JP2006332525A - High-strength complex soft magnetic material having high strength, high magnetic flux density, high resistance and less iron loss, and manufacturing method thereof - Google Patents
High-strength complex soft magnetic material having high strength, high magnetic flux density, high resistance and less iron loss, and manufacturing method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 47
- 239000000696 magnetic material Substances 0.000 title claims abstract description 46
- 230000004907 flux Effects 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 162
- 239000011521 glass Substances 0.000 claims abstract description 87
- 238000002844 melting Methods 0.000 claims abstract description 56
- 229910017135 Fe—O Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 24
- 239000011593 sulfur Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 46
- 239000002243 precursor Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 25
- 239000010419 fine particle Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 150000004703 alkoxides Chemical class 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000748 compression moulding Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
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- 230000003647 oxidation Effects 0.000 claims description 5
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- 239000000463 material Substances 0.000 abstract description 7
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- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 8
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- 229910000859 α-Fe Inorganic materials 0.000 description 8
- 238000010304 firing Methods 0.000 description 6
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- 238000000576 coating method Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
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- 239000011261 inert gas Substances 0.000 description 5
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
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- -1 i-butoxy group Chemical group 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
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- 230000000694 effects Effects 0.000 description 3
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- 238000009413 insulation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910020410 SiO2—B2O3—PbO Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical class 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 125000005594 diketone group Chemical group 0.000 description 1
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- AQEHTQSRENCCBO-UHFFFAOYSA-N ethanolate silicon(4+) tetraethyl silicate Chemical compound C(C)O[Si](OCC)(OCC)OCC.[O-]CC.[Si+4].[O-]CC.[O-]CC.[O-]CC AQEHTQSRENCCBO-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 125000006606 n-butoxy group Chemical group 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 125000001181 organosilyl group Chemical class [SiH3]* 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- PCOBHRURWGDXGK-UHFFFAOYSA-N tripropoxybismuthane Chemical compound CCCO[Bi](OCCC)OCCC PCOBHRURWGDXGK-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- YNPXMOHUBANPJB-UHFFFAOYSA-N zinc;butan-1-olate Chemical compound [Zn+2].CCCC[O-].CCCC[O-] YNPXMOHUBANPJB-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
この発明は、金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に被覆されてなるＭｇ含有酸化鉄膜被覆鉄粉末を低融点ガラスで結合してなる高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材およびその製造方法に関するものであり、この高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材で作製した複合軟磁性材は、低鉄損を必要とする各種電磁気回路部品、例えば、モータ、アクチュエータ、ヨーク、コア、リアクトルなどの各種電磁気部品の素材として使用されるものである。 According to the present invention, an iron powder coated with an Mg-containing iron oxide film in which an Mg-Fe-O ternary oxide deposition film in which metal Fe fine particles are dispersed in a substrate is coated on the surface of the iron powder is made of low melting glass. The present invention relates to a high-strength composite soft magnetic material with low iron loss having high strength, high magnetic flux density, and high resistance, and a method for manufacturing the same, and to low iron loss having high strength, high magnetic flux density, and high resistance. Composite soft magnetic materials made of high-strength composite soft magnetic materials are used as materials for various electromagnetic circuit components that require low iron loss, such as motors, actuators, yokes, cores, reactors, etc. It is.
一般に、各種電磁気回路部品に使用される軟磁性材は、鉄損が小さいことが要求されるため、電気抵抗を高くして渦電流損を低減させ、保磁力を小さくしてヒステリシス損を低減させることは一般に知られている。さらに、近年、電磁気回路の小型化、高応答化が求められているところから、磁束密度がより高いことも重要視されている。 In general, soft magnetic materials used in various electromagnetic circuit components are required to have low iron loss. Therefore, electrical resistance is increased to reduce eddy current loss, and coercive force is reduced to reduce hysteresis loss. It is generally known. Furthermore, in recent years, since the miniaturization and high response of the electromagnetic circuit have been demanded, higher magnetic flux density is also regarded as important.
かかる高比抵抗を有する軟磁性材料を製造するための原料粉末の一例として鉄粉末の表面に化学的な方法によりＭｇ含有フェライト膜を被覆したＭｇ含有酸化鉄膜被覆鉄粉末が知られており（特許文献１参照）、また一般に軟磁性粉末を低融点ガラス粉末と共に混合して得られた混合粉末を圧縮成形し熱処理して圧粉磁性材料などを製造する方法も知られている（特許文献２または３参照）。
しかし、従来のＭｇ含有フェライト膜を被覆したＭｇ含有酸化鉄膜被覆鉄粉末は、鉄粉末の表面にＭｇ含有フェライト膜を化学的方法により被覆するために、プレス成形した圧粉体に高温歪取り焼成を行って得られた複合軟磁性材は、Ｍｇ含有フェライト膜が化学的に不安定となり変化して絶縁性が低下すると共に、鉄粉末の表面に対するＭｇ含有フェライト膜の密着性が十分でなく、従来のＭｇ含有フェライト膜を被覆したＭｇ含有酸化鉄膜被覆鉄粉末を低融点ガラス粉末と混合して得られた混合粉末をプレス成形し熱処理することにより作製した複合軟磁性材は、プレス成形中にＭｇ含有フェライト膜が剥離したり破れるなどして十分な絶縁効果が発揮できず、したがって、十分な高比抵抗が得られないという問題点があった。 However, the conventional iron powder coated with Mg-containing iron oxide film coated with Mg-containing ferrite film has a high-temperature strain-relief effect on press-molded green compacts to coat the Mg-containing ferrite film on the surface of the iron powder by a chemical method. In the composite soft magnetic material obtained by firing, the Mg-containing ferrite film becomes chemically unstable and changes to deteriorate the insulation, and the adhesion of the Mg-containing ferrite film to the surface of the iron powder is not sufficient. The composite soft magnetic material produced by press-molding and heat-treating the mixed powder obtained by mixing the Mg-containing iron oxide film-coated iron powder coated with the conventional Mg-containing ferrite film with the low melting point glass powder is press-molded. There is a problem in that the Mg-containing ferrite film peels off or breaks, so that a sufficient insulating effect cannot be exhibited, and therefore a sufficient high specific resistance cannot be obtained.
本発明者らは、かかる問題点を解決するために、先に、
（ａ）金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に被覆されているＭｇ含有酸化鉄膜被覆鉄粉末、
（ｂ）金属Ｆｅ微粒子が素地中に分散しており、ＭｇおよびＯが表面から内部に向って減少しておりかつＦｅが内部に向って増加している濃度勾配を有するＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に被覆されているＭｇ含有酸化膜被覆鉄粉末、
（ｃ）前記（ａ）および（ｂ）記載のＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に被覆されているＭｇ含有酸化鉄膜被覆鉄粉末であって、前記鉄粉末と前記Ｍｇ−Ｆｅ−Ｏ三元系酸化物堆積膜との界面領域に、鉄粉末の中心部に含まれる硫黄よりも高濃度の硫黄を含む硫黄濃化層を有するＭｇ含有酸化鉄膜被覆鉄粉末、
（ｄ）前記金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、結晶粒径：２００ｎｍ以下の微細結晶組織を有する前記（ａ）、（ｂ）または（ｃ）記載のＭｇ含有酸化鉄膜被覆鉄粉末、
（ｅ）前記金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、その最表面が実質的にＭｇＯで構成されている前記（ａ）、（ｂ）、（ｃ）または（ｄ）記載のＭｇ含有酸化鉄膜被覆鉄粉末、などを発明した。
In order to solve such problems, the present inventors firstly
(A) a Mg-containing iron oxide film-coated iron powder in which an Mg-Fe-O ternary oxide deposition film in which metal Fe fine particles are dispersed in the substrate is coated on the surface of the iron powder;
(B) Mg—Fe—O 3 having a concentration gradient in which metallic Fe fine particles are dispersed in the substrate, Mg and O decrease from the surface toward the inside, and Fe increases toward the inside. Mg-containing oxide film-coated iron powder in which the base oxide film is coated on the surface of the iron powder,
(C) The Mg-containing iron oxide film-coated iron powder in which the Mg—Fe—O ternary oxide deposited film described in (a) and (b) is coated on the surface of the iron powder, the iron powder Mg-containing iron oxide film-coated iron having a sulfur-concentrated layer containing sulfur at a higher concentration than sulfur contained in the center of the iron powder in the interface region between the Mg-Fe-O ternary oxide deposited film and the Mg-Fe-O ternary oxide deposited film Powder,
(D) The Mg—Fe—O ternary oxide deposited film in which the metal Fe fine particles are dispersed in the substrate has the crystal grain size: 200 nm or less (a), (b) or (C) Mg-containing iron oxide film-coated iron powder according to the description,
(E) In the Mg—Fe—O ternary oxide deposited film in which the metal Fe fine particles are dispersed in the substrate, the outermost surface is substantially composed of MgO (a), (b) , (C) or (d) described invented Mg-containing iron oxide film-coated iron powder, and the like.
かかる先に発明した前記（ａ）、（ｂ）、（ｃ）、（ｄ）または（ｅ）記載のＭｇ含有酸化鉄膜被覆鉄粉末は、鉄粉末を予め酸化雰囲気中で加熱するなどして酸化処理を施すことにより鉄粉末の表面に酸化鉄膜を形成した鉄粉末（以下、酸化処理鉄粉末という）を作製し、この酸化処理鉄粉末にＭｇ粉末を添加し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で転動しながら加熱するなどした後さらに酸化性雰囲気中で加熱する酸化処理を施すことにより得られるものであり、これら先に発明したＭｇ含有酸化鉄膜被覆鉄粉末は、
（イ）一般に知られているＭｇＯ−ＦｅＯ−Ｆｅ２Ｏ３系で代表される（Ｍｇ，Ｆｅ）Ｏ、（Ｍｇ，Ｆｅ）３Ｏ４などのＭｇ−Ｆｅ−Ｏ三元系各種酸化物のうちで、金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に形成され、このＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に被覆されたＭｇ含有酸化鉄膜被覆鉄粉末は、従来の鉄粉末の表面にＭｇ含有フェライト膜を化学的に形成したＭｇ含有酸化鉄膜被覆鉄粉末に比べてＭｇ含有酸化鉄膜の鉄粉末に対する密着性が格段に優れることから、プレス成形中に絶縁皮膜である酸化鉄膜が破壊されて鉄粉末同士が接触することが少なく、プレス成形後に焼成を行ってもＭｇ含有酸化鉄膜の絶縁性が低下することなく高抵抗を維持することができるところから渦電流損失が低くなり、さらに歪取り焼成を行った場合に、より保磁力が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、したがって、低鉄損を有する複合軟磁性材料が得られること、
（ロ）前記Ｍｇ含有酸化鉄膜被覆鉄粉末は、鉄粉末と金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜との界面領域には、鉄粉末の中心部に不可避不純物として含まれている硫黄よりも高濃度の硫黄を含む硫黄濃化層が形成されること、
（ハ）前記鉄粉末の表面に形成されている金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は結晶粒径：２００ｎｍ以下の微細結晶組織を有すること、
（ニ）前記鉄粉末の表面に形成されている金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、その最表面に含まれるＭｇＯの量が多いほど好ましく、その最表面は実質的にＭｇＯで構成されていることが最も好ましい、ことなどの知見に基づいて成されたものである。
The Mg-containing iron oxide film-coated iron powder described in (a), (b), (c), (d) or (e) previously invented is obtained by heating the iron powder in an oxidizing atmosphere in advance. An iron powder having an iron oxide film formed on the surface of the iron powder by oxidation treatment (hereinafter referred to as “oxidized iron powder”) is prepared, and the resulting mixture is obtained by adding and mixing Mg powder to this oxidized iron powder. The Mg-containing iron oxide film previously invented is obtained by subjecting the powder to heating while rolling in an inert gas atmosphere or vacuum atmosphere, and then performing an oxidation treatment in which the powder is heated in an oxidizing atmosphere. The coated iron powder is
(A) Various oxides of Mg-Fe-O ternary system such as (Mg, Fe) O, (Mg, Fe) 3 O 4 and the like represented by the generally known MgO-FeO-Fe 2 O 3 system Among them, an Mg—Fe—O ternary oxide deposition film in which metal Fe fine particles are dispersed in the substrate is formed on the surface of the iron powder, and this Mg—Fe—O ternary oxide deposition film is formed of iron. Mg-containing iron oxide film coated iron powder coated on the surface of the powder Compared to the iron powder coated with Mg-containing iron oxide film coated with Mg-containing iron oxide film chemically formed on the surface of the conventional iron powder Since the iron oxide film, which is an insulating film, is broken during press molding, the iron oxide film is less likely to come into contact with each other, and even after firing after press molding, the Mg-containing iron oxide High resistance can be maintained without reducing the insulation of the film As a result, eddy current loss is reduced, and when coercive firing is performed, the coercive force can be further reduced, so that hysteresis loss can be kept low, and thus a composite soft magnetic material having low iron loss can be obtained. thing,
(B) The Mg-containing iron oxide film-coated iron powder is composed of an iron powder and an Mg-Fe-O ternary oxide deposited film in which metal Fe fine particles are dispersed in the substrate. A sulfur-concentrated layer containing sulfur at a higher concentration than sulfur contained as an inevitable impurity in the center,
(C) The Mg—Fe—O ternary oxide deposited film in which the metal Fe fine particles formed on the surface of the iron powder are dispersed in the substrate has a fine crystal structure with a crystal grain size of 200 nm or less. ,
(D) The Mg-Fe-O ternary oxide deposited film in which the metal Fe fine particles formed on the surface of the iron powder are dispersed in the substrate has a larger amount of MgO contained in the outermost surface. Preferably, the outermost surface is made based on the knowledge that it is most preferable that the outermost surface is substantially composed of MgO.
これら先に発明した前記（ａ）〜（ｅ）記載のＭｇ含有酸化鉄膜被覆鉄粉末の製造方法を一層具体的に説明すると、まず、鉄粉末を予め酸化雰囲気中、温度：５０〜５００℃に加熱して酸化処理することにより鉄粉末の表面に酸化鉄膜を形成した酸化処理鉄粉末を作製し、これらの粉末に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転動しながら加熱した後、必要に応じてさらに酸化性雰囲気中、温度：５０〜３５０℃で加熱する酸化処理を施すことにより作製することができる。 The production method of the Mg-containing iron oxide film-coated iron powder according to the above-described inventions (a) to (e) will be described more specifically. First, the iron powder is preliminarily in an oxidizing atmosphere at a temperature of 50 to 500 ° C. The oxidized powder is formed by forming an iron oxide film on the surface of the iron powder by heating and oxidizing the powder, and the mixed powder obtained by adding and mixing the Mg powder to these powders has a temperature of 150 to After heating while rolling in an inert gas atmosphere or vacuum atmosphere of 1100 ° C. and pressure: 1 × 10 −12 to 1 × 10 −1 MPa, if necessary, in an oxidizing atmosphere, temperature: 50 to 350 It can produce by performing the oxidation process heated at degreeC.
また、先に発明した前記（ｅ）記載の金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜の最表面が実質的にＭｇＯで構成されているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、鉄粉末を予め酸化雰囲気中、温度：５０〜５００℃に加熱して酸化処理することにより鉄粉末の表面に酸化鉄膜を形成した酸化処理鉄粉末を作製し、これらの粉末にＭｇ粉末を一層多く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転動しながら加熱した後、さらに酸化性雰囲気中、温度：５０〜３５０℃で一層長時間加熱保持する酸化処理を施すことにより得られる。
「堆積膜」という用語は、通常、真空蒸発やスパッタされた皮膜構成原子が例えば基板上に堆積した皮膜を示すが、前記鉄粉末の表面に形成されている金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、酸化鉄膜を有する鉄粉末表面の酸化鉄（Ｆｅ−Ｏ）とＭｇが反応を伴って当該鉄粉末表面に堆積した皮膜を示す。そして、この鉄粉末の表面に形成されている金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜の膜厚は、圧粉成形した複合軟磁性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。膜厚が５ｎｍより薄いと圧粉成形した複合軟磁性材の比抵抗が充分でなく渦電流損が増加するので好ましくなく、一方、膜厚が５００ｎｍより厚いと圧粉成形した複合軟磁性材の磁束密度が低下して好ましくないからである。さらに好ましい膜厚は５ｎｍ〜２００ｎｍの範囲内である。
Further, the Mg—Fe—O ternary oxide deposited film in which the metal Fe fine particles described in (e) described above are dispersed in the substrate is substantially composed of MgO. The Fe-O ternary oxide deposited film is an oxidized iron powder in which an iron oxide film is formed on the surface of the iron powder by previously oxidizing the iron powder in an oxidizing atmosphere at a temperature of 50 to 500 ° C. An inert gas atmosphere at a temperature of 150 to 1100 ° C. and a pressure of 1 × 10 −12 to 1 × 10 −1 MPa is obtained by adding more Mg powder to these powders and mixing them. Alternatively, after heating while rolling in a vacuum atmosphere, it is further obtained by subjecting it to an oxidation treatment in which it is heated and held at a temperature of 50 to 350 ° C. for a longer time in an oxidizing atmosphere.
The term “deposited film” usually refers to a film in which atoms constituting a film evaporated by vacuum evaporation or sputtering are deposited on a substrate, for example, but metal Fe fine particles formed on the surface of the iron powder are dispersed in the substrate. The Mg—Fe—O ternary oxide deposited film indicates a film in which iron oxide (Fe—O) and Mg on the iron powder surface having an iron oxide film are deposited on the iron powder surface with a reaction. And the film thickness of the Mg-Fe-O ternary oxide deposited film in which the metal Fe fine particles formed on the surface of the iron powder are dispersed in the substrate is higher than that of the compacted composite soft magnetic material. In order to obtain a magnetic flux density and a high specific resistance, it is preferably in the range of 5 nm to 500 nm. If the film thickness is less than 5 nm, the specific resistance of the powder-molded composite soft magnetic material is not sufficient and the eddy current loss increases. On the other hand, if the film thickness is thicker than 500 nm, it is not preferable. This is because the magnetic flux density is lowered, which is not preferable. A more preferable film thickness is in the range of 5 nm to 200 nm.
先に発明した前記（ａ）〜（ｅ）のＭｇ含有酸化鉄膜被覆鉄粉末の表面に形成されている金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、前記金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜と鉄粉末との界面領域に、鉄粉末の中心部に含まれる硫黄よりも高濃度の硫黄を含む硫黄濃化層を有する。この硫黄濃化層を有することはオージェ電子分光法により硫黄濃度を測定し、これをグラフに表すと、硫黄濃度ピークを示すことから確認することができる。界面領域にこの様な硫黄濃化層を有することにより金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜の鉄粉末表面に対する密着性がより一層優れるようになり、圧粉成形時の粉末の変形に堆積膜が追従して被覆の破れを防止することができ、焼成時にも鉄粉末同士の接触結合を防止することができて高抵抗を維持することができ、したがって渦電流損失が低くなる。硫黄濃化層の硫黄は、鉄粉末には不可避不純物として硫黄が含まれており、大部分はこの鉄粉末の表面部分に含まれる硫黄から供給されると考えられる。 Mg-Fe-O ternary oxide deposition in which metal Fe fine particles formed on the surface of the Mg-containing iron oxide film-coated iron powders of the above-described inventions (a) to (e) are dispersed in the substrate. The film has a higher concentration than the sulfur contained in the center of the iron powder in the interface region between the Mg-Fe-O ternary oxide deposited film in which the metal Fe fine particles are dispersed in the substrate and the iron powder. It has a sulfur enriched layer containing sulfur. Having this sulfur-concentrated layer can be confirmed from the fact that the sulfur concentration is measured by Auger electron spectroscopy, and this is shown in a graph, showing a sulfur concentration peak. By having such a sulfur-concentrated layer in the interface region, the adhesion of the Mg-Fe-O ternary oxide deposited film in which the metal Fe fine particles are dispersed in the substrate to the iron powder surface is further improved. Therefore, the deposited film can follow the deformation of the powder at the time of compacting to prevent the coating from being broken, and the contact bonding between the iron powders can be prevented at the time of firing to maintain high resistance. And therefore lower eddy current losses. The sulfur in the sulfur-concentrated layer is considered to be supplied from sulfur contained in the surface portion of the iron powder because the iron powder contains sulfur as an unavoidable impurity.
前記（ａ）〜（ｅ）のＭｇ含有酸化鉄膜被覆鉄粉末の表面に形成されている金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、その結晶粒が微細であるほど好ましく、結晶粒径が２００ｎｍ以下の微細結晶組織を有する事が好ましい。この様な微細結晶組織を有することにより、圧粉成形時の粉末の変形に微結晶Ｍｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が追従して被覆の破れを防止することができ、焼成時にも鉄粉末同士の接触結合を防止することができ、また、高温歪取り焼成を行っても酸化物が安定で絶縁性低下が防止でき高抵抗で渦電流損失が低くなる。結晶粒径が２００ｎｍより大きいと、圧縮成形時に被覆が破れて絶縁性が低下したり、Ｍｇ−Ｆｅ−Ｏ三元系酸化物堆積膜の膜厚が５００ｎｍよりも厚くなったりして圧粉成形した複合軟磁性材の磁束密度が低下するようになるので好ましくない。 The Mg—Fe—O ternary oxide deposited film in which the metal Fe fine particles formed on the surface of the Mg-containing iron oxide film-coated iron powders (a) to (e) are dispersed in the substrate, The finer the crystal grain, the better, and the crystal grain size preferably has a fine crystal structure of 200 nm or less. By having such a fine crystal structure, the microcrystalline Mg—Fe—O ternary oxide deposited film can follow the deformation of the powder during compacting and prevent the coating from being broken. In addition, contact bonding between iron powders can be prevented, and even when high-temperature strain relief firing is performed, the oxide is stable and insulation deterioration can be prevented, and eddy current loss is reduced with high resistance. If the crystal grain size is larger than 200 nm, the coating is broken at the time of compression molding and the insulating property is lowered, or the film thickness of the Mg—Fe—O ternary oxide deposited film becomes thicker than 500 nm. This is not preferable because the magnetic flux density of the composite soft magnetic material is lowered.
さらに、前記（ｅ）記載のＭｇ含有酸化鉄膜被覆鉄粉末の表面に形成されているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、その最表面におけるＭｇＯの含有量が多くなるほど好ましく、実質的にＭｇＯで構成されていることが最も好ましい。最表面が実質的にＭｇＯであると、プレス成形した圧粉体の焼成時にもＦｅの拡散が防止され鉄粉末同士の接触結合を防止することができ絶縁性低下が防止でき高抵抗で渦電流損失が低くなるからである。 Furthermore, the Mg-Fe-O ternary oxide deposited film formed on the surface of the Mg-containing iron oxide film-coated iron powder described in (e) is preferable as the content of MgO on the outermost surface increases. Most preferably, it is substantially composed of MgO. When the outermost surface is substantially MgO, the diffusion of Fe is prevented even during firing of the green compact that has been press-molded, and contact bonding between iron powders can be prevented. This is because loss is reduced.
この発明は、先に発明した（ａ）〜（ｅ）記載のＭｇ含有酸化鉄膜被覆鉄粉末を使用して高強度、高磁束密度および高比抵抗を有する高強度複合軟磁性材およびその製造方法を提供することを目的とするものであって、先に発明した前記（ａ）〜（ｅ）記載のＭｇ含有酸化鉄膜被覆鉄粉末をガラス相で結合してなる高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材およびその製造方法に関するものである。すなわち、この発明は、
（１）金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に被覆されているＭｇ含有酸化鉄膜被覆鉄粉末を低融点ガラスで結合してなる高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材、
（２）金属Ｆｅ微粒子が素地中に分散しており、ＭｇおよびＯが表面から内部に向って減少しておりかつＦｅが内部に向って増加している濃度勾配を有するＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が鉄粉末の表面に被覆されているＭｇ含有酸化膜被覆鉄粉末が、低融点ガラスで結合されてなる高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材、
（３）前記Ｍｇ−Ｆｅ−Ｏ三元系酸化物堆積膜と鉄粉末との界面領域に鉄粉末の中心部に含まれる硫黄よりも高濃度の硫黄を含む硫黄濃化層を有する前記（１）または（２）記載のＭｇ含有酸化鉄膜被覆鉄粉末が、低融点ガラスで結合されてなる高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材、
（４）前記Ｍｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、結晶粒径：２００ｎｍ以下の微細結晶組織を有する前記（１）、（２）または（３）記載の高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材、
（５）前記Ｍｇ−Ｆｅ−Ｏ三元系酸化物堆積膜は、その最表面が実質的にＭｇＯで構成されている前記（１）、（２）、（３）または（４）記載の高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材、
（５）前記（１）、（２）、（３）、（４）または（５）記載のＭｇ含有酸化鉄膜被覆鉄粉末に低融点ガラス粉末を混合して混合粉末を作製し、この混合粉末を圧縮成形したのち熱処理する高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材の製造方法、に特徴を有するものである。
The present invention is a high-strength composite soft magnetic material having high strength, high magnetic flux density and high specific resistance using the Mg-containing iron oxide film-coated iron powder described in (a) to (e) above and the production thereof The object is to provide a method, which is obtained by combining the Mg-containing iron oxide film-coated iron powder described in the above (a) to (e) in a glass phase with a high strength and a high magnetic flux density. The present invention also relates to a high-strength composite soft magnetic material having high resistance and low iron loss, and a method for producing the same. That is, this invention
(1) Mg-Fe-O ternary oxide deposited film in which fine metal Fe particles are dispersed in the substrate is coated on the surface of the iron powder. High strength composite soft magnetic material with low iron loss and high strength, high magnetic flux density and high resistance,
(2) Mg—Fe—O 3 having a concentration gradient in which metallic Fe fine particles are dispersed in the substrate, Mg and O decrease from the surface toward the inside, and Fe increases toward the inside. High strength, low magnetic loss and high strength with high strength, high magnetic flux density and high resistance, where Mg-containing oxide film-coated iron powder with ternary oxide deposited film coated on the surface of iron powder has low melting point glass Composite soft magnetic material,
(3) The sulfur-concentrated layer containing sulfur at a higher concentration than sulfur contained in the center of the iron powder in the interface region between the Mg-Fe-O ternary oxide deposited film and the iron powder (1 ) Or (2) Mg-containing iron oxide film-coated iron powder is a high-strength composite soft magnetic material with low iron loss having high strength, high magnetic flux density and high resistance, which are bonded with low-melting glass,
(4) The Mg—Fe—O ternary oxide deposited film has a high crystallinity and a high magnetic flux density according to (1), (2) or (3), wherein the crystal grain size is 200 nm or less. And high strength composite soft magnetic material with high resistance and low iron loss,
(5) The Mg-Fe-O ternary oxide deposited film has a high surface as described in (1), (2), (3) or (4), wherein the outermost surface is substantially composed of MgO. High strength composite soft magnetic material with low iron loss with strength, high magnetic flux density and high resistance,
(5) A low-melting glass powder is mixed with the Mg-containing iron oxide film-coated iron powder described in (1), (2), (3), (4) or (5) to prepare a mixed powder, and this mixing It is characterized by a method for producing a high-strength composite soft magnetic material having high iron strength, high magnetic flux density, and high resistance and low iron loss, which is heat-treated after compression molding the powder.
前記低融点ガラス粉末は、融点が低くても常温では硬い粉末であり、前記（１）、（２）、（３）、（４）または（５）記載のＭｇ含有酸化鉄膜被覆鉄粉末に低融点ガラス粉末を混合して作製した混合粉末を圧縮成形する際にＭｇ含有酸化鉄膜被覆鉄粉末の表面に形成されているＭｇ含有酸化鉄膜を傷つけたり破損したりする可能性がある。 The low-melting-point glass powder is a hard powder at room temperature even though the melting point is low, and the Mg-containing iron oxide film-coated iron powder described in (1), (2), (3), (4) or (5) There is a possibility that the Mg-containing iron oxide film formed on the surface of the Mg-containing iron oxide film-coated iron powder may be damaged or damaged when the mixed powder prepared by mixing the low melting point glass powder is compression-molded.
これを避けるために、前記（１）、（２）、（３）、（４）または（５）記載のＭｇ含有酸化鉄膜被覆鉄粉末の表面に低融点ガラスを構成する元素の錯体またはアルコキシドを有機溶媒に溶かした溶液を塗布し乾燥することにより低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末を作製し、この低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末における低融点ガラス前駆体の有機成分を加熱分解することによりＭｇ含有酸化鉄膜被覆鉄粉末の表面に低融点ガラスを被覆した低融点ガラスを被覆したＭｇ含有酸化鉄膜被覆鉄粉末を作製し、この低融点ガラスを被覆したＭｇ含有酸化鉄膜被覆鉄粉末を圧縮成形したのち温度：３００〜１０００℃で熱処理するか、または前記（１）、（２）、（３）、（４）または（５）記載のＭｇ含有酸化鉄膜被覆鉄粉末の表面に、低融点ガラスを構成する元素の錯体またはアルコキシドを有機溶媒に溶かした溶液を塗布し乾燥することにより低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末を作製し、この低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末を圧縮成形したのち温度：３００〜１０００℃で熱処理し、前記熱処理する際に低融点ガラス前駆体の有機成分を加熱分解させることにより作製することが一層好ましい。したがって、この発明は、
（６）前記（１）、（２）、（３）、（４）または（５）記載のＭｇ含有酸化鉄膜被覆鉄粉末の表面に、低融点ガラスを構成する元素の錯体またはアルコキシドを有機溶媒に溶かした溶液を塗布し乾燥することにより低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末を作製し、この低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末における低融点ガラス前駆体の有機成分を加熱分解することによりＭｇ含有酸化鉄膜被覆鉄粉末の表面に低融点ガラスを被覆した低融点ガラスを被覆したＭｇ含有酸化鉄膜被覆鉄粉末を作製し、この低融点ガラスを被覆したＭｇ含有酸化鉄膜被覆鉄粉末を圧縮成形したのち熱処理する高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材の製造方法、
（７）前記（１）、（２）、（３）、（４）または（５）記載のＭｇ含有酸化鉄膜被覆鉄粉末の表面に、低融点ガラスを構成する元素の錯体またはアルコキシドを有機溶媒に溶かした溶液を塗布し乾燥することにより低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末を作製し、この低融点ガラス前駆体を被覆したＭｇ含有酸化鉄膜被覆鉄粉末を圧縮成形したのち熱処理し、前記熱処理する際に低融点ガラス前駆体の有機成分を加熱分解させる高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材の製造方法、
（８）前記熱処理の温度は３００〜１０００℃の範囲内である前記（５）、（６）または（７）記載の高強度、高磁束密度および高抵抗を有する鉄損の少ない高強度複合軟磁性材の製造方法、に特徴を有するものである。
In order to avoid this, a complex or alkoxide of an element constituting a low-melting glass on the surface of the Mg-containing iron oxide film-coated iron powder described in (1), (2), (3), (4) or (5) An Mg-containing iron oxide film-coated iron powder coated with a low-melting-point glass precursor was prepared by applying a solution prepared by dissolving an organic solvent in an organic solvent and drying. An Mg-containing iron oxide film-coated iron powder was prepared by thermally decomposing the organic component of the low-melting-point glass precursor in the powder and coating the surface of the Mg-containing iron oxide film-coated iron powder with the low-melting glass coated with the low-melting glass. Then, after compression-molding the Mg-containing iron oxide film-coated iron powder coated with this low-melting glass, heat treatment is performed at a temperature of 300 to 1000 ° C., or (1), (2), (3), (4) or (5) Notes Mg-containing iron oxide film coated with a low-melting-point glass precursor by applying a solution in which an elemental complex or alkoxide constituting the low-melting-point glass is dissolved in an organic solvent on the surface of the Mg-containing iron oxide film-coated iron powder After the film-coated iron powder was produced and the Mg-containing iron oxide film-coated iron powder coated with the low-melting glass precursor was compression-molded, it was heat-treated at a temperature of 300 to 1000 ° C., and the low-melting-point glass precursor was subjected to the heat treatment. It is more preferable to produce the organic component by thermally decomposing it. Therefore, the present invention
(6) An element complex or alkoxide constituting the low-melting glass is organically formed on the surface of the Mg-containing iron oxide film-coated iron powder described in (1), (2), (3), (4) or (5). An Mg-containing iron oxide film-coated iron powder coated with a low-melting glass precursor was prepared by applying a solution dissolved in a solvent and drying, and the Mg-containing iron oxide film-coated iron powder coated with this low-melting glass precursor The organic component of the low-melting glass precursor is thermally decomposed to produce an Mg-containing iron oxide film-coated iron powder coated with a low-melting glass coated with a low-melting glass on the surface of the Mg-containing iron oxide film-coated iron powder. A method for producing a high strength composite soft magnetic material with low iron loss having high strength, high magnetic flux density and high resistance, which is compression-molded and then heat-treated after iron powder coated with Mg-containing iron oxide film coated with low melting point glass,
(7) A complex or alkoxide of an element constituting the low-melting glass is organically formed on the surface of the Mg-containing iron oxide film-coated iron powder described in (1), (2), (3), (4) or (5). An iron powder coated with Mg-containing iron oxide film coated with a low-melting glass precursor was prepared by applying a solution dissolved in a solvent and drying, and the iron powder coated with Mg-containing iron oxide film coated with the low-melting glass precursor was prepared. A method for producing a high-strength composite soft magnetic material having a low iron loss and a high strength, a high magnetic flux density and a high resistance by heat-decomposing the organic component of the low-melting-point glass precursor during the heat treatment after the compression molding;
(8) The temperature of the heat treatment is in the range of 300 to 1000 ° C. The high strength composite softening having high strength, high magnetic flux density and high resistance and low iron loss as described in (5), (6) or (7). It is characterized by a method for manufacturing a magnetic material.
この発明の高強度、高磁束密度および高抵抗を有する鉄損の少ない複合軟磁性焼結材およびその製造方法において、先に発明した前記（ａ）〜（ｅ）記載のＭｇ含有酸化鉄膜被覆鉄粉末の表面に形成する低融点ガラスは、ＳｉＯ2−Ｂ2Ｏ3−Ａｌ2Ｏ3系ガラス、ＳｉＯ2−ＢａＯ−Ａｌ2Ｏ3系ガラス、ＳｉＯ2−ＢａＯ−Ｂ2Ｏ3系ガラス、ＳｉＯ2−ＢａＯ−Ｌｉ2Ｏ3系ガラス、ＳｉＯ2−Ｂ2Ｏ3−ＣａＯ系ガラス、ＳｉＯ2−ＭｇＯ−Ａｌ2Ｏ3系ガラス、Ｂ2Ｏ3−Ｌｉ2Ｏ3系ガラス、ＰｂＯ−Ｂ2Ｏ3系ガラス、ＰｂＯ−Ｂ2Ｏ3−ＺｎＯ系ガラス、Ｂｉ2Ｏ3−Ｂ2Ｏ3系ガラス、Ｌｉ2Ｏ−ＺｎＯ系ガラス、ＳｉＯ2−Ｂ2Ｏ3−ＰｂＯ系ガラス、Ａｌ2Ｏ3−Ｂ2Ｏ3−ＰｂＯ系ガラス、ＳｎＯ−Ｐ2Ｏ5系ガラス、ＺｎＯ−Ｐ2Ｏ5系ガラス、ＣｕＯ−Ｐ2Ｏ5系ガラスなどのリン酸系ガラスなどがあり、これら低融点ガラスはいずれも軟化温度が３００〜８００℃の低軟化温度を有する低融点ガラスである。 In the composite soft magnetic sintered material with low iron loss having high strength, high magnetic flux density and high resistance according to the present invention and the method for producing the same, the Mg-containing iron oxide film coating according to (a) to (e) described above The low melting point glass formed on the surface of the iron powder is SiO 2 —B 2 O 3 —Al 2 O 3 glass, SiO 2 —BaO—Al 2 O 3 glass, SiO 2 —BaO—B 2 O 3 glass. , SiO 2 —BaO—Li 2 O 3 glass, SiO 2 —B 2 O 3 —CaO glass, SiO 2 —MgO—Al 2 O 3 glass, B 2 O 3 —Li 2 O 3 glass, PbO —B 2 O 3 glass, PbO—B 2 O 3 —ZnO glass, Bi 2 O 3 —B 2 O 3 glass, Li 2 O—ZnO glass, SiO 2 —B 2 O 3 —PbO glass , Al 2 O 3 -B 2 O 3 -PbO based glass, SnO-P 2 O 5 based glass, Z O-P 2 O 5 based glass, phosphoric acid-based glass such as CuO-P 2 O 5 based glass, low-melting glass All of these low-melting glass having a softening temperature has a low softening temperature of 300 to 800 ° C. It is.
これら低融点ガラスを形成するための低融点ガラス前駆体である低融点ガラスを構成する元素の錯体としては、ヒドリド錯体、カルボニル錯体、メタロセン錯体、アルキル錯体、シリル錯体、ポルフィリン錯体、アリル錯体、芳香環錯体、オレフィン錯体、ジエン錯体、カルベン錯体、カルビン錯体、アレーン錯体、ホスフィン錯体、アルキン錯体、ジケトン錯体（ジケトナート化合物）を使用することができ、また、低融点ガラスを構成する元素のアルコキシドとしては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基、アミロキシ基、フェノキシ基、ナフトキシ基などのうちの１種または２種以上を官能基として有するアルコキシドを使用することができる。
その他の有機金属、例えばカルボン酸などの有機酸の金属塩なども使用することができるが、有機成分が分解する際に、分解生成物である炭素が粉末表面に残留し易く、圧粉磁心の機械的強度を低下させるので好ましくない。
The complex of the elements constituting the low melting glass, which is a low melting glass precursor for forming these low melting glasses, includes hydride complexes, carbonyl complexes, metallocene complexes, alkyl complexes, silyl complexes, porphyrin complexes, allyl complexes, aromatics. Ring complexes, olefin complexes, diene complexes, carbene complexes, carbene complexes, arene complexes, phosphine complexes, alkyne complexes, diketone complexes (diketonate compounds) can be used, and alkoxides of elements that constitute low-melting glass , Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, amyloxy group, phenoxy group, naphthoxy group, etc. Use an alkoxide having a species or two or more species as functional groups Door can be.
Other organic metals such as metal salts of organic acids such as carboxylic acids can also be used, but when the organic component decomposes, the decomposition product carbon tends to remain on the powder surface, and the dust core This is not preferable because it reduces the mechanical strength.
この発明の高強度、高磁束密度および高抵抗を有する複合軟磁性焼結材の製造方法において、先に発明した前記（ａ）〜（ｅ）記載のＭｇ含有酸化鉄膜被覆鉄粉末の表面に低融点ガラス前駆体または低融点ガラスを被覆した粉末を焼結する温度は、３００〜１０００℃（一層好ましくは４００〜８００℃）の範囲内であることが好ましい。その理由は、焼結温度が３００℃未満ではガラス前駆体またはガラスが溶融せず、したがって、ガラスとの接合が十分行われないので得られた複合軟磁性焼結材の強度が不足するので好ましくなく、一方、１０００℃を越えた温度で焼結すると比抵抗の低下が起こるので好ましくないからである。この時の焼結雰囲気は、大気、水素、不活性ガス、窒素ガス、炭酸ガスまたは真空の内のいずれでも良いが、不活性ガスまたは窒素ガス雰囲気が最も好ましい。 In the method for producing a composite soft magnetic sintered material having high strength, high magnetic flux density and high resistance according to the present invention, the surface of the iron powder coated with Mg-containing iron oxide film described in the above (a) to (e) is invented. The temperature at which the low melting point glass precursor or the powder coated with the low melting point glass is sintered is preferably in the range of 300 to 1000 ° C. (more preferably 400 to 800 ° C.). The reason is that if the sintering temperature is less than 300 ° C., the glass precursor or glass does not melt, and therefore, the composite soft magnetic sintered material obtained is insufficient in strength because it is not sufficiently bonded to the glass. On the other hand, if the sintering is performed at a temperature exceeding 1000 ° C., the specific resistance is lowered, which is not preferable. The sintering atmosphere at this time may be any of air, hydrogen, inert gas, nitrogen gas, carbon dioxide gas or vacuum, but an inert gas or nitrogen gas atmosphere is most preferable.
この発明によると、少量の低融点ガラスの添加により高強度および高抵抗を有し、さらに高磁束密度の複合軟磁性焼結材を提供することができ、電気および電子産業において優れた効果をもたらすものである。 According to the present invention, the addition of a small amount of low-melting glass can provide a composite soft magnetic sintered material having high strength and high resistance, and having a high magnetic flux density, and has excellent effects in the electrical and electronic industries. Is.
原料粉末として、平均粒径：７０μｍを有し不可避不純物として硫黄を含む純鉄粉末を用意し、前記純鉄粉末を大気中、温度：２２０℃、２時間保持の条件で酸化処理することにより表面に酸化鉄膜を有する酸化処理鉄粉末を作製した。さらに、平均粒径：５０μｍのＭｇ粉末を用意した。この酸化処理鉄粉末に対し先に用意したＭｇ粉末を、酸化処理鉄粉末：Ｍｇ粉末＝９９．８質量％：０．２質量％の割合で添加し混合して混合粉末を作製し、得られた混合粉末を温度：６５０℃、圧力：１×１０−４ＭＰａ、１時間保持の条件で転動しながら加熱することにより鉄粉末の表面に堆積膜が被覆されているＭｇ含有酸化鉄膜被覆鉄粉末を作製した。この鉄粉末の表面に形成されている堆積膜の断面組織を電子顕微鏡で観察し、その堆積膜の厚さと最大結晶粒径を求めところ、膜厚は４０ｎｍ、最大結晶粒径は２０ｎｍであることがわかった。 As a raw material powder, a pure iron powder having an average particle diameter of 70 μm and containing sulfur as an inevitable impurity is prepared, and the pure iron powder is oxidized in the atmosphere at a temperature of 220 ° C. for 2 hours to obtain a surface. An oxidized iron powder having an iron oxide film was prepared. Furthermore, Mg powder having an average particle diameter of 50 μm was prepared. To this oxidized iron powder, the previously prepared Mg powder was added at a ratio of oxidized iron powder: Mg powder = 99.8 mass%: 0.2 mass% to prepare a mixed powder. Mg-containing iron oxide film coated with a deposited film on the surface of the iron powder by heating the mixed powder while rolling under conditions of temperature: 650 ° C., pressure: 1 × 10 −4 MPa, and holding for 1 hour Iron powder was produced. The cross-sectional structure of the deposited film formed on the surface of the iron powder is observed with an electron microscope, and the thickness and maximum crystal grain size of the deposited film are obtained. The film thickness is 40 nm and the maximum crystal grain size is 20 nm. I understood.
このＭｇ含有酸化鉄膜被覆鉄粉末の表面に形成された堆積膜をＸ線光電子分光装置により分析を行ない、結合エネルギーを解析したところ、金属Ｆｅ微粒子が素地中に分散していることが解った。また、金属Ｆｅ微粒子が素地中に分散している堆積膜の最表面はＭｇＯで構成されていることが解った。さらに、堆積膜の深さ方向のＭｇ、ＯおよびＦｅの濃度分布をオージェ電子分光装置を用いて調べた結果、ＭｇおよびＯは表面から内部に向って減少しておりかつＦｅは内部に向って増加している濃度勾配を有することが解った。従って、Ｍｇ含有酸化鉄膜被覆鉄粉末の表面に形成された堆積膜は、金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜であること、このＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜はＭｇおよびＯが表面から内部に向って減少しておりかつＦｅが内部に向って増加している濃度勾配を有すること、並びにその最表面はＭｇＯで構成されている堆積膜であることが分かった。
さらに、鉄粉末とＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜との界面領域をオージェ電子分光装置を用いて硫黄の分布を調べた結果、堆積膜と鉄粉末との界面領域に鉄粉末の中心部に含まれる硫黄よりも高濃度の硫黄を含む硫黄濃化層を有することが解った。
The deposited film formed on the surface of the Mg-containing iron oxide film-coated iron powder was analyzed with an X-ray photoelectron spectrometer, and the binding energy was analyzed. As a result, it was found that metal Fe fine particles were dispersed in the substrate. . Further, it was found that the outermost surface of the deposited film in which the metal Fe fine particles are dispersed in the substrate is composed of MgO. Furthermore, as a result of examining the concentration distribution of Mg, O and Fe in the depth direction of the deposited film using an Auger electron spectrometer, Mg and O decreased from the surface toward the inside, and Fe toward the inside. It was found to have an increasing concentration gradient. Therefore, the deposited film formed on the surface of the Mg-containing iron oxide film-coated iron powder is a Mg—Fe—O ternary oxide deposited film in which metal Fe fine particles are dispersed in the substrate. The Fe—O ternary oxide deposited film has a concentration gradient in which Mg and O decrease from the surface toward the inside and Fe increases toward the inside, and the outermost surface is composed of MgO. It was found that this was a deposited film.
Furthermore, as a result of examining the distribution of sulfur in the interface region between the iron powder and the Mg—Fe—O ternary oxide deposited film using an Auger electron spectroscope, the iron powder was found in the interface region between the deposited film and the iron powder. It was found to have a sulfur enriched layer containing a higher concentration of sulfur than the sulfur contained in the center.
さらに、平均粒径：１．４μｍでＳｉＯ2：８０質量％、Ｂ2Ｏ3：２０質量％の組成を有する低融点ガラス粉末を用意し、さらに低融点ガラスを構成する元素の錯体またはアルコキシドとしてＳｉＯ2原料となるシリコンテトラエトキシド（テトラエトキシシラン）、Ｐ2Ｏ5原料となるリン酸トリフェニル、ＳｎＯ原料となるスズアセチルアセトナート、Ｂｉ2Ｏ3原料となるトリ−ｉ−プロポキシビスマス、ＺｎＯ原料となるジ−ｎ−ブトキシ亜鉛、ＢａＯ原料となるバリウムジピバロイルメタナートなどの金属アルコキシドおよび金属錯体を用意した。さらにこれら金属アルコキシドおよび金属錯体を溶かす有機溶媒としてヘキサンを用意した。
実施例１
金属アルコキシドおよび金属錯体を酸化物換算で表１に示される低融点ガラス組成となるように有機溶媒に溶かして溶液を作製し、得られた溶液を先に作製したＭｇ含有酸化鉄膜被覆鉄粉末に表１に示される割合となるように添加して浸漬し、撹拌しながら乾燥することによりＭｇ含有酸化鉄膜被覆鉄粉末の表面に低融点ガラス前駆体を被覆した被覆鉄粉末（以下、前駆体被覆粉末という）Ａ１〜Ａ４を作製した。
Furthermore, a low melting point glass powder having an average particle size of 1.4 μm and a composition of SiO 2 : 80% by mass and B 2 O 3 : 20% by mass is prepared, and further as a complex or alkoxide of the elements constituting the low melting point glass Silicon tetraethoxide (tetraethoxysilane) as a SiO 2 raw material, triphenyl phosphate as a P 2 O 5 raw material, tin acetylacetonate as a SnO raw material, tri-i-propoxybismuth as a Bi 2 O 3 raw material, Metal alkoxides and metal complexes such as di-n-butoxy zinc as a ZnO raw material and barium dipivaloylmethanate as a BaO raw material were prepared. Furthermore, hexane was prepared as an organic solvent for dissolving these metal alkoxides and metal complexes.
Example 1
A metal alkoxide and a metal complex were dissolved in an organic solvent so as to have a low melting point glass composition shown in Table 1 in terms of oxides, and a solution was prepared. The coated iron powder (hereinafter referred to as precursor) coated with a low-melting-point glass precursor on the surface of the Mg-containing iron oxide film-coated iron powder by adding and immersing in the ratio shown in Table 1 and drying while stirring. A1 to A4 (referred to as body-coated powder) were prepared.
これら表１に示される前駆体被覆鉄粉末Ａ１〜Ａ４をそれぞれ内壁に潤滑剤を塗布した金型に充填し、９８０ＭＰａの成形圧力で成形することにより外径：３５ｍｍ、内径：２５ｍｍ、厚さ：５ｍｍの寸法を有するリング状成形体と長さ：６０ｍｍ、幅：１０ｍｍ、厚さ：５ｍｍの寸法を有するバー状成形体を作製し、これらリング状成形体およびバー状成形体を窒素雰囲気中、温度：６００℃、１時間保持の熱処理を施すことにより本発明複合軟磁性材１〜４からなるリング試験片およびバー状試験片を作製した。 These precursor-coated iron powders A1 to A4 shown in Table 1 are filled in dies each having a lubricant applied to the inner wall, and are molded at a molding pressure of 980 MPa, so that the outer diameter is 35 mm, the inner diameter is 25 mm, and the thickness is: A ring-shaped molded body having dimensions of 5 mm and a bar-shaped molded body having dimensions of length: 60 mm, width: 10 mm, and thickness: 5 mm were prepared, and these ring-shaped molded body and bar-shaped molded body were placed in a nitrogen atmosphere. Temperature: 600 ° C. A ring test piece and a bar-shaped test piece made of the composite soft magnetic materials 1 to 4 of the present invention were produced by heat treatment for 1 hour.
本発明複合軟磁性材１〜４からなるリング状試験片の水中密度を測定したのち、巻線を施し、Ｂ−Ｈアナライザにより最大比透磁率、励磁磁束密度、１．５Ｔ、周波数５０Ｈｚおよび１．０Ｔ、周波数４００Ｈｚにおける鉄損Ｗ１．５／５０、Ｗ１．０／４００をそれぞれ測定し、表２に示した。
また、バー状試験片において四端子法により比抵抗を、スパン４５ｍｍの三点曲げにより抗折強度をそれぞれ測定し、それらの結果を表２に示した。
実施例２
実施例１で作製した表１に示される低融点ガラス前駆体をＭｇ含有酸化鉄膜被覆鉄粉末の表面に被覆した前駆体被覆鉄粉末Ａ１〜Ａ４を大気雰囲気中、温度：５５０℃に１時間保持することによりＭｇ含有酸化鉄膜被覆鉄粉末の表面に低融点ガラスを被覆した被覆鉄粉末（以下、低融点ガラス被覆粉末という）ａ１〜ａ４を作製した。
After measuring the underwater density of the ring-shaped test piece comprising the composite soft magnetic materials 1 to 4 of the present invention, winding was performed, and the maximum relative magnetic permeability, excitation magnetic flux density, 1.5 T, frequency 50 Hz and 1 were measured using a BH analyzer. The iron losses W 1.5 / 50 and W 1.0 / 400 at 0.0T and a frequency of 400 Hz were measured and shown in Table 2.
Further, specific resistance was measured for the bar-shaped test piece by the four probe method, and bending strength was measured by three-point bending with a span of 45 mm. The results are shown in Table 2.
Example 2
Precursor-coated iron powders A1 to A4 obtained by coating the surface of the Mg-containing iron oxide film-coated iron powder with the low melting point glass precursor shown in Table 1 prepared in Example 1 in an air atmosphere at a temperature of 550 ° C. for 1 hour. By holding, coated iron powders (hereinafter referred to as low melting point glass-coated powders) a1 to a4 in which the surface of the Mg-containing iron oxide film-coated iron powder was coated with a low melting point glass were produced.
これら低融点ガラス被覆鉄粉末ａ１〜ａ４をそれぞれ内壁に潤滑剤を塗布した金型に充填し、９８０ＭＰａの成形圧力で成形することにより外径：３５ｍｍ、内径：２５ｍｍ、厚さ：５ｍｍの寸法を有するリング状成形体と長さ：６０ｍｍ、幅：１０ｍｍ、厚さ：５ｍｍの寸法を有するバー状成形体を作製し、これらリング状成形体およびバー状成形体を窒素雰囲気中、温度：６００℃、１時間保持の熱処理を施すことにより本発明複合軟磁性材５〜８からなるリング試験片およびバー状試験片を作製した。得られたリング状試験片の水中密度を測定したのち、巻線を施し、Ｂ−Ｈアナライザにより最大比透磁率、励磁磁束密度、１．５Ｔ、周波数５０Ｈｚおよび１．０Ｔ、周波数４００Ｈｚにおける鉄損Ｗ１．５／５０、Ｗ１．０／４００をそれぞれ測定し、表２に示した。
また、バー状試験片において四端子法により比抵抗を、スパン４５ｍｍの三点曲げにより抗折強度をそれぞれ測定し、それらの結果を表２に示した。
実施例３
先に用意したＭｇ含有酸化鉄膜被覆鉄粉末に、先に用意した平均粒径：１．４μｍでＳｉＯ2：８０質量％、Ｂ2Ｏ3：２０質量％の組成を有するガラス粉末を、Ｍｇ含有酸化鉄膜被覆鉄粉末：ガラス粉末＝９９．３質量％：０．７質量％の割合となるように配合し、混合して混合粉末を作製し、得られた混合粉末を金型に入れ、プレス成形して縦：６０ｍｍ、横：１０ｍｍ、厚さ：５ｍｍの寸法を有するバー状圧粉体および外径：３５ｍｍ、内径：２５ｍｍ、高さ：５ｍｍの寸法を有するリング形状圧粉体を成形し、得られた圧粉体を窒素雰囲気中、温度：６００℃、３０分保持の条件で焼結を行い、本発明複合軟磁性材９からなるリング試験片およびバー状試験片を作製した。得られたリング状試験片の水中密度を測定したのち、巻線を施し、Ｂ−Ｈアナライザにより最大比透磁率、励磁磁束密度、１．５Ｔ、周波数５０Ｈｚおよび１．０Ｔ、周波数４００Ｈｚにおける鉄損Ｗ１．５／５０、Ｗ１．０／４００をそれぞれ測定し、表２に示した。
また、バー状試験片において四端子法により比抵抗を、スパン４５ｍｍの三点曲げにより抗折強度をそれぞれ測定し、それらの結果を表２に示した。
従来例１
純鉄粉末の表面にＭｇ含有フェライト層を化学的方法で形成した従来Ｍｇ含有酸化鉄膜被覆鉄粉末を用意し、この従来Ｍｇ含有酸化鉄膜被覆鉄粉末に先に用意した平均粒径：１．４μｍでＳｉＯ2：８０質量％、Ｂ2Ｏ3：２０質量％の組成を有するガラス粉末を、Ｍｇ含有酸化鉄膜被覆鉄粉末：ガラス粉末＝９９．３質量％：０．７質量％の割合となるように配合し、混合して混合粉末を作製し、得られた混合粉末を金型に入れ、プレス成形して縦：６０ｍｍ、横：１０ｍｍ、厚さ：５ｍｍの寸法を有するバー状圧粉体および外径：３５ｍｍ、内径：２５ｍｍ、高さ：５ｍｍの寸法を有するリング形状圧粉体を成形し、得られた圧粉体を窒素雰囲気中、温度：６００℃、３０分保持の条件で焼結を行い、従来複合軟磁性材からなるリング試験片およびバー状試験片を作製した。
得られたリング状試験片の水中密度を測定したのち、巻線を施し、Ｂ−Ｈアナライザにより最大比透磁率、励磁磁束密度、１．５Ｔ、周波数５０Ｈｚおよび１．０Ｔ、周波数４００Ｈｚにおける鉄損Ｗ１．５／５０、Ｗ１．０／４００をそれぞれ測定し、表２に示した。
また、バー状試験片において四端子法により比抵抗を、スパン４５ｍｍの三点曲げにより抗折強度をそれぞれ測定し、それらの結果を表２に示した。
These low melting point glass-coated iron powders a1 to a4 are filled in dies each having an inner wall coated with a lubricant, and are molded at a molding pressure of 980 MPa, so that the outer diameter is 35 mm, the inner diameter is 25 mm, and the thickness is 5 mm. A ring-shaped molded body having a length of 60 mm, a width of 10 mm, and a thickness of 5 mm was prepared, and the ring-shaped molded body and the bar-shaped molded body were heated in a nitrogen atmosphere at a temperature of 600 ° C. A ring test piece and a bar-shaped test piece made of the composite soft magnetic materials 5 to 8 of the present invention were prepared by performing heat treatment for 1 hour. After measuring the underwater density of the obtained ring-shaped test piece, it was wound, and the iron loss at a maximum relative magnetic permeability, excitation magnetic flux density, 1.5 T, frequencies 50 Hz and 1.0 T, and frequency 400 Hz was measured with a BH analyzer. W 1.5 / 50 and W 1.0 / 400 were measured and shown in Table 2.
Further, specific resistance was measured for the bar-shaped test piece by the four probe method, and bending strength was measured by three-point bending with a span of 45 mm. The results are shown in Table 2.
Example 3
To the Mg-containing iron oxide film-coated iron powder prepared in advance, a glass powder having an average particle diameter of 1.4 μm and a composition of SiO 2 : 80% by mass and B 2 O 3 : 20% by mass was prepared. Containing iron oxide film coated iron powder: Glass powder = 99.3 wt%: Blended to a ratio of 0.7 wt% to produce a mixed powder, and put the obtained mixed powder into a mold A bar-shaped green compact having dimensions of 60 mm in length, 10 mm in width, and 5 mm in thickness, and a ring-shaped green compact having dimensions of 35 mm in outer diameter, 25 mm in inner diameter, and 5 mm in height. The green compact thus obtained was sintered in a nitrogen atmosphere at a temperature of 600 ° C. and held for 30 minutes to prepare a ring test piece and a bar-shaped test piece made of the composite soft magnetic material 9 of the present invention. . After measuring the underwater density of the obtained ring-shaped test piece, it was wound, and the iron loss at a maximum relative magnetic permeability, excitation magnetic flux density, 1.5 T, frequencies 50 Hz and 1.0 T, and frequency 400 Hz was measured with a BH analyzer. W 1.5 / 50 and W 1.0 / 400 were measured and shown in Table 2.
Further, specific resistance was measured for the bar-shaped test piece by the four probe method, and bending strength was measured by three-point bending with a span of 45 mm. The results are shown in Table 2.
Conventional Example 1
A conventional Mg-containing iron oxide film-coated iron powder in which a Mg-containing ferrite layer is formed on the surface of pure iron powder by a chemical method is prepared, and the average particle diameter prepared in advance for this conventional Mg-containing iron oxide film-coated iron powder is 1 A glass powder having a composition of SiO 2 : 80% by mass and B 2 O 3 : 20% by mass at 4 μm was used. Mg-containing iron oxide film-coated iron powder: glass powder = 99.3% by mass: 0.7% by mass It mixes so that it may become a ratio, mixes and produces mixed powder, puts the obtained mixed powder into a metal mold, press-molds it, and it is bar shape which has a size of length: 60mm, width: 10mm, thickness: 5mm A green compact and a ring-shaped green compact having an outer diameter of 35 mm, an inner diameter of 25 mm, and a height of 5 mm were molded, and the obtained green compact was maintained at a temperature of 600 ° C. for 30 minutes in a nitrogen atmosphere. Sintering is performed under the conditions, and a conventional ring test made of composite soft magnetic material is performed. To prepare a piece and the bar-shaped test piece.
After measuring the underwater density of the obtained ring-shaped test piece, it was wound, and the iron loss at a maximum relative magnetic permeability, excitation magnetic flux density, 1.5 T, frequencies 50 Hz and 1.0 T, and frequency 400 Hz was measured with a BH analyzer. W 1.5 / 50 and W 1.0 / 400 were measured and shown in Table 2.
Further, specific resistance was measured for the bar-shaped test piece by the four probe method, and bending strength was measured by three-point bending with a span of 45 mm. The results are shown in Table 2.
表１〜２に示される結果から、本発明複合軟磁性材１〜９で作製した試験片は、表２の従来複合軟磁性材で作製した試験片に比べて直流磁気特性、交流磁気特性、機械的強度のいずれも優れた値を示しことから、本発明複合軟磁性焼結材１〜９は、従来複合軟磁性材に比べて優れた特性を示すことが分かる。 From the results shown in Tables 1 and 2, the test pieces prepared with the composite soft magnetic materials 1 to 9 of the present invention were compared with the test pieces prepared with the conventional composite soft magnetic materials shown in Table 2 in terms of DC magnetic characteristics, AC magnetic characteristics, Since all the mechanical strengths show excellent values, it can be seen that the composite soft magnetic sintered materials 1 to 9 of the present invention show superior characteristics as compared with conventional composite soft magnetic materials.
特に本発明複合軟磁性材９と従来複合軟磁性材を比較すると、本発明複合軟磁性材９で作製した試験片は、従来複合軟磁性材と同様に低融点ガラス粉末を使用して作製していても、先に発明した金属Ｆｅ微粒子が素地中に分散しているＭｇ−Ｆｅ−Ｏ三元系酸化物堆積膜が被覆されているＭｇ含有酸化鉄膜被覆鉄粉末は鉄粉末に対する密着性が優れているために、従来の化学的方法で形成したＭｇ含有酸化鉄膜被覆鉄粉末に比べて鉄損が極めて少ないことが分かる。 In particular, when the composite soft magnetic material 9 of the present invention is compared with the conventional composite soft magnetic material, the test piece prepared with the composite soft magnetic material 9 of the present invention is prepared using low melting point glass powder in the same manner as the conventional composite soft magnetic material. However, the Mg-containing iron oxide film-coated iron powder coated with the Mg-Fe-O ternary oxide deposited film in which the metal Fe fine particles previously dispersed in the substrate are adhered to the iron powder. Therefore, it can be seen that the iron loss is extremely small as compared with the iron powder coated with Mg-containing iron oxide film formed by a conventional chemical method.
Claims (9)
9. The high-strength composite soft magnetic material with low iron loss having high strength, high magnetic flux density and high resistance according to claim 6, 7 or 8, wherein the temperature of the heat treatment is in the range of 300 to 1000 ° C. Production method.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060895A1 (en) * | 2007-11-07 | 2009-05-14 | Mitsubishi Materials Pmg Corporation | High-strength soft-magnetic composite material obtained by compaction/burning and process for producing the same |
| JP2009141346A (en) * | 2007-11-16 | 2009-06-25 | Mitsubishi Materials Corp | High-strength high-resistivity low-loss composite soft magnetic material and method of manufacturing the same, and electromagnetic circuit component |
| JP2009246256A (en) * | 2008-03-31 | 2009-10-22 | Mitsubishi Materials Corp | High-strength high-resistivity low loss composite soft magnetic material, its method for manufacturing, and electromagnetic circuit component |
| JP2010251600A (en) * | 2009-04-17 | 2010-11-04 | Toyota Motor Corp | Powder for dust core and dust core, and method of manufacturing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0479302A (en) * | 1990-07-23 | 1992-03-12 | Toshiba Corp | Dust core |
| JPH05335129A (en) * | 1992-05-29 | 1993-12-17 | Mitsui Petrochem Ind Ltd | Fe-based soft magnetic alloy particle and manufacturing method thereof |
| JP2004297036A (en) * | 2002-12-04 | 2004-10-21 | Mitsubishi Materials Corp | Method of manufacturing iron soft magnetic powder coated with spinel ferrite film containing zinc and soft magnetic sintered composite material produced by this method |
-
2005
- 2005-05-30 JP JP2005157436A patent/JP2006332525A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0479302A (en) * | 1990-07-23 | 1992-03-12 | Toshiba Corp | Dust core |
| JPH05335129A (en) * | 1992-05-29 | 1993-12-17 | Mitsui Petrochem Ind Ltd | Fe-based soft magnetic alloy particle and manufacturing method thereof |
| JP2004297036A (en) * | 2002-12-04 | 2004-10-21 | Mitsubishi Materials Corp | Method of manufacturing iron soft magnetic powder coated with spinel ferrite film containing zinc and soft magnetic sintered composite material produced by this method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060895A1 (en) * | 2007-11-07 | 2009-05-14 | Mitsubishi Materials Pmg Corporation | High-strength soft-magnetic composite material obtained by compaction/burning and process for producing the same |
| JP2009117651A (en) * | 2007-11-07 | 2009-05-28 | Mitsubishi Materials Pmg Corp | High-strength soft-magnetic composite material obtained by compaction/burning, and method of manufacturing the same |
| JP2009141346A (en) * | 2007-11-16 | 2009-06-25 | Mitsubishi Materials Corp | High-strength high-resistivity low-loss composite soft magnetic material and method of manufacturing the same, and electromagnetic circuit component |
| JP2009246256A (en) * | 2008-03-31 | 2009-10-22 | Mitsubishi Materials Corp | High-strength high-resistivity low loss composite soft magnetic material, its method for manufacturing, and electromagnetic circuit component |
| JP2010251600A (en) * | 2009-04-17 | 2010-11-04 | Toyota Motor Corp | Powder for dust core and dust core, and method of manufacturing the same |
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