WO2018143472A1 - Soft magnetic flat powder - Google Patents

Soft magnetic flat powder Download PDF

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Publication number
WO2018143472A1
WO2018143472A1 PCT/JP2018/003983 JP2018003983W WO2018143472A1 WO 2018143472 A1 WO2018143472 A1 WO 2018143472A1 JP 2018003983 W JP2018003983 W JP 2018003983W WO 2018143472 A1 WO2018143472 A1 WO 2018143472A1
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WO
WIPO (PCT)
Prior art keywords
soft magnetic
powder
flat powder
magnetic flat
less
Prior art date
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PCT/JP2018/003983
Other languages
French (fr)
Japanese (ja)
Inventor
滉大 三浦
澤田　俊之
亮介 越智
Original Assignee
山陽特殊製鋼株式会社
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Application filed by 山陽特殊製鋼株式会社 filed Critical 山陽特殊製鋼株式会社
Priority to KR1020197020884A priority Critical patent/KR102393236B1/en
Priority to CN201880009552.5A priority patent/CN110234449A/en
Publication of WO2018143472A1 publication Critical patent/WO2018143472A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/35—Iron

Definitions

  • the present invention relates to a soft magnetic flat powder, for example, a soft magnetic flat powder for an electromagnetic wave absorber used in various electronic devices.
  • soft magnetic flat powder does not need to be sintered and solidified like soft magnetic ferrite, but is mixed with resin and molded, so it is flexible and has a high degree of freedom in the mounting part. It is widely used for small electronic devices.
  • This soft magnetic flat powder is produced by a method of flattening metal powder using an attritor device.
  • an organic solvent such as toluene, a metal powder, and a grinding medium (steel ball) are charged into an attritor apparatus, and are pulverized and flattened by rotating blades inside the apparatus.
  • a brittle material such as a soft magnetic alloy Fe—Si—Al alloy is mainly used.
  • Patent Document 1 discloses an Fe—Si—Al alloy manufactured using the above-described method.
  • Patent Document 1 is characterized in that Fe has a high concentration of 84% to 96%, and elements of Ti, V, Cr, Mn, Co, Ni, and Cu are substituted for Fe.
  • Patent Document 2 Si: 9.0% to 12%, Al: 1.0% to 5.0%, Cr: 1.0% to By adding 5.0%, unprecedented high specific resistance and low coercive force are realized.
  • the soft magnetic flat powder is produced by mixing and pulverizing a metal powder and a pulverizing medium in water or an organic solvent by dry or wet processing. At that time, since the metal powder is processed in water or an organic solvent for a long time, the metal powder tends to be oxidized and the magnetic properties tend to deteriorate. Therefore, it is required to prevent the metal powder from being oxidized and flattened.
  • Patent Document 1 compositional deviation due to oxidation during flattening and heat treatment is described, but no clear countermeasure has been taken, and the intention of examining the components is only with respect to magnetic properties. . Further, Fe has a high concentration of 84% to 96%, and although the oxidation resistance and corrosion resistance are not mentioned, it is presumed that these characteristics are low.
  • Patent Document 2 it is stated that the corrosion resistance is improved by containing Al and Cr, but Al is a low value of 5.0% or less. Also, no consideration is given to the deterioration of magnetic properties due to oxidation that occurs during flattening.
  • the present invention includes the following soft magnetic flat powder and magnetic sheet.
  • a soft magnetic flat powder comprising a plurality of soft magnetic flat particles, wherein each of the plurality of soft magnetic flat particles is in mass%, Fe: 78% to 83%, Si: 13% or less. (0 is not included), Al: more than 5.0% and 13% or less, at least one of Cr, Ni, Mo, Cu, and Ti: including 1.0% to 5.0% in total, with the balance being Fe
  • a soft magnetic flat powder which is an alloy particle comprising inevitable impurities.
  • the coercive force measured by applying a magnetic field in the longitudinal direction of the soft magnetic flat particles is 230 A / m or less, and the saturation magnetic flux density of the soft magnetic flat powder is 0.6 T or more and 1.5 T or less.
  • the present invention provides a soft magnetic flat powder that can prevent oxidation during flattening processing of a metal powder and can realize a low coercive force.
  • the soft magnetic flat powder of the present invention is an aggregate of a plurality of soft magnetic flat particles, and each soft magnetic flat particle is in mass%, Fe: 78% to 83%, Si: 13% or less (0 is Not including), Al: more than 5.0% and not more than 13%, at least one of Cr, Ni, Mo, Cu, Ti: including 1.0% to 5.0% in total, the balance being Fe and inevitable Alloy particles made of impurities.
  • the reason for limiting the composition as described above will be described.
  • Fe is an essential element for imparting ferromagnetism to the soft magnetic flat powder and for imparting a high saturation magnetic flux density to the soft magnetic flat powder.
  • the Fe content exceeds 83%, the oxidation resistance and corrosion resistance of the soft magnetic flat powder are reduced.
  • the Fe content is less than 78%, the saturation magnetic flux density of the soft magnetic flat powder is greatly reduced. Therefore, the Fe content is 78% or more and 83% or less.
  • the Fe content is preferably 79% or more and 82% or less, more preferably more than 79% and 81% or less.
  • Si 13% or less (excluding 0)] Si is an essential element for reducing the magnetocrystalline anisotropy constant of the soft magnetic flat powder and reducing the coercive force of the soft magnetic flat powder.
  • the Si content exceeds 13%, the saturation magnetic flux density of the soft magnetic flat powder increases. Decrease. Therefore, the Si content is more than 0% and not more than 13%.
  • the Si content is preferably 3.0% or more and 10% or less, and more preferably 5.0% or more and 9.5% or less.
  • Al is an essential element for reducing the magnetocrystalline anisotropy constant and coercive force of the soft magnetic flat powder, and improving the oxidation resistance and corrosion resistance of the soft magnetic flat powder.
  • the addition amount of Al is 5.0% or less, the corrosion resistance of the soft magnetic flat powder decreases, and the crystal magnetic anisotropy constant and coercive force of the soft magnetic flat powder tend to increase.
  • the Al content exceeds 13%, the saturation magnetic flux density of the soft magnetic flat powder is greatly reduced. Therefore, the Al content is more than 5.0% and 13% or less.
  • the content of Al is preferably more than 5.0% and 10% or less, and more preferably 6.0% or more and 9.0% or less.
  • At least one of Cr, Ni, Mo, Cu, and Ti is an essential element for improving the oxidation resistance and corrosion resistance of the soft magnetic flat powder.
  • Total 1.0% or more and 5.0% or less means that when the soft magnetic flat particles contain one kind of Cr, Ni, Mo, Cu, and Ti, the content of the one kind of element Is 1.0% or more and 5.0% or less, and when the soft magnetic flat particles include two or more of Cr, Ni, Mo, Cu, and Ti, the two or more of the elements It means that the total content is 1.0% or more and 5.0% or less.
  • the total content of at least one of Cr, Ni, Mo, Cu, and Ti is less than 1.0%, the oxidation resistance and corrosion resistance of the soft magnetic flat powder are not improved, and the total content is 5.0. If it exceeds 50%, the coercive force of the soft magnetic flat powder may be greatly increased due to the influence of precipitates and the like. Therefore, the total content of at least one of Cr, Ni, Mo, Cu, and Ti is 1.0% or more and 5.0% or less.
  • the total content of at least one of Cr, Ni, Mo, Cu and Ti is preferably 1.5% or more and 4.5% or less, more preferably 2.0% or more and 4.0% or less. .
  • the coercive force measured by applying a magnetic field (143.6 kA / m) in the longitudinal direction of the soft magnetic flat particles is preferably 230 A / m or less.
  • the frequency band in which the magnetic sheet comprising the soft magnetic flat powder of the present invention is used is preferably 1 to 15 MHz.
  • the coercive force is 230 A / m or less.
  • the coercive force is more preferably 190 A / m or less, and still more preferably 120 A / m or less.
  • the lower limit value of the coercive force is not particularly limited, but is, for example, 200 A / m.
  • the coercive force is calculated based on a value when a soft container is filled with soft magnetic flat powder and magnetized in the diameter direction of the container. Since the longitudinal direction and thickness direction of the soft magnetic flat particles filled in the container correspond to the diameter direction and height direction of the container, respectively, the value when magnetized in the diameter direction of the container is the coercive force in the longitudinal direction. The value when magnetized in the height direction of the container is the coercive force in the thickness direction.
  • the saturation magnetic flux density of the soft magnetic flat powder of the present invention is preferably 0.6 T or more and 1.5 T or less, more preferably 0.8 T or more and 1.5 T or less.
  • the saturation magnetic flux density is measured with an applied magnetic field of 1.2 ⁇ 10 3 kA / m using a vibrating sample magnetometer (VSM).
  • VSM vibrating sample magnetometer
  • the method for producing the soft magnetic flat powder of the present invention can be performed by a conventionally proposed method. Alloy powder as a raw material is produced by various atomizing methods, and this is flattened in a dry or wet manner by a ball mill or an attritor apparatus. Thereafter, the coercive force can be reduced by heat treatment at 500 ° C. or higher.
  • the method for producing the soft magnetic flat powder of the present invention is specifically as follows.
  • the soft magnetic flat powder of the present invention can be produced by a method including a raw material powder preparation step, a flat processing step, and a heat treatment step.
  • the soft magnetic alloy powder used as the raw material powder is an aggregate of a plurality of soft magnetic alloy particles.
  • Each soft magnetic alloy particle is in mass%, Fe: 78% or more and 83% or less, Si: 13% or less. (0 is not included), Al: more than 5.0% and 13% or less, at least one of Cr, Ni, Mo, Cu, and Ti: including 1.0% to 5.0% in total, with the balance being Fe And alloy particles composed of inevitable impurities.
  • the reason for limiting the composition and the preferred content of each element are as described above.
  • the raw material powder can be produced by, for example, various atomizing methods such as a gas atomizing method, a water atomizing method, a disk atomizing method, or a pulverizing method performed after alloying by melting. Since it is preferable that the amount of oxygen contained in the raw material powder is small, the raw material powder is preferably produced by a gas atomizing method, more preferably produced by a gas atomizing method using an inert gas. Since the powder produced by the atomization method has a nearly spherical shape, flattening is more likely to proceed than the powder produced by the pulverization method using attritor processing or the like. Since the powder produced by the pulverization method has a particle size smaller than that of the atomized powder, generation of protrusions on the magnetic sheet surface tends to be suppressed.
  • various atomizing methods such as a gas atomizing method, a water atomizing method, a disk atomizing method, or a pulverizing method performed after alloying by
  • the particle size of the raw material powder is not particularly limited, but according to the purpose of adjusting the average particle size after flattening, the purpose of removing the powder containing a large amount of oxygen, and other manufacturing purposes, the particle size of the raw material powder is determined by classification. You may adjust to a desired range.
  • the raw material powder is flattened. Thereby, a flat powder is obtained.
  • the flat processing method is not particularly limited, and the flat processing of the raw material powder can be performed using, for example, an attritor, a ball mill, a vibration mill, or the like. Among them, it is preferable to use an attritor that is relatively excellent in flat processing ability.
  • an attritor that is relatively excellent in flat processing ability.
  • an inert gas In the case of performing flattening by wet, it is preferable to use an organic solvent.
  • the type of organic solvent used in wet flattening is not particularly limited.
  • the addition amount of the organic solvent is preferably 100 parts by mass or more, and more preferably 200 parts by mass or more with respect to 100 parts by mass of the raw material powder.
  • the upper limit of the addition amount of the organic solvent is not particularly limited, and can be appropriately adjusted according to the balance between the required size and shape of the flat powder and productivity.
  • the organic solvent may be a water-containing organic solvent, but in order to reduce the oxygen content, the water concentration in the organic solvent is preferably 0.002 parts by mass or less with respect to 100 parts by mass of the organic solvent.
  • a flattening aid may be used together with the organic solvent, the addition amount of the flattening aid is preferably 5 parts by mass or less with respect to 100 parts by mass of the raw material powder in order to suppress oxidation.
  • the heat treatment apparatus is not particularly limited as long as a desired heat treatment temperature can be realized.
  • the heat treatment temperature is preferably 500 to 900 ° C, more preferably 600 to 850 ° C. By performing heat treatment at such a temperature, the coercive force can be reduced.
  • the heat treatment time is not particularly limited, and can be appropriately adjusted according to the processing amount, productivity, and the like. However, if the heat treatment time is increased, the productivity is lowered, so the heat treatment time is preferably within 8 hours.
  • the flat powder In the heat treatment process, when the heat treatment atmosphere is air, the flat powder is oxidized. Therefore, in order to suppress oxidation of the flat powder, it is preferable to heat the flat powder in a vacuum or in an inert gas (for example, argon or nitrogen).
  • an inert gas for example, argon or nitrogen
  • the use of the surface-treated soft magnetic flat powder may be suitable, and in the method for producing the soft magnetic flat powder, during the heat treatment step Alternatively, the surface treatment step may be performed as necessary before and after the heat treatment step.
  • heat treatment may be performed in an atmosphere containing a small amount of active gas.
  • the magnetic sheet of the present invention contains the soft magnetic flat powder of the present invention.
  • the magnetic sheet of the present invention has a structure in which, for example, the soft magnetic flat powder of the present invention is dispersed in a matrix material such as rubber, elastomer, or resin.
  • the matrix material can be selected as appropriate, and one kind of matrix material may be used, or two or more kinds of matrix materials may be used.
  • the amount of the soft magnetic flat powder contained in the magnetic sheet can be appropriately adjusted in consideration of the required permeability characteristics and the like.
  • the amount of the soft magnetic flat powder contained in the magnetic sheet (volume filling ratio of the soft magnetic flat powder in the magnetic sheet) is preferably 20 to 60% by volume, for example 20 to 40% by volume or 40 to 60% by volume.
  • the production of the magnetic sheet comprising the soft magnetic flat powder can be performed according to a conventionally proposed method using the soft magnetic flat powder.
  • soft magnetic flat powder is mixed with a solution of chlorinated polyethylene in toluene, applied to a synthetic resin substrate such as polyester resin, and dried, then compressed with various presses, rolls, etc. Can be manufactured.
  • Alloy powders having the compositions shown in Tables 1 and 2 were prepared by gas atomization, classified to 150 ⁇ m or less, and used as raw material powders.
  • the gas atomization method was carried out by using an alumina crucible for melting, discharging molten alloy from a nozzle having a diameter of 5 mm under the crucible, and spraying this with high-pressure argon.
  • the raw material powder was flattened by an attritor device.
  • the attritor was charged with a 4.8 mm diameter ball made by SUJ2 together with the raw material powder and industrial ethanol in a stirring vessel, and the blade rotation speed was 350 rpm.
  • the obtained flat powder was heat-treated in an Ar atmosphere in order to remove distortion introduced during the flat processing.
  • the heat treatment temperature was 500 to 900 ° C. in consideration of the sintering temperature of the powder, and the heat treatment time was 3 hours.
  • the coercive force (Hc) and saturation magnetic flux density (Bs) of the flat powder subjected to heat treatment were measured.
  • the coercive force was measured by applying a magnetic field (143.6 kA / m) in the longitudinal direction of flat particles using a COERCIMETER HC801 manufactured by Qumano. Specifically, the calculation was performed based on the value when a resin container having a diameter of 6 mm and a height of 8 mm was filled with flat powder and magnetized in the diameter direction of the container.
  • the value when magnetized in the diameter direction of the container becomes the longitudinal coercive force
  • the container The value when magnetized in the height direction is the coercive force in the thickness direction.
  • the saturation magnetic flux density was measured with an applied magnetic field of 1.2 ⁇ 10 3 kA / m using a vibrating sample magnetometer (VSM).
  • the corrosion resistance of the flat powder was evaluated.
  • the flat powder was immersed in 25% 20% salt water for 100 hours, and the degree of rusting after immersion was evaluated according to the following criteria.
  • No. 1 to 31 are examples of the present invention. 32 to 43 are comparative examples.
  • Comparative Example No. 32 has a high total coercive force and a low saturation magnetic flux density because the total amount of elements other than Fe, Si and Al (Cr content) is high. Comparative Example No. Since No. 33 has a low Fe content and a high total amount of elements other than Fe, Si, and Al (Ni content), the coercive force is high. Comparative Example No. No. 34 has a high total amount of elements other than Fe, Si, and Al (Mo content), and thus has a high coercive force and inferior corrosion resistance. Comparative Example No. 35 is high in coercive force and poor in corrosion resistance because the total amount of elements other than Fe, Si, and Al (Cu content) is high. Comparative Example No. No. 36 has a low Fe content and a high total amount (Ti content) of elements other than Fe, Si, and Al, and thus has a high coercive force, a low saturation magnetic flux density, and poor corrosion resistance.
  • Comparative Example No. Nos. 37 to 39 each have a low Fe content and a high total amount of elements other than Fe, Si, and Al, so that the coercive force is high and the corrosion resistance is slightly inferior.
  • Comparative Example No. No. 40 has a high coercive force and poor corrosion resistance because the total amount of elements other than Fe, Si, and Al is high.
  • Comparative Example No. No. 41 has a high Si content and a low Al content, and thus has a high coercive force, a low saturation magnetic flux density, and poor corrosion resistance.
  • Comparative Example No. No. 42 has a high Al content and therefore has a high coercive force and a low saturation magnetic flux density. Comparative Example No. Since No. 43 has a low Al content, it has a high coercive force and poor corrosion resistance.
  • the present invention example No. Nos. 1 to 31 all satisfy the conditions of the present invention, and it can be seen that the coercive force, saturation magnetic flux density and corrosion resistance measured by applying a magnetic field in the longitudinal direction are excellent.
  • the present invention can prevent deterioration of magnetic properties due to oxidation during flattening by increasing the content of alloying elements other than Fe than before, and has low coercivity and high corrosion resistance of flat powder.
  • a soft magnetic flat powder capable of simultaneously realizing the above is provided.

Abstract

The purpose of the present invention is to provide a soft magnetic flat powder with which it is possible to prevent oxidation during the flattening of metal powder and achieve a low coercive force. In order to achieve the purpose, there is provided a soft magnetic flat powder comprising a plurality of soft flat particles, wherein each of the plurality of soft magnetic flat particles is a metal particle containing, in mass%, 78-83% of Fe, more than 0% and at most 13% of Si, more than 5.0% and at most 13% of Al, and 1.0-5.0% total of at least one among Cr, Ni, Mo, Cu, and Ti, with the remainder comprising Fe and inevitable impurities.

Description

軟磁性扁平粉末Soft magnetic flat powder 関連出願の相互参照Cross-reference of related applications
　本出願は、２０１７年２月６日に出願された日本国特許出願２０１７－１９３２８号に基づく優先権を主張するものであり、その開示内容の全体が参照により本明細書に組み込まれる。 This application claims priority based on Japanese Patent Application No. 2017-19328 filed on Feb. 6, 2017, the entire disclosure of which is incorporated herein by reference.
　本発明は、軟磁性扁平粉末、例えば、各種電子デバイスに用いられる電磁波吸収体用軟磁性扁平粉末に関する。 The present invention relates to a soft magnetic flat powder, for example, a soft magnetic flat powder for an electromagnetic wave absorber used in various electronic devices.
　近年、パソコン、スマートフォン等の電子機器及び情報機器が急速に発達するのに伴い、情報伝達の高速化が進行している。それにより、電子機器の内部において、電磁波による誤作動が問題になっている。さらに、それら電子機器が放射する電磁波の人体への影響も問題視されている。これら電子機器の電磁波吸収体として、軟磁性フェライト又は軟磁性扁平粉末が使用されている。 In recent years, with the rapid development of electronic devices and information devices such as personal computers and smartphones, the speed of information transmission has been increasing. As a result, malfunction due to electromagnetic waves has become a problem inside electronic devices. Furthermore, the influence of electromagnetic waves radiated from these electronic devices on the human body is also regarded as a problem. As an electromagnetic wave absorber for these electronic devices, soft magnetic ferrite or soft magnetic flat powder is used.
　特に、軟磁性扁平粉末は、軟磁性フェライトのように焼結して固化成形する必要がなく、樹脂等と混合し、成形されることから、フレキシブルで装着部への自由度が高いため、主に小型の電子機器に広く利用されている。 In particular, soft magnetic flat powder does not need to be sintered and solidified like soft magnetic ferrite, but is mixed with resin and molded, so it is flexible and has a high degree of freedom in the mounting part. It is widely used for small electronic devices.
　この軟磁性扁平粉末は、アトライタ装置を使用し、金属粉末を扁平化する手法により作製される。この手法では、トルエンといった有機溶媒、金属粉末及び粉砕媒体（鋼球）をアトライタ装置に装入し、装置内部にある回転羽根によって、粉砕及び扁平化する。このような手法には、主に軟磁性合金のＦｅ－Ｓｉ－Ａｌ合金といった脆い材料が使用される。 This soft magnetic flat powder is produced by a method of flattening metal powder using an attritor device. In this method, an organic solvent such as toluene, a metal powder, and a grinding medium (steel ball) are charged into an attritor apparatus, and are pulverized and flattened by rotating blades inside the apparatus. In such a technique, a brittle material such as a soft magnetic alloy Fe—Si—Al alloy is mainly used.
　例えば、特開２０１４－２０４０５１号公報（特許文献１）では、上述した手法を用いて作製されたＦｅ－Ｓｉ－Ａｌ合金が開示されている。特許文献１では、Ｆｅが８４％～９６％と高濃度であり、かつ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕの元素がＦｅに対して置換されることを特徴としている。 For example, Japanese Unexamined Patent Application Publication No. 2014-204051 (Patent Document 1) discloses an Fe—Si—Al alloy manufactured using the above-described method. Patent Document 1 is characterized in that Fe has a high concentration of 84% to 96%, and elements of Ti, V, Cr, Mn, Co, Ni, and Cu are substituted for Fe.
　また、特開２００８－５０６４４号公報（特許文献２）では、Ｆｅに対して、Ｓｉ：９．０％～１２％、Ａｌ：１．０％～５．０％、Ｃｒ：１．０％～５．０％を添加することで、従来にない高固有抵抗かつ低保磁力を実現している。 In JP 2008-50644 (Patent Document 2), Si: 9.0% to 12%, Al: 1.0% to 5.0%, Cr: 1.0% to By adding 5.0%, unprecedented high specific resistance and low coercive force are realized.
特開２０１４－２０４０５１号公報JP 2014-204051 A 特開２００８－５０６４４号公報JP 2008-50644 A
　上述したように軟磁性扁平粉末は、乾式又は湿式加工によって、水又は有機溶媒中で金属粉末と粉砕媒体とを混合、粉砕して作製される。その際、水又は有機溶媒中で長時間加工されるため、金属粉末は酸化し、磁気特性が劣化する傾向ある。したがって、この金属粉末の酸化を防ぎ、扁平化することが求められている。 As described above, the soft magnetic flat powder is produced by mixing and pulverizing a metal powder and a pulverizing medium in water or an organic solvent by dry or wet processing. At that time, since the metal powder is processed in water or an organic solvent for a long time, the metal powder tends to be oxidized and the magnetic properties tend to deteriorate. Therefore, it is required to prevent the metal powder from being oxidized and flattened.
　しかしながら、上述した特許文献１では、扁平加工時及び熱処理時における酸化による組成ズレについて述べられているが、明確な対策は行われておらず、成分検討の意図はあくまで、磁気特性に関してのみである。さらに、Ｆｅは８４％～９６％と高濃度であり、耐酸化性及び耐食性については、言及されていないものの、これら特性が低いことが推測される。 However, in Patent Document 1 described above, compositional deviation due to oxidation during flattening and heat treatment is described, but no clear countermeasure has been taken, and the intention of examining the components is only with respect to magnetic properties. . Further, Fe has a high concentration of 84% to 96%, and although the oxidation resistance and corrosion resistance are not mentioned, it is presumed that these characteristics are low.
　また、特許文献２では、Ａｌ及びＣｒを含有することで、耐食性を向上させると述べられているが、Ａｌについては５．０％以下と低い値である。また、扁平化加工時に生じる酸化による磁気特性の劣化については考慮されていない。 In Patent Document 2, it is stated that the corrosion resistance is improved by containing Al and Cr, but Al is a low value of 5.0% or less. Also, no consideration is given to the deterioration of magnetic properties due to oxidation that occurs during flattening.
　上述したような特許文献１及び２において考慮されていなかった課題について、本発明者らは鋭意開発を進めた結果、Ａｌの添加量を増加させ、さらに、Ｆｅ、Ｓｉ、Ａｌ以外の元素を意図的に添加することで、耐酸化性及び耐食性を高め、かつ高い磁気特性を得られることを見出し、本発明を完成するに至った。 As a result of diligent development on the problems that have not been considered in Patent Documents 1 and 2 as described above, the present inventors have increased the amount of Al added, and intended elements other than Fe, Si, and Al Thus, the present inventors have found that the oxidation resistance and corrosion resistance can be improved and high magnetic properties can be obtained by adding them steadily, and the present invention has been completed.
　すなわち、本発明は、以下の軟磁性扁平粉末及び磁性シートを包含する。
［１］複数の軟磁性扁平粒子を含んでなる軟磁性扁平粉末であって、前記複数の軟磁性扁平粒子のそれぞれが、質量％で、Ｆｅ：７８％以上８３％以下、Ｓｉ：１３％以下（０は含まない）、Ａｌ：５．０％超１３％以下、Ｃｒ，Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類：合計１．０％以上５．０％以下を含み、残部がＦｅ及び不可避的不純物からなる合金粒子である、軟磁性扁平粉末。
［２］前記軟磁性扁平粒子の長手方向に磁場を印加して測定した保磁力が２３０Ａ／ｍ以下であり、かつ、前記軟磁性扁平粉末の飽和磁束密度が０．６Ｔ以上１．５Ｔ以下である、上記［１］に記載の軟磁性扁平粉末。
［３］上記［１］又は［２］に記載の軟磁性扁平粉末を含有する、磁性シート。 That is, the present invention includes the following soft magnetic flat powder and magnetic sheet.
[1] A soft magnetic flat powder comprising a plurality of soft magnetic flat particles, wherein each of the plurality of soft magnetic flat particles is in mass%, Fe: 78% to 83%, Si: 13% or less. (0 is not included), Al: more than 5.0% and 13% or less, at least one of Cr, Ni, Mo, Cu, and Ti: including 1.0% to 5.0% in total, with the balance being Fe And a soft magnetic flat powder, which is an alloy particle comprising inevitable impurities.
[2] The coercive force measured by applying a magnetic field in the longitudinal direction of the soft magnetic flat particles is 230 A / m or less, and the saturation magnetic flux density of the soft magnetic flat powder is 0.6 T or more and 1.5 T or less. The soft magnetic flat powder according to [1] above.
[3] A magnetic sheet containing the soft magnetic flat powder according to [1] or [2].
　本発明により、金属粉末の扁平化加工時の酸化を防ぎ、低い保磁力を実現することができる軟磁性扁平粉末が提供される。 The present invention provides a soft magnetic flat powder that can prevent oxidation during flattening processing of a metal powder and can realize a low coercive force.
　以下、本発明について説明する。
＜軟磁性扁平粉末の組成＞
　本発明の軟磁性扁平粉末は、複数の軟磁性扁平粒子の集合体であり、それぞれの軟磁性扁平粒子は、質量％で、Ｆｅ：７８％以上８３％以下、Ｓｉ：１３％以下（０は含まない）、Ａｌ：５．０％超１３％以下、Ｃｒ，Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類：合計１．０％以上５．０％以下を含み、残部がＦｅ及び不可避的不純物からなる合金粒子である。以下、組成を上記のように限定した理由を説明する。 The present invention will be described below.
<Composition of soft magnetic flat powder>
The soft magnetic flat powder of the present invention is an aggregate of a plurality of soft magnetic flat particles, and each soft magnetic flat particle is in mass%, Fe: 78% to 83%, Si: 13% or less (0 is Not including), Al: more than 5.0% and not more than 13%, at least one of Cr, Ni, Mo, Cu, Ti: including 1.0% to 5.0% in total, the balance being Fe and inevitable Alloy particles made of impurities. Hereinafter, the reason for limiting the composition as described above will be described.
［Ｆｅ：７８％以上８３％以下］
　Ｆｅは、軟磁性扁平粉末に強磁性を持たせるとともに、軟磁性扁平粉末に高い飽和磁束密度を持たせるための必須元素である。Ｆｅの含有量が８３％を超えると、軟磁性扁平粉末の耐酸化性及び耐食性は減少する。一方、Ｆｅの含有量が７８％未満であると、軟磁性扁平粉末の飽和磁束密度が大きく減少する。したがって、Ｆｅの含有量は、７８％以上８３％以下である。Ｆｅの含有量は、好ましくは７９％以上８２％以下であり、より好ましくは７９％超８１％以下である。 [Fe: 78% to 83%]
Fe is an essential element for imparting ferromagnetism to the soft magnetic flat powder and for imparting a high saturation magnetic flux density to the soft magnetic flat powder. When the Fe content exceeds 83%, the oxidation resistance and corrosion resistance of the soft magnetic flat powder are reduced. On the other hand, when the Fe content is less than 78%, the saturation magnetic flux density of the soft magnetic flat powder is greatly reduced. Therefore, the Fe content is 78% or more and 83% or less. The Fe content is preferably 79% or more and 82% or less, more preferably more than 79% and 81% or less.
［Ｓｉ：１３％以下（０は含まない）］
　Ｓｉは、軟磁性扁平粉末の結晶磁気異方性定数を減少させるとともに、軟磁性扁平粉末の保磁力を減少させるための必須元素である。Ｓｉの添加量が減少すると、軟磁性扁平粉末の結晶磁気異方性定数及び保磁力が増加する傾向にあり、Ｓｉの含有量が１３％を超えると、軟磁性扁平粉末の飽和磁束密度を大きく減少させる。したがって、Ｓｉの含有量は、０％超１３％以下である。Ｓｉの含有量は、好ましくは３．０％以上１０％以下であり、より好ましくは５．０％以上９．５％以下である。 [Si: 13% or less (excluding 0)]
Si is an essential element for reducing the magnetocrystalline anisotropy constant of the soft magnetic flat powder and reducing the coercive force of the soft magnetic flat powder. When the amount of Si decreases, the magnetocrystalline anisotropy constant and coercivity of the soft magnetic flat powder tend to increase. When the Si content exceeds 13%, the saturation magnetic flux density of the soft magnetic flat powder increases. Decrease. Therefore, the Si content is more than 0% and not more than 13%. The Si content is preferably 3.0% or more and 10% or less, and more preferably 5.0% or more and 9.5% or less.
［Ａｌ：５．０％超１３％以下］
　Ａｌは、軟磁性扁平粉末の結晶磁気異方性定数及び保磁力を減少させるとともに、軟磁性扁平粉末の耐酸化性及び耐食性を向上させるための必須元素である。Ａｌの添加量が５．０％以下であると、軟磁性扁平粉末の耐食性が減少するとともに、軟磁性扁平粉末の結晶磁気異方性定数及び保磁力が増加する傾向にある。Ａｌの含有量が１３％を超えると、軟磁性扁平粉末の飽和磁束密度を大きく減少させる。したがって、Ａｌの含有量は、５．０％超１３％以下である。Ａｌの含有量は、好ましくは５．０％超１０％以下であり、より好ましくは６．０％以上９．０％以下である。 [Al: more than 5.0% and 13% or less]
Al is an essential element for reducing the magnetocrystalline anisotropy constant and coercive force of the soft magnetic flat powder, and improving the oxidation resistance and corrosion resistance of the soft magnetic flat powder. When the addition amount of Al is 5.0% or less, the corrosion resistance of the soft magnetic flat powder decreases, and the crystal magnetic anisotropy constant and coercive force of the soft magnetic flat powder tend to increase. When the Al content exceeds 13%, the saturation magnetic flux density of the soft magnetic flat powder is greatly reduced. Therefore, the Al content is more than 5.0% and 13% or less. The content of Al is preferably more than 5.0% and 10% or less, and more preferably 6.0% or more and 9.0% or less.
［Ｃｒ、Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類：合計で１．０％以上５．０％以下］
　Ｃｒ、Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類は、軟磁性扁平粉末の耐酸化性及び耐食性を向上させるための必須元素である。なお、「合計１．０％以上５．０％以下」とは、軟磁性扁平粒子がＣｒ、Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち１種類を含む場合には、当該１種類の元素の含有量が１．０％以上５．０％以下であることを意味し、軟磁性扁平粒子がＣｒ、Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち２種類以上を含む場合には、当該２種類以上の元素の合計含有量が１．０％以上５．０％以下であることを意味する。Ｃｒ、Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類の合計含有量が１．０％未満であると、軟磁性扁平粉末の耐酸化性及び耐食性は向上せず、合計含有量が５．０％を超えると、析出物等の影響により軟磁性扁平粉末の保磁力を大きく増加させる場合がある。したがって、Ｃｒ、Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類の合計含有量は、１．０％以上５．０％以下である。Ｃｒ、Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類の合計含有量は、好ましくは１．５％以上４．５％以下であり、より好ましくは２．０％以上４．０％以下である。 [At least one of Cr, Ni, Mo, Cu, and Ti: 1.0% to 5.0% in total]
At least one of Cr, Ni, Mo, Cu, and Ti is an essential element for improving the oxidation resistance and corrosion resistance of the soft magnetic flat powder. “Total 1.0% or more and 5.0% or less” means that when the soft magnetic flat particles contain one kind of Cr, Ni, Mo, Cu, and Ti, the content of the one kind of element Is 1.0% or more and 5.0% or less, and when the soft magnetic flat particles include two or more of Cr, Ni, Mo, Cu, and Ti, the two or more of the elements It means that the total content is 1.0% or more and 5.0% or less. When the total content of at least one of Cr, Ni, Mo, Cu, and Ti is less than 1.0%, the oxidation resistance and corrosion resistance of the soft magnetic flat powder are not improved, and the total content is 5.0. If it exceeds 50%, the coercive force of the soft magnetic flat powder may be greatly increased due to the influence of precipitates and the like. Therefore, the total content of at least one of Cr, Ni, Mo, Cu, and Ti is 1.0% or more and 5.0% or less. The total content of at least one of Cr, Ni, Mo, Cu and Ti is preferably 1.5% or more and 4.5% or less, more preferably 2.0% or more and 4.0% or less. .
＜軟磁性扁平粉末の磁気特性＞
［保磁力］
　本発明の軟磁性扁平粉末において、軟磁性扁平粒子の長手方向に磁場（１４３．６ｋＡ／ｍ）を印加して測定した保磁力は、好ましくは２３０Ａ／ｍ以下である。本発明の軟磁性扁平粉末を含んでなる磁性シートが利用される周波数帯域は、好ましくは１～１５ＭＨｚであり、その周波数帯域において高い透磁率を得るためには、保磁力は２３０Ａ／ｍ以下であることが好ましい。保磁力は、さらに好ましくは１９０Ａ／ｍ以下、さらに一層好ましくは１２０Ａ／ｍ以下である。保磁力の下限値は特に限定されないが、例えば２００Ａ／ｍである。保磁力は、樹脂製容器に軟磁性扁平粉末を充填し、容器の直径方向に磁化した場合の値に基づいて算出される。容器に充填された軟磁性扁平粒子の長手方向及び厚さ方向は、それぞれ、容器の直径方向及び高さ方向と相当するので、容器の直径方向に磁化した場合の値が長手方向の保磁力となり、容器の高さ方向に磁化した場合の値が厚さ方向の保磁力となる。 <Magnetic properties of soft magnetic flat powder>
[Coercivity]
In the soft magnetic flat powder of the present invention, the coercive force measured by applying a magnetic field (143.6 kA / m) in the longitudinal direction of the soft magnetic flat particles is preferably 230 A / m or less. The frequency band in which the magnetic sheet comprising the soft magnetic flat powder of the present invention is used is preferably 1 to 15 MHz. In order to obtain high magnetic permeability in the frequency band, the coercive force is 230 A / m or less. Preferably there is. The coercive force is more preferably 190 A / m or less, and still more preferably 120 A / m or less. The lower limit value of the coercive force is not particularly limited, but is, for example, 200 A / m. The coercive force is calculated based on a value when a soft container is filled with soft magnetic flat powder and magnetized in the diameter direction of the container. Since the longitudinal direction and thickness direction of the soft magnetic flat particles filled in the container correspond to the diameter direction and height direction of the container, respectively, the value when magnetized in the diameter direction of the container is the coercive force in the longitudinal direction. The value when magnetized in the height direction of the container is the coercive force in the thickness direction.
［飽和磁束密度］
　本発明の軟磁性扁平粉末の飽和磁束密度は、好ましくは０．６Ｔ以上１．５Ｔ以下、より好ましくは０．８Ｔ以上１．５Ｔ以下である。飽和磁束密度は、振動試料型磁力計（ＶＳＭ）を使用して印加磁場１．２×１０３ｋＡ／ｍで測定される。 [Saturation magnetic flux density]
The saturation magnetic flux density of the soft magnetic flat powder of the present invention is preferably 0.6 T or more and 1.5 T or less, more preferably 0.8 T or more and 1.5 T or less. The saturation magnetic flux density is measured with an applied magnetic field of 1.2 × 10 3 kA / m using a vibrating sample magnetometer (VSM).
＜軟磁性扁平粉末の製造方法＞
　本発明の軟磁性扁平粉末の製造方法は従来提案されている方法で可能である。各種のアトマイズ法により、原料となる合金粉末を作製し、これをボールミル又はアトライタ装置によって乾式又は湿式で扁平加工を行う。その後、５００℃以上の熱処理により保磁力を減少させることが可能である。本発明の軟磁性扁平粉末の製造方法は、具体的には以下の通りである。 <Method for producing soft magnetic flat powder>
The method for producing the soft magnetic flat powder of the present invention can be performed by a conventionally proposed method. Alloy powder as a raw material is produced by various atomizing methods, and this is flattened in a dry or wet manner by a ball mill or an attritor apparatus. Thereafter, the coercive force can be reduced by heat treatment at 500 ° C. or higher. The method for producing the soft magnetic flat powder of the present invention is specifically as follows.
＜軟磁性扁平粉末の製造方法＞
　本発明の軟磁性扁平粉末は、原料粉末準備工程、扁平加工工程及び熱処理工程を含む方法により製造することができる。 <Method for producing soft magnetic flat powder>
The soft magnetic flat powder of the present invention can be produced by a method including a raw material powder preparation step, a flat processing step, and a heat treatment step.
［原料粉末準備工程］
　原料粉末としては、軟磁性合金粉末が使用される。原料粉末として使用される軟磁性合金粉末は、複数の軟磁性合金粒子の集合体であり、それぞれの軟磁性合金粒子は、質量％で、Ｆｅ：７８％以上８３％以下、Ｓｉ：１３％以下（０は含まない）、Ａｌ：５．０％超１３％以下、Ｃｒ，Ｎｉ、Ｍｏ、Ｃｕ、Ｔｉのうち少なくとも１種類：合計１．０％以上５．０％以下を含み、残部がＦｅ及び不可避的不純物からなる合金粒子である。組成を限定した理由及び各元素の好ましい含有量は上記の通りである。 [Raw material powder preparation process]
As the raw material powder, soft magnetic alloy powder is used. The soft magnetic alloy powder used as the raw material powder is an aggregate of a plurality of soft magnetic alloy particles. Each soft magnetic alloy particle is in mass%, Fe: 78% or more and 83% or less, Si: 13% or less. (0 is not included), Al: more than 5.0% and 13% or less, at least one of Cr, Ni, Mo, Cu, and Ti: including 1.0% to 5.0% in total, with the balance being Fe And alloy particles composed of inevitable impurities. The reason for limiting the composition and the preferred content of each element are as described above.
　原料粉末は、例えば、ガスアトマイズ法、水アトマイズ法、ディスクアトマイズ法等の各種アトマイズ法、又は、溶融による合金化後に実施される粉砕法によって作製することができる。原料粉末の含有酸素量は少ない方が好ましいため、原料粉末は、ガスアトマイズ法によって製造することが好ましく、不活性ガスを使用したガスアトマイズ法によって製造することがさらに好ましい。アトマイズ法により製造された粉末は形状が球状に近いことから、アトライタ加工等を使用した粉砕法より製造された粉末よりも扁平化が進行しやすい。粉砕法により製造された粉末は粒径がアトマイズ粉末よりも小さいことから、磁性シート表面の突起発生が抑制される傾向がある。 The raw material powder can be produced by, for example, various atomizing methods such as a gas atomizing method, a water atomizing method, a disk atomizing method, or a pulverizing method performed after alloying by melting. Since it is preferable that the amount of oxygen contained in the raw material powder is small, the raw material powder is preferably produced by a gas atomizing method, more preferably produced by a gas atomizing method using an inert gas. Since the powder produced by the atomization method has a nearly spherical shape, flattening is more likely to proceed than the powder produced by the pulverization method using attritor processing or the like. Since the powder produced by the pulverization method has a particle size smaller than that of the atomized powder, generation of protrusions on the magnetic sheet surface tends to be suppressed.
　原料粉末の粒度は特に限定されないが、扁平後の平均粒径を調整する目的、含有酸素量の多い粉末を除去する目的、その他の製造上の目的等に応じて、分級により原料粉末の粒度を所望の範囲に調整してもよい。 The particle size of the raw material powder is not particularly limited, but according to the purpose of adjusting the average particle size after flattening, the purpose of removing the powder containing a large amount of oxygen, and other manufacturing purposes, the particle size of the raw material powder is determined by classification. You may adjust to a desired range.
［扁平加工工程］
　原料粉末準備工程の後、原料粉末を扁平化する。これにより、扁平粉末が得られる。扁平加工方法は、特に限定されるものではなく、原料粉末の扁平加工は、例えば、アトライタ、ボールミル、振動ミル等を使用して行うことができる。中でも、比較的扁平加工能力に優れるアトライタを使用することが好ましい。乾式で扁平加工を行う場合は、不活性ガスを使用することが好ましい。湿式で扁平加工を行う場合は、有機溶媒を使用することが好ましい。 [Flat processing process]
After the raw material powder preparation step, the raw material powder is flattened. Thereby, a flat powder is obtained. The flat processing method is not particularly limited, and the flat processing of the raw material powder can be performed using, for example, an attritor, a ball mill, a vibration mill, or the like. Among them, it is preferable to use an attritor that is relatively excellent in flat processing ability. When flattening is performed by a dry method, it is preferable to use an inert gas. In the case of performing flattening by wet, it is preferable to use an organic solvent.
　湿式の扁平加工で使用される有機溶媒の種類は特に限定されない。有機溶媒の添加量は、原料粉末１００質量部に対して、好ましくは１００質量部以上、さらに好ましくは２００質量部以上である。有機溶媒の添加量の上限は特に限定されず、求められる扁平粉末の大きさ及び形状と、生産性とのバランスに応じて適宜調整が可能である。有機溶媒は、含水有機溶媒であってもよいが、酸素含有量を低くするために、有機溶媒中の水分濃度は、有機溶媒１００質量部に対して、好ましくは０．００２質量部以下である。有機溶媒とともに扁平化助剤を使用してもよいが、酸化を抑えるために、扁平化助剤の添加量は、原料粉末１００質量部に対して、好ましくは５質量部以下である。 The type of organic solvent used in wet flattening is not particularly limited. The addition amount of the organic solvent is preferably 100 parts by mass or more, and more preferably 200 parts by mass or more with respect to 100 parts by mass of the raw material powder. The upper limit of the addition amount of the organic solvent is not particularly limited, and can be appropriately adjusted according to the balance between the required size and shape of the flat powder and productivity. The organic solvent may be a water-containing organic solvent, but in order to reduce the oxygen content, the water concentration in the organic solvent is preferably 0.002 parts by mass or less with respect to 100 parts by mass of the organic solvent. . Although a flattening aid may be used together with the organic solvent, the addition amount of the flattening aid is preferably 5 parts by mass or less with respect to 100 parts by mass of the raw material powder in order to suppress oxidation.
［熱処理工程］
　扁平加工工程の後、扁平粉末を熱処理する。熱処理装置は、所望の熱処理温度を実現し得る限り特に限定されない。熱処理温度は、好ましくは５００～９００℃、さらに好ましくは６００～８５０℃である。このような温度で熱処理を行うことにより、保磁力を減少させることができる。熱処理時間は特に限定されず、処理量、生産性等に応じて適宜調整することができる。但し、熱処理時間が長くなると、生産性が低下するため、熱処理時間は、好ましくは８時間以内である。 [Heat treatment process]
After the flattening process, the flat powder is heat treated. The heat treatment apparatus is not particularly limited as long as a desired heat treatment temperature can be realized. The heat treatment temperature is preferably 500 to 900 ° C, more preferably 600 to 850 ° C. By performing heat treatment at such a temperature, the coercive force can be reduced. The heat treatment time is not particularly limited, and can be appropriately adjusted according to the processing amount, productivity, and the like. However, if the heat treatment time is increased, the productivity is lowered, so the heat treatment time is preferably within 8 hours.
　熱処理工程において、熱処理雰囲気が大気の場合、扁平粉末の酸化が進む。したがって、扁平粉末の酸化を抑えるために、扁平粉末を真空中又は不活性ガス（例えば、アルゴン、窒素）中で熱処理することが好ましい。 In the heat treatment process, when the heat treatment atmosphere is air, the flat powder is oxidized. Therefore, in order to suppress oxidation of the flat powder, it is preferable to heat the flat powder in a vacuum or in an inert gas (for example, argon or nitrogen).
　軟磁性扁平粉末を含んでなる磁性シートの絶縁性を高める等の観点から、表面処理された軟磁性扁平粉末の使用が好適となる場合があり、軟磁性扁平粉末の製造方法において、熱処理工程中又は熱処理工程の前後において、表面処理工程を必要に応じて行ってもよい。例えば、表面処理のために、活性ガスを微量に含む雰囲気下で熱処理されてもよい。また、従来から提案されているシアン系カップリング剤に代表される表面処理により、耐食性、ゴムへの分散性等を改善することも可能である。 From the standpoint of enhancing the insulation of the magnetic sheet comprising the soft magnetic flat powder, the use of the surface-treated soft magnetic flat powder may be suitable, and in the method for producing the soft magnetic flat powder, during the heat treatment step Alternatively, the surface treatment step may be performed as necessary before and after the heat treatment step. For example, for surface treatment, heat treatment may be performed in an atmosphere containing a small amount of active gas. Moreover, it is possible to improve corrosion resistance, dispersibility in rubber, and the like by surface treatment represented by a conventionally proposed cyan coupling agent.
＜磁性シート＞
　本発明の磁性シートは、本発明の軟磁性扁平粉末を含有する。本発明の磁性シートは、例えば、本発明の軟磁性扁平粉末が、ゴム、エラストマー、樹脂等のマトリックス材料中に分散した構造を有する。マトリックス材料は適宜選択可能であり、１種のマトリックス材料を使用してもよいし、２種以上のマトリックス材料を使用してもよい。 <Magnetic sheet>
The magnetic sheet of the present invention contains the soft magnetic flat powder of the present invention. The magnetic sheet of the present invention has a structure in which, for example, the soft magnetic flat powder of the present invention is dispersed in a matrix material such as rubber, elastomer, or resin. The matrix material can be selected as appropriate, and one kind of matrix material may be used, or two or more kinds of matrix materials may be used.
　磁性シートに含まれる軟磁性扁平粉末の量は、要求される透磁率特性等を考慮して適宜調整することができる。磁性シートに含まれる軟磁性扁平粉末の量（磁性シート中の軟磁性扁平粉末の体積充填率）は、好ましくは２０～６０体積％、例えば２０～４０体積％又は４０～６０体積％である。 The amount of the soft magnetic flat powder contained in the magnetic sheet can be appropriately adjusted in consideration of the required permeability characteristics and the like. The amount of the soft magnetic flat powder contained in the magnetic sheet (volume filling ratio of the soft magnetic flat powder in the magnetic sheet) is preferably 20 to 60% by volume, for example 20 to 40% by volume or 40 to 60% by volume.
　軟磁性扁平粉末を含んでなる磁性シートの製造は、軟磁性扁平粉末を使用して、従来提案されている方法に従って行うことが可能である。例えば、トルエンに塩素化ポリエチレン等を溶解したものに軟磁性扁平粉末を混合し、これをポリエステル樹脂等の合成樹脂製の基材に塗布し、乾燥させたものを、各種プレス、ロール等で圧縮することにより製造可能である。 The production of the magnetic sheet comprising the soft magnetic flat powder can be performed according to a conventionally proposed method using the soft magnetic flat powder. For example, soft magnetic flat powder is mixed with a solution of chlorinated polyethylene in toluene, applied to a synthetic resin substrate such as polyester resin, and dried, then compressed with various presses, rolls, etc. Can be manufactured.
　以下、実施例に基づいて、本発明を具体的に説明する。
［扁平粉末の作製］
　ガスアトマイズ法により、表１及び２に示す組成の合金粉末を作製し、１５０μｍ以下に分級し、原料粉末として使用した。ガスアトマイズ法は、アルミナ製坩堝を溶解に使用し、坩堝下の直径５ｍｍのノズルから合金溶湯を出湯し、これに高圧アルゴンを噴霧することにより実施した。 Hereinafter, based on an Example, this invention is demonstrated concretely.
[Production of flat powder]
Alloy powders having the compositions shown in Tables 1 and 2 were prepared by gas atomization, classified to 150 μm or less, and used as raw material powders. The gas atomization method was carried out by using an alumina crucible for melting, discharging molten alloy from a nozzle having a diameter of 5 mm under the crucible, and spraying this with high-pressure argon.
　次いで、原料粉末をアトライタ装置により、扁平加工を行った。アトライタはＳＵＪ２製の直径４．８ｍｍのボールを、原料粉末及び工業エタノールとともに撹拌容器に投入し、羽根の回転数３５０ｒｐｍとして実施した。 Next, the raw material powder was flattened by an attritor device. The attritor was charged with a 4.8 mm diameter ball made by SUJ2 together with the raw material powder and industrial ethanol in a stirring vessel, and the blade rotation speed was 350 rpm.
　得られた扁平粉末を、扁平加工中に導入された歪みを除去するためにＡｒ雰囲気中で熱処理した。熱処理の温度は粉末の焼結温度を考慮して５００～９００℃とし、熱処理の時間は３時間とした。 The obtained flat powder was heat-treated in an Ar atmosphere in order to remove distortion introduced during the flat processing. The heat treatment temperature was 500 to 900 ° C. in consideration of the sintering temperature of the powder, and the heat treatment time was 3 hours.
［扁平粉末の評価］
　熱処理を加えた扁平粉末の保磁力（Ｈｃ）及び飽和磁束密度（Ｂｓ）の測定を行った。保磁力は、Ｑｕｍａｎｏ社製ＣＯＥＲＣＩＭＥＴＥＲ　ＨＣ８０１を使用し、扁平粒子の長手方向に磁場（１４３．６ｋＡ／ｍ）を印加して測定した。具体的には、直径６ｍｍ、高さ８ｍｍの樹脂製容器に扁平粉末を充填し、容器の直径方向に磁化した場合の値に基づいて算出した。容器に充填された扁平粒子の長手方向及び厚さ方向は、それぞれ、容器の直径方向及び高さ方向に相当するので、容器の直径方向に磁化した場合の値が長手方向の保磁力となり、容器の高さ方向に磁化した場合の値が厚さ方向の保磁力となる。飽和磁束密度は、振動試料型磁力計（ＶＳＭ）を使用して印加磁場１．２×１０３ｋＡ／ｍで測定した。 [Evaluation of flat powder]
The coercive force (Hc) and saturation magnetic flux density (Bs) of the flat powder subjected to heat treatment were measured. The coercive force was measured by applying a magnetic field (143.6 kA / m) in the longitudinal direction of flat particles using a COERCIMETER HC801 manufactured by Qumano. Specifically, the calculation was performed based on the value when a resin container having a diameter of 6 mm and a height of 8 mm was filled with flat powder and magnetized in the diameter direction of the container. Since the longitudinal direction and the thickness direction of the flat particles filled in the container correspond to the diameter direction and the height direction of the container, respectively, the value when magnetized in the diameter direction of the container becomes the longitudinal coercive force, and the container The value when magnetized in the height direction is the coercive force in the thickness direction. The saturation magnetic flux density was measured with an applied magnetic field of 1.2 × 10 3 kA / m using a vibrating sample magnetometer (VSM).
　さらに、扁平粉末の耐食性を評価した。耐食性ついては、扁平粉末を２５℃の２０％濃度塩水に１００時間浸漬させ、浸漬後の発錆具合を以下の基準で評価した。
Ａ：発錆なし
Ｂ：発錆具合が小さい
Ｃ：発錆具合が中程度
Ｄ：発錆具合が大きい Furthermore, the corrosion resistance of the flat powder was evaluated. As for the corrosion resistance, the flat powder was immersed in 25% 20% salt water for 100 hours, and the degree of rusting after immersion was evaluated according to the following criteria.
A: No rusting B: Small rusting condition C: Medium rusting condition D: Large rusting condition
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び表２のうち、Ｎｏ．１～３１は本発明例であり、Ｎｏ．３２～４３は比較例である。 Of Table 1 and Table 2, No. 1 to 31 are examples of the present invention. 32 to 43 are comparative examples.
　比較例Ｎｏ．３２は、Ｆｅ，Ｓｉ，Ａｌ以外の元素の合計量（Ｃｒ含有量）が高いため、保磁力が高く、飽和磁束密度が低い。比較例Ｎｏ．３３は、Ｆｅ含有量が低く、Ｆｅ，Ｓｉ，Ａｌ以外の元素の合計量（Ｎｉ含有量）が高いため、保磁力が高い。比較例Ｎｏ．３４は、Ｆｅ，Ｓｉ，Ａｌ以外の元素の合計量（Ｍｏ含有量）が高いため、保磁力が高く、かつ耐食性に劣る。比較例Ｎｏ．３５は、Ｆｅ，Ｓｉ，Ａｌ以外の元素の合計量（Ｃｕ含有量）が高いため、保磁力が高く、耐食性が悪い。比較例Ｎｏ．３６は、Ｆｅ含有量が低く、Ｆｅ，Ｓｉ，Ａｌ以外の元素の合計量（Ｔｉ含有量）が高いため、保磁力が高く、飽和磁束密度が低く、かつ耐食性が劣る。 Comparative Example No. No. 32 has a high total coercive force and a low saturation magnetic flux density because the total amount of elements other than Fe, Si and Al (Cr content) is high. Comparative Example No. Since No. 33 has a low Fe content and a high total amount of elements other than Fe, Si, and Al (Ni content), the coercive force is high. Comparative Example No. No. 34 has a high total amount of elements other than Fe, Si, and Al (Mo content), and thus has a high coercive force and inferior corrosion resistance. Comparative Example No. 35 is high in coercive force and poor in corrosion resistance because the total amount of elements other than Fe, Si, and Al (Cu content) is high. Comparative Example No. No. 36 has a low Fe content and a high total amount (Ti content) of elements other than Fe, Si, and Al, and thus has a high coercive force, a low saturation magnetic flux density, and poor corrosion resistance.
　比較例Ｎｏ．３７～３９は、いずれもＦｅ含有量が低く、Ｆｅ，Ｓｉ，Ａｌ以外の元素の合計量が高いため、保磁力が高く、耐食性がやや劣る。比較例Ｎｏ．４０は、Ｆｅ，Ｓｉ，Ａｌ以外の元素の合計量が高いため、保磁力が高く、耐食性が悪い。比較例Ｎｏ．４１は、Ｓｉ含有量が高く、Ａｌ含有量が低いため、保磁力が高く、飽和磁束密度が低く、かつ耐食性が悪い。比較例Ｎｏ．４２は、Ａｌ含有量が高いため、保磁力が高く、飽和磁束密度が低い。比較例Ｎｏ．４３は、Ａｌ含有量が低いため、保磁力が高く、かつ耐食性が悪い。 Comparative Example No. Nos. 37 to 39 each have a low Fe content and a high total amount of elements other than Fe, Si, and Al, so that the coercive force is high and the corrosion resistance is slightly inferior. Comparative Example No. No. 40 has a high coercive force and poor corrosion resistance because the total amount of elements other than Fe, Si, and Al is high. Comparative Example No. No. 41 has a high Si content and a low Al content, and thus has a high coercive force, a low saturation magnetic flux density, and poor corrosion resistance. Comparative Example No. No. 42 has a high Al content and therefore has a high coercive force and a low saturation magnetic flux density. Comparative Example No. Since No. 43 has a low Al content, it has a high coercive force and poor corrosion resistance.
　これに対し、本発明例Ｎｏ．１～３１は、いずれも本発明条件を満足していることから、長手方向に磁場を印加して測定した保磁力、飽和磁束密度及び耐食性のいずれの特性も優れていることが分かる。 In contrast, the present invention example No. Nos. 1 to 31 all satisfy the conditions of the present invention, and it can be seen that the coercive force, saturation magnetic flux density and corrosion resistance measured by applying a magnetic field in the longitudinal direction are excellent.
　以上のように、本発明は、従来よりもＦｅ以外の合金元素の含有量を高めることで、扁平加工時の酸化による磁気特性の劣化を防止できるとともに、扁平粉末の低い保磁力と高い耐食性とを同時実現できる軟磁性扁平粉末を提供する。 As described above, the present invention can prevent deterioration of magnetic properties due to oxidation during flattening by increasing the content of alloying elements other than Fe than before, and has low coercivity and high corrosion resistance of flat powder. A soft magnetic flat powder capable of simultaneously realizing the above is provided.

Claims (3)

  1. 　複数の軟磁性扁平粒子を含んでなる軟磁性扁平粉末であって、前記複数の軟磁性扁平粒子のそれぞれが、質量％で、Ｆｅ：７８％以上８３％以下、Ｓｉ：１３％以下（０は含まない）、Ａｌ：５．０％超１３％以下、Ｃｒ，Ｎｉ，Ｍｏ，Ｃｕ，Ｔｉのうち少なくとも１種類：合計１．０％以上５．０％以下を含み、残部がＦｅ及び不可避的不純物からなる合金粒子である、軟磁性扁平粉末。 A soft magnetic flat powder comprising a plurality of soft magnetic flat particles, wherein each of the plurality of soft magnetic flat particles is in mass%, Fe: 78% or more and 83% or less, Si: 13% or less (0 is Not including), Al: more than 5.0% and not more than 13%, at least one of Cr, Ni, Mo, Cu, Ti: including 1.0% or more and 5.0% or less in total, the balance being Fe and inevitable Soft magnetic flat powder, which is alloy particles composed of impurities.
  2. 　前記軟磁性扁平粒子の長手方向に磁場を印加して測定した保磁力が２３０Ａ／ｍ以下であり、かつ、前記軟磁性扁平粉末の飽和磁束密度が０．６Ｔ以上１．５Ｔ以下である、請求項１に記載の軟磁性扁平粉末。 The coercive force measured by applying a magnetic field in the longitudinal direction of the soft magnetic flat particles is 230 A / m or less, and the saturation magnetic flux density of the soft magnetic flat powder is 0.6 T or more and 1.5 T or less. Item 2. The soft magnetic flat powder according to Item 1.
  3. 　請求項１又は２に記載の軟磁性扁平粉末を含有する、磁性シート。 A magnetic sheet containing the soft magnetic flat powder according to claim 1.
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