JP6039209B2 - Powder and spherical particle combination and production method thereof, mixed powder of powder and spherical particle combination, magnetic paste containing the mixed powder, inductor and magnetic core material using the magnetic paste - Google Patents
Powder and spherical particle combination and production method thereof, mixed powder of powder and spherical particle combination, magnetic paste containing the mixed powder, inductor and magnetic core material using the magnetic paste Download PDFInfo
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Description
本発明は、アモルファス合金からなり軟磁性を有する粉末及び球状粒子結合体とそれらの製造方法に関する。また、本発明は、それら粉末及び球状粒子結合体の混合粉末、その混合粉末を含む磁性ペースト、並びにその磁性ペーストを用いたインダクタ及び磁心材料に関する。 The present invention relates to a powder and a spherical particle combination made of an amorphous alloy and having soft magnetism, and a method for producing them. The present invention also relates to a mixed powder of the powder and spherical particle combination, a magnetic paste containing the mixed powder, and an inductor and a magnetic core material using the magnetic paste.
アモルファス合金からなり軟磁性を有する粒径の小さい粉末は、渦電流の発生を低減できることから、高周波領域で使用される様々な磁気デバイスに利用される。かかる粉末に加えて、より良い磁気特性を得るため、特許文献１のように、粒径の小さい粉末を棒状に結合してなる球状粒子結合体について提案しているものもある。
A powder having a small particle diameter and made of an amorphous alloy and having soft magnetism can be used for various magnetic devices used in a high frequency region because it can reduce generation of eddy current. In addition to such a powder, there is a proposal of a spherical particle bonded body obtained by bonding a powder having a small particle diameter in a rod shape as in
本発明は、更に優れた軟磁性を有する粒径の小さい粉末及びそれを棒状に結合してなる球状粒子結合体を提供することを目的とする。 An object of the present invention is to provide a powder having a further excellent soft magnetism and a small particle diameter and a spherical particle bonded body obtained by binding the powder in a rod shape.
本発明の発明者らは、研究の結果、還元剤としてジメチルアミンボランとＮａＢＨ４の両方を用いることにより、軟磁性を有するＣｏ−Ｆｅ−Ｂ（−Ｐ）アモルファス合金からなる微粒子及び球状粒子結合体を得ることができることを見出した。本発明は、かかる知見に基づくものであり、具体的には以下に掲げる手段を提供する。 As a result of research, the inventors of the present invention have found that a fine particle and a spherical particle combination made of a Co—Fe—B (—P) amorphous alloy having soft magnetism by using both dimethylamine borane and NaBH 4 as reducing agents. Found that you can get. The present invention is based on such knowledge, and specifically provides the following means.
即ち、本発明は、第１の製造方法として、
Ｆｅ元素を含有する第１金属塩と、Ｃｏ元素を含有する第２金属塩と、錯化剤とを含む原料液に対して、ｐＨ調整剤を加えて、所定のｐＨを有するように調整された中間液を生成するｐＨ調整工程と、
前記中間液を撹拌しながら当該中間液に対してジメチルアミンボランとＮａＢＨ４を含むＢ系還元剤を滴下することにより、アモルファス合金からなり軟磁性を有する粉末を得る還元工程と
を備える粉末の製造方法を提供する。
That is, the present invention provides the first production method as follows:
A pH adjuster is added to the raw material liquid containing the first metal salt containing Fe element, the second metal salt containing Co element, and the complexing agent, and adjusted to have a predetermined pH. A pH adjusting step for producing an intermediate solution;
Production of a powder comprising a reduction step of obtaining a soft magnetic powder made of an amorphous alloy by dropping a B-based reducing agent containing dimethylamine borane and NaBH 4 into the intermediate solution while stirring the intermediate solution Provide a method.
また、本発明は、第２の製造方法として、
Ｆｅ元素を含有する第１金属塩と、Ｃｏ元素を含有する第２金属塩と、錯化剤とを含む原料液に対して、ｐＨ調整剤を加えて、所定のｐＨを有するように調整された中間液を生成するｐＨ調整工程と、
前記中間液を撹拌しながら、永久磁石又は電磁石を用いて７．９ｋＡ／ｍ以上３９５ｋＡ／ｍ以下の磁場を印加しつつ、当該中間液に対してジメチルアミンボランとＮａＢＨ４を含むＢ系還元剤を滴下することにより、アモルファス合金からなり軟磁性を有する球状粒子が棒状に結合されてなる球状粒子結合体を得る還元工程と
を備える球状粒子結合体の製造方法を提供する。
In addition, the present invention provides a second manufacturing method,
A pH adjuster is added to the raw material liquid containing the first metal salt containing Fe element, the second metal salt containing Co element, and the complexing agent, and adjusted to have a predetermined pH. A pH adjusting step for producing an intermediate solution;
While stirring the intermediate solution, applying a magnetic field of 7.9 kA / m or more and 395 kA / m or less using a permanent magnet or an electromagnet, the B solution containing dimethylamine borane and NaBH 4 is applied to the intermediate solution. There is provided a method for producing a spherical particle bonded body comprising a reduction step of obtaining a spherical particle bonded body in which spherical particles made of an amorphous alloy and having soft magnetism are bonded in a rod shape by dropping an agent.
また、本発明は、第３の製造方法として、第１又は第２の製造方法であって、
前記原料液は、Ｐ系還元剤を更に含むものである
製造方法を提供する。
Moreover, this invention is a 1st or 2nd manufacturing method as a 3rd manufacturing method,
The raw material liquid provides a production method further comprising a P-based reducing agent.
また、本発明は、第４の製造方法として、第３の製造方法であって、
前記Ｐ系還元剤は、次亜リン酸ナトリウムからなる
製造方法を提供する。
Moreover, this invention is a 3rd manufacturing method as a 4th manufacturing method,
The P-based reducing agent provides a production method comprising sodium hypophosphite.
また、本発明は、第５の製造方法として、第１乃至第４のいずれかに記載の製造方法であって、
前記ｐＨ調整工程における前記所定のｐＨは、８．５〜１１．０である
製造方法を提供する。
Moreover, this invention is a manufacturing method in any one of 1st thru | or 4 as a 5th manufacturing method,
The said predetermined pH in the said pH adjustment process provides the manufacturing method which is 8.5-11.0.
また、本発明は、第６の製造方法として、第５の製造方法であって、
前記所定のｐＨは、９．２〜９．８である
製造方法を提供する。
Moreover, this invention is a 5th manufacturing method as a 6th manufacturing method,
The manufacturing method in which the predetermined pH is 9.2 to 9.8 is provided.
また、本発明は、第７の製造方法として、第１乃至第６のいずれかに記載の製造方法であって、
前記原料液は、析出核形成剤を含まない
製造方法を提供する。
Moreover, this invention is a manufacturing method in any one of 1st thru | or 6 as a 7th manufacturing method,
The raw material liquid provides a production method that does not contain a precipitation nucleation agent.
更に、本発明は、第１の粉末として、
組成式（Ｆｅ１−ｘＣｏｘ）１００−ａ−ｂＢａＰｂ（ここで、０＜ｘ＜１、１５≦ａ≦３６ａｔ％、０≦ｂ≦３ａｔ％）で示される組成を有するアモルファス合金からなり、且つ、０．０５μｍ以上３．０μｍ以下の平均粒径を有すると共に軟磁性を有する粉末を提供する。
Furthermore, the present invention provides the first powder as
Amorphous having a composition represented by a composition formula (Fe 1-x Co x ) 100-ab B a P b (where 0 <x <1, 15 ≦ a ≦ 36 at%, 0 ≦ b ≦ 3 at%) Provided is a powder which is made of an alloy and has an average particle diameter of 0.05 μm or more and 3.0 μm or less and has soft magnetism.
また、本発明は第２の粉末として、第１の粉末であって、
０．５≦ｘ≦０．９５を満たす粉末を提供する。
を備える球状粒子結合体の製造方法を提供する。
Further, the present invention is the first powder as the second powder,
A powder satisfying 0.5 ≦ x ≦ 0.95 is provided.
A method for producing a spherical particle combination comprising:
また、本発明は第３の粉末として、第１又は第２の粉末であって、
０．０５μｍ以上１．０μｍ以下の平均粒径を有する粉末を提供する。
Moreover, this invention is 1st or 2nd powder as 3rd powder,
Provided is a powder having an average particle size of 0.05 μm or more and 1.0 μm or less.
また、本発明は第４の粉末として、第１乃至第３のいずれかの粉末であって、
１６≦ａ＋ｂ≦２２ａｔ％を満たす粉末を提供する。
Further, the present invention is any one of the first to third powders as the fourth powder,
A powder satisfying 16 ≦ a + b ≦ 22 at% is provided.
また、本発明は球状粒子結合体として、
第１乃至第５のいずれかの粉末を一次粒子とし、前記一次粒子が棒状に結合されてなる球状粒子結合体であって短軸径が０．０５μｍ以上２．０μｍ以下であり且つ長軸径が０．３μｍ以上２０．０μｍ以下の球状粒子結合体を提供する。
In addition, the present invention as a spherical particle combination,
A spherical particle bonded body in which any one of the first to fifth powders is used as primary particles, and the primary particles are bonded in a rod shape, the minor axis diameter is 0.05 μm or more and 2.0 μm or less, and the major axis diameter is Provides a spherical particle bonded body having a particle size of 0.3 μm or more and 20.0 μm or less.
また、本発明は、第１の混合粉末として、上述した球状粒子結合体と、０．１μｍ以下の平均粒径を有する強磁性微粒子とからなる混合粉末を提供する。 Moreover, this invention provides the mixed powder which consists of the spherical particle coupling body mentioned above and the ferromagnetic fine particle which has an average particle diameter of 0.1 micrometer or less as a 1st mixed powder.
また、本発明は、第２の混合粉末として、第１の混合粉末であって、
前記強磁性微粒子は、前記球状粒子結合体を構成する前記一次粒子の平均粒径の１／１０以下の平均粒径を有している
混合粉末を提供する。
Moreover, this invention is 1st mixed powder as 2nd mixed powder,
The ferromagnetic fine particles provide a mixed powder having an average particle size of 1/10 or less of the average particle size of the primary particles constituting the spherical particle combination.
また、本発明は、第３の混合粉末として、第１又は第２の混合粉末であって、
前記強磁性微粒子は、３ｎｍ以上の平均粒径を有している
混合粉末を提供する。
Moreover, this invention is 1st or 2nd mixed powder as 3rd mixed powder,
The ferromagnetic fine particles provide a mixed powder having an average particle diameter of 3 nm or more.
更に、本発明は、第４の混合粉末として、第１乃至第３の混合粉末であって、
前記強磁性微粒子は、ＮｉＺｎフェライト、ＭｎＺｎフェライト、又は、Ｆｅ，Ｎｉ，Ｃｏからなる群から選ばれる一種以上の合金のいずれかからなる
混合粉末を提供する。
Furthermore, the present invention provides the first to third mixed powders as the fourth mixed powder,
The ferromagnetic fine particles provide a mixed powder made of NiZn ferrite, MnZn ferrite, or one or more alloys selected from the group consisting of Fe, Ni and Co.
また、本発明は、第１乃至第４のいずれかの混合粉末を溶剤に分散させてなる磁性ペーストであって、
前記混合粉末の充填率が２０〜６５％であり、粘度が１〜３００Ｐａ・ｓである
磁性ペーストを提供する。
Further, the present invention is a magnetic paste obtained by dispersing any one of the first to fourth mixed powders in a solvent,
A magnetic paste having a filling rate of 20 to 65% and a viscosity of 1 to 300 Pa · s is provided.
また、本発明は、上述した磁性ペーストに対して対称物を浸漬させた状態又は前記磁性ペーストを前記対象物に塗布した状態で磁場を印加しつつ前記磁性ペーストを固化させることにより、前記磁性ペーストに含まれる前記強磁性微粒子を前記球状粒子結合体間に配置させる方法を提供する。 Further, the present invention provides the magnetic paste by solidifying the magnetic paste while applying a magnetic field in a state where a symmetrical object is immersed in the magnetic paste described above or in a state where the magnetic paste is applied to the object. A method for arranging the ferromagnetic fine particles contained in the spherical particle combination is provided.
また、本発明は、上述した磁性ペーストに対して巻き線コイルを浸漬させた状態で磁場を印加しつつ前記磁性ペーストを固化してなるインダクタを提供する。 In addition, the present invention provides an inductor formed by solidifying the magnetic paste while applying a magnetic field in a state in which a wound coil is immersed in the magnetic paste described above.
また、本発明は、シート状の基板上に形成された平面コイルに対して、上述した磁性ペーストを塗布した状態で前記磁性ペーストを固化してなるインダクタを提供する。 The present invention also provides an inductor obtained by solidifying the magnetic paste in a state where the above-described magnetic paste is applied to a planar coil formed on a sheet-like substrate.
また、本発明は、シート状の基板上に対して、上述した磁性ペーストを５μｍ〜５００μｍの厚さを有するように塗布した状態で前記磁性ペーストを固化してなる磁性材料を提供する。 In addition, the present invention provides a magnetic material obtained by solidifying the magnetic paste in a state where the above-described magnetic paste is applied on a sheet-like substrate so as to have a thickness of 5 μm to 500 μm.
本発明によれば、還元剤の適切な組み合わせを見つけることができたことから、Ｃｏ−Ｆｅ−Ｂ（−Ｐ）アモルファス合金からなる粉末及び球状粒子結合体を得ることができる。かかる粉末や球状粒子結合体は、Ｆｅ−Ｂ−Ｐ合金粉末等と比較して優れた軟磁性を有している。 According to the present invention, since an appropriate combination of reducing agents could be found, a powder and spherical particle combination made of a Co—Fe—B (—P) amorphous alloy can be obtained. Such powders and spherical particle bonded bodies have excellent soft magnetism as compared with Fe-BP alloy powders and the like.
特に、本発明によれば、ＰｔＣｌ４Ｎａのような析出核形成材を用いることなく、粒径の揃った粉末又は球状粒子を（従って、球状粒子結合体も）得ることができる。これにより、中心近傍であってもアモルファス相を主相とするような粉末又は球状粒子を（従って、球状粒子結合体も）得ることができる。かかる粉末又は球状粒子（従って、球状粒子結合体）は、それらのアモルファス相に起因して良好な軟磁性を得ることができる。 In particular, according to the present invention, it is possible to obtain powders or spherical particles having a uniform particle size (and thus a spherical particle combination) without using a precipitation nucleation material such as PtCl 4 Na. Thereby, even in the vicinity of the center, powder or spherical particles having an amorphous phase as a main phase can be obtained (thus, a spherical particle combined body). Such powders or spherical particles (and thus spherical particle conjugates) can obtain good soft magnetism due to their amorphous phase.
以下に説明する本発明の実施の形態による粉末は、アモルファス合金からなると共に軟磁性を有するものであり、下記組成式で示される組成を有している。
（Ｆｅ１−ｘＣｏｘ）１００−ａ−ｂＢａＰｂ
ここで、０＜ｘ＜１、１５≦ａ≦３６ａｔ％、０≦ｂ≦３ａｔ％を満たす。
また、上述した粉末の平均粒径は０．０５μｍ以上３．０μｍ以下である。
かかる粉末はアモルファス相に起因して良好な軟磁気特性を有している。
The powder according to the embodiment of the present invention described below is made of an amorphous alloy and has soft magnetism, and has a composition represented by the following composition formula.
(Fe 1-x Co x ) 100-ab B a P b
Here, 0 <x <1, 15 ≦ a ≦ 36 at%, and 0 ≦ b ≦ 3 at% are satisfied.
The average particle size of the powder described above is 0.05 μm or more and 3.0 μm or less.
Such powders have good soft magnetic properties due to the amorphous phase.
特に、平均粒径が１μｍ以下であると、１〜１０ＧＨｚといった高周波領域においても渦電流損失を実質的に無視できる。従って、平均粒径は１μｍ以下であることが好ましい。一方、平均粒径が０．０５μｍより小さい場合には超常磁性が無視できなくなってしまうので、平均粒径の下限は０．０５μｍであることが好ましい。 In particular, when the average particle diameter is 1 μm or less, eddy current loss can be substantially ignored even in a high frequency region of 1 to 10 GHz. Accordingly, the average particle size is preferably 1 μm or less. On the other hand, when the average particle size is smaller than 0.05 μm, superparamagnetism cannot be ignored, so the lower limit of the average particle size is preferably 0.05 μm.
ＦｅとＣｏに関し、Ｆｅ成分が多いと表面の改質が進んでしまうことから、Ｃｏ成分が少なくとも０．５以上であることが好ましい。即ち、ｘ≧０．５であることが好ましい。なお、ａ＋ｂを一定とした場合、ｘ＝０．４〜０．５では飽和磁化が最大となる。また、Ｃｏのみでは結晶粒が析出してしまうため、ｘは１より小さいことが必要となる。特に、ｘ＝０．９５のとき、磁歪定数がゼロとなり、保磁力Ｈｃが小さくなる。即ち、ｘ＝０．９５のとき、粉末は、最も優れた軟磁性を有する。調整のしやすさや良好な軟磁気特性を考慮すると、ｘは０．５≦ｘ≦０．９５を満たすことが好ましい。 Regarding Fe and Co, if the Fe component is large, surface modification proceeds, so the Co component is preferably at least 0.5 or more. That is, it is preferable that x ≧ 0.5. When a + b is constant, the saturation magnetization is maximized at x = 0.4 to 0.5. In addition, since crystal grains precipitate with Co alone, x must be smaller than 1. In particular, when x = 0.95, the magnetostriction constant becomes zero and the coercive force Hc becomes small. That is, when x = 0.95, the powder has the most excellent soft magnetism. In consideration of ease of adjustment and good soft magnetic properties, x preferably satisfies 0.5 ≦ x ≦ 0.95.
ａ＋ｂが２２ａｔ％より大きいと、結晶化温度が上がることが期待できるが、飽和磁化が低下してしまう。一方、ａ＋ｂが１６ａｔ％より小さいと、飽和磁化が上がるが、結晶化温度が低下してしまう。従って、ａ＋ｂは、１６ａｔ％以上２２ａｔ％以下であることが好ましい。 If a + b is greater than 22 at%, it can be expected that the crystallization temperature will increase, but the saturation magnetization will decrease. On the other hand, if a + b is less than 16 at%, the saturation magnetization increases, but the crystallization temperature decreases. Accordingly, a + b is preferably 16 at% or more and 22 at% or less.
Ｐは、アモルファス相の安定化に寄与する。但し、実使用環境を考慮すると、Ｐの量、即ちｂは、できるだけ少ない方が好ましい。 P contributes to stabilization of the amorphous phase. However, considering the actual use environment, the amount of P, that is, b is preferably as small as possible.
上述した粉末の製造方法は、Ｆｅ元素を含有する第１金属塩と、Ｃｏ元素を含有する第２金属塩と、錯化剤とを含む原料液に対して、ｐＨ調整剤を加えて、所定のｐＨを有するように調整された中間液を生成するｐＨ調整工程と、その中間液を撹拌しながら当該中間液に対してジメチルアミンボランとＮａＢＨ４を含むＢ系還元剤を滴下することにより、アモルファス合金からなり軟磁性を有する粉末を得る還元工程とを備えている。 In the above-described powder manufacturing method, a pH adjusting agent is added to a raw material liquid containing a first metal salt containing an Fe element, a second metal salt containing a Co element, and a complexing agent. PH adjustment step for producing an intermediate solution adjusted to have a pH of, and by adding dropwise a B-based reducing agent containing dimethylamine borane and NaBH 4 to the intermediate solution while stirring the intermediate solution, A reduction step of obtaining a powder made of an amorphous alloy and having soft magnetism.
詳しくは、ｐＨ調整工程において、原料となる金属塩、錯化剤をそれぞれ秤量し、蒸留水と共にビーカー等の耐薬品性容器に投入し、これを撹拌しながら溶解することで原料液を製造する。更に、Ｂ系還元剤を秤量し、蒸留水と共に別の耐薬品性容器に投入し、撹拌しながら溶解することで還元剤を製造する。合金の組成にＰも含ませたい場合には、原料液に対して、Ｐ系還元剤も投入する。ここで、金属塩、錯化剤、分散剤及びＰ系還元剤の秤量、並びにＢ系還元剤の秤量は、上述した粉末の組成を考慮して行われる。 Specifically, in the pH adjustment step, the raw material metal salt and the complexing agent are weighed, put into a chemical-resistant container such as a beaker with distilled water, and dissolved while stirring to produce a raw material solution. . Further, the B-type reducing agent is weighed, put into another chemical-resistant container together with distilled water, and dissolved with stirring to produce the reducing agent. When it is desired to include P in the alloy composition, a P-based reducing agent is also added to the raw material liquid. Here, the weighing of the metal salt, the complexing agent, the dispersant and the P-based reducing agent, and the weighing of the B-based reducing agent are performed in consideration of the above-described powder composition.
原料として使用可能な第１金属塩は、Ｆｅ元素を含有する塩化物、硫酸塩、硝酸塩、酢酸塩、しゅう酸塩、金属錯体などであり、原料として使用可能な第２金属塩は、Ｃｏ元素を含有する塩化物、硫酸塩、硝酸塩、酢酸塩、しゅう酸塩、金属錯体などである。 The first metal salt that can be used as a raw material is chloride, sulfate, nitrate, acetate, oxalate, metal complex, etc. containing Fe element, and the second metal salt that can be used as a raw material is Co element Chlorides, sulfates, nitrates, acetates, oxalates, metal complexes and the like containing
原料として使用可能な錯化剤としては、例えば、塩化アンモニウム、クエン酸三ナトリウム、クエン酸カリウム、クエン酸、酢酸ナトリウム、エチレングリコール、アンモニア水、ヒドラジンなどがある。 Examples of complexing agents that can be used as raw materials include ammonium chloride, trisodium citrate, potassium citrate, citric acid, sodium acetate, ethylene glycol, aqueous ammonia, and hydrazine.
原料として使用可能なＰ系還元剤としては、例えば、次亜リン酸ナトリウム、次亜リン酸、次亜リン酸アンモニウム、次亜リン酸カルシウム、亜リン酸などがある。 Examples of the P-based reducing agent that can be used as a raw material include sodium hypophosphite, hypophosphorous acid, ammonium hypophosphite, calcium hypophosphite, phosphorous acid, and the like.
本実施の形態におけるＢ系還元剤は、ジメチルアミンボランとＮａＢＨ４（水素化ホウ素ナトリウム）とからなる。ジメチルアミンボランのみを使用すると、Ｂが十分に合金相に含まれず、アモルファス相ができず、また、還元反応が起き難くなってしまう。逆に、ＮａＢＨ４のみを使用すると、還元反応が速すぎてＢの過剰含有が起きてしまうと共に、粒子の凝集が起こってしまう。粒子の凝集が起こってしまうと、アモルファスであっても軟磁性を有しなくなってしまう。従って、Ｂ系還元剤は、ジメチルアミンボランとＮａＢＨ４（水素化ホウ素ナトリウム）との両方を含んでいる必要がある。 The B-type reducing agent in the present embodiment is composed of dimethylamine borane and NaBH 4 (sodium borohydride). When only dimethylamine borane is used, B is not sufficiently contained in the alloy phase, an amorphous phase cannot be formed, and a reduction reaction is difficult to occur. On the other hand, when only NaBH 4 is used, the reduction reaction is too fast and B is excessively contained, and particles are aggregated. If the particles are aggregated, even if they are amorphous, they do not have soft magnetism. Therefore, the B-based reducing agent needs to contain both dimethylamine borane and NaBH 4 (sodium borohydride).
なお、本実施の形態の製造方法によると、ＰｔＣｌ４Ｎａなどのような析出核形成剤がなくとも小さな粒径の粒子を得ることができるため、原料液には、析出核形成剤を含ませる必要がない。析出核形成剤を用いることなく粒子を形成することができることから、中心近傍でさえもアモルファス相である粒子を得ることができる。 In addition, according to the manufacturing method of the present embodiment, particles having a small particle diameter can be obtained without a precipitation nucleation agent such as PtCl 4 Na. Therefore, the raw material liquid includes the precipitation nucleation agent. There is no need. Since particles can be formed without using a precipitation nucleation agent, particles that are in an amorphous phase can be obtained even near the center.
上述したようにして準備された原料液を耐薬品性容器内で撹拌しながらｐＨ調整剤を投入することで、原料液を還元反応の開始に最適なｐＨに調整する。このｐＨの調整された原料液を以下においては中間液という。 The raw material solution is adjusted to an optimum pH for the start of the reduction reaction by introducing the pH adjuster while stirring the raw material solution prepared as described above in a chemical resistant container. This raw material liquid whose pH has been adjusted is hereinafter referred to as an intermediate liquid.
ここで、所定のｐＨとは、例えば、還元工程における還元反応の開始に最適なｐＨである。後の還元工程においては、ｐＨが１１．０より高いと還元反応が遅くなり合金が析出しなくなってしまい、ｐＨが８．５より低いと還元反応が速くなりすぎて軟磁性が劣化してしまう。従って、所定のｐＨは、８．５〜１１．０であることが好ましい。特に、ｐＨが９．２〜９．８であると、最適な還元反応を生じさせることができる。 Here, the predetermined pH is, for example, the optimum pH for the start of the reduction reaction in the reduction step. In the subsequent reduction step, when the pH is higher than 11.0, the reduction reaction is delayed and the alloy is not precipitated. When the pH is lower than 8.5, the reduction reaction is too fast and the soft magnetism is deteriorated. . Accordingly, the predetermined pH is preferably 8.5 to 11.0. In particular, when the pH is 9.2 to 9.8, an optimal reduction reaction can be caused.
ｐＨ調整剤として使用可能な物質としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア水などがある。 Examples of substances that can be used as a pH adjuster include sodium hydroxide, potassium hydroxide, and aqueous ammonia.
還元工程においては、中間液を撹拌しながら、その中に用意しておいたＢ系還元剤を滴下する。この還元工程によれば、中間液に滴下したＢ系還元剤の作用により、ｐＨ調整後液中に存在する金属イオン（ＣｏイオンとＦｅイオン）が還元され、同時にＢイオン（原料液にＰ系還元剤が含まれている場合にはＰイオンも）が還元されることによって、これらの元素が析出する。その結果、Ｃｏ元素、Ｆｅ元素、Ｂ元素（原料液によってはＰ元素も）を主たる構成元素とするアモルファス合金からなると共に軟磁性を有する粉末が生成される。 In the reduction step, the B-type reducing agent prepared therein is dropped while stirring the intermediate solution. According to this reduction step, the metal ions (Co ions and Fe ions) present in the solution after pH adjustment are reduced by the action of the B-type reducing agent dripped into the intermediate solution, and at the same time, B ions (P-type into the raw material solution). In the case where a reducing agent is contained, these elements are precipitated by reducing P ions). As a result, a powder having soft magnetism and an amorphous alloy containing Co element, Fe element, and B element (also P element depending on the raw material liquid) as main constituent elements is generated.
更に、この還元工程において、磁場を印加しつつ、中間液にＢ系還元剤を滴下すると、上述したようにして析出した粉末（球状粒子）が印加されている磁場の作用によって引き寄せられ、磁場方向に配列しながら互いに結着し、球状粒子が棒状に結合されてなる球状粒子結合体が形成される。 Further, in this reduction step, if a B-based reducing agent is dropped into the intermediate liquid while applying a magnetic field, the powder (spherical particles) deposited as described above is attracted by the action of the applied magnetic field, and the direction of the magnetic field The particles are bound to each other while being arranged in a spherical shape to form a spherical particle bonded body in which spherical particles are bonded in a rod shape.
詳しくは、本実施の形態による球状粒子結合体の製造方法は、Ｆｅ元素を含有する第１金属塩と、Ｃｏ元素を含有する第２金属塩と、錯化剤とを含む原料液に対して、ｐＨ調整剤を加えて、所定のｐＨを有するように調整された中間液を生成するｐＨ調整工程と、その中間液を撹拌しながら、永久磁石又は電磁石を用いて７．９ｋＡ／Ｍ以上３９５ｋＡ／ｍ以下の磁場を印加しつつ、当該中間液に対してジメチルアミンボランとＮａＢＨ４を含むＢ系還元剤を滴下することにより、アモルファス合金からなり軟磁性を有する球状粒子が棒状に結合されてなる球状粒子結合体を得る還元工程とを備えている。 Specifically, the method for producing a spherical particle bonded body according to the present embodiment is based on a raw material liquid containing a first metal salt containing an Fe element, a second metal salt containing a Co element, and a complexing agent. A pH adjusting step of adding an pH adjusting agent to produce an intermediate liquid adjusted to have a predetermined pH, and using a permanent magnet or an electromagnet while stirring the intermediate liquid, 7.9 kA / M or more and 395 kA While applying a magnetic field of / m or less, by adding a B-based reducing agent containing dimethylamine borane and NaBH 4 to the intermediate liquid, spherical particles made of an amorphous alloy and having soft magnetism are bound in a rod shape. And a reduction step for obtaining a spherical particle combination.
この製造方法によれば、上述した球状粒子結合体であって、短軸径が０．０５μｍ以上２．０μｍ以下であり且つ長軸径が０．３μｍ以上２０．０μｍ以下の球状粒子結合体を得ることができる。かかる球状粒子結合体は、アモルファス相からなり、軟磁性を有している。 According to this production method, the above-described spherical particle composite body, which has a short axis diameter of 0.05 μm or more and 2.0 μm or less and a long axis diameter of 0.3 μm or more and 20.0 μm or less, is obtained. Can be obtained. Such a spherical particle combination is composed of an amorphous phase and has soft magnetism.
このようにして製造された粉末や球状粒子結合体は、特許文献１のように、結合材と共に圧粉磁心や磁性シートを製造するために用いられてもよい。圧粉磁心の製造に用いられる結合材としては熱硬化性樹脂が効果的であり、その樹脂の種類は圧粉磁心の用途や必要な耐熱性によって適宜選択することができる。圧粉磁心製造に好適な結合材としては、例えば、エポキシ樹脂、フェノール樹脂、シリコーン樹脂、ポリアミドイミド樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、キシレン樹脂などがある。一方、磁性シートの製造に好適な結合材としては、例えば、ポリエステル系樹脂、ポリ塩化ビニル系樹脂、ポリビニルプチラール樹脂、ポリウレタン樹脂、セルロール系樹脂、ニトリル−ブタジエン系ゴム、スチレン−ブタジエン系ゴム、スチレン−ブタジエン系ゴム等の熱可塑性樹脂、若しくは、エポキシ樹脂、フェノール樹脂、アミド系樹脂、イミド系樹脂等の熱硬化性樹脂等がある。
The powder and spherical particle bonded body manufactured in this way may be used for manufacturing a dust core and a magnetic sheet together with a binder as in
更に、上述した粉末や球状粒子結合体は、磁性ペースト又は磁性塗料（以下、単に「磁性ペースト」という）の形態をとることもできる。特に、球状粒子結合体は、０．１μｍ以下の平均粒径を有する強磁性微粒子と混合することで、混合粉末とし、それを溶剤に分散させて磁性ペーストを構成することとしてもよい。特に、磁性ペーストにおける混合粉末の充填率を２０〜６５％とし、溶剤の粘度を１〜３００Ｐａ・ｓとすると、球状粒子結合体と強磁性微粒子とが溶剤内で移動しやすいことから、磁場を印加しつつ磁性ペーストを固化させた際に、球状粒子結合体の隙間に強磁性微粒子を埋め込むことができ、固化した磁性ペーストの透磁率の向上を図ることができる。 Further, the above-described powder or spherical particle combination may take the form of a magnetic paste or a magnetic paint (hereinafter simply referred to as “magnetic paste”). In particular, the spherical particle combination may be mixed with ferromagnetic fine particles having an average particle size of 0.1 μm or less to form a mixed powder, which is dispersed in a solvent to constitute a magnetic paste. In particular, when the filling ratio of the mixed powder in the magnetic paste is 20 to 65% and the viscosity of the solvent is 1 to 300 Pa · s, the spherical particle combination and the ferromagnetic fine particles easily move in the solvent. When the magnetic paste is solidified while being applied, ferromagnetic fine particles can be embedded in the gaps between the spherical particle combinations, and the magnetic permeability of the solidified magnetic paste can be improved.
詳しくは、磁場を印加すると、溶剤内において、球状粒子結合体が磁場に応じて配向されることになるが、この際、磁場が棒状の球状粒子結合体を飽和させる程度に強いと、球状粒子結合体同士の隙間には非常に強い磁場が局所的に発生することから、強磁性微粒子はそれらの隙間に集まってくる。即ち、配向された球状粒子結合体同士の隙間に強磁性微粒子が埋め込まれる。 Specifically, when a magnetic field is applied, the spherical particle combination is oriented in accordance with the magnetic field in the solvent. If the magnetic field is strong enough to saturate the rod-shaped spherical particle combination, Since a very strong magnetic field is locally generated in the gap between the coupled bodies, the ferromagnetic fine particles gather in the gap. That is, the ferromagnetic fine particles are embedded in the gaps between the aligned spherical particle combinations.
かかる配向と埋め込みとを適切に行うためには、溶剤の粘度が重要な要素の一つとなる。粘度が３００Ｐａ・ｓより高いと、強磁性微粒子が磁場中で動かなくなり配列しにくくなってしまう。一方、粘度が１Ｐａ・ｓよりも低いと、強磁性微粒子が磁場に引き付けられて端部に凝集してしまい、球状粒子結合体同士の隙間に適切に埋め込むことができなくなってしまう。従って、溶剤の粘度は、１〜３００Ｐａ・ｓであることが好ましい。 In order to appropriately perform such orientation and embedding, the viscosity of the solvent is one of the important factors. If the viscosity is higher than 300 Pa · s, the ferromagnetic fine particles do not move in the magnetic field and are difficult to arrange. On the other hand, if the viscosity is lower than 1 Pa · s, the ferromagnetic fine particles are attracted to the magnetic field and aggregate at the end, and cannot be properly embedded in the gap between the spherical particle combinations. Therefore, the viscosity of the solvent is preferably 1 to 300 Pa · s.
溶剤としては、例えば、エポキシ樹脂のような有機溶媒であってもよいし、半田クリームのようなものであってもよい。特に、有機溶媒を溶剤として用いる場合には、溶剤の粘度は、１〜３０Ｐａ・ｓであることが好ましい。 As the solvent, for example, an organic solvent such as an epoxy resin or a solder cream may be used. In particular, when an organic solvent is used as the solvent, the viscosity of the solvent is preferably 1 to 30 Pa · s.
更に、配向された球状粒子結合体同士の隙間に強磁性微粒子を適切に埋め込むためには、強磁性微粒子は、球状粒子結合体を構成する一次粒子の平均粒径の１／１０以下の平均粒径を有していることが好ましい。但し、強磁性微粒子が３ｎｍより小さいと、超常磁性がおきてしまうおそれがあるので、強磁性微粒子は、３ｎｍ以上の平均粒径を有していることが好ましい。強磁性微粒子として使用可能な材料は、例えば、ＮｉＺｎフェライト、ＭｎＺｎフェライト、又は、Ｆｅ，Ｎｉ，Ｃｏからなる群から選ばれる一種以上の軟磁性合金などがある。 Furthermore, in order to appropriately embed the ferromagnetic fine particles in the gaps between the aligned spherical particle conjugates, the ferromagnetic fine particles have an average particle size of 1/10 or less of the average particle size of the primary particles constituting the spherical particle conjugate. It preferably has a diameter. However, if the ferromagnetic fine particles are smaller than 3 nm, superparamagnetism may occur. Therefore, the ferromagnetic fine particles preferably have an average particle diameter of 3 nm or more. Examples of materials that can be used as the ferromagnetic fine particles include NiZn ferrite, MnZn ferrite, or one or more soft magnetic alloys selected from the group consisting of Fe, Ni, and Co.
かかる磁性ペーストには、様々な利用方法がある。 There are various methods of using such magnetic paste.
例えば、デジタル機器の高周波回路においてはインダクタの矮小化が重要である。そのため、金属薄膜、フェライト薄膜、精密加工フェライトなどが試みられているが、生産性、再現性、加工精度、透磁率などの点で十分な性能に達していない。これに対して、上述した磁性ペーストは、形状の自由度、使用量の制御のし易さ、高周波透磁率、絶縁性、閉磁路形成などの点で優れており、実用性が高い。例えば、巻き線コイルのような対象物を磁性ペーストに浸漬させた状態又はシート状の基板のような対象物上に磁性ペーストを塗布した状態で、磁場を印加しつつ、磁性ペーストを固化させることにより、磁性ペーストに含まれる強磁性微粒子を球状粒子結合体間に配置させ、高い透磁率を有する磁性材料を構成することができる。具体的には、巻き線コイルを磁性ペーストに浸漬させた状態で磁性ペーストを固化させることにより巻き線型のインダクタを構成することが可能である。また、上述した磁性ペーストは、スクリーン印刷などの技術を利用することができることから、平面型のインダクタにも適用可能である。 For example, miniaturization of inductors is important in high frequency circuits of digital equipment. For this reason, metal thin films, ferrite thin films, precision-processed ferrites, and the like have been tried, but have not reached sufficient performance in terms of productivity, reproducibility, processing accuracy, magnetic permeability, and the like. On the other hand, the magnetic paste described above is excellent in terms of flexibility in shape, ease of control of the amount used, high-frequency magnetic permeability, insulation, closed magnetic circuit formation, and the like, and is highly practical. For example, solidifying a magnetic paste while applying a magnetic field in a state where an object such as a wound coil is immersed in a magnetic paste or a magnetic paste is applied on an object such as a sheet-like substrate Thus, the ferromagnetic fine particles contained in the magnetic paste can be arranged between the spherical particle bonded bodies to constitute a magnetic material having a high magnetic permeability. Specifically, a wound inductor can be configured by solidifying the magnetic paste in a state where the wound coil is immersed in the magnetic paste. Further, the magnetic paste described above can be applied to a planar inductor because a technique such as screen printing can be used.
更に、デジタル化、高周波化に伴って、電磁ノイズ吸収体のスケールダウンが要求されている。例えば、従来、粉末を樹脂に埋め込んだシート状の電磁ノイズ吸収体が実用化されているが、上述した磁性ペーストは厚さと形状とが自由であり、一種類の磁性ペーストで様々な形状、サイズに対応できる利点があり、シート状材料では不可能なスケールダウンも容易である。例えば、シート状の基板のような対象物上に上述した磁性ペーストを５μｍ〜５００μｍの厚さを有するように塗布した状態で、その磁性ペーストを固化させることも可能である。 Furthermore, with digitalization and high frequency, the electromagnetic noise absorber is required to be scaled down. For example, in the past, sheet-like electromagnetic noise absorbers in which powder is embedded in resin have been put into practical use, but the above-mentioned magnetic paste is free in thickness and shape, and various shapes and sizes can be achieved with one type of magnetic paste. It is easy to scale down, which is not possible with sheet-like materials. For example, the magnetic paste can be solidified in a state where the above-described magnetic paste is applied to an object such as a sheet-like substrate so as to have a thickness of 5 μm to 500 μm.
硫酸鉄と硫酸コバルトとを５対９５となるように秤量し、更に、錯化剤として塩化アンモニウムとクエン酸とを夫々５重量％含む水溶液（原料液）を作成した。 Iron sulfate and cobalt sulfate were weighed so as to have a ratio of 5 to 95, and an aqueous solution (raw material solution) containing 5% by weight of ammonium chloride and citric acid as complexing agents was prepared.
この原料液を室温において撹拌機により回転数：１６０〜３００ｒｐｍで撹拌しながら、ｐＨ調整剤として３０％水酸化ナトリウム水溶液を滴下することで、ｐＨ＝９．５となるように調整し、中間液を得た。 While stirring this raw material liquid at room temperature with a stirrer at a rotation speed of 160 to 300 rpm, a 30% aqueous sodium hydroxide solution was added dropwise as a pH adjusting agent to adjust to pH = 9.5, and an intermediate liquid Got.
次いで、反応浴（ビーカー）のそこに永久磁石を配置して反応浴内に最大で２７６．５ｋＡ／ｍ（３．５ｋＯｅ）の磁場を印加しつつ、撹拌機により回転数：１５０ｒｐｍで撹拌しているｐＨ調整後液に対して、滴下装置を用いて滴下速度：２００ｍｌ／ｈｒでジメチルアミンボランとＮａＢＨ４からなるＢ系還元液の滴下を行った。 Next, a permanent magnet was placed in the reaction bath (beaker), and a magnetic field of 276.5 kA / m (3.5 kOe) at maximum was applied to the reaction bath, and the mixture was stirred at a rotation speed of 150 rpm by a stirrer. The B-based reducing solution composed of dimethylamine borane and NaBH 4 was dropped at a dropping rate of 200 ml / hr using a dropping device.
還元反応の終了後、析出物を水で洗浄し、更に、薄い酸で沈殿物（付着物）を溶解除去した後、不活性雰囲気中で乾燥させた。 After completion of the reduction reaction, the precipitate was washed with water, and further the precipitate (adhered matter) was dissolved and removed with a thin acid, followed by drying in an inert atmosphere.
このようにして得られた析出物は、直径０．２〜０．４μｍの一次粒子が長さ２〜１５μｍの棒状に結合されてなる球状粒子結合体であり、（Ｃｏ９５Ｆｅ５）８４Ｂ１６で示される組成を有するアモルファス合金からなり、軟磁性を有するものであった。また、比透磁率は６０であり、保磁力Ｈｃは１．８３ｋＡ／ｍ（２３Ｏｅ）であった。 The precipitate thus obtained is a spherical particle bonded body in which primary particles having a diameter of 0.2 to 0.4 μm are bonded in a rod shape having a length of 2 to 15 μm, and (Co 95 Fe 5 ) 84 B It was made of an amorphous alloy having a composition indicated by 16 , and had soft magnetism. The relative permeability was 60, and the coercive force Hc was 1.83 kA / m (23 Oe).
更に、Ｃｏ−Ｂや、Ｆｅ−Ｂ−Ｐ、（Ｃｏ５０Ｆｅ５０）Ｂ及び（Ｃｏ９０Ｆｅ１０）Ｂも作成し、それらを熱処理した際の保磁力Ｈｃの温度依存性を測定した。ここで、Ｃｏ−Ｂや結晶相を有するものである。また、測定にあたっては、各温度で３０分ずつ真空中で熱処理を行った。測定結果を図１に示す。 Furthermore, Co—B, Fe—BP, (Co 50 Fe 50 ) B and (Co 90 Fe 10 ) B were also prepared, and the temperature dependence of the coercive force Hc when these were heat-treated was measured. Here, it has Co-B or a crystal phase. In the measurement, heat treatment was performed in vacuum for 30 minutes at each temperature. The measurement results are shown in FIG.
図１を参照すると、（Ｃｏ９５Ｆｅ５）Ｂは最も低い保磁力Ｈｃを示し、結晶化温度付近まで安定した軟磁性を有していることが理解される。 Referring to FIG. 1, it is understood that (Co 95 Fe 5 ) B has the lowest coercive force Hc and has a soft magnetism that is stable up to the vicinity of the crystallization temperature.
Claims (6)
前記中間液を撹拌しながら当該中間液に対してジメチルアミンボランとＮａＢＨ４を含むＢ系還元剤を滴下することにより、アモルファス合金からなり軟磁性を有する粉末を得る還元工程と
を備える粉末の製造方法であって、
前記ｐＨ調整工程における前記所定のｐＨは、８．５〜１１．０である
製造方法。 A pH adjuster is added to the raw material liquid containing the first metal salt containing Fe element, the second metal salt containing Co element, and the complexing agent, and adjusted to have a predetermined pH. A pH adjusting step for producing an intermediate solution;
Production of a powder comprising a reduction step of obtaining a soft magnetic powder made of an amorphous alloy by dropping a B-based reducing agent containing dimethylamine borane and NaBH 4 into the intermediate solution while stirring the intermediate solution A method,
The manufacturing method whose said predetermined pH in the said pH adjustment process is 8.5-11.0.
前記中間液を撹拌しながら、永久磁石又は電磁石を用いて７．９ｋＡ／ｍ以上３９５ｋＡ／ｍ以下の磁場を印加しつつ、当該中間液に対してジメチルアミンボランとＮａＢＨ４を含むＢ系還元剤を滴下することにより、アモルファス合金からなり軟磁性を有する球状粒子が棒状に結合されてなる球状粒子結合体を得る還元工程と
を備える球状粒子結合体の製造方法であって、
前記ｐＨ調整工程における前記所定のｐＨは、８．５〜１１．０である
製造方法。 A pH adjuster is added to the raw material liquid containing the first metal salt containing Fe element, the second metal salt containing Co element, and the complexing agent, and adjusted to have a predetermined pH. A pH adjusting step for producing an intermediate solution;
A B-type reducing agent containing dimethylamine borane and NaBH 4 with respect to the intermediate solution while applying a magnetic field of 7.9 kA / m to 395 kA / m using a permanent magnet or an electromagnet while stirring the intermediate solution. And a reduction step of obtaining a spherical particle bonded body in which spherical particles made of an amorphous alloy and having soft magnetism are bonded in a rod shape by dropping
The manufacturing method whose said predetermined pH in the said pH adjustment process is 8.5-11.0.
前記原料液は、Ｐ系還元剤を更に含むものである
製造方法。 A manufacturing method according to claim 1 or claim 2,
The said raw material liquid is a manufacturing method which further contains a P-type reducing agent.
前記Ｐ系還元剤は、次亜リン酸ナトリウムからなる
製造方法。 It is a manufacturing method of Claim 3, Comprising:
The said P type reducing agent is a manufacturing method which consists of sodium hypophosphite.
前記所定のｐＨは、９．２〜９．８である
製造方法。 A manufacturing method according to any one of claims 1 to 4,
The manufacturing method whose said predetermined pH is 9.2-9.8.
前記原料液は、析出核形成剤を含まない
製造方法。 A manufacturing method according to any one of claims 1 to 5,
The said raw material liquid is a manufacturing method which does not contain a precipitation nucleation agent.
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