WO2015137493A1 - 磁心、コイル部品および磁心の製造方法 - Google Patents
磁心、コイル部品および磁心の製造方法 Download PDFInfo
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- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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- 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
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
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- H01F1/14791—Fe-Si-Al based alloys, e.g. Sendust
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Definitions
- the present invention relates to a magnetic core having a structure including a granular alloy phase, a coil component using the magnetic core, and a method of manufacturing the magnetic core.
- the coil component includes a magnetic core (magnetic core) and a coil formed by winding the magnetic core, and ferrite cores that are excellent in magnetic properties, shape flexibility, and cost are widely used for such magnetic cores.
- the demand for coil components that are small and low in profile and can be used for large currents has increased, and the saturation magnetic flux density is higher than that of ferrite cores.
- Adoption of magnetic cores using metallic magnetic powder is progressing.
- the metal-based magnetic powder for example, pure Fe, Fe-Si-based, Fe-Al-Si-based, Fe-Cr-Si-based Fe-based magnetic alloy particles are known.
- the saturation magnetic flux density of the Fe-based magnetic alloy is, for example, 1 T or more, and the magnetic core using it has excellent DC superposition characteristics even if it is downsized.
- such a magnetic core contains a large amount of Fe, so its specific resistance is small and eddy current loss is large. Therefore, for high frequency applications exceeding 100 kHz, use it without coating the alloy grains with an insulator such as resin or glass. Was considered difficult.
- a magnetic core in which Fe-based magnetic alloy grains are bonded through such an insulator may have a lower strength than a ferrite core due to the influence of the insulator.
- Patent Document 1 discloses a soft magnetic alloy having a composition of Cr: 2 to 8 wt%, Si: 1.5 to 7 wt%, Fe: 88 to 96.5 wt%, Al: 2 to 8 wt%, Si: 1.
- a magnetic core obtained by heat-treating a molded body composed of particles of soft magnetic alloy using a soft magnetic alloy having a composition of 5 to 12 wt% and Fe: 80 to 96.5 wt% in an atmosphere containing oxygen Is disclosed.
- the breaking stress is improved to 20 kgf / mm 2 (196 MPa), but the specific resistance is remarkably reduced to 2 ⁇ 10 2 ⁇ ⁇ cm. It has not yet been secured.
- Patent Document 2 discloses that Fe—Cr—Al based magnetic powder containing Cr: 1.0 to 30.0 mass%, Al: 1.0 to 8.0 mass%, and the balance substantially consisting of Fe is oxidized.
- a magnetic core is disclosed in which heat treatment is performed at 800 ° C. or higher in an atmosphere, whereby an oxide film containing alumina is self-generated on the surface, and then the magnetic powder is solidified by discharge plasma sintering in a vacuum chamber. ing.
- This Fe—Cr—Al based magnetic powder may contain one or two of Ti: 1.0 mass% or less and Zr: 1.0 mass% or less, and Si: 0.5 mass as an impurity element. % Or less.
- the resistance value is only about several m ⁇ , it is not satisfactory when used in high frequency applications or when an electrode is directly formed on the surface of a magnetic core.
- JP 2011-249774 A Japanese Patent Laid-Open No. 2005-220438
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a magnetic core excellent in specific resistance and strength, a coil component using the magnetic core, and a method of manufacturing the magnetic core.
- M1 (where M1 is an element of both Al and Cr), Si and R (where R is Y, Zr, Nb, La, Hf and Ta).
- R is Y, Zr, Nb, La, Hf and Ta.
- a magnetic core comprising an oxide region containing Fe, M1, Si, and R and containing more Al than the alloy phase by mass ratio.
- the sum of Fe, M1, and R is 100 mass%, Al is 3 mass% to 10 mass%, Cr is 3 mass% to 10 mass%, and R is 0.00. It is preferably contained in an amount of 01% by mass or more and 1% by mass or less, with the balance being Fe and inevitable impurities. Moreover, what contains R by 0.3 mass% or more is preferable. Moreover, what contains R at 0.6 mass% or less is preferable.
- M2 (where M2 is any element of Al or Cr), Si and R (where R is Y, Zr, Nb, La, Hf and Ta).
- the magnetic core in the second aspect is configured such that the sum of Fe, M2, Si and R is 100% by mass, M2 is 1.5% by mass and 8% by mass, Si is more than 1% by mass and 7% by mass or less, It is preferable that R is contained in an amount of 0.01% by mass to 3% by mass with the balance being Fe and inevitable impurities. Moreover, what contains R by 0.3 mass% or more is preferable. Moreover, what contains R at 0.6 mass% or less is preferable.
- the oxide region includes a region having a higher R ratio than other regions in the oxide region.
- R is preferably Zr or Hf.
- the magnetic core according to the first aspect of the present invention preferably has a specific resistance of 1 ⁇ 10 5 ⁇ ⁇ m or more and a crushing strength of 120 MPa or more.
- the values of the specific resistance and the crushing strength are values obtained by a measuring method of an example described later.
- the coil component according to the present invention has the above-described magnetic core according to the present invention and a coil applied to the magnetic core.
- the manufacturing method of the magnetic core according to the present invention includes M1 (where M1 is an element of both Al and Cr), Si and R (where R is a group consisting of Y, Zr, Nb, La, Hf and Ta).
- a step of obtaining a mixed powder by mixing Fe-based soft magnetic alloy grains containing at least one selected element) and a binder, a step of pressing the mixed powder to obtain a compact, and an atmosphere containing oxygen Heat-treating the green body in a step to obtain a magnetic core having a structure including an alloy phase formed by the Fe-based soft magnetic alloy grains, and forming the grain boundary phase connecting the alloy phases by the heat treatment
- an oxide region containing Fe, M1, Si, and R in the grain boundary phase and containing more Al than the alloy phase in a mass ratio is generated.
- another magnetic core manufacturing method includes M2 (where M2 is any element of Cr or Al), Si and R (where R is Y, La, Zr, Hf, Nb, And at least one element selected from the group consisting of Ta) containing Fe-based soft magnetic alloy particles and a binder to obtain a mixed powder, and forming the mixed powder to obtain a compact, A step of heat-treating the compact in an atmosphere containing oxygen to obtain a magnetic core having a structure including an alloy phase formed of the Fe-based soft magnetic alloy particles, and the particles that connect the alloy phases by the heat treatment In addition to forming a boundary phase, an oxide region containing Fe, M2, Si, and R in the grain boundary phase and containing more M2 than the alloy phase in a mass ratio is generated.
- a magnetic core excellent in specific resistance and strength can be provided, and a coil component using the magnetic core and a method for manufacturing the magnetic core can be provided.
- the magnetic core in the first aspect includes an alloy phase formed by Fe-based soft magnetic alloy grains containing M1, Si and R, and the alloy phase has a structure connected by a grain boundary phase.
- FIG. 1 has, for example, a cross-sectional microstructure as shown in FIG.
- a cross-sectional microstructure is observed by observation of 600,000 times or more using, for example, a transmission electron microscope (TEM).
- This structure includes a granular alloy phase 20 containing Fe (iron), M1 and Si, and adjacent alloy phases 20 are connected by a grain boundary phase 30.
- M1 is an element of both Al (aluminum) and Cr (chromium).
- the grain boundary phase 30 is mainly formed by heat treatment in an atmosphere containing oxygen as described later.
- the grain boundary phase 30 includes an oxide region containing Fe, M1, Si, and R and containing more Al than the alloy phase 20 by mass ratio.
- the oxide region includes a region containing more R than the alloy phase 20 on the interface side with the alloy phase 20.
- R is at least one element selected from the group consisting of Y (yttrium), Zr (zirconium), Nb (niobium), La (lanthanum), Hf (hafnium), and Ta (tantalum).
- the alloy phase 20 is formed of Fe-based soft magnetic alloy grains containing Al, Cr, Si, and R, with the balance being Fe and inevitable impurities.
- Non-ferrous metals (ie, Al, Cr and R) contained in Fe-based soft magnetic alloy grains have a greater affinity with O (oxygen) than Fe, and when heat treatment is performed in an atmosphere containing oxygen, these non-ferrous metals
- An oxide or a composite oxide with Fe is generated to cover the surface of the Fe-based soft magnetic alloy grains, and further fill the voids between the particles.
- the oxide region is mainly grown by a reaction between Fe-based soft magnetic alloy grains and oxygen by heat treatment, and is formed by an oxidation reaction exceeding the natural oxidation of Fe-based soft magnetic alloy grains.
- the Fe and oxides of the above non-ferrous metals have a higher electric resistance than a single metal, and the grain boundary phase 30 interposed between the alloy phases 20 functions as an insulating layer.
- the Fe-based soft magnetic alloy grains used for forming the alloy phase 20 include Fe as a main component having the highest content ratio among the constituent components, and Al, Cr, Si, Y, Zr, And at least one of Nb, La, Hf, and Ta.
- Y, Zr, Nb, La, Hf, and Ta are all metals that are difficult to dissolve in Fe and have a relatively large absolute value of the standard generation Gibbs energy of the oxide (easy to generate an oxide).
- Fe is a main element constituting Fe-based soft magnetic alloy grains, and affects magnetic characteristics such as saturation magnetic flux density and mechanical characteristics such as strength.
- the Fe-based soft magnetic alloy grains preferably contain Fe in an amount of 80% by mass or more, whereby a soft magnetic alloy having a high saturation magnetic flux density can be obtained.
- Al has a greater affinity with O than Fe and other non-ferrous metals. Therefore, during heat treatment, O in the atmosphere and O contained in the binder are preferentially bonded to Al in the vicinity of the surface of the Fe-based soft magnetic alloy grains, so that chemically stable Al 2 O 3 and other non-ferrous metals A complex oxide is generated on the surface of the alloy phase 20. In addition, since O that attempts to penetrate into the alloy phase 20 reacts with Al, and oxides containing Al are generated one after another, entry of O into the alloy phase 20 is prevented, and the concentration of O as an impurity is reduced. Deterioration of magnetic properties can be prevented by suppressing the increase. Since the oxide region containing Al having excellent corrosion resistance and stability is generated on the surface of the alloy phase 20, the insulation between the alloy phases 20 is enhanced, and the specific resistance of the magnetic core is improved by reducing eddy current loss. it can.
- the Fe-based soft magnetic alloy particles preferably contain Al in an amount of 3% by mass to 10% by mass. If this is less than 3% by mass, the generation of oxide containing Al may not be sufficient, and the insulation and corrosion resistance may be reduced.
- the Al content is more preferably 3.5% by mass or more, still more preferably 4.0% by mass or more, and particularly preferably 4.5% by mass or more. On the other hand, if it exceeds 10% by mass, the magnetic properties may be degraded due to a decrease in the amount of Fe, such as a decrease in saturation magnetic flux density or initial permeability, or an increase in coercive force.
- the Al content is more preferably 8.0% by mass or less, still more preferably 6.0% by mass or less, and particularly preferably 5.0% by mass or less.
- Cr has the highest affinity with O next to Al, and combines with O in the same way as Al during heat treatment to produce chemically stable composite oxides of Cr 2 O 3 and other non-ferrous metals.
- the oxide containing Al is preferentially produced, the amount of Cr in the produced oxide tends to be smaller than that of Al. Since the oxide containing Cr is excellent in corrosion resistance and stability, the insulation between the alloy phases 20 can be improved and eddy current loss can be reduced.
- the Fe-based soft magnetic alloy grains preferably contain Cr in an amount of 3% by mass to 10% by mass. If this is less than 3% by mass, the generation of oxides containing Cr may not be sufficient, and the insulation and corrosion resistance may be reduced.
- the content of Cr is more preferably 3.5% by mass or more, and further preferably 3.8% by mass or more. On the other hand, if it exceeds 10% by mass, the magnetic properties may be degraded due to a decrease in the amount of Fe, such as a decrease in saturation magnetic flux density or initial permeability, or an increase in coercive force.
- the Cr content is more preferably 9.0% by mass or less, still more preferably 7.0% by mass or less, and particularly preferably 5.0% by mass or less.
- the total content of Al and Cr is preferably 7% by mass or more, and more preferably 8% by mass or more.
- the total content of Cr and Al is more preferably 11% by mass or more.
- Al is significantly concentrated in the oxide region between the alloy phases 20 as compared with Cr, it is more preferable to use Fe-based soft magnetic alloy grains having a higher Al content than Cr.
- R (at least one of Y, Zr, Nb, La, Hf and Ta) hardly dissolves in Fe and has a large absolute value of the standard generation Gibbs energy of the oxide.
- Table 1 shows standard Gibbs energies of typical oxides produced by R. In any R oxide, the standard generation Gibbs energy is a negative value, and the absolute value thereof is larger than that of Fe 2 O 3 or Fe 3 O 4 . This indicates that R is more easily oxidized than Fe and is more strongly bonded to O to form a stable oxide such as ZrO 2 .
- an oxide containing R is generated along the edge of the oxide region along the interface between the alloy phase 20 and the grain boundary phase 30, so that the grain boundary phase 30 is transformed from the alloy phase 20. It is possible to effectively suppress the diffusion of Fe to the surface, reduce the contact between the alloy phases, increase the insulation by the oxide region, and improve the specific resistance. Since R is hardly dissolved in Fe as described above, in Fe-based soft magnetic alloy particles produced by the atomization method described later, it is easy to concentrate on the particle surface, and a sufficient effect can be obtained even if a small amount is added.
- the Fe-based soft magnetic alloy particles preferably contain R in an amount of 0.01% by mass to 1% by mass. If this is less than 0.01% by mass, the generation of the oxide containing R is not sufficient, and the effect of improving the specific resistance may not be sufficiently obtained.
- the content of R is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. On the other hand, if this exceeds 1% by mass, the magnetic properties of the magnetic core may not be obtained properly due to an increase in magnetic core loss.
- the content of R is more preferably 0.9% by mass or less, more preferably 0.8% by mass or less, further preferably 0.7% by mass or less, and particularly preferably 0.6% by mass or less.
- R is two or more elements selected from the group consisting of Y, Zr, Nb, La, Hf and Ta, the total amount thereof is preferably 0.01% by mass or more and 1% by mass or less. .
- Ti titanium
- Ti titanium
- Zr and Hf a fourth group element of the same periodic table as Zr and Hf
- the specific resistance tends to decrease although a high initial permeability and a small core loss can be obtained.
- the standard Gibbs energy of TiO 2 is ⁇ 890 kJ / mol, and its absolute value is smaller than that of Fe 3 O 4 , which is considered to be due to the fact that a strong oxide film is not properly formed.
- the specific resistance can be improved while maintaining the strength by using together with the above R.
- the content is preferably less than 0.3% by mass, more preferably less than 0.1% by mass, and still more preferably less than 0.01% by mass. Further, from the viewpoint of appropriately obtaining the magnetic properties of the magnetic core, the total content of R and Ti is preferably 1% by mass or less.
- the Fe-based soft magnetic alloy particles may contain C (carbon), Mn (manganese), P (phosphorus), S (sulfur), O, Ni (nickel), N (nitrogen), etc. as inevitable impurities.
- the contents of these inevitable impurities are respectively C ⁇ 0.05 mass%, Mn ⁇ 1 mass%, P ⁇ 0.02 mass%, S ⁇ 0.02 mass%, O ⁇ 0.5 mass%, Ni It is preferable that ⁇ 0.5% by mass and N ⁇ 0.1% by mass.
- Si silicon may also be included in Fe-based soft magnetic alloy grains as an inevitable impurity.
- Si is usually used as a deoxidizer to remove oxygen O, which is an impurity.
- O oxygen
- the added Si is separated as an oxide and removed during the refining process, but a part of it remains and is often contained in the alloy up to about 0.5 mass% as an inevitable impurity.
- the raw material to be used it may be contained in an alloy to about 1 mass%.
- the Si amount is preferably 0.05 to 1% by mass.
- the range of the amount of Si is a range including not only the case where Si is present as an inevitable impurity (typically 0.5% by mass or less) but also the case where a small amount of Si is added.
- Si amount is within this range, the initial permeability can be increased and the magnetic core loss can be reduced.
- an oxide containing R (for example, Zr) is generated at the edge 30 c of the oxide region along the interface between the alloy phase 20 and the grain boundary phase 30.
- the oxide region contains more Al than the alloy phase 20, and in the oxide region, the edge portion 30c contains more R than the central portion 30a. Since the oxide containing R is generated along the edge portion 30c, the diffusion of Fe from the alloy phase 20 to the grain boundary phase 30 is effectively suppressed, and the insulation by the oxide region is enhanced to reduce the specific resistance. Contributes to improvement.
- the grain boundary phase 30 is substantially formed of an oxide, but an island-like region 30b surrounded by the central portion 30a and the edge portion 30c may be formed as shown in FIG.
- the central portion 30a in the oxide region is referred to as a first region
- the island-shaped region 30b is referred to as a second region
- the edge portion 30c is referred to as a third region.
- the first region 30a and the third region 30c are regions in which the ratio of Al to the sum of Fe, Al, Cr, Si, and R is higher than the ratio of each of Fe, Cr, and R.
- the second region 30b is a region in which the ratio of Fe to the sum of Fe, Cr, Al, Si, and R is higher than the ratio of each of Al, Cr, and R. Since the first region 30a and the third region 30c enriched with Al surround the second region 30b enriched with Fe, a magnetic core having excellent specific resistance can be obtained.
- the alloy phase is granular, and the grains are often polycrystalline composed of a plurality of alloy crystals, but may be a single crystal composed of only a single crystal. Moreover, it is preferable that the alloy phases are not in direct contact with each other and are independent through the grain boundary phase 30.
- the structure of the magnetic core includes an alloy phase 20 and a grain boundary phase 30, and the grain boundary phase 30 is mainly formed by oxidation of Fe-based soft magnetic alloy grains by heat treatment. For this reason, the composition of the alloy phase is different from the composition of the Fe-based soft magnetic alloy grains described above, but composition deviation due to transpiration of Fe, Al, Cr, and R due to heat treatment hardly occurs.
- the composition of the magnetic core excluding O is substantially the same as the composition of the Fe-based soft magnetic alloy grains.
- the composition of such a magnetic core can be quantified by analyzing the cross section of the magnetic core by an analysis method such as energy dispersive X-ray spectroscopy (SEM / EDX) using a scanning electron microscope. Therefore, the magnetic core composed of the Fe-based soft magnetic alloy grains as described above has a sum of Fe, Al, Cr and R of 100 mass%, Al is 3 mass% to 10 mass%, and Cr is 3 mass%. It contains not less than 10% by mass and not more than 10% by mass, R is not less than 0.01% by mass and not more than 1% by mass, and the balance is Fe and inevitable impurities. Moreover, this magnetic core contains Si at 1 mass% or less.
- the coil component according to the present invention has the magnetic core as described above and a coil applied to the magnetic core, and is used as, for example, a choke, an inductor, a reactor, or a transformer.
- An electrode for connecting the ends of the coil may be formed on the surface of the magnetic core by a technique such as plating or baking.
- the coil may be configured by winding a conductive wire directly around a magnetic core, or may be configured by winding the conductive wire around a heat-resistant resin bobbin.
- the coil is wound around the magnetic core or disposed inside the magnetic core, and in the latter case, it is possible to constitute a coil component having a magnetic core with a coil-enclosed structure in which the coil is disposed between a pair of magnetic cores. It is.
- the coil component shown in FIG. 3 has a square core-shaped magnetic core 1 having an integral body 60 between a pair of flanges 50a and 50b, and two terminal electrodes are provided on one surface of one flange 50a. 70 is formed.
- the terminal electrode 70 is formed by printing and baking a silver conductor paste directly on the surface of the magnetic core 1.
- a coil composed of a winding 80 of an enamel conductor is disposed around the body 60. Both end portions of the winding 80 are connected to each of the terminal electrodes 70 by thermocompression bonding to constitute a surface mount type coil component such as a choke coil.
- the flange surface on which the terminal electrode 70 is formed is used as a mounting surface on the circuit board.
- the specific resistance of the magnetic core 1 is high, a conductor can be directly laid on the magnetic core 1 without using a resin case (also called a bobbin) for insulation, and the terminal electrode 70 for connecting the windings can be connected to the magnetic core 1. Since it can be formed on the surface, the coil component can be made compact. In addition, the mounting height of the coil component can be kept low, and stable mounting properties can be obtained. From this viewpoint, the specific resistance of the magnetic core is preferably 1 ⁇ 10 3 ⁇ ⁇ m or more, and more preferably 1 ⁇ 10 5 ⁇ ⁇ m or more.
- the magnetic core 1 is high in strength, when winding a conductor around the trunk portion 60, even if an external force acts on the flange portions 50a, 50b or the trunk portion 60, the magnetic core 1 is not easily broken, and is practical. Excellent. From this viewpoint, the crushing strength of the magnetic core is preferably 120 MPa or more, more preferably 200 MPa or more, and further preferably 250 MPa or more.
- the manufacturing method of the magnetic core is M1 (where M1 is an element of both Al and Cr), Si and R (where R is selected from the group consisting of Y, Zr, Nb, La, Hf and Ta).
- a step of obtaining a mixed powder by mixing Fe-based soft magnetic alloy grains containing one element) and a binder (first step), and a step of pressing the mixed powder to obtain a compact (second step)
- a grain boundary phase 30 that connects adjacent alloy phases 20 as shown in FIG.
- the grain boundary phase 30 contains Fe, M1, Si, and R, and the alloy phase 20 at a mass ratio. This produces an oxide region containing more Al. In the oxide region, the ratio of Al to the sum of Fe, Al, Cr, Si, and R is higher than that in the alloy phase 20.
- Al is 3 mass% to 10 mass%
- Cr is 3 mass% to 10 mass%
- Si is 1 mass% or less
- R is 0.01 mass% to 1 mass%.
- Fe-based soft magnetic alloy grains comprising Fe and inevitable impurities are used. Since a more preferable composition of the Fe-based soft magnetic alloy grains is as described above, a duplicate description is omitted.
- the above-mentioned Fe-based soft magnetic alloy particles preferably have an average particle diameter of 1 to 100 ⁇ m with a median diameter d50 in the cumulative particle size distribution.
- the median diameter d50 is more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less.
- the median diameter d50 is preferably 5 ⁇ m or more.
- an atomizing method such as a water atomizing method or a gas atomizing method suitable for producing a substantially spherical alloy particle that is highly malleable and ductile and difficult to grind.
- a water atomizing method capable of efficiently producing simple alloy grains is particularly preferred.
- the water atomization method a raw material weighed to have a predetermined alloy composition is melted by a high-frequency heating furnace, or an alloy ingot previously prepared to have an alloy composition is melted by a high-frequency heating furnace. Then, by causing the molten metal (molten metal) to collide with water jetted at a high speed and high pressure, it is possible to obtain Fe-based soft magnetic alloy grains by cooling together with the atomization.
- a natural oxide film mainly composed of Al 2 O 3 which is an oxide of Al is formed with a thickness of about 5 to 20 nm.
- This natural oxide film contains Fe, Cr, Si and R in addition to Al.
- R which is difficult to dissolve in Fe, is present in the natural oxide film at a higher concentration than in the alloy grains.
- island-like oxides mainly composed of Fe oxide may be formed on the surface side of this natural oxide film (the outermost surface side when viewed from the whole alloy grain). This island-shaped oxide contains Al, Cr, Si and R in addition to Fe.
- the drying temperature (for example, the temperature in the drying furnace) is preferably 150 ° C. or lower.
- the obtained Fe-based soft magnetic alloy particles have a distribution of particle sizes, when filling the molding die, a large gap is formed between the particles of large particles, and the filling rate does not increase.
- the density of the molded body obtained by pressure molding tends to decrease.
- dry classification such as sieving classification can be used, and it is preferable to obtain alloy grains that are at least under 32 ⁇ m (that is, passed through a sieve having an opening of 32 ⁇ m).
- the binder mixed with the Fe-based soft magnetic alloy particles binds the alloy particles to each other when pressure forming, and imparts strength to the molded body to withstand handling after forming.
- the mixed powder of the Fe-based soft magnetic alloy particles and the binder is preferably granulated by granulation, whereby the fluidity and filling property in the molding die can be improved.
- the kind of binder is not specifically limited, For example, organic binders, such as polyethylene, polyvinyl alcohol, an acrylic resin, can be used. It is possible to use an inorganic binder that remains after heat treatment, but the grain boundary phase produced in the third step works to bind the alloy grains together, so the process is simplified by omitting the inorganic binder. Is preferable.
- the added amount of the binder is not limited as long as the binder can be sufficiently distributed between the Fe-based soft magnetic alloy grains or the strength of the formed body can be sufficiently ensured, but if the added amount of the binder is excessive, the density of the formed body And the strength tends to decrease. From this point of view, the amount of the binder added is preferably 0.2 to 10 parts by weight and more preferably 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the Fe-based soft magnetic alloy grains. preferable.
- the mixing method of the Fe-based soft magnetic alloy particles and the binder is not particularly limited, and conventionally known mixing methods and mixers can be used.
- a granulation method wet granulation methods, such as rolling granulation and spray drying granulation, are employable, for example.
- spray-drying granulation using a spray dryer is preferable, and according to this, the shape of the granules approaches a spherical shape, and the time for exposure to heated air is short, and a large amount of granules can be obtained.
- the resulting granules preferably have a bulk density of 1.5 to 2.5 ⁇ 10 3 kg / m 3 and an average particle size (d50) of 60 to 150 ⁇ m. According to such a granule, the fluidity during molding is excellent, and the gap between the alloy grains is reduced to increase the filling property into the mold, and as a result, the compact becomes dense and the magnetic permeability is reduced. High magnetic core can be obtained. In order to obtain a granule diameter of a desired size, classification using a vibrating sieve or the like can be used.
- a lubricant such as stearic acid or stearate in order to reduce friction between the mixed powder (granules) and the molding die during pressure molding.
- the amount of lubricant added is preferably 0.1 to 2.0 parts by weight with respect to 100 parts by weight of Fe-based soft magnetic alloy grains.
- the lubricant can be applied to the mold.
- the mixed powder of Fe-based soft magnetic alloy particles and binder is preferably granulated as described above and then subjected to pressure molding.
- pressure molding mixed powder is formed into a predetermined shape such as a toroidal shape or a rectangular parallelepiped shape using a press machine such as a hydraulic press or a servo press and a molding die.
- This pressure molding may be room temperature molding, or may be warm molding performed by heating the granules to near the glass transition temperature at which the binder does not disappear depending on the binder material.
- the fluidity of the granules in the molding die can be improved by the shape of the Fe-based soft magnetic alloy particles, the shape of the granules, the selection of their average particle diameter, and the effect of the binder and lubricant.
- the Fe-based soft magnetic alloy grains in the compact obtained by pressure forming are in point contact or surface contact with each other via a binder or natural oxide film, and are partially adjacent to each other through a gap. Even when the Fe-based soft magnetic alloy particles described above are molded at a molding pressure as low as 1 GPa or less, a sufficiently high molding density and crushing strength in the molded body can be obtained. By molding at such a low pressure, the destruction of the natural oxide film containing Al formed on the surface of the Fe-based soft magnetic alloy grains can be reduced, and the corrosion resistance of the molded body can be improved.
- the density of the molded body is preferably 5.6 ⁇ 10 3 kg / m 3 or more.
- the crushing strength of the molded body is preferably 3 MPa or more.
- annealing is performed as a heat treatment on the molded body in order to relieve stress strain introduced by pressure molding and obtain good magnetic properties.
- a grain boundary phase 30 that connects adjacent alloy phases 20 is formed, and the grain boundary phase 30 contains Fe, M1, and R, and contains more Al than the alloy phase 20 by mass ratio.
- An oxide region is generated.
- the organic binder is thermally decomposed by annealing and disappears.
- Annealing is performed in an atmosphere containing oxygen, such as in the air, a mixed gas of oxygen and an inert gas, or an atmosphere containing water vapor, and heat treatment in the air is particularly preferable because it is simple.
- the oxide region is obtained by a reaction between Fe-based soft magnetic alloy grains and oxygen during heat treatment, and is generated by an oxidation reaction that exceeds the natural oxidation of Fe-based soft magnetic alloy grains. By producing such an oxide region, it is possible to obtain a high-strength magnetic core having excellent insulating properties and corrosion resistance and having a large number of Fe-based soft magnetic alloy grains firmly bonded.
- the space factor is preferably in the range of 82 to 90%. As a result, the space factor can be increased and the magnetic characteristics can be improved while suppressing the equipment and cost load.
- the grain boundary phase 30 contains Fe, Al, Cr, Si, and R.
- an oxide containing R appears along the interface between the alloy phase 20 and the grain boundary phase 30 at the edge 30 c of the oxide region in the vicinity of the alloy phase 20.
- the grain boundary phase 30 has a ratio of Al, a ratio of Fe, a ratio of Cr, a ratio of Si, and a ratio of R with respect to a ratio to the sum of Fe, Al, Cr, and R, except for an island-shaped region described later. These regions are higher than each of the above and correspond to the “first region” and the “third region”.
- the “third region” has a higher R ratio than the “first region”, and this oxide region has a higher R ratio than the other regions (first regions) in the oxide region ( A third region).
- the Fe ratio is higher than the Al ratio, the Cr ratio, and the R ratio with respect to the ratio of Fe, Al, Cr, and R.
- the area corresponds to the “second area”.
- the annealing temperature is preferably a temperature at which the molded body is 600 ° C. or higher.
- the insulating properties are reduced due to partial disappearance or alteration of the grain boundary phase 30, or the sintering progresses significantly so that the alloy phases are in direct contact with each other, and the portion (neck portion) where they are partially connected increases.
- the annealing temperature is preferably a temperature at which the compact is 850 ° C. or lower.
- the annealing temperature is more preferably 650 to 830 ° C, and further preferably 700 to 800 ° C.
- the holding time at the annealing temperature is appropriately set according to the size of the magnetic core, the processing amount, the allowable range of characteristic variation, and the like, for example, 0.5 to 3 hours. If the specific resistance or magnetic core loss is not particularly disturbed, it is allowed to form a neck portion in part.
- the average thickness of the grain boundary phase 30 is preferably 100 nm or less, and more preferably 80 nm or less.
- the average thickness of the grain boundary phase 30 is preferably 10 nm or more, more preferably 30 nm or more. preferable.
- the average thickness of the grain boundary phase 30 is a portion where the cross section of the magnetic core is observed with a transmission electron microscope (TEM) at 600,000 times or more, and the contour of the alloy phase in the observation field is confirmed.
- the thickness of the nearest part (minimum thickness) and the thickness of the furthest part (maximum thickness) are measured and calculated by the arithmetic average.
- the average of the maximum diameters of the granular alloy phases is preferably 15 ⁇ m or less, and more preferably 8 ⁇ m or less.
- the average of the maximum diameters of the alloy phases is preferably 0.5 ⁇ m or more. The average of the maximum diameter is calculated by polishing the cross section of the magnetic core and observing under a microscope, reading the maximum diameter for 30 or more particles existing in a field of a certain area, and calculating the number average.
- the Fe-based soft magnetic alloy grains after forming are plastically deformed, most of the alloy phases are exposed in the cross-section of the portion other than the center in the cross-sectional observation, so the average of the maximum diameter is the median diameter d50 evaluated in the powder state. Is a smaller value.
- the abundance ratio of the alloy phase having a maximum diameter of 40 ⁇ m or more is preferably 1% or less in a cross-sectional observation image of 1000 times the magnetic core by SEM. This abundance ratio is determined by measuring the total number K1 of alloy phases surrounded by grain boundaries at least in an observation field of 0.04 mm 2 or more, and the number K2 of alloy phases having a maximum diameter of 40 ⁇ m or more. Divided by and expressed as a percentage. The measurement of K1 and K2 is performed for an alloy phase having a maximum diameter of 1 ⁇ m or more. The high frequency characteristics are improved by making the Fe-based soft magnetic alloy grains constituting the magnetic core fine.
- Example of the first aspect Examples of the first aspect of the present invention will be specifically described.
- a Fe—Al—Cr alloy ingot and a predetermined amount of Zr or Ti both having a purity of 99.8% or more are charged into a crucible and melted at high frequency in an Ar atmosphere, and then the alloy powder is prepared by a water atomization method.
- the produced alloy powder was passed through a sieve of 440 mesh (aperture 32 ⁇ m) to remove coarse particles.
- a melting method you may melt
- the atomizing method is not limited to the water atomizing method, and a gas atomizing method or the like is also possible.
- Table 2 shows the composition analysis results and average particle diameter (median diameter d50) of the powder thus obtained.
- Al and Zr are analysis values obtained by ICP emission analysis, Cr is capacitance, and Si and Ti are absorption spectrophotometry. Other elements of R are also measured by ICP emission spectrometry.
- the average particle diameter is a value measured with a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). Using these Fe-based soft magnetic alloy grains, magnetic cores were produced by the following steps (1) to (3), which were referred to as Reference Example 1, Comparative Example 1, and Examples 1 to 5, respectively.
- the obtained granule was fed into a molding die and pressure-molded at room temperature using a hydraulic press.
- the molding pressure was 0.74 GPa.
- the obtained molded body was a toroidal annular body having an inner diameter of 7.8 mm, an outer diameter of 13.5 mm, and a thickness of 4.3 mm.
- (C) Core loss Pcv Using the magnetic core of the annular body as the object to be measured, the primary side winding and the secondary side winding were wound by 15 turns, respectively, and a maximum magnetic flux density of 30 mT, using a BH analyzer SY-8232 made by Iwatatsu Measurement Co., Ltd. The core loss Pcv (kW / m 3 ) at room temperature was measured at a frequency of 50 kHz to 1000 kHz.
- Table 3 shows the evaluation results of the above characteristics in the magnetic cores of Reference Example 1, Comparative Example 1, and Examples 1 to 5.
- Example 3 As shown in Table 3, in Examples 1, 2, and 4 containing Zr, the specific resistance was greatly improved as compared to Reference Example 1, and both were excellent ratios of 1 ⁇ 10 5 ⁇ ⁇ m or more. Resistance was obtained. On the other hand, in Comparative Example 1 that did not contain Zr and contained Ti, the insulating property was not exhibited, and it is considered that the specific resistance was reduced by the inclusion of Ti. However, in Example 3, the specific resistance was improved by containing Zr while containing the same amount of Ti as in Comparative Example 1, and a specific resistance of 1 ⁇ 10 3 ⁇ ⁇ m or more was obtained. Yes.
- Examples 1 to 5 containing Zr had improved crushing strength as compared with Reference Example 1, and all had excellent crushing strength exceeding 250 MPa. Has been obtained.
- the magnetic core loss and the initial magnetic permeability of Examples 1 to 5 are inferior to those of Reference Example 1, but the magnetic core loss is 691 kW / m 3 or less at 300 kHz, and the initial magnetic permeability exceeds 20, both of which are practical. It was a level without any problem.
- there is no significant difference in the incremental magnetic permeability and it can be said that the DC superposition characteristics are ensured also in Examples 1 to 5.
- FIGS. 9 and 10 are SEM photographs obtained by cross-sectional observation of the magnetic cores of Examples 1 and 2, respectively, and mapping diagrams showing element distributions in the corresponding visual field.
- the mapping diagrams (b) to (f) show the distribution of Fe, Al, Cr, Zr, and O, respectively, and the brighter color tone has more target elements.
- the Al concentration is high in the grain boundary phase between the alloy phases, and yet there is also a large amount of O to generate oxide, and the adjacent alloy phases are bonded via the grain boundary phase. The state of being done is observed. In the grain boundary phase, the Fe concentration is lower than that in the alloy phase. A large concentration distribution was not confirmed for Cr and Zr.
- FIGS. 11 and 12 are TEM photographs obtained by observing the magnetic cores of Reference Example 1 and Example 1 with a transmission electron microscope (TEM) at a magnification of 600,000 times or more, and alloy phases formed of Fe-based soft magnetic alloy grains. The part where the outline of the section of two particles is confirmed is shown.
- the band-shaped portion that traverses in the vertical direction is the grain boundary phase, and is located so as to be adjacent to each other via the grain boundary phase, and the portion having a lower brightness than the grain boundary phase is the alloy phase.
- an oxide region containing Fe, Al, and Cr and containing more Al than the alloy phase is generated in the grain boundary phase that connects adjacent alloy phases. .
- the Al ratio is particularly high at the edge of the oxide region along the interface between the alloy phase and the grain boundary phase.
- region where the ratio of Fe is high is produced
- Zn derived from zinc stearate added as a lubricant was also confirmed, but is omitted (same for Table 5).
- Example 1 the color tone of the grain boundary phase was uniform overall.
- the center part of the grain boundary phase (marker 1), the edge part of the grain boundary phase (edge part A: marker 3), and the island-like part (edge part B: low brightness) in the edge part of the grain boundary phase.
- Table 5 shows the results of composition analysis by TEM-EDX in the region of 1 nm in diameter for the marker 2) and the inside of the alloy phase (marker 4).
- the edge A of the grain boundary phase is located in the vicinity of the alloy phase and at a position approximately 5 nm away from the surface of the alloy grain appearing as a cross-sectional contour.
- the grain boundary phase connecting adjacent alloy phases contains Fe, Al, Cr, Si and Zr, and an oxide region containing more Al than the alloy phase.
- the ratio of Al is high not only at the edge of the oxide region but also at the center of the oxide region, which is different from FIG. Further, among the edges of the oxide region, the edge A close to the interface between the alloy phase and the grain boundary phase contains more Zr than the alloy phase, and contains 2% by mass or more of Zr. In the central part of the oxide phase, almost no Zr is present. Thus, it is considered that the oxide containing Al or Zr covers the surface of the alloy phase, thereby suppressing the diffusion of Fe during the heat treatment and improving the specific resistance.
- the ratio of Al to the sum of Fe, Al, Cr, Si, and Zr is higher than the ratio of each of Fe, Cr, Si, and Zr at the center and edge A of the oxide region.
- the edge A has a higher Zr ratio than the edge B, which corresponds to the third region.
- the ratio of Fe to the sum of Fe, Al, Cr, Si and Zr is higher than the ratio of each of Al, Cr, Si and Zr, and this region is the first in the grain boundary phase. It corresponds to two areas. It is considered that the second region is formed in an island shape surrounded by the first region and the third region, and the diffusion of Fe is suppressed during the heat treatment.
- a magnetic core was prepared by using a spray drying granulation method as a granulation method, and various properties were evaluated.
- Table 6 shows the composition and average particle size of the raw material powder used in this example. Using these raw material powders, spray drying granulation was performed under the following conditions. First, in a stirrer container, soft magnetic alloy particles, PVA as a binder (Poval PVA-205 manufactured by Kuraray Co., Ltd .; solid content: 10%), and ion-exchanged water as a solvent are stirred, mixed, and mixed with slurry (slurry). ). The slurry concentration is 80% by mass.
- the binder was 10 parts by weight with respect to 100 parts by weight of the soft magnetic alloy particles.
- the slurry was sprayed inside the apparatus with a spray dryer, and the slurry was instantly dried with hot air whose temperature was adjusted to 240 ° C., thereby recovering granular granules from the lower part of the apparatus.
- a sieve with a 60 mesh (aperture 250 ⁇ m) was passed, and the average particle diameter of the granules after sieving was in the range of 60 to 80 ⁇ m.
- 0.4 parts by weight of zinc stearate was added to 100 parts by weight of the obtained granules, and the mixture was mixed by a container rotating and shaking type powder mixer.
- the processes after pressure molding and the method for evaluating characteristics are as described in (2), (3) and (A) to (G) above. In this example, the molding pressure was adjusted so that the compact density dg was 6.0 ⁇ 10 3 kg / m 3 during pressure molding.
- Table 7 shows the characteristics evaluation results of the magnetic core obtained above.
- the value of the core loss Pcv in Table 7 is measured at a frequency of 300 kHz and an excitation magnetic flux density of 30 mT.
- the specific resistance is as high as 300 ⁇ 10 3 ⁇ ⁇ m or more. This is because, in this example, compared to Examples 1 to 5 described above, the gap between the metal particles was increased because the density was controlled to be slightly lower at the time of molding, and relatively thick particles were filled to fill the gap during the heat treatment. This is probably due to the formation of a boundary phase.
- Example 11 in which 0.21% by mass of Hf was added instead of Zr, a high specific resistance in the order of 10 6 ⁇ ⁇ m and an improvement in the crushing strength were observed.
- Zr or Hf is included as a metal that hardly dissolves in iron
- at least one of Y, Nb, La, and Ta may be contained.
- These metals are all difficult to dissolve in Fe, and the absolute value of the standard generation Gibbs energy of the oxide is larger than that of ZrO 2 or HfO 2 .
- a strong oxide film that effectively suppresses diffusion is generated in the grain boundary phase, and the specific resistance of the magnetic core can be improved.
- the magnetic core in the second aspect includes an alloy phase formed of Fe-based soft magnetic alloy grains containing M2, Si, and R, and has a structure in which the alloy phase is connected by a grain boundary phase.
- the appearance of the magnetic core according to the second aspect is illustrated in FIG.
- the magnetic core 1 includes a plurality of alloy phases and a grain boundary phase connecting the alloy phases as shown in a cross-sectional observation view of a magnetic core shown in FIG. 13, and has a cross-sectional microstructure as shown in FIG. 14, for example.
- Such a cross-sectional microstructure is observed by observation of 600,000 times or more using, for example, a transmission electron microscope (TEM).
- TEM transmission electron microscope
- This structure includes a granular alloy phase 20 containing Fe, Si, and M 2, and adjacent alloy phases 20 are connected by a grain boundary phase 30.
- M2 is an element of either Al or Cr.
- the grain boundary phase 30 has an oxide region containing Fe, M2, Si, and R, and containing more M2 (ie, Al or Cr) than the alloy phase 20 by mass ratio.
- the oxide region includes a region containing more R than the alloy phase 20 on the interface side with the alloy phase 20.
- R is at least one element selected from the group consisting of Y, La, Zr, Hf, Nb, and Ta.
- the alloy phase 20 is formed of Fe-based soft magnetic alloy grains containing M2, Si, and R, the balance being Fe and inevitable impurities.
- Non-ferrous metals that is, M2, Si and R contained in Fe-based soft magnetic alloy grains have a greater affinity with O (oxygen) than Fe.
- These oxides of non-ferrous metals or composite oxides with Fe form a grain boundary phase 30 between alloy phases.
- Fe and the non-ferrous metal oxide have a higher electric resistance than a single metal, and the oxide region of the grain boundary phase 30 interposed between the alloy phases 20 functions as an insulating layer.
- the Fe-based soft magnetic alloy particles used for forming the alloy phase 20 include Fe as a main component having the highest content ratio among the constituent components, and Si, M2, and R as subcomponents.
- R is a metal that is hardly dissolved in Fe and has a relatively large absolute value of the standard generation Gibbs energy of the oxide (it is easy to generate an oxide).
- the Fe-based soft magnetic alloy grains preferably contain Fe in an amount of 80% by mass or more, whereby a soft magnetic alloy having a high saturation magnetic flux density can be obtained.
- M2 has a large affinity with O. During heat treatment, O in the atmosphere and O contained in the binder are preferentially bonded to M2 of the Fe-based soft magnetic alloy grains, and a chemically stable oxide is formed of the alloy phase 20. Generated on the surface.
- the Fe-based soft magnetic alloy grains preferably contain either Al or Cr in an amount of 1.5% by mass to 8% by mass. If this is less than 1.5% by mass, the generation of an oxide containing Al or Cr may not be sufficient, and the insulation and corrosion resistance may be reduced.
- the content of Al or Cr is more preferably 2.5% by mass or more, and further preferably 3% by mass or more. On the other hand, if it exceeds 8% by mass, the magnetic properties may be deteriorated due to a decrease in the amount of Fe, a decrease in saturation magnetic flux density or initial permeability, or an increase in coercive force.
- the content of Al or Cr is more preferably 7% by mass or less, and further preferably 6% by mass or less.
- Si combines with O like Al and Cr to produce chemically stable SiO 2 and other complex oxides with non-ferrous metals. Since the oxide containing Si is excellent in corrosion resistance and stability, it is possible to increase the insulation between the alloy phases 20 and reduce the eddy current loss of the magnetic core. Si has the effect of improving the magnetic permeability of the magnetic core and reducing the magnetic loss, but if its content is too large, the alloy grains become hard and the filling property in the molding die deteriorates, and pressure molding causes The resulting molded product has a lower density, and the magnetic permeability tends to decrease and the magnetic loss tends to increase.
- the Fe-based soft magnetic alloy grains contain Si in excess of 1% by mass and 7% by mass or less. If this is 1% by mass or less, the generation of oxide containing Si may not be sufficient, the magnetic core loss is deteriorated, and the effect of improving the magnetic permeability by Si cannot be obtained sufficiently.
- the Si content is preferably 3% by mass or more.
- the content of Si is preferably 5% by mass or less in order to reduce the magnetic loss and effectively prevent the magnetic permeability from decreasing while increasing the specific resistance and strength.
- R is hard to dissolve in Fe and has a large absolute value of the standard generation Gibbs energy of the oxide, and is strongly bound to O to easily form a stable oxide. Therefore, it is easy to precipitate as an oxide of R, and together with the oxide of Al or Cr that forms the main part of the oxide region that appears in the grain boundary phase during the heat treatment, forms a strong oxide film.
- the Fe-based soft magnetic alloy grains preferably contain R in an amount of 0.01% by mass to 3% by mass. If this is less than 0.01% by mass, the generation of the oxide containing R is not sufficient, and the effect of improving the specific resistance may not be sufficiently obtained.
- the content of R is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. On the other hand, if this exceeds 3% by mass, the magnetic properties of the magnetic core may not be obtained properly due to an increase in magnetic core loss.
- the content of R is more preferably 1.5% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.7% by mass or less, and particularly preferably 0.6% by mass or less.
- R is two or more elements selected from the group consisting of Y, La, Zr, Hf, Nb, and Ta, the total amount thereof may be 0.01% by mass or more and 3% by mass or less. preferable.
- the Fe-based soft magnetic alloy particles may contain C, Mn, P, S, O, Ni, N, etc. as inevitable impurities. About preferable content of these inevitable impurities, it is as having demonstrated in the 1st aspect.
- an oxide containing R (for example, Zr) is generated at the edge 30c of the oxide region along the interface between the alloy phase 20 and the grain boundary phase 30.
- the oxide region contains more Al or Cr than the alloy phase 20, and in the oxide region, the edge portion 30c contains more R than the central portion. Since the oxide containing R is generated along the edge portion 30c, the diffusion of Fe from the alloy phase 20 to the grain boundary phase 30 is effectively suppressed, and the insulation by the oxide region is enhanced to reduce the specific resistance. Contributes to improvement.
- the alloy phase is granular, the alloy phases are not in direct contact with each other, and are independent via the grain boundary phase.
- the structure of the magnetic core includes an alloy phase and a grain boundary phase, and the grain boundary phase is formed by oxidation of Fe-based soft magnetic alloy grains.
- the composition of the alloy phase is different from the composition of the Fe-based soft magnetic alloy grains described above, but the composition deviation due to the transpiration of Fe, M2, Si and R due to heat treatment such as annealing hardly occurs.
- the composition of the magnetic core excluding O is substantially the same as the composition of the Fe-based soft magnetic alloy grains.
- a magnetic core composed of Fe-based soft magnetic alloy grains as described above has a sum of Fe, M2, Si and R of 100% by mass, M2 is 1.5% by mass and 8% by mass, Si Is 1 mass% and 7 mass% or less, R is 0.01 mass% or more and 3 mass% or less, and the balance is Fe and inevitable impurities.
- the coil component according to the present invention may have a magnetic core as described above and a coil applied to the magnetic core, and an example of the appearance is shown in FIG.
- the configuration of the coil component is as described in the first aspect.
- the crushing strength of the magnetic core is preferably 100 MPa or more.
- the manufacturing method of this magnetic core is selected from the group consisting of M2 (where M2 is any element of Al or Cr), Si and R (where R is Y, Zr, Nb, La, Hf and Ta).
- a step of obtaining a mixed powder by mixing an Fe-based soft magnetic alloy containing at least one element) and a binder (first step); and a step of forming the mixed powder to obtain a compact (second step).
- a heat treatment of the compact in an atmosphere containing oxygen to obtain a magnetic core having a structure including an alloy phase formed by the Fe-based soft magnetic alloy grains and a grain boundary phase (third step) With.
- a grain boundary phase 30 connecting adjacent alloy phases 20 is formed, and the grain boundary phase 30 contains Fe, M2, Si, and R, and more M2 than the alloy phase 20 in mass ratio.
- An oxide region containing is generated. In the oxide region, the ratio of M2 to the sum of Fe, M2, Si, and R is higher than that in the alloy phase 20.
- the sum of Fe, M2, Si and R is 100% by mass, M2 is 1.5% by mass to 8% by mass, Si is more than 1% by mass and 7% by mass or less, and R is 0%.
- Fe-based soft magnetic alloy grains that are contained in an amount of 0.01% by mass or more and 3% by mass or less and the balance of Fe and inevitable impurities are used. Since a more preferable composition of the Fe-based soft magnetic alloy grains is as described above, a duplicate description is omitted.
- the matters relating to the second step, and the matters relating to the third step such as the atmosphere of heat treatment (annealing) and the annealing temperature are all applicable in the second aspect.
- the space factor of the magnetic core obtained through the heat treatment, the thickness of the grain boundary phase, the maximum diameter of the alloy phase and the abundance ratio thereof are also as described in the first embodiment.
- the oxide region generated in the grain boundary phase contains Fe, M2, Si, and R, and contains more M2 than the alloy phase by mass ratio.
- composition analysis shows that the oxide region contains Fe, M2, Si and R.
- an oxide containing R appears along the interface between the alloy phase 20 and the grain boundary phase 30 at the edge 30 c of the oxide region in the vicinity of the alloy phase 20.
- the oxide region is a region in which the ratio of M2 is higher than the ratio of Fe, the ratio of Si, and the ratio of R with respect to the ratio of the sum of Fe, M2, Si, and R.
- Table 8 shows the composition analysis and average particle diameter (median diameter) of alloy grains obtained by preparing Fe-based soft magnetic alloy grains by a water atomization method and then removing coarse particles through a 440 mesh (aperture 32 ⁇ m) sieve. The measurement result of d50) is shown.
- Cr is selected as the selection element M2
- Zr is selected as the selection element R.
- the technique and apparatus used for composition analysis and particle size measurement are as described in the first embodiment.
- magnetic cores were produced by the steps of (1) mixing, (2) pressure forming, and (3) heat treatment, which were designated as Example 12 and Comparative Example 2, respectively.
- the steps (1) to (3) are the same as those in the first mode except that the molding pressure during pressure molding is 0.93 GPa.
- Example 12 containing Zr As shown in Table 9, in Example 12 containing Zr, the specific resistance was improved as compared with Comparative Example 2, and an excellent specific resistance of 1 ⁇ 10 5 ⁇ ⁇ m or more was obtained.
- Example 12 containing Zr Although no significant difference was observed in the density of the magnetic core, in Example 12 containing Zr, the crushing strength was improved as compared with Comparative Example 2, and an excellent crushing strength exceeding 100 MPa was obtained. . Moreover, the initial permeability exceeded 25, which was the same as that of Comparative Example 2 and was at a level that did not hinder practical use.
- Example 12 and Comparative Example 2 These magnetic cores were subjected to cross-sectional observation using a scanning electron microscope (SEM / EDX), and at the same time, the distribution of each constituent element was examined.
- SEM / EDX scanning electron microscope
- the concentration of Cr is high in the grain boundary phase between the alloy phases, and yet an oxide is generated with a large amount of O, and the adjacent alloy phase passes through the oxide region. Are observed.
- the Fe concentration is lower than that in the alloy phase.
- Example 12 The magnetic core of Example 12 was cut, and the cut surface was observed with a transmission electron microscope (TEM) at a magnification of 600,000 to observe an alloy phase and a grain boundary phase connecting the alloy phases.
- TEM transmission electron microscope
- the oxide region of the grain boundary phase exhibits a different color tone in the region including the center part in the thickness direction of the grain boundary phase and the edge side of the grain boundary phase and the interface side with the alloy phase, It was layered.
- an oxide region containing Fe, Si, Cr and Zr and containing more Cr than the alloy phase is generated.
- the oxide containing Cr and Zr covers the surface of the alloy phase, thereby suppressing the diffusion of Fe during the heat treatment and improving the specific resistance.
- Al has a higher affinity with O than Cr, and O in the atmosphere and O contained in the binder are preferentially bonded to Al in the vicinity of the surface of the Fe-based soft magnetic alloy grains, and are chemically stable Al 2 O. 3 or a complex oxide with other non-ferrous metal forms an alloy phase on the surface.
- the selective element R at least one of Y, Nb, La, Hf, and Ta may be contained instead of or in addition to Zr.
- All of these metals are difficult to dissolve in Fe, and the absolute value of the standard Gibbs energy of the oxide is larger than that of ZrO 2 , so that the diffusion of Fe is effectively prevented as in the case of containing Zr.
- a strong oxide film to be suppressed is generated in the grain boundary phase, and the specific resistance and strength of the magnetic core are improved.
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Abstract
Description
本発明の第1の態様について具体的に説明する。後述するように、第1の態様における磁心は、M1、Si及びRを含むFe基軟磁性合金粒により形成された合金相を含み、その合金相が粒界相で繋がれた組織を有する。
本発明の第1の態様の実施例について具体的に説明する。まず、Fe-Al-Cr合金インゴットと所定量のZrやTi(いずれも純度が99.8%以上)をルツボに装入し、Ar雰囲気中で高周波溶解した後、水アトマイズ法により合金粉末を作製した。次に、作製した合金粉末を440メッシュ(目開き32μm)の篩に通して、粗大粒を取り除いた。なお、溶解方法としては、Fe,Al,Crの素原料を使用して溶解してもよい。また、アトマイズ方法としては、水アトマイズ法に限らず、ガスアトマイズ法などでも可能である。このようにして得られた粉末の組成分析結果および平均粒径(メジアン径d50)を表2に示す。AlとZrはICP発光分析法により、Crは容量法により、SiとTiは吸光光度法により、それぞれ得られた分析値である。Rの他の元素もICP発光分析法によって測定される。平均粒径は、レーザー回折散乱式粒度分布測定装置(堀場製作所製LA-920)による測定値である。これらのFe基軟磁性合金粒を用いて下記(1)~(3)の工程により磁心を製造し、それぞれ参考例1、比較例1及び実施例1~5とした。
撹拌擂潰機を用いて、Fe基軟磁性合金粒100重量部に対して、バインダとしてPVA(株式会社クラレ製ポバールPVA-205;固形分10%)を2.5重量部添加して混合した。得られた混合物を120℃で10時間乾燥した後、篩に通して混合粉の顆粒を得て、その平均粒径(d50)を60~80μmの範囲内とした。また、顆粒100重量部に対して、ステアリン酸亜鉛を0.4重量部添加し、容器回転揺動型粉体混合機により混合して、加圧成形に供する混合粉の顆粒を得た。
得られた顆粒を成形金型内に給粉し、油圧プレス機を使用して室温で加圧成形した。成形圧力は0.74GPaとした。得られた成形体は、内径φ7.8mm、外径φ13.5mm、厚み4.3mmのトロイダル形の環状体とした。
得られた成形体を電気炉により大気中で焼鈍し、代表寸法を内径φ7.7mm、外径φ13.4mm、厚み4.3mmとする磁心を得た。熱処理では、室温から焼鈍温度である750℃まで2℃/分で昇温し、その焼鈍温度で1時間保持した後、炉冷した。また、造粒時に添加したバインダなどの有機物が分解されるように、450℃で1時間保持する脱脂工程を熱処理の途中に含めた。
(A)成形体密度dg、焼鈍後密度ds
環状体の成形体と磁心に対し、それらの寸法と質量から体積重量法により密度(kg/m3)を算出し、それぞれを成形体密度dg、焼鈍後密度dsとした。
算出した焼鈍後密度dsを軟磁性合金の真密度で除して磁心の占積率(相対密度)[%]を算出した。なお、上記の真密度は、あらかじめ鋳造して得られた軟磁性合金のインゴットに対する体積重量法により求めた。
環状体の磁心を被測定物として、一次側巻線と二次側巻線とをそれぞれ15ターン巻回し、岩通計測株式会社製B-HアナライザーSY-8232を用いて、最大磁束密度30mT、周波数50kHz~1000kHzの条件で、室温における磁心損失Pcv(kW/m3)を測定した。
環状体の磁心を被測定物として、導線を30ターン巻回し、LCRメータ(アジレント・テクノロジー株式会社製4284A)を用いて、周波数100kHzで室温にてインダクタンスLを測定し、次式により初透磁率μiを求めた。
初透磁率μi=(le×L)/(μ0×Ae×N2)
[le:磁路長(m)、L:試料のインダクタンス(H)、μ0:真空の透磁率=4π×10-7(H/m)、Ae:磁心の断面積(m2)、N:コイルの巻数]
環状体の磁心を被測定物として、導線を30ターン巻回し、10kA/mの直流磁界を印加した状態にて、LCRメータ(アジレント・テクノロジー株式会社製4284A)を用いて、周波数100kHzで室温にてインダクタンスLを測定し、前述した初透磁率μiと同様にして増分透磁率μΔを求めた。
JISZ2507に基づき、引張・圧縮試験機(株式会社島津製作所製オートグラフAG-1)の定盤間に被測定物である環状体の磁心を配置し、その磁心に径方向から荷重を与えて破壊時の最大加重P(N)を測定し、次式から圧環強度σr(MPa)を求めた。
圧環強度σr(MPa)=P(D-d)/(Id2)
[D:磁心の外径(mm)、d:磁心の厚み〔内外径差の1/2〕(mm)、I:磁心の高さ(mm)]
被測定物である磁心の対向する二平面に導電性接着剤を塗り、その接着剤が乾燥し固化してから電極の間に磁心をセットし、電気抵抗測定装置(株式会社エーディーシー製8340A)により50Vの直流電圧を印加して抵抗値R(Ω)を測定し、次式により比抵抗ρ(Ω・m)を算出した。
比抵抗ρ(Ω・m)=抵抗値R×(A/t)
[A:磁心の平面の面積〔電極面積〕(m2)、t:磁心の厚み〔電極間距離〕(m)]
本発明の第2の態様について具体的に説明する。第2の態様は、以下で説明する事柄の他は第1の態様と略同様であるので、共通点を省略して主に相違点について説明する。また、第1の態様において説明した構成に相当する構成には、同一の符号を付し、重複した説明を省略する。後述するように、第2の態様における磁心は、M2、Si及びRを含むFe基軟磁性合金粒により形成された合金相を含み、その合金相が粒界相で繋がれた組織を有する。
本発明の第2の態様の実施例について具体的に説明する。表8には、Fe基軟磁性合金粒を水アトマイズ法により作製した後、440メッシュ(目開き32μm)の篩を通して粗い粒子を取り除いた合金粒について、それらの組成分析と平均粒径(メジアン径d50)の測定結果を示している。本実施例では、選択元素M2としてCrを、選択元素RとしてZrを選択している。組成の分析や粒径の測定に用いた手法や装置は、第1の態様において説明した通りである。これらのFe基軟磁性合金粒を用いて、(1)混合、(2)加圧成形及び(3)熱処理の工程により磁心を製造し、それぞれ実施例12、比較例2とした。この(1)~(3)の工程は、加圧成形時の成形圧力を0.93GPaとしたこと以外は、第1の態様と同じである。
20 合金相
30 粒界相
30a 酸化物領域の第1領域(中央部)
30b 酸化物領域の第2領域
30c 酸化物領域の第3領域(縁部)
Claims (13)
- M1(ただし、M1は、Al及びCrの両方の元素)、Si及びR(ただし、Rは、Y、Zr、Nb、La、Hf及びTaからなる群より選ばれる少なくとも1種の元素)を含むFe基軟磁性合金粒により形成された合金相を含み、前記合金相が粒界相で繋がれた組織を有し、
前記粒界相に、Fe、M1、Si及びRを含み、且つ、質量比で前記合金相よりも多くのAlを含む酸化物領域を備える磁心。 - 前記磁心は、Fe、M1及びRの和を100質量%として、Alを3質量%以上且つ10質量%以下、Crを3質量%以上且つ10質量%以下、Rを0.01質量%以上且つ1質量%以下で含み、残部がFe及び不可避不純物である請求項1に記載の磁心。
- M2(ただし、M2は、Al又はCrのいずれかの元素)、Si及びR(ただし、Rは、Y、Zr、Nb、La、Hf及びTaからなる群より選ばれる少なくとも1種の元素)を含むFe基軟磁性合金粒により形成された合金相を含み、前記合金相が粒界相で繋がれた組織を有し、
前記粒界相に、Fe、M2、Si及びRを含み、且つ、質量比で前記合金相よりも多くのM2を含む酸化物領域を備える磁心。 - 前記磁心は、Fe、M2、Si及びRの和を100質量%として、M2を1.5質量%以上且つ8質量%以下、Siを1質量%超え且つ7質量%以下、Rを0.01質量%以上且つ3質量%以下で含み、残部がFe及び不可避不純物である請求項3に記載の磁心。
- 前記酸化物領域が、その前記酸化物領域内の他の領域よりもRの比率が高い領域を備える請求項1~4のいずれか1項に記載の磁心。
- RがZr又はHfである請求項1~5のいずれか1項に記載の磁心。
- Rを0.3質量%以上で含む請求項2または4に記載の磁心。
- Rを0.6質量%以下で含む請求項2,4または7に記載の磁心。
- 前記粒界相が、Fe、M1、Si及びRの和に対するAlの比率がFe、Cr、Si及びRの各々の比率よりも高い第1領域と、Fe、M1、Si及びRの和に対するFeの比率がM1、Si及びRの各々の比率よりも高い第2領域とを有している請求項1または2に記載の磁心。
- 比抵抗が1×105Ω・m以上で、圧環強度が120MPa以上である請求項1または2に記載の磁心。
- 請求項1~10のいずれか1項に記載の磁心と、その磁心に施されたコイルとを有するコイル部品。
- M1(ただし、M1は、Al及びCrの両方の元素)、Si及びR(ただし、Rは、Y、Zr、Nb、La、Hf及びTaからなる群より選ばれる少なくとも1種の元素)を含むFe基軟磁性合金粒とバインダとを混合して混合粉を得る工程と、
前記混合粉を加圧成形して成形体を得る工程と、
酸素を含む雰囲気中で前記成形体を熱処理して、前記Fe基軟磁性合金粒により形成された合金相を含む組織を有する磁心を得る工程とを備え、
前記熱処理によって、前記合金相を繋ぐ粒界相を形成するとともに、前記粒界相に、Fe、M1、Si及びRを含み、且つ、質量比で前記合金相よりも多くのAlを含む酸化物領域を生成する磁心の製造方法。 - M2(ただし、M2は、Cr又はAlのいずれかの元素)、Si及びR(ただし、Rは、Y、La、Zr、Hf、Nb、及びTaからなる群より選ばれる少なくとも1種の元素)を含むFe基軟磁性合金粒とバインダとを混合して混合粉を得る工程と、
前記混合粉を成形して成形体を得る工程と、
酸素を含む雰囲気中で前記成形体を熱処理して、前記Fe基軟磁性合金粒により形成された合金相を含む組織を有する磁心を得る工程とを備え、
前記熱処理によって、前記合金相を繋ぐ粒界相を形成するとともに、前記粒界相に、Fe、M2、Si及びRを含み、且つ、質量比で前記合金相よりも多くのM2を含む酸化物領域を生成する磁心の製造方法。
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