CN116848600A - Magnetic composite body - Google Patents
Magnetic composite body Download PDFInfo
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- CN116848600A CN116848600A CN202280010058.7A CN202280010058A CN116848600A CN 116848600 A CN116848600 A CN 116848600A CN 202280010058 A CN202280010058 A CN 202280010058A CN 116848600 A CN116848600 A CN 116848600A
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- Prior art keywords
- ferrite
- ferrite layer
- magnetic
- magnetic composite
- base material
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 206
- 239000002131 composite material Substances 0.000 title claims abstract description 143
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 391
- 229910052751 metal Inorganic materials 0.000 claims abstract description 137
- 239000002184 metal Substances 0.000 claims abstract description 137
- 239000000463 material Substances 0.000 claims abstract description 114
- 239000011029 spinel Substances 0.000 claims abstract description 33
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 33
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- 239000010949 copper Substances 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 239000011572 manganese Substances 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 239000006096 absorbing agent Substances 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000000696 magnetic material Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
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- 230000000694 effects Effects 0.000 description 16
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- 239000011248 coating agent Substances 0.000 description 14
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
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- 229920002799 BoPET Polymers 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
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- 238000004804 winding Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000003302 ferromagnetic material Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 230000006866 deterioration Effects 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 4
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- 239000003990 capacitor Substances 0.000 description 3
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- 229910052709 silver Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003962 NiZn Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 2
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 2
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
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- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
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- 238000007772 electroless plating Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iron (Fe) ions Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000012762 magnetic filler Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
Provided is a magnetic composite body, which is compact, has a thick film, has excellent magnetic properties and electrical properties, and has good adhesion. A magnetic composite body having a metal base material and a ferrite layer provided on the surface of the metal base material, the metal base material having a thickness (d M ) Is 20 μm or more, the ferrite layer thickness (d F ) An integrated intensity (I) of a (222) plane in X-ray diffraction analysis, which is 2.0 μm or more and contains spinel ferrite as a main component 222 ) Integral intensity (I) relative to (311) plane 311 ) Ratio (I) 222 /I 311 ) Is 0.00-0.03.
Description
Technical Field
The present disclosure relates to a magnetic composite.
Background
With the rapid development of electronic information communication technology in recent years, the use of electromagnetic waves has been rapidly increased, and the use of electromagnetic waves has been increased in frequency and in bandwidth, and more specifically, in addition to systems in quasi-microwave frequency bands such as cellular phones (1.5, 2.0 GHz) and wireless LANs (2.45 GHz), new systems using radio waves in millimeter wave bands such as high-speed wireless LANs (65 GHz) and collision avoidance radar (76.5 GHz) have been introduced.
With the expansion of electromagnetic wave utilization and the development of high frequency, problems of electromagnetic interference such as malfunction of electronic equipment and adverse effects on human body due to electromagnetic noise are attracting attention, and demands for countermeasure against EMC (Electromagnetic Compatibility) are increasing. As one method for countermeasures against EMC, a method of absorbing unnecessary electromagnetic waves using an electromagnetic wave absorber (radio wave absorber) and preventing the intrusion thereof is known.
The electromagnetic wave absorber uses a material exhibiting conductive loss, dielectric loss, and/or magnetic loss. Ferrite having high magnetic permeability and high electric resistance is often used as a material exhibiting magnetic loss. The ferrite causes a resonance phenomenon at a specific frequency to absorb electromagnetic waves, and converts the absorbed electromagnetic wave energy into heat energy and emits the heat energy to the outside. As an electromagnetic wave absorber using ferrite, a composite material or ferrite film containing ferrite powder and a binder resin is proposed. In addition, in applications other than electromagnetic wave absorbers, a technique of forming a ferrite film on a substrate is known.
For example, patent document 1 describes that ferrite powder containing mn—zn ferrite or the like is: 20 to 80 mass% of carbon black powder: 3 to 60% by mass, and the remainder of the resin, is coated on at least one surface of the metal plate to produce a coated metal plate (patent document 1 claims 1 to 6). In addition, patent document 1 describes that the coating composition has excellent heat radiation properties and good electromagnetic wave absorption performance in a wide frequency band (see [0060] of patent document 1).
Patent document 2 discloses an electromagnetic wave absorber which is characterized by being obtained by physically depositing a ferromagnetic material on a substrate made of an organic polymer, and which is excellent in electromagnetic wave absorption characteristics, small in size, light in weight, flexible, and firm (patent document 2 claims 1 and [0008 ]). In patent document 2, it is described that an oxide-based soft magnetic material is mainly used as the ferromagnetic material, and ferrite is preferable as the oxide-based soft magnetic material, and EB vapor deposition, ion plating, magnetron sputtering, counter-target magnetron sputtering, or the like can be used in the physical vapor deposition method (patent document 2 [0009], [0010] and [0017 ]).
Patent document 3 discloses a composite magnetic film having an electromagnetic wave absorbing function, which is composed of a magnetic phase composed of a metal magnetic material and a high-resistance phase of a high-insulation ferrite dispersed in an island shape in the magnetic phase (claim 1 of patent document 3). Patent document 3 describes that the composite magnetic film is formed by an Aerosol Deposition (AD) method in which a raw material fine particle powder is aerosolized and is caused to collide with a substrate or the like as a film formation object to form a thick film. By applying the AD method, a composite magnetic film having a desired film thickness can be formed at a high speed (see [0029] and [0033] of patent document 3).
In patent document 4, the following is disclosed: an electromagnetic wave absorber is a composite in which metal particles are dispersed in a ceramic matrix such as ferrite (claims 1 and 8 of patent document 4). Patent document 4 describes that an electromagnetic wave absorber is often formed on a substrate and used, and in this case, if the metal is a substrate, the electromagnetic wave absorber is reflected at the interface between the electromagnetic wave absorber and the substrate, and re-absorption in the electromagnetic wave absorber can be expected; in manufacturing the electromagnetic wave absorber, a gas deposition method or an aerosol deposition method (patent document 4 [0029] and [0031 ]) can be used.
Patent documents 1 to 4 propose the production of electromagnetic wave absorbers by forming a ferrite-containing layer on a substrate such as a metal plate. In addition, in applications other than electromagnetic wave absorbers, it has also been proposed to form a ferrite-containing layer on a substrate. For example, patent document 5 discloses an inductor element including a magnetic substrate, a coil formed on a surface of the magnetic substrate by an electric conductor, and a magnetic layer formed by embedding the coil on the magnetic substrate by an aerosol deposition method (claim 1 of patent document 5).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2004-027064
Patent document 2: japanese patent application laid-open No. 2005-045193
Patent document 3: japanese patent application laid-open No. 2007-088121
Patent document 4: japanese patent application laid-open No. 2007-180289
Patent document 5: japanese patent application laid-open No. 2007-250924
Summary of the invention
Technical problem to be solved by the invention
Although it has been proposed to apply a composite formed by forming a ferrite-containing layer on a substrate to applications of electronic devices including electromagnetic wave absorbers and inductors, there is room for improvement in the prior art. For example, the composite material containing ferrite powder proposed in patent document 1 contains a large amount of resin as a nonmagnetic material, and therefore has poor magnetic properties. Therefore, there is a limitation in improving electromagnetic wave absorption characteristics. The ferrite thin film proposed in patent document 2 is difficult to form thick films in terms of manufacturing, and has a limitation in improving characteristics such as magnetic characteristics. In addition, even if the film can be formed thickly, there is a problem that the film is easily peeled from the substrate. The composite proposed in patent document 3 and patent document 4 contains a metal magnetic material having high electrical conductivity, and therefore cannot be applied to applications requiring electrical insulation. Further, the element proposed in patent document 5 has a limitation in improving characteristics such as electrical characteristics and adhesion.
The present inventors have conducted intensive studies in view of these problems. The following findings were obtained as a result: in a magnetic composite comprising a metal substrate and a ferrite layer, the crystal state of the ferrite layer is important, and by controlling the crystal state, a ferrite layer which is dense and relatively thick, has excellent magnetic and electrical properties, heat resistance, and good adhesion can be obtained.
The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a magnetic composite body including a ferrite layer which is dense and has a relatively thick film thickness, magnetic properties (tan δ is small at a high frequency of 500MHz or more), electric properties (surface resistance is high without being affected by a metal base material), heat resistance, and adhesion.
Technical means for solving the technical problems
The present invention includes the following modes (1) to (6). In the present specification, the expression "to" includes numerical values at both ends thereof. That is, "X to Y" are synonymous with "X to Y.
(1) A magnetic composite comprising a metal base material and a ferrite layer provided on the surface of the metal base material,
the thickness (d) of the metal base material M ) Is not less than 0.001 mu m,
the ferrite layer thickness (d F ) An integrated intensity (I) of a (222) plane in X-ray diffraction analysis, which is 2.0 μm or more and contains spinel ferrite as a main component 222 ) Integral intensity (I) relative to (311) plane 311 ) Ratio (I) 222 /I 311 ) Is 0.00-0.03.
(2) The magnetic composite according to the above (1),
the ferrite layer alpha-Fe 2 O 3 The content of (2) is not less than 0.0% by mass and not more than 20.0% by mass.
(3) The magnetic composite according to the above (1) or (2),
the ferrite layer contains iron (Fe) and oxygen (O), and further contains at least one element selected from the group consisting of lithium (Li), magnesium (Mg), aluminum (Al), titanium (Ti), manganese (Mn), zinc (Zn), nickel (Ni), copper (Cu), and cobalt (Co).
(4) The magnetic composite according to any one of the above (1) to (3),
the surface arithmetic average roughness (Ra) of the ferrite layer is relative to the thickness (d) F ) Ratio (Ra/d) F ) Is 0.00-0.20.
(5) The magnetic composite according to any one of the above (1) to (4),
the ferrite layer contains ferrite constituent components, and the remainder has unavoidable impurity constituents.
(6) An element or component having a coil and/or an inductor function, an electronic device, an electronic component housing, an electromagnetic wave absorber, an electromagnetic wave shield, or an element or component having an antenna function, each including the magnetic composite according to any one of (1) to (5).
Effects of the invention
According to the present invention, there is provided a magnetic composite body having a ferrite layer which is dense and relatively thick in film thickness, has excellent magnetic and electric properties, heat resistance, and good adhesion.
Drawings
Fig. 1 shows one embodiment of a magnetic composite.
Fig. 2 shows another embodiment of the magnetic composite.
Fig. 3 shows another embodiment of the magnetic composite.
Fig. 4 shows still other modes of the magnetic composite.
Fig. 5 shows an example of a magnetic composite suitable for use in an inductor.
Fig. 6 shows an example in which the magnetic composite is applied to an LC filter.
Fig. 7 shows other examples of a magnetic composite suitable for use in the inductor.
Fig. 8 shows an example in which a magnetic composite is applied to a magnetic sensor.
Fig. 9 shows an example in which the magnetic composite is applied to an antenna element (UHF-ID tag).
Fig. 10 shows an example in which the magnetic composite is applied to an electromagnetic wave absorber.
Fig. 11 shows an example in which the magnetic composite is applied to a housing for accommodating electronic components.
Fig. 12 shows an example in which a magnetic composite is used for a cable coating material.
Fig. 13 shows an example in which the magnetic composite is applied to a wound-type inductor.
Fig. 14 shows an example in which the magnetic composite is applied to a temperature sensor.
Fig. 15 shows an example of the configuration of an aerosol deposition film forming apparatus.
Fig. 16 shows a cross-sectional element map of the ferrite layer obtained in example 2.
Fig. 17 is a graph showing the saturation magnetization temperature dependence of the magnetic composite obtained in table example 2.
Fig. 18 is a graph showing the saturation magnetization temperature dependence of the magnetic composite obtained in table example 10.
Fig. 19 is a graph showing the saturation magnetization temperature dependence of the magnetic composite obtained in table example 14.
Fig. 20 is a graph showing the saturation magnetization temperature dependence of the magnetic composite obtained in table example 15.
FIG. 21 shows the magnetic permeability (real part μ', imaginary part μ ") of the magnetic composite obtained in example 2.
Detailed Description
A specific embodiment of the present invention (hereinafter referred to as "this embodiment") will be described. The present invention is not limited to the following embodiments, and various modifications can be made without changing the gist of the present invention.
Magnetic composite body
The magnetic composite of the present embodiment includes a metal base material and a ferrite layer provided on the metal base material. Thickness of metal base material (d M ) Is more than 0.001 μm. Thickness of ferrite layer (d F ) Is more than 2.0 mu m. The ferrite layer contains spinel-type ferrite as a main component, and has an integrated intensity (I) of the (222) plane in X-ray diffraction analysis 222 ) Integral intensity (I) relative to (311) plane 311 ) Ratio (I) 222 /I 311 ) Is 0.00-0.03. The magnetic composite will be described in detail below.
The metal base material functions as a support for the magnetic composite. The shape of the metal base material is not particularly limited as long as it functions as a support. For example, the sheet, foil, rod, box, wire, or belt may be used. In addition, the metal base material has conductivity, and thus can function as an electrode. Further, when the magnetic composite is used for an electromagnetic wave absorber, the metal base material can be made to function as a reflector for electromagnetic waves. That is, when the ferrite layer of the magnetic composite faces the electromagnetic wave incident side, a part of the electromagnetic wave is incident on the ferrite layer. The incident electromagnetic wave is attenuated in intensity during passage through the ferrite layer. The attenuated electromagnetic wave is reflected on the surface of the metal substrate, passes through the ferrite layer again, and is radiated from the surface thereof.
The metal constituting the metal base material is not particularly limited. May be a single metal or may be an alloy. Preferably, the metal is at least one selected from the group consisting of copper (Cu), aluminum (Al), nickel (Ni), iron (Fe), cobalt (Co), chromium (Cr), gold (Au), and silver (Ag). These metals are inexpensive. The metal may be at least one selected from nickel (Ni), iron (Fe) and cobalt (Co). The metal base material is more preferably a ferromagnetic material. By using the ferromagnetic metal base material, a synergistic effect with excellent magnetic characteristics of the ferrite layer can be exhibited. .
The metal base material may be composed of only metal, or may be a laminate of a nonmetallic base material and a metal layer. In this case, the metal layer laminated on the nonmetallic substrate corresponds to the metallic substrate. As the nonmetallic substrate, a resin film such as a PET film can be used. As the metal layer, a layer formed by a thin film formation method on a non-metal substrate can be used.
Thickness of metal base material (d) M ) The limit is more than 0.001 μm. If the metal base material is too thin, the effect of the metal base material may not be sufficiently obtained depending on the applicable frequency. The thickness of the metal base material is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 1 μm or more, particularly preferably 10 μm or more. The upper limit of the thickness is not limited. However, by properly thin-coating the metal base material, flexibility can be imparted to the magnetic composite. Such a kind of The effect is particularly pronounced in the case of using a metal substrate. The thickness may be 1000 μm or less, 500 μm or less, 200 μm or less, 100 μm or less, or 50 μm or less. The metal base material may be in the form of a wire, a tape, a plate, or a foil. However, foil-like is preferred. For example, a magnetic composite body excellent in flexibility can be produced by using a foil-shaped metal base material (metal foil).
The ferrite layer of the present embodiment is a polycrystalline body containing spinel-type ferrite as a main component. I.e. an aggregate of crystalline particles composed of spinel type ferrite. Spinel type ferrites are composite oxides of iron (Fe) having a spinel type crystal structure, most of which exhibit soft magnetism. The magnetic properties of the magnetic composite are excellent by providing a layer containing spinel type ferrite as a main component. The kind of spinel type ferrite is not particularly limited. For example, at least one selected from the group consisting of manganese (Mn) -based ferrite, manganese zinc (MnZn) -based ferrite, magnesium (Mg) -based ferrite, magnesium zinc (MgZn) -based ferrite, nickel (Ni) -based ferrite, nickel copper (NiCu) -based ferrite, nickel copper zinc (NiCuZn) -based ferrite, cobalt (Co) -based ferrite, and cobalt zinc (CoZn) -based ferrite. In the present specification, the main component means a component having a content of 50.0 mass% or more. In order to use the excellent magnetic properties of spinel ferrite, the content of spinel ferrite (ferrite phase) in the ferrite layer is preferably 60.0 mass% or more, more preferably 70.0 mass% or more, still more preferably 80.0 mass% or more, and particularly preferably 90.0 mass% or more.
Thickness (d) of ferrite layer of the present embodiment F ) Is limited to 2.0 μm or more. If the ferrite layer is too thin, the film thickness of the ferrite layer becomes uneven, and there is a possibility that the magnetic characteristics and electrical characteristics (electrical insulation) may deteriorate. The thickness is preferably 3.0 μm or more, more preferably 4.0 μm or more. The upper limit of the thickness is not limited. However, it is difficult to form an excessively thick ferrite layer while maintaining compactness. In addition, if the ferrite layer is too thick, the internal stress of the ferrite layer becomes too large, which may cause the ferrite layer to peel off. Further, a magnetic composite is provided withIn the case of flexibility, the ferrite layer is preferably suitably thin. The thickness is preferably 100.0 μm or less, more preferably 50.0 μm or less, still more preferably 20.0 μm or less, particularly preferably 10.0 μm or less.
The ferrite layer of the present embodiment has an integrated intensity (I) of the (222) plane in X-ray diffraction (XRD) analysis 222 ) Integral intensity (I) relative to (311) plane 311 ) Ratio (I) 222 /I 311 ) Is 0.00-0.03 (0.00.ltoreq.I) 222 /I 311 Less than or equal to 0.03). That is, if the ferrite layer is analyzed by the X-ray diffraction method, a diffraction peak at the (222) plane due to the spinel phase is hardly observed in the X-ray diffraction curve. This is because crystal particles constituting the ferrite layer are composed of crystallites. The crystal particles of the ferrite layer of the present embodiment undergo plastic deformation at the time of manufacturing the magnetic composite. Therefore, the crystal diameter is small, and the distribution of lattice constants is wide. As a result, XRD peaks broadened, and no diffraction peak was observed (222). I 222 /I 311 Preferably 0.02 or less, more preferably 0.01 or less. On the other hand, a general spinel-type ferrite material has high crystallinity even in a polycrystalline state. Thus, the (222) plane diffraction peak was observed to be strong. Specifically, XRD peak intensity ratio (I 222 /I 311 ) About 0.04 to 0.05 (4 to 5%).
XRD peak intensity ratio (I) 222 /I 311 ) The smaller ferrite layer of this embodiment has dense features. This is because the crystalline particles subjected to plastic deformation are easily densely packed. The ferrite layer of the present embodiment has an effect of excellent adhesion to the metal base material. This is because the crystalline particles undergo plastic deformation and the contact area with the metal base material increases. In addition, the bonding with the metal constituting the base material becomes strong due to the small crystal diameter and the periodically disturbed crystal structure. The ferrite layer of the present embodiment has a feature of small magnetic loss (tan δ) in a high frequency region of 500MHz or more. It is presumed that the crystal diameter is small, and the relevant length of the magnetic moment becomes short, so that the movement of the magnetic wall in the high frequency region can be smoothly performed. In contrast, in a general spinel type ferrite material, the magnetic moment is related to each otherThe length is longer. Although the magnetic wall movement can be performed by an external magnetic field in the low frequency region, the magnetic wall movement cannot follow the fluctuation of the external magnetic field in the high frequency region of 100MHz or more, and the magnetic loss becomes large.
Preferably, the ferrite layer has a crystal diameter of 1nm to 10 nm. By reducing the crystal diameter to 10nm or less, the density and adhesion of the ferrite layer become higher, and the effect of suppressing the increase in magnetic loss becomes more remarkable. Further, by setting the crystal diameter to 1nm or more, the ferrite layer can be prevented from being amorphized, and deterioration of magnetic characteristics can be prevented. The crystal diameter is more preferably 1nm to 5nm, still more preferably 1nm to 2 nm.
Preferably, the spinel type ferrite contained in the ferrite layer has a lattice constant ofAbove->The following is given. By making the lattice constant +.>Above->Hereinafter, the effect of improving the magnetic properties of the raw material particles can be obtained. The lattice constant is more preferably +.>Above->Hereinafter, it is more preferable that +.>Above->The following is given.
PreferablyFor the thickness (d) F ) Thickness (d) relative to the metal substrate M ) Ratio (d) F /d M ) Is 0.05 to 200 (d is 0.05 to less than or equal to d) F /d M And is less than or equal to 200). If the thickness ratio (d F /d M ) If the thickness of the ferrite layer is too small, the film thickness becomes uneven, and the magnetic characteristics and electrical characteristics (electrical insulation) are lowered. Thickness ratio (d) F /d M ) More preferably 0.10 or more. In addition, if the thickness ratio (d F /d M ) If the thickness is too large, the metal base material cannot resist the internal stress of the ferrite layer, and there is a risk of bending the composite. Thickness ratio (d) F /d M ) More preferably 10.0 or less, still more preferably 1.00 or less, particularly preferably 0.50 or less, and most preferably 0.30 or less.
In addition, in the case where the substrate is a laminate composed of a plurality of layers, the thickness of the layer in direct contact with the ferrite layer corresponds to the thickness of the substrate. In the case where the substrate has irregularities, the arithmetic average of the thinnest portion and thickest portion of the substrate on which the ferrite layer is formed is set as the thickness d of the substrate M Arithmetic averaging of the thinnest and thickest portions of the composite and thickness d of the substrate M The difference is set as the thickness d of the ferrite layer F . In the case where ferrite layers are formed on both sides of the composite body, the arithmetic average of the thinnest part and thickest part of the composite body and the thickness d of the base material M The difference was regarded as 2 times the thickness of the ferrite layer, and the thickness d was calculated F . Substrate thickness d M Above 2000 μm, the substrate thickness d M The thickness ratio (d) was calculated as 2000. Mu.m F /d M )。
Preferably, the ferrite layer is alpha-Fe 2 O 3 The content of (hematite) is 0.0 mass% or more and 20.0 mass% or less. alpha-Fe 2 O 3 Is free iron oxide that does not form spinel phases. Unlike spinel, which is a ferromagnetic material, α -Fe 2 O 3 Is a normal magnetic body. Thus if alpha-Fe 2 O 3 Too much, there is a risk of deterioration of the magnetic properties of the ferrite layer. alpha-Fe 2 O 3 The amount is more preferably 15.0 mass% or less, and still more preferably 10.0 mass% or less. In addition, alpha-Fe 2 O 3 Is a stable compound with high resistance. The ferrite layer is formed by properly containing alpha-Fe 2 O 3 The conductive path in the ferrite layer can be cut off, thereby further improving the resistance. Particularly, manganese (Mn) ferrite and manganese zinc (MnZn) ferrite contain manganese (Mn) ions and iron (Fe) ions whose valence is unstable, and thus the resistance is liable to be lowered. So that these ferrites are made to contain alpha-Fe 2 O 3 The effect of improving the resistance can be remarkably exhibited. In addition, by properly containing alpha-Fe 2 O 3 Densification of the ferrite layer and improvement of the adhesion force can be achieved. alpha-Fe 2 O 3 The ferrite layer is produced in a ferrite layer forming step in the manufacture of the magnetic composite. That is, ferrite crystal particles are plastically deformed and reoxidized during the film forming step to form α -Fe 2 O 3 . The plastic deformation and reoxidation play an important role in improving the densification and adhesion of the ferrite layer. Therefore, it moderately contains alpha-Fe 2 O 3 The density and adhesion of the ferrite layer are high. alpha-Fe 2 O 3 The amount is more preferably 0.1 mass% or more, still more preferably 1.0 mass% or more, particularly preferably 5.0 mass% or more.
Preferably, the ferrite layer includes iron (Fe) and oxygen (O), and further includes at least one element selected from the group consisting of lithium (Li), magnesium (Mg), aluminum (Al), titanium (Ti), manganese (Mn), zinc (Zn), nickel (Ni), copper (Cu), and cobalt (Co). The element contained in the ferrite layer can be confirmed by an analytical method and an analytical apparatus such as ICP, EDX, SIMS and/or XRF.
Preferably, the surface arithmetic average roughness (Ra) of the ferrite layer is equal to the thickness (d F ) Ratio (Ra/d) F ) Is 0.00-0.20 (0.00 < Ra/d) F Less than or equal to 0.20). If roughness ratio (Ra/d F ) If the thickness of the ferrite layer is too large, the thickness tends to be uneven. Therefore, when a high voltage is applied, the electric field is locally concentrated, and there is a risk of leakage current. Roughness ratio (Ra/d) F ) More preferably from 0.00 to 0.10, still more preferably from 0.00 to 0.05.
The density of the ferrite layer of the present embodiment is relatively high. This is because the ferrite crystal particles constituting the ferrite layer repeatedly undergo plastic deformation, and small crystal particles are deposited as the ferrite layer. The relative density of the ferrite layer (density of the ferrite layer/true specific gravity of the ferrite powder) is preferably 0.60 or more, more preferably 0.70 or more, still more preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more. By increasing the density, the effect of improving the magnetic properties, electrical properties, and adhesion of the ferrite layer is more remarkable.
The ferrite layer of the present embodiment has relatively high resistance. This is because the ferrite layer has a high density, and the adsorption of conductive components such as moisture, which is a factor of deterioration in electrical resistance, is small. In addition, the small crystal diameter of ferrite crystal particles constituting the ferrite layer also has an effect. In practice, the resistance of a typical MnZn ferrite material is relatively low, and the volume resistance thereof is 10 4 ～10 5 Omega cm. In contrast, the ferrite layer of the present embodiment exhibits a higher resistance value than that of the ferrite layer, and the reason for this can be determined by the size of the crystal diameter. Furthermore, by containing an appropriate amount of alpha-Fe 2 O 3 The resistance of the ferrite layer can be further improved. The surface resistance of the ferrite layer is preferably 10 4 Omega or more, more preferably 10 5 Omega or more. By increasing the surface resistance, the ferrite layer can be made more excellent in insulation properties, and when the magnetic composite is applied to a device, problems such as eddy current generation can be suppressed.
The ferrite layer preferably contains ferrite constituent components, and the remainder has a composition of unavoidable impurities. That is, it is preferable that the ferrite component does not contain an organic component or an inorganic component other than the ferrite component in excess of the unavoidable impurity amount. The ferrite layer of the present embodiment can be sufficiently densified without adding a resin component such as a binder or an inorganic additive component such as a sintering aid. By minimizing the content of the nonmagnetic material, excellent magnetic characteristics due to ferrite can be fully utilized. The ferrite constituent means a constituent constituting spinel type ferrite as a main component. For example, in the case where the ferrite layer is composed mainly of manganese zinc (MnZn) ferrite, the ferrite component is composed of iron (Fe), manganese (Mn), zinc (Zn) and oxygen (O). In the case where the ferrite layer is composed mainly of nickel copper zinc (NiCuZn) ferrite, the ferrite component is composed of iron (Fe), nickel (Ni), copper (Cu), zinc (Zn) and oxygen (O). Further, the unavoidable impurities are components which are inevitably mixed in at the time of production, and the content thereof is typically 1000ppm or less. In particular, the ferrite layer preferably contains no metal component other than oxide.
The magnetic composite preferably comprises a step (preparation step) of preparing a metal substrate and a spinel-type ferrite powder having an average particle diameter (D50) of 1.0 μm or more and 10.0 μm or less, and a step (film forming step) of forming a film of the ferrite powder on the surface of the metal substrate by aerosol deposition, wherein the ferrite powder is produced by a method in which the ratio (LCf/LCp) of the lattice constant (LCf) of the spinel phase contained in the ferrite layer to the lattice constant (LCp) of the spinel phase contained in the spinel-type ferrite powder is 0.95 to 1.05 (0.95.ltoreq. LCf/LCp.ltoreq.1.05).
The form of the magnetic composite is not particularly limited either. As shown in fig. 1, a ferrite layer (ferrite film) may be provided on the entire surface of the metal base material. As shown in fig. 2, the ferrite layer may be provided only on a part of the surface of the metal base material. Not only one surface of the metal base material but also two surfaces of the metal base material may be provided with ferrite layers. As shown in fig. 3, a ferrite layer whose thickness varies locally may be provided on the surface of the metal base material. Further, as shown in fig. 4, a ferrite layer may be wound around the outer periphery of a rod-shaped metal base material.
The magnetic composite material can be applied to various applications. Examples of such applications include a coil having a magnetic composite and/or an element or component having an inductor function, an electronic device, a housing for housing an electronic component, an electromagnetic wave absorber, an electromagnetic wave shield, or an element or component having an antenna function.
An example of the application of the magnetic composite to an inductor is shown in fig. 5. The magnetic composite includes a metal base material, a ferrite layer (ferrite film) provided on one surface of the metal base material, and a coil provided on the surface of the ferrite layer. A metal base material made of a conductive material can be made to function as the back electrode. The coil is made of a conductive material such as metal, and has a circuit pattern in a spiral shape. Thus exhibiting an inductor function. The circuit pattern of the coil may be formed by electroless plating, screen printing using paste containing metal colloid particles, ink jet, sputtering, vapor deposition, or the like. By forming a circuit pattern on the ferrite layer, a thin element having an inductor function can be obtained.
An example of the application of the magnetic composite to an LC filter is shown in fig. 6. The magnetic composite body includes a metal base material made of a conductive material, a ferrite layer (ferrite film) provided on a part of the surface of the metal base material, and a coil provided on the surface of the ferrite layer. In addition, a dielectric and a capacitor electrode provided on the surface of the dielectric are provided at a portion where the ferrite layer of the metal base material is not provided. The portion provided with the ferrite layer functions as an inductor element, while the portion provided with the dielectric layer functions as a capacitor element. The metal base material made of a conductive material can function as a common electrode for the inductor element and the capacitor element, and the entire can function as an LC filter.
Another example of the application of a magnetic composite to an inductor is shown in fig. 7. In this example, ferrite layers (ferrite films) and coils are provided on both surfaces of a metal base material. The coil on the front side and the coil on the back side are electrically connected through via holes (connection electrodes) provided in the metal base material and the ferrite layer. By providing the inductor function on both sides of the metal base material, a miniaturized inductor can be manufactured.
An example of the application of the magnetic composite to a magnetic inductor is shown in fig. 8. In this example, inductor elements having ferrite layers (ferrite films) and coils are arranged in an array on both sides of a metal base material. When the magnetic sensor is operated, the voltages generated by the respective combinations of the lateral inductor electrodes a and B … (lateral) disposed on the back surface of the substrate and the longitudinal inductor electrodes a, B, and c … disposed on the front surface of the substrate are measured in order with an external ac magnetic field applied. When no magnetic material is present in the vicinity of the coil, the inductor on the front surface of the substrate and the inductor on the back surface show the same inductor gap, and therefore no voltage is generated. When the magnetic material is present, the inductance of the inductor in the vicinity of the magnetic material changes, and thus a voltage is generated. The position of the magnetic body can be detected from the combination of the inductors generating the voltage.
An example of the application of the magnetic composite to an antenna element (UHF-ID tag) is shown in fig. 9. The antenna element (magnetic composite) includes a metal base material formed into an antenna pattern, a ferrite layer (ferrite film) provided on the back surface of the metal base material, and an ID tag chip provided on the front surface of the metal base material. Since the ferrite layer has higher magnetic permeability than the surrounding space, electromagnetic waves are easily concentrated in the ferrite layer. By providing an antenna pattern on the ferrite layer, the antenna sensitivity can be improved.
An example of applying the magnetic composite body to the electromagnetic wave absorber is shown in fig. 10. The electromagnetic wave absorber (magnetic composite) has a structure in which a metal base material and ferrite layers (ferrite films) provided on the surface of the metal base material are alternately laminated. In addition, a base material having excellent heat conductivity is provided at the lowermost surface.
An example of application of the magnetic composite body to the housing for electronic structure is shown in fig. 11. In this example, a ferrite layer (ferrite film) is provided on the surface of a metal base material, on which an electronic structure is mounted. A ferrite layer is also provided on the inner surface side of the metal base material serving as the cover of the housing. By providing the ferrite layer having an electromagnetic wave shielding effect on the case, leakage of unnecessary electromagnetic waves emitted from the electronic component to the surrounding environment can be prevented.
An example of using the magnetic composite for the signal cable is shown in fig. 12. In this example, ferrite layers (ferrite films) are provided on the outer and inner surfaces of a tubular metal base material, and signal lines covered with a resin layer (insulating layer) are disposed inside the tubular metal base material. When a high-frequency signal is applied to the signal line, the leakage electromagnetic wave is radiated to the surroundings. By providing the ferrite layer, the leakage electromagnetic wave can be prevented from being emitted to the surroundings.
An example of applying the magnetic composite to a wound-type inductor is shown in fig. 13. In this example, (a) ferrite layers (ferrite films) are provided on both surfaces of the flexible metal base material. Further, by winding a metal base material from an end portion so that a ferrite layer provided on one surface side is disposed inside, (b) a winding type inductor (hollow core) can be manufactured. Further, (c) if the hollow core portion is filled with a paste containing a magnetic filler, a coil-type inductor containing a magnetic core is obtained. Since a part of the metal base material is not in direct contact with other parts through the ferrite layer, not only insulation can be ensured, but also an effect of suppressing leakage magnetic flux can be obtained by the presence of the ferrite layer between the windings.
An example of applying the magnetic composite to a temperature sensor is shown in fig. 14. The temperature sensor (magnetic composite) includes a plurality of antenna elements including: the antenna comprises a metal base material forming an antenna pattern, a ferrite layer (ferrite film) provided on the back surface of the metal base material, and an ID tag chip provided on the front surface of the metal base material. Further, ferrite layers provided on the respective antenna elements are different from each other in composition. By constructing the temperature sensor in such a configuration, it is possible to measure the temperature of an object in a noncontact manner in an environment where the reading wiring cannot be provided, for example, in a vacuum or in an atmosphere other than the atmosphere. In addition, by using a plurality of ID tags lined with ferrite layers having different compositions in combination, it is possible to measure the temperature with high accuracy using the difference in frequency characteristics and the difference in temperature characteristics. Since a metal base material is used, a temperature region where the resin cannot be measured can be measured.
2, method for producing magnetic composite body >
The method of producing the magnetic composite according to the present embodiment is not limited as long as the above-described requirements are satisfied. However, the preferred manufacturing method includes the following steps; a step (preparation step) of preparing a metal substrate, a step (preparation step) of preparing spinel-type ferrite powder having an average particle diameter (D50) of 2.5 μm to 10.0 μm, and a step (film forming step) of forming a film on the surface of the metal substrate by an aerosol deposition method.
Thus, by forming a film by an aerosol deposition method (AD method) using ferrite powder having a specific particle diameter as a raw material, a relatively thick ferrite layer can be produced at a high film forming rate. The ferrite layer is dense, has excellent magnetic, electrical and heat resistance, and has excellent adhesion to a substrate. Therefore, the method is suitable as a method for producing a magnetic composite. The following describes each step in detail.
< preparation procedure >
In the preparation step, a metal base material and spinel-type ferrite powder are prepared. Details of the metal substrate are as described above. Further, as the spinel type ferrite powder, a powder having an average particle diameter (D50) of 1.0 μm or more and 10.0 μm or less was prepared. The average particle diameter is preferably 2.5 μm to 7.0 μm. By adjusting the average particle diameter to be within the above range, a ferrite layer having high adhesion and compactness can be obtained in the subsequent film forming step.
The method for producing the ferrite powder is not limited. However, it is preferable that the ferrite raw material mixture is subjected to main firing in an atmosphere having an oxygen concentration lower than that of the atmosphere to produce a fired product, and the obtained fired product is pulverized to produce particles of an indefinite shape having a specific particle diameter. The ferrite raw material mixture may be subjected to a pre-firing, pulverizing and/or granulating treatment before firing. As the ferrite raw material, known ferrite raw materials such as oxides, carbonates, and hydroxides can be used.
The ferrite powder is preferably amorphous in shape. Specifically, the average value of the shape factor (SF-2) of the ferrite powder is preferably 1.02 to 1.50, more preferably 1.02 to 1.35, still more preferably 1.02 to 1.25. Here, SF-2 is an index indicating the degree of the particle's amorphous form, and as the particle is closer to 1, it is indicated as a sphere, and as the particle is larger, it is indicated as an amorphous form. If SF-2 is too small, the particles become too round. As a result, the particles are less likely to be occluded in the substrate, and the film formation rate cannot be increased. In addition, if SF-2 is too large, the irregularities on the particle surface become too large. Accordingly, although the film forming speed is high, voids are likely to remain in the obtained ferrite layer due to the surface irregularities of the particles. If SF-2 is within the above range, a dense ferrite layer can be obtained at a high film formation rate. SF-2 is obtained from the following expression (1).
Number 1
The average value of the aspect ratio of the ferrite powder is preferably 1.00 to 2.00, more preferably 1.02 to 1.50, and even more preferably 1.02 to 1.25. When the aspect ratio is within the above range, the flow of the supplied raw material is stable at the time of film formation. If the amount exceeds the above range, the raw material tends to clog the piping from the raw material supply container to the nozzle. Therefore, the film formation rate may become unstable with the passage of the film formation time. The aspect ratio is obtained from the following expression (2).
Number 2
Further, the ferrite powder preferably has a CV value of particle diameter of 0.5 to 2.5. The CV value herein indicates the degree of variation in the particle diameter of particles in the powder, and the smaller the particle diameter becomes, the larger the unevenness becomes. In a general pulverizing method (bead mill, jet mill, etc.) for obtaining amorphous particles, it is difficult to obtain powder having a CV value of less than 0.5. In addition, the powder having a CV value exceeding 2.5 is liable to be clogged in the piping from the raw material supply container to the nozzle. Therefore, the film formation rate may become unstable with the passage of the film formation time. The CV value was obtained from the following expression (3) using 10% cumulative diameter (D10), 50% cumulative diameter (D50; average particle diameter) and 90% cumulative diameter (D90) in the volume particle size distribution.
Number 3
Presintering ferrite powderIn this case, for example, the firing may be performed under the atmospheric environment at 500 to 1100 ℃ for 1 to 24 hours. The main firing may be performed under an atmosphere such as the atmosphere or a reducing atmosphere at 800 to 1350 ℃ for 4 to 24 hours. In addition, the oxygen concentration at the time of final firing is preferably low. Thus, lattice defects can be intentionally generated in spinel crystals of ferrite powder. If crystal defects are contained in the crystal, plastic deformation is likely to occur with the crystal defects as a starting point when the raw material particles collide with the base material in the subsequent film forming step. Therefore, a ferrite layer which is dense and has high adhesion can be easily obtained. The oxygen concentration is preferably 0.001 to 10% by volume, more preferably 0.001 to 5% by volume, and still more preferably 0.001 to 2% by volume. Further, when the ferrite has a composition containing copper (Cu), it is preferable to perform firing in a reducing atmosphere. Upon calcination in a reducing atmosphere, copper (II) oxide (CuO) releases part of oxygen atoms and becomes copper (I) oxide (Cu) 2 O). At this time, lattice defects are easily generated. In addition, it is also effective to obtain a dense ferrite layer by making ferrite powder into a composition rich in iron (Fe).
The fired product is preferably pulverized by a pulverizer such as a dry bead mill. By dry grinding, the burned product is subjected to mechanochemical treatment, the crystal diameter becomes small, and the surface activity becomes high. The combination of the high surface activity of the pulverized powder with the effect of the moderate particle diameter contributes to densification of the ferrite layer obtained in the subsequent film forming process. The ferrite powder preferably has a crystal diameter (CSp) of 2nm to 100 nm. More preferably 2nm to 50nm, still more preferably 4nm to 25 nm. By using ferrite powder having a fine crystal diameter, a dense ferrite layer can be obtained.
< film Forming Process >
In the film forming step (deposition step), ferrite powder is formed on the surface of the metal substrate by an aerosol deposition method. The aerosol deposition method (AD method) is a method of forming a film by spraying aerosolized raw material particles onto a substrate at a high speed and performing an impact curing phenomenon at normal temperature. Since the normal temperature impact curing phenomenon is utilized, a dense film with high adhesion can be formed. Further, since fine particles are used for supplying the raw material, a thick film can be obtained at a higher film formation rate than a thin film formation method such as a sputtering method or a vapor deposition method in which the raw material is separated to an atomic level. Further, since film formation at normal temperature is possible, the device does not need to be complicated in structure, and the manufacturing cost can be reduced.
An example of the structure of the aerosol deposition film forming apparatus is shown in fig. 15. The aerosol layer deposition device (20) comprises an aerosolization chamber (2), a film forming chamber (4), a delivery gas source (6) and a vacuum exhaust system (8). The aerosolization chamber (2) includes a vibrator (10) and a source material container (12) disposed thereon. A nozzle (14) and a stage (16) are provided in the film forming chamber (4). The stage (16) is configured to be vertically movable with respect to the ejection direction of the nozzle (14).
During film formation, a transport gas is introduced from a transport gas source (6) into a raw material container (12), and a vibrator (10) is operated. The raw material container (12) is filled with raw material particles (ferrite powder). The raw material particles are mixed with the transport gas by vibration, and aerosolized. The film forming chamber (4) is evacuated by a vacuum evacuation system (8), and the chamber is depressurized. The aerosol raw material particles are transported into the film forming chamber (4) by a pressure difference and are ejected from the nozzle (14). The ejected raw material particles collide with the surface of a substrate (base material) placed on a placement table (16), and are deposited there. In this case, in the raw material particles accelerated by the gas transport, the kinetic energy is locally opened at the time of collision with the substrate, and the substrate-particle and particle-particle bonding are realized. Thus, a dense film can be formed. By moving the stage (16) during film formation, a film that is expandable in the surface direction can be formed.
The reason why the dense ferrite layer is obtained by the manufacturing method of the present embodiment is presumed to be as follows. That is, ceramics are generally referred to as materials having a high elastic limit and being not easily plastically deformed. However, if the raw material fine particles collide with the substrate at a high speed at the time of film formation by the vapor deposition method, the impact force becomes larger as the elastic limit is exceeded, and thus the fine particles are plastically deformed. Specifically, defects such as crystal face shift and dislocation movement are generated in the interior of the fine particles, and the defect is compensated forThe defect is compensated for to generate plastic deformation, and the crystalline structure becomes fine. In addition, material movement occurs while the nascent dough is being formed. As a result of these complexing actions, the substrate-particle and particle-particle bonding forces are increased, resulting in a dense film. Further, during plastic deformation, a part of ferrite is decomposed and reoxidized to produce α -Fe contributing to high resistance 2 O 3 . In addition, at the initial stage of film formation, particles that collide with a metal substrate as a substrate intrude into the substrate, and by causing the intruded particles to exhibit an anchor effect, it is estimated whether or not the adhesion force between the ferrite layer and the substrate is improved.
The average particle size of the raw ferrite powder is important in obtaining a dense ferrite layer. In the present embodiment, the ferrite powder average particle diameter (D50) is set to 1.0 μm or more and 10.0 μm or less. When the average particle diameter is 1.0 μm or less, it is difficult to obtain a dense film. The powder having a small average particle diameter is because the mass of particles constituting the powder is small. The aerosolized feedstock particles collide with the substrate at high velocity along with the transport gas. The transport gas colliding with the substrate changes its direction and flows as exhaust gas. Particles having a small particle diameter and a small mass are washed away by the discharge flow of the transport gas, and the collision velocity against the substrate surface and the impact force generated by the collision velocity are reduced. When the impact force is small, plastic deformation of the microparticles is insufficient, and the crystal diameter does not decrease. The film after film formation is not dense, and is a compressed powder of which the powder is only compressed. Such a compact contains a plurality of voids therein, and the magnetic properties and electrical properties are deteriorated. Further, the adhesion force to the base material does not become high. When the average particle diameter is 10.0 μm or more and too large, the impact force applied to 1 particle is large, but the number of contact points between particles becomes small. Therefore, plastic deformation and sealing become insufficient, and it is difficult to obtain a dense film.
The film forming conditions according to the aerosol deposition method are not particularly limited as long as a ferrite layer having high adhesion and compactness can be obtained. As the transport gas, air or inert gas (nitrogen, argon, helium, etc.) can be used. Particularly preferred are gases which are easy to handle. The flow rate of the transport gas may be, for example, 1.0 to 20.0L/min. The internal pressure of the film forming chamber may be, for example, 10 to 50Pa before film formation, or 50 to 400Pa during film formation. The scanning speed (moving speed) of the metal substrate (stage) may be, for example, 1.0 to 10.0 mm/sec. The coating (film formation) may be performed only once, or may be performed a plurality of times. In particular, it is preferable to perform the process a plurality of times in order to sufficiently secure the film thickness of the obtained ferrite layer. The number of coating times is, for example, 5 times or more and 100 times or less.
The ratio (LCf/LCp) of the lattice constant (LCf) of the spinel phase contained in the ferrite layer to the lattice constant (LCp) of the spinel phase contained in the raw ferrite powder is preferably 0.95 to 1.05 (0.95.ltoreq. LCf/LCp.ltoreq.1.05). The spinel phase in the raw ferrite powder is a composition lacking oxygen element, and has lattice defects. Therefore, the lattice constant is larger than that in a state where no lattice defect exists. In addition, if the aerosol deposition film forming process is performed on the raw ferrite powder, plastic deformation occurs starting from lattice defects. In addition, an active surface is generated due to plastic deformation, and the active surface is oxidized. The lattice constant changes due to the reconstitution of the crystalline structure and the reoxidation of the active surface. By controlling the lattice constant ratio (LCf/LCp) within the range, alpha-Fe can be reduced with the reconstruction of the crystal structure and the reoxidation of the active surface 2 O 3 As a result, a ferrite layer having excellent electrical characteristics (electrical insulation) can be formed while maintaining excellent magnetic characteristics. The lattice constant ratio (LCf/LCp) is more preferably 0.99 to 1.04.
The degree of variation in lattice constant varies depending on the manufacturing conditions and composition of the raw ferrite powder, and the material and type of the base material. Specifically, when the ferrite composition is a stoichiometric composition or an iron (Fe) rich composition (M x Fe 3-x O 4 :0 < x.ltoreq.1, M is a metal atom), the amount of oxygen contained in the raw material ferrite powder tends to be substantially smaller than the stoichiometric ratio, depending on the firing conditions. Therefore, the lattice constant of the raw ferrite powder tends to be large. In addition, in the ferrite layer formed by the AD method, the crystal structure is formed by oxidation accompanying plastic deformation of the raw material particlesThe lattice constant tends to be smaller than that of the raw ferrite powder because of the reconstitution. In particular, when ferrite powder containing lithium (Li) or manganese (Mn) or ferrite powder fired at an oxygen concentration lower than that of the atmosphere is used, this tendency is remarkable. Therefore, LCf/LCp is easily smaller than 1.00 in this case.
The Fe content is less than the stoichiometric ratio (M) x Fe 3-x O 4 :1 < x, M is a metal atom), the amount of oxygen contained in the ferrite is equivalent to the stoichiometric ratio. In addition, in the ferrite layer formed by the AD method, lattice defects increase due to plastic deformation, so that the lattice constant tends to be large. In particular, when ferrite powder containing Cu or ferrite powder sintered in an atmospheric environment is used, this tendency is remarkable. Therefore, in this case, LCf/LCp tends to exceed 1.00.
In the case where the base material contains copper (Cu) or silver (Ag), LCf/LCp tends to be small. Since Cu and Ag are more difficult to oxidize than ferrite particles, oxygen tends to be supplied to the ferrite film. In this case LCf/LCp is easily smaller than 1.00. In addition, when the base material contains iron (Fe) or nickel (Ni), LCf/LCp tends to be large, and Fe and Ni tend to be oxidized more easily than ferrite particles, and oxygen tends to be extracted from the ferrite film. In this case LCf/LCp easily exceeds 1.00.
The lattice constant ratio (LCf/LCp) can also be adjusted by controlling the conditions under which the aerosol is deposited. That is, by increasing the collision velocity of the raw material particles, the progress of deformation and reoxidation can be promoted. The collision speed of the raw material particles can be changed by adjusting the indoor pressure or the like. In addition, by changing the film formation rate, excessive progress of reoxidation can be prevented. Since the reoxidation is performed from the surface of the raw material particles, if the film forming speed of the ferrite layer is increased, the exposure time of the raw material particles to the atmosphere is shortened, and the reoxidation is suppressed. A step of
The ratio (CSf/CSP) of the crystal diameter (CSf) of the spinel phase contained in the ferrite layer to the crystal diameter (CSp) of the spinel phase contained in the raw material ferrite powder is preferably 0.01 to 0.50 (0.01. Ltoreq.CSf/CSP. Ltoreq.0.50). By depositing the film via an aerosol, the crystal diameter of the ferrite changes. This is because deformation occurs upon collision with the substrate, and the active surface reoxidizes. Even when the film is formed under the condition that the crystal diameter ratio (CSf/Csp) becomes too small, a ferrite layer which is dense and has high adhesion cannot be obtained. This is because the internal stress of the ferrite layer becomes excessive. In addition, even if film is formed, the ferrite layer is easily peeled off due to internal stress. And thus lacks stability over time. The crystal diameter ratio (CSf/CSP) is more preferably 0.05 to 0.30, still more preferably 0.10 to 0.20.
Thus, the magnetic composite of the present embodiment can be obtained. In the obtained magnetic composite, since the ferrite layer is dense, the magnetic properties and the electrical properties (electrical insulation properties) are excellent. In addition, the adhesion force with the metal base material is high. In fact, the present inventors have succeeded in producing a magnetic composite having a ferrite layer with a relative density of 0.95 or more and a binding force of 9H in terms of pencil hardness. Further, the ferrite layer has relatively small magnetic loss in a high frequency region. Further, although not limited thereto, the use of a thinned metal base material can impart flexibility to the magnetic composite body, and can produce a device having a complicated shape. The magnetic composite body having such ferrite layer can be used not only for electromagnetic wave absorber but also for electronic structures such as transformer, inductor element and impedance element, and is particularly suitable for UHF tag, 5G filter and high frequency inductor.
The technique for producing the magnetic composite according to the present embodiment is not known to the present inventors. For example, the composite material containing ferrite powder proposed in patent document 1 contains a large amount of resin as a nonmagnetic material, and thus has poor magnetic properties. In addition, the ferrite thin film proposed in patent document 2 is difficult to be thick and film-formed in terms of production. Further, the composite magnetic material proposed in patent document 3 contains a metal magnetic material having high conductivity, and therefore cannot be applied to applications requiring electrical insulation. The magnetic composite of the present embodiment can be sufficiently applied to applications requiring electrical insulation, even if the ferrite layer does not contain a resin or a metal component.
Patent document 3 also discloses that iron powder is usedA technique of producing a composite magnetic film with a content of (metal magnetic material) of 0% (patent document 3 [0048 ]]). However, the peak of the (222) plane exists in the X-ray diffraction curve (fig. 3 of patent document 3), and it is estimated that the ferrite layer in the magnetic film is not in a microcrystalline state, and the compactness and the adhesion are poor. In patent document 3, as ferrite raw materials, other than NiZn ferrite, mnZn ferrite, and the like, α -Fe is exemplified 2 O 3 (patent document 3 [0036 ]]). However, patent document 3 does not disclose that a predetermined amount of α -Fe is contained in the ferrite layer 2 O 3 And thereby cutting off the conductive path in the ferrite layer, the resistance becomes high. In practice, alpha-Fe is used as a raw material 2 O 3 Coarse alpha-Fe 2 O 3 Is contained in ferrite layer, the coarse alpha-Fe 2 O 3 As a result of the obstruction of the movement of the ferrite component magnetic wall, the deterioration of magnetic characteristics is caused.
Examples
The invention will be described in more detail using the following examples. However, the present invention is not limited to the following examples.
(1) Fabrication of magnetic composite
Example 1
In example 1, ferrite powder containing MnZn ferrite as a main component was prepared, and the obtained ferrite powder was formed into a film on the front and back surfaces of a copper (Cu) foil (metal base) having a thickness of 30 μm, respectively, to prepare a magnetic composite. The ferrite powder was produced and film-formed in the following manner.
< production of ferrite powder >)
As a raw material, iron oxide (Fe 2 O 3 ) Manganese tetraoxide (Mn) 3 O 4 ) And zinc oxide (ZnO), in Fe 2 O 3 ：Mn 3 O 4 : the raw materials were weighed and mixed in a molar ratio of zno=53:12.3:10. Mixing was performed using a henschel mixer. The obtained mixture was molded using a roll compactor to obtain a pellet (pre-pellet).
Next, the granulated raw material mixture (pre-granulated material) was pre-calcined to prepare a pre-calcined material. The pre-firing was performed in a rotary kiln at 880℃for 2 hours under atmospheric conditions.
Then, the obtained pre-baked product was pulverized and granulated to prepare a granulated product (primary granulated product). The pre-fired product was first ground using a dry bead mill (3/16 inchSteel ball beads of (a) by coarse grinding, adding water, and grinding with wet bead mill>Zirconia beads of (a) are subjected to micro-pulverization and slurrying. The solid content concentration of the obtained slurry was 50 mass%, and the particle diameter of the pulverized powder (slurry particle diameter) was 2.15. Mu.m. An ammonium polycarboxylate salt was added as a dispersant to the obtained slurry in a proportion of 50cc relative to the solid content in 25kg of the slurry, and a 10 mass% aqueous solution of polyvinyl alcohol (PVA) was further added as a binder in an addition amount of 500 cc. Thereafter, the slurry containing the dispersant and the binder was granulated using a spray dryer to obtain a final granulated product.
Then, the obtained primary granulated material was baked (primary baking) under a non-oxidizing atmosphere at 1250℃for 4 hours using an electric furnace to prepare a baked material. The resultant fired product was then dried using a dry bead mill (3/16 inch Steel ball beads) of the powder are crushed to obtain a crushed and sintered product.
< film Forming >
Ferrite layers are formed on the front and back surfaces of the metal base material, respectively, using the obtained pulverized and fired product. As the metal base material, a copper (Cu) foil having a thickness of 30 μm was used. The film formation was performed by vapor deposition (AD) under the following conditions. Further, film formation was performed 30 times on the front and back surfaces of the metal base material, respectively.
Carrier gas (transport gas): air-conditioner
-gas flow rate: 2.5L/min
Film forming chamber pressure (before film forming): 30Pa
Film forming chamber pressure (in film formation): 100Pa
-substrate scanning speed: 5 mm/sec
Number of coating applications: 30 times +30 times
Distance of substrate to nozzle: 20mm of
Nozzle shape: 10mm by 0.4mm
Film shape: sheet-like shape
Example 2
In example 2, ferrite layers were formed only on the surface (one side) of the metal base material (Cu foil), and the number of coating layers was changed to 15. A magnetic composite was produced in the same manner as in example 1.
EXAMPLE 3
In example 3, the number of coating layers at the time of film formation was changed to 40. A magnetic composite was produced in the same manner as in example 2.
EXAMPLE 4
In example 4, a laminate obtained by vapor deposition of aluminum (Al) having a thickness of 0.05 μm on a PET film having a thickness of 100 μm was used as a metal base, and a ferrite layer was formed on the vapor-deposited surface of the laminate. A magnetic composite was produced in the same manner as in example 3.
EXAMPLE 5
In example 5, an aluminum (Al) foil having a thickness of 30 μm was used as the metal base material. A magnetic composite was produced in the same manner as in example 3.
EXAMPLE 6
In example 6, a nickel (Ni) foil having a thickness of 30 μm was used as the metal base material. A magnetic composite was produced in the same manner as in example 3.
EXAMPLE 7
In example 7, fe was used as Fe in the production of ferrite powder 2 O 3 ：Mn 3 O 4 : znO = 51.5:9.3: the raw materials were weighed and mixed in a molar ratio of 20.5. A magnetic composite was produced in the same manner as in example 1.
EXAMPLE 8
In example 8, fe is used as Fe in the preparation of ferrite powder 2 O 3 ：Mn 3 O 4 : znO = 52:8:24, and the raw materials were weighed and mixed in a molar ratio. A magnetic composite was produced in the same manner as in example 1.
Example 9
In example 9, a raw material powder (ferrite powder) containing NiCuZn ferrite as a main component was prepared, and then the obtained ferrite powder was formed into a film on the front and back surfaces of a copper (Cu) foil (metal base) having a thickness of 30 μm, respectively, to prepare a magnetic composite. The ferrite powder was produced and film-formed in the following manner.
As a raw material, iron oxide (Fe 2 O 3 ) Zinc oxide (ZnO), nickel oxide (NiO) and copper oxide (CuO), in Fe 2 O 3 : znO: niO: cuO = 48.5:29.25:16: the raw materials were weighed and mixed in a molar ratio of 6.25. The preliminary firing was performed under the condition of 850 ℃ in the atmospheric environment for 2 hours, and the main firing was performed under the condition of 1100 ℃ in the oxidizing environment for 4 hours. A magnetic composite was produced in the same manner as in example 1.
EXAMPLE 10
In example 10, fe was used as Fe in the production of ferrite powder 2 O 3 : znO: niO: cuO = 48.5:33:12.5:6, the raw materials were weighed and mixed. The pre-firing was performed under an atmospheric atmosphere at 910℃for 2 hours. The amount of the binder to be added was 250cc, and a final granulated product was obtained. A magnetic composite was produced in the same manner as in example 9.
EXAMPLE 11
In example 11, ferrite layers were formed only on the surface (one side) of a copper (Cu) foil (metal base material), and the number of coating layers was changed to 15. Except for this, a magnetic composite was produced in the same manner as in example 10.
EXAMPLE 12
In example 12, a raw material powder (ferrite powder) containing a NiZn ferrite as a main component was prepared, and then the obtained ferrite powder was formed into a film on the front and back surfaces of a copper (Cu) foil (metal base) having a thickness of 30 μm, respectively, to prepare a magnetic composite. The ferrite powder was produced and film-formed in the following manner.
As a raw material, iron oxide (Fe 2 O 3 ) Zinc oxide (ZnO) and nickel oxide (NiO), in Fe 2 O 3 : znO: nio=48: 32.5: the raw materials were weighed and mixed in a molar ratio of 19.5. The preliminary firing was performed under atmospheric conditions at 950 ℃ x 2 hours, and the final firing was performed under oxidizing conditions at 1250 ℃ x 4 hours. A magnetic composite was produced in the same manner as in example 1.
Example 13
In example 13, a raw material powder (ferrite powder) containing MnMg ferrite as a main component was prepared, and then the obtained ferrite powder was formed into films on the front and back surfaces of a copper (Cu) foil (metal base) having a thickness of 30 μm, respectively, to prepare a magnetic composite material. The ferrite powder was produced and film-formed in the following manner.
As a raw material, iron oxide (Fe 2 O 3 ) Manganese tetraoxide (Mn) 3 O 4 ) And magnesium oxide (MgO), in Fe 2 O 3 ：Mn 3 O 4 : mgo=50.1: 13.3: the raw materials were weighed and mixed in a molar ratio of 10. The pre-firing was performed under conditions of 920℃for 2 hours in an atmospheric environment, and the final firing was performed under conditions of 1180℃for 4 hours in a non-oxidizing environment. A magnetic composite was produced in the same manner as in example 1.
EXAMPLE 14
In example 14, a raw material powder (ferrite powder) containing Mn ferrite as a main component was prepared, and then the obtained ferrite powder was formed into a film on the front and back surfaces of a copper (Cu) foil (metal base) having a thickness of 30 μm, respectively, to prepare a magnetic composite. The ferrite powder was produced and film-formed in the following manner.
As a raw material, iron oxide (Fe 2 O 3 ) And trimanganese tetraoxide (Mn) 3 O 4 ) In Fe 2 O 3 ：Mn 3 O 4 =80: the raw materials were weighed and mixed in a molar ratio of 6.67. In addition, the pre-firing is carried out under the condition of 900 ℃ multiplied by 2 hours in the atmospheric environment, and the final firing temperature is the same as that of the pre-firingThe reaction was carried out at 1300℃for 4 hours under a non-oxidizing atmosphere. A magnetic composite was produced in the same manner as in example 1.
EXAMPLE 15
In example 15, a raw material powder (ferrite powder) containing Zn ferrite as a main component was prepared, and then the obtained ferrite powder was formed into a film on the front and back surfaces of a copper (Cu) foil (metal base) having a thickness of 30 μm, respectively, to prepare a magnetic composite. The ferrite powder was produced and film-formed in the following manner.
As a raw material, iron oxide (Fe 2 O 3 ) And zinc oxide (ZnO), in Fe 2 O 3 : znO = 80.7: the raw materials were weighed and mixed in a molar ratio of 19.3. At this time, relative to Fe 2 O 3 And ZnO in a total amount of 1 mass%, carbon (carbon black) was added. Further, the pre-firing was performed under a non-oxidizing atmosphere at 1000 ℃ for 2 hours, and the amount of the binder to be added was 1000cc, to obtain a final granulated product, and the final firing was performed under a non-oxidizing atmosphere at 1300 ℃ for 4 hours. Further, film formation was performed 20 times on the front and back surfaces of the metal base material, respectively. A magnetic composite was produced in the same manner as in example 1.
EXAMPLE 16
In example 16, a raw material powder (ferrite powder) containing Zn ferrite as a main component was prepared, and then the obtained ferrite powder was formed into a film on a copper (Cu) foil (metal base) having a thickness of 30 μm, to prepare a magnetic composite material. The ferrite powder was produced and film-formed in the following manner.
As a raw material, iron oxide (Fe 2 O 3 ) And zinc oxide (ZnO), in Fe 2 O 3 : znO = 85.7:14.3, the raw materials were weighed and mixed. At this time, relative to Fe 2 O 3 And ZnO in a total amount of 1.2 mass%, carbon (carbon black) was added. A magnetic composite was produced in the same manner as in example 15.
Example 17 (comparative example)
In example 17, ferrite layers were formed only on the surface (one side) of a copper (Cu) foil (metal base material), and the number of coating times was changed to 1. A magnetic composite was produced in the same manner as in example 1.
EXAMPLE 18 (comparative example)
In example 18, a ferrite layer was produced by a coating method. Specifically, ferrite powder was prepared in the same manner as in example 1, and 50 parts by mass of the obtained ferrite powder was dispersed and mixed with 50 parts by mass of the photocurable resin. Thereafter, the resulting mixture was coated on a PET film. The coating was performed using an applicator to obtain a coating film having a thickness of 12 μm. Next, the obtained coating film was cured with ultraviolet rays to form a film, and the coating film peeled from the PET film was used as a magnetic sheet.
Example 9 (comparative example)
In example 19, a ferrite layer was produced by a coating method. Specifically, ferrite powder was prepared in the same manner as in example 9, and 50 parts by mass of the obtained ferrite powder was dispersed and mixed with 50 parts by weight of the photocurable resin. Then, the resulting mixture was coated on a PET film. The coating was performed using an applicator to obtain a coating film having a thickness of 12 μm. Next, the obtained coating film was cured with ultraviolet rays to form a film, and the coating film peeled from the PET film was used as a magnetic sheet.
Table 1 and table 2 show the production conditions of ferrite powder and magnetic composite in examples 1 to 19.
TABLE 1
TABLE 2
TABLE 2 conditions for producing magnetic composite
Note that "1") indicates a comparative example.
(2) Evaluation
Regarding examples 1 to 19, various properties of ferrite powder, metal base material and magnetic composite were evaluated as follows.
< particle shape (raw material powder) >
The average value of SF-2 and the average value of the aspect ratio of the ferrite powder were obtained as follows. Ferrite powder was analyzed by a particle image analyzer (spectra corporation, moforti G3), and projected perimeter, projected area, major axis iron diameter, and minor axis iron diameter were obtained for 30000 particles. Analysis was performed using an objective lens with a magnification of 20 times. Then, SF-2 and aspect ratio were calculated for each particle according to the following formulas (1) and (2) using the obtained data, and the average value was obtained.
Number 4
/>
Number 5
Particle size distribution (raw material powder) >)
The particle size distribution of the ferrite powder was measured as follows. First, 0.1g of the sample and 20ml of water were placed in a 30ml beaker, and 2 drops of sodium hexametaphosphate were added as a dispersing agent. Next, dispersion was performed using an ultrasonic homogenizer (model UH-150, esculet, co., ltd.). At this time, the output level of the ultrasonic homogenizer was set to 4, and dispersion was performed for 20 seconds. Thereafter, bubbles formed on the surface of the beaker were removed, and the mixture was introduced into a laser diffraction type particle size distribution measuring apparatus (SALD-7500 nano, shimadzu corporation) for measurement. By this measurement, 10% cumulative diameter (D10), 50% cumulative diameter (D50; average particle diameter) and 90% cumulative diameter (D90) in the volume particle size distribution were obtained. The measurement conditions were set to 7 pump speed, 30 internal ultrasonic irradiation time, and refractive index of 1.70 to 050i. Then, using D10, D50, and D90, CV values were calculated according to the following formula (3).
Number 6
XRD (raw material powder, ferrite layer) >)
The ferrite powder and the ferrite layer of the magnetic composite were analyzed by X-ray diffraction (XRD). The analysis conditions are shown below.
-an X-ray diffraction device: x' pertMPD (including high speed detector) manufactured by Panaritic company
-a line source: co-K alpha
Tube voltage: 45kV
-tube current: 40mA
Scanning speed: 0.002 DEG/sec (continuous scanning)
-scan range (2θ): 15-90 DEG
From the obtained X-ray diffraction curve, the integrated intensity (I) of the (222) plane diffraction peak of the spinel phase was obtained 222 ) And (311) integrated intensity of plane diffraction peak (I) 311 ) Calculate XRD peak intensity ratio (I) 222 /I 311 ). In addition, the spinel Dan Xiangyu alpha-Fe is measured according to an X-ray diffraction curve 2 O 3 The content ratio of each.
Further, lattice constants (LCp, LCf) of the spinel phase are estimated by performing a Rit band analysis on the X-ray diffraction distribution, and crystal grain diameters (CSp, CSf) of the spinel phase are determined according to the scherrer formula. Then, the rate of change of the lattice constant (LCf/LCp) and the rate of change of the crystal diameter (CSf/Csp) of the spinel phase before and after the film formation were calculated.
< magnetic Property (raw powder, metal substrate, magnetic composite) >)
The magnetic properties (saturation magnetization, residual magnetization, and coercive force) of the ferrite powder, the metal base material, and the magnetic composite were measured as follows. First, a sample was placed in a cell having an inner diameter of 5mm and a height of 2mm, and the cell was mounted in a vibrating sample type magnetic measuring apparatus (VSM-C7-10A, tokyo Co., ltd.). Applying a magnetic field to 5kOe was added to scan, followed by decreasing the applied magnetic field to form a hysteresis curve. From the obtained curve data, the saturation magnetization (σs), residual magnetization (σr), and coercive force (Hc) of the sample were obtained.
< true specific gravity (raw material powder) >)
The raw material powder has a true specific gravity according to JIS Z8837:2018 is measured by a gas displacement method.
Thickness and element distribution (ferrite layer)
The ferrite layer was observed for its cross section by a field emission scanning electron microscope (FE-SEM) to determine the thickness. Then, an elemental mapping analysis in a cross section was performed using an energy dispersive X-ray analysis device (EDX) with a microscope to obtain a mapped image.
< Density (ferrite layer) >)
The density of the ferrite layer was measured as follows. First, the mass of the metal base material monomer before the ferrite layer was formed was measured. Next, the mass of the metal base material after the ferrite layer was formed was measured, and the difference between the mass of the metal base material and the mass of the metal base material was calculated to obtain the mass of the ferrite layer. In addition, the film formation area and film thickness of the ferrite layer were measured. The film thickness was obtained by observing the cross section of the ferrite layer by a Scanning Electron Microscope (SEM). Then, the density of the ferrite layer was calculated according to the following expression (4).
Number 7
Surface roughness (ferrite layer) >, and
the surface of the ferrite layer was evaluated for arithmetic average roughness (Ra) and maximum height (Rz) using a laser microscope (OPTELICS HYBRID). The average value of each sample was determined by measuring 10 points. The measurement was carried out in accordance with JIS B0601-2001. In addition, according to the arithmetic average roughness (Ra) and the thickness (d) of the ferrite layer F ) The roughness ratio (Ra/d was calculated F )。
Surface resistance (ferrite layer) >, and method for producing the same
The surface resistance of the ferrite layer was measured using a resistivity meter (mitsubishi chemical Co., ltd., lorestaHP MCP-T410).
< magnetic permeability (magnetic composite) >)
The magnetic permeability of the magnetic composite was measured by a microstrip line complex permeability measurement method using a vector network analyzer (Keysight, PNAN5222B, 10MHz to 26.5 GHz) and a jig for measuring magnetic permeability (kem corporation). Specifically, the magnetic composite was cut out and set as a measurement sample on a jig for measuring magnetic permeability. At this time, the sheet-like sample was cut into pieces of 16mm in length and 5mm in width for use. In the case of using an annular sample, the shape of the sample was set to have an outer diameter of 6.75mm and an inner diameter of 3.05mm. Next, the measurement frequency in the range of 100MHz to 10GHz is scanned on a logarithmic scale. The real part μ' and imaginary part μ″ of the complex permeability at the frequency of 1GHz are obtained, and the loss factor (tan δ) is calculated according to the following expression (5).
Number 8
Bending (magnetic composite body) >, bending strength and bending strength
The magnetic composite material was wound on an inch pipe to evaluate the bendability. Specifically, 3 kinds of inch pipes each having an outer diameter of 1/16 inch, an outer diameter of 1/8 inch, and an outer diameter of 1/4 inch were prepared, and the magnetic composite was wound around each of the inch pipes so that the ferrite layer was outside. Then, the ferrite layer was visually observed, and rated from o to x according to the following criteria.
O: no change in ferrite layer was found before and after winding.
Delta: cracks are generated on the ferrite layer after winding.
X: the ferrite layer falls off after winding.
< adhesion (magnetic composite) >
The adhesion of the ferrite layer to the metal substrate was evaluated by a pencil hardness test (pencil scratch test). The measurement was performed in accordance with the old JIS K5400. In each test, the pencil was repeatedly passed 5 times with the same density mark. In this process, the tip of the pencil lead is ground every time it is scratched. The higher pencil hardness in the order of 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H, and 10H means higher hardness and more excellent adhesion.
< Curie Point (magnetic Complex) >)
The curie point (Tc) of the magnetic composite was measured using a vibrating sample magnetic measurement device (VSM). Specifically, a magnetic composite cut into a predetermined size (length 8mm, width 6 mm) was placed in a measuring cell and set in a vibration sample type magnetic measuring apparatus (model VSM-5, eastern industry co.). The sample was heated from room temperature to 500 c at a rate of 0.3 c/sec in a state where a magnetic field of 10kOe was applied, and the saturation magnetization during heating was measured. The curie point is calculated from the temperature dependence of the saturation magnetization obtained.
(3) Evaluation results
The characteristics of the ferrite powder and the characteristics of the metal base material are shown in tables 3 and 4, respectively, for examples 1 to 19. The properties of the magnetic composite are shown in tables 5 and 6.
As shown in Table 3, the content of spinel phase in the ferrite powder used for film formation in examples 1 to 19 was as high as 90 mass% or more, and the synthesis of spinel type ferrite was sufficiently performed. In addition, XRD peak intensity ratio (I 222 /I 311 ) About 2.5 to 5%, and is equivalent to the conventional spinel type ferrite. The average particle diameter (D50) is 3.6 to 5.2. Mu.m, and the crystal diameter is about 6 to 18 nm.
As shown in Table 4, the saturation magnetization (. Sigma.s) of the metal base material (Ni foil) of example 6 as a ferromagnetic material was as high as 56.6emu/g, whereas the saturation magnetization of the metal base materials (Cu foil, al foil) of examples 1 to 5 and examples 7 to 17 as a normal magnetic material was almost zero.
As shown in tables 5 and 6, the thicknesses (d) of the ferrite layers of the magnetic composites of examples 1 to 16 F ) At least 3.5 μm, XRD peak intensity ratio (I 222 /I 311 ) Zero (0). In addition alpha-Fe 2 O 3 The amount is 0.5 to 37.3 mass% and the crystal diameter is as small as 2.05nm or less. Thus, these samples have higher relative densities, adhesion, and surface resistances. In particular, the relative densities of examples 2 and 6 were very high, ranging from 0.96 to 0.97. In addition, the pencil hardness of examples 1, 2, 6 to 16 was as high as 9H or more, and the results of the adhesion test were good. Further, the results of the bending test of examples 1, 2, 4 to 6 and 8 to 13 Good. In addition, the pencil hardness of examples 4 and 5 was slightly lower. This is because aluminum having low strength is used as a base material.
In addition, ferrite layer thickness (d F ) Example 17, which was 0.6 μm and smaller, had a large crystal diameter although the relative density was high. Further, since ferrite layer formation cannot be performed uniformly, the roughness ratio (Ra/d F ) Large, poor surface smoothness, and as a result, the influence of the base material is large and the surface resistance is small. Further, since the ferrite layer formed in example 17 was thin and the uniformity of the ferrite layer was poor, the bendability was also poor. In examples 18 and 19, which were prepared by the coating method, it was found that the imaginary part (μ ") and tan δ of the complex permeability were large and the magnetic loss was large. In addition, by generating pinholes in the magnetic sheet, cracks are generated in the magnetic sheet, the bendability is poor, and the resin is decomposed at a temperature exceeding 200 ℃ and the temperature stability is poor.
The ferrite layer of the magnetic composite obtained in example 2 has cross-sectional element mapping images as shown in fig. 16 (a) to (f). Here, fig. 16 (a) to (f) are electron beam images (a), carbon (C) images (b), copper (Cu) images (C), iron (Fe) images (d), manganese (Mn) images (e), and oxygen (O) images (f), respectively. Fig. 16 (a) to (f) show the metal base material (Cu foil) on the upper side and the ferrite layer (MnZn ferrite layer) on the lower side.
The constituent elements of the metal base material (Cu foil) and the ferrite layer (MnZn ferrite layer) are clearly separated. That is, copper (Cu) is present on the substrate side, and manganese (Mn), iron (Fe), and oxygen (O) are present only on the ferrite layer side. It is clear from this that no diffusion of elements occurs between the metal base material and the ferrite layer due to the reaction. In addition, carbon (C) was not confirmed in both the metal base material and the ferrite layer.
Fig. 17 to 20 show the temperature dependence of saturation magnetization of the magnetic composites obtained in examples 2, 10, 14, and 15, respectively. The saturation magnetization of all samples decreased with increasing temperature, showing typical temperature characteristics of ferrite. The curie points (Tc) are 310 ℃ (example 2), 180 ℃ (example 10), 320 ℃ (example 14) and 470 ℃ (example 15), respectively, and represent values corresponding to the composition of the ferrite layers contained in the respective samples.
The magnetic permeability (real part μ', imaginary part μ ") of the magnetic composite obtained in example 2 is shown in fig. 21. From this, it is clear that μ″ is almost always 0 from the low frequency side to the high frequency region of 1GHz or more, and μ' shows a constant value, and μ″ takes a maximum value at a frequency of 1GHz or more.
From these results, the magnetic composite of the present embodiment has a ferrite layer which is dense, has a relatively large film thickness, and is excellent in various characteristics such as magnetic characteristics.
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 4 Properties of the Metal substrate
Note that "x" is expressed as a comparative example.
TABLE 5
TABLE 6
Industrial applicability
The present application can provide a magnetic composite body having a compact ferrite layer with a relatively large film thickness, excellent magnetic properties and electric properties, and good adhesion.
Although the present application has been described in detail with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
The present application is based on Japanese patent application No. 2021-004514, applied for 1 month 14 of 2021 (Japanese patent application No. 2021-004514), applied for 7 month 1 of 2022 (Japanese patent application No. 2022-001607), the contents of which are incorporated herein by reference.
Symbol description
2 aerosolization chamber
4 film forming chamber
6 conveying air source
8 vacuum exhaust system
10 vibrator
12 raw material container
14 nozzle
16 stage
20 aerosol deposition film forming apparatus
Claims (6)
1. A magnetic composite body, which comprises a magnetic material,
which comprises a metal substrate and a ferrite layer arranged on the surface of the metal substrate,
thickness d of the metal base material M Is not less than 0.001 mu m,
thickness d of ferrite layer F An integrated intensity I of a (222) plane in X-ray diffraction analysis, which is 2.0 μm or more and contains spinel ferrite as a main component 222 Integrated intensity I relative to (311) plane 311 Ratio I 222 /I 311 Is 0.00-0.03.
2. The magnetic composite body according to claim 1,
alpha-Fe of the ferrite layer 2 O 3 The content is not less than 0.0% by mass and not more than 20.0% by mass.
3. The magnetic composite according to claim 1 or 2,
the ferrite layer contains iron Fe and oxygen O, and further contains at least one element selected from the group consisting of lithium Li, magnesium Mg, aluminum Al, titanium Ti, manganese Mn, zinc Zn, nickel Ni, copper Cu, and cobalt Co.
4. The magnetic composite according to any one of claim 1 to 3,
the surface arithmetic average roughness Ra of the ferrite layer relative to the thickness d thereof F Ratio Ra/d F Is 0.00-0.20.
5. The magnetic composite according to any one of claim 1 to 4,
the ferrite layer has a composition containing ferrite constituent components, and the remainder is unavoidable impurities.
6. An element or component having a coil and/or an inductor function, an electronic device, an electronic component housing, an electromagnetic wave absorber, an electromagnetic wave shield, or an element or component having an antenna function, each including the magnetic composite body according to any one of claims 1 to 5.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-004514 | 2021-01-14 | ||
| JP2022001607A JP2022109234A (en) | 2021-01-14 | 2022-01-07 | magnetic composite |
| JP2022-001607 | 2022-01-07 | ||
| PCT/JP2022/000988 WO2022154058A1 (en) | 2021-01-14 | 2022-01-13 | Magnetic composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116848600A true CN116848600A (en) | 2023-10-03 |
Family
ID=88169280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280010058.7A Pending CN116848600A (en) | 2021-01-14 | 2022-01-13 | Magnetic composite body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116848600A (en) |
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2022
- 2022-01-13 CN CN202280010058.7A patent/CN116848600A/en active Pending
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