WO2022009502A1 - 金属粉末及びその圧粉体並びにそれらの製造方法 - Google Patents
金属粉末及びその圧粉体並びにそれらの製造方法 Download PDFInfo
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- WO2022009502A1 WO2022009502A1 PCT/JP2021/015972 JP2021015972W WO2022009502A1 WO 2022009502 A1 WO2022009502 A1 WO 2022009502A1 JP 2021015972 W JP2021015972 W JP 2021015972W WO 2022009502 A1 WO2022009502 A1 WO 2022009502A1
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- metal powder
- resin
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 109
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 86
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 19
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
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- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- 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
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- 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
- H01F1/22—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 pressed, sintered, or bound together
- H01F1/24—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 pressed, sintered, or bound together the particles being insulated
- H01F1/26—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 pressed, sintered, or bound together the particles being insulated by macromolecular organic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0206—Manufacturing of magnetic cores by mechanical means
- H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
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- 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
- B22F1/14—Treatment of metallic powder
- B22F1/148—Agglomerating
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- 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
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- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
Definitions
- the present invention relates to a metal powder and a green compact thereof, and particularly to a metal powder made of an iron alloy suitable for a core for an inductor used at a high frequency, a green compact obtained by bonding the same with a resin, and a method for producing them.
- a ferrite material has been used for the choke coil.
- the saturation magnetic flux density of ferrite is low, when the core is miniaturized, the DC superimposition characteristics deteriorate due to the saturation of the core, and a large current cannot flow.
- iron-based metal magnetic fine particles having a high saturation magnetic flux density have been attracting attention as a core (magnetic core) material for a small inductor.
- the composition formula is Fe 100-ab Si a Cr b (0 ⁇ a ⁇ 8, 0 ⁇ b ⁇ 3 in weight%), and a part or the whole of the powder surface is an insulating oxide.
- a soft magnetic metal powder that is covered with and has a higher Cr concentration on the surface of the powder than the center of the powder is disclosed. Further, it is preferable that the total oxygen content of the soft magnetic metal powder containing the insulating oxide is 10% by mass or less.
- This soft magnetic metal powder is produced by mixing a raw material powder and an alkoxide solution, drying them, and then heat-treating them at 700 ° C. or higher to significantly reduce both the eddy current loss and the hysteresis loss of the dust core. It is possible to reduce the amount to.
- Patent Document 2 a crystalline basic composition, the composition formula Fe 100-xy Si x Cr y (where, x: 0 ⁇ 15at%, y: 0 ⁇ 15at%, x + y: 0 ⁇ 25at% Is represented by), and one or more magnetically modified trace components selected from the group 4 to 6 transition metal group of Nb, V, Ta, Ti, and W with respect to 100 parts by mass of the total amount of the composition formula.
- the powder magnetic core produced of the iron-based soft magnetic powder described in Patent Document 2 can have a high magnetic permeability and does not increase the magnetic core loss.
- Patent Document 3 discloses a magnetic material which is a particle molded body obtained by heat-treating metal particles made of a Fe—Cr—Si based alloy in an oxidizing atmosphere.
- the metal particles used are Fe Oxide , which is the sum of the integrated values of the peaks of 709.6 eV, 710.7 eV, and 710.9 eV by XPS of the metal particles before molding , and Fe Metal, which is the integrated value of the peak of 706.9 eV.
- Fe Metal / (Fe Metal + Fe Oxide ) is 0.2 or more
- Fe—Cr—Si based alloy particles are used.
- the Cr content range is 2.0 to 15 wt%.
- the obtained particle molded body has a plurality of metal particles, an oxide film made of an oxide of the metal particles covering the metal particles, and a bonding portion between the oxide films, whereby high insulation with high magnetic permeability is provided. It is said that it can be used as a resistance magnetic material.
- Patent Document 4 has a composition in which Fe contains Si: 7 to 9% and Cr: 2 to 8% in mass% with unavoidable impurities, and the average particle size D50 is 1 to 40 ⁇ m, and oxygen is used.
- An Fe-based soft magnetic metal powder having an amount suppressed to 0.60% by mass or less is disclosed. As a result, high magnetic permeability can be obtained, iron loss can be suppressed to a small extent, and a magnetic core having excellent corrosion resistance can be obtained.
- Patent Document 5 discloses a soft magnetic metal powder containing 100 to 995 ppm of carbon and 3 to 15% of Si in mass%, which is a powder containing iron as a main component, and oxygen contained in the particles is disclosed. It is preferably 500 ppm or less, and may contain Ni: 30 to 80% and Cr: 10% or less. As a result, a soft magnetic metal powder having a low coercive force can be obtained, and it is said that the loss of the dust core can be improved by using this soft magnetic metal powder.
- Patent Document 6 contains Fe as a main component, 1 to 10% of Si, 1 to 13% of Cr, and 10 to 10000 ppm of Cl in mass%, preferably O in mass%.
- a metal powder containing 1 to 7% (oxygen) and having an average particle size of 0.1 to 3.0 ⁇ m is disclosed.
- Japanese Unexamined Patent Publication No. 2008-195986 Japanese Patent No. 5354101 Japanese Unexamined Patent Publication No. 2013-26356 Japanese Unexamined Patent Publication No. 2014-78629 JP-A-2017-92481 Japanese Unexamined Patent Publication No. 2020-76135
- the affinity with the resin is increased and the packing density is improved, so that the magnetic core loss as the powder magnetic core (hereinafter, also referred to as “iron loss”).
- the core for inductors used at high frequencies is a battle against heat generation, and the iron loss is reduced to meet the strict demands for further miniaturization and thinning.
- the magnetic core characteristics from the viewpoint of that is, reduction of calorific value
- the present invention solves the problems of the prior art and provides excellent magnetic core characteristics such as high magnetic flux density and low iron loss to meet the stricter demands for miniaturization and thinning as an inductor core used at high frequency.
- the present inventors have diligently studied the magnetic and electrical properties of the green compact in order to achieve the above-mentioned object. As a result, it was found that it is important to prepare a metal powder (iron alloy powder) containing an appropriate amount of Si, Cr, and an appropriate amount of Cl and S (sulfur) in Fe. In particular, the presence of appropriate amounts of Cl and S (sulfur) enhances the affinity with the resin, increases the packing density of the powder, and facilitates the production of a dust core with a high magnetic flux density and low iron loss. was newly discovered.
- the present invention has been completed with further studies based on such findings. That is, the gist of the present invention is as follows. [1] In terms of mass concentration, Si: 1.0 to 15.0%, Cr: 1.0 to 13.0%, Cl: 10 to 10000 ppm, S (sulfur): 100 to 10000 ppm and O (oxygen): 0. A metal powder containing .2 to 7.0% and consisting of a balance Fe and unavoidable impurities, wherein the average particle size of the metal powder is 0.1 to 2.0 ⁇ m. .. [2] A pressure powder, which is a composite product of the metal powder according to [1] and a resin.
- the present invention it is possible to easily produce a metal powder having a low coercive force, excellent resin adhesion, and excellent rust resistance, which facilitates the production of a dust core having a high magnetic flux density and a low iron loss. , It has a remarkable effect on the industry.
- the metal powder of the present invention is a metal powder (iron alloy powder) containing Fe as a main component. That is, the metal powder of the present invention has Si: 1.0 to 15.0%, Cr: 1.0 to 13.0%, Cl: 10 to 10000 ppm, S (sulfur): 100 to 10000 ppm and so on in mass concentration.
- % and ppm in the composition mean mass concentration.
- Si 1.0 to 15.0%
- Si is an element that dissolves in the metal (Fe) and contributes to an increase in the electric resistance of the metal powder and a decrease in magnetic strain.
- the magnetostriction decreases as the Si content increases, becomes almost zero at a content of about 6.5%, and when the content is further increased, the magnetostriction further decreases and becomes a negative value.
- the electrical resistivity increases greatly as the Si content increases. Decreasing the absolute value of magnetostriction contributes to the reduction of hysteresis loss, and increasing electrical resistance contributes to the reduction of eddy current loss.
- the ratio of hysteresis loss to the total loss is large, so the loss is minimized at a composition with a Si content of around 6.5%, and near this composition.
- the content is suitable.
- the ratio of the eddy current loss to the total loss increases, so that the composition having a higher Si content minimizes the loss and is suitable.
- the ratio of the eddy current loss to the total loss further increases, so that the composition having a higher Si content minimizes the loss and is suitable.
- Si has a suitable effect in a wide composition range depending on the application, but when the Si content is less than 1.0%, the effect of reducing magnetostriction and the increase of electrical resistance are not sufficient. Not suitable. Further, when the Si content exceeds 15.0%, the absolute value of magnetostriction is large and the decrease in saturation magnetization is very large. Therefore, the desired magnetic characteristics can be obtained even when a powder magnetic core is produced. No. Therefore, Si was limited to the range of 1.0 to 15.0%. It is preferably 3.0 to 15.0%, and more preferably 6.0 to 14.0%.
- Cr 1.0 to 13.0%
- Cr is an element that lowers the magnetic properties of the metal powder but improves the corrosion resistance, and is preferably contained in an amount of 1.0% or more in order to obtain the effect of the corrosion resistance in the metal powder of the present invention.
- Cr is as low as less than 1.0%, rust is likely to occur on the particle surface.
- the saturation magnetization emu / g
- Cr is limited to the range of 1.0 to 13.0%. It is preferably 1.0 to 6.0%. More preferably, it is 1.0 to 4.0%.
- the corrosion resistance is the rust resistance described later.
- Cl chlorine
- Cl is an element that contributes to improving the affinity between the surface of metal particles and the resin, and has the effect of improving the packing density of the metal powder when used as a dust core and improving the magnetic flux density of the dust core.
- the content of 10 ppm or more is required.
- Cl is as small as less than 10 ppm, the affinity between the particle surface of the metal powder and the resin is low, voids are likely to occur around the metal powder particles, and the desired packing density cannot be achieved.
- Cl was limited to the range of 10 to 10000 ppm. It is preferably 10 to 1000 ppm. More preferably, it is 10 to 500 ppm.
- S (sulfur) 100 to 10000 ppm
- S (sulfur) is an element that further improves the affinity between the surface of metal particles and the resin by adding it in the presence of Cl, and the packing density of the metal powder (that is, in the resin) when the powder magnetic core is used.
- the volume ratio of the metal powder in (%) is further improved as compared with the case where Cl alone is added, and this improvement in the packing density has an effect of greatly improving the magnetic permeability of the dust core. In order to obtain such an effect, the content of 100 ppm or more is required.
- S (sulfur) is as small as less than 100 ppm, the additional effect of improving the affinity between the powder particle surface and the resin is not recognized, and only 70% of the packing density, which is the same level as when Cl alone is added, can be achieved.
- S (sulfur) is limited to the range of 100 to 10000 ppm. It is preferably 200 to 8000 ppm, more preferably 300 to 6000 ppm.
- the improvement range of the volume ratio of the metal powder in the dust core is a seemingly small value of 2% from 70% of the comparative example to 72% of the invention example.
- An additional + 2% forms a compact skeleton above 70%, which approaches the geometric volume limit of 74% for a single-sized rigid sphere densely packed model.
- the saturation magnetic flux density of the dust core which is one of the factors affecting the iron loss of the dust core, is almost proportional to the volume ratio of the metal powder in the powder core, the stage near the upper limit of the filling volume ratio. From now on, no further big improvement can be expected.
- the magnetic permeability of the dust core which is also a factor that greatly affects the iron loss of the dust core, is greatly affected by the distance between the particles, and therefore approaches the filling limit (that is, the distance between the particles is zero).
- the demagnetizing field decreases sharply and the magnetic permeability increases sharply. Therefore, the steady improvement of the volume fraction of the metal powder leads to the reduction of the iron loss, and the iron loss of the dust core, which is already at a sufficiently small level before the volume fraction improvement, is further greatly reduced by the present invention. The result was brought about.
- O (oxygen) exists as an oxide on the surface and has an action of suppressing activation of the surface of the metal powder. In order to obtain such an effect, it is preferable to contain O (oxygen) in an amount of 0.2% or more. A small amount of O (oxygen) does not adversely affect the magnetic properties of the powder, but if it is less than 0.2%, the surface of the metal powder is active and easily ignites, making it difficult to handle in the atmosphere. On the other hand, if it is contained in a large amount exceeding 7.0%, the saturation magnetization is lowered. Therefore, O (oxygen) was limited to the range of 0.2 to 7.0%. It should be noted that it is preferably 0.3 to 3.0%. More preferably, it is 1.0 to 2.0%.
- Ni is mentioned as an impurity element.
- Fe—Ni alloy scrap, austenitic stainless scrap, or the like is used as a raw material as the Fe source, Ni is mixed as an impurity element.
- Ni is an element that lowers the saturation magnetization of the metal powder when mixed as an auxiliary material or an impurity to reduce the Fe content, and it is desirable to reduce it as much as possible.
- Ni is compared with other impurity elements. Since the coercive force is rarely increased and the action of lowering the saturation magnetization is slow, a content of 10% or less is acceptable.
- Ni is more preferably 5% or less, still more preferably 3% or less.
- unavoidable impurities other than Ni include C, N, P, Mn, Cu, Al and the like. These elements are elements that reduce the saturation magnetization of the metal powder, and if the total content is 3% or less, the deterioration of magnetic properties, which can be said to be fatal in practical use, does not occur, so it is acceptable, but the total. It is more preferable that the amount is 1% or less.
- the metal powder of the present invention has the above-mentioned composition and has an average particle size of 0.1 to 2.0 ⁇ m as particles (powder).
- the "average particle size” referred to here is the number-based D50 obtained by observing metal powder particles with a scanning electron microscope (SEM), imaging them, and analyzing 1000 to 2000 particles measured by SEM image analysis at a magnification of 20,000 times. And. If the average particle size is less than 0.1 ⁇ m, aggregation is likely to occur when kneaded with the resin, and the filling rate does not increase, so that the saturation magnetic flux density as the dust core decreases.
- the average particle size of the metal powder of the present invention is limited to the range of 0.1 to 2.0 ⁇ m. It is preferably 0.1 to 1.5 ⁇ m. More preferably, it is 0.1 to 1.0 ⁇ m.
- [Magnetic properties of metal powder] [Coercive force]
- the metal powder is placed in a predetermined container, paraffin is melted, solidified and fixed, and the applied magnetic field is 1200 kA / m using a vibrating sample magnetometer (VSM). It was measured under the condition of. It is desirable that the coercive force is small in applications such as the magnetic core of an inductor or a transformer, which is the object of the present invention.
- the saturation magnetization of the metal powder in the present invention was measured using a VSM under the condition of an applied magnetic field of 1200 kA / m, as in the measurement of the coercive force described above. It is desirable that the saturation magnetization is large in applications such as the magnetic core of an inductor or a transformer, which is the object of the present invention.
- the metal powder of the present invention can be produced by a gas atomization method, a water atomization method, or the like, but it is preferably produced by a chemical vapor deposition (hereinafter referred to as “CVD”).
- CVD chemical vapor deposition
- the chloride gas of each element generated by reacting the alloy elements of Fe, Si and Cr with the high temperature chlorine gas, or the chloride of each element of Fe, Si and Cr is heated to a high temperature.
- Si, Cr , S (sulfur)-containing metal powder having a desired composition is obtained.
- the method for producing a metal powder by CVD of the present invention is preferable because the concentration of chloride gas, the reaction temperature and the reaction time can be adjusted so as to have a desired average particle size.
- the cleaning step is a step of cleaning the obtained metal powder with a solvent and adjusting Cl to 10,000 ppm or less.
- a solvent that dissolves unreduced chloride or a by-product produced by the reduction reaction.
- examples of such a solvent include water-soluble inorganic solvents such as water and organic solvents such as fatty alcohols such as ethyl alcohol.
- the resin to be mixed as a binder is preferably a resin having an improved affinity with the surface of the metal powder, and specifically, a thermosetting resin, an ultraviolet curable resin or a thermoplastic resin is preferable.
- a thermosetting resin include epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, polyurethane resin, diallyl phthalate resin and the like.
- the ultraviolet curable resin include urethane acrylate resin, epoxy acrylate resin, polyester acrylate resin and the like.
- examples of the thermoplastic resin include polyphenylene sulfide resin and nylon resin (polyamide resin). These resins were effective in improving the affinity with the surface of the metal powder.
- the mixture or granulated powder is filled in the mold and compression-molded to obtain a molded body (compact magnetic core) having the shape of the compact to be produced.
- a thermosetting resin is used as the resin
- heat treatment may be performed at 50 to 200 ° C.
- the obtained green compact is a bond in which the metal powder and the resin are tightly bonded.
- Magnetic core loss is a loss that occurs due to the physical characteristics of the magnetic core in a coil such as an inductor or transformer that has a magnetic core made of magnetic material, and is one of the factors that reduce the efficiency of transformers and the like. It is one.
- the mixed powder obtained by mixing and dispersing the metal powder in the epoxy resin is filled in a ring-shaped mold (outer diameter: 13.0 mm, inner diameter: 8.0 mm), press-molded, and then the resin is used. It was cured to form a toroidal core (powder core) having a thickness of 3.0 mm, and a coil was provided with 20 turns on the primary side and 20 turns on the secondary side.
- the iron loss of the coil was measured using a BH analyzer (SY-8218 manufactured by Iwadori Measurement Co., Ltd.) under the conditions of a magnetic flux density of 0.025 T and a frequency of 1 MHz.
- the iron loss of the green compact of the present invention is 500 kW / m 3 or less. More preferably, it is 450 kW / m 3 or less.
- Fe chloride, Si chloride, and Cr chloride were prepared as raw materials. Then, these chlorides were heated to a high temperature (900 to 1200 ° C., preferably about 1000 ° C.) by a CVD reactor to vaporize the chlorides to generate chloride gas of each element. Further, S (sulfur) was vaporized and heated at a high temperature (900 to 1200 ° C.) to generate a gas. Chloride gas of each element generated and gas vaporized with S (sulfur) are mixed by changing the mixing ratio so as to have the composition of the target metal powder, and a mixed gas mainly composed of metal chloride is mixed.
- a high temperature 900 to 1200 ° C., preferably about 1000 ° C.
- S sulfur
- Chloride gas of each element generated and gas vaporized with S (sulfur) are mixed by changing the mixing ratio so as to have the composition of the target metal powder, and a mixed gas mainly composed of metal chloride is mixed.
- the obtained mixed gas is sent to a CVD reactor together with hydrogen gas and nitrogen gas as a carrier gas (gas temperature: 900 to 1200 ° C., gas flow rate of 10 to 500 Nl / min) to a predetermined reactor temperature (900 to 1200 ° C.).
- the reaction was carried out in 1 to reduce the chloride to obtain a metal powder.
- the composition of the metal powder is controlled by the mixing ratio of the metal chloride gas or the like, and the average particle size is controlled by the chloride gas concentration of the raw material, the high or low reaction temperature, and the length of the reaction time.
- Table 1 shows the composition of the prepared metal powder, its powder characteristics, and the characteristics of the green compact.
- the content of alloying elements (Si, Cr) contained in the metal powder was measured using ICP (inductively coupled plasma).
- Cl, S (sulfur) and O (oxygen) contained in the metal powder were measured by using a combustion method. Further, the obtained metal powder was observed and imaged by the above-mentioned method and conditions using SEM, and D50 was obtained by image analysis and used as the average particle size.
- the magnetic properties (coercive force, saturation magnetization) and rust resistance, as well as the packing density (volume ratio) and iron loss of the green compact of the metal powder were investigated.
- the survey method is as described above, but the specifics are as follows.
- the coercive force and saturation magnetization of the obtained various metal powders were measured using a vibration sample magnetometer (manufactured by Toei Kogyo Co., Ltd.).
- the rust resistance the presence or absence of rust was observed in the obtained various metal powders by the above-mentioned rust resistance measurement test, and the ratio of rusted particles (rusting rate) was calculated.
- the packing density was expressed as a volume-based ratio (volume fraction:%) of the metal powder in the resin. Iron loss was also measured by the method and conditions described above.
- All of the examples of the present invention are metal powders having a low coercive force of 12 Oe or less, holding a high saturation magnetization of 170 emu / g or more, and having excellent rust resistance, and further, when a dust core is used, the iron loss is 500 kW. It has a remarkable effect of being able to produce a dust core with low iron loss of / m 3 or less.
- comparative examples outside the scope of the present invention are metal powders having a high coercive force of more than 12 Oe, a low saturation magnetization of less than 170 emu / g, or a deteriorated rust resistance.
- the volume ratio of the metal powder in the resin is as low as 70% or less, and the iron loss exceeds 650 kW / m 3 , resulting in a dust core with a high iron loss.
- the metal powder No. In 1 to 9 O (oxygen) was 0.3%, and the data in which Si was changed, No. In 10 to 20, O (oxygen) was 1.0%, and the data in which Si was changed, No. 21 to 28 are data in which Cr is changed and Si is partially changed, No. 29 to 37 are data in which Cl is changed and Si is partially changed, No. 38 to 49 are data in which S (sulfur) is changed and Si is partially changed, No. 50 to 54 are data in which O (oxygen) is changed, No. Reference numerals 55 to 75 are data in which the average particle size is changed and some Si is also changed. Further, the underlined data indicates that the data is out of the preferable range, and further, for example, "50 ⁇ " means "greater than 50".
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Abstract
Description
〔1〕質量濃度で、Si:1.0~15.0%、Cr:1.0~13.0%、Cl:10~10000ppm、S(硫黄):100~10000ppm及びO(酸素):0.2~7.0%を含有し、残部Fe及び不可避的不純物からなる金属粉末であって、前記金属粉末の平均粒径が、0.1~2.0μmであることを特徴とする金属粉末。
〔2〕〔1〕に記載の前記金属粉末と樹脂との結合物であることを特徴とする圧粉体。
〔3〕〔2〕において、前記樹脂が、熱硬化性樹脂、紫外線硬化型樹脂又は熱可塑性樹脂であることを特徴とする圧粉体。
〔4〕化学的気相法により、質量濃度で、Si:1.0~15.0%、Cr:1.0~13.0%、Cl:10~10000ppm、S(硫黄):100~10000ppm及びO(酸素):0.2~7.0%を含有し、残部Fe及び不可避的不純物からなる金属粉末であって、前記金属粉末の平均粒径が、0.1~2.0μmである前記金属粉末を生成することを特徴とする金属粉末の製造方法。
〔5〕化学的気相法により、質量濃度で、Si:1.0~15.0%、Cr:1.0~13.0%、Cl:10~10000ppm、S(硫黄):100~10000ppm及びO(酸素):0.2~7.0%を含有し、残部Fe及び不可避的不純物からなる金属粉末を生成し、前記金属粉末に、樹脂を混合し、圧縮成形したことを特徴とする圧粉体の製造方法。
〔6〕〔5〕において、前記樹脂が、熱硬化性樹脂、紫外線硬化型樹脂又は熱可塑性樹脂であることを特徴とする圧粉体の製造方法。
本発明の金属粉末は、Feを主成分とする金属粉末(鉄合金粉末)である。つまり、本発明の金属粉末は、質量濃度で、Si:1.0~15.0%、Cr:1.0~13.0%、Cl:10~10000ppm、S(硫黄):100~10000ppm及びO(酸素):0.2~7.0%を含有し、残部Fe及び不可避的不純物からなる金属粉末であって、前記金属粉末の平均粒径が、0.1~2.0μmである。以下、組成における%およびppmは、質量濃度であることを意味する。
Feを主成分とする金属粉末(鉄合金粉末)では、Siは、金属(Fe)中に固溶して、金属粉末の電気抵抗の増大と磁歪の減小に寄与する元素である。磁歪はSi含有量の増大とともに減小し、6.5%程度の含有量でほぼゼロとなりさらに含有量を増大させると、磁歪はさらに減小して負の値になる。一方、電気抵抗(比抵抗)は、Si含有量の増大と共に大きく増大する。磁歪の絶対値の減小は、ヒステリシス損失の低減に寄与し、電気抵抗の増大は、渦電流損失の低減に寄与する。
Crは、金属粉末の磁気特性を低下させるが、耐食性を向上させる元素であり、本発明の金属粉末において耐食性の効果を得るには、1.0%以上含有させることが好ましい。Crが1.0%未満と少ない場合には、粒子表面に錆が発生しやすくなる。一方、13.0%を超えて多量に含有すると、飽和磁化(emu/g)が低下する。このため、Crは1.0~13.0%の範囲に限定した。なお、好ましくは1.0~6.0%である。さらに好ましくは、1.0~4.0%である。ここで、耐食性とは、後述する耐錆性のことである。
Cl(塩素)は、金属粒子表面と樹脂との親和性向上に寄与する元素であり、圧粉磁心とした場合の金属粉末の充填密度を向上させ、圧粉磁心の磁束密度を向上させる効果を有する。このような効果を得るためには、10ppm以上の含有を必要とする。Clが10ppm未満と少ない場合には、金属粉末の粒子表面と樹脂との親和性が低く、金属粉末粒子の周囲に空隙が生じやすく、所望の充填密度を達成できない。一方、Clの含有量が10000ppmを超えて多量に含有すると、表面からの吸湿による錆発生が促進されるおそれがある。このため、Clは、10~10000ppmの範囲に限定した。なお、好ましくは、10~1000ppmである。より好ましくは、10~500ppmである。
S(硫黄)は、Clの存在下で添加することで、金属粒子表面と樹脂との親和性をさらに向上させる元素であり、圧粉磁心とした場合の金属粉末の充填密度(即ち、樹脂中の金属粉末の体積率%)を、Cl単独添加の場合に比べてさらに向上させ、この充填密度の向上は、圧粉磁心の透磁率を大きく向上させる効果を有する。このような効果を得るためには、100ppm以上の含有を必要とする。S(硫黄)が100ppm未満と少ない場合には、粉末粒子表面と樹脂との親和性改善の追加の効果が認められず、Cl単独添加の場合と同レベルの70%の充填密度しか達成できない。一方、S(硫黄)の含有量が10000ppmを超えて多量に含有すると、表面からの吸湿による錆が発生し、樹脂との親和性が低下し、充填密度も低下する。このため、本発明ではS(硫黄)は100~10000ppmの範囲に限定した。なお、好ましくは、200~8000ppm、より好ましくは、300~6000ppmである。
O(酸素)は、表面に酸化物として存在し、金属粉末表面が活性化するのを抑制する作用を有する。このような効果を得るためには、O(酸素)を0.2%以上含有することが好ましい。O(酸素)が少ないことで、粉末の磁気特性に悪影響を及ぼすことは無いが、0.2%未満では、金属粉末表面が活性で、発火しやすくなり、大気中での取り扱いが難しくなる。一方、7.0%を超えて多量に含有すると、飽和磁化が低下する。このようなことから、O(酸素)は0.2~7.0%の範囲に限定した。なお、好ましくは、0.3~3.0%である。より好ましくは、1.0~2.0%である。
上記した成分以外の残部は、Fe及び不可避的不純物である。
不純物元素としては、まず、Niが挙げられる。Fe源として、Fe-Ni合金スクラップやオーステナイト系ステンレススクラップ等を原料として使用した場合等に、不純物元素としてNiが混入してくる。Niは、副原料あるいは不純物として、混入し、Fe含有量を低下させた場合、金属粉末の飽和磁化を低下させる元素であり、できるだけ低減することが望ましいが、Niは、他の不純物元素に比べ、保磁力を増加させることも少なく、また飽和磁化を低下させる作用が緩慢であるため、10%以下の含有量であれば許容できる。なお、コアとしての飽和磁束密度の向上のためには、Niは、5%以下とすることがより好ましく、さらに好ましくは3%以下である。
次に、本発明の金属粉末は、上記した組成を有し、平均粒径が、0.1~2.0μmの粒子(粉末)とするものである。ここでいう「平均粒径」は、金属粉末粒子を走査型電子顕微鏡(SEM)観察し、撮像して倍率2万倍で測定粒子数1000~2000個のSEM画像解析により求めた個数基準のD50とする。平均粒径が0.1μm未満では、樹脂と混錬した場合に凝集が発生しやすく、充填率が上がらないため、圧粉磁心としての飽和磁束密度が低下する。一方、平均粒径が2.0μmを超えると、鉄損、特に高周波における鉄損が増加する。このため、本発明の金属粉末の平均粒径は、0.1~2.0μmの範囲に限定した。なお、好ましくは0.1~1.5μmである。より好ましくは、0.1~1.0μmである。
[保磁力]
本発明における金属粉末の保磁力の測定は、金属粉末を所定の容器に入れ、パラフィンを融解、凝固させて固定したものを振動試料型磁力計(VSM)を用いて、印加磁界:1200kA/mの条件で測定した。本発明の目的とするインダクタや変圧器の磁心などの用途では保磁力は小さいことが望ましい。
本発明における金属粉末の飽和磁化の測定は、前記の保磁力の測定と同様に、VSMを用いて、印加磁界:1200kA/mの条件で測定した。本発明の目的とするインダクタや変圧器の磁心などの用途では飽和磁化は大きいことが望ましい。
金属粉末の耐錆性測定方法としては、金属粉末を樹脂に埋め込み固定した後、断面を鏡面研磨して、耐錆性測定用試験片とし、この試験片を恒温恒湿槽中に所定時間保持した後、試験片内の粒子について、ランダムに20個を選定し、発錆の有無を観察し、発錆している粒子の割合(発錆率)を算出した。なお、恒温恒湿槽は、温度:60℃、相対湿度:95%の条件で保持した。また、恒温恒湿槽中の保持時間は2000時間とした。こうして求めた本発明の金属粉末の発錆率は、使用上の不具合が発生しないことから10%以下であることが好ましい。さらに、5%以下であることがより好ましい。
続いて、本発明の金属粉末の製造方法について説明する。
本発明の金属粉末は、ガスアトマイズ法や水アトマイズ法などでも製造可能であるが、化学的気相法(Chemical Vapor Deposition:以下、「CVD」という。)を用いて製造することが好ましい。
本発明の金属粉末を樹脂中で分散させることにより、充填密度の高い低磁心損失の圧粉体を製作することが容易になる。
圧粉体の製造方法としては、特段の制約はなく、公知の方法で製造が可能である。まず、前記金属粉末と、結合剤としての樹脂とを混合し、前記金属粉末が樹脂中に分散した混合物を得る。また、必要に応じて、得られた混合物を造粒して造粒物としてもよい。その混合物または造粒物を圧縮成形することにより、成形体(圧粉体)が得られる。
磁心損失(鉄損)は、磁性材の磁心を持つインダクタや変圧器などのコイルにおいて、その磁心の物性のために発生する損失のことであって、変圧器などの効率を低下させる要因の一つである。鉄損の測定は、金属粉末をエポキシ樹脂中に混合し分散させた混合粉をリング状金型(外径:13.0mm、内径:8.0mm)に充填し、プレス成型したのち、樹脂を硬化させて、厚さ:3.0mmのトロイダルコア(圧粉磁心)とし、1次側20ターン、2次側20ターンの巻線を与えてコイルとした。そのコイルをB-Hアナライザ(岩通計測株式会社製SY-8218)を用いて、磁束密度0.025T、周波数1MHzの条件で鉄損を測定した。本発明の圧粉体の鉄損は、500kW/m3以下である。さらに好ましくは、450kW/m3以下である。
作製した金属粉末の組成およびその粉末特性、並びに圧粉体の特性を表1に示す。
耐錆性については、得られた各種金属粉末を、前述した耐錆性測定試験により、発錆の有無を観察し、発錆している粒子の割合(発錆率)を算出した。
充填密度は、樹脂中における金属粉末の体積基準の割合(体積率:%)で表した。
鉄損についても、前述した方法および条件にて測定した。
Claims (6)
- 質量濃度で、Si:1.0~15.0%、Cr:1.0~13.0%、Cl:10~10000ppm、S(硫黄):100~10000ppm及びO(酸素):0.2~7.0%を含有し、残部Fe及び不可避的不純物からなる金属粉末であって、前記金属粉末の平均粒径が、0.1~2.0μmであることを特徴とする金属粉末。
- 請求項1に記載の前記金属粉末と樹脂との結合物であることを特徴とする圧粉体。
- 前記樹脂が、熱硬化性樹脂、紫外線硬化型樹脂又は熱可塑性樹脂であることを特徴とする請求項2に記載の圧粉体。
- 化学的気相法により、質量濃度で、Si:1.0~15.0%、Cr:1.0~13.0%、Cl:10~10000ppm、S(硫黄):100~10000ppm及びO(酸素):0.2~7.0%を含有し、残部Fe及び不可避的不純物からなる金属粉末であって、前記金属粉末の平均粒径が、0.1~2.0μmである前記金属粉末を生成することを特徴とする金属粉末の製造方法。
- 化学的気相法により、質量濃度で、Si:1.0~15.0%、Cr:1.0~13.0%、Cl:10~10000ppm、S(硫黄):100~10000ppm及びO(酸素):0.2~7.0%を含有し、残部Fe及び不可避的不純物からなる金属粉末を生成し、前記金属粉末に、樹脂を混合し、圧縮成形したことを特徴とする圧粉体の製造方法。
- 前記樹脂が、熱硬化性樹脂、紫外線硬化型樹脂又は熱可塑性樹脂であることを特徴とする請求項5に記載の圧粉体の製造方法。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008195986A (ja) | 2007-02-09 | 2008-08-28 | Hitachi Metals Ltd | 軟磁性金属粉末、圧粉体、および軟磁性金属粉末の製造方法 |
JP2013026356A (ja) | 2011-07-19 | 2013-02-04 | Taiyo Yuden Co Ltd | 磁性材料およびそれを用いたコイル部品 |
JP5354101B2 (ja) | 2010-06-09 | 2013-11-27 | 新東工業株式会社 | 鉄族基軟磁性粉末材 |
JP2014078629A (ja) | 2012-10-11 | 2014-05-01 | Daido Steel Co Ltd | Fe基軟磁性金属粉体 |
JP2017092481A (ja) | 2015-05-14 | 2017-05-25 | Tdk株式会社 | 軟磁性金属粉末、および、軟磁性金属圧粉コア。 |
JP2020070499A (ja) * | 2018-10-30 | 2020-05-07 | Dowaエレクトロニクス株式会社 | 軟磁性粉末、軟磁性粉末の熱処理方法、軟磁性材料、圧粉磁心及び圧粉磁心の製造方法 |
JP2020076135A (ja) | 2018-11-09 | 2020-05-21 | Jfeミネラル株式会社 | 金属粉末 |
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CN112566741B (zh) * | 2018-08-23 | 2023-06-02 | 株式会社博迈立铖 | 磁芯用粉末、使用其的磁芯和线圈部件、和磁芯用粉末的制造方法 |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008195986A (ja) | 2007-02-09 | 2008-08-28 | Hitachi Metals Ltd | 軟磁性金属粉末、圧粉体、および軟磁性金属粉末の製造方法 |
JP5354101B2 (ja) | 2010-06-09 | 2013-11-27 | 新東工業株式会社 | 鉄族基軟磁性粉末材 |
JP2013026356A (ja) | 2011-07-19 | 2013-02-04 | Taiyo Yuden Co Ltd | 磁性材料およびそれを用いたコイル部品 |
JP2014078629A (ja) | 2012-10-11 | 2014-05-01 | Daido Steel Co Ltd | Fe基軟磁性金属粉体 |
JP2017092481A (ja) | 2015-05-14 | 2017-05-25 | Tdk株式会社 | 軟磁性金属粉末、および、軟磁性金属圧粉コア。 |
JP2020070499A (ja) * | 2018-10-30 | 2020-05-07 | Dowaエレクトロニクス株式会社 | 軟磁性粉末、軟磁性粉末の熱処理方法、軟磁性材料、圧粉磁心及び圧粉磁心の製造方法 |
JP2020076135A (ja) | 2018-11-09 | 2020-05-21 | Jfeミネラル株式会社 | 金属粉末 |
Non-Patent Citations (1)
Title |
---|
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