JP2008244347A - Manufacturing method of high-strength soft magnetism compound consolidation burning material, and the high-strength soft magnetism compound consolidation burning material - Google Patents
Manufacturing method of high-strength soft magnetism compound consolidation burning material, and the high-strength soft magnetism compound consolidation burning material 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軟磁性複合圧密焼成材およびその製造方法に関する。 The present invention relates to a high-strength soft magnetic composite compacted fired 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, and a method for manufacturing the same.
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。この種の軟磁性焼結材にあっては、磁束密度が高い反面、比抵抗が低いために、高周波特性が悪いという問題がある。そこで比抵抗を高めて高周波特性を向上させるために、軟磁性金属粒子を水ガラスまたは低融点ガラスにより結合した圧粉軟磁性材料などが提案されている（特許文献１または特許文献２参照）。
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 Soft magnetic sintered material obtained by sintering Fe-Si based iron-based soft magnetic alloy powder, Fe-Si-Al based iron-based soft magnetic alloy powder (hereinafter collectively referred to as soft magnetic metal particles) It has been known. This type of soft magnetic sintered material has a high magnetic flux density but a low specific resistance, which has a problem of poor high frequency characteristics. Therefore, in order to increase the specific resistance and improve the high frequency characteristics, a dust soft magnetic material in which soft magnetic metal particles are bonded with water glass or low-melting glass has been proposed (see
しかし、前記軟磁性金属粒子を水ガラスまたは低融点ガラスで結合した複合軟磁性焼結材は、軟磁性金属粒子と水ガラスまたは低融点ガラスとは密着性が悪いために、軟磁性金属粒子を水ガラスまたは低融点ガラスで結合して強度を確保しようとすると、水ガラスまたは低融点ガラスの中に軟磁性金属粒子が分散する程度に大量の水ガラスまたは低融点ガラスと混合しなければならず、このように水ガラスまたは低融点ガラスを大量に使用して得られた圧粉軟磁性材料の比抵抗は大きくなるものの磁束密度が極端に低下し、モータ、アクチュエータ、磁気センサの磁心など各種電子部品の材料として使用することができない問題があった。 However, the composite soft magnetic sintered material obtained by bonding the soft magnetic metal particles with water glass or low melting glass has poor adhesion between the soft magnetic metal particles and water glass or low melting glass. In order to secure strength by bonding with water glass or low melting glass, it must be mixed with a large amount of water glass or low melting glass to such an extent that soft magnetic metal particles are dispersed in water glass or low melting glass. The powder soft magnetic material obtained by using a large amount of water glass or low-melting glass in this way has a large specific resistance, but the magnetic flux density is extremely reduced, and various electronic devices such as motors, actuators, magnetic sensor magnetic cores, etc. There was a problem that it could not be used as a material for parts.
そこで、高磁束密度と高比抵抗の両立を図る目的において、軟磁性金属粒子相とこれを包囲する粒界相からなり、前記粒界相が六方晶構造を有するＺｎＯ型相、立方晶構造を有するＦｅとＺｎの混合酸化物相およびガラス相とからなり、前記六方晶構造を有するＺｎＯ型相が前記軟磁性金属粒子相に接して分散されており、前記ガラス相が前記立方晶構造を有するＦｅとＺｎの混合酸化物相が前記ＺｎＯ型相に接して分散されており、前記ガラス相が前記立方晶構造を有するＦｅとＺｎの混合酸化物相に接して挟まれて分散されている組織を有する複合軟磁性焼結材が提供されている。（特許文献３参照）
一方、化学メッキなどの化学的な方法あるいは塗布法などによりＭｇ含有フェライト膜を被覆したＭｇ含有酸化鉄被覆鉄粉末を低融点ガラス粉末とともに混合してから圧密形成し、熱処理して圧粉磁性材を製造する方法も知られている。（特許文献４参照）
On the other hand, Mg-containing iron oxide coated iron powder coated with Mg-containing ferrite film by chemical method such as chemical plating or coating method is mixed with low melting point glass powder, then compacted, heat treated and powdered magnetic material A method of manufacturing is also known. (See Patent Document 4)
前記特許文献３に記載されている複合軟磁性焼結材によれば、ＦｅとＺｎの混合酸化物相が６００℃を越える温度で加熱すると分解してしまう問題がある。しかし、この分解が生じない程度の温度での焼成、例えば、６００℃での焼成では特許文献３に記載されているガラス粉末は溶融しないために、軟磁性金属粒子相同士の結着性を高めることが難しく、高強度の軟磁性複合圧密焼成材を得ることが難しかった。
また、ガラス粉末を酸化亜鉛被覆軟磁性金属粒子に添加混合して成形すると、ガラス粉末−酸化亜鉛被膜（絶縁層）の摩擦が発生し、酸化亜鉛被膜が損傷しやすいために、高比抵抗の軟磁性複合圧密焼成材を得ることが難しかった。
According to the composite soft magnetic sintered material described in
In addition, when glass powder is added to zinc oxide-coated soft magnetic metal particles and molded, friction between the glass powder and zinc oxide coating (insulating layer) occurs, and the zinc oxide coating is easily damaged. It was difficult to obtain a soft magnetic composite compacted fired material.
一方、Ｍｇ含有酸化鉄被覆鉄粉末を圧密焼成してなる軟磁性複合圧密焼成材では、軟磁性金属粒子の表面にＭｇ含有フェライト膜を化学的方法によって被覆しているために、フェライト膜が不安定となり変化して絶縁性が低下するとともに、軟磁性金属粒子の表面に対するＭｇ含有フェライト膜の密着性が充分ではなくなり、Ｍｇ含有酸化鉄膜被覆粉末を低融点ガラスとプレス成形した後に焼成しても、充分な強度の軟磁性複合圧密焼成材を提供することができなくなるおそれがあった。 On the other hand, in the soft magnetic composite compacted fired material obtained by compacting the Mg-containing iron oxide-coated iron powder, the ferrite film is not formed because the surface of the soft magnetic metal particles is coated with the Mg-containing ferrite film by a chemical method. It becomes stable and changes in insulation, and the adhesion of the Mg-containing ferrite film to the surface of the soft magnetic metal particles is not sufficient, and the Mg-containing iron oxide film-coated powder is fired after being press-molded with a low-melting glass. However, there is a possibility that a soft magnetic composite compacted fired material having sufficient strength cannot be provided.
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、６００℃を越える温度、例えば７００℃での焼成を可能とする耐熱性に優れるＭｇＯ被膜を備えた構造とすることで高比抵抗を維持しながら歪取り焼鈍が可能で低保磁力とすることが可能であり、また、軟磁性金属粒子同士を結合する界面をＦｅ３Ｏ４を主体とする酸化鉄を含む低融点ガラスまたは金属酸化物の粒界層で充填することで軟磁性金属粒子同士を強く結合することができ、高い抗折強度を発揮する高強度軟磁性複合圧密焼成材の提供を目的とする。 The present invention has been made in view of the above problems, and its purpose is to provide a structure having a MgO film having excellent heat resistance that enables firing at a temperature exceeding 600 ° C., for example, 700 ° C. It is possible to perform strain relief annealing while maintaining a high specific resistance and to have a low coercive force, and a low melting point containing iron oxide mainly composed of Fe 3 O 4 as an interface for bonding soft magnetic metal particles to each other. An object of the present invention is to provide a high-strength soft magnetic composite compacted fired material capable of strongly bonding soft magnetic metal particles by filling with a grain boundary layer of glass or metal oxide and exhibiting high bending strength.
本発明者らは、Ｆｅ系の軟磁性焼結材の研究を行い、プレス成形時においても絶縁被膜が破壊されることが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 in which the insulating coating is not destroyed even during press 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 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.
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、プレス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、プレス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 that of conventional materials, the oxide film, which is an insulating film, is less likely to break during press molding, and the oxide film is composed of Fe-based soft magnetic powders. Therefore, even if high-temperature strain relief firing is performed after press molding, the insulating properties of the oxide film are not reduced 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軟磁性複合圧密焼成材の製造方法は、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含有酸化膜とを具備してなるＭｇ含有酸化物被覆軟磁性粒子と、Ｓｉレジン、低融点ガラス、金属酸化物の少なくとも１種とを混合して圧密し、非酸化性雰囲気において焼成処理して軟磁性複合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、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含有酸化膜とを具備してなるＭｇ含有酸化物被覆軟磁性粒子を、前記の如く混合したＳｉレジン、低融点ガラス、金属酸化物の少なくとも１種の成分を含む粒界層を介し複数結合してなる焼成体とすることを特徴とする。
（２）上記目的を達成するために本発明の高強度軟磁性複合圧密焼成材の製造方法は、前記Ｍｇ含有酸化物被覆軟磁性粒子間の粒界層を、前記焼成処理と前記熱処理により、少なくとも酸化鉄を含むシリコン酸化物、または、少なくともＭｇを含む鉄酸化物の充填物とす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軟磁性複合圧密焼成材の製造方法は、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を、前記Ｆｅ系の軟磁性金属粒子からＦｅ成分を粒界に析出させて酸化物として分散成長させたものとすることを特徴とする。
(1) In order to achieve the above object, a method for producing a high-strength soft magnetic composite compacted fired material according to the present invention comprises Fe-based soft magnetic metal particles, an Mg-containing oxide film coated on the surface of the soft magnetic metal particles, Mixed with Mg-containing oxide-coated soft magnetic particles and at least one of Si resin, low-melting glass, and metal oxide, and compacted, and baked in a non-oxidizing atmosphere to be soft magnetic composite compacted Mg-containing oxide comprising Fe-based soft magnetic metal particles and an Mg-containing oxide film coated on the surface of the soft magnetic metal particles by heat treatment in an oxidizing atmosphere after forming a precursor of the fired material The object-coated soft magnetic particles are made into a fired body formed by bonding a plurality of grains through a grain boundary layer containing at least one component of Si resin, low melting point glass, and metal oxide mixed as described above.
(2) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired material according to the present invention comprises subjecting the grain boundary layer between the Mg-containing oxide-coated soft magnetic particles to the firing treatment and the heat treatment. It is characterized by being a silicon oxide containing at least iron oxide or an iron oxide containing at least Mg.
(3) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired material according to the present invention uses the Fe-based iron oxide present in the grain boundary layer between the Mg-containing oxide-coated soft magnetic particles. It is characterized in that the Fe component is precipitated from the soft magnetic metal particles at grain boundaries and dispersed and grown as an oxide.
（４）上記目的を達成するために本発明の高強度軟磁性複合圧密焼成材の製造方法は、前記非酸化性雰囲気として、窒素ガス雰囲気、アルゴンガス雰囲気などの不活性ガス雰囲気、あるいは水素ガス雰囲気とす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軟磁性複合圧密焼成材の製造方法は、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。
（６）上記目的を達成するために本発明の高強度軟磁性複合圧密焼成材の製造方法は、前記焼成処理の温度を５５０℃〜７５０℃の範囲とす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軟磁性複合圧密焼成材の製造方法は、 前記非酸化性雰囲気において焼成処理することにより、粒界層にＭｇとＦｅを含む（Ｍｇ,Ｆｅ）Ｏのウスタイトを生成させ、前記酸化性雰囲気において熱処理することにより前記ウスタイトを含む粒界層を少なくとも酸化鉄を含むシリコン酸化物、少なくともＭｇを含有する鉄酸化物のいずれかを含む充填物とすることを特徴とする請求項１〜６のいずれかに記載の高強度軟磁性複合圧密焼成材の製造方法。
前記非酸化性雰囲気において焼成処理することにより、粒界層にＭｇとＦｅを含む（Ｍｇ,Ｆｅ）Ｏのウスタイトを生成させ、前記酸化性雰囲気において熱処理することにより前記ウスタイトを含む粒界層を少なくとも酸化鉄を含むシリコン酸化物、少なくともＭｇを含有する鉄酸化物のいずれかを含む充填物とすることを特徴とする。
(4) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired material according to the present invention uses an inert gas atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere, or a hydrogen gas as the non-oxidizing atmosphere. It is characterized by an atmosphere.
(5) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired 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.
(6) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired material according to the present invention is characterized in that the temperature of the firing treatment is in the range of 550 ° C to 750 ° C.
(7) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired material of the present invention includes Mg and Fe in the grain boundary layer by firing in the non-oxidizing atmosphere (Mg, Fe A filler containing either a silicon oxide containing at least iron oxide or an iron oxide containing at least Mg as a grain boundary layer containing wustite by generating Fe) O wustite and heat-treating in the oxidizing atmosphere. The method for producing a high-strength soft magnetic composite compacted fired material according to any one of
By firing in the non-oxidizing atmosphere, (Mg, Fe) O wustite containing Mg and Fe is generated in the grain boundary layer, and the grain boundary layer containing wustite is formed by heat treatment in the oxidizing atmosphere. It is characterized by being a filling containing either silicon oxide containing at least iron oxide or iron oxide containing at least Mg.
（８）上記目的を達成するために本発明の高強度軟磁性複合圧密焼成材の製造方法は、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含有酸化膜とを具備してなる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と、Ｍｇを含有する鉄酸化物のいずれか１種以上を主体とする粒界層を介し複数結合されてな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軟磁性複合圧密焼成材の製造方法は、前記金属酸化物として、Ａｌ２Ｏ３、Ｂ２Ｏ３、Ｓｂ２Ｏ３、ＭｏＯ３のいずれかからなるものを用い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軟磁性複合圧密焼成材は、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含有酸化膜とを具備してなるＭｇ含有酸化物被覆軟磁性粒がＦｅ３Ｏ４を主体とする酸化鉄を含むＳｉレジン、Ｆｅ３Ｏ４を主体とする酸化鉄を含む低融点ガラス、または、Ｆｅ３Ｏ４を主体とする酸化鉄を含む金属酸化物のいずれかを主体とする粒界層を介し複数結合されてなることを特徴とする。
（１１）上記目的を達成するために本発明の高強度軟磁性複合圧密焼成材において、前記Ｍｇ含有酸化物被覆軟磁性粒子間の粒界層が、Ｆｅ３Ｏ４あるいはＦｅＯを主体とする酸化鉄を含むシリコン酸化物の充填物からな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軟磁性複合圧密焼成材は、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、Ｓｉレジン、低融点ガラスまたは金属酸化物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Ｆｅ系の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含有酸化膜から得られたものであることを特徴とする。
(8) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired material of the present invention comprises Fe-based soft magnetic metal particles, an Mg-containing oxide film coated on the surface of the soft magnetic metal particles, Mg-containing oxide-coated soft magnetic particles comprising a plurality of particles are bonded via a grain boundary layer mainly composed of at least one of silicon oxide containing iron oxide and iron oxide containing Mg. It is characterized by becoming.
(9) In order to achieve the above object, the method for producing a high-strength soft magnetic composite compacted fired material according to the present invention includes Al 2 O 3 , B 2 O 3 , Sb 2 O 3 , and MoO 3 as the metal oxide. One of them is used.
(10) In order to achieve the above object, the high-strength soft magnetic composite compacted fired material of the present invention comprises Fe-based soft magnetic metal particles and an Mg-containing oxide film coated on the surface of the soft magnetic metal particles. Si resin containing iron oxide consisting Te Mg-containing oxide-coated soft-magnetic particles is mainly composed of Fe 3 O 4, the low-melting glass containing iron oxide consisting mainly of Fe 3 O 4, or mainly of Fe 3 O 4 It is characterized in that a plurality of them are bonded through a grain boundary layer mainly composed of any of the metal oxides containing iron oxide.
(11) In order to achieve the above object, in the high-strength soft magnetic composite compacted fired material of the present invention, the grain boundary layer between the Mg-containing oxide-coated soft magnetic particles is oxidized mainly with Fe 3 O 4 or FeO. It consists of the filling of the silicon oxide containing iron.
(12) In order to achieve the above object, the high-strength soft magnetic composite compacted fired material of the present invention has a combination of the plurality of Mg-containing oxide-coated soft magnetic particles via the grain boundary layer and the soft magnetic metal particles. Bond obtained by mixed consolidation heat treatment of Mg-containing oxide-coated soft magnetic particles comprising Mg-containing oxide film coated on the surface of soft magnetic metal particles and Si resin, low melting glass or metal oxide The iron oxide present in the grain boundary layer between the Mg-containing oxide-coated soft magnetic particles was dispersed and grown by forming an Fe component at the grain boundary from the Fe-based soft magnetic metal particles to form an oxide. The Mg-containing oxide film adjacent to the grain boundary layer is obtained from the Mg-containing oxide film provided in the Mg-containing oxide-coated soft magnetic particles before the mixed consolidation firing process. Features.
（１３）上記目的を達成するために本発明の高強度軟磁性複合圧密焼成材は、前記酸化鉄がＦｅ３Ｏ４あるいはＦｅＯを主体とするものであって、前記Ｆｅ３Ｏ４あるいはＦｅＯ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含有酸化物被覆膜とを具備してなるＭｇ含有酸化物被覆軟磁性粒子と、前記Ｓｉレジン、低融点ガラスまたは金属酸化物との混合後の非酸化性雰囲気中における焼成処理と、その後の酸化性雰囲気中における熱処理により粒界層に分散成長されたものであ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軟磁性複合圧密焼成材は、前記Ｆｅ系の軟磁性金属粒子が、Ｆｅに、Ｓｉ、Ａｌ、Ｎｉ、Ｃｒ、Ｃｏ、Ｖのうちの少なくとも１種以上を添加してなる組成系とされてな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高強度軟磁性複合圧密焼成材は、前記Ｍｇ含有酸化膜が（Ｍｇ，Ｆｅ）Ｏを主体として構成され、前記低融点ガラスがＳｉＯ２、Ｂｉ２Ｏ３−Ｂ２Ｏ３、ＳｎＯ−Ｐ２Ｏ３、ＳｉＯ２−Ｂ２Ｏ３−ＺｎＯ、ＳｉＯ２−Ｂ２Ｏ３−Ｒ２Ｏ、Ｌｉ２Ｏ−ＺｎＯのいずれかからなることを特徴とする。
（１６）上記目的を達成するために本発明の高強度軟磁性複合圧密焼成材は、前記Ｍｇ含有酸化膜が（Ｍｇ，Ｆｅ）Ｏを主体として構成され、前記金属酸化物がＡｌ２Ｏ３、Ｂ２Ｏ３、Ｓｂ２Ｏ３、ＭｏＯ３のいずれかからなることを特徴とする。
(13) In order to achieve the above object, in the high-strength soft magnetic composite consolidated fired material of the present invention, the iron oxide is mainly composed of Fe 3 O 4 or FeO, and the Fe 3 O 4 or FeO is A Mg-containing oxide-coated soft magnetic particle comprising the soft-magnetic metal particle and an Mg-containing oxide coating film coated on the surface of the soft magnetic metal particle, the Si resin, a low-melting glass, or a metal It is characterized by being dispersedly grown in the grain boundary layer by a baking treatment in a non-oxidizing atmosphere after mixing with an oxide and a subsequent heat treatment in an oxidizing atmosphere.
(14) In order to achieve the above object, in the high-strength soft magnetic composite compacted fired material of the present invention, the Fe-based soft magnetic metal particles include Fe, Si, Al, Ni, Cr, Co, and V. It is characterized in that it is a composition system formed by adding at least one kind.
(15) In order to achieve the above object, in the high strength soft magnetic composite consolidated fired material of the present invention, the Mg-containing oxide film is mainly composed of (Mg, Fe) O, and the low melting point glass is made of SiO 2 , Bi. 2 O 3 -B 2 O 3, SnO-P 2
(16) In order to achieve the above object, in the high-strength soft magnetic composite compacted fired material of the present invention, the Mg-containing oxide film is mainly composed of (Mg, Fe) O, and the metal oxide is Al 2 O 3. , B 2 O 3 , Sb 2 O 3 , or MoO 3 .
本発明の製造方法においては、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したＭｇ含有酸化物被覆膜とを良好な密着性でもって形成することができ、更にＭｇ含有酸化物被覆膜を備えたＦｅ系の軟磁性金属粒子どうしを、それらの粒界層に存在する前記の如く混合したＳｉレジン、低融点ガラス、金属酸化物のいずれかの成分を含む粒界層で接合し、しかも接合部分の粒界に酸化鉄を分散成長させているので、粒界層とＭｇ含有酸化物被覆膜との密着力も高いものとできるので、高強度な軟磁性複合圧密焼成材を得ることができる。
しかも、前記Ｍｇ含有酸化物被覆膜は圧密成形後もＦｅ系の軟磁性金属粒子の周囲に確実に存在させることができるので高い比抵抗を得ることができ、渦電流損失の低い軟磁性複合圧密焼成材を得ることができる。
In the production method of the present invention, Fe-based soft magnetic metal particles and an Mg-containing oxide coating film coated on the surface of the soft magnetic metal particles can be formed with good adhesion, and further Mg-containing Grain boundary containing any component of Si resin, low melting point glass, and metal oxide mixed in the grain boundary layer of Fe-based soft magnetic metal particles provided with an oxide coating film as described above. In addition, since iron oxide is dispersed and grown at the grain boundaries of the joint portion, the adhesion between the grain boundary layer and the Mg-containing oxide coating film can be increased, so high strength soft magnetic composite consolidation A fired material can be obtained.
Moreover, since the Mg-containing oxide coating film can be reliably present around the Fe-based soft magnetic metal particles even after the compacting, a high specific resistance can be obtained and a soft magnetic composite with low eddy current loss. A consolidated fired material can be obtained.
本発明の製造方法により得られた軟磁性複合圧密焼成材は、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 soft magnetic composite compacted fired material obtained by the production method of the present invention has high density, high strength, high specific resistance and high magnetic flux density, the soft magnetic composite compacted fired material of the present invention has high strength and high magnetic flux. It has excellent density and high frequency and low iron loss characteristics, and can be used as a material for various electromagnetic circuit components that take advantage of these characteristics.
前記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を行うことができる効果がある。
The electromagnetic circuit component can be used as, 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, a magnetic sensor core, etc. It is possible to provide an electromagnetic circuit component capable of exhibiting the above.
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 performance and size and weight can be reduced.
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、以下の各種の原料粉末を用い、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％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％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。
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, the following various 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. This 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%, and the balance is Fe. And an Fe—Al-based iron-based soft magnetic alloy powder (for example, an alpalm powder having a composition of Fe-15% Al) made of inevitable impurities.
また、Ｆｅ−Ｎｉ系鉄基軟磁性合金粉末はＮｉ：３５〜８５％を含有し、必要に応じてＭｏ：５％以下、Ｃｕ：５％以下、Ｃｒ：２％以下、Ｍｎ：０．５％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％Ｎｉ粉末）であり、Ｆｅ−Ｃｒ系鉄基軟磁性合金粉末はＣｒ：１〜２０％を含有し、必要に応じてＡｌ：５％以下、Ｎｉｌ５％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％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％、Ａｌ：０．１〜２０％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−Ｃ−Ｖ系鉄基軟磁性合金粉末は、Ｃ：０．１〜５２％、Ｖ：０．１〜３％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−Ｃ系鉄基軟磁性合金粉末は、Ｃ：０．１〜５２％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％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（以上、％は質量％を示す）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%, and Mo: 5% or less, Cu: 5% or less, Cr: 2% or less, Mn: 0.5 if necessary. % Nickel-based soft magnetic alloy powder (for example, Fe-49% Ni powder) containing one or two or more of Fe and inevitable impurities, and Fe-Cr-based iron-based soft magnetism The alloy powder contains Cr: 1-20%, and if necessary, contains Al: 5% or less,
The Fe-Si-Al-based iron-based soft magnetic alloy powder contains Si: 0.1 to 10%, Al: 0.1 to 20%, and the balance is Fe-Si-Al composed of Fe and inevitable impurities. Iron-based soft magnetic alloy powder, Fe-CV-based iron-based soft magnetic alloy powder contains C: 0.1-52%, V: 0.1-3%, the balance is Fe and inevitable Fe-Co-V iron-based soft magnetic alloy powder made of impurities, Fe-C iron-based soft magnetic alloy powder contains C: 0.1-52%, the balance consists of Fe and inevitable impurities Fe-Co-based iron-based soft magnetic alloy powder, Fe-P-based iron-based soft magnetic alloy powder contains P: 0.5 to 1%, the balance is Fe-P-based iron consisting of Fe and inevitable impurities It is preferably a base soft magnetic alloy powder (wherein% indicates mass%).
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 particles 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 metal particles 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 metal particles increases and the magnetic permeability at high frequency decreases.
（Ａ）これらの各種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粒子（粉末）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分散することのない組織が得られる。
(A) It is obtained by using any one of these various soft magnetic metal particles as a raw material powder and subjecting it to an oxidation treatment in which it is maintained at room temperature to 500 ° C. in an oxidizing atmosphere, and then adding and mixing Mg powder to this raw material powder. The mixed powder was 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, a temperature of 50 When heated at ˜400 ° C., Mg-containing oxide-coated soft magnetic particles (powder) having an oxide insulating film containing Mg on the surface of the soft magnetic metal particles are 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 has 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 and dispersed 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粉末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) After adding and mixing the silicon monoxide powder to the oxide-coated soft magnetic powder in which an oxide is formed on the surface of the soft magnetic powder by maintaining the soft magnetic metal particles in an oxidizing atmosphere at room temperature to 500 ° C. Alternatively, heating is performed in a vacuum atmosphere with mixing at a temperature of 600 to 1200 ° C., and further, after adding and mixing Mg powder or heating in a vacuum atmosphere with mixing at a temperature of 400 to 800 ° C. An Mg-Si-containing oxide-coated soft magnetic powder in which an Mg-Si-containing oxide film is formed on the surface of the soft magnetic powder is obtained, and is produced using the Mg-Si-containing oxide-coated soft magnetic powder produced by this method. The composite soft magnetic sintered material is higher in density and bending strength than the composite soft magnetic sintered material obtained by compression molding and sintering a mixture of a compound that generates SiO and MgCO or MgO. 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、比抵抗およぴ磁束密度が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 adding silicon monoxide powder to the Mg-containing oxide-coated soft magnetic powder and mixing it or heating it in a vacuum atmosphere while mixing, the temperature is maintained at 600 to 1200 ° C., and the surface of the soft magnetic powder is coated with Mg. -A composite soft magnetic sintered material produced using an Mg-Si-containing oxide-coated soft magnetic powder obtained by this method, wherein an Mg-Si-containing oxide-coated soft magnetic powder having a Si-containing oxide film formed thereon is obtained If so, the density, bending strength, specific resistance, and resistivity of the composite soft magnetic sintered material obtained by compression-molding and sintering a mixture of a compound that generates SiO 2 and MgCO or MgO powder will be described. The magnetic flux 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％に限定したのは、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, the addition amount of Mg powder was limited to 0.05-1 mass%, the addition amount of Mg powder was 0.05 mass% Is less than the thickness of the Mg film formed on the surface of the oxide-coated soft magnetic powder, the amount of Mg contained in the Mg-Si-containing oxide film is insufficient. Since an oxide film cannot be obtained, it is not preferable. On the other hand, when it exceeds 1% by mass, the formed Mg film becomes too thick, and the obtained Mg-Si-containing oxide-coated soft magnetic powder is reduced. This is because the density of the soft magnetic composite compacted fired material obtained by compacting and firing becomes undesirably low.
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 is 1200 ° C. is that a SiO film having a sufficient thickness or an Mg—Si-containing oxide film cannot be obtained even when heated below 600 ° C. because the vapor pressure of SiO is small. This is because mixing above 1200 ° C. is not preferable because 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.
「軟磁性複合圧密焼成材の製造」
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軟磁性複合圧密焼成材を製造するには、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絶縁性の結着材としてのＳｉレジン、低融点ガラスあるいは金属酸化物のいずれかを混合してから通常の方法で圧粉成形し、不活性ガス雰囲気中、あるいは、非酸化性雰囲気中において焼成して軟磁性複合圧密焼成材の前駆体を製造する。
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。
"Manufacture of soft magnetic composite compacted fired materials"
To produce a soft magnetic composite compacted fired material using the Mg-containing oxide-coated soft magnetic particles prepared as described above by the method described above, first, the Mg-containing oxide-coated soft magnetic particles prepared by the method described above. After mixing with Si resin as an insulating binder, low melting point glass or metal oxide, it is compacted by the usual method, in an inert gas atmosphere or in a non-oxidizing atmosphere The precursor of the soft magnetic composite compacted fired material is manufactured by firing.
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.
前述の方法により作製したＭｇ含有酸化物被覆軟磁性粒子に、Ｓｉレジン、あるいは、Ｂｉ２Ｏ３−Ｂ２Ｏ３、ＳｎＯ−Ｐ２Ｏ３、ＳｉＯ２−Ｂ２Ｏ３−ＺｎＯ、ＳｉＯ２−Ｂ２Ｏ３−Ｒ２Ｏ、Ｌｉ２Ｏ−ＺｎＯのいずれかからなる低融点ガラスを規定量配合する。
Ｓｉレジンの添加量は、０．２〜１．５質量％の範囲内とすることができる。
あるいは、先のＳｉレジンあるいは低融点ガラスに代えて、Ｍｇ含有酸化物被覆軟磁性粒子に、酸化アルミニウム、酸化棚素、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、得られた圧粉成形体を温度：５００〜１０００℃で非酸化性雰囲気中において焼成し、軟磁性複合圧密焼成材の前駆体を製造し、その後において酸化性雰囲気中において熱処理することにより軟磁性複合圧密焼成材を作製することができる。また、金属酸化物としてステアリン酸亜鉛を用いることもできる。
先の焼成雰囲気として例えば、窒素ガス雰囲気などの不活性ガス雰囲気、あるいは水素ガス雰囲気などの非酸化性雰囲気を選択することができる。
The Mg-containing oxide-coated soft magnetic particles produced by the above-described method are added to Si resin, Bi 2 O 3 —B 2 O 3 , SnO—P 2 O 3 , SiO 2 —B 2 O 3 —ZnO, or SiO 2. A specified amount of low-melting-point glass composed of any one of —B 2 O 3 —R 2 O and Li 2 O—ZnO is blended.
The addition amount of Si resin can be in the range of 0.2 to 1.5 mass%.
Alternatively, instead of the above Si resin or low-melting glass, Mg-containing oxide-coated soft magnetic particles may be replaced with one or two of aluminum oxide, shelf oxide, vanadium oxide, bismuth oxide, antimony oxide, and molybdenum oxide. The above metal oxides are blended within a range of 0.05 to 1% by mass in terms of B 2 O 3 , V 2 O 5 , Bi 2 O 3 , Sb 2 O 3 , and MoO 3 , mixed, and then compacted. The obtained green compact is fired at a temperature of 500 to 1000 ° C. in a non-oxidizing atmosphere to produce a precursor of a soft magnetic composite compacted fired material, and then heat-treated in an oxidizing atmosphere. A soft magnetic composite compacted fired material can be produced. Moreover, zinc stearate can also be used as a metal oxide.
For example, an inert gas atmosphere such as a nitrogen gas atmosphere or a non-oxidizing atmosphere such as a hydrogen gas atmosphere can be selected as the previous firing atmosphere.
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している。
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が変成し、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、Ｆｅ３Ｏ４あるいはＦｅＯを主体とする酸化鉄を含むＳｉレジンなどのシリコン酸化物）、低融点ガラスの成分を含む酸化物、Ｍｇを含有する鉄酸化物のいずれかを主体とす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軟磁性複合圧密焼成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. Has been given.
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 ( And the Mg—Fe—O ternary oxide deposited film containing (Mg, Fe) O present at the interface between them was modified and coated on the surface of the soft magnetic metal particles and the soft magnetic metal particles An Mg-containing oxide-coated soft magnetic particle comprising an Mg-containing oxide contains silicon oxide containing iron oxide (for example, silicon oxide such as Si resin containing iron oxide mainly composed of Fe 3 O 4 or FeO). ), An oxide containing a low melting point glass component, or an iron oxide containing Mg. A calcined material can be obtained
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、Ｆｅ３Ｏ４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（４ＦｅＯ→Ｆｅ３Ｏ４＋Ｆｅ）により強度が発現しないおそれがある。
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, if the temperature is less than 400 ° C., there is a problem that the formation of Fe 3 O 4 is not promoted and strength is not developed. There is a possibility that strength is not developed due to formation and decomposition (4FeO → Fe 3 O 4 + Fe).
前述のスチーム雰囲気中においてＦｅ３Ｏ４を主体とする酸化鉄がＳｉ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Ｆｅ３Ｏ４を主体とする酸化鉄が成長し粒界を充填するか、または、Ｆｅ３Ｏ４に加えて一部ＦｅＯを含む粒界層を充填し、強度が向上すると考えられる。 In the steam atmosphere described above, iron oxide mainly composed of Fe 3 O 4 diffuses and grows inside the Si resin because the Fe is formed between the fine cracks generated during molding and the crystal grains constituting the MgO film. It may be caused by diffusion. The diffused Fe is oxidized during the heat treatment in the oxidizing atmosphere, and iron oxide mainly composed of Fe 3 O 4 grows to fill the grain boundary, or the grain boundary partially containing FeO in addition to Fe 3 O 4 It is thought that the layer is filled and the strength is improved.
以上説明の方法により得られた軟磁性複合圧密焼成材は、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、前述の低融点ガラスまたは金属酸化物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含有酸化膜から得られたものである。
前記Ｍｇ含有酸化膜被覆軟磁性粒子を囲む粒界層にあっては、酸化鉄を含むシリコン酸化物（例えば、Ｆｅ３Ｏ４あるいはＦｅＯを主体とする酸化鉄を含むＳｉレジンなどのシリコン酸化物）、低融点ガラスの成分を含む酸化物、Ｍｇを含有する鉄酸化物のいずれかを主体とする組織を有する。
In the soft magnetic composite compacted fired material obtained by the method described above, the bonds through the grain boundary layers of the plurality of Mg-containing oxide-coated soft magnetic particles are bonded to the surface of the soft magnetic metal particles and the soft magnetic metal particles. The Mg-containing oxide is a bond obtained by a mixed compaction heat treatment of the Mg-containing oxide-coated soft magnetic particles comprising the coated Mg-containing oxide film and the above-described low melting glass or metal oxide. The iron oxide present in the grain boundary layer between the coated soft magnetic particles is the one in which the Fe component is precipitated from the soft magnetic metal particles at the grain boundary and is dispersed and grown, and is adjacent to the grain boundary layer. The Mg-containing oxide film is obtained from the Mg-containing oxide film provided in the Mg-containing oxide-coated soft magnetic particles before the mixed consolidation firing process.
In the grain boundary layer surrounding the Mg-containing oxide film-coated soft magnetic particles, silicon oxide containing iron oxide (for example, silicon oxide such as Si resin containing iron oxide mainly composed of Fe 3 O 4 or FeO) ), A structure mainly composed of either an oxide containing a component of low-melting glass or an iron oxide containing Mg.
図１はこの種の軟磁性複合圧密焼成材の一例の組織を拡大した図を示すが、Ｆｅ系の軟磁性金属粒子１の表面を覆うようにＭｇ含有酸化膜２を形成してＭｇ含有酸化物被覆軟磁性粒子３が形成され、複数のＭｇ含有酸化物被覆軟磁性粒子３が粒界層５を介し接合されて軟磁性複合圧密焼成材が構成されている。
なお、前述した如く軟磁性複合圧密焼成材は、複数のＭｇ含有酸化物被覆軟磁性粒子１を圧密し、焼成と熱処理を施して製造されるので、Ｍｇ含有酸化物被覆軟磁性粒子１は不定形であり、かつ、その表面の全面にＭｇ含有酸化膜２が形成されていることが望ましいが、圧密と成形の状態によってはＭｇ含有酸化物被覆軟磁性粒子１の表面に部分的にＭｇ含有酸化膜２が形成されていない部位の存在も考えられるが、少なくとも軟磁性複合圧密焼成材全体として見た場合の比抵抗が低下しないように各Ｍｇ含有酸化物被覆軟磁性粒子１がＭｇ含有酸化膜２で覆われていることが望ましい。その意味から見ると、図１のように３つのＭｇ含有酸化物被覆軟磁性粒子１が集合している粒界三重点の界面においては粒界層５が他の部分の粒界層５よりも厚いものである場合、あるいは部分的にＭｇ含有酸化膜２の厚さに差異があったり、部分的に被覆不足の部分が生じていたとしても、本発明に係る軟磁性複合圧密焼成材の全体として比抵抗が高ければ差し支えない。
FIG. 1 shows an enlarged structure of an example of this kind of soft magnetic composite compacted fired material. An Mg-containing
As described above, the soft magnetic composite compacted fired material is manufactured by compacting a plurality of Mg-containing oxide-coated soft
以上の製造方法により得られた軟磁性複合圧密焼成材は高密度、高強度、高比抵抗および高磁束密度を有し、この軟磁性複合圧密焼成材は、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軟磁性複合圧密焼成材にあっては、（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低融点ガラスあるいは金属酸化物を酸化雰囲気において焼成することにより、成長させたＦｅ３Ｏ４を主体とする酸化鉄を含む低融点ガラスの成分を含む粒界層、または、Ｆｅ３Ｏ４を主体とする酸化鉄を含む金属酸化物を主体とする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、抗折強度を更に高くすることができ、高強度軟磁性複合圧密焼成材を得ることができる。その上、本製造方法により得られた軟磁性複合圧密焼成材は、高磁束密度で高周波低鉄損の特徴を兼ね備える優れた特徴を有する。
The soft magnetic composite compacted fired material obtained by the above manufacturing method has high density, high strength, high specific resistance and high magnetic flux density. This soft magnetic composite compacted fired material has high magnetic flux density, high frequency and low iron loss. Because of its characteristics, it can be used as a material for various electromagnetic circuit components that take advantage of this characteristic.
Further, in the soft magnetic composite compacted fired material obtained by the above manufacturing method, the Mg—Fe—O ternary oxide deposited film containing (Mg, Fe) O and the low melting point glass present at the interface thereof Alternatively, by firing a metal oxide in an oxidizing atmosphere, a grain boundary layer containing a component of a low melting point glass containing iron oxide mainly composed of Fe 3 O 4 , or oxidized mainly composed of Fe 3 O 4 Since it has a grain boundary layer mainly composed of a metal oxide containing iron, the Mg-containing oxide-coated soft magnetic particles are particularly well bonded to each other, and the bending strength can be further increased. A strength soft magnetic composite compacted fired material can be obtained. In addition, the soft magnetic composite compacted fired material obtained by this production method has excellent characteristics that combine high magnetic flux density with high frequency and low iron loss.
粒径１００〜２００μｍ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０〜６０分間行った。ここでＭｇＯ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ので、Ｍｇの添加量は必要最小限度で良く、鉄粉に対して０．１質量％のＭｇ粉末を配合し、この配合粉末をアルゴンガス雰囲気中、造粒転動攪拌混合装置によって転動することによりＭｇ含有酸化物被覆軟磁性粒子を作製した。
Ｍｇ含有酸化物被覆軟磁性粒子の外周面に形成されている（Ｍｇ,Ｆｅ）Ｏを含むＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜（表１にはＭｇＯ膜と略記する）の膜厚を測定した結果を表１に示す。この膜の膜厚は、前述の大気中加熱処理で生成される酸化膜厚に比例するので、ＭｇＯ膜厚２０〜８０ｎｍのものを試験試料として用いた。
A soft magnetic powder (pure iron powder) having a particle size of 100 to 200 μm was subjected to heat treatment at 220 ° C. in the atmosphere for 0 to 60 minutes. Here, since the MgO film is proportional to the oxide film thickness generated by the heat treatment in the air at 220 ° C. in the previous stage, the amount of Mg added may be the minimum necessary, and 0.1% by mass of Mg powder with respect to the iron powder. The compounded powder was rolled by an agglomerated rolling stirring and mixing apparatus in an argon gas atmosphere to produce Mg-containing oxide-coated soft magnetic particles.
Film thickness of Mg-Fe-O ternary oxide deposited film (abbreviated as MgO film in Table 1) containing (Mg, Fe) O formed on the outer peripheral surface of Mg-containing oxide-coated soft magnetic particles The results of measuring are shown in Table 1. Since the thickness of this film is proportional to the oxide film thickness generated by the above-described heat treatment in the atmosphere, a MgO film thickness of 20 to 80 nm was used as a test sample.
前記各ＭｇＯ膜厚の試料に対し、Ｓｉレジンを質量％で表１に示す如く０．３〜１．５％の範囲で添加し、表１に示す成形圧力、焼成条件にて焼成した。 As shown in Table 1, Si resin was added in the range of 0.3 to 1.5% by mass% to each MgO film thickness sample and fired under the molding pressure and firing conditions shown in Table 1.
表１に示す焼成条件で焼成することにより、（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レジンによる軟磁性複合圧密焼成材の前駆体を得た後、更にスチーム雰囲気あるいは大気中において、即ち、酸化性雰囲気中において、表２に示す温度条件、処理時間で熱処理を行い、目的の軟磁性複合圧密焼成材を得た。 By firing under the firing conditions shown in Table 1, a precursor of a soft magnetic composite compacted fired material composed of an Mg—Fe—O ternary oxide deposited film containing (Mg, Fe) O and Si resin present at the interface thereof Then, heat treatment was performed in a steam atmosphere or air, that is, in an oxidizing atmosphere under the temperature conditions and processing time shown in Table 2, to obtain the intended soft magnetic composite compacted fired material.
得られた軟磁性複合圧密焼成材の各試料において抗折強度、比抵抗、密度、保磁力、磁束密度を測定した結果を表２に示す。 Table 2 shows the results of measuring the bending strength, specific resistance, density, coercive force, and magnetic flux density of each sample of the obtained soft magnetic composite compacted fired material.
表２に示す結果から、表２に示す焼成後熱処理を施していないＮｏ.１〜３の試料は、抗折強度が５２〜９４の範囲であるが、窒素ガス雰囲気中あるいは水素ガス雰囲気中などの非酸化性雰囲気中において５５０℃を越える温度〜６５０℃で焼成した後に、４００〜５６０℃で熱処理を施しているＮｏ.４〜１２、Ｎｏ.１５、１７〜２６の試料は抗折強度がいずれも向上している。
しかし、焼成処理を大気中、即ち、非酸化性雰囲気ではなく、酸化性雰囲気中において施したＮｏ.１３の試料は抗折強度が８３であり、向上していない。また、Ｓｉレジンを添加していない試料は比抵抗が極めて低い値となった。更に、焼成処理を７５０℃で行ったＮｏ.１６の試料は比抵抗が極めて低い値となった。また、Ｎｏ.６の試料はＭｇＯの膜厚が８０ｎｍと厚いために、磁束密度が低下した。
以上の結果から、ＭｇＯの膜厚は２０〜８０ｎｍの範囲内が好ましい。
以上の結果から、熱処理条件は４００℃〜５６０℃の範囲が好ましい。
From the results shown in Table 2, the samples No. 1 to 3 not subjected to the post-firing heat treatment shown in Table 2 have a bending strength in the range of 52 to 94, but in a nitrogen gas atmosphere or a hydrogen gas atmosphere. No. 4-12, No. 15, 17-26 samples subjected to heat treatment at 400 to 560 ° C. after firing at a temperature exceeding 550 ° C. in a non-oxidizing atmosphere of No. 4 have a bending strength. Both have improved.
However, the No. 13 sample subjected to the baking treatment in the atmosphere, that is, not in the non-oxidizing atmosphere but in the oxidizing atmosphere has a bending strength of 83 and is not improved. Further, the specific resistance of the sample to which no Si resin was added was extremely low. Furthermore, the specific resistance of the No. 16 sample subjected to the firing treatment at 750 ° C. was a very low value. In addition, since the No. 6 sample had a thick MgO film thickness of 80 nm, the magnetic flux density decreased.
From the above results, the thickness of MgO is preferably in the range of 20 to 80 nm.
From the above results, the heat treatment conditions are preferably in the range of 400 ° C to 560 ° C.
図２は実施例において得られた本発明に係る高強度軟磁性複合圧密焼成材試料Ｎｏ.８の金属組織を示す拡大写真である。
この図２に示す金属組織上の１１１位置、１１２位置、１１３位置、１１４位置、１１５位置、１１６位置においてエネルギー分散型蛍光Ｘ線分析（ＥＤＸ）を行った。その結果を図３〜図８に示す。
図３に示す１１１位置の分析結果は軟磁性金属粒子の部分の分析結果、図４に示す１１２位置の分析結果は軟磁性金属粒子の外周部分の分析結果、図５に示す１１３位置の分析結果は軟磁性金属粒子の外方のＭｇ含有酸化膜と思われる部分の分析結果、図６に示す１１４位置の分析結果は軟磁性金属粒子の外方の界面層と思われる部分の分析結果、図７に示す１１５位置の分析結果は軟磁性金属粒子の外方のＭｇ含有酸化膜と思われる部分の分析結果、図８に示す１１６位置の分析結果は軟磁性金属粒子の外周部分の分析結果である。
FIG. 2 is an enlarged photograph showing the metal structure of the high-strength soft magnetic composite compacted fired material sample No. 8 according to the present invention obtained in the examples.
Energy dispersive X-ray fluorescence analysis (EDX) was performed at the 111 position, 112 position, 113 position, 114 position, 115 position, and 116 position on the metal structure shown in FIG. The results are shown in FIGS.
The analysis result at the 111 position shown in FIG. 3 is the analysis result of the soft magnetic metal particle portion, the analysis result at the 112 position shown in FIG. 4 is the analysis result of the outer peripheral portion of the soft magnetic metal particle, and the analysis result at the 113 position shown in FIG. Is the analysis result of the portion of the soft magnetic metal particle that seems to be the Mg-containing oxide film, and the analysis result at the
図２〜図８に示す結果から、図３、図４と図８に示す軟磁性金属粒子の内部側の分析結果においてはＦｅのピークのみが強く表れているのに対し、図５と図７に示すＭｇ含有酸化膜部分と思われる部位の分析結果ではＦｅのピーク以外にＭｇ、Ｏの大きなピークが見られ、図４に示す粒界層部分と思われる部位の分析結果ではＦｅのピーク以外にＭｇ、Ｓｉの大きなピークが見られることから、本発明で意図する組織になっていることがわかる。 From the results shown in FIG. 2 to FIG. 8, only the Fe peak appears strongly in the analysis results on the inner side of the soft magnetic metal particles shown in FIG. 3, FIG. 4, and FIG. In the analysis result of the portion considered to be the Mg-containing oxide film shown in FIG. 4, large peaks of Mg and O are seen in addition to the Fe peak, and in the analysis result of the portion considered to be the grain boundary layer portion shown in FIG. Since large peaks of Mg and Si are observed, it can be seen that the structure intended in the present invention is obtained.
図９は、実施例において得られた本発明に係る高強度軟磁性複合圧密焼成材試料Ｎｏ.８の金属組織を示す拡大写真である。
この図９に示す金属組織上の１の位置、２の位置、３の位置、４の位置、５の位置、６の位置においてＸ線回折分析を行った。その結果を図１０〜図１５に示す。
図９において１の位置と２の位置は３つのＭｇ含有酸化膜被覆軟磁性粒子の境界となる三粒界点位置の分析結果、３の位置は他の三粒界点位置の分析結果、４の位置と５の位置は２つのＭｇ含有酸化膜被覆軟磁性粒子の境界部分の分析結果、６の位置は３つのＭｇ含有酸化膜被覆軟磁性粒子の境界となる三粒界点に近い位置での分析結果を示す。
FIG. 9 is an enlarged photograph showing the metal structure of high strength soft magnetic composite compacted fired material sample No. 8 according to the present invention obtained in the examples.
X-ray diffraction analysis was performed at
In FIG. 9, the
各図に示す結果から、境界層部分にＦｅとＯとＭｇが存在していることが分かり、本発明で意図する組織になっていることが理解できる。
なお、図１４、図１５に示すＭｎは、鉄粉中の不純物であり、酸素との親和力が大きいので、酸化熱処理中に選択酸化され、鉄粉表面に出てきたものと考えられる。
From the results shown in each figure, it can be seen that Fe, O, and Mg are present in the boundary layer portion, and it can be understood that the structure is intended in the present invention.
Note that Mn shown in FIGS. 14 and 15 is an impurity in the iron powder and has a high affinity with oxygen, so it is considered that it was selectively oxidized during the oxidation heat treatment and came out on the surface of the iron powder.
図１６は実施例において得られた本発明に係る高強度軟磁性複合圧密焼成材試料Ｎｏ.８の金属組織を示す拡大写真である。
図１６に示す如く軟磁性金属粒子の外周部分にＭｇ含有酸化物膜が３０ｎｍ〜５０ｎｍ程度の厚さで存在し、それらの間に同じ程度の幅の薄い境界層が存在している状況を確認することができた。
FIG. 16 is an enlarged photograph showing the metal structure of high strength soft magnetic composite compacted fired material sample No. 8 according to the present invention obtained in the examples.
As shown in FIG. 16, it is confirmed that the Mg-containing oxide film is present at a thickness of about 30 nm to 50 nm on the outer peripheral portion of the soft magnetic metal particle, and a thin boundary layer having the same width exists between them. We were able to.
本発明による軟磁性材は、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ができる。
The soft magnetic material according to the present invention can be used as an electromagnetic circuit component, for example, as 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 a magnetic sensor core. In any case, the present invention can be applied to an electromagnetic circuit component 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. Performance and small size can be reduced.
１ Ｆｅ系軟磁性金属粒子、
２ Ｍｇ含有酸化膜、
３ Ｍｇ含有酸化物被覆軟磁性粒子、
５ 粒界層、
1 Fe-based soft magnetic metal particles,
2 Mg-containing oxide film,
3 Mg-containing oxide-coated soft magnetic particles,
5 Grain boundary layer,
Claims (16)
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含有酸化膜とを具備してなるＭｇ含有酸化物被覆軟磁性粒子を、前記の如く混合したＳｉレジン、低融点ガラス、金属酸化物の少なくとも１種の成分を含む粒界層を介し複数結合してなる焼成体とすることを特徴とする高強度軟磁性複合圧密焼成材の製造方法。 Mg-containing oxide-coated soft magnetic particles comprising Fe-based soft magnetic metal particles and an Mg-containing oxide film coated on the surface of the soft magnetic metal particles, Si resin, low melting point glass, metal oxide At least one kind is mixed and consolidated, fired in a non-oxidizing atmosphere to be a precursor of a soft magnetic composite consolidated fired material, and then heat treated in an oxidizing atmosphere,
Si resin, low-melting glass, in which Mg-containing oxide-coated soft magnetic particles comprising Fe-based soft magnetic metal particles and Mg-containing oxide film coated on the surface of the soft magnetic metal particles are mixed as described above A method for producing a high-strength soft magnetic composite compacted fired material, characterized in that a sintered body is formed by bonding a plurality of grains through a grain boundary layer containing at least one component of a metal oxide.
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Ｆｅ系の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含有酸化物被覆膜から得られたものであることを特徴とする請求項１０または１１に記載の高強度軟磁性複合圧密焼成材。 The Mg-containing oxide comprising a bond through the grain boundary layer of the plurality of Mg-containing oxide-coated soft magnetic particles comprising the soft magnetic metal particles and an Mg-containing oxide film coated on the surface of the soft magnetic metal particles. A bond obtained by a mixed compaction heat treatment of an object-coated soft magnetic particle and at least one of Si resin, low-melting glass, and metal oxide,
The iron oxide present in the grain boundary layer between the Mg-containing oxide-coated soft magnetic particles is the one in which the Fe component is precipitated from the Fe-based soft magnetic metal particles at the grain boundary and is oxide-dispersed and grown. The Mg-containing oxide film adjacent to the grain boundary layer is obtained from the Mg-containing oxide coating film provided in the Mg-containing oxide-coated soft magnetic particles before the mixed consolidation firing process. The high-strength soft magnetic composite compacted fired material according to claim 10 or 11, characterized in that
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