JP5550013B2 - Magnetic nanocomposite and method for producing the same - Google Patents
Magnetic nanocomposite and method for producing the same Download PDFInfo
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本発明は、磁性ナノコンポジット、特にＭｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４フェライト／パーマロイＦｅ−Ｎｉ合金系・ナノ磁性コンポジット、及びその製造方法に関する。 The present invention, the magnetic nanocomposite, especially Mg (Mn x Fe 1-x ) 2 O 4 ferrite / permalloy Fe-Ni alloy system nano magnetic composite, and a method of manufacturing the same.
電子機器に使用される軟磁性材料には、高い飽和磁束密度（Ｂｓ）を有し、かつ、高周波領域で使用可能な高い電気抵抗率（ρ）と高い透磁率（μ）を有することが求められているが、単相のバルク磁性材料でこれらの要求を満足するものは知られていない。
飽和磁束密度の高い金属磁性材料粒子の表面を高電気抵抗のフェライトで被覆して緻密化した複合材料（磁性ナノコンポジット）は、両者の長所を合わせもつ高周波用磁性材料として期待できるが、金属と酸化物という全く性質の異なる物質を熱処理によって緻密化することは、熱平衡下での酸化物の還元・分解や磁性金属の酸化、金属と酸化物間の塑性変形能の差異等により、通常の粉末冶金のプロセスでの製造は至難となっている。
これまでの、高周波領域で使用可能な高効率化・小型化に対応した磁性材料の研究事例としては、例えば、以下の非特許文献１〜４に示されるものが挙げられ、これら非特許文献には、センダスト（８５Ｆｅ‐９．５Ｓｉ‐５．５Ａｌ系(重量%)）と酸化物皮膜との熱間静水圧プレス（ＨＩＰ）を用いた焼結（非特許文献１）、ＭｇＦｅ２Ｏ４とスーパーセンダスト（８６．５Ｆｅ‐６Ｓｉ‐４Ａｌ‐３．５Ｎｉ系(重量%)）との混合粉体の放電プラズマ焼結（非特許文献２）、テルミット法による鉄‐フェライト複合粉体を合成する方法（非特許文献３）、酸化処理および蒸着処理により作製したＺｎフェライト被覆鉄粉の作製（非特許文献４）がそれぞれ開示されている。
Soft magnetic materials used in electronic equipment have a high saturation magnetic flux density (B s ) and a high electrical resistivity (ρ) and high magnetic permeability (μ) that can be used in a high frequency region. Although required, no single-phase bulk magnetic material that satisfies these requirements is known.
A composite material (magnetic nanocomposite), in which the surface of metal magnetic material particles with high saturation magnetic flux density is coated with high electrical resistance ferrite and densified, can be expected as a high-frequency magnetic material that combines the advantages of both. Densification of materials with completely different properties, such as oxides, is due to the reduction or decomposition of oxides under thermal equilibrium, oxidation of magnetic metals, differences in plastic deformability between metals and oxides, etc. Manufacturing in the metallurgical process has become difficult.
Examples of research on magnetic materials that are compatible with high efficiency and downsizing that can be used in the high-frequency region so far include, for example, those shown in Non-Patent Documents 1 to 4 below. Is sintered using a hot isostatic press (HIP) of Sendust (85Fe-9.5Si-5.5Al system (wt%)) and an oxide film (Non-patent Document 1), MgFe 2 O 4 and Discharge plasma sintering of powder mixture with super sendust (86.5Fe-6Si-4Al-3.5Ni system (wt%)) (Non-patent Document 2), Method of synthesizing iron-ferrite composite powder by thermite method (Non-Patent Document 3), preparation of Zn ferrite-coated iron powder produced by oxidation treatment and vapor deposition treatment (Non-Patent Literature 4) is disclosed.
しかしながら、高温で焼結を行った場合、Fe-Ni系高透磁率磁性合金のパーマロイが酸化されて、同時に逆にフェライトは還元され、また、磁性金属と酸化物粉体の混合原料からなる成形体に圧力を加えて緻密化させる時、金属粒子の塑性変形に対してフェライトが追従できなくなって、金属粒子同士が接触するという問題点があるため、これまでに高周波領域においても使用できる充分に高い磁束密度・透磁率および電気抵抗を有した軟磁性材料が作製されていないのが現状である。 However, when sintered at high temperature, the permalloy of Fe-Ni high magnetic permeability magnetic alloy is oxidized, and at the same time, ferrite is reduced, and the molding is made of a mixed raw material of magnetic metal and oxide powder. When pressure is applied to the body to make it dense, there is a problem that the ferrite cannot follow the plastic deformation of the metal particles and the metal particles come into contact with each other. At present, no soft magnetic material having a high magnetic flux density / permeability and electrical resistance has been produced.
本発明は、高周波領域においても使用可能な高磁束密度・高透磁率および高電気抵抗を有した磁性ナノコンポジット、特にＭｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４フェライト／パーマロイＦｅ−Ｎｉ合金系・ナノ磁性コンポジット、並びに当該磁性ナノコンポジットの製造方法を提供することを課題とする。
本発明者等は、金属磁性材料として、Ｎ２‐アトマイズ法で製造し高磁気特性を有するパーマロイ（Ｆｅ‐Ｎｉ）合金を用い、電気的絶縁層を形成する磁性酸化物として、低温での塑性変形能が高い酸化マグネシウムＭｇＯを構成成分とするＭｇフェライト系を用い、このＭｇフェライトに、フェライト層の磁気特性を向上させるためにＭｎを添加し
てこれらを複合化した新軟磁性材料の開発を行った結果、合金粒子表面にＭｇＯ微粒子及びＦｅ２Ｏ３微粒子、好ましくはさらにＭｎＯ微粒子、を均一にコーティングした後、高静水圧下で相対密度８０％以上に成形し、さらに高速昇温可能なパルス通電加圧焼結（SPS）により、金属酸化物の混合物をフェライト層とし、かつ試料全体を相対密度９２％以上に緻密化した後、熱間静水圧プレス（ＨＩＰ）で金属／フェライト相が残存するようにして熱処理条件を最適化すると、高周波領域でも電気・磁気損失の少ない磁性ナノコンポジット、Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（０≦ｘ≦０．４）が得られることを見出して、本発明を完成した。
The present invention, the magnetic nanocomposite having a high magnetic flux density, high magnetic permeability and high electrical resistance that can be used in a high frequency range, in particular Mg (Mn x Fe 1-x ) 2 O 4 ferrite / permalloy Fe-Ni alloy system It is an object to provide a nanomagnetic composite and a method for producing the magnetic nanocomposite.
The present inventors use a permalloy (Fe—Ni) alloy produced by the N 2 -atomizing method as a metal magnetic material and having high magnetic properties, and as a magnetic oxide for forming an electrically insulating layer, plasticity at a low temperature. Development of a new soft magnetic material that uses Mg ferrite with a highly deformable magnesium oxide MgO as a constituent component and adds Mn to this Mg ferrite to improve the magnetic properties of the ferrite layer and combine them. As a result, the surface of the alloy particles is uniformly coated with MgO fine particles and Fe 2 O 3 fine particles, preferably MnO fine particles, and then molded to a relative density of 80% or more under high hydrostatic pressure, and further high temperature increase is possible. By applying pulsed current pressure sintering (SPS), the metal oxide mixture is made into a ferrite layer and the entire sample is densified to a relative density of 92% or more, and then the hot isostatic pressing is performed. If the metal / ferrite phase scan (HIP) to optimize to the heat treatment conditions so that the remaining, less magnetic nanocomposite of electric and magnetic loss in a high frequency region, Mg (Mn x Fe 1- x) 2 O 4 (0 ≦ The present invention was completed by finding that x ≦ 0.4) was obtained.
前記課題を解決可能な本発明のＭｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４フェライト／パーマロイＦｅ‐Ｎｉ合金系・ナノ磁性コンポジットは、パーマロイＦｅ‐Ｎｉ合金粒子の表面が、Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（０≦ｘ≦０．４）からなるフェライト層にて被覆された状態で緻密化された微細構造を有することを特徴とする。
又、本発明のＭｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４フェライト／パーマロイＦｅ‐Ｎｉ合金系・ナノ磁性コンポジット（０≦ｘ≦０．４）の製造方法は、
工程Ａ：Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（０≦ｘ≦０．４）となる量の、ＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子をそれぞれ秤量し、当該ＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子をＦｅ‐Ｎｉ合金粉末と混合することによってコーティングを行い、前記Ｆｅ‐Ｎｉ合金粉末の表面が、前記ＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子からなる金属酸化物の混合物により被覆されたコンポジット粉末を製造する工程、
工程Ｂ：前記工程Ａで得られたコンポジット粉末を仮成形し、得られた仮成形体に超高静水圧プレスにて圧力を加えて成形体を製造する加圧工程、
工程Ｃ：前記工程Ｂで得られた成形体をパルス通電加圧焼結することにより、前記金属酸化物の混合物をフェライト相とし、相対密度が９２％以上の焼結体を製造するパルス通電加圧焼結工程、及び
工程Ｄ：前記工程Ｃで得られた焼結体を熱間静水圧プレスで処理し、焼結体の相対密度９４％以上とする熱間静水圧プレス工程
を含むことを特徴とする。
The Mg (Mn x Fe 1-x ) 2 O 4 ferrite / permalloy Fe-Ni alloy system / nanomagnetic composite of the present invention that can solve the above-mentioned problems is obtained when the surface of the permalloy Fe-Ni alloy particles is Mg (Mn x Fe 1-x ) 2 O 4 (0 ≦ x ≦ 0.4) having a fine structure that is densified in a state of being covered with a ferrite layer.
In addition, the production method of the Mg (Mn x Fe 1-x ) 2 O 4 ferrite / permalloy Fe-Ni alloy system / nanomagnetic composite (0 ≦ x ≦ 0.4) of the present invention is as follows:
Step A: MgO fine particles, Fe 2 O 3 fine particles, and MnO fine particles in amounts such that Mg (Mn x Fe 1-x ) 2 O 4 (0 ≦ x ≦ 0.4) are weighed, and the MgO fine particles, Fe Coating is performed by mixing 2 O 3 fine particles and MnO fine particles with Fe—Ni alloy powder, and the surface of the Fe—Ni alloy powder is made of a metal oxide composed of the MgO fine particles, Fe 2 O 3 fine particles, and MnO fine particles. Producing a composite powder coated with the mixture,
Step B: Pressurizing step of temporarily molding the composite powder obtained in Step A above and producing a molded body by applying pressure to the obtained temporary molded body with an ultrahigh hydrostatic pressure press,
Step C: Pulsed energization for producing a sintered body having a relative density of 92% or more by converting the metal oxide mixture into a ferrite phase by subjecting the formed body obtained in Step B to pulse energization and pressure sintering. Pressure sintering step, and step D: including a hot isostatic pressing step in which the sintered body obtained in the step C is processed by hot isostatic pressing to make the relative density of the sintered body 94% or more. Features.
又、本発明は、上記の特徴を有した製造方法において、上記工程Ｃにおけるパルス通電加圧焼結が、不活性ガス雰囲気下、焼結温度４５０〜５５０℃、加圧力５０〜１５０ＭＰａ、焼結時間３〜１０分の条件にて行われることを特徴とするものでもある。 Further, the present invention provides a manufacturing method having the above-described characteristics, in which the pulsed current pressure sintering in the step C is performed under a inert gas atmosphere, a sintering temperature of 450 to 550 ° C., a pressure of 50 to 150 MPa, It is also characterized by being performed under conditions of time 3 to 10 minutes.
更に、本発明は、上記の特徴を有した製造方法において、上記工程Ｄにおける熱間静水圧プレス処理が、圧力１００ＭＰａ以上の不活性ガス雰囲気下で７００℃〜９００℃未満の温度を一定時間維持して熱処理を行うことを特徴とするものでもある。 Furthermore, the present invention provides a manufacturing method having the above-described features, wherein the hot isostatic pressing in the step D maintains a temperature of 700 ° C. to less than 900 ° C. for a certain time in an inert gas atmosphere having a pressure of 100 MPa or more. Then, heat treatment is performed.
本発明の製造方法の場合、ＡｌやＳｉを含まない磁性合金を採用することで、熱処理後に金属／フェライト間の界面に非磁性酸化物のＳｉＯ２やＡｌ２Ｏ３が生成せず、コンポジットの磁気特性の劣化が少なくなるという利点がある。また、塑性変形するＭｇＯ微粒子を磁性金属粒子の表面に均一にコーティングすることにより、最終的にはコンポジット内のフェライト層の膜厚が一定となり、良好な電気的絶縁層を形成させることができる。
本発明の製造方法を用いることによって、金属粒子と酸化物間の固相反応を出来るだけ抑制し、金属粒子の粒界を完全にフェライト層で被覆して、金属粒子相互の直接接触を防止し、試料全体の電気抵抗を高め、高周波領域でも電気・磁気損失の少ない磁性ナノコンポジットを製造することができる。
In the case of the production method of the present invention, by adopting a magnetic alloy containing no Al or Si, non-magnetic oxide SiO 2 or Al 2 O 3 is not generated at the metal / ferrite interface after the heat treatment, and the composite There is an advantage that the deterioration of magnetic characteristics is reduced. In addition, by uniformly coating the surface of the magnetic metal particles with the plastically deformed MgO fine particles, the thickness of the ferrite layer in the composite is finally constant, and a good electrical insulating layer can be formed.
By using the production method of the present invention, the solid phase reaction between the metal particles and the oxide is suppressed as much as possible, and the grain boundaries of the metal particles are completely covered with a ferrite layer to prevent direct contact between the metal particles. It is possible to increase the electrical resistance of the entire sample and to produce a magnetic nanocomposite with little electric / magnetic loss even in a high frequency region.
本発明の磁性ナノコンポジットの製造方法における各工程について以下に説明する。
図１は、本発明の製造方法における好ましい一例の手順を示すフローチャートである。 まず、本発明の製法における工程Ａでは、Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（０≦ｘ≦０．４）となる量の、ＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子をそれぞれ秤量し、これらＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子をＦｅ‐Ｎｉ合金粉末と混合することによってＦｅ‐Ｎｉ合金粉末表面へのコーティングを行う。本発明では、水‐アトマイズ法で精製された金属磁性材料よりも粒子内ひずみの小さいＮ２‐アトマイズ法で精製された金属磁性材料のパーマロイ(５３Ｆｅ‐４７Ｎｉ(重量%)以下Ｆｅ‐４７Ｎｉと記す)合金粉末を使用することが好ましく、一方、Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４のフェライト層を形成するための原料としては、純度９９．９％以上で、ｎｍオーダーの粒子径を有する市販のＭｇＯ微粒子、ＭｎＯ微粒子、Ｆｅ２Ｏ３微粒子が使用できる。尚、本発明では、焼結性を改善するために、ＭｎＯ粉末を予め粉砕（例えば粒子径２００ｎｍ以下）することが好ましく、この際の粉砕方法は特に限定されるものではないが、遊星ボールミルにより酸化ジルコニウム製のポットとボールを用いて一定時間粉砕を行うのが好ましい。
Ｆｅ‐Ｎｉ合金粉末の表面が、ＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子からなる金属酸化物の混合物により均一にコーティングされたコンポジット粉末を製造するには、混合を行う際、不活性ガス雰囲気下でメカノフュージョンシステム（ホソカワミクロン（株）製）を使用することが好ましく、このシステムでは、軸固定され、高速回転チャンバーとのギャップが１ｍｍ程度のインナーピースによって粉末混合物に強力な剪断応力が加えられ（圧密複合化）、インナーピースを通過した粉末がスクレーパによって掻き落とされるという工程が繰り返されることで、Ｆｅ‐Ｎｉ合金粉末の表面に、金属酸化物の混合物を均一にコーティングすることができる。
Each step in the method for producing a magnetic nanocomposite of the present invention will be described below.
FIG. 1 is a flowchart showing a procedure of a preferred example in the production method of the present invention. First, in step A in the production method of the present invention, MgO fine particles, Fe 2 O 3 fine particles, and MnO fine particles in amounts of Mg (Mn x Fe 1-x ) 2 O 4 (0 ≦ x ≦ 0.4) are respectively added. The surface of the Fe—Ni alloy powder is coated by weighing and mixing the MgO fine particles, Fe 2 O 3 fine particles and MnO fine particles with the Fe—Ni alloy powder. In the present invention, permalloy (53Fe-47Ni (% by weight) or less) of metal magnetic material purified by the N 2 -atomizing method has a smaller intra-particle strain than metal magnetic material purified by the water-atomizing method. ) Alloy powder is preferably used. On the other hand, the raw material for forming the ferrite layer of Mg (Mn x Fe 1-x ) 2 O 4 has a purity of 99.9% or more and a particle size of nm order. Commercially available MgO fine particles, MnO fine particles, and Fe 2 O 3 fine particles can be used. In the present invention, in order to improve the sinterability, it is preferable to pulverize the MnO powder in advance (for example, a particle diameter of 200 nm or less), and the pulverization method is not particularly limited. It is preferable to grind for a certain period of time using a pot and balls made of zirconium oxide.
In order to produce a composite powder in which the surface of the Fe-Ni alloy powder is uniformly coated with a mixture of metal oxides composed of MgO fine particles, Fe 2 O 3 fine particles and MnO fine particles, an inert gas atmosphere is used during mixing. It is preferable to use a mechanofusion system (manufactured by Hosokawa Micron Co., Ltd.) under this system. In this system, a strong shear stress is applied to the powder mixture by an inner piece that is fixed to the shaft and has a gap of about 1 mm with respect to the high-speed rotation chamber. (Consolidation composite) The process of scraping the powder that has passed through the inner piece with a scraper is repeated, whereby the surface of the Fe—Ni alloy powder can be uniformly coated with the metal oxide mixture.
そして、次の工程Ｂ（加圧工程）においては、前記工程Ａで得られたコンポジット粉末を仮成形し、焼結性を上げるために、得られた仮成形体に超高静水圧プレスにて圧力を加えて緻密化された高密度（相対密度８０％以上）の成形体を製造する。このコンポジット粉末の仮成形は、一般的には５０〜１００ＭＰａ程度の圧力の冷間等方圧プレス（ＣＩＰ）にて行うことが好ましく、超高静水圧プレス時の圧力は１ＧＰａ程度が好ましい。 In the next step B (pressurizing step), the composite powder obtained in step A is temporarily formed, and the obtained temporary molded body is subjected to an ultrahigh hydrostatic press in order to increase the sinterability. A compact with high density (relative density of 80% or more) is produced by applying pressure. The temporary molding of the composite powder is generally preferably performed by cold isostatic pressing (CIP) at a pressure of about 50 to 100 MPa, and the pressure at the time of ultrahigh isostatic pressing is preferably about 1 GPa.
そして、次工程の工程Ｃ（パルス通電加圧焼結工程）では、前記工程Ｂで得られた成形体を、高速昇温可能なパルス通電加圧焼結装置を用いてパルス通電加圧焼結（ＳＰＳ）することにより、ＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子からなる金属酸化物の混合物をフェライト相とし、相対密度が９２％以上（９２〜９６％程度、より好ましくは９３〜９５％）の焼結体を製造する。このパルス通電加圧焼結では、低電圧でパルス状直流大電流を投入して粒子間に火花放電現象を生じさせ、これにより瞬時に高エネルギーを発生させることができ、急激なジュール加熱により高速拡散が起きることで、短時間かつ、比較的低温で粒成長を抑制した緻密な焼結体が得られ、高強度、高靭性なセラミックスを作製することが可能となる。
本発明では、使用する原料粉末の粒子径や配合割合等に応じて、工程Ｃにおけるパルス通電加圧焼結の条件を適宜選択することができるが、不活性ガス雰囲気下、焼結温度４５０〜５５０℃、加圧力５０〜１５０ＭＰａ、焼結時間３〜１０分の条件にて行うことが好ましく、特に好ましいパルス通電加圧焼結の条件は、アルゴンガス雰囲気下で、焼結温度５５０℃、加圧力１００ＭＰａ、焼結時間３分である。この際、焼結温度が４５０℃より低い温度では、金属も塑性変形しにくくなり緻密化が困難になり、加えてフェライト相が生じにくく、かつ脆性破壊し易くなり、逆に、焼結温度が５５０℃を超えると還元性酸化物のＦｅＯが生成するので好ましくない。
Then, in the next step C (pulse current pressure sintering step), the compact obtained in step B is subjected to pulse current pressure sintering using a pulse current pressure sintering apparatus capable of high-temperature heating. (SPS) makes a mixture of metal oxides composed of MgO fine particles, Fe 2 O 3 fine particles and MnO fine particles a ferrite phase, and has a relative density of 92% or more (about 92 to 96%, more preferably 93 to 95%). ) Is produced. In this pulse current pressurization sintering, a pulsed direct current is applied at a low voltage to cause a spark discharge phenomenon between particles, thereby instantly generating high energy, and rapid joule heating enables high speed. Due to the diffusion, a dense sintered body in which grain growth is suppressed at a relatively low temperature in a short time can be obtained, and high strength and high toughness ceramics can be produced.
In the present invention, depending on the particle diameter, blending ratio, etc. of the raw material powder to be used, the conditions for pulse current pressurization and sintering in the step C can be appropriately selected. In an inert gas atmosphere, the sintering temperature is 450 to 450. It is preferable to carry out under the conditions of 550 ° C., pressing force of 50 to 150 MPa, and sintering time of 3 to 10 minutes, and particularly preferable conditions for pulsed electric current pressure sintering are a sintering temperature of 550 ° C. under an argon gas atmosphere. The pressure is 100 MPa and the sintering time is 3 minutes. At this time, when the sintering temperature is lower than 450 ° C., the metal is also difficult to be plastically deformed and difficult to be densified. In addition, the ferrite phase is not easily generated and brittle fracture is easily caused. A temperature exceeding 550 ° C. is not preferable because FeO, which is a reducing oxide, is generated.
最終工程である工程Ｄ（熱間静水圧プレス工程）においては、前記工程Ｃで得られた焼結体を、金属／フェライト相が残存するような熱処理条件にて熱間静水圧プレスで処理し、最終的に得られる磁性ナノコンポジットの相対密度をさらに高める（９４％以上、好ましくは９５％以上まで）。本発明における熱間静水圧プレス工程では、圧力１００ＭＰａ以上、好ましくは２００ＭＰａの不活性ガス雰囲気下で７００℃〜９００℃未満、好ましくは７５０〜８５０℃の温度を一定時間（３〜８時間、好ましくは６時間）維持して熱処理を行うことが好ましい。不活性ガスとしては、アルゴンガスや、０．０１％Ｏ２を含むアルゴンガスが好ましい。 In step D (hot isostatic pressing step) which is the final step, the sintered body obtained in step C is processed by hot isostatic pressing under heat treatment conditions such that the metal / ferrite phase remains. The relative density of the finally obtained magnetic nanocomposite is further increased (94% or more, preferably 95% or more). In the hot isostatic pressing step in the present invention, a temperature of 700 ° C. to less than 900 ° C., preferably 750 to 850 ° C. is maintained for a certain period of time (3 to 8 hours, preferably under a pressure of 100 MPa or more, preferably 200 MPa. Is preferably maintained for 6 hours). As the inert gas, argon gas or argon gas containing 0.01% O 2 is preferable.
本発明においてｘが０≦ｘ≦０．４の範囲に限定されるのは、この範囲がＭｎを添加したＭｇＦｅ２Ｏ４フェライト固溶体生成領域だからであり、ｘが０．４を超えた場合（例えばｘ＝０．５の場合）には、固溶限界を超えるのでスピネルフェライト相以外のγ-Ｍ２Ｏ３相が析出して磁気特性が低下し、複合体の透磁率も低下し、実用化できなくなるという問題が生じる。
本発明の製造方法では、上記のＭｎの添加範囲（０≦ｘ≦０．４）において、７００℃〜９００℃未満の温度で熱間静水圧プレス工程を行うことにより、高周波領域で電気・磁気損失を少ない磁性コンポジットが得られる。
In the present invention, x is limited to a range of 0 ≦ x ≦ 0.4 because this range is a MgFe 2 O 4 ferrite solid solution generation region to which Mn is added, and when x exceeds 0.4 ( For example, in the case of x = 0.5), the solid solution limit is exceeded, so that the γ-M 2 O 3 phase other than the spinel ferrite phase is precipitated, the magnetic properties are lowered, and the permeability of the composite is also lowered. The problem that it becomes impossible to become.
In the production method of the present invention, in the above-mentioned Mn addition range (0 ≦ x ≦ 0.4), a hot isostatic pressing process is performed at a temperature of 700 ° C. to less than 900 ° C., so that electric and magnetic fields are generated in a high frequency region. A magnetic composite with low loss can be obtained.
実施例１：本製法による本発明のＭｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４フェライト／パーマロイＦｅ‐Ｎｉ合金系・ナノ磁性コンポジット（０≦ｘ≦０．４）の製造例
金属磁性材料として、Ｎ２‐アトマイズ法で製造されたＦｅ‐４７Ｎｉパーマロイ合金（福田金属箔粉工業（株）製、平均粒径Ｐｓ：２０μｍ）を準備し、Ｆｅ２Ｏ３微粒子には堺化学（株）製の平均粒径Ｐｓ＝６０ｎｍのものを使用し、ＭｇＯ微粒子には宇部マテリアル（株）製の平均粒径Ｐｓ＝５０ｎｍφのもの（純度９９．９８％）を使用した。尚、ＭｎＯ微粒子としては、高純度化学（株）製の平均粒径Ｐｓ＝１０μｍの市販品（純度９９．９％）を遊星ボールミル（酸化ジルコニウムボール：０．３ｍｍ）にて３５０ｒｐｍで８時間粉砕を行い、微粒子化したものを用いた。微粒子化されたＭｎＯ微粒子の平均粒径Ｐｓは約２００ｎｍであった。
上記のＭｇＯ微粒子、ＭｎＯ微粒子及びＦｅ２Ｏ３微粒子を、Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（ｘ＝０．２）のフェライト相となるようにそれぞれ７．６３ｇ、５．３７ｇ、２４．１７ｇ秤量し、これら金属酸化物微粒子を上記Ｆｅ‐４７Ｎｉ合金粉末１５０ｇと混合し、この混合物を、市販のメカノフュージョン装置（ホソカワミクロン（株）製ＡＭＳ−ＭＩＮＩ）を用いて、アルゴンガス雰囲気下、高速回転チャンバーとインナーピースとのギャップ１ｍｍ、回転数４５００ｒｐｍ、混合時間３０分の条件にてコーティングを行い、Ｆｅ‐４７Ｎｉ合金粉末の表面に、ＭｇＯ‐ＭｎＯ‐Ｆｅ２Ｏ３が均質にコーティングされたコンポジット粉末を得た。そして、得られたコンポジット粉末を用いて６８．６ＭＰａの圧力でＣＩＰ仮成形し、その後、超高静水圧プレスで１ＧＰａの圧力で緻密化した。その後、上記成形体を市販のパルス通電加圧焼結装置（シンテック（株）製、ＳＰＳ−５１０Ａ）を用いて、異なる焼結温度（５５０℃、５７５℃、６００℃）で、アルゴンガス雰囲気下、加圧力１００ＭＰａ、昇温速度１００℃／分、焼結時間３分の条件にてパルス通電加圧焼結し、焼結体を得た。
図２には、このようにして得られた焼結体のＸＲＤパターンが示されており、ＸＲＤ測定には、リガク社製の自動Ｘ線回折装置ＲＩＮＴ−２２００を用いた。
この図２の実験結果から、５５０℃より高い温度で焼結を行うと、反磁性酸化物のＦｅＯのピークが現れることが分かり、焼結温度は５５０℃が最適であると考えられる。
Example 1: Production Example metallic magnetic material Mg (Mn x Fe 1-x ) 2 O 4 ferrite / permalloy Fe-Ni alloy system nano magnetic composite (0 ≦ x ≦ 0.4) of the present invention according to the method , N 2 - Fe-47Ni permalloy alloy manufactured by the atomizing method (Fukuda metal foil & powder Co., Ltd., average particle size P s: 20 [mu] m) were prepared, Fe 2 O 3 in fine Sakai chemical industry Co., using an average particle size P s = 60 nm of the manufacturing, the MgO particles were used Ube material Co., Ltd. having an average particle size of P s = 50 nm phi (purity 99.98%). As the MnO fine particles, a commercially available product (purity 99.9%) having an average particle size P s = 10 μm manufactured by High Purity Chemical Co., Ltd. was used for 8 hours at 350 rpm with a planetary ball mill (zirconium oxide ball: 0.3 mm). After pulverization, fine particles were used. The average particle size P s of micronized MnO particles was about 200 nm.
The above MgO fine particles, MnO fine particles and Fe 2 O 3 fine particles were converted into a ferrite phase of Mg (Mn x Fe 1-x ) 2 O 4 (x = 0.2), 7.63 g, 5.37 g, 24.17 g was weighed, and these metal oxide fine particles were mixed with 150 g of the Fe-47Ni alloy powder, and this mixture was mixed under an argon gas atmosphere using a commercially available mechanofusion apparatus (AMS-MINI manufactured by Hosokawa Micron Corporation). Coating is performed under the conditions of a gap of 1 mm between the high-speed rotating chamber and the inner piece, a rotational speed of 4500 rpm, and a mixing time of 30 minutes, and the surface of the Fe-47Ni alloy powder is uniformly coated with MgO-MnO-Fe 2 O 3 A composite powder was obtained. Then, CIP temporary molding was performed using the obtained composite powder at a pressure of 68.6 MPa, and then densification was performed at a pressure of 1 GPa with an ultrahigh hydrostatic pressure press. Thereafter, the molded body was subjected to a different sintering temperature (550 ° C., 575 ° C., 600 ° C.) under an argon gas atmosphere using a commercially available pulsed electric current pressure sintering apparatus (manufactured by Shintech Co., Ltd., SPS-510A). Then, pulsed current pressure sintering was performed under the conditions of a pressure of 100 MPa, a temperature increase rate of 100 ° C./min, and a sintering time of 3 minutes to obtain a sintered body.
FIG. 2 shows an XRD pattern of the sintered body thus obtained, and an automatic X-ray diffractometer RINT-2200 manufactured by Rigaku Corporation was used for the XRD measurement.
From the experimental results shown in FIG. 2, it can be seen that when sintering is performed at a temperature higher than 550 ° C., the peak of FeO of the diamagnetic oxide appears, and the optimum sintering temperature is 550 ° C.
そして、同様にして、上記ＭｇＯ微粒子、Ｆｅ２Ｏ３微粒子及びＭｎＯ微粒子を、Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（ｘ＝０，０．４）のフェライト相となる量にてそれぞれ秤量し、これら金属酸化物微粒子を上記Ｆｅ‐４７Ｎｉ合金粉末と混合し、この混合物を、上記メカノフュージョン装置を用いて、上記の条件にてコーティングを行い、Ｆｅ‐４７Ｎｉ合金粉末の表面に、ＭｇＯ‐Ｆｅ２Ｏ３又はＭｇＯ‐ＭｎＯ‐Ｆｅ２Ｏ３が均質にコーティングされたコンポジット粉末を得た。そして、得られたコンポジット粉末を用いて上記のＣＩＰ仮成形を行ない、その後、超高静水圧プレスで緻密化を行った。以下の表１には、このようにして得られた成形体（ｘ＝０，０．２，０．４）の成形密度、理論密度、相対密度が示されている。 Similarly, the MgO fine particles, the Fe 2 O 3 fine particles, and the MnO fine particles are each in an amount that becomes a ferrite phase of Mg (Mn x Fe 1-x ) 2 O 4 (x = 0, 0.4). These metal oxide fine particles are weighed and mixed with the Fe-47Ni alloy powder, and this mixture is coated under the above conditions using the mechanofusion apparatus, and the surface of the Fe-47Ni alloy powder is coated with MgO. A composite powder uniformly coated with -Fe 2 O 3 or MgO-MnO-Fe 2 O 3 was obtained. And said CIP temporary molding was performed using the obtained composite powder, and it densified by the ultra-high hydrostatic pressure press after that. Table 1 below shows the molding density, theoretical density, and relative density of the molded body (x = 0, 0.2, 0.4) thus obtained.
その後、上記成形体を市販のパルス通電加圧焼結装置（SPSシンテック（株）製、ＳＰＳ−５１０Ａ）を用いて、アルゴンガス雰囲気下、焼結温度５５０℃、加圧力１００ＭＰａ、昇温速度１００℃／分、焼結時間３分の条件にてパルス通電加圧焼結し、焼結体を得た。以下の表２には、このようにして得られた焼結体（ｘ＝０，０．２，０．４）の焼結密度、理論密度、相対密度が示されている。 Thereafter, the molded body was sintered at a sintering temperature of 550 ° C., a pressing force of 100 MPa, and a heating rate of 100 using a commercially available pulsed electric current pressure sintering apparatus (SPS-510A, manufactured by SPS Shintec Co., Ltd.). The sintered body was obtained by pulse-current pressure sintering under conditions of ° C / min and sintering time of 3 minutes. Table 2 below shows the sintered density, theoretical density, and relative density of the sintered body (x = 0, 0.2, 0.4) thus obtained.
上記表１及び表２の結果より、上記の超高静水圧プレス処理と低温高圧パルス通電加圧焼結処理によって、相対密度９３％以上の高密度焼結体が得られることがわかった。一般に相対密度が９２〜９３％以上の高密度になると、焼結体表面の気孔が閉気孔となってガスが焼結体内部に侵入せず、焼結体を高圧ガス雰囲気下においた場合、密閉式の容器(カプセル)に試料を入れなくても、高圧下の熱間静水圧プレス処理を行うことができる。このカプセルフリー熱間静水圧プレス処理は、高密度焼結体の作製が低コストになるとともにカプセルの大きさや形状の制限を受けずに試料の高密度化が可能となる。 From the results shown in Tables 1 and 2, it was found that a high-density sintered body having a relative density of 93% or more can be obtained by the ultra-high hydrostatic pressure pressing process and the low-temperature high-pressure pulse current pressing sintering process. In general, when the relative density is 92 to 93% or higher, the pores on the surface of the sintered body become closed pores and the gas does not enter the sintered body, and the sintered body is placed in a high-pressure gas atmosphere. Even if a sample is not put in a hermetically sealed container (capsule), hot isostatic pressing under high pressure can be performed. This capsule-free hot isostatic pressing process makes it possible to produce a high-density sintered body at low cost and to increase the density of the sample without being restricted by the size and shape of the capsule.
そして次に、熱間静水圧プレス処理における最適温度を検討するために、上記のパルス通電加圧焼結処理にて得られた焼結体（ｘ＝０．２）を、市販の熱間静水圧プレス装置（（株）神戸製鋼所製、ＳＹＳ−５Ｘ）を用いて、異なる焼結温度（７００℃、８００℃、９００℃）で、アルゴンガス雰囲気下、二次熱処理圧力２００ＭＰａ、焼結時間６時間の条件にて熱間静水圧プレス（熱間等方圧加圧）し、高密度焼結体を得た。
図３には、このようにして得られた３種類の焼結体のＸＲＤパターンが示されており、この図３の実験結果から、７００℃及び８００℃で熱間静水圧プレス処理を行った場合は殆ど反磁性体のＦｅＯは生成しないが、９００℃で熱処理した場合には、ＦｅＯの生成を顕著に確認することができ、９００℃以上で熱間静水圧プレス処理を行うと金属パーマロイが酸化されること(フェライト相が還元されること)がわかった。
Then, in order to examine the optimum temperature in the hot isostatic pressing process, a sintered body (x = 0.2) obtained by the above-mentioned pulse current pressurizing and sintering process is used as a commercially available hot isostatic press. Using a hydraulic press machine (SYS-5X, manufactured by Kobe Steel), secondary heat treatment pressure 200 MPa, sintering time at different sintering temperatures (700 ° C., 800 ° C., 900 ° C.) under an argon gas atmosphere. Hot isostatic pressing (hot isostatic pressing) was performed for 6 hours to obtain a high-density sintered body.
FIG. 3 shows XRD patterns of the three types of sintered bodies thus obtained. From the experimental results of FIG. 3, hot isostatic pressing was performed at 700 ° C. and 800 ° C. In this case, almost no diamagnetic FeO is produced, but when heat treatment is performed at 900 ° C., the formation of FeO can be remarkably confirmed. When hot isostatic pressing is performed at 900 ° C. or higher, metal permalloy is formed. It was found that it was oxidized (the ferrite phase was reduced).
又、図４には、熱間静水圧プレス処理前と処理後における焼結体のＸＲＤパターンの変化が示されており、上側の図が熱間静水圧プレス時の温度が７００℃の場合、下側の図が８００℃の場合である。この結果から、パルス通電加圧焼結処理だけの試料と比べても組成の変化は見られず、マグネシウムマンガンフェライトのピークが強くなって結晶性が向上していることがわかり、熱間静水圧プレスの最適温度は８００℃であると考えられる。 FIG. 4 shows changes in the XRD pattern of the sintered body before and after the hot isostatic pressing, and the upper diagram shows the case where the temperature during the hot isostatic pressing is 700 ° C. The lower diagram shows the case at 800 ° C. From this result, it can be seen that there is no change in composition even when compared with the sample with only pulse current pressure sintering treatment, the peak of magnesium manganese ferrite is strengthened and the crystallinity is improved. The optimum temperature for the press is considered to be 800 ° C.
そこで、上記のパルス通電加圧焼結処理にて得られた焼結体（ｘ＝０．２）について、焼結温度８００℃にて上記熱間静水圧プレス処理を行い、得られた焼結体の焼結密度を測定した。以下の表３に、このようにして得られた焼結体の焼結密度、理論密度、相対密度を示す。 Therefore, the sintered body (x = 0.2) obtained by the pulse current pressure sintering process is subjected to the hot isostatic pressing process at a sintering temperature of 800 ° C. The sintered density of the body was measured. Table 3 below shows the sintered density, theoretical density, and relative density of the sintered body thus obtained.
又、以下の表４には、熱間静水圧プレス処理前と処理後における焼結体（ｘ＝０．２）の焼結密度及び相対密度の変化が示されている。 Table 4 below shows changes in the sintered density and relative density of the sintered body (x = 0.2) before and after the hot isostatic pressing.
上記表４の実験結果から、パルス通電加圧焼結後に熱間静水圧プレス処理を行うことによって、それぞれの温度条件において焼結体密度の上昇がみられた。しかし、熱間静水圧プレス操作の９００℃の条件では、あまり焼結体密度の上昇が見られなかった。この原因として、パルス通電加圧焼結操作によりできた焼結体に閉空間気孔が残っていため、熱間静水圧プレス操作で等方的に圧力をかけても気孔が焼結体内に残ったものと考えられる。 From the experimental results shown in Table 4 above, an increase in the sintered body density was observed under each temperature condition by performing a hot isostatic pressing process after pulsed current pressure sintering. However, under the condition of 900 ° C. in the hot isostatic pressing operation, the density of the sintered body was not significantly increased. As a cause of this, since closed space pores remain in the sintered body made by the pulse current pressure sintering operation, the pores remained in the sintered body even when isotropic pressure was applied in the hot isostatic pressing operation. It is considered a thing.
実施例２：本発明の製法における成形体及び焼結体のＳＥＭ観察結果
Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（ｘ＝０．４）のフェライト相を形成するための、パルス通電加圧焼結処理前の成形体（工程Ｂ終了時の未焼結体）の破断面を、電界放射型走査電子顕微鏡（ＦＥ−ＳＥＭ、日本電子社製：JSM７００１F）により観察した。図５は、この成形体の破断面のＳＥＭ画像（３０００倍〜５００００倍）であり、図６は、この成形体の破断面のＳＥＭ画像（３００倍及び７００倍）である。
又、図７は、焼結温度５５０℃でパルス通電加圧焼結を行うことにより得られた焼結体表面のＳＥＭ画像（１０００倍及び３０００倍）であり、図８は、この焼結体表面の、ＳＥＭ画像と同じ場所のＥＤＳ（エネルギー分散型Ｘ線分光分析）マップで、Ｆｅ，Ｎｉ，Ｏ，Ｍｎ，Ｍｇの元素分布が示されている。ＥＤＳによる元素分析には、エネルギー分散型Ｘ線分光分析装置（日本電子社製：JED2300）を使用した。図８のＥＤＳマップとＳＥＭ画像から、Ｍｇ，Ｏの分布する位置が、金属粒子の粒界位置と対応していることが確認された。
図９は、８００℃での熱間静水圧プレス処理後の焼結体表面のＳＥＭ画像（１０００倍及び３０００倍）であり、図７と図９の比較から、パルス通電加圧焼結操作のみの焼結体よりも、パルス通電加圧焼結＋熱間静水圧プレス操作の焼結体の方が緻密になっていることが確認でき、これは、表４に示された焼結密度及び相対密度の上昇と一致している。
Example 2: to form the ferrite phase of the SEM observation of the molded body and the sintered body in the process of the present invention Mg (Mn x Fe 1-x ) 2 O 4 (x = 0.4), the pulse current pressure The fracture surface of the compact before pressure sintering treatment (unsintered body at the end of step B) was observed with a field emission scanning electron microscope (FE-SEM, manufactured by JEOL Ltd .: JSM7001F). FIG. 5 is an SEM image (3000 to 50000 times) of the fracture surface of this molded body, and FIG. 6 is an SEM image (300 and 700 times) of the fracture surface of this molded body.
FIG. 7 is an SEM image (1000 times and 3000 times) of the surface of the sintered body obtained by performing pulsed current pressure sintering at a sintering temperature of 550 ° C. FIG. 8 shows this sintered body. The element distribution of Fe, Ni, O, Mn, and Mg is shown by an EDS (energy dispersive X-ray spectroscopic analysis) map on the same location as the SEM image on the surface. For elemental analysis by EDS, an energy dispersive X-ray spectrometer (manufactured by JEOL Ltd .: JED2300) was used. From the EDS map and SEM image of FIG. 8, it was confirmed that the positions where Mg and O are distributed correspond to the grain boundary positions of the metal particles.
FIG. 9 is an SEM image (1000 times and 3000 times) of the surface of the sintered body after hot isostatic pressing at 800 ° C. From the comparison between FIG. 7 and FIG. It can be confirmed that the sintered body of the pulse current pressure sintering + hot isostatic pressing operation is denser than the sintered body of This is consistent with the increase in relative density.
実施例３：本発明の製法により得られた焼結体（ナノ磁性コンポジット）の磁気特性の測定
Ｍｇ（ＭｎｘＦｅ１−ｘ）２Ｏ４（ｘ＝０．２）のフェライト層が形成されたパーマロイＦｅ‐Ｎｉ系合金・ナノ磁性コンポジットについて、ＶＳＭ解析によりヒステリシス曲線を作成した。図１０は、種々のＨＩＰ処理温度（７００℃、８００℃、９００℃）にて得られた各焼結体（ｘ＝０．２）の磁気特性を示すＢＨカーブであり、以下の表５には、各焼結体の飽和磁束密度が要約されている。
Example 3: ferrite layer measurement Mg magnetic properties of the sintered body obtained by the method of the present invention (nanomagnetic composite) (Mn x Fe 1-x ) 2 O 4 (x = 0.2) is formed Hysteresis curves were prepared by VSM analysis for permalloy Fe-Ni alloys and nanomagnetic composites. FIG. 10 is a BH curve showing the magnetic properties of each sintered body (x = 0.2) obtained at various HIP processing temperatures (700 ° C., 800 ° C., 900 ° C.). Summarizes the saturation magnetic flux density of each sintered body.
図１０のＢＨカーブ及び表５から、熱間静水圧プレス処理温度が７００，８００℃である場合の焼結体の磁束密度Ｂｓは１［Ｔ］を超えており、優れた磁気特性を有する磁性材料であることがわかった。
図１１には、ＨＩＰ処理温度８００℃にて得られた焼結体（ｘ＝０．２）における保磁力と磁束密度の関係が示されており、図１２には、金属磁性材料であるパーマロイ（市販のＦｅ‐Ｎｉ合金）と、本製法にて得られたＭｇ（Ｍｎ０．２Ｆｅ０．８）２Ｏ４／Ｆｅ‐４７Ｎｉコンポジットの、測定周波数と比透磁率の関係が示されている。図１２の右側に位置するグラフは、１０３〜１０５Ｈｚの高周波領域における周波数と比透磁率の関係を示すものである。
図１２のグラフから、２００００Ｈｚを超える高周波領域においては、市販の金属磁性材料（パーマロイ）よりも、本発明の製法を用いて得られたナノ磁性コンポジットの透磁率が高いことがわかった。
From the BH curve of FIG. 10 and Table 5, the magnetic flux density B s of the sintered body when the hot isostatic pressing temperature is 700,800 ° C. exceeds 1 [T] and has excellent magnetic properties. It turned out to be a magnetic material.
FIG. 11 shows the relationship between the coercive force and the magnetic flux density in a sintered body (x = 0.2) obtained at a HIP treatment temperature of 800 ° C., and FIG. 12 shows a permalloy that is a metallic magnetic material. The relationship between the measurement frequency and relative permeability of (commercially available Fe-Ni alloy) and Mg (Mn 0.2 Fe 0.8 ) 2 O 4 / Fe-47Ni composite obtained by this production method is shown. Yes. The graph located on the right side of FIG. 12 shows the relationship between the frequency and relative permeability in a high frequency region of 10 3 to 10 5 Hz.
From the graph of FIG. 12, it was found that the magnetic permeability of the nanomagnetic composite obtained by using the production method of the present invention is higher than that of a commercially available metal magnetic material (Permalloy) in a high frequency region exceeding 20000 Hz.
本発明の製造方法を用いることで、高周波領域でも電気・磁気損失の少ない磁性ナノコンポジットが製造でき、電子機器だけでなく種々の用途に応用展開が可能である。 By using the production method of the present invention, a magnetic nanocomposite with little electric / magnetic loss can be produced even in a high frequency region, and can be applied to various applications as well as electronic devices.
Claims (1)
工程Ａ：Ｍｇ（Ｍｎ ｘ Ｆｅ １−ｘ ） ２ Ｏ ４ （０≦ｘ≦０．４）となる量の、ＭｇＯ微粒子、Ｆｅ ２ Ｏ ３ 微粒子及びＭｎＯ微粒子をそれぞれ秤量し、当該ＭｇＯ微粒子、Ｆｅ ２ Ｏ ３ 微粒子及びＭｎＯ微粒子をＦｅ‐Ｎｉ合金粉末と混合することによってコーティングを行い、前記Ｆｅ‐Ｎｉ合金粉末の表面が、前記ＭｇＯ微粒子、Ｆｅ ２ Ｏ ３ 微粒子及びＭｎＯ微粒子からなる金属酸化物の混合物により被覆されたコンポジット粉末を製造する工程、
工程Ｂ：前記工程Ａで得られたコンポジット粉末を仮成形し、得られた仮成形体に超高静水圧プレスにて圧力を加えて成形体を製造する加圧工程、
工程Ｃ：前記工程Ｂで得られた成形体を、不活性ガス雰囲気下、焼結温度４５０〜５５０℃、加圧力５０〜１５０ＭＰａ、焼結時間３〜１０分の条件にてパルス通電加圧焼結することにより、前記金属酸化物の混合物をフェライト相とし、相対密度が９２％以上の焼結体を製造するパルス通電加圧焼結工程、及び
工程Ｄ：前記工程Ｃで得られた焼結体を、圧力１００ＭＰａ以上の不活性ガス雰囲気下で７００℃〜９００℃未満の温度を一定時間維持して熱間静水圧プレスで処理し、焼結体の相対密度９４％以上とする熱間静水圧プレス工程
を含むことを特徴とする磁性ナノコンポジットの製造方法。 A Mg (Mn x Fe 1-x ) 2 O 4 ferrite / permalloy Fe-Ni alloy system Magnetic nanocomposite method for manufacturing, the method comprising
Step A: MgO fine particles, Fe 2 O 3 fine particles, and MnO fine particles in amounts such that Mg (Mn x Fe 1-x ) 2 O 4 (0 ≦ x ≦ 0.4) are weighed, and the MgO fine particles, Fe Coating is performed by mixing 2 O 3 fine particles and MnO fine particles with Fe—Ni alloy powder, and the surface of the Fe—Ni alloy powder is made of a metal oxide composed of the MgO fine particles, Fe 2 O 3 fine particles, and MnO fine particles. Producing a composite powder coated with the mixture,
Step B: Pressurizing step of temporarily molding the composite powder obtained in Step A above and producing a molded body by applying pressure to the obtained temporary molded body with an ultrahigh hydrostatic pressure press,
Process C: Pulsed pressurization firing of the molded body obtained in the above process B under the conditions of an inert gas atmosphere under a sintering temperature of 450 to 550 ° C., a pressing force of 50 to 150 MPa, and a sintering time of 3 to 10 minutes. A pulsed current pressure sintering process for producing a sintered body having a relative density of 92% or more, wherein the mixture of the metal oxides is a ferrite phase, and
Step D: The sintered body obtained in Step C is treated with a hot isostatic press while maintaining a temperature of 700 ° C. to less than 900 ° C. for a certain time in an inert gas atmosphere at a pressure of 100 MPa or more. Hot isostatic pressing process with a body relative density of 94% or more
The manufacturing method of the magnetic nanocomposite characterized by the above-mentioned .
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