JP2018031041A - Soft magnetic metal powder body and composite magnetic sheet body containing the same - Google Patents
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Abstract
Description
本発明は、扁平形状を有するＦｅ−Ｓｉ系合金からなる軟磁性金属粉体及びこれを含む複合磁性シート体に関し、特に、向上した磁気特性を有する軟磁性金属粉体及びこれを含む複合磁性シート体に関する。 The present invention relates to a soft magnetic metal powder comprising a flat Fe-Si alloy and a composite magnetic sheet including the same, and more particularly, a soft magnetic metal powder having improved magnetic properties and a composite magnetic sheet including the same. About the body.
電磁波を吸収する電磁波吸収シートは、電子機器の筐体の内面に沿って与えられて電子機器内部の基板等からの電磁波を筐体外部へ漏出することを防ぎ、あるいは電子機器を筐体外部の電磁波から保護する目的で使用され得る。かかる電磁波吸収シートのうち、ゴムや樹脂からなるシート体の内部に扁平形状を有する軟磁性金属粉体を配向分散させた複合磁性シート体は、軽量且つ加工容易であり、小型軽量化を強く要求され、また意匠性を高めるために複雑形状になりがちな携帯電子機器などに広く用いられている。 An electromagnetic wave absorbing sheet that absorbs electromagnetic waves is provided along the inner surface of the casing of the electronic device to prevent leakage of electromagnetic waves from a substrate or the like inside the electronic device to the outside of the casing, or It can be used for the purpose of protecting from electromagnetic waves. Among such electromagnetic wave absorbing sheets, a composite magnetic sheet body in which soft magnetic metal powder having a flat shape is oriented and dispersed inside a sheet body made of rubber or resin is light and easy to process, and strongly demands a reduction in size and weight. In addition, it is widely used in portable electronic devices and the like that tend to have complicated shapes in order to improve design.
一般的に、複合磁性シート体に使用される扁平形状を有する軟磁性金属粉体は、粒状粉体を扁平加工して製造される。例えば、アトマイズ法で作製された軟磁性合金からなる粒状粉体を不活性雰囲気中の所定温度で熱処理してから容器内に有機溶媒、粉砕メディア（硬質の粉砕用ボール）とともに入れて攪拌し扁平加工する製造方法が知られている。 Generally, a soft magnetic metal powder having a flat shape used for a composite magnetic sheet is produced by flattening a granular powder. For example, a granular powder made of a soft magnetic alloy produced by an atomizing method is heat-treated at a predetermined temperature in an inert atmosphere, and then placed in a container together with an organic solvent and pulverizing media (hard pulverizing balls). Manufacturing methods for processing are known.
特許文献１には、Ｆｅ−Ｓｉ−Ａｌ合金（センダスト）からなる扁平形状を有する軟磁性金属粉体の製造方法として、アトマイズ法で作製されたセンダスト粒状粉体をアルゴンガス等の不活性ガス雰囲気中で８００〜１２００℃の温度で熱処理する熱処理工程を経た上で、トルエン等の１価アルコールの存在下でアトライター装置により攪拌し混合・粉砕して扁平形状を有する軟磁性金属粉体に加工する方法が開示されている。 In Patent Document 1, as a method for producing a soft magnetic metal powder having a flat shape made of an Fe—Si—Al alloy (Sendust), Sendust granular powder produced by an atomizing method is used in an inert gas atmosphere such as argon gas. It is processed into a soft magnetic metal powder having a flat shape by stirring and mixing and pulverizing with an attritor device in the presence of a monohydric alcohol such as toluene after undergoing a heat treatment step at 800 to 1200 ° C. A method is disclosed.
ここで、軟磁性金属粉体を配向分散させた複合磁性シート体において、軟磁性金属粉体を同じ充填率で分散させると、その粒径が大きいほど磁性シートの実部透磁率μ’をより大きくできる。特許文献１では、熱処理工程及び扁平加工工程の制御により、アスペクト比（＝粒径／厚さ）を２０以上、５０％粒子径Ｄ５０を５０μｍ以上とした扁平形状を有する軟磁性金属粉体を得ており、これを用いた複合磁性シート体では、実部透磁率μ’を１３０以上とでき得るとしている。 Here, in the composite magnetic sheet body in which the soft magnetic metal powder is oriented and dispersed, when the soft magnetic metal powder is dispersed at the same filling rate, the larger the particle size, the more the real part permeability μ ′ of the magnetic sheet. Can be bigger. In Patent Document 1, a soft magnetic metal powder having a flat shape with an aspect ratio (= particle diameter / thickness) of 20 or more and a 50% particle diameter D50 of 50 μm or more is obtained by controlling the heat treatment process and the flat working process. In the composite magnetic sheet body using this, the real part permeability μ ′ can be 130 or more.
複合磁性シート体には、携帯電話等の通信機器の高機能化に伴ってより確実な、高い電磁シールド性が求められるようになっている。つまり、より高い電磁波の減衰能が求められ、これには複合磁性シート体としての透磁率を高めることが必要となり、その複合磁性シート体に含まれる軟磁性金属粉体の磁気特性を高くすることが求められる。一方、減衰能とともにシート体表面での電磁波の反射抑制も重要となるが、これには、軟磁性金属粉体の体積抵抗率を高めることが求められる。そして、透磁率及び体積抵抗率のいずれも、軟磁性金属粉体の形状に依存する。 The composite magnetic sheet body is required to have a more reliable and high electromagnetic shielding property as the function of communication devices such as mobile phones becomes higher. In other words, higher electromagnetic wave attenuation capability is required, which requires increasing the magnetic permeability of the composite magnetic sheet body, and increasing the magnetic properties of the soft magnetic metal powder contained in the composite magnetic sheet body. Is required. On the other hand, it is important to suppress the reflection of electromagnetic waves on the surface of the sheet body as well as the attenuation capability, and this requires increasing the volume resistivity of the soft magnetic metal powder. Both the magnetic permeability and the volume resistivity depend on the shape of the soft magnetic metal powder.
本発明は、以上のような状況に鑑みてなされたものであって、その目的とするところは、軟磁性金属粉体の形状を規定することにより、電磁波の高い減衰能と反射抑制に優れた複合磁性シート体及びこれを与える軟磁性金属粉体を提供することにある。 The present invention has been made in view of the above situation, and the object of the present invention is to provide a high electromagnetic wave attenuation ability and reflection suppression by defining the shape of the soft magnetic metal powder. It is an object of the present invention to provide a composite magnetic sheet and a soft magnetic metal powder that provides the same.
本発明による軟磁性金属粉体は、扁平形状を有するＦｅ−Ｓｉ系合金からなる軟磁性金属粉体であって、１０％平均粒径Ｄ１０と、５０％平均粒径Ｄ５０と、９０％平均粒径Ｄ９０と、かさ密度ＴＤと、真比重ＲＤと、に基づいて、以下の（１）式から算出したγ値が、０．０５以上かつ１０以下であるとともに、表面酸化層の厚さが２ｎｍ以上かつ１００ｎｍ以下であることを特徴とする。ここで、
γ＝Ｄ５０／{（Ｄ９０−Ｄ１０）／（ＴＤ／ＲＤ）} ・・・（１）
である。
The soft magnetic metal powder according to the present invention is a soft magnetic metal powder made of an Fe-Si alloy having a flat shape, and has a 10% average particle diameter D10, a 50% average particle diameter D50, and a 90% average particle. Based on the diameter D90, the bulk density TD, and the true specific gravity RD, the γ value calculated from the following formula (1) is 0.05 or more and 10 or less, and the thickness of the surface oxide layer is 2 nm. It is above and 100 nm or less, It is characterized by the above-mentioned. here,
γ = D50 / {(D90−D10) / (TD / RD)} (1)
It is.
かかる発明によれば、軟磁性金属粉体の形状とともに粒度分布の適正化を図ることにより、従来の軟磁性金属粉体に比べて、より高い透磁率と体積抵抗率とを両立して得られ、電磁波の高い減衰能と反射抑制に優れた複合磁性シート体を与え得るのである。 According to this invention, by optimizing the particle size distribution as well as the shape of the soft magnetic metal powder, it is possible to obtain both higher magnetic permeability and volume resistivity than the conventional soft magnetic metal powder. Thus, a composite magnetic sheet having excellent electromagnetic wave attenuation and reflection suppression can be provided.
上記した発明において、前記γ値が１以上かつ７以下であることを特徴としてもよい。かかる発明によれば、より高い透磁率と体積抵抗率とを安定して得られ、電磁波の高い減衰能と反射抑制に優れた複合磁性シート体を与え得るのである。 In the above-described invention, the γ value may be 1 or more and 7 or less. According to this invention, higher magnetic permeability and volume resistivity can be obtained stably, and a composite magnetic sheet body excellent in high electromagnetic wave attenuation and reflection suppression can be obtained.
また、上記した発明において、前記Ｆｅ−Ｓｉ系合金がＦｅ−Ｓｉ−Ａｌ系合金又はＦｅ−Ｓｉ−Ｃｒ系合金であることを特徴としてもよい。また、Ｆｅ及びＳｉのそれぞれの濃度不安定層の厚さが１０ｎｍ以上かつ２００ｎｍ以下であることを特徴としてもよい。かかる発明によれば、より高い透磁率と体積抵抗率とをより安定して得られ、電磁波の高い減衰能と反射抑制に優れた複合磁性シート体を与え得るのである。 In the above-described invention, the Fe—Si based alloy may be a Fe—Si—Al based alloy or a Fe—Si—Cr based alloy. Moreover, the thickness of each concentration unstable layer of Fe and Si may be 10 nm or more and 200 nm or less. According to this invention, higher magnetic permeability and volume resistivity can be obtained more stably, and a composite magnetic sheet body excellent in high electromagnetic wave attenuation and reflection suppression can be obtained.
さらに、本発明による軟磁性金属粉体は、ゴム又はポリマーと混合することにより複合磁性シート体（例えば、電磁波吸収シート）に適用することができる。このような構成によれば、高い透磁率と体積抵抗率とを安定して得ることができる。 Furthermore, the soft magnetic metal powder according to the present invention can be applied to a composite magnetic sheet (for example, an electromagnetic wave absorbing sheet) by mixing with rubber or polymer. According to such a configuration, high magnetic permeability and volume resistivity can be obtained stably.
本発明による１つの実施例としての扁平形状を有する軟磁性金属粉体を配向分散させた複合磁性シート体について、図１を用いて説明する。 A composite magnetic sheet body in which soft magnetic metal powder having a flat shape as one embodiment according to the present invention is oriented and dispersed will be described with reference to FIG.
図１に示すように、電磁波吸収シートなどに用いられ得る複合磁性シート体１００は、ゴムや樹脂などからなる薄膜状のシート２０に、Ｆｅ−Ｓｉ系合金の軟磁性金属からなる扁平薄片状の金属粉体１０をその主面に沿う方向に配向分散させたシートである。複合磁性シート体１００は、例えば、電子機器の筐体の内面に沿って与えられて、該筐体の外内及び／又は内外へ向けて通過しようとする電磁波を吸収し反射するものである。 As shown in FIG. 1, a composite magnetic sheet 100 that can be used for an electromagnetic wave absorbing sheet or the like is a thin sheet 20 made of rubber, resin, or the like, and a flat flaky piece made of a soft magnetic metal of an Fe—Si based alloy. This is a sheet in which the metal powder 10 is oriented and dispersed in the direction along the main surface. The composite magnetic sheet body 100 is provided along the inner surface of the casing of the electronic device, for example, and absorbs and reflects electromagnetic waves that attempt to pass inside and / or outside the casing.
金属粉体１０は、透磁率の高い金属単体や合金であり得るが、後述するパラメータで磁気特性を規定でき得るＦｅ−Ｓｉ系合金、特に、Ｆｅ−Ｓｉ−Ｃｒ合金、Ｆｅ−Ｓｉ−Ａｌ合金であり、これにＮｉやＭｏなどを添加した合金とすることも可能である。また、不可避的不純物として、質量％で、Ｃ：０．０４％以下、Ｍｎ：０．３％以下、Ｐ：０．０６％以下、Ｓ：０．０６％以下、Ｎ：０．０６％以下、Ｃｕ：０．０５％以下、Ｏ（酸素）：１％以下が含まれ得る。かかる合金のミクロ構造としては、結晶合金としてだけでなく、アモルファス合金であってもよい。また、これらの混合物からなっていてもよい。 The metal powder 10 can be a single metal or alloy having high magnetic permeability, but can be an Fe—Si based alloy that can define magnetic properties with parameters to be described later, in particular, an Fe—Si—Cr alloy, an Fe—Si—Al alloy. It is also possible to use an alloy obtained by adding Ni or Mo to the alloy. Further, as unavoidable impurities, by mass, C: 0.04% or less, Mn: 0.3% or less, P: 0.06% or less, S: 0.06% or less, N: 0.06% or less Cu: 0.05% or less, O (oxygen): 1% or less. The microstructure of such an alloy may be not only a crystalline alloy but also an amorphous alloy. Moreover, you may consist of these mixtures.
金属粉体１０は、後述するように、上記した合金の粒状粉体を扁平加工して与えられるが、従来品に比べて向上した磁気特性の複合磁性シート体１００を与えるには、少なくとも高い透磁率と体積抵抗率とを兼ね備えることが必要となる。つまり、扁平加工の工程を経て得られる金属粉体１０の形状を規定するとともに、この扁平加工工程に伴う金属粉体１０の性状も規定する必要がある。ここでは、「γ値」、「表面酸化層の厚さｄ１」及び「濃度不安定層の厚さｄ２」をパラメータとして特定する。 As will be described later, the metal powder 10 is provided by flattening the granular powder of the above-described alloy. However, in order to provide the composite magnetic sheet body 100 having improved magnetic properties compared to the conventional product, at least a high permeability is required. It is necessary to combine both magnetic susceptibility and volume resistivity. That is, it is necessary to define the shape of the metal powder 10 obtained through the flattening process and also to define the properties of the metal powder 10 associated with the flattening process. Here, “γ value”, “surface oxide layer thickness d1” and “concentration unstable layer thickness d2” are specified as parameters.
「γ値」とは、金属粉体１０の１０％平均粒径Ｄ１０と、５０％平均粒径Ｄ５０と、９０％平均粒径Ｄ９０と、かさ密度ＴＤと、真比重ＲＤと、に基づいて、以下の（１）式から算出した値として定義する。
γ＝Ｄ５０／{（Ｄ９０−Ｄ１０）／（ＴＤ／ＲＤ）} ・・・（１）
“Γ value” is based on the 10% average particle diameter D10, 50% average particle diameter D50, 90% average particle diameter D90, bulk density TD, and true specific gravity RD of the metal powder 10. It is defined as a value calculated from the following equation (1).
γ = D50 / {(D90−D10) / (TD / RD)} (1)
図４に示すように、「表面酸化層」とは、金属粉体１０の表面酸素濃度分析を行ったデータにおいて（図４では、Ｆｅ−Ｓｉ−Ａｌ合金における酸素濃度分析を示している。）、表層の酸素濃度の最大値（Ｍｍａｘ）から金属粉体の中心方向に酸素濃度が最小値となる位置（Ｍｍｉｎ）までの差分の１／２となる深さｄ１までの層として定義する。したがって、「表面酸化層の厚さ」のパラメータは、金属粉体１０の表面から酸素濃度が１／２となる位置までの深さｄ１である。 As shown in FIG. 4, the “surface oxide layer” is data obtained by analyzing the surface oxygen concentration of the metal powder 10 (FIG. 4 shows the oxygen concentration analysis in the Fe—Si—Al alloy). The layer is defined as a layer from the maximum value (M max ) of the oxygen concentration of the surface layer to a depth d1 that is ½ of the difference from the position (M min ) where the oxygen concentration becomes the minimum value in the center direction of the metal powder. . Therefore, the parameter “thickness of the surface oxide layer” is the depth d1 from the surface of the metal powder 10 to the position where the oxygen concentration becomes ½.
図５に示すように、「濃度不安定層」とは、金属粉体１０の表面におけるＦｅ及びＳｉの濃度分析を行ったデータにおいて（図５では、Ｆｅ−Ｓｉ−Ａｌ合金におけるＦｅの濃度分析を示している。）、表面からの深さに対する当該元素の濃度との濃度勾配（図５の白四角印参照）の絶対値が所定値（ここでは、０．１）を超えた深さｄ２までの層として定義する。したがって、「濃度不安定層の厚さ」のパラメータは、金属粉体１０の表面から測定した元素の濃度勾配の絶対値が所定値（ここでは、０．１）を超えた位置までの深さｄ２である。 As shown in FIG. 5, the “concentration unstable layer” is data obtained by analyzing the concentration of Fe and Si on the surface of the metal powder 10 (in FIG. 5, the concentration analysis of Fe in the Fe—Si—Al alloy). Depth d2 in which the absolute value of the concentration gradient (see white squares in FIG. 5) with respect to the depth from the surface exceeds the predetermined value (here, 0.1) Define as a layer up to. Therefore, the parameter “thickness of the concentration unstable layer” is the depth to the position where the absolute value of the concentration gradient of the element measured from the surface of the metal powder 10 exceeds a predetermined value (here, 0.1). d2.
「γ値」、「表面酸化層の厚さｄ１」及び「濃度不安定層の厚さｄ２」のパラメータは、概ね、以下のような指標である。 The parameters of “γ value”, “surface oxide layer thickness d 1” and “concentration unstable layer thickness d 2” are generally the following indices.
「γ値」は、扁平度及び粒度から与えられる磁気特性に関する１つの指標となる。すなわち、かさ密度は金属粉体１０の扁平度を間接的に表す指標の１つであり、かさ密度の高い方がより高い扁平度となって、その粒度が大きくなる。一方で、扁平加工（扁平化）工程によって粒度を大きくしようとすると、粒度分布の幅が広がってしまう。金属粉体１０の粒度を大きくかつ粒度分布の幅を狭くすることで、シート化された後の磁気特性を向上させ得るから、γ値には磁気特性との間で好適な範囲が存在する。このγ値は、Ｆｅ−Ｓｉ系合金では、０．０５以上かつ１０以下であり、好ましくは、０．０５以上かつ８．０以下である。 The “γ value” is an index relating to the magnetic properties given from the flatness and the particle size. That is, the bulk density is one of the indexes that indirectly indicate the flatness of the metal powder 10, and the higher the bulk density, the higher the flatness and the larger the particle size. On the other hand, if it is attempted to increase the particle size by the flattening (flattening) step, the width of the particle size distribution is widened. Since the magnetic properties after being formed into a sheet can be improved by increasing the particle size of the metal powder 10 and narrowing the width of the particle size distribution, the γ value has a suitable range between the magnetic properties. This γ value is 0.05 or more and 10 or less, preferably 0.05 or more and 8.0 or less, in the case of an Fe—Si based alloy.
なお、後述するが、γ値の制御は扁平化ステップＳ１０３を中心に複合的になされ得るが、熱処理ステップＳ１０２において扁平化前の結晶粒を十分に成長させておくことで扁平化ステップＳ１０３における粉砕時の粒径を制御でき、γ値を制御でき得る。 As will be described later, the γ value can be controlled in a complex manner centering on the flattening step S103, but by sufficiently growing the crystal grains before flattening in the heat treatment step S102, the pulverization in the flattening step S103 is performed. The particle size at the time can be controlled, and the γ value can be controlled.
「表面酸化層の厚さｄ１」は、磁気特性に関係する１つの指標となる。すなわち、金属粉体１０においては、表面酸化層の厚さｄ１が厚くなると粒内の磁性体としての有効体積が少なくなるため、表面酸化層ｄ１は薄い方が磁気特性に優れる。特に、扁平度が高く、粒度が小さい場合には影響が大である。一方で、表面酸化層ｄ１が薄くなり過ぎると、電気抵抗が小さくなって、複合磁性シート体としたときの体積抵抗率が小さくなってしまう。つまり、表面酸化層の厚さｄ１は所定の範囲に制御することが望ましい。 The “surface oxide layer thickness d1” is an index related to the magnetic characteristics. That is, in the metal powder 10, since the effective volume as the magnetic substance in the grain decreases as the thickness d1 of the surface oxide layer increases, the thinner the surface oxide layer d1, the better the magnetic characteristics. In particular, when the flatness is high and the particle size is small, the influence is great. On the other hand, if the surface oxide layer d1 is too thin, the electrical resistance is reduced, and the volume resistivity when the composite magnetic sheet is formed is reduced. That is, it is desirable to control the thickness d1 of the surface oxide layer within a predetermined range.
なお、後述するが、表面酸化層の厚さｄ１の制御は、扁平化ステップＳ１０３の処理時間や、乾燥・熱処理ステップＳ１０４の熱処理条件の選択によって可能である。 As will be described later, the thickness d1 of the surface oxide layer can be controlled by selecting the treatment time in the flattening step S103 and the heat treatment conditions in the drying / heat treatment step S104.
「濃度不安定層の厚さｄ２」は、磁気特性に関係する他の１つの指標となる。すなわち、金属粉体１０においては、粒内に１重量％以上含まれる元素は、結晶粒及びその粒界での組織変化をもたらすため、金属粉体１０の軟磁性特性に直接、影響を及ぼすこととなる。つまり、粒内における特定元素、Ｆｅ−Ｓｉ系合金ではＦｅ及びＳｉの濃度差を小さくする方が望ましい。そこで、金属粉体の表面から中心方向における微小領域でのこれら元素の濃度勾配の絶対値を所定値以下、典型的には、０．１以下とすべきである。 The “thickness d2 of the concentration unstable layer” is another index related to the magnetic characteristics. That is, in the metal powder 10, the element contained in the grain at 1% by weight or more directly affects the soft magnetic properties of the metal powder 10 because it causes a change in the structure of the crystal grains and the grain boundaries. It becomes. That is, it is desirable to reduce the concentration difference between Fe and Si in the specific element, Fe—Si based alloy in the grain. Therefore, the absolute value of the concentration gradient of these elements in the minute region in the center direction from the surface of the metal powder should be a predetermined value or less, typically 0.1 or less.
かかる「γ値」、「表面酸化層の厚さｄ１」及び「濃度不安定層の厚さｄ２」のパラメータの値が所定の範囲を満たす金属粉体１０によれば、結果として、複合磁性シート体１００に高い透磁率を付与でき、高い減衰能による優れた電磁波遮蔽性能などを得られるとともに、高い体積抵抗率による優れた反射抑制性能を得られ、良好な磁気特性を与え得るのである。 According to the metal powder 10 in which the values of the parameters “γ value”, “surface oxide layer thickness d1”, and “concentration unstable layer thickness d2” satisfy a predetermined range, as a result, the composite magnetic sheet A high magnetic permeability can be imparted to the body 100, an excellent electromagnetic wave shielding performance due to a high damping ability, and the like, and an excellent antireflection performance due to a high volume resistivity can be obtained, thereby giving good magnetic properties.
次に、上記した金属粉体１０の製造方法について、図２に沿って説明するが、上記パラメータの値の範囲を得られれば、製造方法は特に以下に限定されるものではない。 Next, the manufacturing method of the metal powder 10 described above will be described with reference to FIG. 2, but the manufacturing method is not particularly limited to the following as long as the range of the parameter values can be obtained.
まず、所定の成分組成のＦｅ−Ｓｉ系合金からなる粒状の原料粉体を準備する（原料粉体準備ステップＳ１０１）。原料粉体は、最終的な金属粉体１０と同じ合金成分を有する粉体であって、市販のものを用いても良いし、金属溶湯を噴霧して粒状に粉体化するアトマイズ法などによって作製しても良い。このとき原料粉体は、所定の粒サイズに分級しておくことが好ましい。 First, a granular raw material powder made of an Fe—Si alloy having a predetermined component composition is prepared (raw material powder preparation step S101). The raw material powder is a powder having the same alloy component as that of the final metal powder 10 and may be a commercially available powder, or by an atomizing method in which a molten metal is sprayed into powder. It may be produced. At this time, the raw material powder is preferably classified into a predetermined grain size.
原料粉体は、不活性ガス雰囲気又は還元性雰囲気において、結晶粒径を調整する熱処理を行っておくことが好ましい（熱処理ステップＳ１０２）。結晶粒を十分に成長させておくことで、続く扁平化ステップＳ１０３における粉砕時の粒径を均一かつ大きくできる傾向を与えるのである。 The raw material powder is preferably subjected to a heat treatment for adjusting the crystal grain size in an inert gas atmosphere or a reducing atmosphere (heat treatment step S102). By sufficiently growing the crystal grains, the grain size at the time of pulverization in the subsequent flattening step S103 tends to be uniform and large.
次に、原料粉体をアトライター装置にて扁平化させる（扁平化ステップＳ１０３）。アトライター装置を用いると、ボールミル装置などよりも原料粉体に与えられる剪断力が大きく、扁平化とともに破砕も大きく進み、粒度分布が大きくなる傾向にある。この場合、磁気特性に与えるγ値の寄与が特に大きくなる。 Next, the raw material powder is flattened by an attritor device (flattening step S103). When an attritor device is used, the shearing force applied to the raw material powder is larger than that of a ball mill device or the like, and the flattening and the crushing progress greatly, and the particle size distribution tends to increase. In this case, the contribution of the γ value to the magnetic characteristics is particularly large.
図６に示すように、アトライター装置２００は、原料粉体を含むスラリーＳを収容するタンク状の容器２１０と、容器２１０内のスラリーＳを攪拌する複数の回転羽根（アーム）２２２を放射状に取り付けられた攪拌棒２２０と、スラリーＳを容器２１０の底部からポンプ２３４により汲み上げて容器２１０の上部に還流させる還流配管２３０と、により構成される。還流配管２３０には、スラリーＳの流れを制御する排出バルブ２３２を設けておくことが好ましい。ここで、容器２１０は、図示しない水冷機構により冷却され得る。 As shown in FIG. 6, the attritor apparatus 200 radially includes a tank-shaped container 210 that contains a slurry S containing raw material powder, and a plurality of rotating blades (arms) 222 that stir the slurry S in the container 210. The attached stirring rod 220 and the reflux pipe 230 for pumping the slurry S from the bottom of the container 210 by the pump 234 and returning it to the upper part of the container 210 are configured. The reflux pipe 230 is preferably provided with a discharge valve 232 for controlling the flow of the slurry S. Here, the container 210 can be cooled by a water cooling mechanism (not shown).
原料粉体を扁平化する動作は、具体的には、アトライター装置２００の容器２１０内に原料粉体とともに、溶剤、粉砕メディア及び潤滑剤を適宜、投入し、周面に回転羽根２２２を設けられた攪拌棒２２０を回転させて、容器２１０内のスラリーＳを攪拌する。すると、容器２１０内では、スラリーＳの上側に、スラリー境界面ＳＢとメディア境界面ＭＢとが形成される。そして、粉砕メディアが原料粉体に衝突し衝撃を与えて、原料粉体を平たく変形させながら粉砕させ、扁平化させていく。このとき、アトライター装置２００の容器２１０内で攪拌されるスラリーＳを、還流配管２３０に設けたポンプ２３４を制御することにより所定の流速で循環させる。 Specifically, the operation of flattening the raw material powder is performed by appropriately supplying the raw material powder together with the solvent, the pulverizing media, and the lubricant into the container 210 of the attritor apparatus 200, and providing the rotating blades 222 on the peripheral surface. The obtained stirring rod 220 is rotated to stir the slurry S in the container 210. Then, in the container 210, the slurry boundary surface SB and the media boundary surface MB are formed above the slurry S. Then, the pulverization media collides with the raw material powder and gives an impact, and the raw material powder is pulverized and flattened while being deformed flat. At this time, the slurry S stirred in the container 210 of the attritor device 200 is circulated at a predetermined flow rate by controlling the pump 234 provided in the reflux pipe 230.
ここで、溶剤としては、炭化水素溶媒、例えば、ナフテン系の溶媒を用い得るがこれに限定されるものではない。また、潤滑剤としては、ステアリン酸塩、特に、ステアリン酸亜鉛が好ましいが、やはりこれに限定されるものではない。 Here, as the solvent, a hydrocarbon solvent, for example, a naphthenic solvent may be used, but it is not limited thereto. The lubricant is preferably a stearate, particularly zinc stearate, but is not limited thereto.
攪拌後のスラリーは、アトライター装置から取り出してバット等の容器に流し込み、加熱しながら、適宜、熱処理を与えるとともに、静置乾燥させる（乾燥・熱処理ステップＳ１０４）。金属粉体１０を酸化させることなく熱処理、乾燥させるためには、不活性ガス雰囲気又は還元性雰囲気、例えば、窒素雰囲気や水素雰囲気の加熱炉や、あるいは真空加熱炉等の中で加熱して熱処理するとともに、振動させながら、凝固固化させないように、乾燥させることが好ましい。また、静置乾燥させることも可能である。 The slurry after stirring is taken out from the attritor device, poured into a container such as a bat, and is appropriately heat-treated while being heated, and is allowed to stand still (drying / heat treatment step S104). In order to heat-treat and dry the metal powder 10 without being oxidized, heat treatment is performed by heating in an inert gas atmosphere or a reducing atmosphere, for example, a heating furnace in a nitrogen atmosphere or a hydrogen atmosphere, or a vacuum heating furnace. At the same time, it is preferable to dry it so as not to solidify and solidify while vibrating. Moreover, it is also possible to stand and dry.
更に、金属粉体１０を配向分散させた複合磁性シート体１００の製造方法についてはこれに限定されるものではないが、その代表的な製造方法について図３に沿って簡単に説明する。 Further, the manufacturing method of the composite magnetic sheet body 100 in which the metal powder 10 is oriented and dispersed is not limited to this, but a typical manufacturing method will be briefly described with reference to FIG.
まず、金属粉体１０を、熱可塑性樹脂やその他のゴム系樹脂、例えば、塩素化ポリエチレンなどに、希釈溶剤及び架橋材とともにペースト状になるまで混練し、ペースト体を得る（混練ステップＳ２０１）。続いて、得られたペースト体をドクターブレード法により、所定の厚さとなるように基材上に塗布して、シート体を成形する（シート成形ステップＳ２０２）。最後に、シート体を乾燥させて、所定の条件で熱プレスし、複合磁性シート体１００を得る（熱プレスステップＳ２０３）。 First, the metal powder 10 is kneaded into a thermoplastic resin or other rubber-based resin, such as chlorinated polyethylene, together with a diluting solvent and a cross-linking material until a paste is obtained, thereby obtaining a paste body (kneading step S201). Then, the obtained paste body is apply | coated on a base material by doctor blade method so that it may become predetermined thickness, and a sheet | seat body is shape | molded (sheet | molding step S202). Finally, the sheet body is dried and hot-pressed under predetermined conditions to obtain the composite magnetic sheet body 100 (hot-press step S203).
以上述べてきたように、Ｆｅ−Ｓｉ系合金、特に、Ｆｅ−Ｓｉ−Ａｌ合金又はＦｅ−Ｓｉ−Ｃｒ合金からなる金属粉体１０を用いることで、電磁波を吸収しやすい良好な磁気特性を有する複合磁性シート体１００を製造することができるが、「γ値」、「表面酸化層の厚さ」及び「濃度不安定層の厚さ」のパラメータの値を所定の範囲を満たす金属粉体１０を用いることで、より良好な磁気特性を与えるのである。 As described above, by using the metal powder 10 made of Fe-Si alloy, particularly Fe-Si-Al alloy or Fe-Si-Cr alloy, it has good magnetic properties that easily absorb electromagnetic waves. Although the composite magnetic sheet body 100 can be manufactured, the metal powder 10 satisfying a predetermined range of parameter values of “γ value”, “surface oxide layer thickness” and “concentration unstable layer thickness”. By using, better magnetic properties are given.
図７乃至図１１を用いて、金属粉体１０及びこれを用いた複合磁性シート体（電磁波吸収シート）１００を製造した具体例を説明する。 The specific example which manufactured the metal powder 10 and the composite magnetic sheet body (electromagnetic wave absorption sheet) 100 using the same using FIG. 7 thru | or FIG. 11 is demonstrated.
図７に示すように、ここで用いた合金は、Ｆｅ−Ｓｉ−Ａｌ合金（合金Ａ）とＦｅ−Ｓｉ−Ｃｒ合金（合金Ｂ）である。これら合金溶湯を窒素雰囲気中で噴霧（アトマイズ）して、粒状粉体を作成した（原料粉体準備ステップＳ１０１）。続いて、図８に示すように、粉体を水素雰囲気中で６００〜１０００℃の各温度で５時間の熱処理を行って原料粉体とした（熱処理ステップＳ１０２）。 As shown in FIG. 7, the alloys used here are an Fe—Si—Al alloy (alloy A) and an Fe—Si—Cr alloy (alloy B). The molten alloy was sprayed (atomized) in a nitrogen atmosphere to prepare a granular powder (raw material powder preparation step S101). Subsequently, as shown in FIG. 8, the powder was heat-treated at 600 to 1000 ° C. in a hydrogen atmosphere for 5 hours to obtain a raw material powder (heat treatment step S102).
次に、熱処理後の軟磁性金属の原料粉体をアトライター装置に入れ、溶剤、粉砕メディア及び潤滑剤とともに攪拌し、混合・粉砕すること扁平化処理を行った（扁平化ステップＳ１０３）。ここで、アトライター装置は、容器容量２００リットルである。混合する軟磁性粉体を３４〜３６ｋｇとしたとき、ナフテン系の溶剤（商品名：ナフテゾール１６０）を２００リットル、ステアリン酸亜鉛の潤滑剤を粉体重量比で０．０８〜１．６を加えた混合物に、高炭素クロム軸受鋼のＳＵＪ２からなる直径４．８ｍｍの粉砕メディア（ボール）を５５０ｋｇで混合し、扁平化処理を行った。また、アトライター装置による扁平化処理中、容器内に流入させる上記混合物の流量を容器容量で除した値を「無次元化流速」と定義し、これを調整することによって攪拌及び混合処理中のスラリーの流速を制御した。 Next, the soft magnetic metal raw material powder after the heat treatment was put into an attritor apparatus, stirred together with a solvent, a grinding medium and a lubricant, mixed and ground to perform a flattening process (flattening step S103). Here, the attritor device has a container capacity of 200 liters. When the soft magnetic powder to be mixed is 34 to 36 kg, 200 liters of a naphthenic solvent (trade name: Naphthezol 160) and 0.08 to 1.6 by weight of a zinc stearate lubricant are added. The mixture was mixed with 550 kg of a 4.8 mm diameter grinding medium (ball) made of high carbon chromium bearing steel SUJ2, and flattened. Also, during the flattening process by the attritor device, the value obtained by dividing the flow rate of the mixture flowing into the container by the container volume is defined as “non-dimensional flow velocity”, and by adjusting this, the stirring and mixing process is performed. The flow rate of the slurry was controlled.
次に、扁平化処理した軟磁性金属粉体を、真空あるいは窒素雰囲気中で、８１０〜８３０℃の温度で３時間の加熱・乾燥処理を行った（乾燥・熱処理ステップＳ１０４）。その後、必要に応じて表面処理及び／又は酸化膜の調整を行い、最終的な扁平形状を有する金属粉体とした。ただし、上記温度は、７５０〜８５０℃の範囲で適宜調整可能である。 Next, the flattened soft magnetic metal powder was heated and dried for 3 hours at a temperature of 810 to 830 ° C. in a vacuum or a nitrogen atmosphere (drying and heat treatment step S104). Thereafter, surface treatment and / or oxide film adjustment were performed as necessary to obtain a final metal powder having a flat shape. However, the said temperature can be suitably adjusted in the range of 750-850 degreeC.
製造された金属粉体について、ＪＩＳ−Ｋ−５１０１に準拠した試験方法により、かさ比重測定器を用いて「かさ密度ＴＤ」の測定を行い、レーザー回折・散乱方式の粒度分布測定装置を用いて、金属粉体１０の「１０％平均粒径Ｄ１０」、「５０％平均粒径Ｄ５０」及び「９０％平均粒径Ｄ９０」をそれぞれ測定した。また、オージェ電子分光装置を用いて、金属粉体１０の表面から内部に向かう方向における元素（例えば、Ｏ、Ｆｅ、Ｓｉ等）の濃度分布を測定した。 The produced metal powder is measured for “bulk density TD” using a bulk specific gravity measuring device by a test method based on JIS-K-5101, and using a particle size distribution measuring apparatus of a laser diffraction / scattering method. The “10% average particle diameter D10”, “50% average particle diameter D50”, and “90% average particle diameter D90” of the metal powder 10 were measured, respectively. Further, the concentration distribution of elements (for example, O, Fe, Si, etc.) in the direction from the surface of the metal powder 10 toward the inside was measured using an Auger electron spectrometer.
次に、上記した金属粉体を複合磁性シート体に加工した。まず、重量比で３００対１５の比率で混合したトルエンと塩素化ポリエチレンのゴム溶液中に金属粉体を攪拌し混合して、分散液（ペースト体）を作成した。得られた分散液をポリエステル樹脂からなる基板上に乾燥後の厚みが０．０８ｍｍとなるような厚さで塗布した。さらに、基板上の分散液を自然乾燥した後、１３０℃の温度及び１５ＭＰａの圧力下で４分間のプレス加工を行い、最終的な複合磁性シート体とした。 Next, the above metal powder was processed into a composite magnetic sheet. First, a metal powder was stirred and mixed in a rubber solution of toluene and chlorinated polyethylene mixed at a weight ratio of 300: 15 to prepare a dispersion (paste body). The obtained dispersion was applied on a substrate made of a polyester resin so as to have a thickness after drying of 0.08 mm. Furthermore, after the dispersion liquid on the substrate was naturally dried, press working was performed for 4 minutes under a temperature of 130 ° C. and a pressure of 15 MPa to obtain a final composite magnetic sheet.
得られた複合磁性シート体については、インピーダンスアナライザーを用いて周波数１ＭＨｚにおけるインダクタンスを測定し、そのインダクタンス値から実部透磁率μ´を算出した。また、複合磁性シート体に通電試験を行って、この体積抵抗率を測定した。 For the obtained composite magnetic sheet, the inductance at a frequency of 1 MHz was measured using an impedance analyzer, and the real part permeability μ ′ was calculated from the inductance value. In addition, the volume resistivity was measured by conducting a current test on the composite magnetic sheet.
＜実施例１＞
合金Ａ（Ｆｅ−Ｓｉ−Ａｌ合金、図７参照）を用いた金属粉体及び複合磁性シート体の各特性データを図８及び図９にそれぞれ示す。
<Example 1>
Each characteristic data of the metal powder using the alloy A (Fe—Si—Al alloy, see FIG. 7) and the composite magnetic sheet is shown in FIGS.
実施例であるＮｏ．１乃至６では、無次元化流速を０．０２〜０．４Ｌ／ｍｉｎ、潤滑剤添加量を０．７〜１．３ｗｔ％の範囲で調整しつつ攪拌・混合し、窒素雰囲気下で８１０℃の熱処理を行うことにより、γ値が０．０５〜６．８、酸化層の厚さｄ１が２〜７５ｎｍで、Ｆｅ及びＳｉの濃度不安定層の厚さｄ２がそれぞれ２０〜２１４ｎｍ及び２５〜２９８ｎｍとなる扁平度（アスペクト比）が３０以上の扁平形状を有する金属粉体が得られた。 No. as an example. In Nos. 1 to 6, the dimensionless flow rate was 0.02 to 0.4 L / min, and the amount of lubricant added was adjusted in the range of 0.7 to 1.3 wt% while stirring and mixing, and 810 ° C in a nitrogen atmosphere. , The γ value is 0.05 to 6.8, the oxide layer thickness d1 is 2 to 75 nm, and the Fe and Si concentration unstable layer thicknesses d2 are 20 to 214 nm and 25 to 25 nm, respectively. A metal powder having a flat shape with a flatness (aspect ratio) of 30 or more at 298 nm was obtained.
この金属粉体を用いた複合磁性シート体については、実部透磁率が２０５〜２３０、体積抵抗率が１０５Ωｃｍを安定して超える磁気特性であった。なお、Ｎｏ．１では、アトマイズ処理後の熱処理を省略したが、実部透磁率が２０５で体積抵抗率が１０６Ωｃｍとなる高い透磁率と体積抵抗率の特性が得られた。 The composite magnetic sheet body using this metal powder had magnetic properties that the real part permeability stably exceeded 205 to 230 and the volume resistivity exceeded 10 5 Ωcm stably. In addition, No. In No. 1, the heat treatment after the atomization treatment was omitted, but high magnetic permeability and volume resistivity characteristics were obtained in which the real part permeability was 205 and the volume resistivity was 10 6 Ωcm.
一方、比較例であるＮｏ．７では、攪拌・混合処理での無次元化流速を０．０１Ｌ／ｍｉｎ、潤滑剤添加量を０．３ｗｔ％としたことにより、金属粉体のγ値が０．０３となり、複合磁性シート体の透磁率が１８９と低下した。また、Ｎｏ．８では、アトライター装置による攪拌・混合処理後の熱処理を真空中で行ったことにより、金属粉体の酸化層の厚さｄ１が１ｎｍとなり、複合磁性シート体の体積抵抗率が１０３Ωｃｍと低下した。また、Ｎｏ．９では、アトライター装置による攪拌・混合処理において潤滑剤を添加せずに実行したことにより、金属粉体の酸化層の厚さｄ１が１ｎｍとなり、複合磁性シート体の体積抵抗率が１０３Ωｃｍと低下した。また、Ｎｏ．１０では、扁平化処理後に表面酸化処理を行ったことにより、金属粉体の酸化層の厚さｄ１が１２５ｎｍとなり、複合磁性シート体の透磁率が１９０と低下した。さらに、Ｎｏ．１１では、攪拌・混合処理での無次元化流速を０．６Ｌ／ｍｉｎとしたことにより、金属粉体のγ値が１１．２となり、複合磁性シート体の透磁率が１９０と低下した。 On the other hand, No. which is a comparative example. 7, the dimensionless flow rate in the agitation / mixing process was 0.01 L / min, and the amount of lubricant added was 0.3 wt%, so that the γ value of the metal powder was 0.03, and the composite magnetic sheet body The magnetic permeability of 189 decreased to 189. No. In No. 8, the heat treatment after the stirring / mixing process by the attritor apparatus was performed in vacuum, so that the thickness d1 of the oxide layer of the metal powder became 1 nm, and the volume resistivity of the composite magnetic sheet body was 10 3 Ωcm. Declined. No. In No. 9, the thickness d1 of the oxidized layer of the metal powder was 1 nm and the volume resistivity of the composite magnetic sheet body was 10 3 Ωcm by performing the stirring / mixing process by the attritor apparatus without adding a lubricant. And declined. No. In No. 10, the surface oxidation treatment was performed after the flattening treatment, whereby the thickness d1 of the oxide layer of the metal powder became 125 nm, and the magnetic permeability of the composite magnetic sheet body decreased to 190. Furthermore, no. 11, the dimensionless flow rate in the stirring / mixing process was set to 0.6 L / min, so that the γ value of the metal powder was 11.2 and the magnetic permeability of the composite magnetic sheet body was reduced to 190.
＜実施例２＞
合金Ｂ（Ｆｅ−Ｓｉ−Ｃｒ合金、図７参照）を用いた金属粉体及び複合磁性シート体の各特性データを図１０及び図１１にそれぞれ示す。
<Example 2>
Each characteristic data of the metal powder using the alloy B (Fe—Si—Cr alloy, see FIG. 7) and the composite magnetic sheet is shown in FIGS. 10 and 11, respectively.
実施例であるＮｏ．１２乃至１４では、無次元化流速を０．０８〜０．５Ｌ／ｍｉｎ、潤滑剤添加量を０．５乃至１ｗｔ％の範囲で調整しつつ攪拌・混合処理し、窒素雰囲気下で８３０℃の熱処理を行うことにより、γ値が０．０５〜７．３、酸化層の厚さｄ１が５〜２０ｎｍで、Ｆｅ及びＳｉの濃度不安定層の厚さｄ２がそれぞれ１０〜３０ｎｍ及び１２〜３５ｎｍとなる扁平度（アスペクト比）が３０以上の扁平形状を有する金属粉体が得られた。また、この金属粉体を用いた複合磁性シート体については、実部透磁率が５０〜５８、体積抵抗率が１０４Ωｃｍを安定して超える特性が得られた。 No. as an example. 12 to 14, the dimensionless flow rate was 0.08 to 0.5 L / min, and the amount of lubricant added was adjusted in the range of 0.5 to 1 wt% while stirring and mixing, and the temperature was 830 ° C. in a nitrogen atmosphere. By performing the heat treatment, the γ value is 0.05 to 7.3, the oxide layer thickness d1 is 5 to 20 nm, and the Fe and Si concentration unstable layer thicknesses d2 are 10 to 30 nm and 12 to 35 nm, respectively. A metal powder having a flat shape with a flatness (aspect ratio) of 30 or more was obtained. Moreover, about the composite magnetic sheet | seat body using this metal powder, the real part magnetic permeability was 50-58, and the volume resistivity exceeded the 10 < 4 > ohm cm stably.
一方、比較例であるＮｏ．１５では、攪拌・混合処理での無次元化流速を０．０１Ｌ／ｍｉｎ、潤滑剤添加量を０．３ｗｔ％としたことにより、金属粉体のγ値が０．０３となり、複合磁性シート体の透磁率が４５と低下した。また、Ｎｏ．１６では、攪拌・混合拌処理での無次元化流速を０．８Ｌ／ｍｉｎとしたことにより、金属粉体のγ値が１１．５となり、複合磁性シート体の透磁率が４７と低下した。 On the other hand, No. which is a comparative example. 15, the dimensionless flow rate in the stirring / mixing process was set to 0.01 L / min, and the lubricant addition amount was set to 0.3 wt%, so that the γ value of the metal powder became 0.03, and the composite magnetic sheet body As a result, the permeability decreased to 45. No. In No. 16, the non-dimensional flow rate in the stirring / mixing stirring process was 0.8 L / min, so that the γ value of the metal powder was 11.5, and the magnetic permeability of the composite magnetic sheet body was reduced to 47.
以上、実施例１及び２からわかるように、金属粉体の製造工程において、原料粉体及び／又はこれを扁平化処理した後の粉体の熱処理、アトライター装置による攪拌・混合処理におけるスラリーの流速や潤滑剤の添加量、あるいは攪拌・混合処理後の熱処理の各条件を適宜調整することにより、上記（１）式で定義されるγ値が０．０５以上かつ１０以下であって、表面酸化層の厚さが２ｎｍ以上かつ１００ｎｍ以下である扁平形状を有する金属粉体を製造できる。このような金属粉体を用いた複合磁性シート体は、従来品に比べて安定して高い透磁率と体積抵抗率を両立して得ることができる。 As described above, as can be seen from Examples 1 and 2, in the metal powder manufacturing process, the raw material powder and / or the heat treatment of the powder after flattening the raw material powder, the slurry in the stirring / mixing process by the attritor device By appropriately adjusting the flow rate, the addition amount of the lubricant, or each condition of the heat treatment after the stirring / mixing treatment, the γ value defined by the above formula (1) is 0.05 or more and 10 or less, A metal powder having a flat shape in which the thickness of the oxide layer is 2 nm or more and 100 nm or less can be produced. A composite magnetic sheet body using such a metal powder can be obtained with both high magnetic permeability and volume resistivity stably compared to conventional products.
以上、本発明の代表的な実施例を説明したが、本発明は必ずしもこれらに限定されるものではなく、当業者であれば、本発明の主旨又は添付した特許請求の範囲を逸脱することなく、種々の代替実施例及び改変例を見出すことができるであろう。 As mentioned above, although the typical Example of this invention was described, this invention is not necessarily limited to these, Those skilled in the art will not deviate from the main point of this invention, or the attached claim. Various alternative embodiments and modifications may be found.
１０ 軟磁性金属粉体
２０ ゴム系樹脂
１００ 複合磁性シート体
２００ アトライタ装置
２１０ 水冷容器
２２０ 攪拌棒
DESCRIPTION OF SYMBOLS 10 Soft magnetic metal powder 20 Rubber-type resin 100 Composite magnetic sheet body 200 Attritor apparatus 210 Water cooling container 220 Stirring rod
Claims (5)
１０％平均粒径Ｄ１０と、５０％平均粒径Ｄ５０と、９０％平均粒径Ｄ９０と、かさ密度ＴＤと、真比重ＲＤと、に基づいて、以下の（１）式から算出したγ値が、０．０５以上かつ１０以下であるとともに、
表面酸化層の厚さが２ｎｍ以上かつ１００ｎｍ以下であることを特徴とする軟磁性金属粉体。
γ＝Ｄ５０／{（Ｄ９０−Ｄ１０）／（ＴＤ／ＲＤ）} ・・・（１） A soft magnetic metal powder made of an Fe-Si alloy having a flat shape,
Based on the 10% average particle diameter D10, the 50% average particle diameter D50, the 90% average particle diameter D90, the bulk density TD, and the true specific gravity RD, the γ value calculated from the following equation (1) is 0.05 or more and 10 or less,
A soft magnetic metal powder, wherein the thickness of the surface oxide layer is 2 nm or more and 100 nm or less.
γ = D50 / {(D90−D10) / (TD / RD)} (1)
The composite magnetic sheet body with which the soft magnetic metal powder as described in any one of Claims 1 thru | or 4 and rubber | gum or a polymer were mixed.
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| WO2020090849A1 (en) * | 2018-10-30 | 2020-05-07 | Ｄｏｗａエレクトロニクス株式会社 | Soft magnetic powder, soft magnetic powder heat treatment method, soft magnetic material, dust core, and dust core manufacturing method |
| KR20220073553A (en) * | 2020-11-26 | 2022-06-03 | 한국교통대학교산학협력단 | Electromagnetic wave shielding sheet and electronic device comprising the same |
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| JP2016089242A (en) * | 2014-11-10 | 2016-05-23 | 山陽特殊製鋼株式会社 | Soft magnetic flat powder and production method thereof |
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| JP2020070499A (en) * | 2018-10-30 | 2020-05-07 | Ｄｏｗａエレクトロニクス株式会社 | Soft magnetic powder, soft magnetic powder heat treatment method, soft magnetic material, dust core, and dust core manufacturing method |
| WO2020090849A1 (en) * | 2018-10-30 | 2020-05-07 | Ｄｏｗａエレクトロニクス株式会社 | Soft magnetic powder, soft magnetic powder heat treatment method, soft magnetic material, dust core, and dust core manufacturing method |
| JP2021077894A (en) * | 2018-10-30 | 2021-05-20 | Ｄｏｗａエレクトロニクス株式会社 | Soft magnetic powder, soft magnetic material, dust core, and manufacturing method of dust core |
| JP7049435B2 (en) | 2018-10-30 | 2022-04-06 | Ｄｏｗａエレクトロニクス株式会社 | Manufacturing method of soft magnetic powder, soft magnetic material, dust core and powder magnetic core |
| KR20220073553A (en) * | 2020-11-26 | 2022-06-03 | 한국교통대학교산학협력단 | Electromagnetic wave shielding sheet and electronic device comprising the same |
| KR102495696B1 (en) * | 2020-11-26 | 2023-02-06 | 한국교통대학교산학협력단 | Electromagnetic wave shielding sheet and electronic device comprising the same |
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