JP2009141346A - High-strength high-resistivity low-loss composite soft magnetic material and method of manufacturing the same, and electromagnetic circuit component - Google Patents
High-strength high-resistivity low-loss composite soft magnetic material and method of manufacturing the same, and electromagnetic circuit component Download PDFInfo
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Abstract
Description
本発明は、モータ、アクチュエータ、リアクトル、トランス、チョークコア、磁気センサコアなどの各種電磁気回路部品の素材として使用される高強度高比抵抗低損失複合軟磁性材とその製造方法及び電磁気回路部品に関する。 The present invention relates to a high-strength, high-resistivity, low-loss composite soft magnetic material used as a material for various electromagnetic circuit components such as a motor, an actuator, a reactor, a transformer, a choke core, and a magnetic sensor core, a manufacturing method thereof, and an electromagnetic circuit component.
従来、モータ、アクチュエータ、磁気センサなどの磁心用材料として、鉄粉末、Ｆｅ−Ａｌ系鉄基軟磁性合金粉末、Ｆｅ−Ｎｉ系鉄基軟磁性合金粉末、Ｆｅ−Ｃｒ系鉄基軟磁性合金粉末、Ｆｅ−Ｓｉ系鉄基軟磁性合金粉末、Ｆｅ−Ｓｉ−Ａｌ系鉄基軟磁性合金粉末（以下、これらを軟磁性金属粒子と総称する）を焼結して得られた軟磁性焼結材が知られている。また、鉄粉末や合金粉末をガス又はアトマイズ法で粉末化して作製した場合、鉄粉末や合金粉末は単体では比抵抗が低いため、鉄粉末や合金粉末の表面に絶縁皮膜の被覆を行うか、形状の平滑化を行う、あるいは、有機化合物を混合して比抵抗を上げるなどの対策を講じている。
この種の軟磁性焼結材において、磁歪や実効透磁率を高め、渦電流損失を抑制するために、鉄を含む金属磁性粒子の表面を非鉄金属の下層被膜と無機化合物を含む絶縁膜とで覆った圧粉軟磁性材料などが提案されている（特許文献１参照）。
Conventionally, as magnetic core materials for motors, actuators, magnetic sensors, etc., iron powder, Fe-Al iron-based soft magnetic alloy powder, Fe-Ni iron-based soft magnetic alloy powder, Fe-Cr iron-based soft magnetic alloy powder , Fe-Si-based iron-based soft magnetic alloy powder, Fe-Si-Al-based iron-based soft magnetic alloy powder (hereinafter referred to collectively as soft magnetic metal particles), and a soft magnetic sintered material obtained by sintering It has been known. In addition, when iron powder or alloy powder is made by pulverization by gas or atomization method, iron powder or alloy powder alone has low specific resistance, so the surface of iron powder or alloy powder is coated with an insulating film, Measures are taken such as smoothing the shape or increasing specific resistance by mixing organic compounds.
In this kind of soft magnetic sintered material, in order to increase magnetostriction and effective magnetic permeability and to suppress eddy current loss, the surface of metallic magnetic particles containing iron is covered with a non-ferrous metal underlayer coating and an insulating film containing an inorganic compound. A covered powder soft magnetic material has been proposed (see Patent Document 1).
また、金属磁性材粉末と、絶縁性結着剤とを混合してなる複合磁性材料において、１〜１０重量％程度の絶縁性結着剤を混合し、ＣｒとＳｉ、Ａｌを規定量含有させ、圧粉磁心あるいは磁性素子を作成する技術が知られている。（特許文献２参照）
更に、金属磁性粒子とその周囲の絶縁性下地膜と、上昇被膜と下層被膜に設けられた金属酸化物の分散粒子を具備した圧粉磁心が開示されている。（特許文献３）
更に、Ｆｅ、Ｃｏ、Ｎｉの１種以上で示される元素に添加金属元素として、Ｈｆ、Ｚｒ、Ｗ、Ｔｉなどを添加してなる軟磁性合金粉末と合成樹脂とからなることを特徴とする高周波用複合材料が知られている。（特許文献４）
Furthermore, a dust core is disclosed that includes metal magnetic particles, an insulating base film around the metal magnetic particles, and metal oxide dispersed particles provided on the rising film and the lower film. (Patent Document 3)
Further, the high frequency characterized by comprising a soft magnetic alloy powder obtained by adding Hf, Zr, W, Ti or the like as an additive metal element to an element represented by one or more of Fe, Co, and Ni, and a synthetic resin. Composite materials are known. (Patent Document 4)
前記特許文献に記載の技術を用いて複合磁性材料の特性改善を行ったとしても、圧密成形時に粉末同士が圧縮される際、粉末周囲に被覆した絶縁皮膜に亀裂が生じたり、樹脂材料では歪取りを行う焼鈍温度までの耐熱性が無いこと、更に粉末圧密時に粉末の粒界３重点などに添加物が集合する傾向があるなどの問題があり、高強度で高比抵抗の複合磁性材料を提供することが難しかった。
このような背景から本出願人は、鉄粉末の表面にＭｇ−Ｆｅ−Ｏの三元系酸化物を含む堆積膜を形成した酸化膜被覆鉄粉末について研究開発を進めており、粉末圧密時においても亀裂が生じ難く、高比抵抗であり、耐熱性にも優れた軟磁性複合材料を提供しようとしている。
Even when the characteristics of the composite magnetic material are improved using the technique described in the above-mentioned patent document, when the powders are compressed during compaction molding, cracks occur in the insulating film coated around the powder, or the resin material is strained. There is a problem that there is no heat resistance up to the annealing temperature to perform the removal, and there is a tendency for additives to collect at the triple point of the grain boundary of the powder during powder compaction. It was difficult to provide.
From such a background, the present applicant is researching and developing oxide-coated iron powder in which a deposited film containing a ternary oxide of Mg—Fe—O is formed on the surface of the iron powder. However, it is intended to provide a soft magnetic composite material that is difficult to crack, has a high specific resistance, and is excellent in heat resistance.
このような研究課程において本発明者らは、Ｆｅ系の軟磁性焼結材の研究を行い、プレス成形時に圧密成形しても絶縁被膜が破壊されることがない圧密体を得るための技術の一環として、Ｍｇ含有酸化物被覆型の軟磁性粉末を提供している。
即ち、Ｆｅ系の軟磁性粉末を予め酸化雰囲気中で加熱することにより軟磁性粉末の表面に酸化鉄の膜を形成した酸化処理軟磁性粉末を作製し、この酸化処理軟磁性粉末にＭｇ粉末を添加し、造粒転動攪拌混合装置で混合して得られた混合粉末を不活性ガス雰囲気または真空雰囲気中において加熱するなどしたのち、更に、必要に応じて酸化性雰囲気中で加熱する酸化処理を施す技術である。この技術によれば、一般に知られているＭｇＯ−ＦｅＯ−Ｆｅ２Ｏ３系の中で代表される（Ｍｇ,Ｆｅ）Ｏ、（Ｍｇ,Ｆｅ）３Ｏ４などのＭｇ−Ｆｅ−Ｏ三元系各種酸化物のうちで、少なくとも（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が軟磁性粉末粒子の表面に形成されたものを得ることができる。
In such a research course, the present inventors conducted research on Fe-based soft magnetic sintered materials, and developed a technique for obtaining a compact that does not break the insulating coating even if it is compacted during press molding. As part of this, Mg-containing oxide-coated soft magnetic powder is provided.
That is, by heating an Fe-based soft magnetic powder in an oxidizing atmosphere in advance, an oxidized soft magnetic powder in which an iron oxide film is formed on the surface of the soft magnetic powder is produced, and Mg powder is added to the oxidized soft magnetic powder. Addition and heating the mixed powder obtained by mixing with a granulation rolling agitation and mixing device in an inert gas atmosphere or vacuum atmosphere, and further heating in an oxidizing atmosphere as necessary It is a technology to apply. According to this technique, Mg—Fe—O ternary elements such as (Mg, Fe) O and (Mg, Fe) 3 O 4 represented by the generally known MgO—FeO—Fe 2 O 3 system. Among various oxides of the series, it is possible to obtain an Mg—Fe—O ternary oxide deposited film containing at least (Mg, Fe) O formed on the surface of the soft magnetic powder particles.
更なる研究課程において本発明者らは、鉄粉末の表面にＭｇ−Ｆｅ−Ｏの三元系酸化物堆積膜を形成した酸化膜被覆鉄粉末の圧密体を更に高強度とするため、圧密体に水分含有雰囲気中において加熱処理することを研究している。
本発明者らの研究によりこの水分含有雰囲気において加熱処理を行うと、強度を向上できることは判明したが、この処理を行うと、鉄粉末中のＦｅとスチーム中のＨ２Ｏが反応してＦｅ３Ｏ４が増加し、比抵抗が低下するおそれがあった。
In a further research course, the inventors of the present invention have made it possible to further increase the strength of the compacted oxide powder-coated iron powder in which the Mg—Fe—O ternary oxide deposition film is formed on the surface of the iron powder. We are studying heat treatment in a moisture-containing atmosphere.
It has been found by the inventors' research that heat treatment in this moisture-containing atmosphere can improve the strength. However, when this treatment is performed, Fe in the iron powder reacts with H 2 O in the steam to cause Fe to react. 3 O 4 may increase and the specific resistance may decrease.
本発明は前記の問題に鑑みて創案されたものであり、その目的は、Ｍｇ含有酸化物被覆軟磁性粒子を圧密する場合に２価金属を添加して粒界層に拡散させ、粒界層におけるＦｅの２価サイトを２価金属で一部置換することによって、相対的に粒界層におけるＦｅの濃度を下げることができ、水分含有雰囲気における加熱処理後においても高抵抗化することができ、低損失かつ高強度と優れた軟磁気特性を確保できる高強度高比抵抗低損失複合軟磁性材の提供とその製造方法並びに磁気回路部品の提供を目的とする。
また、本願発明は、Ｍｇ含有酸化物被覆軟磁性粒子を圧密し、焼成して得ることができる高強度高比抵抗低損失複合軟磁性材において、水分雰囲気における加熱処理時に、Ｆｅ濃度を下げてＦｅの２価サイトの置換を行うことができる技術の提供を目的とする。
The present invention was devised in view of the above-mentioned problems, and its purpose is to add a divalent metal in the case of compacting Mg-containing oxide-coated soft magnetic particles and diffuse it into the grain boundary layer. By partially substituting the divalent site of Fe with a divalent metal, the Fe concentration in the grain boundary layer can be relatively lowered, and the resistance can be increased even after heat treatment in a moisture-containing atmosphere. An object of the present invention is to provide a high-strength, high-resistivity, low-loss composite soft magnetic material capable of ensuring low loss, high strength, and excellent soft magnetic properties, a manufacturing method thereof, and a magnetic circuit component.
The present invention also relates to a high-strength, high-resistivity, low-loss composite soft magnetic material that can be obtained by compacting and firing Mg-containing oxide-coated soft magnetic particles, and lowering the Fe concentration during heat treatment in a moisture atmosphere. An object of the present invention is to provide a technique capable of replacing a divalent site of Fe.
本発明者らは、Ｆｅ系の軟磁性焼結材の研究を行い、圧密成形時においても絶縁被膜が破壊される虞が少ない技術の一例として、Ｍｇ含有酸化物被覆型の軟磁性粉末を提供している。
即ち、Ｆｅ系の軟磁性粉末を予め酸化雰囲気中で加熱することにより軟磁性粉末の表面に酸化鉄の膜を形成した酸化処理軟磁性粉末を作製し、この酸化処理軟磁性粉末にＭｇ粉末を添加し、造粒転動攪拌混合装置で混合して得られた混合粉末を不活性ガス雰囲気または真空雰囲気中において加熱するなどしたのち、更に、必要に応じて酸化性雰囲気中で加熱する酸化処理を施す技術により得られる軟磁性粉末である。この技術によれば、一般に知られているＭｇＯ−ＦｅＯ−Ｆｅ２Ｏ３系の中で代表される（Ｍｇ,Ｆｅ）Ｏ、（Ｍｇ,Ｆｅ）３Ｏ４などのＭｇ−Ｆｅ−Ｏ三元系各種酸化物のうちで、少なくとも（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が軟磁性粉末粒子の表面に形成されたものを得ることができる。
The present inventors conducted research on Fe-based soft magnetic sintered materials and provided Mg-containing oxide-coated soft magnetic powder as an example of a technique that is less likely to break the insulating coating even during compaction molding. is doing.
That is, by heating an Fe-based soft magnetic powder in an oxidizing atmosphere in advance, an oxidized soft magnetic powder in which an iron oxide film is formed on the surface of the soft magnetic powder is produced, and Mg powder is added to the oxidized soft magnetic powder. Addition and heating the mixed powder obtained by mixing with a granulation rolling agitation and mixing device in an inert gas atmosphere or vacuum atmosphere, and further heating in an oxidizing atmosphere as necessary It is a soft magnetic powder obtained by the technology of applying. According to this technique, Mg—Fe—O ternary elements such as (Mg, Fe) O and (Mg, Fe) 3 O 4 represented by the generally known MgO—FeO—Fe 2 O 3 system. Among various oxides of the series, it is possible to obtain an Mg—Fe—O ternary oxide deposited film containing at least (Mg, Fe) O formed on the surface of the soft magnetic powder particles.
この少なくとも（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜をＦｅ系の軟磁性粉末の表面に形成したＭｇ含有酸化物被覆軟磁性粉末にあっては、Ｆｅ系の軟磁性粉末に対する酸化膜の密着性が従来材料に比べて格段に優れていることから、圧密成形時に絶縁皮膜である酸化膜が破壊されることが少なく、酸化膜がＦｅ系の軟磁性粉末同士の間に確実に存在するので、圧密成形後に高温歪取り焼成を行っても酸化膜の絶縁性が低下することがなく、高比抵抗を維持できるので、渦電流損失が低くなり、更に歪取り焼成後に保磁力を低減できることから、ヒステリシス損失を低く抑えることができ、従って低損失の軟磁性複合圧密焼成材を得ることができる技術であった。
本発明者らはこの技術に着目し、前述のＭｇ含有酸化物被覆軟磁性粉末を圧密成形して得られる圧密材を研究したところ、本願発明に到達した。
In the Mg-containing oxide-coated soft magnetic powder in which the Mg—Fe—O ternary oxide deposited film containing at least (Mg, Fe) O is formed on the surface of the Fe-based soft magnetic powder, Since the adhesion of the oxide film to the soft magnetic powder is much better than the conventional material, the oxide film that is an insulating film is less likely to be destroyed during compaction molding, and the oxide film is composed of Fe-based soft magnetic powders. Therefore, even if high temperature strain relief firing is performed after compaction molding, the insulating properties of the oxide film are not lowered, and a high specific resistance can be maintained, resulting in low eddy current loss and further strain relief. Since the coercive force can be reduced after firing, the hysteresis loss can be kept low, and thus a low-loss soft magnetic composite compacted fired material can be obtained.
The inventors of the present invention focused on this technique and studied a compacting material obtained by compacting the above-mentioned Mg-containing oxide-coated soft magnetic powder, and reached the present invention.
（１）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材は、Ｆｅ系の軟磁性金属粒子と該軟磁性金属粒子の表面に被覆されたＭｇ含有酸化物皮膜を具備してなるＭｇ含有酸化物被覆軟磁性粒子が、焼成処理により得られた複合化合物からなる絶縁性の粒界層を介し複数結合され、前記粒界層中に少なくともＦｅと２価金属とＭｇとＯが拡散され、前記粒界層が前記Ｆｅと２価金属とＭｇとＯの複合酸化物を主体としてなるとともに、前記Ｍｇ含有酸化物被覆軟磁性粒子間に位置する粒界層中に２価金属の高濃度領域と低濃度領域とが存在し、前記粒界層中にＦｅの高濃度領域と低濃度領域とが存在することを特徴とする。
複数のＭｇ含有酸化物被覆軟磁性粒子どうしが粒界層を介して結合され、粒界層に２価金属が存在することにより、粒界層に存在するＦｅの一部を２価金属により置換した粒界層構造とすることができ、粒界層の比抵抗を向上できる。
（２）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材は、前記Ｍｇ含有酸化物被覆軟磁性粒子間に位置する粒界層中に２価金属が、前記粒界層の厚さ方向内部側で高濃度に前記粒界層の縁部側で低濃度となるように拡散された領域を少なくとも有していることを特徴とする。
（３）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材は、前記粒界層が前記Ｆｅと２価金属とＭｇの複合酸化物中にＳｉが存在された構造とされてなることを特徴とする。
(1) In order to achieve the above object, the high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention comprises an Fe-based soft magnetic metal particle and an Mg-containing oxide film coated on the surface of the soft magnetic metal particle. A plurality of Mg-containing oxide-coated soft magnetic particles are bonded via an insulating grain boundary layer made of a composite compound obtained by firing, and at least Fe and a divalent metal are contained in the grain boundary layer. Mg and O are diffused, the grain boundary layer is mainly composed of the composite oxide of Fe, divalent metal, Mg and O, and in the grain boundary layer located between the Mg-containing oxide-coated soft magnetic particles A high concentration region and a low concentration region of a divalent metal exist, and a high concentration region and a low concentration region of Fe exist in the grain boundary layer.
A plurality of Mg-containing oxide-coated soft magnetic particles are bonded to each other through a grain boundary layer, and a divalent metal is present in the grain boundary layer, whereby a part of Fe present in the grain boundary layer is replaced with a divalent metal. Therefore, the specific resistance of the grain boundary layer can be improved.
(2) In order to achieve the above object, the high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention has a divalent metal in the grain boundary layer located between the Mg-containing oxide-coated soft magnetic particles, It has at least a region diffused so as to have a high concentration on the inner side in the thickness direction of the grain boundary layer and a low concentration on the edge side of the grain boundary layer.
(3) In order to achieve the above object, in the high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention, the grain boundary layer contains Si in the composite oxide of Fe, divalent metal, and Mg. It is characterized by being structured.
（４）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材は、前記２価金属が、Ｚｎ、Ｍｇ、Ｃｏ、Ｎｉ、Ｍｎ、Ｃｕ、Ｃａのいずれか１種または２種以上であることを特徴とする。
（５）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材は、前記粒界層に、前記Ｍｇ含有酸化物皮膜のＭｇと前記Ｆｅ系の軟磁性金属粒子のＦｅが相互拡散されて前記粒界層に前記Ｍｇ含有酸化物被覆が複合一体化されてなることを特徴とする。
（６）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材は、前記Ｍｇ含有酸化物被覆軟磁性粒子間に位置する粒界層中に２価金属が高濃度で存在する領域が生成され、その領域におけるＦｅの２価サイトが２価金属に置換されてＦｅの濃度が低下され、前記粒界層が高比抵抗化されてなることを特徴とする。
（７）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材は、前記Ｍｇ含有酸化物皮膜が、（Ｍｇ、Ｆｅ）Ｏを主体として構成され、前記Ｓｉを含む化合物がＳｉ−Ｏ−Ｃ化合物であることを特徴とする。
(4) In order to achieve the above object, in the high strength, high specific resistance, low loss composite soft magnetic material of the present invention, the divalent metal is any one of Zn, Mg, Co, Ni, Mn, Cu, and Ca. Or it is characterized by being 2 or more types.
(5) In order to achieve the above object, the high-strength, high-resistivity, low-loss composite soft magnetic material according to the present invention includes the Mg-containing oxide film Mg and the Fe-based soft magnetic metal particles on the grain boundary layer. Fe is interdiffused and the Mg-containing oxide coating is combined and integrated with the grain boundary layer.
(6) In order to achieve the above object, the high strength, high specific resistance, low loss composite soft magnetic material of the present invention has a high concentration of divalent metal in the grain boundary layer located between the Mg-containing oxide-coated soft magnetic particles. A region existing in the region is generated, a divalent site of Fe in the region is replaced with a divalent metal, the concentration of Fe is reduced, and the grain boundary layer is increased in specific resistance.
(7) In order to achieve the above object, in the high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention, the Mg-containing oxide film is mainly composed of (Mg, Fe) O and contains Si. The compound is a Si—O—C compound.
（８）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材の製造方法は、Ｆｅ系の軟磁性金属粒子と該軟磁性金属粒子の表面に被覆されたＭｇ含有酸化物皮膜を具備してなるＭｇ含有酸化物被覆軟磁性粒子を２価金属またはその酸化物と混合して圧密し、非酸化性雰囲気において焼成処理して軟磁性金属圧密焼成材の前駆体とした後、酸化性雰囲気において熱処理することにより、前記Ｍｇ含有酸化物被覆軟磁性粒子を、少なくともＦｅと２価金属とＭｇとＯが拡散された複合化合物からなる絶縁性の粒界層を介し複数結合し、該粒界層中に２価金属の高濃度領域と低濃度領域とが存在され、前記粒界層中にＦｅの高濃度領域と低濃度領域とが存在された高強度高比抵抗低損失複合軟磁性材を製造することを特徴とする
（９）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材の製造方法は、前記酸化性雰囲気として４００℃〜６００℃のスチーム雰囲気または大気中とすることを特徴とする。
（１０）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材の製造方法は、Ｍｇ含有酸化物被覆軟磁性粒子と２価金属またはその酸化物を圧密する前に、バインダーを混合してから圧密することを特徴とする。
(8) In order to achieve the above object, a method for producing a high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention comprises Fe-based soft magnetic metal particles and Mg-containing coating on the surface of the soft magnetic metal particles. Mg-containing oxide-coated soft magnetic particles comprising an oxide film are mixed and mixed with a divalent metal or its oxide, and calcined in a non-oxidizing atmosphere to be a precursor of a soft magnetic metal compacted fired material, Thereafter, the Mg-containing oxide-coated soft magnetic particles are subjected to heat treatment in an oxidizing atmosphere so that a plurality of the Mg-containing oxide-coated soft magnetic particles are interposed via an insulating grain boundary layer composed of a composite compound in which at least Fe, a divalent metal, Mg and O are diffused. High strength and high specific resistance in which a high concentration region and a low concentration region of divalent metal exist in the grain boundary layer, and a high concentration region and a low concentration region of Fe exist in the grain boundary layer It is characterized by manufacturing low-loss composite soft magnetic materials ( 9) In order to achieve the above object, the method for producing a high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention is characterized in that the oxidizing atmosphere is a steam atmosphere of 400 ° C. to 600 ° C. or in the air. To do.
(10) In order to achieve the above object, the method for producing a high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention is performed before compacting the Mg-containing oxide-coated soft magnetic particles and the divalent metal or oxide thereof. , And compacting after mixing the binder.
（１１）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材の製造方法は、前記２価金属として、Ｚｎ、Ｍｇ、Ｃｏ、Ｎｉ、Ｍｎ、Ｃｕ、Ｃａのいずれか１種または２種以上を選択することを特徴とする。
（１２）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材の製造方法は、前記２価金属をＺｎＯ、ＭｇＯ、ＣｏＯ、ＮｉＯ、ＭｎＯ、ＣｕＯ、ＣａＯのいずれか１種または２種の酸化物の状態で添加することを特徴とする。
（１３）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材の製造方法は、前記Ｍｇ含有酸化物皮膜として、（Ｍｇ、Ｆｅ）Ｏを主体としてなるＭｇ含有酸化物皮膜を用い、前記シリコン化合物としてＳｉ−Ｏ−Ｃ化合物を用いることを特徴とする。
（１４）上記目的を達成するために本発明の高強度高比抵抗低損失複合軟磁性材の製造方法は、前記２価金属の酸化物として平均粒径１０〜５００ｎｍの酸化物粉末を用いることを特徴とする。
（１５）上記目的を達成するために本発明の電磁気回路部品は、先の（１）〜（７）のいずれかに記載の高強度高比抵抗低損失複合軟磁性材からなることを特徴とする。
(11) In order to achieve the above object, the method of producing a high strength, high specific resistance, low loss composite soft magnetic material of the present invention includes any one of Zn, Mg, Co, Ni, Mn, Cu, and Ca as the divalent metal. 1 type or 2 types or more are selected.
(12) In order to achieve the above object, the method for producing a high-strength, high-resistivity, low-loss composite soft magnetic material according to the present invention is characterized in that the divalent metal is any one of ZnO, MgO, CoO, NiO, MnO, CuO, and CaO. It adds in the state of 1 type or 2 types of oxides, It is characterized by the above-mentioned.
(13) In order to achieve the above object, the method for producing a high-strength, high-resistivity, low-loss composite soft magnetic material according to the present invention comprises a Mg-containing oxide mainly composed of (Mg, Fe) O as the Mg-containing oxide film. A physical film is used, and a Si—O—C compound is used as the silicon compound.
(14) In order to achieve the above object, the method for producing a high-strength, high-resistivity, low-loss composite soft magnetic material of the present invention uses an oxide powder having an average particle diameter of 10 to 500 nm as the oxide of the divalent metal. It is characterized by.
(15) In order to achieve the above object, the electromagnetic circuit component of the present invention is characterized by comprising the high-strength, high-resistivity, low-loss composite soft magnetic material according to any one of (1) to (7) above. To do.
本発明の高強度高比抵抗低損失複合軟磁性材によれば、Ｍｇ含有酸化物被覆軟磁性粒子がＦｅと２価金属とＭｇとＯを拡散させてなる粒界層を介し結合され、該粒界層中に２価金属の濃度勾配とＦｅの濃度勾配を有し、焼成時にＭｇ含有酸化物被覆軟磁性粒子から粒界層中に熱拡散されているＦｅの一部が２価金属で一部置換された構造の粒界層とされているので、粒界層が高比抵抗の状態とされる。
即ち、Ｍｇ含有酸化物被覆軟磁性粒子が個々に高比抵抗の粒界層で分離されているので、Ｍｇ含有酸化物被覆軟磁性粒子が本来有する優れた軟磁気特性を維持しながら、高比抵抗で渦電流損失の抑制された低損失の高強度高比抵抗低損失複合軟磁性材を提供できる。 また、２価金属を焼成時の熱拡散により粒界層に拡散させるならば、複数のＭｇ含有酸化物被覆軟磁性粒子が構成する粒界三重点に２価金属を偏析させることがなく、Ｍｇ含有酸化物被覆軟磁性粒子を前述の粒界層を介して焼成時に結合できるので、高強度を示すＭｇ含有酸化物被覆軟磁性粒子を提供することが可能となる。
According to the high strength, high specific resistance, low loss composite soft magnetic material of the present invention, Mg-containing oxide-coated soft magnetic particles are bonded via a grain boundary layer formed by diffusing Fe, a divalent metal, Mg, and O, The grain boundary layer has a divalent metal concentration gradient and an Fe concentration gradient, and a part of Fe thermally diffused from the Mg-containing oxide-coated soft magnetic particles into the grain boundary layer during firing is a divalent metal. Since the grain boundary layer has a partially substituted structure, the grain boundary layer is in a high specific resistance state.
In other words, since the Mg-containing oxide-coated soft magnetic particles are individually separated by a high resistivity grain boundary layer, while maintaining the excellent soft magnetic properties inherent in the Mg-containing oxide-coated soft magnetic particles, A low-loss, high-strength, high-resistivity, low-loss composite soft magnetic material in which eddy current loss is suppressed by resistance can be provided. Further, if the divalent metal is diffused into the grain boundary layer by thermal diffusion during firing, the divalent metal is not segregated at the grain boundary triple point formed by the plurality of Mg-containing oxide-coated soft magnetic particles. Since the containing oxide-coated soft magnetic particles can be bonded through the above-mentioned grain boundary layer during firing, it is possible to provide Mg-containing oxide-coated soft magnetic particles exhibiting high strength.
複数のＭｇ含有酸化物被覆軟磁性粒子間に存在する粒界層が、２価金属とＦｅとＭｇとＯの複合酸化物中にＳｉが存在された構造であると、Ｍｇ含有酸化物被覆軟磁性粒子同士の結合力も高く、高強度な高比抵抗低損失複合軟磁性材が得られる。
２価金属として、Ｚｎ、Ｍｇ、Ｃｏ、Ｎｉ、Ｍｎ、Ｃｕ、Ｃａのいずれか１種または２種以上が粒界層中に拡散されているならば、Ｆｅの一部の２価のサイトを置換する形で粒界層中に存在するＦｅの量を削減できるので、焼成後の粒界層の低損失化を図ることができる。
When the grain boundary layer existing between a plurality of Mg-containing oxide-coated soft magnetic particles has a structure in which Si is present in a composite oxide of a divalent metal, Fe, Mg, and O, the Mg-containing oxide-coated soft magnetic particle High binding strength between magnetic particles and high strength, high specific resistance and low loss composite soft magnetic material can be obtained.
If one or more of Zn, Mg, Co, Ni, Mn, Cu, and Ca are diffused in the grain boundary layer as a divalent metal, a part of the divalent site of Fe Since the amount of Fe present in the grain boundary layer in the form of substitution can be reduced, the loss of the grain boundary layer after firing can be reduced.
本発明の製造方法により得られた高強度高比抵抗低損失複合軟磁性材は、高密度、高強度、高比抵抗および高磁束密度を有するので、本発明の軟磁性複合圧密焼成材は、高強度と高磁束密度、かつ、高周波低鉄損の特徴を兼ね備えた優れたものであり、これらの特徴を生かした各種電磁気回路部品の材料として使用できる。 Since the high-strength, high-resistivity, low-loss composite soft magnetic material obtained by the manufacturing method of the present invention has high density, high strength, high specific resistance, and high magnetic flux density, It is an excellent combination of high strength, high magnetic flux density, and high frequency and low iron loss, and can be used as a material for various electromagnetic circuit components that make use of these characteristics.
前記高強度高比抵抗低損失複合軟磁性材を用いて構成される電磁気回路部品として、例えば、磁心、電動機コア、発電機コア、ソレノイドコア、イグニッションコア、リアクトルコア、トランスコア、チョークコイルコアまたは磁気センサコアなどとしての利用が可能であり、いずれにおいても優れた特性を発揮し得る電磁気回路部品を提供できる。
そして、これら電磁気回路部品を組み込んだ電気機器には、電動機、発電機、ソレノイド、インジェクタ、電磁駆動弁、インバータ、コンバータ、変圧器、継電器、磁気センサシステム等があり、これら電気機器の高効率高性能化や小型軽量化に寄与するという効果がある。
As an electromagnetic circuit component configured using the high strength, high specific resistance, low loss composite soft magnetic material, for example, a magnetic core, a motor core, a generator core, a solenoid core, an ignition core, a reactor core, a transformer core, a choke coil core or An electromagnetic circuit component that can be used as a magnetic sensor core or the like and can exhibit excellent characteristics in any case can be provided.
Electric devices incorporating these electromagnetic circuit components include motors, generators, solenoids, injectors, electromagnetically driven valves, inverters, converters, transformers, relays, magnetic sensor systems, etc. There is an effect that it contributes to performance improvement and reduction in size and weight.
「Ｍｇ含有酸化物被覆軟磁性粒子の製造」
本発明ではまず、（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が軟磁性金属粒子の表面に被覆形成されたＭｇ含有酸化物被覆軟磁性粒子（粉末）を作製する。
この被覆軟磁性金属粒子を得るためには、以下のいずれかの原料粉末を用い、後述する（Ａ）〜（Ｄ）に記載の方法のいずれかを選択して実施すれば良い。
この発明のＭｇ含有酸化物被覆軟磁性金属粒子の製造方法において使用する原料粉末としてのＦｅ系軟磁性金属粒子は、従来から一般に知られている鉄粉末、絶縁処理鉄粉末、Ｆｅ−Ａｌ系鉄基軟磁性合金粉末、Ｆｅ−Ｎｉ系鉄基軟磁性合金粉末、Ｆｅ−Ｃｒ系鉄基軟磁性合金粉末、Ｆｅ−Ｓｉ系鉄基軟磁性合金粉末、Ｆｅ−Ｓｉ−Ａｌ系鉄基軟磁性合金粉末、Ｆｅ−Ｃｏ系鉄基軟磁性合金粉末、Ｆｅ−Ｃｏ−Ｖ系鉄基軟磁性合金粉末またはＦｅ−Ｐ系鉄基軟磁性合金粉末であることが好ましい。
更に具体的には、鉄粉末は純鉄粉末であり、絶縁処理鉄粉末は、リン酸塩被覆鉄粉末、またはシリカのゾルゲル溶液（シリケート）もしくはアルミナのゾルゲル溶液などの湿式溶液を添加し混合して鉄粉末表面に被覆したのち乾燥して焼成した酸化ケイ素もしくは酸化アルミニウム被覆鉄粉末であり、Ｆｅ−Ａｌ系鉄基軟磁性合金粉末はＡ１：０．１〜２０質量％を含有し、残部がＦｅおよび不可避不純物からなるＦｅ−Ａｌ系鉄基軟磁性合金粉末（例えば、Ｆｅ−１５質量％Ａｌからなる組成を有するアルパーム粉末）であることが好ましい。
"Production of Mg-containing oxide-coated soft magnetic particles"
In the present invention, first, Mg-containing oxide-coated soft magnetic particles (powder) in which a Mg—Fe—O ternary oxide deposition film containing (Mg, Fe) O is coated on the surface of soft magnetic metal particles are produced. To do.
In order to obtain the coated soft magnetic metal particles, any one of the following raw material powders may be used by selecting one of the methods described in (A) to (D) described later.
Fe-based soft magnetic metal particles as a raw material powder used in the method for producing Mg-containing oxide-coated soft magnetic metal particles of the present invention are conventionally known iron powder, insulated iron powder, Fe-Al based iron. -Based soft magnetic alloy powder, Fe-Ni-based iron-based soft magnetic alloy powder, Fe-Cr-based iron-based soft magnetic alloy powder, Fe-Si-based iron-based soft magnetic alloy powder, Fe-Si-Al-based iron-based soft magnetic alloy Preferably, it is a powder, Fe-Co iron-based soft magnetic alloy powder, Fe-Co-V iron-based soft magnetic alloy powder or Fe-P iron-based soft magnetic alloy powder.
More specifically, the iron powder is a pure iron powder, and the insulation-treated iron powder is a phosphate-coated iron powder or a wet solution such as a silica sol-gel solution (silicate) or an alumina sol-gel solution. It is a silicon oxide or aluminum oxide coated iron powder that is coated on the surface of the iron powder and then dried and fired. The Fe—Al-based iron-based soft magnetic alloy powder contains A1: 0.1 to 20% by mass, with the balance being An Fe—Al-based iron-based soft magnetic alloy powder composed of Fe and inevitable impurities (for example, an alpalm powder having a composition composed of Fe-15 mass% Al) is preferable.
また、Ｆｅ−Ｎｉ系鉄基軟磁性合金粉末はＮｉ：３５〜８５質量％を含有し、必要に応じてＭｏ：５質量％以下、Ｃｕ：５質量％以下、Ｃｒ：２質量％以下、Ｍｎ：０．５質量％以下の内の１種または２種以上を含有し、残部がＦｅおよび不可避不純物からなるニッケル基軟磁性合金粉末（例えば、Ｆｅ−４９質量％Ｎｉ粉末）であり、Ｆｅ−Ｃｒ系鉄基軟磁性合金粉末はＣｒ：１〜２０質量％を含有し、必要に応じてＡｌ：５質量％以下、Ｎｉ：ｌ５質量％以下の内の１種または２種を含有し、残部がＦｅおよび不可避不純物からなるＦｅ−Ｃｒ系鉄基軟磁性合金粉末であり、Ｆｅ−Ｓｉ系鉄基軟磁性合金粉末は、Ｓｉ：０．１〜１０質量％を含有し、残部がＦｅおよび不可避不純物からなるＦｅ−Ｓｉ系鉄基軟磁性合金粉末であることが好ましい。
また、Ｆｅ−Ｓｉ−Ａｌ系鉄基軟磁性合金粉末は、Ｓｉ：０．１〜１０質量％、Ａｌ：０．１〜２０質量％を含有し、残部がＦｅおよび不可避不純物からなるＦｅ−Ｓｉ−Ａｌ系鉄基軟磁性合金粉末であり、Ｆｅ−Ｃｏ−Ｖ系鉄基軟磁性合金粉末は、Ｃｏ：０．１〜５２質量％、Ｖ：０．１〜３質量％を含有し、残部がＦｅおよび不可避不純物からなるＦｅ−Ｃｏ−Ｖ系鉄基軟磁性合金粉末であり、Ｆｅ−Ｃｏ系鉄基軟磁性合金粉末は、Ｃｏ：０．１〜５２質量％を含有し、残部がＦｅおよび不可避不純物からなるＦｅ−Ｃｏ系鉄基軟磁性合金粉末であり、Ｆｅ−Ｐ系鉄基軟磁性合金粉末は、Ｐ：０．５〜１質量％を含有し、残部がＦｅおよび不可避不純物からなるＦｅ−Ｐ系鉄基軟磁性合金粉末であることが好ましい。
Further, the Fe—Ni-based iron-based soft magnetic alloy powder contains Ni: 35 to 85% by mass, and Mo: 5% by mass or less, Cu: 5% by mass or less, Cr: 2% by mass or less, and Mn as required. : A nickel-based soft magnetic alloy powder (for example, Fe-49 mass% Ni powder) containing one or more of 0.5 mass% or less, with the balance being Fe and inevitable impurities, Fe— Cr-based iron-based soft magnetic alloy powder contains Cr: 1 to 20% by mass, and optionally contains one or two of Al: 5% by mass or less, Ni: 15% by mass or less, and the balance Is an Fe—Cr-based iron-based soft magnetic alloy powder composed of Fe and inevitable impurities, and the Fe—Si-based iron-based soft magnetic alloy powder contains Si: 0.1 to 10% by mass, with the balance being Fe and inevitable It must be Fe-Si iron-based soft magnetic alloy powder made of impurities. Masui.
The Fe—Si—Al-based iron-based soft magnetic alloy powder contains Si: 0.1 to 10% by mass, Al: 0.1 to 20% by mass, and the balance is Fe—Si composed of Fe and inevitable impurities. -Al-based iron-based soft magnetic alloy powder, Fe-Co-V-based iron-based soft magnetic alloy powder contains Co: 0.1 to 52 mass%, V: 0.1 to 3 mass%, the balance Is an Fe—Co—V-based iron-based soft magnetic alloy powder comprising Fe and inevitable impurities, and the Fe—Co-based iron-based soft magnetic alloy powder contains 0.1% to 52% by mass of Co, with the balance being Fe. And Fe—Co-based iron-based soft magnetic alloy powder composed of inevitable impurities, Fe—P-based iron-based soft magnetic alloy powder contains P: 0.5 to 1% by mass, and the balance is Fe and inevitable impurities. The Fe-P-based iron-based soft magnetic alloy powder is preferable.
そして、これらＦｅ系の軟磁性金属粒子は平均粒径：５〜５００μｍの範囲内にある軟磁性金属粉末（粒子）を使用することが好ましい。その理由は、平均粒径が５μｍより小さすぎると、粉末の圧縮性が低下し、軟磁性金属粒子の体積割合が低くなるために磁束密度の値が低下するので好ましくなく、一方、平均粒径が５００μｍより大きすぎると、軟磁性金属粒子内部の渦電流が増大して高周波における透磁率が低下することによるものである。 These Fe-based soft magnetic metal particles are preferably soft magnetic metal powders (particles) having an average particle diameter in the range of 5 to 500 μm. The reason is that if the average particle size is less than 5 μm, the compressibility of the powder is lowered, and the volume ratio of the soft magnetic metal particles is lowered, so the value of the magnetic flux density is lowered. If the value is larger than 500 μm, the eddy current inside the soft magnetic metal particles increases and the magnetic permeability at high frequency decreases.
（Ａ）これら各種のＦｅ系軟磁性金属粒子のいずれかを原料粉末とし、酸化雰囲気中で室温〜５００℃に保持する酸化処理を施した後、この原料粉末にＭｇ粉末を添加し混合して得られた混合粉末を温度：１５０〜１１００℃、圧力：１×１０−１２〜１×１０−１ＭＰａの不活性ガス雰囲気または真空雰囲気中で加熱し、さらに必要に応じて酸化雰囲気中、温度：５０〜４００℃で加熱すると、軟磁性金属粒子表面にＭｇを含む酸化絶縁被膜を有するＭｇ含有酸化物被覆軟磁性粉末（粒子）が得られる。
このＭｇ含有酸化物被覆軟磁性粒子は、従来のＭｇフェライト膜を形成したＭｇ含有酸化物被覆軟磁性粒子に比べて密着性が格段に優れたものとなり、このＭｇ含有酸化物被覆軟磁性粒子をプレス成形して圧粉体を作製しても絶縁被膜が破壊し剥離することが少なく、また、このＭｇ含有酸化物被覆軟磁性粒子の圧粉体を温度：４００〜１３００℃で焼成して得られた軟磁性複合圧密焼成材は粒界にＭｇ含有酸化膜が均一に分散し、粒界三重点にＭｇ含有酸化膜が集中していない組織が得られる。
(A) Any one of these various Fe-based soft magnetic metal particles is used as a raw material powder, subjected to an oxidation treatment that is maintained at room temperature to 500 ° C. in an oxidizing atmosphere, and then Mg powder is added to the raw material powder and mixed. The obtained mixed powder is heated in an inert gas atmosphere or a vacuum atmosphere at a temperature of 150 to 1100 ° C. and a pressure of 1 × 10 −12 to 1 × 10 −1 MPa, and further in an oxidizing atmosphere if necessary. When heated at 50 to 400 ° C., an Mg-containing oxide-coated soft magnetic powder (particles) having an oxide insulating film containing Mg on the surface of the soft magnetic metal particles is obtained.
The Mg-containing oxide-coated soft magnetic particles have much better adhesion than the conventional Mg-containing oxide-coated soft magnetic particles formed with an Mg ferrite film. Even if the green compact is produced by press molding, the insulating coating is less likely to break and peel off, and the green compact of the Mg-containing oxide-coated soft magnetic particles is obtained by firing at a temperature of 400 to 1300 ° C. The resulting soft magnetic composite compacted fired material provides a structure in which the Mg-containing oxide film is uniformly dispersed at the grain boundaries and the Mg-containing oxide film is not concentrated at the grain boundary triple points.
前述の製造方法の場合、酸化処理した軟磁性金属粒子を原料粉末とし、この原料粉末にＭｇ粉末を添加し混合して得られた混合粉末を温度：１５０〜１１００℃、圧力：１×１０−１２〜１×１０−１ＭＰａの不活性ガス雰囲気または真空雰囲気中で加熱するには、前記混合粉末を転動させながら加熱することが好ましい。 In the case of the above-mentioned production method, oxidized soft magnetic metal particles are used as raw material powder, and mixed powder obtained by adding and mixing Mg powder to this raw material powder is temperature: 150 to 1100 ° C., pressure: 1 × 10 − In order to heat in an inert gas atmosphere or a vacuum atmosphere of 12 to 1 × 10 −1 MPa, it is preferable to heat the mixed powder while rolling.
（Ｂ）前記軟磁性金属粒子を酸化雰囲気中で室温〜５００℃に保持することにより軟磁性金属粒子の表面に酸化物を形成した酸化物被覆軟磁性粉末に一酸化ケイ素粉末を添加し混合した後または混合しながら真空雰囲気中、温度：６００〜１２００℃保持の条件で加熱し、さらにＭｇ粉末を添加し混合した後または混合しながら真空雰囲気中、温度：４００〜８００℃保持の条件で加熱すると、軟磁性粉末の表面にＭｇ−Ｓｉ含有酸化膜が形成されたＭｇ−Ｓｉ含有酸化物被膜軟磁性粉末が得られ、この方法で作製したＭｇ−Ｓｉ含有酸化物被膜軟磁性粉末を用いて作製した複合軟磁性焼結材は、従来のＳｉＯを生成する化合物とＭｇＣＯまたはＭｇＯの粉末からなる混合物を圧縮成形し焼結して得られた複合軟磁性焼結材よりも密度、抗折強度、比抵抗および磁束密度が優れている。 (B) Silicon monoxide powder was added to and mixed with the oxide-coated soft magnetic powder in which an oxide was formed on the surface of the soft magnetic metal particles by maintaining the soft magnetic metal particles at room temperature to 500 ° C. in an oxidizing atmosphere. Heating is performed in a vacuum atmosphere at a temperature of 600 to 1200 ° C. after or while mixing, and further, added and mixed with Mg powder, or heated in a vacuum atmosphere at a temperature of 400 to 800 ° C. while mixing. Then, an Mg-Si-containing oxide-coated soft magnetic powder in which an Mg-Si-containing oxide film was formed on the surface of the soft magnetic powder was obtained, and the Mg-Si-containing oxide-coated soft magnetic powder produced by this method was used. The produced composite soft magnetic sintered material has a density and bending resistance higher than those of a composite soft magnetic sintered material obtained by compression molding and sintering a mixture of a compound that generates SiO and MgCO or MgO powder. Time, resistivity and magnetic flux density is excellent.
（Ｃ）前記軟磁性金属粒子を酸化雰囲気中で室温〜５００℃に保持することにより軟磁性金属粒子の表面に鉄の酸化膜を形成した酸化物被覆軟磁性粉末に一酸化ケイ素粉末およびＭｇ粉末を同時に添加し混合した後、または、混合しながら真空雰囲気中、温度：４００〜１２００℃保持の条件で加熱すると、軟磁性金属粒子の表面にＭｇ−Ｓｉ含有酸化物膜が形成されたＭｇ−Ｓｉ含有酸化物被膜軟磁性粉末が得られる。この方法で作製したＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末を用いて作製した複合軟磁性焼結材は、従来のＳｉＯ２を生成する化合物とＭｇＣＯ３またはＭｇＯの粉末からなる混合物を圧縮成形し焼結して得られた複合軟磁性焼結材よりも密度、抗折強度、比抵抗および磁束密度を優れさせることができる。
（Ｄ）前記軟磁性金属粒子を酸化雰囲気中で室温〜５００℃に保持することにより軟磁性金属粒子の表面に鉄の酸化膜を形成した酸化物被覆軟磁性粉末にＭｇ粉末を添加し混合した後または混合しながら真空雰囲気中、温度：４００〜８００℃保持の条件で加熱すると軟磁性粉末の表面にＭｇ含有酸化膜が形成されたＭｇ含有酸化物被覆軟磁性粉末が得られる。
このＭｇ含有酸化物被覆軟磁性粉末にさらに一酸化ケイ素粉末を添加し混合した後または混合しながら真空雰囲気中、温度：６００〜１２００℃保持の条件で加熱すると、軟磁性粉末の表面にＭｇ−Ｓｉ含有酸化物膜が形成されたＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末が得られ、この方法で作製したＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末を用いて作製した複合軟磁性焼結材であれば、従来のＳｉＯ２を生成する化合物とＭｇＣＯ３またはＭｇＯの粉末からなる混合物を圧縮成形し焼結して得られた複合軟磁性焼結材よりも密度、抗折強度、比抵抗および磁束密度を優れさせることができる。
前記一酸化ケイ素粉末の添加量は０．０１〜１質量％の範囲内にあることが好ましく、前記Ｍｇ粉末の添加量は０．０５〜１質量％の範囲内にあることが好ましい。
前記真空雰囲気は、圧力：１×１０−１２〜１×１０−１ＭＰａの真空雰囲気であることが好ましい。
(C) A silicon monoxide powder and an Mg powder in an oxide-coated soft magnetic powder in which an iron oxide film is formed on the surface of the soft magnetic metal particles by maintaining the soft magnetic metal particles in an oxidizing atmosphere at room temperature to 500 ° C. Are added and mixed at the same time, or when mixed and heated in a vacuum atmosphere at a temperature of 400 to 1200 ° C., Mg—Si-containing oxide film is formed on the surface of the soft magnetic metal particles. Si-containing oxide-coated soft magnetic powder is obtained. The composite soft magnetic sintered material produced using the Mg-Si-containing oxide-coated soft magnetic powder produced by this method is a compression molding of a conventional mixture of a compound that generates SiO 2 and MgCO 3 or MgO powder. The density, bending strength, specific resistance, and magnetic flux density can be made superior to the composite soft magnetic sintered material obtained by sintering.
(D) Mg powder was added to and mixed with the oxide-coated soft magnetic powder in which an iron oxide film was formed on the surface of the soft magnetic metal particles by maintaining the soft magnetic metal particles in an oxidizing atmosphere at room temperature to 500 ° C. When heated at a temperature of 400 to 800 ° C. in a vacuum atmosphere after or while mixing, an Mg-containing oxide-coated soft magnetic powder in which an Mg-containing oxide film is formed on the surface of the soft magnetic powder is obtained.
After further adding and mixing silicon monoxide powder to this Mg-containing oxide-coated soft magnetic powder or heating in a vacuum atmosphere while mixing and maintaining the temperature: 600-1200 ° C., the surface of the soft magnetic powder is Mg— An Mg-Si-containing oxide-coated soft magnetic powder having a Si-containing oxide film formed thereon is obtained, and a composite soft magnetic sintered material produced using the Mg-Si-containing oxide-coated soft magnetic powder produced by this method. If present, the density, bending strength, specific resistance, and magnetic flux are higher than those of a composite soft magnetic sintered material obtained by compression molding and sintering a mixture of a compound that generates SiO 2 and MgCO 3 or MgO powder. The density can be improved.
The addition amount of the silicon monoxide powder is preferably in the range of 0.01 to 1% by mass, and the addition amount of the Mg powder is preferably in the range of 0.05 to 1% by mass.
The vacuum atmosphere is preferably a vacuum atmosphere at a pressure of 1 × 10 −12 to 1 × 10 −1 MPa.
前記の製造方法に用いる一酸化ケイ素（ＳｉＯ）粉末は、酸化ケイ素の内でも最も蒸気圧が高い酸化物であるところから、加熱により軟磁性金属粒子の表面に酸化ケイ素成分を蒸着させ易く、蒸気圧の低い二酸化ケイ素（ＳｉＯ２）粉末を混合して加熱しても軟磁性金属粒子の表面に十分な厚さの酸化ケイ素膜が形成されないおそれがある。酸化物被覆軟磁性粉末に一酸化ケイ素（ＳｉＯ）粉末を添加し混合した後または混合しながら真空雰囲気中、温度：６００〜１２００℃に保持することにより軟磁性金属粒子の表面にＳｉＯｘ（ただし、ｘ；１〜２）膜を形成した酸化ケイ素膜被覆軟磁性粉末が生成し、この酸化ケイ素膜被覆軟磁性粉末にさらにＭｇ粉末を添加し混合しながら真空雰囲気中で加熱すると、Ｍｇ−Ｓｉ−Ｆｅ−ＯからなるＭｇ−Ｓｉ含有酸化物膜が軟磁性粉末に被覆したＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末が得られる。 The silicon monoxide (SiO) powder used in the above production method is an oxide having the highest vapor pressure among silicon oxides. Therefore, it is easy to deposit a silicon oxide component on the surface of soft magnetic metal particles by heating. Even if silicon dioxide (SiO 2 ) powder having a low pressure is mixed and heated, a silicon oxide film having a sufficient thickness may not be formed on the surface of the soft magnetic metal particles. After the silicon monoxide (SiO) powder is added to the oxide-coated soft magnetic powder and mixed, or in a vacuum atmosphere with mixing, the temperature is maintained at 600 to 1200 ° C., so that SiOx (however, x: 1-2) A silicon oxide film-coated soft magnetic powder having a film formed thereon was formed, and when Mg powder was further added to the silicon oxide film-coated soft magnetic powder and heated in a vacuum atmosphere while mixing, Mg-Si- An Mg—Si-containing oxide-coated soft magnetic powder in which an Mg—Si-containing oxide film made of Fe—O is coated on a soft magnetic powder is obtained.
前述の酸化物被覆軟磁性粉末は、軟磁性金属粒子を酸化雰囲気中（例えば、大気中）、温度：室温〜５００℃に保持することにより軟磁性粉末の表面に鉄酸化膜を形成して作製することができる。そして、この鉄酸化膜はＳｉＯおよび／またはＭｇの被覆性を向上させる効果がある。酸化物被覆軟磁性粉末を作製する際に酸化雰囲気中で５００℃を越えて加熱すると、軟磁性金属粒子が凝集して軟磁性金属粒子の集合体が生成し、焼結したりして均一な表面酸化ができなくなるので好ましくない。したがって、酸化物被覆軟磁性粉末の製造時の加熱温度は室温〜５００℃に定めた。一層好ましい範囲は室温〜３００℃である。酸化雰囲気は乾燥した酸化雰囲気であることが一層好ましい。 The above oxide-coated soft magnetic powder is produced by forming an iron oxide film on the surface of the soft magnetic powder by maintaining the soft magnetic metal particles in an oxidizing atmosphere (for example, in the air) at a temperature of room temperature to 500 ° C. can do. This iron oxide film has the effect of improving the coverage of SiO and / or Mg. When an oxide-coated soft magnetic powder is produced and heated above 500 ° C. in an oxidizing atmosphere, the soft magnetic metal particles agglomerate to form an aggregate of soft magnetic metal particles, which can be uniformly sintered. It is not preferable because the surface cannot be oxidized. Therefore, the heating temperature during the production of the oxide-coated soft magnetic powder was set to room temperature to 500 ° C. A more preferred range is from room temperature to 300 ° C. More preferably, the oxidizing atmosphere is a dry oxidizing atmosphere.
この発明で用いるＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末において、酸化物被覆軟磁性粉末に添加するＳｉＯ粉末量を０．０１〜１質量％に限定したのは、ＳｉＯ粉末の添加量が０．０１質量％未満では酸化物被覆軟磁性粉末の表面に形成される酸化ケイ素膜の厚さが不足するのでＭｇ−Ｓｉ含有酸化物膜に含まれるＳｉの量が不足し、したがって、比抵抗の高いＭｇ−Ｓｉ含有酸化物膜が得られないので好ましくなく、一方、１質量％を越えて添加すると、形成されるＳｉＯｘ（ｘ；１〜２）酸化ケイ素膜の厚さが厚くなり過ぎて、得られたＭｇ−Ｓｉ含有酸化物被覆軟磁性金属粒子を圧粉し焼成して得られた軟磁性複合圧密焼成材の密度が低下するようになるおそれがある。 In the Mg—Si-containing oxide-coated soft magnetic powder used in the present invention, the amount of SiO powder added to the oxide-coated soft magnetic powder is limited to 0.01 to 1% by mass. If it is less than 01% by mass, the thickness of the silicon oxide film formed on the surface of the oxide-coated soft magnetic powder is insufficient, so the amount of Si contained in the Mg-Si-containing oxide film is insufficient, and therefore the specific resistance is high. An Mg-Si-containing oxide film cannot be obtained, which is not preferable. On the other hand, if it exceeds 1% by mass, the thickness of the SiOx (x; 1-2) silicon oxide film to be formed becomes too thick. There is a possibility that the density of the soft magnetic composite compacted fired material obtained by compacting and firing the Mg-Si-containing oxide-coated soft magnetic metal particles may be lowered.
また、この発明のＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末の製造方法において、Ｍｇ粉末の添加量を０．０５〜１質量％が好ましいと規定したのは、Ｍｇ粉末の添加量が０．０５質量％未満では酸化物被覆軟磁性粉末の表面に形成されるＭｇ膜の厚さが不足してＭｇ−Ｓｉ含有酸化物膜に含まれるＭｇの量が不足し、従って、十分な厚さのＭｇ−Ｓｉ酸化物膜が得られないので好ましくなく、一方、１質量％を越えて添加すると、形成されるＭｇ膜の厚さが厚くなり過ぎて、得られたＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末を圧粉し焼成して得られた軟磁性複合圧密焼成材の密度が低下するようになるので好ましくないからである。 Moreover, in the manufacturing method of Mg-Si containing oxide covering soft magnetic powder of this invention, it was prescribed that the addition amount of Mg powder is preferably 0.05 to 1% by mass. If it is less than mass%, the thickness of the Mg film formed on the surface of the oxide-coated soft magnetic powder is insufficient, and the amount of Mg contained in the Mg-Si-containing oxide film is insufficient. -Si oxide film cannot be obtained, which is not preferable. On the other hand, if it exceeds 1% by mass, the formed Mg film becomes too thick, and the resulting Mg-Si-containing oxide-coated soft magnetism This is because the density of the soft magnetic composite compacted fired material obtained by compacting and firing the powder is not preferable.
この発明で用いるＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末の製造方法において、酸化物被覆軟磁性粉末にＳｉＯ粉末、Ｍｇ粉末またはＳｉＯ粉末およびＭｇ粉末の混合粉末を添加し混合する条件を温度６００〜１２００℃の真空雰囲気が好ましいとしたのは、６００℃未満で加熱してもＳｉＯの蒸気圧が小さいために十分な厚さのＳｉＯ膜またはＭｇ−Ｓｉ含有酸化物被膜が得られないためであり、一方、１２００℃を越えて混合すると軟磁性粉末が焼結するようになって所望のＭｇ−Ｓｉ含有酸化物被覆軟磁性粉末が得られないので好ましくないからである。また、その時の加熱雰囲気は圧力：１×１０−１２〜１×１０−１ＭＰａの真空雰囲気中であることが好ましく、更に転動しながら加熱することが一層好ましい。 In the method for producing an Mg-Si-containing oxide-coated soft magnetic powder used in the present invention, the conditions for adding and mixing SiO powder, Mg powder, or a mixed powder of SiO powder and Mg powder to the oxide-coated soft magnetic powder are set at a temperature of 600 to The reason why the vacuum atmosphere at 1200 ° C. is preferred is that even when heated below 600 ° C., the vapor pressure of SiO is low, so that a sufficiently thick SiO film or Mg—Si-containing oxide film cannot be obtained. On the other hand, if the mixing temperature exceeds 1200 ° C., the soft magnetic powder is sintered and the desired Mg—Si-containing oxide-coated soft magnetic powder cannot be obtained. Further, the heating atmosphere at that time is preferably in a vacuum atmosphere at a pressure of 1 × 10 −12 to 1 × 10 −1 MPa, and more preferably heated while rolling.
酸化物被覆軟磁性粉末を作製するときに使用する軟磁性金属粒子は平均粒径：５〜５００μｍの範囲内にある軟磁性粉末を使用することが好ましい。その理由は、平均粒径が５μｍより小さすぎると、粉末の圧縮性が低下し、軟磁性粉末の体積割合が低くなるために磁束密度の値が低下するので好ましくなく、一方、平均粒径が５００μｍより大きすぎると、軟磁性粉末内部の渦電流が増大して高周波における透磁率が低下することによるものである。
軟磁性金属粒子の酸化処理は、Ｍｇの被覆性を向上させる効果があり、酸化雰囲気中、温度１５０〜５００℃または蒸留水または純水中、温度：５０〜１００℃に保持することにより行う。この場合、いずれも５０℃未満では効率的でなく、一方、酸化雰囲気中で５００℃を越えて保持すると焼結が起るために好ましくないからである。酸化雰囲気は乾燥した酸化雰囲気であることが一層好ましい。
The soft magnetic metal particles used when producing the oxide-coated soft magnetic powder are preferably soft magnetic powders having an average particle size in the range of 5 to 500 μm. The reason is that if the average particle size is less than 5 μm, the compressibility of the powder is lowered, and the volume ratio of the soft magnetic powder is lowered, so the value of the magnetic flux density is lowered. If it is larger than 500 μm, the eddy current inside the soft magnetic powder increases and the magnetic permeability at high frequency decreases.
The oxidation treatment of the soft magnetic metal particles has an effect of improving the coverage of Mg, and is performed by maintaining the temperature at 50 to 100 ° C. in an oxidizing atmosphere at a temperature of 150 to 500 ° C. or distilled water or pure water. In this case, it is not efficient when the temperature is less than 50 ° C., and on the other hand, if the temperature exceeds 500 ° C. in an oxidizing atmosphere, sintering occurs, which is not preferable. More preferably, the oxidizing atmosphere is a dry oxidizing atmosphere.
「堆積膜」という用語は、通常、真空蒸着やスパッタされた皮膜構成原子が例えば基板上に堆積された皮膜を示すが、本発明において用いる堆積膜とは、酸化鉄膜を有するＦｅ系軟磁性粉末の酸化鉄（Ｆｅ−Ｏ）とＭｇが反応を伴って当該Ｆｅ系軟磁性金属粒子表面に堆積した皮膜を示す。このＦｅ系軟磁性金属粒子の表面に形成されているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜の膜厚は、圧粉成形後に軟磁性複合圧密焼成材の高磁束密度と高比抵抗を得るために、５ｎｍ〜５００ｎｍの範囲内にあることが好ましい。ここでの膜厚が５ｎｍより薄いと、圧粉成形した軟磁性複合圧密焼成材の比抵抗が充分ではなく、渦電流損失が増加するので好ましくなく、膜厚が５００ｎｍを越える厚さでは、圧粉成形した軟磁性複合圧密焼成材の磁束密度が低下するので好ましくない。このような範囲において更に好ましい膜厚は、５ｎｍ〜２００ｎｍの範囲内である。 The term “deposited film” usually indicates a film in which atoms constituting a film deposited by vacuum evaporation or sputtering are deposited on a substrate, for example. The deposited film used in the present invention is an Fe-based soft magnetic film having an iron oxide film. A film in which powdered iron oxide (Fe—O) and Mg are deposited on the surface of the Fe-based soft magnetic metal particles with a reaction is shown. The film thickness of the Mg-Fe-O ternary oxide deposited film formed on the surface of the Fe-based soft magnetic metal particles is such that the high magnetic flux density and high specific resistance of the soft magnetic composite compacted fired material after compacting are reduced. In order to obtain it, it is preferable to exist in the range of 5 nm-500 nm. If the film thickness is less than 5 nm, the specific resistance of the compacted soft magnetic composite compacted fired material is not sufficient, and eddy current loss increases. Since the magnetic flux density of the powder-molded soft magnetic composite compacted fired material is lowered, it is not preferable. In such a range, a more preferable film thickness is in the range of 5 nm to 200 nm.
前述の方法により作製されたＭｇ含有酸化物被覆軟磁性粒子は、その表面にＭｇ含有酸化膜が形成され、このＭｇ含有酸化膜は酸化ケイ素や酸化アルミニウムと反応して複合酸化物が形成され、軟磁性粉末の粒界に高抵抗を有する複合酸化物が介在した高比抵抗を有する軟磁性複合圧密焼成材が最終的に得られるとともに、酸化ケイ素や酸化アルミニウムを介して焼結されるために機械的強度の優れた軟磁性複合圧密焼成材を製造することができる。この場合、酸化ケイ素や酸化アルミニウムが主体となって焼結されるところから保磁力を小さく保つことができ、したがって、ヒステリシス損の少ない軟磁性複合圧密焼成材を製造することができる、前記焼成は、不活性ガス雰囲気中あるいは非酸化性ガス雰囲気中において、温度：４００〜１３００℃で行われることが好ましい。 The Mg-containing oxide-coated soft magnetic particles produced by the above-described method have an Mg-containing oxide film formed on the surface thereof, and this Mg-containing oxide film reacts with silicon oxide or aluminum oxide to form a composite oxide. In order to finally obtain a soft magnetic composite compacted fired material having a high specific resistance in which a composite oxide having a high resistance is interposed at the grain boundary of the soft magnetic powder and to be sintered through silicon oxide or aluminum oxide A soft magnetic composite compacted fired material having excellent mechanical strength can be produced. In this case, the coercive force can be kept small from being sintered mainly with silicon oxide or aluminum oxide, and thus a soft magnetic composite compacted fired material with less hysteresis loss can be produced. In an inert gas atmosphere or a non-oxidizing gas atmosphere, the temperature is preferably 400 to 1300 ° C.
「高強度高比抵抗低損失複合軟磁性材の製造方法」
以上説明した方法により前述の如く作製したＭｇ含有酸化物被覆軟磁性粒子を使用して高強度高比抵抗低損失複合軟磁性材を製造するには、まず、前述の方法で作製したＭｇ含有酸化物被覆軟磁性粒子に対し、バインダー材としてのシリコーンレジンなどのＳｉを含むバインダー材と、２価金属粉末（粒子）を混合してから通常の方法で圧粉成形し、この成形体をアルゴン雰囲気中、窒素雰囲気中、水素雰囲気中などの非酸化性雰囲気において５００〜１０００℃で焼成して高強度高比抵抗低損失複合軟磁性材の前駆体を形成する。
そして、この焼成後、先の前駆体を後述する如く、スチーム雰囲気、大気などの酸化性雰囲気中において４００〜６００℃の範囲内の温度で熱処理することにより、本発明で目的とする軟磁性複合圧密焼成材を得ることができる。
"Production method of high strength, high specific resistance, low loss composite soft magnetic material"
In order to produce a high-strength, high-resistivity, low-loss composite soft magnetic material using the Mg-containing oxide-coated soft magnetic particles prepared as described above by the method described above, first, the Mg-containing oxide prepared by the method described above is used. For material-coated soft magnetic particles, a binder material containing Si such as silicone resin as a binder material and a divalent metal powder (particles) are mixed and then compacted by an ordinary method. A precursor of a high-strength, high-resistivity, low-loss composite soft magnetic material is formed by firing at 500 to 1000 ° C. in a non-oxidizing atmosphere such as in a nitrogen atmosphere or a hydrogen atmosphere.
Then, after the firing, as described later, the precursor is subjected to a heat treatment at a temperature in the range of 400 to 600 ° C. in an oxidizing atmosphere such as a steam atmosphere or the air, so that the soft magnetic composite intended in the present invention is obtained. A consolidated fired material can be obtained.
図１はＭｇ含有酸化物被覆軟磁性粒子を製造する場合において、原料を準備するための最初の工程から、スチーム雰囲気において最終処理するまでの工程順の一例を記載したもので、図１の工程Ｓ１において用意した原料としての軟磁性合金粉末の原料を工程Ｓ２において焼鈍し、工程Ｓ３において平滑化し、工程Ｓ４において前酸化し、工程Ｓ５においてＭｇを蒸着し、工程Ｓ６においてカップリング混合し、この混合物を工程Ｓ７において乾燥し、工程Ｓ８においてバインダーと混合し、この混合物を工程Ｓ９において乾燥し、工程Ｓ１０において成形し、工程Ｓ１１において焼成し、工程Ｓ１２においてスチーム処理することにより、先に説明した如く本発明に係る高強度高比抵抗低損失複合軟磁性材を得ることができる。以上説明した工程Ｓ１〜Ｓ１２において選択するべき各種の条件は前述した条件、あるいは後述する条件が好ましい。 FIG. 1 shows an example of the order of steps from the initial step for preparing raw materials to the final treatment in a steam atmosphere when producing Mg-containing oxide-coated soft magnetic particles. The raw material of the soft magnetic alloy powder prepared in S1 is annealed in Step S2, smoothed in Step S3, pre-oxidized in Step S4, Mg is deposited in Step S5, and coupled and mixed in Step S6. The mixture was dried in step S7, mixed with the binder in step S8, this mixture was dried in step S9, shaped in step S10, fired in step S11, and steamed in step S12, as described above. Thus, the high strength, high specific resistance and low loss composite soft magnetic material according to the present invention can be obtained. The various conditions to be selected in the above-described steps S1 to S12 are preferably the conditions described above or the conditions described later.
なお、２価金属粉末（粒子）を混合するタイミングは、Ｍｇ含有酸化物被覆軟磁性粒子を製造した直後であっても、後にバインダーと混合する以前に行っても、Ｍｇ含有酸化物被覆軟磁性粒子の製造と同時に行っても良い。
２価金属粉末として、Ｚｎ、Ｍｇ、Ｃｏ、Ｎｉ、Ｍｎ、Ｃｕ、Ｃａのいずれか１種の単体金属粉末、２種以上の混合粉末、合金粉末、あるいは、これらの２価金属の酸化物粉末などの化合物粉末であっても差し支えない。酸化物粉末として添加する場合、ＺｎＯ粉末、ＭｇＯ粉末、ＣｏＯ粉末、ＮｉＯ粉末、ＭｎＯ粉末、ＣｕＯ粉末、ＣａＯ粉末のいずれか１種以上を用いることができる。
これらの粉末を微細な粉末として均一に添加することが好ましい。前述の方法により作製されたＭｇ含有酸化物被覆軟磁性粒子は、その表面にＭｇ含有酸化膜が形成され、その膜厚は５ｎｍ〜５００ｎｍの範囲内にあるのが好ましいので、この膜厚より大きな２価金属粉末を添加すると、圧密成形時にＭｇ含有酸化膜が損傷するおそれがあるので、Ｍｇ含有酸化膜の膜厚よりも粒径の小さな２価金属粉末を用いることが好ましい。
２価金属の添加量は０．１〜０．５質量％の範囲が好ましく、０．１〜０．１５質量％の範囲がより好ましい。２価金属の好ましい添加量、粉末の好ましい粒径等については後に詳述する。
The timing of mixing the divalent metal powder (particles) may be immediately after the Mg-containing oxide-coated soft magnetic particles are produced or before mixing with the binder later. You may carry out simultaneously with manufacture of particle | grains.
As the divalent metal powder, any one of single metal powder of Zn, Mg, Co, Ni, Mn, Cu, and Ca, two or more mixed powders, alloy powder, or oxide powder of these divalent metals A compound powder such as can be used. When adding as oxide powder, any 1 or more types of ZnO powder, MgO powder, CoO powder, NiO powder, MnO powder, CuO powder, and CaO powder can be used.
These powders are preferably added uniformly as fine powders. The Mg-containing oxide-coated soft magnetic particles produced by the above-described method have an Mg-containing oxide film formed on the surface thereof, and the film thickness is preferably in the range of 5 nm to 500 nm. If the divalent metal powder is added, the Mg-containing oxide film may be damaged during the compacting. Therefore, it is preferable to use a divalent metal powder having a particle diameter smaller than that of the Mg-containing oxide film.
The addition amount of the divalent metal is preferably in the range of 0.1 to 0.5% by mass, and more preferably in the range of 0.1 to 0.15% by mass. A preferable addition amount of the divalent metal, a preferable particle diameter of the powder, and the like will be described in detail later.
なお、前記したＳｉを含むバインダーの代わりに、低融点ガラスあるいは金属酸化物のいずれかからなるバインダーを用いても良い。
前記低融点ガラスを用いる場合は、Ｂｉ２Ｏ３−Ｂ２Ｏ３、ＳｎＯ−Ｐ２Ｏ５、ＳｉＯ２−Ｂ２Ｏ３−ＺｎＯ、ＳｉＯ２−Ｂ２Ｏ３−Ｒ２Ｏ（Ｒはアルカリ土類金属）、Ｌｉ２Ｏ−ＺｎＯのいずれかを用いることができる。これらの添加量は、０．２〜１．５質量％の範囲内とすることができる。
あるいは、前記Ｍｇ含有酸化物被覆軟磁性粒子に、酸化アルミニウム、酸化ホウ素、酸化バナジウム、酸化ビスマス、酸化アンチモンおよび酸化モリブデンの内の１種または２種以上の金属酸化物をＢ２Ｏ３、Ｖ２Ｏ５、Ｂｉ２Ｏ３、Ｓｂ２Ｏ３、ＭｏＯ３換算で０．０５〜１質量％の範囲内で配合し、混合した後に圧粉、成形し、得られた圧粉体を温度５００〜１０００℃で真空中、アルゴン雰囲気、窒素雰囲気、水素雰囲気、大気中のいずれかにおいて焼成することにより高強度高比抵抗低損失複合軟磁性材を作製することができる。前記焼成雰囲気は、望ましくは窒素雰囲気、水素雰囲気が良く、中でも水素雰囲気が好ましい。
前記バインダーとして混合する低融点ガラス、金属酸化物は、粉末状態でも良く、ゾルゲル溶液あるいは金属有機物などの前駆体溶液なども用いることができる。
Note that a binder made of either a low-melting glass or a metal oxide may be used instead of the binder containing Si.
When the low melting point glass is used, Bi 2 O 3 —B 2 O 3 , SnO—P 2 O 5 , SiO 2 —B 2 O 3 —ZnO, SiO 2 —B 2 O 3 —R 2 O (R is Either alkaline earth metal) or Li 2 O—ZnO can be used. These addition amounts can be in the range of 0.2 to 1.5 mass%.
Alternatively, one or more metal oxides of aluminum oxide, boron oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide are added to the Mg-containing oxide-coated soft magnetic particles with B 2 O 3 , V 2 O 5 , Bi 2 O 3 , Sb 2 O 3 and MoO 3 are mixed within a range of 0.05 to 1% by mass, mixed and then compacted and molded. A high-strength, high-resistivity, low-loss composite soft magnetic material can be produced by firing in a vacuum, argon atmosphere, nitrogen atmosphere, hydrogen atmosphere, or air at ˜1000 ° C. The firing atmosphere is desirably a nitrogen atmosphere or a hydrogen atmosphere, and a hydrogen atmosphere is particularly preferable.
The low-melting glass and metal oxide to be mixed as the binder may be in a powder state, and a precursor solution such as a sol-gel solution or a metal organic substance can also be used.
本発明では、先の軟磁性複合圧密焼成材の前駆体の抗折強度を高めるなどの目的において、スチーム雰囲気などの酸化性雰囲気中において、４００℃〜６００℃の温度範囲内に加熱する熱処理を施す。
ここでの酸化性雰囲気における熱処理により、前駆体における（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜を軟磁性金属粒子の表面に被覆形成した被覆軟磁性金属粒子（粉末）と、それらの界面に存在する（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜と、この堆積膜の周囲に形成されたバインダー層が存在し、添加した２価金属粉末からなる２価金属が前記Ｍｇ−Ｆｅ−Ｏ三元系酸化物堆積膜に拡散し、更に軟磁性金属粒子からＦｅがこれらの各層に拡散する結果、軟磁性金属粒子と該軟磁性金属粒子の表面に被覆されたＭｇ含有酸化物とを具備してなるＭｇ含有酸化物被覆軟磁性粒子が、酸化鉄を含むシリコン酸化物（例えば、Ｆｅ２Ｏ４あるいはＦｅＯを主体とする酸化鉄と２価金属「Ｍ（ＩＩ）」を含むシリコーンレジンなどのシリコン酸化物を主体とする（ＭｇＭ（ＩＩ）Ｆｅ）Ｏなる組成あるいは（ＭｇＭ（ＩＩ）Ｆｅ）Ｆｅ２Ｏ４なる組成の複合酸化物を主体としてなる粒界層を介し複数結合されてなる構造となり、最終的に目的とする高強度高比抵抗低損失複合軟磁性材を得ることができる。
In the present invention, for the purpose of increasing the bending strength of the precursor of the soft magnetic composite compacted fired material, the heat treatment is performed in a temperature range of 400 ° C. to 600 ° C. in an oxidizing atmosphere such as a steam atmosphere. Apply.
By the heat treatment in an oxidizing atmosphere, the coated soft magnetic metal particles (the Mg—Fe—O ternary oxide deposited film containing (Mg, Fe) O in the precursor) are formed on the surface of the soft magnetic metal particles ( Powder), an Mg—Fe—O ternary oxide deposition film containing (Mg, Fe) O present at the interface between them, and a binder layer formed around this deposition film, and added 2 As a result of the divalent metal consisting of the valent metal powder diffusing into the Mg—Fe—O ternary oxide deposited film, and further from the soft magnetic metal particles, Fe diffuses into these layers. An Mg-containing oxide-coated soft magnetic particle comprising an Mg-containing oxide coated on the surface of a metal particle is a silicon oxide containing iron oxide (for example, iron oxide mainly composed of Fe 2 O 4 or FeO). And the divalent metal “M (II)” Mainly of silicon oxide such as recone resin (MgM (II) Fe) multiple bonds through the grain boundary layer made of O a composition or (MgM (II) Fe) composite oxide of Fe 2 O 4 having a composition of mainly Thus, it is possible to finally obtain a target high strength, high specific resistance, low loss composite soft magnetic material.
前述の酸化性雰囲気として好ましくは、４００℃〜６００℃のスチーム雰囲気を選択できるが、この他に、大気中などの酸化性雰囲気中において前述の温度範囲内に熱処理する条件でも差し支えない。
前述のスチーム雰囲気における加熱処理条件として、４００℃未満の温度とすると、（ＭｇＭ（ＩＩ）Ｆｅ）Ｏなる組成あるいは（ＭｇＭ（ＩＩ）Ｆｅ）Ｆｅ２Ｏ４なる組成の複合酸化物の形成が促進されず、強度が発現しない問題があり、逆に６００℃を越える加熱条件とすると、ＦｅＯの形成と分解により望ましい強度が発現しないおそれがある。また、スチーム雰囲気中での加熱処理条件として、前記ＦｅＯをできるだけ生成しないためには、４００℃〜５６０℃の範囲がより好ましい。
A steam atmosphere of 400 ° C. to 600 ° C. can be preferably selected as the above-mentioned oxidizing atmosphere, but other conditions such as heat treatment in an oxidizing atmosphere such as air may be used.
As a heat treatment condition in the steam atmosphere described above, when the temperature is lower than 400 ° C., formation of a composite oxide having a composition of (MgM (II) Fe) O or a composition of (MgM (II) Fe) Fe 2 O 4 is promoted. However, there is a problem that the strength does not develop. On the contrary, if the heating condition exceeds 600 ° C., the desired strength may not be developed due to the formation and decomposition of FeO. Moreover, as heat processing conditions in a steam atmosphere, in order to produce | generate the said FeO as much as possible, the range of 400 to 560 degreeC is more preferable.
前述のスチーム雰囲気中において酸化鉄がシリコーンレジンの内部に拡散し成長するのは、成形時に生じた微小な亀裂やＭｇＯ膜を構成する結晶粒の粒間をＦｅが拡散するのが原因ではないかと考えられる。この拡散したＦｅが酸化雰囲気熱処理の過程で酸化して酸化鉄が成長し粒界を充填するか、または、一部ＦｅＯを含む粒界層を充填し、強度が向上するためであると考えられる。
（Ｍｇ，Ｆｅ）Ｏを含む酸化物堆積膜を軟磁性金属粒子の表面に被覆形成したＭｇ含有酸化物被覆軟磁性粉末（粒子）については、（Ｍｇ，Ｆｅ）Ｏを含む酸化物堆積膜はウスタイト相を主とした堆積膜であるが、焼成時にバインダー層中に拡散し、Ｍｇ、Ｆｅ、バインダー成分、Ｏからなるウスタイト相を主とした粒界層を形成する。例えば、バインダーがシリコーンレジンの場合に粒界層は、Ｍｇ、２価金属、Ｓｉ、Ｏ、Ｆｅ、Ｃからなる粒界化合物を形成し、比抵抗の増大を図ることができる。なお、この組成の粒界化合物に対して本実施形態では、２価金属を含有させているので、加熱後の熱拡散により、Ｍｇ、Ｓｉ、Ｏ、Ｆｅ、Ｃからなるウスタイト相を主体とした粒界化合物中に２価金属が拡散された構造となる。粒界層として例えば、[ＭｇＭ（ＩＩ）Ｆｅ]Ｏなる組成か、あるいは、[ＭｇＭ（ＩＩ）Ｆｅ]Ｆｅ２Ｏ４なる組成式で示される複合酸化物にＳｉが拡散されている粒界層が得られると考えられる。
The reason why iron oxide diffuses and grows inside the silicone resin in the steam atmosphere described above may be due to minute cracks generated during molding or diffusion of Fe between the crystal grains constituting the MgO film. Conceivable. This is because the diffused Fe is oxidized during the heat treatment in the oxidizing atmosphere and iron oxide grows and fills the grain boundary, or partially fills the grain boundary layer containing FeO and improves the strength. .
For the Mg-containing oxide-coated soft magnetic powder (particles) formed by coating the oxide magnetic film containing (Mg, Fe) O on the surface of the soft magnetic metal particles, the oxide film containing (Mg, Fe) O is Although it is a deposited film mainly composed of a wustite phase, it diffuses into the binder layer during firing, and forms a grain boundary layer mainly composed of a wustite phase composed of Mg, Fe, a binder component, and O. For example, when the binder is a silicone resin, the grain boundary layer can form a grain boundary compound composed of Mg, divalent metal, Si, O, Fe, and C to increase the specific resistance. In this embodiment, since a divalent metal is contained in the grain boundary compound having this composition, a wustite phase composed of Mg, Si, O, Fe, and C is mainly formed by thermal diffusion after heating. A structure in which a divalent metal is diffused in the grain boundary compound is obtained. As the grain boundary layer, for example, a grain boundary layer in which Si is diffused in a composite oxide represented by a composition of [MgM (II) Fe] O or a composition formula of [MgM (II) Fe] Fe 2 O 4 Can be obtained.
図２〜図４はＭｇ含有酸化物被覆軟磁性粒子とその周囲の堆積膜における２価金属と鉄との拡散反応により生成される粒界化合物としての粒界層の生成を説明するためのモデル図である。
図２に示す如く軟磁性金属粒子１の周囲に前述の（Ｍｇ，Ｆｅ）Ｏを含む酸化物堆積膜２が形成され、対向する軟磁性粒子１の酸化物堆積膜２どうしの間にバインダー層３が形成され、これらの間に２価金属粒子４が分散された状態が示されている。
図２の状態から前述の如く窒素雰囲気中などの非酸化性雰囲気において５００〜１０００℃で焼成することにより、Ｍｇ含有酸化物被覆軟磁性粒子中のＦｅが拡散して酸化物堆積膜２とバインダー層３側に拡散した結果の焼成体としての前駆体が図３に示すように形成され、更にスチーム雰囲気中において加熱することで、図４に示す如く２価金属粒子の成分が拡散されて酸化鉄を含むシリコン酸化物３’（例えば、Ｆｅ２Ｏ４あるいはＦｅＯを主体とする酸化鉄と２価金属「Ｍ（ＩＩ）」を含むシリコーンレジンなどのシリコン酸化物）を主体とする（ＭｇＭ（ＩＩ）Ｆｅ）Ｏなる組成あるいは（ＭｇＭ（ＩＩ）Ｆｅ）Ｆｅ２Ｏ４なる組成の複合酸化物を主体としてなる粒界層５を介し複数結合されてなる構造となり、最終的に目的とする高強度高比抵抗低損失複合軟磁性材６を得ることができる。
FIGS. 2 to 4 are models for explaining the formation of a grain boundary layer as a grain boundary compound produced by a diffusion reaction between a divalent metal and iron in a Mg-containing oxide-coated soft magnetic particle and a surrounding deposited film. FIG.
As shown in FIG. 2, the
By firing at 500 to 1000 ° C. in a non-oxidizing atmosphere such as a nitrogen atmosphere as described above from the state of FIG. 2, Fe in the Mg-containing oxide-coated soft magnetic particles diffuses and the
次に、図２〜図４を基に説明した工程により製造される高強度高比抵抗低損失複合軟磁性材の粒界層を生成する際のモデル構造の更に２つの例について、図５を基に以下に説明する。
図５（Ａ）に示す如く、Ｆｅを主体とする軟磁性金属粒子１０、１０の周囲に（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜１１を備えたＭｇ含有酸化物被覆軟磁性粒子どうしの間の粒界層１２として、圧密成形した後の工程Ｓ１１において、粒界層１２にはシリコーンレジンの内部に２価金属粉末粒子としてのＺｎＯ粉末粒子が分散された状態となっている。この状態から焼成すると、図５（Ｂ）に示す如く粒界層１３はＳｉＯ２とＺｎＯの拡散混合された状態になると推定できる。この状態からスチーム処理を施すと、外部から水分が粒界に拡散侵入するので、[ＭｇＺｎＦｅ]Ｆｅ２Ｏ４＋ＳｉＯ２ の状態となり、Ｆｅ２＋とＺｎ２＋が一部置換し、比抵抗が向上して粒界層１４が生成するものと推定できる。
Next, two more examples of the model structure when generating a grain boundary layer of a high-strength, high-resistivity, low-loss composite soft magnetic material manufactured by the process described with reference to FIGS. This will be described below.
As shown in FIG. 5 (A), Mg containing Fe-O-ternary
なおまた、図５の説明では粒界層に添加した２価金属の粒子が完全に拡散しているモデル構造として説明したが、粒界層に添加する粒子の大きさによっては粒子の形態が部分的に残留したまま、２価金属が粒界層に拡散し、スチーム処理後に２価金属の粒子が粒界層に残留したままの状態となっていても差し支えない。 In addition, in the description of FIG. 5, the model structure is described in which the divalent metal particles added to the grain boundary layer are completely diffused. However, depending on the size of the particles added to the grain boundary layer, the shape of the particles may be partially However, the divalent metal may diffuse into the grain boundary layer while remaining, and the divalent metal particles may remain in the grain boundary layer after the steam treatment.
ところで、これまで説明してきた粒界層における酸化物（Ｍｇ２＋Ｆｅ２＋Ｆｅ３＋）１−ｘＯおよび／又は（Ｍｇ２＋Ｆｅ２＋）Ｆｅ３＋ ２Ｏ４ の電気伝導は、Ｆｅ２＋とＦｅ３＋の電荷交換によるホッピング電導が支配的と考えられる。このため、（Ｍｇ２＋Ｆｅ２＋Ｆｅ３＋）１−ｘＯの比抵抗を向上させるためには、酸化雰囲気のスチーム処理後は一定比率で粒界層にＦｅ２＋とＦｅ３＋の共存が避けられず、（Ｍｇ、Ｆｅ）Ｏ膜中でのＦｅ原子そのものを低減する必要があると本発明者は考慮した。また、（Ｍｇ２＋Ｆｅ２＋）Ｆｅ３＋ ２Ｏ４ の比抵抗を向上させるためには、Ｆｅ２＋の低減が必要であると考えられる。このため、本願発明では２価金属元素によるＦｅの置換が有効であると考えて本願発明に到達している。 By the way, the electrical conduction of the oxide (Mg 2+ Fe 2+ Fe 3+ ) 1-x O and / or (Mg 2+ Fe 2+ ) Fe 3+ 2 O 4 in the grain boundary layer described so far is the same as that of Fe 2+ and Fe 3+ . It is thought that hopping conduction by charge exchange is dominant. For this reason, in order to improve the specific resistance of (Mg 2+ Fe 2+ Fe 3+ ) 1-x O, coexistence of Fe 2+ and Fe 3+ is inevitable in the grain boundary layer at a constant ratio after the steam treatment in the oxidizing atmosphere. The present inventor considered that it was necessary to reduce Fe atoms themselves in the (Mg, Fe) O film. Further, in order to improve the specific resistance of (Mg 2+ Fe 2+ ) Fe 3+ 2 O 4 , it is considered that Fe 2+ needs to be reduced. For this reason, the present invention has reached the present invention on the assumption that substitution of Fe with a divalent metal element is effective.
以上説明の方法により得られた高比抵抗低損失複合軟磁性材は、前記複数のＭｇ含有酸化物被覆軟磁性粒子の粒界層を介する結合が、前記軟磁性金属粒子と該軟磁性金属粒子の表面に被覆されたＭｇ含有酸化膜とを具備してなるＭｇ含有酸化物被覆軟磁性粒子と、前述のシリコーンレジンなどのバインダー成分との混合圧密熱処理により得られた結合であり、前記Ｍｇ含有酸化物被覆軟磁性粒子間の粒界層に存在する酸化鉄が、前記軟磁性金属粒子から粒界にＦｅ成分が析出され酸化物とされて分散成長されたものであり、前記粒界層に隣接するＭｇ含有酸化膜が、前記混合圧密焼成処理以前のＭｇ含有酸化物被覆軟磁性粒子に備えられていたＭｇ含有酸化膜から拡散して得られ、更にそこに２価金属の粉末から拡散された２価金属が介在し、Ｆｅ２＋の一部と置換する形で例えばＺｎ２＋が拡散され反応された粒界層を有する構造である。 The high specific resistance and low loss composite soft magnetic material obtained by the above-described method is such that the bonding through the grain boundary layer of the plurality of Mg-containing oxide-coated soft magnetic particles is combined with the soft magnetic metal particles and the soft magnetic metal particles. A Mg-containing oxide-coated soft magnetic particle comprising a Mg-containing oxide film coated on the surface of the material and a bond obtained by mixing and compacting heat treatment with a binder component such as the above-mentioned silicone resin, and containing the Mg The iron oxide present in the grain boundary layer between the oxide-coated soft magnetic particles is the one in which the Fe component is precipitated from the soft magnetic metal particles at the grain boundary to form an oxide, and is dispersed and grown. An adjacent Mg-containing oxide film is obtained by diffusing from the Mg-containing oxide film provided in the Mg-containing oxide-coated soft magnetic particles before the mixed compaction firing process, and further diffused from the divalent metal powder there. Interstitial divalent metal Some in the form, for example, Zn 2+ substituting for Fe 2+ has a structure having a grain boundary layer which is a diffusion reaction.
以上の製造方法により得られた高強度高比抵抗低損失複合軟磁性材は、高密度、高強度、高比抵抗および高磁束密度を有し、この高比抵抗低損失複合軟磁性材は、高磁束密度で高周波低鉄損の特徴を有する事から、この特徴を生かした各種電磁気回路部品の材料として使用できる。
また、以上の製造方法により得られた高強度高比抵抗低損失複合軟磁性材にあっては、（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜と、その界面に存在するＳｉを含むバインダー成分と２価金属を熱拡散させた、粒界層を備えているので、特にＭｇ含有酸化物被覆軟磁性粒子同士の接合が良好になされていて、強度が高く、２価金属の拡散により比抵抗の高い、渦電流損失の少ない、低鉄損失の軟磁気特性に優れた高強度高比抵抗低損失複合軟磁性材を得ることができる。
The high-strength, high-resistivity, low-loss composite soft magnetic material obtained by the above manufacturing method has high density, high strength, high specific resistance, and high magnetic flux density. Since it has the characteristics of high magnetic flux density and high frequency and low iron loss, it can be used as a material for various electromagnetic circuit components utilizing this characteristic.
Further, in the high strength, high specific resistance, low loss composite soft magnetic material obtained by the above manufacturing method, the Mg—Fe—O ternary oxide deposited film containing (Mg, Fe) O and its interface In particular, the Mg-containing oxide-coated soft magnetic particles are well bonded to each other, and the strength is high. A high strength, high specific resistance and low loss composite soft magnetic material having a high specific resistance, low eddy current loss and excellent soft magnetic properties with low iron loss can be obtained by diffusion of a divalent metal.
粒径（１００）μｍの軟磁性粉末（純鉄粉末）に対して大気中２２０℃にて加熱処理を行って表面に酸化膜を形成し、この軟磁性粉末に対して０．１質量％のＭｇ粉末を配合し、この配合粉末を造粒転動攪拌混合装置によって真空中、６５０℃にて１時間転動することにより膜厚３０ｎｍのＭｇ含有酸化物皮膜（以下、ＭｇＯ膜と略記する）を形成した軟磁性粒子を作製した。ここでＭｇ含有酸化皮膜は前段の２２０℃大気中加熱処理で生成される酸化膜厚に比例する。従って、Ｍｇの添加量は必要最小限度で良い。 A soft magnetic powder (pure iron powder) having a particle size (100) μm is heat-treated at 220 ° C. in the atmosphere to form an oxide film on the surface. An Mg-containing oxide film (hereinafter abbreviated as MgO film) having a film thickness of 30 nm is prepared by blending Mg powder and rolling the blended powder in a vacuum at 650 ° C. for 1 hour using a granulation rolling stirring and mixing device. The soft magnetic particles formed were prepared. Here, the Mg-containing oxide film is proportional to the oxide film thickness generated by the heat treatment in the air at 220 ° C. in the previous stage. Therefore, the minimum amount of Mg may be added.
前記膜厚のＭｇＯ膜を備えたＭｇ含有酸化物被覆軟磁性粒子にバインダー溶液（シリコーンレジン：信越化学工業社製ＫＲ−３１１、０．３％溶液）を混合する際、２価金属として平均粒径３０ｎｍのＺｎＯ粉末を必要量添加混合し、８ｔｏｎ／ｃｍ２の圧力で圧密後、窒素雰囲気中、６５０℃にて０．５時間焼成し、その後、５６０℃のスチーム雰囲気中において６時間加熱するスチーム処理を施して高強度高比抵抗低損失複合軟磁性材を得た。
また、比較例試料として、２価金属を添加していない試料も製造した。得られた各試料のＺｎ換算質量％（全体に対するＺｎの純量換算）、密度（ｇ／ｃｍ３）、比抵抗（μΩ・ｍ）、飽和磁束密度Ｂ2kA/m、飽和磁束密度Ｂ10kA/m、保磁力（Ｈｃ）、最大透磁率（μmax）、コアロス（Ｐcm）、ヒステリシス損（Ｐhm）、渦電流損（Ｐem）、圧環強度（ＭＰａ）の値を測定した結果を表１に示す。
When mixing the binder solution (silicone resin: KR-311 manufactured by Shin-Etsu Chemical Co., Ltd., 0.3% solution) with the Mg-containing oxide-coated soft magnetic particles having the MgO film having the above-described thickness, the average particle as a divalent metal A necessary amount of ZnO powder having a diameter of 30 nm is added and mixed. After compaction at a pressure of 8 ton / cm 2 , the powder is fired in a nitrogen atmosphere at 650 ° C. for 0.5 hour, and then heated in a steam atmosphere at 560 ° C. for 6 hours. A high strength, high specific resistance and low loss composite soft magnetic material was obtained by steam treatment.
Moreover, the sample which did not add a bivalent metal as a comparative example sample was also manufactured. Zn mass% of each obtained sample (in terms of pure Zn), density (g / cm 3 ), specific resistance (μΩ · m), saturation magnetic flux density B 2k A / m, saturation magnetic flux density B 10k Table 1 shows the measurement results of A / m, coercivity (Hc), maximum permeability (μmax), core loss (Pcm), hysteresis loss (Phm), eddy current loss (Pem), and crushing strength (MPa). Show.
表１に示す試験例の試料１〜９において、Ｚｎの添加量が０質量％の試料１はスチーム処理後（スチーム後）の比抵抗が１７７．５（μΩ・ｍ）となっており、Ｚｎを０．０３質量％以上〜０．５質量％まで添加した試料３〜９に比べて比抵抗が低くなっている。このことから、粒界に２価金属としてのＺｎを添加することにより比抵抗を増大できることが判明したなお、Ｚｎ添加量において０．０３質量％を添加した試料から効果が出始め、０．０６％以上添加した試料４〜９の比抵抗が特に高くなっている。従ってＺｎ添加量として、０．０３質量％以上が好ましく、０．０６質量％以上がより好ましいと考えられる。
また、Ｚｎ添加量について０．５質量％の試料９においても良好な軟磁気特性と高い比抵抗を発揮したが、試料６〜８との軟磁気特性の対比（特に、最大透磁率と飽和磁束密度）などから、軟磁気特性の面から見て特性が低下する傾向となるので、０．５質量％以下が好ましく、０．３質量％以下がより好ましいと考えられる。
次に、表１に示すスチーム処理前の圧環強度の測定結果とスチーム処理後の圧環強度の測定結果から、スチーム処理を施すことで著しく強度が向上している（約４〜５倍向上）ことが明らかである。
In
In addition, the
Next, from the measurement results of the crushing strength before steam treatment and the measurement results of the crushing strength after steam treatment shown in Table 1, the strength is remarkably improved by applying the steam treatment (approximately 4 to 5 times improvement). Is clear.
次に、表１の試料６について粒界の組織写真（ＴＥＭ像）を図６に示す。図６において下部に示した縮尺ラインは０．２μｍを示す。この試料について図６の白線矢印ライン上の数値１で示す位置から、数値の２、３、４、５で示す位置の方向にライン分析（ＴＥＭ−ＥＤＸ：透過型電子顕微鏡−エネルギー分散型Ｘ線分析法）を行った結果を以下の表２、表３と図７、図８に示す。
図７、図８は粒界の厚さ方向に沿って、粒界に接する一方のＭｇ含有酸化物被覆軟磁性粒子から他方のＭｇ含有酸化物被覆軟磁性粒子までをライン分析した結果を示す。図７は分析値のまま、図８はバインダーとして添加したシリコーンレジンの焼成物であるＳｉを除いた他の元素の割合を示す。
図７、図８に示す分析値から明らかなように、粒界の厚さ方向についてＺｎ、Ｍｇ、Ｆｅ共に拡散が進行しており、Ｚｎ濃度の勾配、Ｆｅ濃度の勾配、Ｍｇ濃度の勾配を有している。
Next, the structure photograph (TEM image) of the grain boundary is shown in FIG. In FIG. 6, the scale line shown at the bottom indicates 0.2 μm. Line analysis (TEM-EDX: transmission electron microscope-energy dispersive X-ray) of this sample from the position indicated by the
7 and 8 show the results of line analysis from one Mg-containing oxide-coated soft magnetic particle in contact with the grain boundary to the other Mg-containing oxide-coated soft magnetic particle along the thickness direction of the grain boundary. FIG. 7 shows the analysis values, and FIG. 8 shows the ratio of other elements excluding Si, which is a fired product of silicone resin added as a binder.
As is clear from the analysis values shown in FIGS. 7 and 8, diffusion of Zn, Mg, and Fe proceeds in the grain boundary thickness direction. The Zn concentration gradient, the Fe concentration gradient, and the Mg concentration gradient are determined as follows. Have.
次に、表１の試料６について粒界の組織写真（ＴＥＭ像）を図９に示す。この試料について図９の数値１で示す位置から数値の２、３、４、５で示す白線位置の方向にライン分析（ＴＥＭ−ＥＤＸ：透過型電子顕微鏡−エネルギー分散型Ｘ線分析法）を行った結果を以下の表４、表５と図１０、図１１に示す。なお、図９には、粒界の組織写真に加えて、同粒界位置におけるＭｇの分布状態、Ｏの分布状態、Ｚｎの分布状態、Ｆｅの分布状態、Ｓｉの分布状態を濃淡で示した写真も隣接して示す。
図１０、図１１はＭｇ含有酸化物被覆軟磁性粒子の粒界の長さ方向に沿ってライン分析した結果を示すものである。
Next, FIG. 9 shows a structure photograph (TEM image) of grain boundaries for
10 and 11 show the results of line analysis along the grain boundary length direction of the Mg-containing oxide-coated soft magnetic particles.
図６、図７、図８と表２、表３に示す結果、並びに、図９、図１０、図１１と表４、表５に示す結果において、特に粒界の長さ方向に沿って得られた表４の測定結果から、Ｚｎ含有量は分析点１〜５において０．８６〜１．０６原子％の範囲を示しており、これは質量％に換算すると、約３質量％のＺｎが存在することを示す。
また、図６に示す如く粒界の厚さ方向にライン分析した結果を示す表２、表３、並びに、その関係をグラフ化した図７、図８から、粒界の厚さ方向にＺｎの濃度勾配、Ｍｇの濃度勾配、Ｆｅの濃度勾配を有していることが明らかである。また、粒界の長さ方向にライン分析した結果を示す図１０、図１１から、粒界の長さ方向においてはＯ、Ｆｅ、Ｍｇ、Ｚｎがほぼ同程度の濃度で存在することがわかる。
以上のことから、窒素雰囲気における焼成処理とスチーム処理とによって、ＺｎとＭｇとＦｅが拡散したことを示し、粒界においてこれら元素の拡散により、本発明の目的とする２価金属を添加した粒界層を備えた高強度高比抵抗低損失複合軟磁性材が得られていることが判る。
In the results shown in FIGS. 6, 7, 8 and Tables 2 and 3, and the results shown in FIGS. 9, 10, 11, 4, and 5, particularly along the grain boundary length direction. From the measurement results obtained in Table 4, the Zn content is in the range of 0.86 to 1.06 atomic% at the analysis points 1 to 5, which is about 3% by mass of Zn when converted to mass%. Indicates that it exists.
Further, from Tables 2 and 3 showing the results of line analysis in the grain boundary thickness direction as shown in FIG. 6 and FIGS. 7 and 8 which graph the relationship, Zn in the grain boundary thickness direction is shown. It is clear that it has a concentration gradient, Mg concentration gradient, and Fe concentration gradient. 10 and 11 that show the results of line analysis in the grain boundary length direction, it can be seen that O, Fe, Mg, and Zn are present at substantially the same concentration in the grain boundary length direction.
From the above, it was shown that Zn, Mg and Fe were diffused by the firing treatment and steam treatment in a nitrogen atmosphere, and the grains in which the divalent metal targeted by the present invention was added by the diffusion of these elements at the grain boundaries. It can be seen that a high-strength, high-resistivity, low-loss composite soft magnetic material having a boundary layer is obtained.
図１２〜図１５は２価金属としてＺｎを粒界に添加した場合において、Ｚｎ添加量と比抵抗の関係、Ｚｎ添加量と保磁力の関係、Ｚｎ添加量と飽和磁束密度の関係、Ｚｎ添加量と鉄損の関係を先の表１に記載したデータから一部抜き出して示す。
これらの結果を総合し、２価金属としてのＺｎ添加量は、０．０３〜０．５質量％の範囲が好ましく、０．０６〜０．３０質量％の範囲がより好ましい範囲と思われる。
12 to 15 show the relationship between the Zn addition amount and the specific resistance, the relationship between the Zn addition amount and the coercive force, the relationship between the Zn addition amount and the saturation magnetic flux density, and the Zn addition when Zn is added to the grain boundary as a divalent metal. The relationship between the amount and the iron loss is shown by extracting a part from the data described in Table 1 above.
By combining these results, the amount of Zn added as a divalent metal is preferably in the range of 0.03 to 0.5 mass%, and more preferably in the range of 0.06 to 0.30 mass%.
次に、２価金属の添加として、先の例の如くＺｎＯを添加することに代えて、Ｚｎ粉末を添加する試験を行った。
先の実施例で使用したＭｇ含有酸化物皮膜を形成した軟磁性粒子を用い、バインダーとして０．０５％ＫＢＰ−９０（信越化学工業社製シランカップリング剤溶液）と、０．３％ＫＲ−３１１溶液（信越化学工業社製ＫＲ−３１１、０．３％溶液）を混合したものを用い、バインダー添加時に溶液中に分散させる方法によりＺｎ粉末を用いて試料を作成した。添加量は原子として０．１０質量％とし、成形条件、焼成条件、スチーム処理条件は先の試験例と同等の条件とした。
得られた試料の試験結果を以下に示す。
Next, as a divalent metal addition, a test was conducted in which Zn powder was added instead of adding ZnO as in the previous example.
Using the soft magnetic particles formed with the Mg-containing oxide film used in the previous examples, 0.05% KBP-90 (a silane coupling agent solution manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.3% KR- Using a mixture of 311 solution (KR-311 manufactured by Shin-Etsu Chemical Co., Ltd., 0.3% solution), a sample was prepared using Zn powder by a method of dispersing in the solution when the binder was added. The addition amount was 0.10% by mass as atoms, and the molding conditions, firing conditions, and steam treatment conditions were the same as those in the previous test example.
The test results of the obtained sample are shown below.
表６に示す結果から、ＺｎＯ粉末に代えて、ＭｇＯ粉末、Ｚｎ粉末を添加することにより粒界に２価金属としてＺｎを添加した複合軟磁性材においても、スチーム処理後において高比抵抗かつ低損失であり、軟磁気特性に優れたものを得られることが判明した。 From the results shown in Table 6, even in the composite soft magnetic material in which Zn is added as a divalent metal to the grain boundary by adding MgO powder or Zn powder instead of ZnO powder, high specific resistance and low after steam treatment It was found that it was a loss and an excellent soft magnetic property could be obtained.
次に、本発明に係る複合軟磁性材に２価金属を添加する際、バインダーの溶液に粉末の形態で２価金属を添加し、このバインダー混合時にＭｇ含有酸化物被覆軟磁性粒子の周囲に２価金属を供給し、更に全体を圧密して焼成し、スチーム処理を施すが、バインダーに供給する際の粉末の粒径による試料への影響について試験した。
先の最初の実施例を実施する際、ＺｎＯ粉末として平均粒径１０ｎｍの粉末、平均粒径３０ｎｍの粉末、平均粒径５００ｎｍの粉末、平均粒径１μｍの粉末を別々に用意し、バインダーとして０．０５％ＫＢＰ−９０（信越化学工業社製商品名：シランカップリング剤）溶液と、０．３％ＫＲ−３１１溶液（信越化学工業社製ＫＲ−３１１、０．３％溶液）を混合したものを用い、これらを使い分け、Ｚｎ原子としての添加量を０．１０質量％に規定し、各試料を作成した。
成形条件は、８ｔｏｎ／ｃｍ２の圧力、温度１５０℃で圧密後、窒素雰囲気中、６５０℃にて０．５時間焼成し、その後、５６０℃のスチーム雰囲気中において６時間加熱するスチーム処理を２回施して高強度高比抵抗低損失複合軟磁性材を得た。
得られた各試料のスチーム処理前の特性評価とスチーム処理後の特性評価を行った結果を表７、表８に示すとともに、図１６〜図２１に示す。
Next, when adding the divalent metal to the composite soft magnetic material according to the present invention, the divalent metal is added to the binder solution in the form of a powder, and around the Mg-containing oxide-coated soft magnetic particles when the binder is mixed. A divalent metal was supplied, and the whole was compacted and fired and subjected to a steam treatment. The influence of the particle size of the powder upon supplying to the binder was tested.
In carrying out the first embodiment, a ZnO powder having an average particle size of 10 nm, an average particle size of 30 nm, an average particle size of 500 nm, and an average particle size of 1 μm were prepared separately, and the binder was 0. .05% KBP-90 (trade name: silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.) solution and 0.3% KR-311 solution (KR-311 manufactured by Shin-Etsu Chemical Co., Ltd., 0.3% solution) were mixed. Each sample was prepared by properly using these materials and defining the addition amount as Zn atoms to 0.10% by mass.
The molding conditions were 2 tons of steam treatment in which after compacting at a pressure of 8 ton / cm 2 and a temperature of 150 ° C., firing in a nitrogen atmosphere at 650 ° C. for 0.5 hours and then heating in a steam atmosphere at 560 ° C. for 6 hours. Spinning gave a high strength, high specific resistance, low loss composite soft magnetic material.
Tables 7 and 8 show the results of the characteristic evaluation of each sample obtained before the steam treatment and the characteristic evaluation after the steam treatment, and are also shown in FIGS.
表７、表８に示された結果と図１６〜図２１に示された結果においてスチーム処理後の特性から考察し、２価金属としてＺｎＯを添加していない試料とＺｎＯを粉末状態で添加した試料とを比較すると、いずれの粒径のＺｎＯ粉末を添加しても保磁力、ヒステリシス損、渦電流損については、ＺｎＯを添加した試料の方が優れていることが分かる。また、最大透磁率、飽和磁束密度に関しては２価金属としてＺｎＯを添加していない試料と添加した試料の差は生じていない。これらに対し、図１８に示す比抵抗の試験結果では、平均粒径１０ｎｍ、３０ｎｍ、５００ｎｍのＺｎＯ粉末を添加した試料に対し、平均結晶粒径１μｍのＺｎＯ粉末を添加した試料はスチーム処理後の比抵抗が低下して、添加無しの試料より比抵抗において若干高い同程度、軟磁気特性において若干低下した結果になった。
これらのことから、低保磁力、低ヒステリシス損、低渦電流損を示し、高い最大透磁率と高い飽和磁束密度を示す優れた軟磁気特性を満たしながら、比抵抗を高めるためには、ＺｎＯ粉末として、１０〜５００ｎｍ程度の微細な粉末状態としてＭｇ含有酸化物被覆軟磁性粒子の周囲に供給することが望ましいことが明らかになった。
これは、添加するＺｎＯの粉末の粒径が大きすぎると圧密成形時にＭｇＯの皮膜が破れ易くなるためではないかと推定できる。
In consideration of the characteristics after the steam treatment in the results shown in Tables 7 and 8 and the results shown in FIGS. 16 to 21, a sample in which ZnO was not added as a divalent metal and ZnO were added in a powder state. Comparing with the sample, it can be seen that the sample added with ZnO is superior in terms of coercive force, hysteresis loss, and eddy current loss even when ZnO powder of any particle size is added. Further, regarding the maximum magnetic permeability and saturation magnetic flux density, there is no difference between the sample not added with ZnO as a divalent metal and the sample added. On the other hand, in the specific resistance test results shown in FIG. 18, the sample added with ZnO powder with an average crystal grain size of 1 μm was compared with the sample after addition of ZnO powder with an average grain size of 10 nm, 30 nm, and 500 nm. As a result, the specific resistance decreased, and the specific resistance was slightly higher than that of the sample without addition, and the soft magnetic characteristics were slightly decreased.
In order to increase the specific resistance while satisfying the excellent soft magnetic properties showing low coercive force, low hysteresis loss, low eddy current loss, high maximum magnetic permeability and high saturation magnetic flux density, ZnO powder As a result, it has become clear that it is desirable to supply the powder around the Mg-containing oxide-coated soft magnetic particles in a fine powder state of about 10 to 500 nm.
It can be estimated that this is because if the particle diameter of the ZnO powder to be added is too large, the MgO film is easily broken during compaction molding.
次に、他の２価金属添加試験を行った。
先の実施例で使用したＭｇ含有酸化物皮膜を形成した軟磁性粒子を用い、バインダーとして０．０５％ＫＢＰ−９０（信越シリコン社製商品名：シランカップリング剤）溶液と、０．３％ＫＲ−３１１溶液（信越化学工業社製ＫＲ−３１１、０．３％溶液）を混合したものを用い、バインダー添加時に溶液中に分散させる方法によりＣｕＯ粉末を用いて試料を作成した。添加量は原子として０．１０質量％とし、成形条件、焼成条件、スチーム処理条件は先の試験例と同等の条件とした。また、同じ条件において２価金属の添加を行っていない試料と、ＺｎＯ粉末を用いて製造した試料も製造し、それらの特性も比較のために測定した。
得られた各試料の試験結果を以下の表９、表１０と図２２〜図２７に示す。
Next, another divalent metal addition test was performed.
Using the soft magnetic particles formed with the Mg-containing oxide film used in the previous examples, a 0.05% KBP-90 (trade name: silane coupling agent, manufactured by Shin-Etsu Silicon Co.) solution as a binder, and 0.3% Using a mixture of KR-311 solution (KR-311 manufactured by Shin-Etsu Chemical Co., Ltd., 0.3% solution), a sample was prepared using CuO powder by a method of dispersing in the solution when the binder was added. The addition amount was 0.10% by mass as atoms, and the molding conditions, firing conditions, and steam treatment conditions were the same as those in the previous test example. Moreover, the sample which did not add a bivalent metal on the same conditions and the sample manufactured using ZnO powder were also manufactured, and those characteristics were also measured for the comparison.
The test results of the obtained samples are shown in the following Tables 9 and 10 and FIGS.
表９、表１０に示す結果と、図２２〜図２７に示す結果から、２価金属としてＺｎに代えてＣｕを添加した各試料の試験結果から、ＺｎＯ粉末を添加した試験例と同様に優れた高強度高比抵抗低損失複合軟磁性材を得られることが判明した。
即ち、２価金属無添加の試料と比較し、同等の保磁力、同等のヒステリシス損、同等の最大透磁率、飽和磁束密度を有した上に、高い比抵抗、低い渦電流損失の高強度高比抵抗低損失複合軟磁性材を得られることが判明した。
From the results shown in Tables 9 and 10 and the results shown in FIGS. 22 to 27, the test results of each sample in which Cu was added instead of Zn as a divalent metal were excellent as in the test example in which ZnO powder was added. It was also found that a high strength, high specific resistance, low loss composite soft magnetic material can be obtained.
In other words, compared to the sample with no divalent metal added, it has the same coercive force, the same hysteresis loss, the same maximum magnetic permeability, and the saturation magnetic flux density, but also has a high specific resistance, low eddy current loss, and high strength. It was found that a specific resistance low loss composite soft magnetic material can be obtained.
本発明による高強度高比抵抗低損失複合軟磁性材は、電磁気回路部品として、例えば、磁心、電動機コア、発電機コア、ソレノイドコア、イグニッションコア、リアクトルコア、トランスコア、チョークコイルコアまたは磁気センサコアなどとしての利用が可能であり、いずれにおいても優れた特性を発揮し得る電磁気回路部品へ適用ができる。
そして、これら電磁気回路部品を組み込んだ電気機器には、電動機、発電機、ソレノイド、インジェクタ、電磁駆動弁、インバータ、コンバータ、変圧器、継電器、磁気センサシステム等があり、これら電気機器の高効率高性能化や小型軽量化を推進できる。
The high-strength, high-resistivity, low-loss composite soft magnetic material according to the present invention includes, for example, a magnetic core, an electric motor core, a generator core, a solenoid core, an ignition core, a reactor core, a transformer core, a choke coil core, or a magnetic sensor core. And can be applied to electromagnetic circuit components that can exhibit excellent characteristics.
Electric devices incorporating these electromagnetic circuit components include motors, generators, solenoids, injectors, electromagnetically driven valves, inverters, converters, transformers, relays, magnetic sensor systems, etc. Increase performance and reduce size and weight.
１…軟磁性金属粒子、２…酸化物体積膜、３…バインダー層、４…２価金属粒子、
５…粒界層、６…高強度高比抵抗低損失複合軟磁性材、１０…軟磁性金属粒子、
１１…Ｍｇ−Ｆｅ−Ｏ三元系酸化物体積膜、１２、１３、１４…粒界層、
DESCRIPTION OF
5 ... Grain boundary layer, 6 ... High strength, high specific resistance, low loss composite soft magnetic material, 10 ... soft magnetic metal particles,
11 ... Mg-Fe-O ternary oxide volume film, 12, 13, 14 ... grain boundary layer,
Claims (15)
前記Ｍｇ含有酸化物被覆軟磁性粒子間に位置する粒界層中に２価金属の高濃度領域と低濃度領域とが存在し、前記粒界層中にＦｅの高濃度領域と低濃度領域とが存在することを特徴とする高強度高比抵抗低損失複合軟磁性材。 An Mg-containing oxide-coated soft magnetic particle comprising an Fe-based soft magnetic metal particle and an Mg-containing oxide film coated on the surface of the soft magnetic metal particle is composed of a composite compound obtained by firing treatment. And at least Fe, divalent metal, Mg and O are diffused in the grain boundary layer, and the grain boundary layer is mainly composed of a composite oxide of Fe, divalent metal and Mg. As
A high concentration region and a low concentration region of a divalent metal exist in the grain boundary layer located between the Mg-containing oxide-coated soft magnetic particles, and a high concentration region and a low concentration region of Fe in the grain boundary layer. A high-strength, high-resistivity, low-loss composite soft magnetic material characterized by the presence of
前記Ｍｇ含有酸化物被覆軟磁性粒子を、少なくともＦｅと２価金属とＭｇとＯが拡散された複合化合物からなる絶縁性の粒界層を介し複数結合し、該粒界層中に２価金属の高濃度領域と低濃度領域とを存在させ、前記粒界層中にＦｅの高濃度領域と低濃度領域とを存在させた高強度高比抵抗低損失複合軟磁性材を製造することを特徴とする高強度高比抵抗低損失複合軟磁性材の製造方法。 Mg-containing oxide-coated soft magnetic particles comprising an Fe-based soft magnetic metal particle and an Mg-containing oxide film coated on the surface of the soft magnetic metal particle are mixed with a divalent metal oxide and consolidated. , After being fired in a non-oxidizing atmosphere to form a precursor of a soft magnetic metal compacted fired material, heat treatment in an oxidizing atmosphere,
A plurality of the Mg-containing oxide-coated soft magnetic particles are bonded via an insulating grain boundary layer made of a composite compound in which at least Fe, a divalent metal, and Mg and O are diffused, and the divalent metal is contained in the grain boundary layer. A high-strength, high-resistivity, low-loss composite soft magnetic material in which a high-concentration region and a low-concentration region are present and a high-concentration region and a low-concentration region of Fe are present in the grain boundary layer is manufactured. A method for producing a high strength, high specific resistance, low loss composite soft magnetic material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013168648A (en) * | 2012-01-18 | 2013-08-29 | Kobe Steel Ltd | Method of manufacturing dust core, and dust core manufactured by that method |
| JP2014060183A (en) * | 2012-09-14 | 2014-04-03 | Aisin Seiki Co Ltd | Soft magnetic material and method for manufacturing the same |
| CN108649810A (en) * | 2018-05-18 | 2018-10-12 | 崔香玉 | A kind of direct-current transmission converter valve using high-voltage isulation new material |
| CN109759581A (en) * | 2019-01-17 | 2019-05-17 | 深圳市众诚达应用材料科技有限公司 | A kind of 3D printing dusty material and preparation method thereof and a kind of 3D printing product |
| JP2021089999A (en) * | 2019-12-05 | 2021-06-10 | 日本特殊陶業株式会社 | Powder magnetic core |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0888115A (en) * | 1994-09-19 | 1996-04-02 | Mitsubishi Materials Corp | Yoke |
| JPH0974011A (en) * | 1995-09-07 | 1997-03-18 | Tdk Corp | Dust core and manufacture thereof |
| JP2005243794A (en) * | 2004-02-25 | 2005-09-08 | Matsushita Electric Ind Co Ltd | Method of manufacturing composite sintered magnetic material |
| JP2006245183A (en) * | 2005-03-02 | 2006-09-14 | Mitsubishi Materials Pmg Corp | Iron powder covered with laminated oxide film |
| JP2006241504A (en) * | 2005-03-02 | 2006-09-14 | Mitsubishi Materials Pmg Corp | Stacked oxide film-coated iron powder |
| JP2006332525A (en) * | 2005-05-30 | 2006-12-07 | Mitsubishi Materials Pmg Corp | High-strength complex soft magnetic material having high strength, high magnetic flux density, high resistance and less iron loss, and manufacturing method thereof |
| JP2007035826A (en) * | 2005-07-26 | 2007-02-08 | Nec Tokin Corp | Composite magnetic material, and dust core and magnetic element using the same |
| JP2007042891A (en) * | 2005-08-03 | 2007-02-15 | Sumitomo Electric Ind Ltd | Soft magnetic material, its manufacturing method, powder magnetic core, and its manufacturing method |
| JP2007070719A (en) * | 2005-05-31 | 2007-03-22 | Mitsubishi Materials Pmg Corp | DEPOSITION OXIDE FILM COATED Fe-Si BASED FERROUS SOFT MAGNETIC POWDER, AND METHOD FOR PRODUCING THE SAME |
-
2008
- 2008-11-14 JP JP2008292804A patent/JP2009141346A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0888115A (en) * | 1994-09-19 | 1996-04-02 | Mitsubishi Materials Corp | Yoke |
| JPH0974011A (en) * | 1995-09-07 | 1997-03-18 | Tdk Corp | Dust core and manufacture thereof |
| JP2005243794A (en) * | 2004-02-25 | 2005-09-08 | Matsushita Electric Ind Co Ltd | Method of manufacturing composite sintered magnetic material |
| JP2006245183A (en) * | 2005-03-02 | 2006-09-14 | Mitsubishi Materials Pmg Corp | Iron powder covered with laminated oxide film |
| JP2006241504A (en) * | 2005-03-02 | 2006-09-14 | Mitsubishi Materials Pmg Corp | Stacked oxide film-coated iron powder |
| JP2006332525A (en) * | 2005-05-30 | 2006-12-07 | Mitsubishi Materials Pmg Corp | High-strength complex soft magnetic material having high strength, high magnetic flux density, high resistance and less iron loss, and manufacturing method thereof |
| JP2007070719A (en) * | 2005-05-31 | 2007-03-22 | Mitsubishi Materials Pmg Corp | DEPOSITION OXIDE FILM COATED Fe-Si BASED FERROUS SOFT MAGNETIC POWDER, AND METHOD FOR PRODUCING THE SAME |
| JP2007035826A (en) * | 2005-07-26 | 2007-02-08 | Nec Tokin Corp | Composite magnetic material, and dust core and magnetic element using the same |
| JP2007042891A (en) * | 2005-08-03 | 2007-02-15 | Sumitomo Electric Ind Ltd | Soft magnetic material, its manufacturing method, powder magnetic core, and its manufacturing method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013168648A (en) * | 2012-01-18 | 2013-08-29 | Kobe Steel Ltd | Method of manufacturing dust core, and dust core manufactured by that method |
| JP2014060183A (en) * | 2012-09-14 | 2014-04-03 | Aisin Seiki Co Ltd | Soft magnetic material and method for manufacturing the same |
| CN108649810A (en) * | 2018-05-18 | 2018-10-12 | 崔香玉 | A kind of direct-current transmission converter valve using high-voltage isulation new material |
| CN108649810B (en) * | 2018-05-18 | 2019-01-22 | 崔香玉 | A kind of direct-current transmission converter valve using high-voltage isulation new material |
| CN109759581A (en) * | 2019-01-17 | 2019-05-17 | 深圳市众诚达应用材料科技有限公司 | A kind of 3D printing dusty material and preparation method thereof and a kind of 3D printing product |
| JP2021089999A (en) * | 2019-12-05 | 2021-06-10 | 日本特殊陶業株式会社 | Powder magnetic core |
| JP7334109B2 (en) | 2019-12-05 | 2023-08-28 | 日本特殊陶業株式会社 | dust core |
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