記リン酸水溶液から取り出して乾燥して、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金粉を得ること、及び
前記Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金粉を塩酸水溶液に浸漬し、前記塩酸水溶液から取り出して乾燥して、表面にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を得ること、
を含む、ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の製造方法を対象とする。 The present disclosure is to prepare Si-containing Fe-based alloy powder.
The Si-containing Fe-based alloy powder is immersed in a phosphoric acid aqueous solution, taken out from the phosphoric acid aqueous solution and dried to obtain a Si-containing Fe-based alloy powder having a Fe—O—Si—P-based coating, and the above. A Si-containing Fe-based alloy powder having a Fe—O—Si—P-based coating is immersed in an aqueous hydrochloric acid solution, taken out from the aqueous hydrochloric acid solution and dried, and the Si-containing Fe-based alloy powder having a SiO 2 -containing coating on the surface is removed. To get,
A method for producing a Si-containing Fe-based alloy powder having a SiO 2 -containing film, which comprises the above.

本開示はまた、表面にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粒子を対象とする。 The present disclosure also covers Si-containing Fe-based alloy particles having a SiO 2 -containing coating on the surface.

本開示によれば、従来よりも膜厚が安定しており絶縁性が高く低コストの絶縁皮膜を有する金属磁性粉末を得ることができる。 According to the present disclosure, it is possible to obtain a metallic magnetic powder having a stable film thickness, high insulating properties, and a low-cost insulating film as compared with the conventional case.

図１は、Ｆｅ－Ｓｉ合金粉の走査型電子顕微鏡写真である。FIG. 1 is a scanning electron micrograph of Fe—Si alloy powder. 図２は、Ｆｅ－Ｓｉ－Ａｌ合金粉の走査型電子顕微鏡写真である。FIG. 2 is a scanning electron micrograph of Fe—Si—Al alloy powder. 図３は、Ｆｅ－Ｓｉ－Ｂ－Ｃｒ－Ｃ合金粉の走査型電子顕微鏡写真である。FIG. 3 is a scanning electron micrograph of Fe—Si—B—Cr—C alloy powder. 図４は、Ｆｅ－Ｓｉ－Ｂ－Ｐ－Ｃ－Ｎｂ－Ｃｒ合金粉の走査型電子顕微鏡写真である。FIG. 4 is a scanning electron micrograph of Fe—Si—B—P—C—Nb—Cr alloy powder. 図５は、準備したＳｉ含有Ｆｅ基合金粉の断面模式図である。FIG. 5 is a schematic cross-sectional view of the prepared Si-containing Fe-based alloy powder. 図６は、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面模式図である。FIG. 6 is a schematic cross-sectional view of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment. 図７は、リン酸処理後に塩酸処理を行ったＳｉ含有Ｆｅ基合金粉１２の断面模式図である。FIG. 7 is a schematic cross-sectional view of the Si-containing Fe-based alloy powder 12 that has been treated with hydrochloric acid after being treated with phosphoric acid. 図８は、準備したＳｉ含有Ｆｅ基合金粒子、リン酸処理をしたＳｉ含有Ｆｅ合粒子、及びリン酸処理後に塩酸処理をしたＳｉ含有Ｆｅ基合金粒子の内部の一部を可視化した模式図である。FIG. 8 is a schematic diagram showing a part of the inside of the prepared Si-containing Fe-based alloy particles, the phosphoric acid-treated Si-containing Fe compound particles, and the phosphoric acid-treated Si-containing Fe-based alloy particles. be. 図９は、図３に記載のＦｅ－Ｓｉ－Ｂ－Ｃｒ－Ｃ合金粉をリン酸処理したＳｉ含有Ｆｅ基合金粉の走査型電子顕微鏡写真である。FIG. 9 is a scanning electron micrograph of the Si-containing Fe-based alloy powder obtained by treating the Fe—Si—B—Cr—C alloy powder shown in FIG. 3 with phosphoric acid. 図１０は、図３の準備したＳｉ含有Ｆｅ基合金粉及び図９のリン酸処理を行ったＳｉ含有Ｆｅ基合金粉について分析した粉末Ｘ線回折プロファイルである。FIG. 10 is a powder X-ray diffraction profile analyzed for the prepared Si-containing Fe-based alloy powder of FIG. 3 and the phosphoric acid-treated Si-containing Fe-based alloy powder of FIG. 図１１は、準備したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 11 is a scanning electron microscope (SEM) photograph of a cross section of the prepared Si-containing Fe-based alloy powder. 図１２は、濃度０．００００１ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 12 is a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 6 hours using a phosphoric acid aqueous solution having a concentration of 0.00001 wt%. 図１３は、濃度０．０００１ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 13 is a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 6 hours using a phosphoric acid aqueous solution having a concentration of 0.0001 wt%. 図１４は、濃度０．００１ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 14 is a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 6 hours using a phosphoric acid aqueous solution having a concentration of 0.001 wt%. 図１５は、濃度０．０１ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 15 is a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 6 hours using a phosphoric acid aqueous solution having a concentration of 0.01 wt%. 図１６は、濃度０．１ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 16 is a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 6 hours using a phosphoric acid aqueous solution having a concentration of 0.1 wt%. 図１７は、濃度０．０１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 17 is a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 20 minutes using a phosphoric acid aqueous solution having a concentration of 0.01 wt%. 図１８は、濃度０．１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真である。FIG. 18 is a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 20 minutes using a phosphoric acid aqueous solution having a concentration of 0.1 wt%. 図１９は、準備したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 19 is a scanning electron micrograph of a cross section of the prepared Si-containing Fe-based alloy powder. 図２０は、濃度１％でリン酸処理したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 20 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder treated with phosphoric acid at a concentration of 1%. 図２１は、濃度５％でリン酸処理したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 21 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder treated with phosphoric acid at a concentration of 5%. 図２２は、準備したＳｉ含有Ｆｅ基合金粉のオージェ電子分光法による深さ方向分析の結果である。FIG. 22 shows the results of the depth direction analysis of the prepared Si-containing Fe-based alloy powder by Auger electron spectroscopy. 図２３は、濃度１％でリン酸処理したＳｉ含有Ｆｅ基合金粉のオージェ電子分光法による深さ方向分析の結果である。FIG. 23 shows the results of depth direction analysis of Si-containing Fe-based alloy powder treated with phosphoric acid at a concentration of 1% by Auger electron spectroscopy. 図２４は、濃度２％でリン酸処理したＳｉ含有Ｆｅ基合金粉のオージェ電子分光法による深さ方向分析の結果である。FIG. 24 is the result of the depth direction analysis of the Si-containing Fe-based alloy powder treated with phosphoric acid at a concentration of 2% by Auger electron spectroscopy. 図２５は、０．００００１～１ｗｔ％のリン酸水溶液の濃度と、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉のＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚さとの関係を表すグラフである。FIG. 25 is a graph showing the relationship between the concentration of the phosphoric acid aqueous solution of 0.00001 to 1 wt% and the thickness of the Fe—O—Si—P-based coating film of the phosphoric acid-treated Si-containing Fe-based alloy powder. .. 図２６は、リン酸水溶液の濃度と、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の飽和磁化Ｍｓ及びＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚さとの関係を表すグラフである。FIG. 26 is a graph showing the relationship between the concentration of the phosphoric acid aqueous solution, the saturation magnetization Ms of the phosphoric acid-treated Si-containing Fe-based alloy powder, and the thickness of the Fe—O—Si—P coating. 図２７は、図９に示したリン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５％で２時間塩酸処理したＳｉ含有Ｆｅ基合金粉の走査型電子顕微鏡写真である。FIG. 27 is a scanning electron micrograph of the Si-containing Fe-based alloy powder obtained by treating the phosphoric acid-treated Si-containing Fe-based alloy powder shown in FIG. 9 with hydrochloric acid at a concentration of 5% for 2 hours. 図２８は、図９に示したリン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５％で４時間塩酸処理したＳｉ含有Ｆｅ基合金粉の走査型電子顕微鏡写真である。FIG. 28 is a scanning electron micrograph of the Si-containing Fe-based alloy powder obtained by treating the phosphoric acid-treated Si-containing Fe-based alloy powder shown in FIG. 9 with hydrochloric acid at a concentration of 5% for 4 hours. 図２９は、濃度０．０１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に１０分間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 29 shows a Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 20 minutes using a phosphoric acid aqueous solution having a concentration of 0.01 wt% in a hydrochloric acid aqueous solution having a concentration of 1 wt% for 10 minutes. It is a scanning electron micrograph of a cross section. 図３０は、濃度０．０１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に３０分間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 30 shows a Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 20 minutes using a phosphoric acid aqueous solution having a concentration of 0.01 wt% in a hydrochloric acid aqueous solution having a concentration of 1 wt% for 30 minutes. It is a scanning electron micrograph of a cross section. 図３１は、濃度０．０１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に１時間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 31 shows a Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 20 minutes using a phosphoric acid aqueous solution having a concentration of 0.01 wt% in a hydrochloric acid aqueous solution having a concentration of 1 wt% for 1 hour. It is a scanning electron micrograph of a cross section. 図３２は、濃度０．１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に１０分間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 32 shows a Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder that has been treated with a phosphoric acid solution having a concentration of 0.1 wt% for 20 minutes in a hydrochloric acid aqueous solution having a concentration of 1 wt% for 10 minutes. It is a scanning electron micrograph of a cross section. 図３３は、濃度０．１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に３０分間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 33 shows a Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder that has been treated with a phosphoric acid solution having a concentration of 0.1 wt% for 20 minutes in a hydrochloric acid aqueous solution having a concentration of 1 wt% for 30 minutes. It is a scanning electron micrograph of a cross section. 図３４は、濃度０．１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に１時間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 34 shows a Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder that has been treated with a phosphoric acid solution having a concentration of 0.1 wt% for 20 minutes in a hydrochloric acid aqueous solution having a concentration of 1 wt% for 1 hour. It is a scanning electron micrograph of a cross section. 図３５は、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５％で２時間塩酸処理したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 35 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder treated with phosphoric acid and treated with hydrochloric acid at a concentration of 5% for 2 hours. 図３６は、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５％で４時間塩酸処理したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 36 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder treated with phosphoric acid and treated with hydrochloric acid at a concentration of 5% for 4 hours. 図３７は、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５％で４時間塩酸処理したＳｉ含有Ｆｅ基合金粉のオージェ電子分光法による深さ方向分析の結果である。FIG. 37 shows the results of a depth direction analysis of Si-containing Fe-based alloy powder treated with phosphoric acid at a concentration of 5% for 4 hours by Auger electron spectroscopy. 図３８は、塩酸処理時間と飽和磁化Ｍｓとの関係を表すグラフである。FIG. 38 is a graph showing the relationship between the hydrochloric acid treatment time and the saturation magnetization Ms. 図３９は、塩酸水溶液の濃度と、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚み、ＳｉＯ2含有被膜の厚み、及び被膜の全体厚みとの関係を表すグラフである。FIG. 39 is a graph showing the relationship between the concentration of the aqueous hydrochloric acid solution, the thickness of the Fe—O—Si—P coating, the thickness of the SiO 2 containing coating, and the total thickness of the coating. 図４０は、塩酸処理時間と、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚み、ＳｉＯ2含有被膜の厚み、及び被膜の全体厚みとの関係を表すグラフである。FIG. 40 is a graph showing the relationship between the hydrochloric acid treatment time, the thickness of the Fe—O—Si—P coating, the thickness of the SiO 2 containing coating, and the total thickness of the coating. 図４１は、準備したＳｉ含有Ｆｅ基合金粉、６時間のリン酸処理をしたＳｉ含有Ｆｅ基合金粉、次いで０．５時間、１．０時間、及び４．０時間の塩酸処理をしたＳｉ含有Ｆｅ基合金粉の、Ｘ線光電子分光法（ＸＰＳ）によるＦｅ２ｐスペクトルである。FIG. 41 shows the prepared Si-containing Fe-based alloy powder, the Si-containing Fe-based alloy powder treated with phosphoric acid for 6 hours, and then the Si treated with hydrochloric acid for 0.5 hours, 1.0 hours, and 4.0 hours. It is Fe2p spectrum by X-ray photoelectron spectroscopy (XPS) of the contained Fe-based alloy powder. 図４２は、準備したＳｉ含有Ｆｅ基合金粉、６時間のリン酸処理をしたＳｉ含有Ｆｅ基合金粉、次いで０．５時間、１．０時間、及び４．０時間の塩酸処理をしたＳｉ含有Ｆｅ基合金粉の、Ｘ線光電子分光法（ＸＰＳ）によるＳｉ２ｐスペクトルである。FIG. 42 shows the prepared Si-containing Fe-based alloy powder, the Si-containing Fe-based alloy powder treated with phosphoric acid for 6 hours, and then the Si treated with hydrochloric acid for 0.5 hours, 1.0 hours, and 4.0 hours. It is a Si2p spectrum by X-ray photoelectron spectroscopy (XPS) of the contained Fe-based alloy powder. 図４３は、フッ酸処理前のＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 43 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder having a SiO 2 -containing film before hydrofluoric acid treatment. 図４４は、ＨＦ濃度が１％及びＮＨ4Ｆ濃度が３．３％のバッファードフッ酸を用いてフッ酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 44 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder subjected to hydrofluoric acid treatment using buffered hydrofluoric acid having an HF concentration of 1% and an NH 4F concentration of 3.3%. 図４５は、ＨＦ濃度が５％及びＮＨ4Ｆ濃度が１６．５％のバッファードフッ酸を用いてフッ酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 45 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder subjected to hydrofluoric acid treatment using buffered hydrofluoric acid having an HF concentration of 5 % and an NH 4F concentration of 16.5%. 図４６は、ＨＦ濃度が１０％及びＮＨ4Ｆ濃度が３３％のバッファードフッ酸を用いてフッ酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真である。FIG. 46 is a scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder treated with hydrofluoric acid using buffered hydrofluoric acid having an HF concentration of 10% and an NH 4F concentration of 33%. 図４７は、準備したＳｉ含有Ｆｅ基合金粉、フッ酸処理前のＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉、並びにＨＦ濃度が１％及びＮＨ4Ｆ濃度が３．３％のバッファードフッ酸、ＨＦ濃度が５％及びＮＨ4Ｆ濃度が１６．５％のバッファードフッ酸、及びＨＦ濃度が１０％及びＮＨ4Ｆ濃度が３３％のバッファードフッ酸を用いてフッ酸処理を行ったＳｉ含有Ｆｅ基合金粉のエネルギー分散型Ｘ線分析（ＥＤＳ）プロファイルである。FIG. 47 shows the prepared Si-containing Fe-based alloy powder, the Si-containing Fe-based alloy powder having a SiO 2 -containing film before hydrofluoric acid treatment, and a buffer having an HF concentration of 1% and an NH 4F concentration of 3.3%. Hydrofluoric acid treatment with hydrofluoric acid, buffered hydrofluoric acid with 5 % HF and 16.5% NH 4F, and buffered hydrofluoric acid with 10 % HF and 33% NH 4F. It is an energy dispersion type X-ray analysis (EDS) profile of the Si-containing Fe-based alloy powder which carried out. 図４８は、各種磁性材料の対応周波数及び飽和磁束密度を示す図である。FIG. 48 is a diagram showing corresponding frequencies and saturation magnetic flux densities of various magnetic materials.

本開示の方法においては、ＦｅベースのＳｉ含有Ｆｅ基合金粒子からなるＳｉ含有Ｆｅ基合金粉を準備する。Ｓｉ含有Ｆｅ基合金粉は、Ｆｅ及びＳｉと所望の磁気特性に応じた任意の添加元素とを含む合金粒子で構成される。以下、Ｓｉ含有Ｆｅ基合金粉とＳｉ含有Ｆｅ基合金粒子とをまとめて、Ｓｉ含有Ｆｅ基合金粉とよぶことがある。 In the method of the present disclosure, a Si-containing Fe-based alloy powder composed of Fe-based Si-containing Fe-based alloy particles is prepared. The Si-containing Fe-based alloy powder is composed of alloy particles containing Fe and Si and arbitrary additive elements according to desired magnetic properties. Hereinafter, the Si-containing Fe-based alloy powder and the Si-containing Fe-based alloy particles may be collectively referred to as Si-containing Fe-based alloy powder.

Ｓｉ含有Ｆｅ基合金粉のＦｅ含有量は、ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の全質量を基準にして、好ましくは８２．０～９７．０ｗｔ％であり、より好ましくは８５．０～９５．５ｗｔ％であり、さらに好ましくは８７．０～９３．５ｗｔ％である。Ｓｉ含有Ｆｅ基合金粉のＳｉ含有量は、ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の全質量を基準にして、好ましくは３．０～１８．０ｗｔ％、より好ましくは４．５～１５．０ｗｔ％、さらに好ましくは６．５～１３．０ｗｔ％である。上記範囲のＦｅ含有量及びＳｉ含有量を有するＳｉ含有Ｆｅ基合金粉を用いることで、所望の磁気特性を有し且つ十分な厚みのＳｉＯ2含有被膜を有するＳｉ含有Ｆｅ基合金粉を得ることができる。 The Fe content of the Si-containing Fe-based alloy powder is preferably 82.0 to 97.0 wt%, more preferably 85, based on the total mass of the Si-containing Fe-based alloy powder having the SiO 2 -containing coating. It is 9.0 to 95.5 wt%, more preferably 87.0 to 93.5 wt%. The Si content of the Si-containing Fe-based alloy powder is preferably 3.0 to 18.0 wt%, more preferably 4.5, based on the total mass of the Si-containing Fe-based alloy powder having the SiO 2 -containing coating. It is ~ 15.0 wt%, more preferably 6.5 ~ 13.0 wt%. By using a Si-containing Fe-based alloy powder having an Fe content and a Si content in the above range, a Si-containing Fe-based alloy powder having a desired magnetic property and having a SiO 2 -containing film having a sufficient thickness can be obtained. Can be done.

Ｓｉ含有Ｆｅ基合金粉は、Ｆｅ含有量及びＳｉ含有量が上記範囲内であれば、その他の元素を含んでもよい。Ｓｉ含有Ｆｅ基合金粉は、所望の磁気特性等を得るためにＦｅ及びＳｉに加えて、Ａｌ、Ｂ、Ｃｒ、Ｃ、Ｎｉ、Ｃｏ、Ｎｂ等を含んでもよい。Ｓｉ含有Ｆｅ基合金粉は、好ましくはＢを含む３元系合金粉であり、より好ましくはＢ及びＣを含む４元系合金粉であり、さらに好ましくはＢ、Ｃ、及びＡｌを含む５元系合金粉であり、さらにより好ましくは、Ｂ、Ｃ、Ａｌ、及びＣｒを含む６元系合金粉である。 The Si-containing Fe-based alloy powder may contain other elements as long as the Fe content and the Si content are within the above ranges. The Si-containing Fe-based alloy powder may contain Al, B, Cr, C, Ni, Co, Nb and the like in addition to Fe and Si in order to obtain desired magnetic properties and the like. The Si-containing Fe-based alloy powder is preferably a ternary alloy powder containing B, more preferably a quaternary alloy powder containing B and C, and further preferably 5 elements containing B, C, and Al. It is a system alloy powder, and even more preferably, it is a hex alloy powder containing B, C, Al, and Cr.

Ｓｉ含有Ｆｅ基合金粉は、多結晶合金、アモルファス合金、または金属ガラスであることができ、好ましくはアモルファス合金または金属ガラスである。 The Si-containing Fe-based alloy powder can be a polycrystalline alloy, an amorphous alloy, or a metallic glass, preferably an amorphous alloy or a metallic glass.

Ｓｉ含有Ｆｅ基合金粉が多結晶合金の場合でも、従来よりも膜厚が安定しており絶縁性が高く低コストの絶縁皮膜を有する粒径が小さい金属磁性粉末を得ることができる。ただし、多結晶合金はリン酸処理による溶解速度が速く、特に結晶粒界の溶解が速いために均一に溶解しにくく、Ｓｉ含有Ｆｅ基合金粒子の表面が荒れやすく、ＳｉＯ2含有被膜の厚みが比較的不均一になりやすい。アモルファス合金及び金属ガラスはリン酸処理による溶解速度が遅く、Ｓｉ含有Ｆｅ基合金粒子の表面が均一に溶解して表面が滑らかになりやすい。そのため、比較的均一な厚みを有するＳｉＯ2含有被膜を形成することができる。 Even when the Si-containing Fe-based alloy powder is a polycrystalline alloy, it is possible to obtain a metal magnetic powder having a stable film thickness, high insulating properties, a low-cost insulating film, and a small particle size. However, the polycrystalline alloy has a high dissolution rate due to the phosphoric acid treatment, and in particular, it is difficult to dissolve uniformly because the crystal grain boundaries are dissolved quickly, the surface of the Si-containing Fe-based alloy particles is easily roughened, and the thickness of the SiO 2 -containing film is thick. It tends to be relatively non-uniform. Amorphous alloys and metallic glasses have a slow dissolution rate due to phosphoric acid treatment, and the surface of Si-containing Fe-based alloy particles is likely to be uniformly dissolved and the surface tends to be smooth. Therefore, it is possible to form a SiO 2 -containing film having a relatively uniform thickness.

Ｓｉ含有Ｆｅ基合金であれば、多結晶合金、アモルファス合金、または金属ガラスの組成は特に限定されないが、例えば、多結晶合金としてはＦｅＳｉ合金及びＦｅＳｉＡｌ合金、アモルファス合金としてはＦｅＳｉＢＣｒＣ合金、金属ガラスとしてはＦｅＳｉＢＰＣＮｂＣｒ合金が挙げられる。 The composition of the polycrystalline alloy, the amorphous alloy, or the metallic glass is not particularly limited as long as it is a Si-containing Fe-based alloy. Examples include FeSiBPCNbCr alloy.

図１にＦｅ－Ｓｉ合金粉、図２にＦｅ－Ｓｉ－Ａｌ合金粉、図３にＦｅ－Ｓｉ－Ｂ－Ｃｒ－Ｃ合金粉、図４にＦｅ－Ｓｉ－Ｂ－Ｐ－Ｃ－Ｎｂ－Ｃｒ合金粉の走査型電子顕微鏡（ＳＥＭ）写真を示す。 1 is Fe—Si alloy powder, FIG. 2 is Fe—Si—Al alloy powder, FIG. 3 is Fe—Si—B—Cr—C alloy powder, and FIG. 4 is Fe—Si—B—P—C—Nb—. A scanning electron microscope (SEM) photograph of Cr alloy powder is shown.

Ｓｉ含有Ｆｅ基合金粉は、図１～４に示すような略球形状でもよいし、略扁平形状でもよい。 The Si-containing Fe-based alloy powder may have a substantially spherical shape as shown in FIGS. 1 to 4 or a substantially flat shape.

Ｓｉ含有Ｆｅ基合金粉は、好ましくは１～５０μｍ、より好ましくは３～２０μｍ、さらに好ましくは５～１０μｍの平均メジアン径（Ｄ５０）を有する。Ｓｉ含有Ｆｅ基合金粉の粒径は、レーザー回折散乱式粒度分布計で測定される。 The Si-containing Fe-based alloy powder has an average median diameter (D50) of preferably 1 to 50 μm, more preferably 3 to 20 μm, and even more preferably 5 to 10 μm. The particle size of the Si-containing Fe-based alloy powder is measured by a laser diffraction / scattering type particle size distribution meter.

本開示の方法においては、Ｓｉ含有Ｆｅ基合金粉をリン酸水溶液に浸漬し、リン酸水溶液から取り出して乾燥して、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金粉が得られる。以下、この工程をリン酸処理またはリン酸処理工程ともいう。 In the method of the present disclosure, the Si-containing Fe-based alloy powder is immersed in a phosphoric acid aqueous solution, taken out from the phosphoric acid aqueous solution and dried to obtain a Si-containing Fe-based alloy powder having a Fe—O—Si—P coating. can get. Hereinafter, this step is also referred to as a phosphoric acid treatment or a phosphoric acid treatment step.

リン酸処理工程では、Ｓｉ含有Ｆｅ基合金粉をリン酸水溶液に浸漬することにより、Ｓｉ含有Ｆｅ基合金粉の表面からＦｅが溶出しつつ、Ｓｉ含有Ｆｅ基合金粉の表面に残留したＦｅがＳｉ含有Ｆｅ基合金粉の表面にＦｅ－Ｏ－Ｓｉ－Ｐ系被膜を形成することができる。 In the phosphoric acid treatment step, by immersing the Si-containing Fe-based alloy powder in the phosphoric acid aqueous solution, Fe is eluted from the surface of the Si-containing Fe-based alloy powder, while the Fe remaining on the surface of the Si-containing Fe-based alloy powder is left. A Fe—O—Si—P-based film can be formed on the surface of the Si-containing Fe-based alloy powder.

図５及び６に、準備したＳｉ含有Ｆｅ基合金粉１０及びリン酸処理を行ったＳｉ含有Ｆｅ基合金粉１２の断面模式図を示す。リン酸処理を行ったＳｉ含有Ｆｅ基合金粉１２は、表面にＦｅ－Ｏ－Ｓｉ－Ｐ系被膜２０を有する。 5 and 6 show schematic cross-sectional views of the prepared Si-containing Fe-based alloy powder 10 and the phosphoric acid-treated Si-containing Fe-based alloy powder 12. The phosphoric acid-treated Si-containing Fe-based alloy powder 12 has a Fe—O—Si—P-based coating 20 on its surface.

Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０は、Ｆｅ、Ｏ、Ｓｉ、及びＰを含有する被膜である。Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０のＦｅ及びＳｉは、Ｓｉ含有Ｆｅ基合金粉１０由来であり、Ｐはリン酸水溶液由来であり、ＯはＳｉ含有Ｆｅ基合金粉がリン酸水溶液で酸化されることにより形成された酸化膜及び自然酸化膜に含まれる。したがって、Ｓｉ含有Ｆｅ基合金粉１０がＦｅ及びＳｉに加えて、Ｂ、Ｃｒ、Ｃ等を含む場合は、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０にはそれらの元素も含まれ得る。 The Fe—O—Si—P-based coating 20 is a coating containing Fe, O, Si, and P. Fe and Si of the Fe—O—Si—P coating 20 are derived from the Si-containing Fe-based alloy powder 10, P is derived from the phosphoric acid aqueous solution, and O is the Si-containing Fe-based alloy powder oxidized by the phosphoric acid aqueous solution. It is contained in the oxide film and the natural oxide film formed by the phosphoric acid. Therefore, when the Si-containing Fe-based alloy powder 10 contains B, Cr, C and the like in addition to Fe and Si, the Fe—O—Si—P-based coating 20 may also contain those elements.

Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０は、リン酸処理によりＳｉ含有Ｆｅ基合金粉１０の表面層が変化して形成される。準備したＳｉ含有Ｆｅ基合金粉１０とＦｅ－Ｏ－Ｓｉ－Ｐ系被膜２０との外径は実質的に同じであり、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉１２の外径は準備したＳｉ含有Ｆｅ基合金粉１０の外径よりも小さい。Ｓｉ含有Ｆｅ基合金粉の本体の外径が減少する分、表面に形成されるＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚みが大きくなる。Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０の厚みは、最終的に得られるＳｉＯ2含有被膜の厚みの上限になる。 The Fe—O—Si—P-based coating 20 is formed by changing the surface layer of the Si-containing Fe-based alloy powder 10 by the phosphoric acid treatment. The outer diameters of the prepared Si-containing Fe-based alloy powder 10 and the Fe—O—Si—P-based coating 20 are substantially the same, and the outer diameter of the phosphoric acid-treated Si-containing Fe-based alloy powder 12 is prepared. It is smaller than the outer diameter of the Si-containing Fe-based alloy powder 10. As the outer diameter of the main body of the Si-containing Fe-based alloy powder decreases, the thickness of the Fe—O—Si—P-based coating formed on the surface increases. The thickness of the Fe—O—Si—P coating 20 is the upper limit of the thickness of the finally obtained SiO 2 containing coating.

リン酸処理工程におけるリン酸水溶液の濃度、時間、及び温度は、最終的に必要なＳｉＯ2含有被膜の厚みに応じて調整することができる。 The concentration, time, and temperature of the aqueous phosphoric acid solution in the phosphoric acid treatment step can be adjusted according to the thickness of the SiO 2 -containing film finally required.

リン酸水溶液の濃度は、好ましくは０．００００１～１０．００ｗｔ％、より好ましくは０．２５～５．００ｗｔ％、さらに好ましくは０．５０～３．００ｗｔ％である。リン酸水溶液の温度は、好ましくは３０～８０℃、より好ましくは４５～６５℃、さらに好ましくは５０～６０℃である。Ｓｉ含有Ｆｅ基合金粉をリン酸水溶液に浸漬する時間は、好ましくは２０分間～１０時間、より好ましくは１～８時間、さらに好ましくは２～６時間である。 The concentration of the aqueous phosphoric acid solution is preferably 0.00001 to 10.00 wt%, more preferably 0.25 to 5.00 wt%, still more preferably 0.50 to 3.00 wt%. The temperature of the aqueous phosphoric acid solution is preferably 30 to 80 ° C, more preferably 45 to 65 ° C, and even more preferably 50 to 60 ° C. The time for immersing the Si-containing Fe-based alloy powder in the aqueous phosphoric acid solution is preferably 20 minutes to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 6 hours.

リン酸水溶液の濃度、温度、及び浸漬時間を上記範囲内にすることにより、Ｓｉ含有Ｆｅ基合金粉の表面に所望の厚みを有するＦｅ－Ｏ－Ｓｉ－Ｐ系被膜をより効率良く形成することができる。例えば、リン酸水溶液の濃度が高いほどＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚みは増加する。 By keeping the concentration, temperature, and immersion time of the phosphoric acid aqueous solution within the above ranges, a Fe—O—Si—P-based film having a desired thickness can be more efficiently formed on the surface of the Si-containing Fe-based alloy powder. Can be done. For example, the higher the concentration of the aqueous phosphoric acid solution, the thicker the Fe—O—Si—P coating.

リン酸処理では溶出したＦｅがリン酸鉄を形成し、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金の表面にも付着し得るが、リン酸鉄は塩酸処理工程で実質的に除去することができる。 In the phosphate treatment, the eluted Fe forms iron phosphate and can adhere to the surface of the Si-containing Fe-based alloy having the Fe—O—Si—P-based coating, but the iron phosphate is substantially in the hydrochloric acid treatment step. Can be removed.

準備したＳｉ含有Ｆｅ基合金粉は、表面領域で酸化膜を有する。Ｓｉ含有Ｆｅ基合金粉をリン酸処理することにより、Ｓｉ含有Ｆｅ基合金粉の表面から所定の深さ範囲でＦｅ－Ｓｉ－Ｐ－Ｏ系被膜が形成される。Ｆｅ－Ｓｉ－Ｐ－Ｏ系被膜には、Ｆｅ、Ｓｉ、Ｐ、及びＯに加えてＣｒ、Ｃ等が含まれ得る。 The prepared Si-containing Fe-based alloy powder has an oxide film in the surface region. By treating the Si-containing Fe-based alloy powder with phosphoric acid, a Fe—Si—PO-based film is formed within a predetermined depth range from the surface of the Si-containing Fe-based alloy powder. The Fe—Si—P—O-based coating may contain Cr, C, etc. in addition to Fe, Si, P, and O.

Ｓｉ含有Ｆｅ基合金粉のリン酸水溶液への浸漬は、好ましくは超音波洗浄機にかけながら行う。超音波洗浄機内で浸漬することによりＳｉ含有Ｆｅ基合金粉の凝集を防ぐことができる。 Immersion of the Si-containing Fe-based alloy powder in the phosphoric acid aqueous solution is preferably carried out while being subjected to an ultrasonic cleaner. By immersing in an ultrasonic cleaner, aggregation of Si-containing Fe-based alloy powder can be prevented.

リン酸処理工程における乾燥方法は、Ｓｉ含有Ｆｅ基合金粉を乾燥することができれば特にされないが、例えば１００℃の大気中で行うことができる。 The drying method in the phosphoric acid treatment step is not particularly limited as long as the Si-containing Fe-based alloy powder can be dried, but it can be carried out in the air at, for example, 100 ° C.

本開示の方法においては、リン酸処理後のＳｉ含有Ｆｅ基合金粉を、塩酸水溶液に浸漬し、塩酸水溶液から取り出して乾燥して、表面にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉が得られる。以下、この工程を塩酸処理または塩酸処理工程ともいう。 In the method of the present disclosure, the Si-containing Fe-based alloy powder after the phosphoric acid treatment is immersed in a hydrochloric acid aqueous solution, taken out from the hydrochloric acid aqueous solution and dried, and the Si-containing Fe-based alloy powder having a SiO 2 -containing film on the surface is provided. Is obtained. Hereinafter, this step is also referred to as a hydrochloric acid treatment or a hydrochloric acid treatment step.

塩酸処理工程では、リン酸処理をしたＳｉ含有Ｆｅ基合金粉を塩酸水溶液に浸漬することにより、リン酸鉄を溶解させ、且つＦｅ－Ｏ－Ｓｉ－Ｐ系被膜からＦｅ、Ｐ等の元素を溶出させてＳｉＯ2含有被膜を形成することができる。 In the hydrochloric acid treatment step, iron phosphate is dissolved by immersing the phosphoric acid-treated Si-containing Fe-based alloy powder in an aqueous hydrochloric acid solution, and elements such as Fe and P are removed from the Fe—O—Si—P-based coating film. It can be eluted to form a SiO 2 -containing film.

ＳｉＯ2含有被膜は、実質的にＳｉＯ2単相であることが好ましいが、所望の抵抗が得られる限り、ＳｉＯ2以外にＣｒ、Ｂ、Ｐ、Ｃ等の元素が含まれてもよい。 The SiO 2 -containing film is preferably substantially a SiO 2 single-phase, but may contain elements such as Cr, B, P, and C in addition to SiO 2 as long as a desired resistance can be obtained.

図７に、リン酸処理後に塩酸処理を行ったＳｉ含有Ｆｅ基合金粉１２の断面模式図を示す。塩酸処理を行ったＳｉ含有Ｆｅ基合金粉１４は、表面にＳｉＯ2含有被膜３０を有する。塩酸処理を行ったＳｉ含有Ｆｅ基合金粉１４は、Ｓｉ含有Ｆｅ基合金粉１４とＳｉＯ2含有被膜３０との間にＦｅ－Ｏ－Ｓｉ－Ｐ系被膜２２を有してもよい。 FIG. 7 shows a schematic cross-sectional view of the Si-containing Fe-based alloy powder 12 that has been treated with hydrochloric acid after being treated with phosphoric acid. The Si-containing Fe-based alloy powder 14 that has been treated with hydrochloric acid has a SiO 2 -containing film 30 on its surface. The Si-containing Fe-based alloy powder 14 that has been treated with hydrochloric acid may have an Fe—O—Si—P-based coating 22 between the Si-containing Fe-based alloy powder 14 and the SiO 2 -containing coating 30.

ＳｉＯ2含有被膜３０は、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０の少なくとも一部が塩酸処理で変化して形成される。そのため、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２２は、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０の厚みよりも小さく、塩酸処理を十分に行った場合は、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２０が全てＳｉＯ2含有被膜３０に変化し、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜２２は存在しない。 The SiO 2 -containing film 30 is formed by changing at least a part of the Fe—O—Si—P-based film 20 by hydrochloric acid treatment. Therefore, the Fe—O—Si—P coating 22 is smaller than the thickness of the Fe—O—Si—P coating 20, and when the hydrochloric acid treatment is sufficiently performed, the Fe—O—Si—P coating 20 Is all changed to the SiO 2 containing film 30, and the Fe—O—Si—P film 22 does not exist.

図８に、準備したＳｉ含有Ｆｅ基合金粒子、リン酸処理をしたＳｉ含有Ｆｅ合粒子、及びリン酸処理後に塩酸処理をしたＳｉ含有Ｆｅ基合金粒子の内部の一部を可視化した模式図を示す。 FIG. 8 is a schematic diagram showing a part of the inside of the prepared Si-containing Fe-based alloy particles, the phosphoric acid-treated Si-containing Fe compound particles, and the phosphoric acid-treated Si-containing Fe-based alloy particles. show.

塩酸処理工程における塩酸水溶液の濃度、時間、及び温度は、リン酸処理工程で生成してＳｉ含有Ｆｅ基合金粉の周囲に付着しているリン酸鉄を所望の程度に溶解することができる範囲で、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚みのうちＳｉＯ2含有被膜に変える所望の厚みに応じて調整することができる。 The concentration, time, and temperature of the aqueous hydrochloric acid solution in the hydrochloric acid treatment step are within the range in which the iron phosphate generated in the phosphoric acid treatment step and adhering to the periphery of the Si-containing Fe-based alloy powder can be dissolved to a desired degree. Therefore, the thickness of the Fe—O—Si—P-based coating can be adjusted according to the desired thickness to be changed to the SiO 2 -containing coating.

リン酸鉄が付着しているとその体積分磁気特性が低下するため、リン酸鉄を溶解することによりＳｉ含有Ｆｅ基合金粉の磁気特性を向上することができる。ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を回収するために、リン酸鉄を全て溶解することが好ましいが、リン酸鉄が残っていても、磁石等を用いてＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉のみを回収してもよい。 Since the volume integral magnetic property thereof is deteriorated when iron phosphate is attached, the magnetic property of the Si-containing Fe-based alloy powder can be improved by dissolving iron phosphate. In order to recover the Si-containing Fe-based alloy powder having the SiO 2 -containing film, it is preferable to dissolve all the iron phosphate. However, even if iron phosphate remains, the SiO 2 -containing film is formed by using a magnet or the like. Only the provided Si-containing Fe-based alloy powder may be recovered.

塩酸水溶液の濃度は、好ましくは０．５０～１０．００ｗｔ％、より好ましくは１．００～８．００ｗｔ％である、さらに好ましくは２．００～６．００ｗｔ％である。塩酸水溶液の温度は、好ましくは３０～８０℃、より好ましくは４５～６５℃、さらに好ましくは５０～６０℃である。塩酸水溶液に浸漬する時間は、好ましくは１０分～１０．０時間、より好ましくは１．０～７．０時間、さらに好ましくは１．５～４．０時間である。 The concentration of the aqueous hydrochloric acid solution is preferably 0.50 to 10.00 wt%, more preferably 1.00 to 8.00 wt%, still more preferably 2.00 to 6.00 wt%. The temperature of the aqueous hydrochloric acid solution is preferably 30 to 80 ° C, more preferably 45 to 65 ° C, and even more preferably 50 to 60 ° C. The time for soaking in the aqueous hydrochloric acid solution is preferably 10 minutes to 10.0 hours, more preferably 1.0 to 7.0 hours, and even more preferably 1.5 to 4.0 hours.

塩酸水溶液の濃度、温度、及び浸漬時間を上記範囲内にすることにより、より効率的に、ＳｉＯ2含有被膜を単相のＳｉＯ2に近づけ且つ所望の厚みを有するＳｉＯ2含有被膜を形成することができる。例えば、塩酸処理の時間が短いとリン酸鉄が残留し、磁性粉末の飽和磁化が小さくなる。塩酸処理の時間が長くなるにつれて、リン酸鉄の占める体積割合が少なくなり磁性粉末の飽和磁化の減少が抑制され、且つＦｅ－Ｏ－Ｓｉ－Ｐ系被膜がＳｉＯ2含有被膜に変化してＳｉＯ2含有被膜の厚みを増加することができる。 By keeping the concentration, temperature, and immersion time of the aqueous hydrochloric acid solution within the above ranges, the SiO 2 -containing film can be brought closer to the single-phase SiO 2 and a SiO 2 -containing film having a desired thickness can be formed more efficiently. Can be done. For example, if the hydrochloric acid treatment time is short, iron phosphate remains and the saturation magnetization of the magnetic powder becomes small. As the hydrochloric acid treatment time becomes longer, the volume ratio occupied by iron phosphate decreases, the decrease in saturation magnetization of the magnetic powder is suppressed, and the Fe—O—Si—P-based coating changes to a SiO 2 -containing coating, and SiO 2 is contained. 2 The thickness of the contained film can be increased.

Ｓｉ含有Ｆｅ基合金粉の塩酸水溶液への浸漬は、好ましくは超音波洗浄機にかけながら行う。超音波洗浄機内で浸漬することによりＳｉ含有Ｆｅ基合金粉の凝集を防ぐことができる。 Immersion of the Si-containing Fe-based alloy powder in an aqueous hydrochloric acid solution is preferably carried out while being subjected to an ultrasonic cleaner. By immersing in an ultrasonic cleaner, aggregation of Si-containing Fe-based alloy powder can be prevented.

塩酸処理工程における乾燥方法は、Ｓｉ含有Ｆｅ基合金粉を乾燥することができれば特にされないが、例えば１００℃の大気中で行うことができる。 The drying method in the hydrochloric acid treatment step is not particularly limited as long as the Si-containing Fe-based alloy powder can be dried, but can be carried out, for example, in the air at 100 ° C.

上記の方法によれば、従来よりも膜厚が安定しており絶縁性が高く安価な、ＳｉＯ２含有被膜を備えたＳｉ含有Ｆｅ基合金粉を高収率で得ることができる。ＳｉＯ２のＳｉは準備した本体のＳｉ含有Ｆｅ基合金粉由来であり、従来技術のような外部から形成するものではないためＳｉＯ２含有被膜は膜厚が安定している。また、ＳｉＯ２含有被膜は、上記のようにリン酸水溶液及び塩酸水溶液に浸漬するだけで形成することができるため、コストも小さい。Ｓｉ含有Ｆｅ基合金粉の表面に形成されたＳｉＯ2含有被膜は高抵抗であり、少なくとも最表面は実質的に単相のＳｉＯ2被膜でありさらに高抵抗であるため、これらの磁性粉末を用いて作製されるコンポジット磁性材料では渦電流損が低減され、１ＭＨｚ以上の高周波数領域に対応可能となる。また、上記のようにＳｉＯ2含有被膜は高抵抗であるため膜厚が比較的薄くてもよく、その分、本体のＳｉ含有Ｆｅ基合金粉の体積を大きくすることができ、粉末同士の静磁結合を強くできるため、コンポジット磁性材料の透磁率の向上に寄与するなど優れた磁気特性を得ることができる。 According to the above method, it is possible to obtain a Si-containing Fe-based alloy powder having a SiO 2 -containing coating, which has a stable film thickness, high insulating properties, and is inexpensive, in a high yield. Since Si of SiO 2 is derived from the prepared Si-containing Fe-based alloy powder of the main body and is not formed from the outside as in the prior art, the film thickness of the SiO 2 -containing film is stable. Further, since the SiO 2 -containing film can be formed only by immersing it in the phosphoric acid aqueous solution and the hydrochloric acid aqueous solution as described above, the cost is low. Since the SiO 2 -containing film formed on the surface of the Si-containing Fe-based alloy powder has high resistance, and at least the outermost surface is substantially a single-phase SiO 2 film and has high resistance, these magnetic powders are used. The eddy current loss is reduced in the composite magnetic material produced in the above-mentioned method, and it becomes possible to cope with a high frequency region of 1 MHz or more. Further, as described above, since the SiO 2 -containing film has high resistance, the film thickness may be relatively thin, and the volume of the Si-containing Fe-based alloy powder of the main body can be increased by that amount, so that the powders are static. Since the magnetic bond can be strengthened, excellent magnetic properties such as contributing to the improvement of the magnetic permeability of the composite magnetic material can be obtained.

ＳｉＯ2含有被膜の膜厚は、好ましくは３～１０００ｎｍ、より好ましくは４～５００ｎｍ、さらに好ましくは５～１００ｎｍ、さらにより好ましくは６～２０ｎｍである。ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を１００ｋＨｚ～１０ＭＨｚの周波数領域で用いる場合は、ＳｉＯ2含有被膜の膜厚は１０ｎｍ以下、例えば３～１０ｎｍ、４～１０ｎｍ、５～１０ｎｍ、６～１０ｎｍ、または７～１０ｎｍが好ましく、１０ＭＨｚ超の周波数領域で用いる場合はＳｉＯ2含有被膜の膜厚は１０ｎｍ超、例えば１０ｎｍ超～１０００ｎｍ、１０ｎｍ超～１００ｎｍ、または１０ｎｍ超～２０ｎｍが好ましい。 The film thickness of the SiO 2 -containing film is preferably 3 to 1000 nm, more preferably 4 to 500 nm, still more preferably 5 to 100 nm, and even more preferably 6 to 20 nm. When a Si-containing Fe-based alloy powder having a SiO 2 -containing film is used in the frequency region of 100 kHz to 10 MHz, the film thickness of the SiO 2 -containing film is 10 nm or less, for example, 3 to 10 nm, 4 to 10 nm, 5 to 10 nm, 6 The thickness of the SiO 2 -containing film is preferably more than 10 nm, for example, more than 10 nm to 1000 nm, more than 10 nm to 100 nm, or more than 10 nm to 20 nm when used in a frequency region of more than 10 MHz, preferably to 10 nm or 7 to 10 nm.

被膜内側の残留Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜の膜厚は、好ましくは０～１０ｎｍ、より好ましくは０～５ｎｍである。 The film thickness of the residual Fe—O—Si—P-based film on the inside of the film is preferably 0 to 10 nm, more preferably 0 to 5 nm.

本開示の方法で得られるＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉は、本体のＳｉ含有Ｆｅ基合金部分の寸法を小さくすることができるので、ＤＣ－ＤＣコンバータの鉄心以外に電波吸収体等にも好適に用いることができる。 Since the Si-containing Fe-based alloy powder having the SiO 2 -containing film obtained by the method of the present disclosure can reduce the size of the Si-containing Fe-based alloy portion of the main body, it absorbs radio waves in addition to the iron core of the DC-DC converter. It can also be suitably used for the body and the like.

上記リン酸処理及び塩酸処理を行ったＳｉ含有Ｆｅ基合金粉を、フッ酸処理してＳｉＯ2含有被膜を取り除くことによって、準備したＳｉ含有Ｆｅ基合金粉よりも寸法が小さい第２のＳｉ含有Ｆｅ基合金粉を得ることができる。 The Si-containing Fe-based alloy powder that has been subjected to the phosphoric acid treatment and the hydrochloric acid treatment is treated with a hydrofluoric acid to remove the SiO 2 -containing film, whereby the second Si-containing powder having a smaller size than the prepared Si-containing Fe-based alloy powder is contained. Fe-based alloy powder can be obtained.

ＳｉＯ2含有被膜はフッ酸に溶解するため、フッ酸処理を行うことによって、Ｓｉ含有Ｆｅ基合金粉からＳｉＯ2含有被膜を取り除くことができる。取り除かれたＳｉＯ2含有被膜部分は、準備したＳｉ含有Ｆｅ基合金粉の表面をＦｅ－Ｏ－Ｓｉ－Ｐ系被膜に変えた部分の少なくとも一部であるため、第２のＳｉ含有Ｆｅ基合金粉の寸法は、準備したＳｉ含有Ｆｅ基合金粉よりも小さくなる。また、フッ酸処理時間を調整すれば、ＳｉＯ2含有被膜を残留させることができる。これによって、準備したＳｉ含有Ｆｅ基合金粉よりも全体の直径が小さいＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を得ることができる。 Since the SiO 2 -containing film dissolves in hydrofluoric acid, the SiO 2 -containing film can be removed from the Si-containing Fe-based alloy powder by performing hydrofluoric acid treatment. Since the removed SiO 2 -containing coating portion is at least a part of the portion where the surface of the prepared Si-containing Fe-based alloy powder is changed to the Fe—O—Si—P-based coating, the second Si-containing Fe-based alloy is formed. The size of the powder is smaller than that of the prepared Si-containing Fe-based alloy powder. Further, by adjusting the hydrofluoric acid treatment time, the SiO 2 containing film can be left. As a result, it is possible to obtain a Si-containing Fe-based alloy powder having a SiO 2 -containing film having a smaller overall diameter than the prepared Si-containing Fe-based alloy powder.

フッ酸処理は、フッ酸水溶液を用いた溶液処理であることができる。 The hydrofluoric acid treatment can be a solution treatment using a hydrofluoric acid aqueous solution.

フッ酸水溶液としては、ＨＦ濃度が１～１０％及びＮＨ4Ｆ濃度が３．３～３３％のＮＨ4ＦとＨＦとの混合物であるバッファードフッ酸が挙げられる。 Examples of the hydrofluoric acid aqueous solution include buffered hydrofluoric acid, which is a mixture of NH 4 F and HF having an HF concentration of 1 to 10% and an NH 4 F concentration of 3.3 to 33%.

溶液処理は、室温のフッ酸水溶液中に例えば５～２０分間浸漬することにより行われる。 The solution treatment is carried out by immersing in a hydrofluoric acid aqueous solution at room temperature for, for example, 5 to 20 minutes.

第２のＳｉ含有Ｆｅ基合金粉の直径は、好ましくは０．１～５．０μｍ、より好ましくは０．３～２．０μｍ、さらに好ましくは０．５～１．０μｍの平均メジアン径（Ｄ５０）を有する。第２のＳｉ含有Ｆｅ基合金粉の粒径は、レーザー回折散乱式粒度分布計で測定される。上記のように、サブミクロン～数ミクロン範囲の粒径が小さい金属磁性粉末を安定的に得ることができるので、さらに高周波の領域でうず電流損の小さいコンポジット磁性材料を提供できる。 The diameter of the second Si-containing Fe-based alloy powder is preferably 0.1 to 5.0 μm, more preferably 0.3 to 2.0 μm, and even more preferably 0.5 to 1.0 μm, with an average median diameter (D50). ). The particle size of the second Si-containing Fe-based alloy powder is measured by a laser diffraction / scattering type particle size distribution meter. As described above, since a metal magnetic powder having a small particle size in the submicron to several micron range can be stably obtained, it is possible to provide a composite magnetic material having a small eddy current loss in a higher frequency region.

第２のＳｉ含有Ｆｅ基合金粉に、上記のリン酸処理及び塩酸処理を行ってもよい。第２のＳｉ含有Ｆｅ基合金粉は、出発材料として最初に準備したＳｉ含有Ｆｅ基合金粉よりも寸法が小さいので、より高周波領域に対応可能な、第２のＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を得ることができる。 The above-mentioned phosphoric acid treatment and hydrochloric acid treatment may be performed on the second Si-containing Fe-based alloy powder. Since the second Si-containing Fe-based alloy powder has a smaller size than the Si-containing Fe-based alloy powder initially prepared as a starting material, Si having a second SiO 2 -containing coating capable of supporting a higher frequency region is provided. The contained Fe-based alloy powder can be obtained.

第２のＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金をさらに、フッ酸処理を行い、さらに小さい粒径のＳｉ含有Ｆｅ基合金粉を得ることができる。さらに、リン酸処理、塩酸処理、及びフッ酸処理を繰り返して、さらにより小さい粒径のＳｉ含有Ｆｅ基合金粉を得ることができる。リン酸処理、塩酸処理、及びフッ酸処理を繰り返す際に、塩酸処理で終われば粒径が小さいＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金を得ることができ、フッ酸処理で終われば、粒径が小さいＳｉ含有Ｆｅ基合金を得ることができる。 The Si-containing Fe-based alloy provided with the second SiO 2 -containing film can be further treated with hydrofluoric acid to obtain a Si-containing Fe-based alloy powder having a smaller particle size. Further, the phosphoric acid treatment, the hydrochloric acid treatment, and the hydrofluoric acid treatment can be repeated to obtain a Si-containing Fe-based alloy powder having a smaller particle size. When the phosphoric acid treatment, the hydrochloric acid treatment, and the hydrofluoric acid treatment are repeated, a Si-containing Fe-based alloy having a SiO 2 -containing film having a small particle size can be obtained if the hydrochloric acid treatment is completed, and if the hydrofluoric acid treatment is completed, the Si-containing Fe-based alloy can be obtained. A Si-containing Fe-based alloy having a small particle size can be obtained.

本開示の方法で得られたＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を利用して、表面にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粒子からなるＳｉ含有Ｆｅ基合金粉を含むコンポジット磁性材料及びコンポジット磁性材料コアを作製することができる。Ｓｉ含有Ｆｅ基合金粉を含むコンポジット磁性材料及びコンポジット磁性材料コアは、１ＭＨｚ以上の高周波数領域でも損失が少なく、高周波特性に優れたインダクタやトランスを得ることができる。ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉と、エポキシまたはシリコーンゴムの前駆体の溶液とを混合してスラリーを調製し、スラリーを鋳型に流し込み鋳造することによって、コンポジット磁性材料及びコンポジット磁性材料コアを作製することができる。直径が５μｍ以下のＳｉ含有Ｆｅ基合金粉を用いる場合、上記鋳造プロセスで作製したコンポジット磁性材料コアと、ダストコアの作製と同様にプレスする方法で作製したトロイダルコアは特性がほぼ同じであり、上記鋳造プロセスは、高圧プレスを用いないのでコスト面で有利である。 Using the Si-containing Fe-based alloy powder having a SiO 2 -containing coating obtained by the method of the present disclosure, a Si-containing Fe-based alloy powder composed of Si-containing Fe-based alloy particles having a SiO 2 -containing coating on the surface can be obtained. A composite magnetic material containing and a composite magnetic material core can be manufactured. The composite magnetic material and the composite magnetic material core containing Si-containing Fe-based alloy powder have little loss even in a high frequency region of 1 MHz or more, and an inductor or a transformer having excellent high frequency characteristics can be obtained. A composite magnetic material and composite magnetism are prepared by mixing a Si-containing Fe-based alloy powder having a SiO 2 -containing coating and a solution of an epoxy or silicone rubber precursor to prepare a slurry, and casting the slurry into a mold. Material cores can be made. When a Si-containing Fe-based alloy powder having a diameter of 5 μm or less is used, the characteristics of the composite magnetic material core produced by the casting process and the toroidal core produced by the same pressing method as in the production of the dust core are almost the same. The casting process is cost advantageous because it does not use a high pressure press.

（実施例１）
Ｆｅ－Ｓｉ－Ｂ－Ｃｒ－Ｃ系のＳｉ含有Ｆｅ基合金粉（ＥＰＳＯＮ ＡＴＭＩＸ社製の水アトマイズ法で作製された鉄系アモルファス合金粉）を準備した。図３に、準備したＦｅ－Ｓｉ－Ｂ－Ｃｒ－Ｃ系合金粉の走査型電子顕微鏡（ＳＥＭ）写真を示す。準備したＳｉ含有Ｆｅ基合金粉は、８７．８３Ｆｅ－６．５９Ｓｉ－２．５４Ｂ－２．５３Ｃｒ－０．５１Ｃ(ｗｔ％）の組成を有し、メジアン平均径（Ｄ５０）は２．５７μｍであり、ＶＳＭで測定した飽和磁化は１４１．７ｅｍｕ／ｇであり、保磁力測定器で測定した保磁力は１．６９Ｏｅであった。 (Example 1)
Fe—Si—B—Cr—C-based Si-containing Fe-based alloy powder (iron-based amorphous alloy powder manufactured by EPSON ATMIX by the water atomization method) was prepared. FIG. 3 shows a scanning electron microscope (SEM) photograph of the prepared Fe—Si—B—Cr—C based alloy powder. The prepared Si-containing Fe-based alloy powder has a composition of 87.83Fe-6.59Si-2.54B-2.53Cr-0.51C (wt%) and has a median average diameter (D50) of 2.57 μm. The saturation magnetization measured by VSM was 141.7 emu / g, and the coercive force measured by the coercive force measuring instrument was 1.69 Oe.

準備したＳｉ含有Ｆｅ基合金粉を、濃度が０．００００１ｗｔ％～５ｗｔ％で６０℃のリン酸水溶液に２０分間～６時間浸漬し、リン酸水溶液から取り出して乾燥して、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金粉を得た。 The prepared Si-containing Fe-based alloy powder is immersed in a phosphoric acid aqueous solution at a concentration of 0.00001 wt% to 5 wt% at 60 ° C. for 20 minutes to 6 hours, taken out from the phosphoric acid aqueous solution, dried, and Fe—O—Si. A Si-containing Fe-based alloy powder having a −P-based coating was obtained.

次いで、リン酸処理で得られたＦｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金粉を、濃度が１～６ｗｔ％で６０℃の塩酸水溶液に１０分～４時間浸漬し、塩酸水溶液から取り出して乾燥して、表面にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を得た。 Next, the Si-containing Fe-based alloy powder having the Fe—O—Si—P-based coating obtained by the phosphoric acid treatment was immersed in a hydrochloric acid aqueous solution at a concentration of 1 to 6 wt% at 60 ° C. for 10 minutes to 4 hours. It was taken out from the aqueous hydrochloric acid solution and dried to obtain a Si-containing Fe-based alloy powder having a SiO 2 -containing film on the surface.

図９に、濃度５ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の走査型電子顕微鏡（ＳＥＭ）写真を示す。図１０に、準備したＳｉ含有Ｆｅ基合金粉及び濃度５ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉について分析した粉末Ｘ線回折プロファイルを示す。 FIG. 9 shows a scanning electron microscope (SEM) photograph of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 6 hours using a phosphoric acid aqueous solution having a concentration of 5 wt%. FIG. 10 shows a powder X-ray diffraction profile analyzed for a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 6 hours using the prepared Si-containing Fe-based alloy powder and a phosphoric acid aqueous solution having a concentration of 5 wt%.

リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の写真には不定形の物質がみられるが、これは、粉末Ｘ線回折プロファイルに示されるように、リン酸処理で形成されたリン酸鉄である。リン酸鉄は、Ｓｉ含有Ｆｅ基合金の表面にも付着し得る。 Atypical substances can be seen in the photographs of the phosphoric acid-treated Si-containing Fe-based alloy powder, which are iron phosphate formed by the phosphoric acid treatment, as shown in the powder X-ray diffraction profile. be. Iron phosphate may also adhere to the surface of the Si-containing Fe-based alloy.

図１１～１６に、準備したＳｉ含有Ｆｅ基合金粉の断面、並びに濃度０．００００１ｗｔ％、０．０００１ｗｔ％、０．００１ｗｔ％、０．０１ｗｔ％、及び０．１ｗｔ％のリン酸水溶液を用いてそれぞれ６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真を示す。図１７及び１８に、濃度０．０１ｗｔ％及び０．１ｗｔ％のリン酸水溶液をそれぞれ用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真を示す。図１９～２１に、準備したＳｉ含有Ｆｅ基合金粉の断面、濃度１ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面、及び濃度５ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡（ＳＥＭ）写真を示す。Ｓｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真は、樹脂中にＳｉ含有Ｆｅ基合金粉を固めて研磨及びイオンミリングにより断面をだして、走査型電子顕微鏡で観察することにより得られる。 11 to 16 show the cross section of the prepared Si-containing Fe-based alloy powder, and phosphoric acid aqueous solutions having concentrations of 0.00001 wt%, 0.0001 wt%, 0.001 wt%, 0.01 wt%, and 0.1 wt%. The scanning electron microscope (SEM) photograph of the cross section of the Si-containing Fe-based alloy powder which was treated with phosphoric acid for 6 hours is shown. FIGS. 17 and 18 show scanning electron microscope (SEM) photographs of cross sections of Si-containing Fe-based alloy powders that have been subjected to phosphoric acid treatment for 20 minutes using phosphoric acid aqueous solutions having concentrations of 0.01 wt% and 0.1 wt%, respectively. show. 19 to 21 show a cross section of the prepared Si-containing Fe-based alloy powder, a cross section of the Si-containing Fe-based alloy powder treated with phosphoric acid for 6 hours using a phosphoric acid aqueous solution having a concentration of 1 wt%, and phosphorus having a concentration of 5 wt%. FIG. 3 shows a scanning electron microscope (SEM) photograph of a cross section of a Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment using an acid aqueous solution for 6 hours. A scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder can be obtained by solidifying the Si-containing Fe-based alloy powder in a resin, polishing and ion milling to obtain a cross section, and observing with a scanning electron microscope.

濃度０．００００１ｗｔ％、０．０００１ｗｔ％、０．００１ｗｔ％、０．０１ｗｔ％、及び０．１ｗｔ％のリン酸水溶液を用いてそれぞれ６時間リン酸処理を行って得られたＳｉ含有Ｆｅ基合金粉の表面にはＦｅ－Ｏ－Ｓｉ－Ｐ系被膜が形成されており、図１２～１６の断面ＳＥＭ観察で測定したＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚みはそれぞれ、７．０ｎｍ、９．０ｎｍ、１５．５ｎｍ、１９．０ｎｍ、２７．０ｎｍであった。濃度０．０１ｗｔ％及び０．１ｗｔ％のリン酸水溶液をそれぞれ用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の表面にもＦｅ－Ｏ－Ｓｉ－Ｐ系被膜が形成されており、図１７及び１８の断面ＳＥＭ観察で測定したＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚みはそれぞれ、１８ｎｍ及び３１ｎｍであった。図２０及び２１に示す濃度１％及び５％のリン酸処理を行って得られたＳｉ含有Ｆｅ基合金粉断面において中心部の白い箇所は、図１９に示す準備したＳｉ含有Ｆｅ基合金粉と同じ組成を有し、その周囲の灰色の箇所はＦｅ－Ｏ－Ｓｉ－Ｐ系被膜である。図２１において、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜の外部に小片がみられるが、この小片はリン酸鉄である。 Si-containing Fe-based alloy obtained by performing phosphoric acid treatment for 6 hours using phosphoric acid aqueous solutions having concentrations of 0.00001 wt%, 0.0001 wt%, 0.001 wt%, 0.01 wt%, and 0.1 wt%, respectively. A Fe—O—Si—P coating is formed on the surface of the powder, and the thicknesses of the Fe—O—Si—P coating measured by SEM observation of the cross sections of FIGS. 12 to 16 are 7.0 nm and 9, respectively. It was 9.0 nm, 15.5 nm, 19.0 nm, and 27.0 nm. A Fe—O—Si—P-based film is also formed on the surface of the Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment for 20 minutes using phosphoric acid aqueous solutions having concentrations of 0.01 wt% and 0.1 wt%, respectively. The thicknesses of the Fe—O—Si—P-based coatings measured by the cross-sectional SEM observations of FIGS. 17 and 18 were 18 nm and 31 nm, respectively. In the cross section of the Si-containing Fe-based alloy powder obtained by performing the phosphoric acid treatment at concentrations of 1% and 5% shown in FIGS. 20 and 21, the white portion in the center is the Si-containing Fe-based alloy powder prepared as shown in FIG. It has the same composition, and the gray part around it is a Fe—O—Si—P based film. In FIG. 21, small pieces are found outside the Fe—O—Si—P-based coating, and these small pieces are iron phosphate.

図２２～２４に、準備したＳｉ含有Ｆｅ基合金粉、濃度１ｗｔ％のリン酸水溶液を用いてリン酸処理を行ったＳｉ含有Ｆｅ基合金粉、及び濃度２ｗｔ％のリン酸水溶液を用いてリン酸処理を行ったＳｉ含有Ｆｅ基合金粉のオージェ電子分光法による深さ方向分析の結果を示す。 FIGS. 22 to 24 show phosphorus using the prepared Si-containing Fe-based alloy powder, the Si-containing Fe-based alloy powder treated with phosphoric acid using a phosphoric acid aqueous solution having a concentration of 1 wt%, and the phosphoric acid aqueous solution having a concentration of 2 wt%. The results of the depth direction analysis of the acid-treated Si-containing Fe-based alloy powder by Auger electron spectroscopy are shown.

準備したＳｉ含有Ｆｅ基合金粉は、表面から８ｎｍの深さ範囲で酸素量が多く酸化膜が形成されていることが分かる。濃度１ｗｔ％のリン酸水溶液を用いたリン酸処理により、表面から４２ｎｍの深さの範囲でＦｅ、Ｓｉ、Ｐ、Ｃｒ、Ｃ、及びＯが検出され、Ｃｒ及びＣを含むＦｅ－Ｓｉ－Ｐ－Ｏ系被膜が形成されていることが分かる。濃度２ｗｔ％のリン酸水溶液を用いたリン酸処理により、表面から６９ｎｍの深さの範囲でＦｅ、Ｓｉ、Ｐ、Ｃｒ、Ｃ、及びＯが検出され、Ｃｒ及びＣを含むＦｅ－Ｏ－Ｓｉ－Ｐ系被膜が形成されていることが分かる。検出されたＦｅ、Ｓｉ、Ｃｒ、及びＣは、準備した本体のＳｉ含有Ｆｅ基合金粉由来であり、Ｐはリン酸水溶液由来である。ＯはＳｉ含有Ｆｅ基合金粉がリン酸水溶液で酸化されることにより形成された酸化膜及び自然酸化膜に含まれる。 It can be seen that the prepared Si-containing Fe-based alloy powder has a large amount of oxygen and an oxide film is formed in a depth range of 8 nm from the surface. Fe, Si, P, Cr, C, and O were detected in a depth range of 42 nm from the surface by phosphoric acid treatment using a phosphoric acid aqueous solution having a concentration of 1 wt%, and Fe-Si-P containing Cr and C was detected. It can be seen that an O-based film is formed. Fe, Si, P, Cr, C, and O were detected in a depth range of 69 nm from the surface by phosphoric acid treatment using a phosphoric acid aqueous solution having a concentration of 2 wt%, and Fe—O—Si containing Cr and C was detected. -It can be seen that a P-based film is formed. The detected Fe, Si, Cr, and C are derived from the prepared Si-containing Fe-based alloy powder of the main body, and P is derived from the phosphoric acid aqueous solution. O is contained in an oxide film and a natural oxide film formed by oxidizing Si-containing Fe-based alloy powder with an aqueous phosphoric acid solution.

図２５に、０．００００１～１ｗｔ％のリン酸水溶液の濃度と、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉のＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚さとの関係を表すグラフを示す。０．００００１～１％のリン酸水溶液を用いて３ｎｍ～４９ｎｍの厚みのＦｅ－Ｏ－Ｓｉ－Ｐ系被膜が得られた。図２６に、０．２５ｗｔ％～５ｗｔ％のリン酸水溶液の濃度と、リン酸処理を行ったＳｉ含有Ｆｅ基合金粉の飽和磁化Ｍｓ及びＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚さとの関係を表すグラフを示す。リン酸水溶液の濃度が高いほどＦｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚みが増加し、その分飽和磁化が低下することが分かる。 FIG. 25 shows a graph showing the relationship between the concentration of the phosphoric acid aqueous solution of 0.00001 to 1 wt% and the thickness of the Fe—O—Si—P-based coating film of the phosphoric acid-treated Si-containing Fe-based alloy powder. .. A Fe—O—Si—P-based film having a thickness of 3 nm to 49 nm was obtained using a 0.00001 to 1% aqueous phosphoric acid solution. FIG. 26 shows the relationship between the concentration of the phosphoric acid aqueous solution of 0.25 wt% to 5 wt%, the saturation magnetization Ms of the phosphoric acid-treated Si-containing Fe-based alloy powder, and the thickness of the Fe—O—Si—P coating. The graph showing is shown. It can be seen that the higher the concentration of the phosphoric acid aqueous solution, the thicker the Fe—O—Si—P coating, and the lower the saturation magnetization.

図２７及び２８に、濃度５ｗｔ％のリン酸水溶液を用いてリン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５ｗｔ％の塩酸水溶液に２．０時間浸漬したＳｉ含有Ｆｅ基合金粉、及び濃度５ｗｔ％の塩酸水溶液に４．０時間浸漬したＳｉ含有Ｆｅ基合金粉の走査型電子顕微鏡写真を示す。 FIGS. 27 and 28 show Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder treated with a phosphoric acid solution having a concentration of 5 wt% in a hydrochloric acid aqueous solution having a concentration of 5 wt% for 2.0 hours. And a scanning electron micrograph of a Si-containing Fe-based alloy powder immersed in a hydrochloric acid aqueous solution having a concentration of 5 wt% for 4.0 hours is shown.

図９に示すように濃度５ｗｔ％のリン酸水溶液を用いてリン酸処理を行ったＳｉ含有Ｆｅ基合金粉の周囲には、不定形のリン酸鉄がみられるが、図２７及び２８に示すように、塩酸処理によりリン酸鉄は除去された。 As shown in FIG. 9, atypical iron phosphate is found around the Si-containing Fe-based alloy powder that has been subjected to phosphoric acid treatment using a phosphoric acid aqueous solution having a concentration of 5 wt%, which are shown in FIGS. 27 and 28. As described above, iron phosphate was removed by the hydrochloric acid treatment.

図２９～３１に、濃度０．０１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に１０分間、３０分間、及び１時間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真を示す。図３２～３４に、濃度０．１ｗｔ％のリン酸水溶液を用いて２０分間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度１ｗｔ％の塩酸水溶液に１０分間、３０分間、及び１時間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真を示す。図３５及び３６に、濃度５ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５ｗｔ％の塩酸水溶液に２．０時間及び４．０時間浸漬したＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真を示す。 In FIGS. 29 to 31, the Si-containing Fe-based alloy powder subjected to phosphoric acid treatment using a phosphoric acid aqueous solution having a concentration of 0.01 wt% for 20 minutes was put into a hydrochloric acid aqueous solution having a concentration of 1 wt% for 10 minutes, 30 minutes, and 1 hour. A scanning electron micrograph of a cross section of the soaked Si-containing Fe-based alloy powder is shown. In FIGS. 32 to 34, the Si-containing Fe-based alloy powder obtained by phosphoric acid treatment with a phosphoric acid aqueous solution having a concentration of 0.1 wt% for 20 minutes was put into a hydrochloric acid aqueous solution having a concentration of 1 wt% for 10 minutes, 30 minutes, and 1 hour. A scanning electron micrograph of a cross section of the soaked Si-containing Fe-based alloy powder is shown. In FIGS. 35 and 36, the Si-containing Fe-based alloy powder that had been subjected to phosphoric acid treatment for 6 hours using a 5 wt% phosphoric acid aqueous solution was immersed in a 5 wt% hydrochloric acid aqueous solution for 2.0 hours and 4.0 hours. A scanning electron micrograph of a cross section of a Si-containing Fe-based alloy powder is shown.

リン酸処理及び塩酸処理を行って得られたＳｉ含有Ｆｅ基合金粉の表面にはＳｉＯ２含有被膜が形成されており、図２９～３４の断面ＳＥＭ観察で測定したＳｉＯ２含有被膜の厚みはそれぞれ、１４ｎｍ、９ｎｍ、１３ｎｍ、２３ｎｍ、１３ｎｍ、２０ｎｍであった。図３５及び３６において、中心部の白い箇所が、準備したＳｉ含有Ｆｅ基合金粉と実質的に同じ組成を有し、その周囲に二層の被膜が形成されている。二層の被膜のうち外側の比較的黒い層がＳｉＯ2含有被膜であり、内側の比較的白い層がＦｅ－Ｏ－Ｓｉ－Ｐ系被膜である。 A SiO 2 -containing film is formed on the surface of the Si-containing Fe-based alloy powder obtained by the phosphoric acid treatment and the hydrochloric acid treatment, and the thickness of the SiO 2 -containing film measured by observing the cross section SEM of FIGS. 29 to 34 is It was 14 nm, 9 nm, 13 nm, 23 nm, 13 nm, and 20 nm, respectively. In FIGS. 35 and 36, the white portion in the center has substantially the same composition as the prepared Si-containing Fe-based alloy powder, and a two-layer film is formed around the white portion. Of the two layers, the outer relatively black layer is the SiO 2 -containing film, and the inner relatively white layer is the Fe—O—Si—P-based film.

図３７に、濃度５ｗｔ％のリン酸水溶液を用いてリン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５ｗｔ％の塩酸水溶液に４．０時間浸漬したＳｉ含有Ｆｅ基合金粉のオージェ電子分光法による深さ方向分析の結果を示す。 FIG. 37 shows Auger electrons of a Si-containing Fe-based alloy powder obtained by immersing a Si-containing Fe-based alloy powder treated with a phosphoric acid solution having a concentration of 5 wt% in a hydrochloric acid aqueous solution having a concentration of 5 wt% for 4.0 hours. The result of the depth direction analysis by the spectroscopy is shown.

濃度５ｗｔ％の塩酸水溶液を用いた塩酸処理により、表面から３５０ｎｍの深さ範囲でＦｅ、Ｓｉ、Ｃｒ、Ｃ、及びＯが検出され、Ｃｒ及びＣを含むＳｉＯ2含有被膜が形成されていることが分かる。３５０～４９０ｎｍの深さ範囲では、酸素量が大きく減少しており、Ｆｅ、Ｓｉ、Ｐ、Ｂ、Ｃｒ、及びＯが検出され、この範囲にＢ及びＣｒを含むＦｅ－Ｏ－Ｓｉ－Ｐ系被膜が残存している。 Fe, Si, Cr, C, and O are detected in a depth range of 350 nm from the surface by hydrochloric acid treatment using a hydrochloric acid aqueous solution having a concentration of 5 wt%, and a SiO 2 containing film containing Cr and C is formed. I understand. In the depth range of 350 to 490 nm, the amount of oxygen is greatly reduced, Fe, Si, P, B, Cr, and O are detected, and Fe-O-Si-P system containing B and Cr in this range. The coating remains.

図３８に、濃度５ｗｔ％のリン酸水溶液を用いてリン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５ｗｔ％の塩酸水溶液に１．０～４．０時間浸漬した場合の浸漬時間と飽和磁化Ｍｓとの関係を表すグラフを示す。飽和磁化Ｍｓは、Ｓｉ含有Ｆｅ基合金粉をエポキシ樹脂と混合して鋳造し、焼成して得られたトロイダルコアについて測定して得られた値である。塩酸処理の時間が短いとトロイダルコア中のリン酸鉄の占める体積割合が多くなり飽和磁化が小さくなる。塩酸処理の時間が長くなるにつれて、トロイダルコア中のリン酸鉄の占める体積割合が少なくなり飽和磁化が大きくなった。 FIG. 38 shows the immersion time when the Si-containing Fe-based alloy powder subjected to the phosphoric acid treatment using the phosphoric acid aqueous solution having a concentration of 5 wt% was immersed in the hydrochloric acid aqueous solution having a concentration of 5 wt% for 1.0 to 4.0 hours. The graph showing the relationship with the saturation magnetization Ms is shown. The saturation magnetization Ms is a value obtained by measuring the toroidal core obtained by mixing Si-containing Fe-based alloy powder with an epoxy resin, casting, and firing. When the hydrochloric acid treatment time is short, the volume ratio of iron phosphate in the toroidal core increases and the saturation magnetization decreases. As the hydrochloric acid treatment time became longer, the volume ratio of iron phosphate in the toroidal core decreased and the saturation magnetization increased.

図３９に、濃度５ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度３～６ｗｔ％の塩酸水溶液に３．０時間浸漬した場合の、塩酸水溶液の濃度と、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚み、ＳｉＯ2含有被膜の厚み、及び被膜の全体厚みとの関係を表すグラフを示す。塩酸水溶液の濃度が高くなるにつれて、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜がＳｉＯ2含有被膜に変化した。 FIG. 39 shows a hydrochloric acid aqueous solution obtained by immersing a Si-containing Fe-based alloy powder that has been subjected to a phosphoric acid treatment for 6 hours using a phosphoric acid aqueous solution having a concentration of 5 wt% in a hydrochloric acid aqueous solution having a concentration of 3 to 6 wt% for 3.0 hours. A graph showing the relationship between the concentration of Fe—O—Si—P-based coating, the thickness of the SiO 2 -containing coating, and the total thickness of the coating is shown. As the concentration of the aqueous hydrochloric acid solution increased, the Fe—O—Si—P-based coating changed to a SiO 2 -containing coating.

図４０に、濃度５ｗｔ％のリン酸水溶液を用いて６時間リン酸処理を行ったＳｉ含有Ｆｅ基合金粉を、濃度５ｗｔ％の塩酸水溶液に１．０～４．０時間浸漬した場合の、浸漬時間と、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜の厚み、ＳｉＯ2含有被膜の厚み、及び被膜の全体厚みとの関係を表すグラフを示す。塩酸処理の時間が長くなるにつれて、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜がＳｉＯ2含有被膜に変化した。 FIG. 40 shows a case where a Si-containing Fe-based alloy powder that had been subjected to phosphoric acid treatment for 6 hours using a 5 wt% phosphoric acid aqueous solution was immersed in a 5 wt% hydrochloric acid aqueous solution for 1.0 to 4.0 hours. The graph which shows the relationship between the immersion time, the thickness of a Fe—O—Si—P coating film, the thickness of a SiO 2 containing film, and the total thickness of a film is shown. As the hydrochloric acid treatment time became longer, the Fe—O—Si—P-based coating changed to a SiO 2 -containing coating.

図４１及び４２に、準備したＳｉ含有Ｆｅ基合金粉、濃度５ｗｔ％のリン酸水溶液を用いてリン酸処理を行ったＳｉ含有Ｆｅ基合金粉、次いで濃度５ｗｔ％の塩酸水溶液に０．５時間、１．０時間、及び４．０時間浸漬して塩酸処理をしたＳｉ含有Ｆｅ基合金粉の、Ｘ線光電子分光法（ＸＰＳ）によるＦｅ２ｐスペクトル及びＳｉ２ｐスペクトルを示す。 In FIGS. 41 and 42, the prepared Si-containing Fe-based alloy powder, the Si-containing Fe-based alloy powder subjected to the phosphoric acid treatment using the phosphoric acid aqueous solution having a concentration of 5 wt%, and then the hydrochloric acid aqueous solution having a concentration of 5 wt% were added for 0.5 hours. The Fe2p spectrum and the Si2p spectrum of the Si-containing Fe-based alloy powder which has been immersed in hydrochloric acid for 1.0 hour and 4.0 hours and treated with hydrochloric acid by X-ray photoelectron spectroscopy (XPS) are shown.

Ｆｅ２ｐスペクトルから、準備したＳｉ含有Ｆｅ基合金粉の表面には金属Ｆｅが存在していることが分かる。準備したＳｉ含有Ｆｅ基合金粉に濃度５ｗｔ％のリン酸水溶液を用いてリン酸処理を行うと金属Ｆｅのピークがなくなり、表面は鉄酸化物の状態になる。次いで濃度５ｗｔ％の塩酸水溶液を用いて０．５時間、１．０時間、及び４．０時間の塩酸処理を行うと、７０５～７４０ｅＶの結合エネルギー範囲でピークがなくなる。このＸＰＳの分析結果から、リン酸処理を行うと金属Ｆｅの表面は鉄酸化物となり、塩酸処理を行うと鉄酸化物は除去されることが分かる。 From the Fe2p spectrum, it can be seen that the metal Fe is present on the surface of the prepared Si-containing Fe-based alloy powder. When the prepared Si-containing Fe-based alloy powder is subjected to phosphoric acid treatment using a phosphoric acid aqueous solution having a concentration of 5 wt%, the peak of metal Fe disappears and the surface becomes an iron oxide state. Then, when hydrochloric acid treatment is performed for 0.5 hours, 1.0 hours, and 4.0 hours using a hydrochloric acid aqueous solution having a concentration of 5 wt%, the peak disappears in the binding energy range of 705 to 740 eV. From the results of this XPS analysis, it can be seen that the surface of the metal Fe becomes iron oxide when the phosphoric acid treatment is performed, and the iron oxide is removed when the hydrochloric acid treatment is performed.

Ｓｉ２ｐスペクトルから、準備したＳｉ含有Ｆｅ基合金粉の表面にはＳｉ2Ｏ3またはそれに近い構造のＳｉ酸化物が存在していることが分かる。準備したＳｉ含有Ｆｅ基合金粉に濃度５ｗｔ％のリン酸水溶液を用いてリン酸処理を行うと、ＳｉＯ2またはそれに近い構造のＳｉ酸化物になり、次いで濃度５ｗｔ％の塩酸水溶液を用いて０．５時間、１．０時間、及び４．０時間の塩酸処理を行うと、塩酸処理時間が長くなるとともにＳｉＯ2のピークが大きくなり、ＳｉＯ2相が増加することが分かる。 From the Si2p spectrum, it can be seen that Si 2O 3 or a Si oxide having a structure similar to that is present on the surface of the prepared Si-containing Fe-based alloy powder. When the prepared Si-containing Fe-based alloy powder is subjected to phosphoric acid treatment using a phosphoric acid aqueous solution having a concentration of 5 wt%, it becomes Si oxide having a structure similar to SiO 2 , and then 0 using a hydrochloric acid aqueous solution having a concentration of 5 wt%. It can be seen that when the hydrochloric acid treatment for 5.5 hours, 1.0 hour, and 4.0 hours is performed, the hydrochloric acid treatment time becomes longer, the peak of SiO 2 becomes larger, and the SiO 2 phase increases.

このようにＳｉ含有Ｆｅ基合金粉をリン酸処理し、次いで塩酸処理することによって、Ｓｉ含有Ｆｅ基合金粉は、図８に模式的に示すように、表面にＳｉＯ2含有被膜を形成する。Ｓｉ含有Ｆｅ基合金粉は、Ｓｉ含有Ｆｅ基合金粉と表面のＳｉＯ2含有被膜との間にＦｅ－Ｏ－Ｓｉ－Ｐ系被膜を有してもよい。 By treating the Si-containing Fe-based alloy powder with phosphoric acid and then with hydrochloric acid in this way, the Si-containing Fe-based alloy powder forms a SiO 2 -containing film on the surface as schematically shown in FIG. The Si-containing Fe-based alloy powder may have an Fe—O—Si—P-based coating between the Si-containing Fe-based alloy powder and the SiO 2 -containing coating on the surface.

（実施例２）
実施例１において、濃度５ｗｔ％で６０℃のリン酸水溶液を用いて６時間リン酸処理を行い、次いで、濃度５ｗｔ％で６０℃の塩酸水溶液を用いて４．０時間塩酸処理をして得られたＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉に、フッ酸処理として、フッ酸水溶液を用いた溶液処理を行った。 (Example 2)
In Example 1, a phosphoric acid treatment was carried out for 6 hours using a phosphoric acid aqueous solution at a concentration of 5 wt% and 60 ° C., and then a hydrochloric acid treatment was carried out for 4.0 hours using a hydrochloric acid aqueous solution at a concentration of 5 wt% and 60 ° C. The Si-containing Fe-based alloy powder having the obtained SiO 2 -containing film was treated with a solution using an aqueous solution of hydrofluoric acid as a hydrofluoric acid treatment.

フッ酸水溶液として、ＨＦ濃度が１～１０％及びＮＨ4Ｆ濃度が３．３～３３％のＮＨ4ＦとＨＦとの混合物であるバッファードフッ酸を用いた。室温のバッファードフッ酸中にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を１０分間浸漬し、取り出して乾燥した。 As the aqueous hydrofluoric acid solution, buffered hydrofluoric acid, which is a mixture of NH 4 F and HF having an HF concentration of 1 to 10% and an NH 4 F concentration of 3.3 to 33%, was used. A Si-containing Fe-based alloy powder having a SiO 2 -containing film was immersed in buffered hydrofluoric acid at room temperature for 10 minutes, taken out, and dried.

図４３～４６に、フッ酸処理前のＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の断面、並びにＨＦ濃度が１％及びＮＨ4Ｆ濃度が３．３％のバッファードフッ酸、ＨＦ濃度が５％及びＮＨ4Ｆ濃度が１６．５％のバッファードフッ酸、及びＨＦ濃度が１０％及びＮＨ4Ｆ濃度が３３％のバッファードフッ酸を用いてフッ酸処理を行ったＳｉ含有Ｆｅ基合金粉の断面の走査型電子顕微鏡写真を示す。 FIGS. 43-46 show the cross section of the Si-containing Fe-based alloy powder having the SiO 2 -containing film before the hydrofluoric acid treatment, and the buffered hydrofluoric acid and HF having an HF concentration of 1% and an NH 4F concentration of 3.3%. Si-containing hydrofluoric acid treated with buffered hydrofluoric acid having a concentration of 5% and NH 4 F concentration of 16.5%, and buffered hydrofluoric acid having an HF concentration of 10% and an NH 4 F concentration of 33%. A scanning electron micrograph of a cross section of Fe-based alloy powder is shown.

図４７に、準備したＳｉ含有Ｆｅ基合金粉、フッ酸処理前のＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉、並びにＨＦ濃度が１％及びＮＨ4Ｆ濃度が３．３％のバッファードフッ酸、ＨＦ濃度が５％及びＮＨ4Ｆ濃度が１６．５％のバッファードフッ酸、及びＨＦ濃度が１０％及びＮＨ4Ｆ濃度が３３％のバッファードフッ酸を用いてフッ酸処理を行ったＳｉ含有Ｆｅ基合金粉のエネルギー分散型Ｘ線分析（ＥＤＳ）プロファイルを示す。図４４～４７から、フッ酸処理を行うことにより、ＳｉＯ2含有被膜が除去されることが分かる。 FIG. 47 shows the prepared Si-containing Fe-based alloy powder, the Si-containing Fe-based alloy powder having a SiO 2 -containing film before hydrofluoric acid treatment, and a buffer having an HF concentration of 1% and an NH 4F concentration of 3.3%. Hydrofluoric acid treatment with hydrofluoric acid, buffered hydrofluoric acid with 5 % HF and 16.5% NH 4F, and buffered hydrofluoric acid with 10 % HF and 33% NH 4F. The energy-dispersed X-ray analysis (EDS) profile of the Si-containing Fe-based alloy powder obtained in the above-mentioned method is shown. From FIGS. 44 to 47, it can be seen that the SiO 2 -containing film is removed by performing the hydrofluoric acid treatment.

１０ 準備したＳｉ含有Ｆｅ基合金粉
１２ リン酸処理を行ったＳｉ含有Ｆｅ基合金粉
２０ Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜
２２ 塩酸処理を行ったＦｅ－Ｏ－Ｓｉ－Ｐ系被膜
３０ ＳｉＯ2含有被膜 10 Prepared Si-containing Fe-based alloy powder 12 Phosphate-treated Si-containing Fe-based alloy powder 20 Fe-O-Si-P-based coating 22 Hydrochloric acid-treated Fe-O-Si-P-based coating 30 SiO 2 Containing film

Claims (18)

Ｓｉ含有Ｆｅ基合金粉を準備すること、
前記Ｓｉ含有Ｆｅ基合金粉をリン酸水溶液に浸漬し、前記リン酸水溶液から取り出して乾燥して、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金粉を得ること、及び
前記Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えたＳｉ含有Ｆｅ基合金粉を塩酸水溶液に浸漬し、前記塩酸水溶液から取り出して乾燥して、表面にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉を得ること、
を含む、ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の製造方法。 Preparing Si-containing Fe-based alloy powder,
The Si-containing Fe-based alloy powder is immersed in a phosphoric acid aqueous solution, taken out from the phosphoric acid aqueous solution and dried to obtain a Si-containing Fe-based alloy powder having a Fe—O—Si—P-based coating, and the above. A Si-containing Fe-based alloy powder having a Fe—O—Si—P-based coating is immersed in an aqueous hydrochloric acid solution, taken out from the aqueous hydrochloric acid solution and dried, and the Si-containing Fe-based alloy powder having a SiO 2 -containing coating on the surface is removed. To get,
A method for producing a Si-containing Fe-based alloy powder having a SiO 2 -containing coating. 前記ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉が、前記Ｓｉ含有Ｆｅ基合金粉の本体と前記ＳｉＯ2含有被膜との間に、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を有する、請求項１に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 The claim that the Si-containing Fe-based alloy powder provided with the SiO 2 -containing coating has an Fe—O—Si—P-based coating between the main body of the Si-containing Fe-based alloy powder and the SiO 2 -containing coating. The method for producing a Si-containing Fe-based alloy powder according to 1. 前記ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉は、前記ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の全質量を基準にして、３．０～１８．０ｗｔ％のＳｉを含む、請求項１または２に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 The Si-containing Fe-based alloy powder having the SiO 2 -containing coating contains 3.0 to 18.0 wt% of Si based on the total mass of the Si-containing Fe-based alloy powder having the SiO 2 -containing coating. The method for producing a Si-containing Fe-based alloy powder according to claim 1 or 2. 前記Ｓｉ含有Ｆｅ基合金は、多結晶合金、アモルファス合金、または金属ガラスである、請求項１～３のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 The method for producing a Si-containing Fe-based alloy powder according to any one of claims 1 to 3, wherein the Si-containing Fe-based alloy is a polycrystalline alloy, an amorphous alloy, or a metallic glass. 前記Ｓｉ含有Ｆｅ基合金は、アモルファス合金粉または金属ガラス粉である、請求項１～４のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 The method for producing a Si-containing Fe-based alloy powder according to any one of claims 1 to 4, wherein the Si-containing Fe-based alloy is an amorphous alloy powder or a metallic glass powder. 前記リン酸水溶液は０．００００１～１０．００ｗｔ％の濃度を有する、請求項１～５のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 The method for producing a Si-containing Fe-based alloy powder according to any one of claims 1 to 5, wherein the phosphoric acid aqueous solution has a concentration of 0.00001 to 10.00 wt%. 前記塩酸水溶液は０．５０～１０．００ｗｔ％の濃度を有する、請求項１～６のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 The method for producing a Si-containing Fe-based alloy powder according to any one of claims 1 to 6, wherein the aqueous hydrochloric acid solution has a concentration of 0.50 to 10.00 wt%. （Ａ）前記ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉をフッ酸処理して前記ＳｉＯ2含有被膜を取り除き、前記準備したＳｉ含有Ｆｅ基合金粉よりも寸法が小さい第２のＳｉ含有Ｆｅ基合金粉を得ること、
（Ｂ）前記第２のＳｉ含有Ｆｅ基合金粉を、リン酸水溶液に浸漬し、前記リン酸水溶液から取り出して乾燥して、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えた第２のＳｉ含有Ｆｅ基合金粉を得ること、及び
（Ｃ）前記Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えた第２のＳｉ含有Ｆｅ基合金粉を塩酸水溶液に浸漬し、前記塩酸水溶液から取り出して乾燥して、表面にＳｉＯ2含有被膜を備えた第２のＳｉ含有Ｆｅ基合金粉を得ること、
を含む、請求項１～７のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 (A) The Si-containing Fe-based alloy powder having the SiO 2 -containing film is treated with hydrofluoric acid to remove the SiO 2 -containing film, and the second Si-containing powder having a smaller size than the prepared Si-containing Fe-based alloy powder is contained. Obtaining Fe-based alloy powder,
(B) The second Si-containing Fe-based alloy powder is immersed in a phosphoric acid aqueous solution, taken out from the phosphoric acid aqueous solution and dried to contain a second Si-containing film having an Fe—O—Si—P-based coating film. The Fe-based alloy powder is obtained, and (C) the second Si-containing Fe-based alloy powder having the Fe—O—Si—P-based coating is immersed in a hydrochloric acid aqueous solution, taken out from the hydrochloric acid aqueous solution, and dried. To obtain a second Si-containing Fe-based alloy powder having a SiO 2 -containing film on the surface,
The method for producing a Si-containing Fe-based alloy powder according to any one of claims 1 to 7, which comprises. 前記フッ酸処理、リン酸水溶液への浸漬及び乾燥、及び塩酸水溶液への浸漬及び乾燥をさらに繰り返すことを含む、請求項８に記載のＳｉ含有Ｆｅ基合金粉の製造方法。 The method for producing a Si-containing Fe-based alloy powder according to claim 8, further comprising repeating the hydrofluoric acid treatment, immersion and drying in a phosphoric acid aqueous solution, and immersion and drying in a hydrochloric acid aqueous solution. 請求項１～７のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉の製造方法で得られたＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉をフッ酸処理して前記ＳｉＯ2含有被膜を取り除き、前記準備したＳｉ含有Ｆｅ基合金粉よりも粒子の寸法が小さい第２のＳｉ含有Ｆｅ基合金粉を得ることを含む、Ｓｉ含有Ｆｅ基合金粉の製造方法。 The Si-containing Fe-based alloy powder provided with the SiO 2 -containing film obtained by the method for producing the Si-containing Fe-based alloy powder according to any one of claims 1 to 7 is treated with hydrofluoric acid to treat the SiO 2 -containing film. A method for producing a Si-containing Fe-based alloy powder, which comprises removing the above-mentioned material to obtain a second Si-containing Fe-based alloy powder having a particle size smaller than that of the prepared Si-containing Fe-based alloy powder. 請求項１０に記載の製造方法で得られた第２のＳｉ含有Ｆｅ基合金粉を、リン酸水溶液に浸漬し、前記リン酸水溶液から取り出して乾燥して、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えた第３のＳｉ含有Ｆｅ基合金粉を得ること、
前記Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を備えた第３のＳｉ含有Ｆｅ基合金粉を塩酸水溶液に浸漬し、前記塩酸水溶液から取り出して乾燥して、表面にＳｉＯ2含有被膜を備えた第３のＳｉ含有Ｆｅ基合金粉を得ること、及び
前記第３のＳｉ含有Ｆｅ基合金粉をフッ酸処理して前記ＳｉＯ2含有被膜を取り除き、前記第２のＳｉ含有Ｆｅ基合金粉よりも粒子の寸法が小さい第３のＳｉ含有Ｆｅ基合金粉を得ることを含む、Ｓｉ含有Ｆｅ基合金粉の製造方法。 The second Si-containing Fe-based alloy powder obtained by the production method according to claim 10 is immersed in a phosphoric acid aqueous solution, taken out from the phosphoric acid aqueous solution and dried to obtain an Fe—O—Si—P-based coating film. To obtain a third Si-containing Fe-based alloy powder comprising
The third Si-containing Fe-based alloy powder having the Fe—O—Si—P-based coating was immersed in a hydrochloric acid aqueous solution, taken out from the hydrochloric acid aqueous solution and dried, and the surface was provided with a SiO 2 containing coating. Si-containing Fe-based alloy powder is obtained, and the third Si-containing Fe-based alloy powder is treated with hydrofluoric acid to remove the SiO 2 -containing film, and the particles are more particles than the second Si-containing Fe-based alloy powder. A method for producing a Si-containing Fe-based alloy powder, which comprises obtaining a third Si-containing Fe-based alloy powder having a small size. 表面にＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粒子からなるＳｉ含有Ｆｅ基合金粉。 Si-containing Fe-based alloy powder composed of Si-containing Fe-based alloy particles having a SiO 2 -containing film on the surface. 前記Ｓｉ含有Ｆｅ基合金粒子が、前記Ｓｉ含有Ｆｅ基合金粒子と前記ＳｉＯ2含有被膜との間に、Ｆｅ－Ｏ－Ｓｉ－Ｐ系被膜を有する、請求項１２に記載のＳｉ含有Ｆｅ基合金粉。 The Si-containing Fe-based alloy according to claim 12, wherein the Si-containing Fe-based alloy particles have a Fe—O—Si—P-based film between the Si-containing Fe-based alloy particles and the SiO 2 -containing film. powder. 前記Ｓｉ含有Ｆｅ基合金粒子は、前記ＳｉＯ2含有被膜を備えたＳｉ含有Ｆｅ基合金粉の全質量を基準にして３．０～１８．０ｗｔ％のＳｉを含む、請求項１２または１３に記載のＳｉ含有Ｆｅ基合金粉。 The Si-containing Fe-based alloy particles according to claim 12 or 13, wherein the Si-containing Fe-based alloy particles contain 3.0 to 18.0 wt% of Si based on the total mass of the Si-containing Fe-based alloy powder having the SiO 2 -containing coating. Si-containing Fe-based alloy powder. 前記Ｓｉ含有Ｆｅ基合金は、多結晶合金、アモルファス合金、または金属ガラスである、請求項１２～１４のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉。 The Si-containing Fe-based alloy powder according to any one of claims 12 to 14, wherein the Si-containing Fe-based alloy is a polycrystalline alloy, an amorphous alloy, or a metallic glass. 前記Ｓｉ含有Ｆｅ基合金は、アモルファス合金または金属ガラスである、請求項１２～１５のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉。 The Si-containing Fe-based alloy powder according to any one of claims 12 to 15, wherein the Si-containing Fe-based alloy is an amorphous alloy or a metallic glass. 請求項１２～１６のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉を含むコンポジット磁性材料。 A composite magnetic material containing the Si-containing Fe-based alloy powder according to any one of claims 12 to 16. 請求項１２～１６のいずれか一項に記載のＳｉ含有Ｆｅ基合金粉を含むコンポジット磁性材料コア。 A composite magnetic material core containing the Si-containing Fe-based alloy powder according to any one of claims 12 to 16.
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