JP3655321B2

JP3655321B2 - Method for producing Fe-based soft magnetic alloy powder

Info

Publication number: JP3655321B2
Application number: JP13919592A
Authority: JP
Inventors: 準斉藤; 弘幸小松; 洋渡辺
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 1992-05-29
Filing date: 1992-05-29
Publication date: 2005-06-02
Anticipated expiration: 2020-06-02
Also published as: JPH05335129A

Description

【０００１】
【産業上の利用分野】
本発明は、特に良好な軟磁気特性を有するＦｅ基軟磁性合金粉末およびその製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来から、軟磁気特性に優れた合金粉末としては、Ｆｅ−Ｎｉ合金粉末、Ｆｅ−Ｓｉ−Ａｌ合金粉末、Ｆｅ−Ｓｉ合金粉末が知られており、これら粉末を用いた圧粉磁心が使用されている。また最近ではＦｅ系やＣｏ系の非晶質合金粉末も作製されており、これについても、圧粉磁心やシールド材等の応用が検討されている。
【０００３】
しかしながら、Ｆｅ−Ｎｉ合金粉末は軟磁気特性には優れるものの飽和磁束密度が低い問題点があり、Ｆｅ−Ｓｉ−Ａｌ合金粉末、Ｆｅ−Ｓｉ合金粉末については飽和磁束密度はＦｅ−Ｎｉ合金粉末よりは高いものの、軟磁気特性は十分ではない。Ｆｅ系非晶質合金粉末は飽和磁束密度は高いが磁歪が大きいため、軟磁気特性は良好ではない。Ｃｏ系非晶質合金粉末は磁歪が小さいため軟磁気特性はＦｅ系と比較して良好であるが、飽和磁束密度が低く高価であるという問題点がある。
【０００４】
これに対し、近年液体急冷法によって作成されたＦｅ基非晶質合金を熱処理してその金属組織を１００オングストローム程度の微結晶とすることにより、従来のＦｅ基非晶質合金より優れた軟磁気特性が得られることが報告された（特開昭６４−７９３４２号公報、特開平１−１５６４５２号公報、Ｕ.Ｓ.Ｐ.4,881,989等）。このＦｅ基軟磁性合金は、ＦｅＳｉＢを基準組成とし、これにＣｕとＮｂ等の高融点金属等を加えたもので組織が１００オングストローム程度の微結晶よりなり、飽和磁歪が小さくなっているため、軟磁気特性が改善されている。この合金より作製した粉末も、良好な軟磁気特性を示す（特開昭６４−２８３０１号公報）。しかしながら、Ｃｕを添加した場合には、Ｃｕ同士が寄り集って組成ずれを引き起こす可能性がある。
【０００５】
本願発明は、このような従来の軟磁性合金粉末に代わる粉末軟磁性材料であって、しかも飽和磁歪が極めて小さく、軟磁気特性に優れ、かつ十分な飽和磁束密度をもつ新規なＦｅ基軟磁性合金粉末を提供することを目的とする。
更に、本発明は比較的低融点の金属メタロイド系合金であって、従来の超急冷装置および粉末製造装置等を利用して製造することのできるＦｅ基軟磁性合金粉末を提供することを目的とする。
【０００６】
【課題を解決するための手段】
このような目的を達成するため本発明者は、Ｆｅ基軟磁性合金について鋭意研究の結果、Ｆｅ−Ｓｉ−Ｂ系Ｆｅ基軟磁性合金にＡｌを添加した場合、優れた軟磁気特性を示し、例えば極めて飽和磁歪が低いこと、またこのようなＦｅ−Ｓｉ−Ｂ−Ａｌ系Ｆｅ基軟磁性合金に下記Ｍ'で示される他の特定の元素（金属）、特にＮｂを添加した場合に極めて優れた軟磁気特性を示すことを見い出し、かつこの合金粉末を製造する方法を見い出し、本発明に至ったものである。
【０００７】
即ち、本発明のＦｅ基軟磁性合金粉末は、一般式（Ｆｅ_1-XＭ_{X)100-a-b-c-d}Ｓｉ_aＡｌ_bＢ_cＭ'_d（式中、ＭはＣｏ及び／又はＮｉ、Ｍ'はＮｂ、Ｍｏ、Ｚｒ、Ｗ、Ｔａ、Ｈｆ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｙ、Ｐｄ、Ｒｕ、Ｇａ、Ｇｅ、Ｃ、Ｐから選ばれる１種類以上の元素を表わす。ｘは原子比を、ａ、ｂ、ｃ、ｄは原子％を示し、それぞれ０≦ｘ≦０.１５、０≦ａ≦２４、２＜ｂ≦１５、４≦ｃ≦２０、０≦ｄ≦１０を満たすものとする）により表わされるものであり、特にその組織の少なくとも３０％以上が結晶質（微細な結晶粒）で生成されていることが好ましく、更に結晶質は鉄を主体としたｂｃｃ固溶体から成るものである。また、Ｍ'としてはＮｂが好適である。
【０００８】
本発明のＦｅ基軟磁性合金粉末において磁性特性の面から銅（Ｃｕ）は０．５原子％以下、好適には０．１原子％以下であり、最も好ましくはＣｕが全く混入しないほうがよい。
本発明のＦｅ基軟磁性合金粉末において、Ｆｅは原子比ｘが０から０．１５の範囲でＣｏ及び／又はＮｉで置換することができる。Ｃｏ及びＮｉは、Ｆｅと負の相互作用パラメータを示すので、本発明のＦｅ基合金粉末を熱処理する際に生成するＦｅを主体としたｂｃｃ固溶体に固溶し、ｂｃｃ構造格子に置換されるものと考えられる。これにより、ｂｃｃ固溶体が持つ、磁歪定数、結晶磁気異方性定数を低減できると考えられる。本発明の合金粉末においてｘが０≦ｘ＜０．０２、特にｘ＝０、即ちＮｉ（及び／又はＣｏ）を全く含まない場合には高透磁率が得られるため、高透磁率が要求される用途、電磁シールド等の用途（の磁心材料）に好適である。
【０００９】
一方、Ｎｉ（及び又はＣｏ）の含有量ｘが０．０２≦ｘ≦０．１５を満たすときは、高透磁率が得られるだけでなく上述した磁歪定数、結晶磁気異方性定数の低減という効果及び磁場熱処理により誘導異方性の付与が大きいという効果が得られる。なお、Ｎｉ（及び又はＣｏ）の含有量ｘは好ましくは０．０２≦ｘ≦０．１５、更に好ましくは０．０３≦ｘ≦０．１である。
【００１０】
Ａｌは本発明の合金の必須元素であり、Ａｌを特定量（２原子％を超え１５原子％以下）添加することにより、結晶磁気異方性の小さい軟磁性を示す結晶（Ｆｅ基ｂｃｃ固溶体）の結晶化温度（ＴX₁）と軟磁性を阻害する結晶（例えばＦｅ−Ｂ系結晶）の結晶化温度（ＴX₂）との温度差（△Ｔ）を大きくすることができ、熱処理時のＦｅ−Ｂ系結晶等の生成を抑制すると共に、比較的低い温度の熱処理で軟磁気特性を導出することができる。図１にＦｅＳｉＢ系合金粉末にＡｌを添加した場合の結晶化温度とＡｌ量（原子％）との関係を示した。図１より、Ａｌ量を増加するとＴX₁は単調に減少するが、一方ＴX₂はほぼ一定値をとり、ＴX₁とＴX₂との温度差（△Ｔ）が増加することがわかる。
【００１１】
本発明においてＡｌの含有量ｂは、２原子％を超え１５原子％以下、好ましくは２．５〜１５原子％、更に好ましくは３〜１２原子％である。３〜１２原子％の範囲において、特に透磁率が高く、鉄損の小さい合金粉末を得ることができる。なお、本発明の合金粉末においてｘが０≦ｘ＜０．０２、特にｘ＝０の場合には、Ａｌの含有量ｂは好ましくは６〜１２原子％、更に好ましくは６〜１０原子％、最も好ましくは７〜１０原子％とする。
【００１２】
ＡｌはＮｉ（Ｃｏ）と同様にＦｅとの相互パラメータが負であるため、Ａｌを添加することによりＦｅを主体とした固溶体中に固溶され、即ちα−Ｆｅ結晶構造のＦｅ原子の位置に置換される形で固溶されｂｃｃ結晶を安定化するため、熱処置に結晶化されやすい環境を作るものと推定される。従って、上述のようにＡｌ添加によって結晶磁気異方性の小さい結晶粒が選択的に作成されるので、これによって優れた軟磁気特性が発現すると思われる。
【００１３】
Ｓｉ、Ｂは本発明のＦｅ基軟磁性合金を初期状態（熱処理前）で非晶質化させる元素である。Ｓｉの含有量ａは０〜２４原子％、好ましくは６〜１８原子％、更に好ましくは１０〜１６原子％である。Ｓｉの含有量をこの範囲とすることにより、初期状態（熱処理前）における非晶質形成能を高めることができるので好ましい。
【００１４】
Ｂの含有量ｃは４〜２０原子％、好ましくは６〜１５原子％、更に好ましくは１０〜１４原子％である。この範囲であれば充分な結晶化温度の温度差が得られ、かつ非晶質化させやすいので好ましい。なお、Ｂの含有量９原子％を境にしてアモルファス形成能が異なり、Ｂが９．５〜１５原子％、特に１０〜１４原子％の範囲ではＡｌを入れた場合の上記組成のアモルファス合金のアモルファス形成能に優れ、熱処理後均一な結晶粒が得られる。
【００１５】
本発明のＦｅ基軟磁性合金の基本的組成は上述のＦｅ（Ｍ）、Ｂ、Ｓｉ、Ａｌであるが、更に耐食性、磁気特性を向上させるために他の元素Ｍ'を加えることができる。Ｍ'としては、Ｎｂ、Ｍｏ、Ｚｒ、Ｗ、Ｔａ、Ｈｆ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｙ、Ｐｄ、Ｒｕ、Ｇａ、Ｇｅ、Ｃ、Ｐから選ばれる１種以上が挙げられる。さらにＭ'の添加は、基本組成のＦｅ−Ｓｉ−Ａｌ−Ｂ合金の非晶質形成能を向上させる働きがある。
【００１６】
Ｎｂ、Ｗ、Ｔａ、Ｚｒ、Ｈｆ及びＭｏは特に軟磁気特性を阻害するＦｅ−Ｂ系結晶の析出を抑制し、又はＦｅ−Ｂ系結晶の析出温度を高い温度に移動させる効果があり、合金粉末の軟磁気特性を改善する。また上記元素（金属）の添加は結晶粒の微細化に寄与する。Ｖ、Ｃｒ、Ｍｎ、Ｙ及びＲｕは特に合金の耐腐食性を改善するのに効果的である。Ｃ、Ｇｅ、Ｐ及びＧａは特にアモルファスを形成するのに効果がある。上記元素の１以上を添加することができる。これら元素のうち特にＮｂ、Ｔａ、Ｗ、Ｍｎ、Ｍｏ、Ｖが好ましい。このうち、Ｎｂを加えた場合には軟磁気特性、特に抗磁力、透磁率、鉄損が著しく改善される。これらの元素の添加量ｄは、１〜１０原子％、好ましくは１〜８原子％、更に好ましくは１〜６原子％である。この範囲とすることにより、非晶質形成能および磁気特性が劣化することを防止することができる。
【００１７】
また、本発明においてはＮ、Ｓ、Ｏなどの不可避的不純物を、目的とする特性が劣化しない程度に含有している合金も本発明に含むものである。
本発明のＦｅ基軟磁性合金粉末は組織全体の少なくとも３０％以上（３０％〜１００％）が結晶質（微細な結晶粒）から成り、合金組成の結晶粒以外の部分は主に非晶質である。本発明では、結晶粒の割合が上記範囲にあるとき優れた（軟）磁気特性を示す。なお、本発明では微細結晶粒の割合が実質的に１００％であっても優れた（軟）磁気特性を示す。本発明のＦｅ基軟磁性合金粉末においては磁気特性の面から、組織全体の少なくとも６０％以上が微細な結晶粒から成ることが特に好ましく、８０％以上が微細な結晶粒から成ることが最も好ましい。
【００１８】
また本発明の合金粉末の結晶粒はｂｃｃ構造を有しており、Ｆｅを主体としてＳｉ、Ｂ、Ａｌ（場合により更にＮｉ及び／又はＣｏ）が固溶していると考えられる。この結晶粒は１０００オングストローム以下、好ましくは５００オングストローム以下、更に好ましくは５０〜３００オングストロームの平均粒径を有している。本発明では平均粒径が１０００オングストローム以下であることにより、優れた磁気特性が得られるものである。
【００１９】
なお、本発明において結晶粒の全体に占める割合は、実験的にＸ線回折法等により評価することができる。即ち、完全に結晶化した状態（Ｘ線回折強度が飽和した状態）のＸ線回折強度を基準とし、これに対する測定すべき磁性合金材料のＸ線回折強度の割合をもって実験的に評価することができる。また、結晶化に伴い小受るＸ線回折線のＸ線回折強度と、結晶化に伴い減少する非晶質特有のハローによるＸ線回折強度との比から評価することもできる。また、本発明において平均粒径はＸ線回折図形のｂｃｃピーク反射（１１０）を用い、シェラーの式（ｔ＝０．９λ／βｃｏｓθ）によって導出したものである（カリティ著、新版Ｘ線回折要論（Element of X-ray Diffraction (Second Edition）、B.D. Cullity）、９１〜９４頁)。
【００２０】
本発明のＦｅ基軟磁性合金粉末は通常、以下の方法によって製造することができる。
【００２１】
第一の方法は前記組成の合金溶湯を超急冷し非晶質合金粉末を製造する工程と、これを加熱し組織の少なくとも３０％以上を結晶質とする熱処理工程からなる製造方法である。非晶質合金粉末の製造方法としては、水アトマイズ法やガスアトマイズ法、スプレー法、キャビテーション法、スパークエロージョン法、回転液中射出法等がある。非晶質合金粉末は完全な非晶質状態が望ましいが結晶質を含んでいてもよい。熱処理は組織の少なくとも３０％以上を結晶質とする目的で行なわれ、結晶化温度より高い温度に加熱される。
【００２２】
第二の方法は前記組成の合金溶湯を超急冷し非晶質合金薄帯あるいは非晶質合金フレークあるいは非晶質合金線等の非晶質合金を得る工程と、この非晶質合金をその結晶化温度より低い温度で脆化させるのに十分な時間加熱し、脆化した非晶質合金を粉砕する工程と、脆化した非晶質合金粉末をその結晶化温度より高い温度に加熱し、組織の少なくとも３０％以上を結晶質とする熱処理工程からなる製造方法である。非晶質合金薄帯、非晶質合金フレークあるいは非晶質合金線を得る方法として、単ロール法、双ロール法、遠心急冷法、回転液中紡糸法等がある。
【００２３】
第三の方法は前記組成の合金溶湯を超急冷し非晶質合金薄帯あるいは非晶質合金フレークあるいは非晶質合金線等の非晶質合金を得る工程と、この非晶質合金をその結晶化温度より低い温度で脆化させるのに十分な時間水素を導入し、次いでこの脆化した非晶質合金を粉砕する工程と、このようにして得た非晶質合金粉末をその結晶化温度より高い温度に加熱し、組織の少なくとも３０％以上を結晶質とする熱処理工程からなる製造方法である。水素を導入する方法として加圧下で非晶質合金を水素雰囲気にさらすことや、あるいは水素製造電解浴におけるカソードとして用いることにより電解的に導入する方法がある。
【００２４】
第四の方法は前記組成の合金溶湯を超急冷し非晶質合金薄帯あるいは非晶質合金フレークあるいは非晶質合金線等の非晶質合金を得る工程と、この非晶質合金をその結晶化温度より高い温度に加熱し、組織の少なくとも３０％以上を結晶質とする熱処理工程と、得られた合金を粉砕する工程からなる製造方法である。結晶化温度より高い温度に加熱した合金は脆化し、容易にボールミル、振動ミル等により粉砕できる。
【００２５】
本発明の合金粉末は前記組成の非晶質合金を結晶化温度以上に加熱して熱処理し、少なくとも一部、好ましくは試料全体の３０％以上を結晶化することにより得られる。このための熱処理は真空中あるいはアルゴンガスもしくは窒素ガスなど不活性ガス、Ｈ２等の還元性ガスもしくは空気等の酸化性ガス雰囲気中で行なう。熱処理温度は約２００〜８００℃程度、好ましくは４００〜７００℃程度、更に好ましくは５２０〜６８０℃程度とする。熱処理時間は０．１〜１０時間程度、好ましくは１〜５時間程度とすることが好ましい。また、熱処理は無磁場中でも、また磁場を印加して行なってもよい。本発明では上記の温度範囲で且つ上記範囲の熱処理時間で上記組成の非晶質合金を熱処理することにより本発明の特性に優れた軟磁性合金粉末を得ることができる。
【００２６】
以下、実施例を挙げて更に説明する。
【００２７】
【実施例】
実施例１〜９
単ロール法を用いて、Ｆｅ、Ｓｉ、Ａｌ、Ｂ、（Ｎｂ）を含有する溶湯からアルゴンガス１気圧雰囲気中で幅１．０〜５mm程度、板厚約１４〜２０μｍの急冷薄帯を作成し、得られた薄帯を結晶化温度以下において窒素ガスの存在下で、約１時間熱処理した。熱処理された非晶質薄帯をボールミルを用いて粉砕し粉末とした後、さらに結晶化温度以上で同様に窒素ガスの存在下で、約１時間熱処理した。
【００２８】
表１に上記の方法でＦｅ、Ｓｉ、Ａｌ、Ｂ、Ｎｂの組成を変えて作成した合金粉末について、抗磁力Ｈｃ（mOe）および飽和磁化Ｍｓ（emu/g）を示した。磁化測定は振動試料型磁力計を用いて最大印加磁場１８kOeの範囲で行なった。なお組成はＩＣＰ分析によって決定した。
【００２９】
また比較例としてＦｅ₇₈Ｓｉ₉Ｂ₁₃合金粉末（比較例１、市販品）及びＦｅＣｕＳｉＢＮｂ合金粉末（比較例２、特開昭６４−２８３０１号公報に記載されるＣｕ含有するＦｅ基軟磁性合金粉末）の抗磁力、飽和磁化、を併せて表１に示した。
【００３０】
【表１】

【００３１】
表１からも明らかなように、抗磁力についてはＭ’としてＮｂを含有する実施例７ではＦｅＳｉＢ系に比べかなり低い値を示した。この値は、比較例２の抗磁力（１８ mOe）とほぼ同等の値を示している。また実施例３、４では、飽和磁化を除いてＦｅＳｉＢ系アモルファス合金と同等あるいはそれ以上の磁気特性を示した。
【００３２】
図２は上記の方法で得たＦｅＳｉＡｌＢ合金粉末の抗磁力Ｈｃの組成依存性を示す図であるが、線で囲んだ組成範囲において、抗磁力１００ mOe 以下の良好な軟磁気特性を示した。又、図３は、ＦｅＳｉＡｌＢ合金粉末の飽和磁化Ｍｓの組成依存性を示す図であるが、抗磁力Ｈｃが１００ mOe 以下の組成範囲内で高い飽和磁化１６５ emu/g を示す試料（Ｆｅ₇₃Ｓｉ₈Ａｌ₁₀Ｂ₉）が得られた。
【００３３】
このうち、抗磁力が従来のＦｅＳｉＢ系非晶質合金（比較例１）より小さい実施例４（Ｆｅ₆₉Ａｌ₈Ｓｉ₁₄Ｂ₉）及び実施例７（Ｆｅ₆₈Ａｌ₈Ｓｉ₁₄Ｂ₉Ｎｂ₁）について、結晶定数ａ（オングストローム）、結晶粒径Ｄ（オングストローム）、第１結晶化温度ＴX₁（℃）及び第２結晶化温度ＴX₂（℃）を測定した。その結果を表２に示す。
【００３４】
【表２】

【００３５】
表２の数値は実施例４及び実施例７のΔＴ値は比較例２に比べ有意に大きいことを示している。また表２からも明らかなように、本発明合金粉末は、熱処理により結晶化することで鉄を主体とした３００オングストローム程度のｂｃｃ固溶体の結晶粒が形成されていることが確認された。
また第１結晶化温度ＴX₁はこれらのＦｅ基軟磁性合金粉末が従来の熱処理装置を利用して製造可能な温度であり、更に第２結晶化温度ＴX₂との差も実施例４で９５℃、実施例７で１２５℃、「比較例２で３０℃」であり、熱処理温度を適当に選ぶことにより軟磁性を阻害する結晶の生成を充分抑制できることが示された。
【００３６】
抗磁力において特に優れた特性を示す実施例９の合金（Fe₆₆Si₁₄Al₈Nb₃B₉）について更に詳細な検討を行なった結果について、以下説明する。
まず片ロール法によって幅２．８mm、厚１７μｍの薄帯を製造し、液体急冷後、４５０℃で窒素ガス雰囲気中で１時間熱処理した後、ボールミルを用いて粉砕した粉末、およびこの粉末を５８０℃で窒素ガス雰囲気中で１時間熱処理した後のＸ線回折像を得た。これらＸ線回折図形を図４に示す。図中、（ａ）は４５０℃で熱処理した後、ボールミルを用いて粉砕した粉末の場合で、非晶質合金に典型的なハローパターンが見られる。また（ｂ）は５８０℃で熱処理後の場合で、典型的なｂｃｃ結晶の回折ピークを示しており、低角度領域にはＤＯ３構造の規則格子反射を示すピークが認められる。
【００３７】
同じく実施例９の合金（Fe₆₆Si₁₄Al₈Nb₃B₉）粉末の抗磁力Ｈｃ（mOe）の熱処理温度依存性を図５に示した。図から明らかなように抗磁力Ｈｃは５８０℃で１２mOeの最小値をとった後、熱処理温度の上昇とともに増加する。
【００３８】
同じく実施例９の合金粉末のｂｃｃ結晶の（１１０）回折強度ピークの半値幅からシェラーの式を用いて導出した結晶粒径Ｄ１１０（オングストローム）及びｂｃｃ結晶の（１１０）回折ピークから求めた格子定数ａ（オングストローム）の熱処理温度依存性を図６に示した。図６から明らかなように、結晶粒径は熱処理温度の上昇によらずほぼ１４０オングストローム程度となった。一方、格子定数は熱処理温度の上昇に伴い、徐々に減少することがわかった。
【００３９】
実施例１０〜２５
単ロール法を用いて、Ｆｅ、Ｓｉ、Ａｌ、Ｂ、Ｎｂを含有する溶湯からアルゴンガス１気圧雰囲気中で幅１．３mm、厚さ１８μｍの非晶質薄帯を作成し、得られた薄帯を結晶化温度以下において窒素ガスの存在下で、約１時間熱処理した。熱処理した薄帯をボールミルを用いて粉砕し粉末とした後、さらに結晶化温度以上で同様に窒素ガスの存在下で、約１時間熱処理した。得られた粉末の抗磁力Ｈｃ（mOe）の結果を表３に示す。
【００４０】
【表３】

【００４１】
表３からも明らかなように、Ｎｉを含まない実施例１０〜２５の合金粉末は５０mOe以下の小さい抗磁力を示した。
実施例２６〜４５比較例３
【００４２】
【表４】

【００４３】
表４からも明らかなようにＢの含有量が９原子％を超えた合金粉末は、抗磁力が小さくなった。
表４からもわかるようにＭ’としてＮｂ以外の元素を用いた非晶質合金（実施例２５〜４５）においても、またＮｂとそれ以外の元素を併用した場合にもいずれも優れた磁気特性を示した。
【００４４】
【発明の効果】
以上の実施例からも明らかなように、本発明のＦｅ基軟磁性合金粉末によれば、Ｆｅ−Ｓｉ−Ｂ系合金にＡｌを添加することにより、軟磁性特性の優れた新規なＦｅ基軟磁性合金粉末を得ることができる。また本発明のＦｅ基軟磁性合金粉末は良好な軟磁性を示す結晶の結晶化温度と軟磁性を阻害する結晶の結晶化温度との温度差が大きいので、従来の非晶質合金粉末の熱処理温度範囲に比べて充分大きな熱処理温度範囲が得られる。
【００４５】
また本発明のＦｅ基軟磁性合金粉末によれば、Ａｌを加えるとともにＦｅの一部をＮｉ（Ｃｏ）で置換することにより、良好な軟磁気特性を得ることができる。
更に本発明によれば、Ｆｅ−Ｓｉ−Ａｌ−Ｂ系合金粉末にＮｂ等の元素を添加することにより、優れた軟磁性特性、特に極めて低抗磁力を有する新規なＦｅ基軟磁性合金粉末を得ることができる。
【００４６】
本発明の合金粉末は上記のように優れた軟磁性特性を有するため、例えば圧粉磁心、シールド材等の用途（の磁心材料）に好適に用いられる。
【図面の簡単な説明】
【図１】Ｆｅ基軟磁性合金粉末の結晶化温度とＡｌ量との関係を示す図。
【図２】Ｆｅ基軟磁性合金粉末の抗磁力（Ｈｃ）と組成との相関を示す図。
【図３】Ｆｅ基軟磁性合金粉末の飽和磁気（Ｍｓ）と組成との相関を示す図。
【図４】本発明によるＦｅ基軟磁性合金の非晶質合金粉末及び結晶合金粉末の各Ｘ線回折図形を示す図。
【図５】本発明によるＦｅ基軟磁性合金粉末の抗磁力の温度依存性を示す図。
【図６】本発明によるＦｅ基軟磁性合金粉末のｂｃｃ結晶の結晶粒径及び格子定数の温度依存性を示す図。[0001]
[Industrial application fields]
The present invention relates to an Fe-based soft magnetic alloy powder having particularly good soft magnetic properties and a method for producing the same.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, Fe-Ni alloy powder, Fe-Si-Al alloy powder, and Fe-Si alloy powder are known as alloy powders with excellent soft magnetic properties, and dust cores using these powders are used. ing. Recently, Fe-based and Co-based amorphous alloy powders have also been produced, and application of dust cores, shield materials, and the like has also been studied.
[0003]
However, although the Fe-Ni alloy powder is excellent in soft magnetic properties, there is a problem that the saturation magnetic flux density is low. For the Fe-Si-Al alloy powder and the Fe-Si alloy powder, the saturation magnetic flux density is higher than that of the Fe-Ni alloy powder. However, soft magnetic properties are not sufficient. The Fe-based amorphous alloy powder has a high saturation magnetic flux density but a large magnetostriction, so that the soft magnetic properties are not good. Since the Co-based amorphous alloy powder has small magnetostriction, the soft magnetic properties are better than those of the Fe-based powder, but there is a problem that the saturation magnetic flux density is low and expensive.
[0004]
On the other hand, soft magnetic properties superior to conventional Fe-based amorphous alloys are achieved by heat-treating Fe-based amorphous alloys recently prepared by the liquid quenching method to make the microstructure of microcrystals of about 100 angstroms. It has been reported that characteristics can be obtained (Japanese Patent Laid-Open No. 64-79342, Japanese Patent Laid-Open No. 1-156452, US Pat. No. 4,881,989, etc.). This Fe-based soft magnetic alloy has FeSiB as a reference composition, and is added with a high melting point metal such as Cu and Nb, and the structure is made of microcrystals of about 100 Å, and the saturation magnetostriction is small. Soft magnetic properties are improved. Powders made from this alloy also show good soft magnetic properties (Japanese Patent Laid-Open No. 64-28301). However, when Cu is added, Cu may gather together and cause a composition shift.
[0005]
The present invention is a powder soft magnetic material that replaces such conventional soft magnetic alloy powder, and has a very low saturation magnetostriction, excellent soft magnetic properties, and a sufficient saturation magnetic flux density. An object is to provide an alloy powder.
Another object of the present invention is to provide a Fe-based soft magnetic alloy powder which is a metal metalloid alloy having a relatively low melting point and can be manufactured using a conventional ultra-quenching apparatus and a powder manufacturing apparatus. To do.
[0006]
[Means for Solving the Problems]
In order to achieve such an object, as a result of intensive studies on the Fe-based soft magnetic alloy, the present inventor showed excellent soft magnetic characteristics when Al was added to the Fe-Si-B-based Fe-based soft magnetic alloy, For example, the saturation magnetostriction is extremely low, and it is extremely excellent when such a Fe-Si-B-Al-based Fe-based soft magnetic alloy is added with another specific element (metal) represented by M 'below, particularly Nb. The present inventors have found that the present invention exhibits a soft magnetic property and has found a method for producing the alloy powder, thereby achieving the present invention.
[0007]
That is, the Fe-based soft magnetic alloy powder of the present invention has a general formula (Fe _1-X M _{X) 100-abcd} Si _a Al _b B _c M ′ _d (where M is Co and / or Ni, and M ′ is One or more elements selected from Nb, Mo, Zr, W, Ta, Hf, Ti, V, Cr, Mn, Y, Pd, Ru, Ga, Ge, C, and P. x represents an atomic ratio, “a”, “b”, “c”, and “d” represent atomic% and satisfy 0 ≦ x ≦ 0.15, 0 ≦ a ≦ 24, 2 <b ≦ 15, 4 ≦ c ≦ 20, and 0 ≦ d ≦ 10, respectively. In particular, it is preferable that at least 30% or more of the structure is produced in crystalline form (fine crystal grains), and the crystalline substance is composed of a bcc solid solution mainly composed of iron. . Moreover, Nb is suitable as M ′.
[0008]
In the Fe-based soft magnetic alloy powder of the present invention, copper (Cu) is 0.5 atomic% or less, preferably 0.1 atomic% or less from the viewpoint of magnetic properties, and most preferably Cu is not mixed at all.
In the Fe-based soft magnetic alloy powder of the present invention, Fe can be substituted with Co and / or Ni when the atomic ratio x is in the range of 0 to 0.15. Co and Ni exhibit negative interaction parameters with Fe. Therefore, the Fe-based alloy powder of the present invention is dissolved in a bcc solid solution mainly composed of Fe and is replaced with a bcc structure lattice. it is conceivable that. Thereby, it is considered that the magnetostriction constant and the magnetocrystalline anisotropy constant of the bcc solid solution can be reduced. In the alloy powder of the present invention, when x is 0 ≦ x <0.02, especially x = 0, that is, when Ni (and / or Co) is not included at all, high permeability is obtained, and thus high permeability is required. It is suitable for applications (magnetic core materials) such as electromagnetic shields.
[0009]
On the other hand, when the content x of Ni (and Co) satisfies 0.02 ≦ x ≦ 0.15, not only high permeability can be obtained, but also the reduction of the magnetostriction constant and magnetocrystalline anisotropy constant described above. The effect that the induction anisotropy is imparted greatly is obtained by the effect and the magnetic field heat treatment. The content x of Ni (and / or Co) is preferably 0.02 ≦ x ≦ 0.15, more preferably 0.03 ≦ x ≦ 0.1.
[0010]
Al is an essential element of the alloy of the present invention, and by adding a specific amount of Al (more than 2 atomic% to 15 atomic% or less), crystals exhibiting soft magnetism with small magnetocrystalline anisotropy (Fe-based bcc solid solution) The temperature difference (ΔT) between the crystallization temperature (TX ₁ ) and the crystallization temperature (TX ₂ ) of a crystal that inhibits soft magnetism (for example, Fe-B crystal) can be increased. In addition to suppressing the formation of -B based crystals and the like, soft magnetic properties can be derived by heat treatment at a relatively low temperature. FIG. 1 shows the relationship between the crystallization temperature and the Al content (atomic%) when Al is added to the FeSiB alloy powder. As can be seen from FIG. 1, when the Al content is increased, TX ₁ decreases monotonously, whereas TX ₂ takes a substantially constant value, and the temperature difference (ΔT) between TX ₁ and TX ₂ increases.
[0011]
In the present invention, the Al content b is more than 2 atom% and 15 atom% or less, preferably 2.5 to 15 atom%, more preferably 3 to 12 atom%. In the range of 3 to 12 atomic%, an alloy powder having particularly high magnetic permeability and small iron loss can be obtained. In the alloy powder of the present invention, when x is 0 ≦ x <0.02, particularly x = 0, the Al content b is preferably 6 to 12 atomic%, more preferably 6 to 10 atomic%, Most preferably, it is 7 to 10 atomic%.
[0012]
Since Al has a negative mutual parameter with Fe like Ni (Co), it is dissolved in a solid solution mainly composed of Fe by adding Al, that is, at the position of Fe atoms in the α-Fe crystal structure. In order to stabilize the bcc crystal by being dissolved in a substituted form, it is presumed that an environment that is easily crystallized by heat treatment is created. Therefore, as described above, crystal grains having small magnetocrystalline anisotropy are selectively produced by adding Al, and it is considered that excellent soft magnetic characteristics are exhibited.
[0013]
Si and B are elements that make the Fe-based soft magnetic alloy of the present invention amorphous in the initial state (before heat treatment). The Si content a is 0 to 24 atomic%, preferably 6 to 18 atomic%, more preferably 10 to 16 atomic%. By setting the Si content in this range, it is preferable because the amorphous forming ability in the initial state (before heat treatment) can be enhanced.
[0014]
The content c of B is 4 to 20 atomic%, preferably 6 to 15 atomic%, more preferably 10 to 14 atomic%. Within this range, a sufficient temperature difference of the crystallization temperature can be obtained and it is easy to make it amorphous. The amorphous forming ability differs with the B content of 9 atomic% as a boundary, and the amorphous alloy having the above composition when Al is added when B is in the range of 9.5 to 15 atomic%, particularly 10 to 14 atomic%. Excellent amorphous forming ability, and uniform crystal grains can be obtained after heat treatment.
[0015]
The basic composition of the Fe-based soft magnetic alloy of the present invention is the above-mentioned Fe (M), B, Si, Al, but other elements M ′ can be added to further improve the corrosion resistance and magnetic properties. Examples of M ′ include one or more selected from Nb, Mo, Zr, W, Ta, Hf, Ti, V, Cr, Mn, Y, Pd, Ru, Ga, Ge, C, and P. Furthermore, the addition of M ′ serves to improve the amorphous forming ability of the Fe—Si—Al—B alloy having the basic composition.
[0016]
Nb, W, Ta, Zr, Hf, and Mo have an effect of suppressing the precipitation of Fe—B based crystals that particularly impair soft magnetic properties, or moving the precipitation temperature of Fe—B based crystals to a high temperature. Improve the soft magnetic properties of the powder. The addition of the element (metal) contributes to the refinement of crystal grains. V, Cr, Mn, Y and Ru are particularly effective in improving the corrosion resistance of the alloy. C, Ge, P and Ga are particularly effective in forming an amorphous state. One or more of the above elements can be added. Of these elements, Nb, Ta, W, Mn, Mo, and V are particularly preferable. Among these, when Nb is added, soft magnetic properties, particularly coercive force, magnetic permeability, and iron loss are remarkably improved. The addition amount d of these elements is 1 to 10 atomic%, preferably 1 to 8 atomic%, more preferably 1 to 6 atomic%. By setting this range, it is possible to prevent the amorphous forming ability and the magnetic characteristics from deteriorating.
[0017]
In the present invention, an alloy containing inevitable impurities such as N, S, and O to such an extent that the intended characteristics are not deteriorated is also included in the present invention.
In the Fe-based soft magnetic alloy powder of the present invention, at least 30% (30% to 100%) of the entire structure is composed of crystalline (fine crystal grains), and the portion other than the crystal grains of the alloy composition is mainly amorphous. It is. In the present invention, excellent (soft) magnetic properties are exhibited when the proportion of crystal grains is in the above range. In the present invention, excellent (soft) magnetic properties are exhibited even when the proportion of fine crystal grains is substantially 100%. In the Fe-based soft magnetic alloy powder of the present invention, from the viewpoint of magnetic properties, it is particularly preferable that at least 60% or more of the entire structure is composed of fine crystal grains, and most preferably 80% or more is composed of fine crystal grains. .
[0018]
Further, the crystal grains of the alloy powder of the present invention have a bcc structure, and it is considered that Si, B, and Al (or Ni and / or Co in some cases) are mainly dissolved in Fe as a main component. The crystal grains have an average grain size of 1000 angstroms or less, preferably 500 angstroms or less, more preferably 50 to 300 angstroms. In the present invention, excellent magnetic properties can be obtained when the average particle size is 1000 angstroms or less.
[0019]
In the present invention, the ratio of the crystal grains to the whole can be experimentally evaluated by the X-ray diffraction method or the like. That is, it is possible to experimentally evaluate the ratio of the X-ray diffraction intensity of the magnetic alloy material to be measured with respect to the X-ray diffraction intensity in a completely crystallized state (a state where the X-ray diffraction intensity is saturated). it can. It can also be evaluated from the ratio between the X-ray diffraction intensity of the X-ray diffraction line received with crystallization and the X-ray diffraction intensity due to the amorphous halo that decreases with crystallization. In the present invention, the average particle diameter is derived from Scherrer's equation (t = 0.9λ / βcosθ) using the bcc peak reflection (110) of the X-ray diffraction pattern (Kariti, new edition X-ray diffraction required). (Element of X-ray Diffraction (Second Edition), BD Cullity), pages 91-94).
[0020]
The Fe-based soft magnetic alloy powder of the present invention can usually be produced by the following method.
[0021]
The first method is a production method comprising a step of super-cooling a molten alloy having the above composition to produce an amorphous alloy powder, and a heat treatment step of heating this to make at least 30% of the structure crystalline. As a method for producing the amorphous alloy powder, there are a water atomizing method, a gas atomizing method, a spray method, a cavitation method, a spark erosion method, a rotating liquid injection method, and the like. The amorphous alloy powder is preferably in a completely amorphous state, but may contain a crystalline material. The heat treatment is performed for the purpose of making at least 30% of the structure crystalline, and is heated to a temperature higher than the crystallization temperature.
[0022]
In the second method, a molten alloy having the above composition is rapidly quenched to obtain an amorphous alloy such as an amorphous alloy ribbon, amorphous alloy flake, or amorphous alloy wire, Heating for a time sufficient to cause embrittlement at a temperature lower than the crystallization temperature, crushing the embrittled amorphous alloy, and heating the embrittled amorphous alloy powder to a temperature higher than the crystallization temperature. A manufacturing method comprising a heat treatment step in which at least 30% of the structure is crystalline. Examples of methods for obtaining amorphous alloy ribbons, amorphous alloy flakes, or amorphous alloy wires include a single roll method, a twin roll method, a centrifugal quenching method, and a spinning method in a rotating liquid.
[0023]
In the third method, the molten alloy having the above composition is rapidly quenched to obtain an amorphous alloy such as an amorphous alloy ribbon, an amorphous alloy flake, or an amorphous alloy wire; Introducing hydrogen for a time sufficient to cause embrittlement at a temperature lower than the crystallization temperature, and then crushing the embrittled amorphous alloy; and crystallization of the amorphous alloy powder thus obtained. It is a manufacturing method comprising a heat treatment step of heating to a temperature higher than the temperature and making at least 30% of the structure crystalline. As a method for introducing hydrogen, there are a method in which an amorphous alloy is exposed to a hydrogen atmosphere under pressure, or electrolytically introduced by using it as a cathode in a hydrogen production electrolytic bath.
[0024]
In the fourth method, the molten alloy having the above composition is rapidly quenched to obtain an amorphous alloy such as an amorphous alloy ribbon, an amorphous alloy flake, or an amorphous alloy wire, It is a manufacturing method comprising a heat treatment step of heating to a temperature higher than the crystallization temperature to make at least 30% of the structure crystalline, and a step of pulverizing the obtained alloy. An alloy heated to a temperature higher than the crystallization temperature becomes brittle and can be easily pulverized by a ball mill, a vibration mill or the like.
[0025]
The alloy powder of the present invention can be obtained by heating an amorphous alloy having the above composition to a temperature equal to or higher than the crystallization temperature, and crystallizing at least a part, preferably 30% or more of the entire sample. The heat treatment for this is performed in a vacuum or in an inert gas atmosphere such as argon gas or nitrogen gas, a reducing gas such as H2, or an oxidizing gas atmosphere such as air. The heat treatment temperature is about 200 to 800 ° C, preferably about 400 to 700 ° C, more preferably about 520 to 680 ° C. The heat treatment time is about 0.1 to 10 hours, preferably about 1 to 5 hours. Further, the heat treatment may be performed in the absence of a magnetic field or by applying a magnetic field. In the present invention, a soft magnetic alloy powder excellent in the characteristics of the present invention can be obtained by heat-treating an amorphous alloy having the above composition within the above-mentioned temperature range and the above-mentioned heat treatment time.
[0026]
Hereinafter, an example is given and it demonstrates further.
[0027]
【Example】
Examples 1-9
Using a single roll method, a quenched ribbon with a width of about 1.0 to 5 mm and a plate thickness of about 14 to 20 μm is created from a molten metal containing Fe, Si, Al, B, (Nb) in an atmosphere of argon gas at 1 atmosphere. Then, the obtained ribbon was heat-treated for about 1 hour in the presence of nitrogen gas below the crystallization temperature. The heat-treated amorphous ribbon was pulverized using a ball mill to form a powder, and further heat-treated in the presence of nitrogen gas at a temperature equal to or higher than the crystallization temperature for about 1 hour.
[0028]
Table 1 shows the coercive force Hc (mOe) and the saturation magnetization Ms (emu / g) of the alloy powder prepared by changing the composition of Fe, Si, Al, B, and Nb by the above method. Magnetization was measured using a vibrating sample magnetometer in the range of a maximum applied magnetic field of 18 kOe. The composition was determined by ICP analysis.
[0029]
As comparative examples, Fe ₇₈ Si ₉ B ₁₃ alloy powder (Comparative Example 1, commercially available) and FeCuSiBNb alloy powder (Comparative Example 2, Fe-based soft magnetic alloy powder described in JP-A No. 64-28301) Table 1 shows the coercive force and saturation magnetization.
[0030]
[Table 1]

[0031]
As is clear from Table 1, the coercive force of Example 7 containing Nb as M ′ was considerably lower than that of the FeSiB system. This value is almost equal to the coercive force (18 mOe) of Comparative Example 2. In Examples 3 and 4, the magnetic characteristics were equal to or higher than those of the FeSiB amorphous alloy except for the saturation magnetization.
[0032]
FIG. 2 is a diagram showing the composition dependence of the coercive force Hc of the FeSiAlB alloy powder obtained by the above method. In the composition range surrounded by the line, the soft magnetic property having a coercive force of 100 mOe or less was shown. FIG. 3 is a graph showing the composition dependence of the saturation magnetization Ms of the FeSiAlB alloy powder. A sample (Fe ₇₃ Si) having a high saturation magnetization of 165 emu / g within a composition range where the coercive force Hc is 100 mOe or less. ₈ Al ₁₀ B ₉ ) was obtained.
[0033]
Among them, Example 4 (Fe ₆₉ Al ₈ Si ₁₄ B ₉ ) and Example 7 (Fe ₆₈ Al ₈ Si ₁₄ B ₉ Nb ₁ ) whose coercive force is smaller than the conventional FeSiB-based amorphous alloy (Comparative Example ₁ ). The crystal constant a (angstrom), the crystal grain size D (angstrom), the first crystallization temperature TX ₁ (° C.) and the second crystallization temperature TX ₂ (° C.) were measured. The results are shown in Table 2.
[0034]
[Table 2]

[0035]
The numerical values in Table 2 indicate that the ΔT values of Example 4 and Example 7 are significantly larger than those of Comparative Example 2. Further, as is apparent from Table 2, it was confirmed that the alloy powder of the present invention formed crystal grains of bcc solid solution of about 300 angstrom mainly composed of iron by crystallization by heat treatment.
The first crystallization temperature TX ₁ is a temperature at which these Fe-based soft magnetic alloy powders can be produced using a conventional heat treatment apparatus, and the difference from the second crystallization temperature TX ₂ is 95 in Example 4. C., 125 ° C. in Example 7, and “30 ° C. in Comparative Example 2”. It was shown that the formation of crystals that inhibit soft magnetism can be sufficiently suppressed by appropriately selecting the heat treatment temperature.
[0036]
The results of further detailed investigations on the alloy of Example 9 (Fe ₆₆ Si ₁₄ Al ₈ Nb ₃ B ₉ ) exhibiting particularly excellent coercive force characteristics will be described below.
First, a thin strip having a width of 2.8 mm and a thickness of 17 μm is manufactured by a single roll method, liquid-quenched, heat-treated in a nitrogen gas atmosphere at 450 ° C. for 1 hour, and then pulverized using a ball mill, and 580 An X-ray diffraction image was obtained after heat treatment in a nitrogen gas atmosphere at 1 ° C. for 1 hour. These X-ray diffraction patterns are shown in FIG. In the figure, (a) is the case of a powder that is heat-treated at 450 ° C. and then pulverized using a ball mill, and a halo pattern typical of an amorphous alloy is seen. Further, (b) shows a case of a typical bcc crystal diffraction peak after heat treatment at 580 ° C., and a peak exhibiting regular lattice reflection of DO3 structure is observed in a low angle region.
[0037]
Similarly, FIG. 5 shows the heat treatment temperature dependence of the coercive force Hc (mOe) of the alloy (Fe ₆₆ Si ₁₄ Al ₈ Nb ₃ B ₉ ) powder of Example 9. As is apparent from the figure, the coercive force Hc increases with increasing heat treatment temperature after taking a minimum value of 12 mOe at 580 ° C.
[0038]
Similarly, the lattice constant determined from the grain size D110 (angstrom) derived from the half width of the (110) diffraction intensity peak of the bcc crystal of the alloy powder of Example 9 and the (110) diffraction peak of the bcc crystal from the half-width of the Scherrer equation. FIG. 6 shows the heat treatment temperature dependence of a (angstrom). As is apparent from FIG. 6, the crystal grain size was approximately 140 Å regardless of the increase in the heat treatment temperature. On the other hand, it was found that the lattice constant gradually decreased as the heat treatment temperature increased.
[0039]
Examples 10-25
Using a single roll method, an amorphous ribbon having a width of 1.3 mm and a thickness of 18 μm was prepared from a molten metal containing Fe, Si, Al, B, and Nb in an atmosphere of argon gas at 1 atm. The band was heat treated for about 1 hour in the presence of nitrogen gas below the crystallization temperature. The heat-treated ribbon was pulverized into a powder using a ball mill, and further heat-treated in the presence of nitrogen gas at a temperature equal to or higher than the crystallization temperature for about 1 hour. Table 3 shows the results of the coercive force Hc (mOe) of the obtained powder.
[0040]
[Table 3]

[0041]
As is apparent from Table 3, the alloy powders of Examples 10 to 25 containing no Ni exhibited a small coercive force of 50 mOe or less.
Examples 26-45 Comparative Example 3
[0042]
[Table 4]

[0043]
As apparent from Table 4, the coercive force of the alloy powder with the B content exceeding 9 atomic% was small.
As can be seen from Table 4, both the amorphous alloys using elements other than Nb as M ′ (Examples 25 to 45) and excellent magnetic properties when Nb and other elements are used in combination. showed that.
[0044]
【The invention's effect】
As is clear from the above examples, according to the Fe-based soft magnetic alloy powder of the present invention, by adding Al to the Fe-Si-B-based alloy, a novel Fe-based soft magnetic material having excellent soft magnetic properties can be obtained. Magnetic alloy powder can be obtained. In addition, since the Fe-based soft magnetic alloy powder of the present invention has a large temperature difference between the crystallization temperature of crystals exhibiting good soft magnetism and the crystallization temperature of crystals that inhibit soft magnetism, heat treatment of conventional amorphous alloy powders A sufficiently large heat treatment temperature range can be obtained compared to the temperature range.
[0045]
Further, according to the Fe-based soft magnetic alloy powder of the present invention, good soft magnetic characteristics can be obtained by adding Al and replacing part of Fe with Ni (Co).
Furthermore, according to the present invention, by adding an element such as Nb to the Fe-Si-Al-B alloy powder, a novel Fe-based soft magnetic alloy powder having excellent soft magnetic properties, particularly extremely low coercive force, can be obtained. Can be obtained.
[0046]
Since the alloy powder of the present invention has excellent soft magnetic properties as described above, it is suitably used for applications (magnetic core materials) such as dust cores and shield materials.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the crystallization temperature of Fe-based soft magnetic alloy powder and the amount of Al.
FIG. 2 is a graph showing the correlation between coercive force (Hc) and composition of Fe-based soft magnetic alloy powder.
FIG. 3 is a diagram showing the correlation between the saturation magnetism (Ms) and the composition of Fe-based soft magnetic alloy powder.
FIG. 4 is a diagram showing X-ray diffraction patterns of an amorphous alloy powder and a crystal alloy powder of an Fe-based soft magnetic alloy according to the present invention.
FIG. 5 is a graph showing the temperature dependence of the coercive force of the Fe-based soft magnetic alloy powder according to the present invention.
FIG. 6 is a graph showing the temperature dependence of the crystal grain size and lattice constant of a bcc crystal of Fe-based soft magnetic alloy powder according to the present invention.

Claims

Formula (Fe 1-X M X) 100-abcd Si a Al b B c M 'd ( wherein, M is Co and / or Ni, M' is Nb, Mo, Zr, W, Ta, Hf, Ti , V, Cr, Mn, Y, Pd, Ru, Ga, Ge, C, P represents one or more elements, x represents an atomic ratio, a, b, c, d represents atomic%, each 0 ≦ x ≦ 0. 15,0 ≦ a ≦ 24,2 <b ≦ 15,4 ≦ c ≦ 20,0 ≦ d ≦ 10 and satisfies the) was rapidly quenched molten alloy having a composition represented by non A process for obtaining an amorphous alloy such as an amorphous alloy ribbon, amorphous alloy flake or amorphous alloy wire, and a time sufficient to embrittle the amorphous alloy at a temperature lower than its crystallization temperature. Heating and crushing the embrittled amorphous alloy, and heating the amorphous alloy powder thus obtained to a temperature higher than its crystallization temperature. Method of manufacturing a Fe-based soft magnetic alloy powder of at least 30% or more, characterized in that it consists of a heat treatment step of the crystalline.

Formula (Fe 1-X M X) 100-abcd Si a Al b B c M 'd ( wherein, M is Co and / or Ni, M' is Nb, Mo, Zr, W, Ta, Hf, Ti , V, Cr, Mn, Y, Pd, Ru, Ga, Ge, C, P represents one or more elements, x represents an atomic ratio, a, b, c, d represents atomic%, each 0 ≦ x ≦ 0. 15,0 ≦ a ≦ 24,2 <b ≦ 15,4 ≦ c ≦ 20,0 ≦ d ≦ 10 and satisfies the) was rapidly quenched molten alloy having a composition represented by non A process for obtaining an amorphous alloy such as an amorphous alloy ribbon, amorphous alloy flake or amorphous alloy wire, and a time sufficient to embrittle the amorphous alloy at a temperature lower than its crystallization temperature. Introducing hydrogen and then crushing the embrittled amorphous alloy, and the amorphous alloy powder thus obtained is higher than its crystallization temperature. Was heated to every method of the Fe-based soft magnetic alloy powder characterized by comprising more than at least 30% of the tissue from the heat treatment step to crystalline.

Formula (Fe 1-X M X) 100-abcd Si a Al b B c M 'd ( wherein, M is Co and / or Ni, M' is Nb, Mo, Zr, W, Ta, Hf, Ti , V, Cr, Mn, Y, Pd, Ru, Ga, Ge, C, P represents one or more elements, x represents an atomic ratio, a, b, c, d represents atomic%, each 0 ≦ x ≦ 0. 15,0 ≦ a ≦ 24,2 <b ≦ 15,4 ≦ c ≦ 20,0 ≦ d ≦ 10 and satisfies the) was rapidly quenched molten alloy having a composition represented by non A step of obtaining an amorphous alloy such as a crystalline alloy ribbon, amorphous alloy flake or amorphous alloy wire, and heating the amorphous alloy to a temperature higher than its crystallization temperature, so that at least 30% of the structure A process for producing an Fe-based soft magnetic alloy powder characterized by comprising a heat treatment step in which the above is crystalline and a step of pulverizing the obtained alloy Law.