JP4934947B2 - Ceramic porcelain composition and method for producing the same - Google Patents
Ceramic porcelain composition and method for producing the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims description 84
- 239000000919 ceramic Substances 0.000 title claims description 63
- 229910052573 porcelain Inorganic materials 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000463 material Substances 0.000 claims description 100
- 229910000859 α-Fe Inorganic materials 0.000 claims description 75
- 239000000696 magnetic material Substances 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 13
- -1 B 2 O 3 Inorganic materials 0.000 claims description 8
- 238000011156 evaluation Methods 0.000 description 35
- 239000000843 powder Substances 0.000 description 26
- 239000010949 copper Substances 0.000 description 18
- 239000011812 mixed powder Substances 0.000 description 15
- 230000035699 permeability Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000007858 starting material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000007088 Archimedes method Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
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- Magnetic Ceramics (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は、セラミック磁器組成物及びその製造方法に関し、更に詳しくは、例えば、インダクタンス素子、アンテナ素子等の電子部品に好適に用いられるセラミック磁器組成物及びその製造方法に関するものである。 The present invention relates to a ceramic porcelain composition and its production how, more particularly, for example, those related to the preferred ceramic porcelain composition are used and a manufacturing methods from electronic components such as inductance elements, the antenna elements .
携帯電話、無線ＬＡＮ等の移動体通信機器において、回路整合等を目的としたインダクタンス素子等の電子部品が多く用いられる。最近の移動体通信機器の高周波化に伴い、これらに用いられる電子部品に対して数１００ＭＨｚ〜数ＧＨｚ帯領域で使用可能な特性が求められている。従来は、数１００ＭＨｚ〜数ＧＨｚ帯領域ではガラス等の誘電体材料がインダクタンス素子等の磁芯として用いられてきた。 In mobile communication devices such as mobile phones and wireless LANs, electronic components such as inductance elements for the purpose of circuit matching are often used. With recent increases in the frequency of mobile communication devices, characteristics that can be used in the range of several hundreds of MHz to several GHz for electronic components used in these devices are required. Conventionally, a dielectric material such as glass has been used as a magnetic core for an inductance element or the like in the region of several hundred MHz to several GHz.
しかしながら、ガラス等の誘電体材料は透磁率が全周波数帯で１であるため、電子部品の小型化に伴い、ガラス等の誘電体材料では大きなインダクタンス値が得られないという問題がある。また、従来から磁性体材料として用いられているＮｉ−Ｃｕ−Ｚｎフェライトは、透磁率の周波数限界（スネークの限界）があるため、数１００ＭＨｚ〜数ＧＨｚ帯領域では十分な透磁率が得られず、その周波数帯域でのインダクタ材料に適用することができなかった。 However, since the dielectric material such as glass has a magnetic permeability of 1 in all frequency bands, there is a problem that a large inductance value cannot be obtained with a dielectric material such as glass as the electronic component is downsized. Further, Ni—Cu—Zn ferrite conventionally used as a magnetic material has a permeability frequency limit (a limit of snakes), so that sufficient permeability cannot be obtained in the region of several hundred MHz to several GHz. It could not be applied to inductor materials in that frequency band.
そこで、透磁率がスピネルフェライトの周波数限界を超えた周波数領域まで伸びている六方晶フェライト材料が数１００ＭＨｚ〜数ＧＨｚ帯領域での磁性体材料として提案されている。六方晶フェライトは、ｃ軸に対して垂直な面内に磁化容易軸を持ち、フェロックスプレーナ型フェライトとも呼ばれる磁性体材料であり、１９５７年にフィリップスから報告された。フェロックスプレーナ型の代表的な磁性体材料としては、Ｃｏ置換系Ｚ型六方晶フェライト３ＢａＯ・２ＣｏＯ・１２Ｆｅ２Ｏ３（Ｃｏ２Ｚ）、Ｃｏ置換系Ｙ型六方晶フェライト２ＢａＯ・２ＣｏＯ・６Ｆｅ２Ｏ３（Ｃｏ２Ｙ）、Ｃｏ置換系Ｗ型六方晶フェライトＢａＯ・２ＣｏＯ・８Ｆｅ２Ｏ３（Ｃｏ２Ｗ）等が知られている。フェロックスプレーナ型フェライトの中でも、Ｃｏ２Ｙ単相の合成温度（約１０５０℃）は、Ｃｏ２Ｚ単相（１３００℃）及びＣｏ２Ｗ単相（１２００℃）それぞれの合成温度に比べて低く、また、Ｃｏ２Ｙは、透磁率の周波数限界が３ＧＨｚ以上まで伸びているため、数１００ＭＨｚ〜数ＧＨｚ帯領域での磁性体材料として有望視されている。 Therefore, a hexagonal ferrite material whose magnetic permeability extends to a frequency region exceeding the frequency limit of spinel ferrite has been proposed as a magnetic material in the region of several hundred MHz to several GHz. Hexagonal ferrite is a magnetic material having an easy axis of magnetization in a plane perpendicular to the c-axis, and is also called a ferro-planar ferrite, and was reported by Philips in 1957. As a typical magnetic material of the Ferroc planar type, Co-substituted Z-type hexagonal ferrite 3BaO.2CoO.12Fe 2 O 3 (Co 2 Z), Co-substituted Y-type hexagonal ferrite 2BaO.2CoO.6Fe 2 O 3 (Co 2 Y), Co-substituted W-type hexagonal ferrite BaO.2CoO.8Fe 2 O 3 (Co 2 W), and the like are known. Among the Ferro-spreader type ferrites, the synthesis temperature of the Co 2 Y single phase (about 1050 ° C.) is lower than the synthesis temperature of each of the Co 2 Z single phase (1300 ° C.) and the Co 2 W single phase (1200 ° C.). In addition, Co 2 Y is promising as a magnetic material in the region of several hundred MHz to several GHz because the frequency limit of permeability extends to 3 GHz or more.
例えば、特許文献１にはＹ型またはＭ型六方晶フェライトを主要相とする磁性体材料からなる高周波用磁性体材料が提案されている。この高周波磁性体材料は、数１００ＭＨｚ〜数ＧＨｚ帯域で使用でき、１０００℃以下の温度で焼成可能で、相対Ｘ線密度が９０％以上のものである。また、特許文献２にはＣｏ置換Ｙ型六方晶フェライトからなる複合磁性材料が提案されている。この複合磁性材料は、数ＭＨｚから数ＧＨｚの周波数帯において比較的大きな透磁率を持ち、かつ、高いＱ値を維持し得るものである。 For example, Patent Document 1 proposes a high-frequency magnetic material made of a magnetic material whose main phase is Y-type or M-type hexagonal ferrite. This high-frequency magnetic material can be used in the several hundred MHz to several GHz band, can be fired at a temperature of 1000 ° C. or less, and has a relative X-ray density of 90% or more. Patent Document 2 proposes a composite magnetic material made of Co-substituted Y-type hexagonal ferrite. This composite magnetic material has a relatively large magnetic permeability in a frequency band of several MHz to several GHz and can maintain a high Q value.
また、電子部品が小型化し、数１００ＭＨｚ〜数ＧＨｚ帯領域におけるインダクタンス素子やアンテナ素子として高いインダクタンス値を得るためには、使用される磁性体材料のＱ値（＝μ’／μ”）が同周波数帯領域で高いことが必要不可欠である。 In addition, in order to reduce the size of electronic components and obtain high inductance values as inductance elements and antenna elements in the several hundred MHz to several GHz band region, the Q value (= μ ′ / μ ″) of the magnetic material used is the same. It is essential to be high in the frequency band region.
しかしながら、特許文献１、２に記載の従来のＹ型六方晶フェライトは、透磁率が数１００ＭＨｚ〜数ＧＨｚ帯領域まで伸びるが、同周波数帯領域でのＱ値が約４０〜８０程度と低いため、インダクタンス素子やアンテナ素子等の電子部品用の磁性体材料としての用途には向かないという課題があった。 However, the conventional Y-type hexagonal ferrite described in Patent Documents 1 and 2 has a magnetic permeability extending from several hundred MHz to several GHz, but the Q value in the same frequency band is as low as about 40 to 80. There is a problem that it is not suitable for use as a magnetic material for electronic parts such as an inductance element and an antenna element.
本発明は、上記課題を解決するためになされたもので、数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値が１００以上の磁性体材料を得ることができるセラミック磁器組成物、その製造方法及びセラミック焼結体の製造方法を提供することを目的としている。 The present invention has been made to solve the above-mentioned problems, and a ceramic porcelain composition capable of obtaining a magnetic material having a Q value of 100 or more in a region of several hundred MHz to several GHz, a method for producing the same, and ceramic firing It aims at providing the manufacturing method of a zygote.
本発明者は、Ｙ型六方晶フェライト材料のＱ値について種々検討した結果、特定のＹ型六方晶フェライト材料と非磁性体材料とを特定比率で混合することによって、数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値を１００以上に高められることを知見した。 As a result of various studies on the Q value of the Y-type hexagonal ferrite material, the present inventor has mixed a specific Y-type hexagonal ferrite material and a non-magnetic material at a specific ratio, so that several hundred MHz to several GHz band region is obtained. It was found that the Q value at 100 can be increased to 100 or more.
本発明は、上記知見に基づいてなされたもので、本発明の請求項１に記載のセラミック磁器組成物は、組成式（１−ａ−ｂ）（Ｂａ１−ｘＳｒｘ）・ａ（Ｃｏ１−ｙＣｕｙ）Ｏ・ｂＦｅ２Ｏ３（但し、０．２０５≦ａ≦０．２５、０．５５≦ｂ≦０．５９５、０≦ｘ≦０．５０、及び０．２５≦ｙ≦０．７５）で表されるＹ型六方晶フェライト材料４０〜９５体積％と、非磁性体材料５〜６０体積％と、を含み、上記非磁性体材料は、組成式（Ｂａ １−ｚ Ｓｒ ｚ ）Ｏ・ｃＦｅ ２ Ｏ ３ （但し、０≦ｚ≦１．０及び０．７５≦ｃ≦１．２５）で表されることを特徴とするものである。 The present invention has been made based on the above findings, the ceramic porcelain composition according to claim 1 of the present invention, the composition formula (1-a-b) ( Ba 1-x Sr x) · a (Co 1-y Cu y ) O · bFe 2 O 3 (where 0.205 ≦ a ≦ 0.25, 0.55 ≦ b ≦ 0.595, 0 ≦ x ≦ 0.50, and 0.25 ≦ y ≦ and 40 to 95 vol% Y-type hexagonal ferrite material represented by 0.75), and 5 to 60% by volume non-magnetic material, only including, the non-magnetic material, composition formula (Ba 1-z Sr z ) O · cFe 2 O 3 (where 0 ≦ z ≦ 1.0 and 0.75 ≦ c ≦ 1.25) .
また、本発明の請求項２に記載のセラミック磁器組成物は、組成式（１−ａ−ｂ）（Ｂａ １−ｘ Ｓｒ ｘ ）・ａ（Ｃｏ １−ｙ Ｃｕ ｙ ）Ｏ・ｂＦｅ ２ Ｏ ３ （但し、０．２０５≦ａ≦０．２５、０．５５≦ｂ≦０．５９５、０≦ｘ≦０．５０、及び０．２５≦ｙ≦０．７５）で表されるＹ型六方晶フェライト材料４０〜９５体積％と、非磁性体材料５〜６０体積％と、を含み、上記非磁性体材料は、少なくともＳｉＯ２、Ｂ２Ｏ３、ＣａＯを含み、上記ＳｉＯ ２ の含有量が６０〜８５モル％であるガラス材料であることを特徴とするものである。 Also, the ceramic porcelain composition according to claim 2 of the present invention, the composition formula (1-a-b) ( Ba 1-x Sr x) · a (Co 1-y Cu y) O · bFe 2 O 3 (Provided that 0.205 ≦ a ≦ 0.25, 0.55 ≦ b ≦ 0.595, 0 ≦ x ≦ 0.50, and 0.25 ≦ y ≦ 0.75) includes a ferrite material 40 to 95% by volume, 5 to 60 and percent by volume non-magnetic material, and the non-magnetic material, viewing contains at least SiO 2, B 2 O 3, CaO, the content of the SiO 2 Is a glass material of 60 to 85 mol% .
また、本発明の請求項３に記載のセラミック磁器組成物の製造方法は、組成式（１−ａ−ｂ）（Ｂａ１−ｘＳｒｘ）・ａ（Ｃｏ１−ｙＣｕｙ）Ｏ・ｂＦｅ２Ｏ３（但し、０．２０５≦ａ≦０．２５、０．５５≦ｂ≦０．５９５、０≦ｘ≦０．５０、及び０．２５≦ｙ≦０．７５）で表されるＹ型六方晶フェライト材料と、組成式（Ｂａ１−ｚＳｒｚ）Ｏ・ｃＦｅ２Ｏ３（但し、０≦ｚ≦１．０及び０．７５≦ｃ≦１．２５）で表される非磁性体材料と、をそれぞれ得る工程と、上記Ｙ型六方晶フェライト材料４０〜９５体積％と上記非磁性体材料５〜６０体積％とを混合する工程と、上記Ｙ型六方晶フェライト材料と上記非磁性体材料との混合物を焼成して焼結体を得る工程と、を備えたことを特徴とするものである。 A method for manufacturing a ceramic porcelain composition according to claim 3 of the present invention, the composition formula (1-a-b) ( Ba 1-x Sr x) · a (Co 1-y Cu y) O · bFe Y represented by 2 O 3 (where 0.205 ≦ a ≦ 0.25, 0.55 ≦ b ≦ 0.595, 0 ≦ x ≦ 0.50, and 0.25 ≦ y ≦ 0.75) and type hexagonal ferrite material, non-magnetic represented by the composition formula (Ba 1-z Sr z) O · cFe 2 O 3 ( where, 0 ≦ z ≦ 1.0 and 0.75 ≦ c ≦ 1.25) A body material, a step of mixing the Y-type hexagonal ferrite material 40 to 95% by volume and the non-magnetic material 5 to 60% by volume, the Y-type hexagonal ferrite material and the non-material. And a step of obtaining a sintered body by firing a mixture with a magnetic material .
また、本発明の請求項４に記載のセラミック磁器組成物の製造方法は、組成式（１−ａ−ｂ）（Ｂａ１−ｘＳｒｘ）・ａ（Ｃｏ１−ｙＣｕｙ）Ｏ・ｂＦｅ２Ｏ３（但し、０．２０５≦ａ≦０．２５、０．５５≦ｂ≦０．５９５、０≦ｘ≦０．５０、及び０．２５≦ｙ≦０．７５）で表されるＹ型六方晶フェライト材料と、少なくともＳｉＯ２、Ｂ２Ｏ３、ＣａＯを含み、上記ＳｉＯ２の含有量が６０〜８５モル％であるガラス材料である非磁性体材料と、をそれぞれ得る工程と、上記Ｙ型六方晶フェライト材料４０〜９５体積％と上記非磁性体材料５〜６０体積％とを混合する工程と、上記Ｙ型六方晶フェライト材料と上記非磁性体材料との混合物を焼成して焼結体を得る工程と、を備えたことを特徴とするものである。 A method for manufacturing a ceramic porcelain composition according to claim 4 of the present invention, the composition formula (1-a-b) ( Ba 1-x Sr x) · a (Co 1-y Cu y) O · bFe Y represented by 2 O 3 (where 0.205 ≦ a ≦ 0.25, 0.55 ≦ b ≦ 0.595, 0 ≦ x ≦ 0.50, and 0.25 ≦ y ≦ 0.75) and type hexagonal ferrite material, a step of obtaining at least comprises SiO 2, B 2 O 3, CaO, and a non-magnetic material which is a glass material content of the SiO 2 is 60 to 85 mol%, respectively, A step of mixing 40 to 95% by volume of the Y-type hexagonal ferrite material and 5 to 60% by volume of the nonmagnetic material, and firing a mixture of the Y-type hexagonal ferrite material and the nonmagnetic material. And a step of obtaining a sintered body .
また、本発明の請求項５に記載のセラミック磁器組成物の製造方法は、請求項３または請求項４の発明において、上記Ｙ型六方晶フェライト材料と上記非磁性体材料との混合物を焼成する温度が、上記Ｙ型六方晶フェライト材料を得る時の温度より低い温度であることを特徴とすることを特徴とするものである。 According to a fifth aspect of the present invention, there is provided a method for producing a ceramic porcelain composition according to the third or fourth aspect, wherein the mixture of the Y-type hexagonal ferrite material and the non-magnetic material is fired. The temperature is lower than the temperature at which the Y-type hexagonal ferrite material is obtained.
而して、本発明のセラミック磁器組成物は、組成式（１−ａ−ｂ）（Ｂａ１−ｘＳｒｘ）・ａ（Ｃｏ１−ｙＣｕｙ）Ｏ・ｂＦｅ２Ｏ３（但し、０．２０５≦ａ≦０．２５、０．５５≦ｂ≦０．５９５、０≦ｘ≦０．５０、及び０．２５≦ｙ≦０．７５）で表されるＹ型六方晶フェライト材料４０〜９５体積％と、非磁性体材料５〜６０体積％と、を含む混合物である。Ｙ型六方晶フェライト材料と非磁性体材料を上記混合比率で含むため、Ｙ型六方晶フェライト材料相と非磁性体材料相の２相に分離したセラミック焼結体を得ることができる。Ｙ型六方晶フェライト材料相と非磁性体材料相の２相に分離することによって、セラミック焼結体の数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値を１００以上に高めることができると共に透磁率μ’を１以上に大きくすることができる。セラミック焼結体の透磁率μ’を１以上に大きくすることができるため、例えばインダクタンス素子を作製した場合にはコイルの巻き数を減少させ、導体損失を低減することができる。この焼結体は、上記Ｙ型六方晶フェライト材料の混合比率が低いほどＱ値を高めることができるが、その混合比率が４０体積％未満になると焼結体の透磁率μ’が小さくなってインダクタンス素子等の電子部品の磁性体材料として適さなくなる虞がある。また、上記Ｙ型六方晶フェライト材料の混合比率が９５体積％を超えるとＹ型六方晶フェライト材料単体の焼結体のＱ値に近づいてＱ値が低くなるため好ましくない。 And Thus, the ceramic porcelain composition of the present invention, the composition formula (1-a-b) ( Ba 1-x Sr x) · a (Co 1-y Cu y) O · bFe 2 O 3 ( where, 0 205 ≦ a ≦ 0.25, 0.55 ≦ b ≦ 0.595, 0 ≦ x ≦ 0.50, and 0.25 ≦ y ≦ 0.75) Y-type hexagonal ferrite material 40˜ It is a mixture containing 95% by volume and 5-60% by volume of a non-magnetic material. Since the Y-type hexagonal ferrite material and the non-magnetic material are contained in the above-mentioned mixing ratio, a ceramic sintered body separated into two phases of the Y-type hexagonal ferrite material phase and the non-magnetic material phase can be obtained. By separating the Y-type hexagonal ferrite material phase and the non-magnetic material phase into two phases, the Q value of the ceramic sintered body in the several hundred MHz to several GHz band region can be increased to 100 or more and the magnetic permeability μ 'Can be increased to 1 or more. Since the magnetic permeability μ ′ of the ceramic sintered body can be increased to 1 or more, for example, when an inductance element is manufactured, the number of turns of the coil can be reduced and the conductor loss can be reduced. In this sintered body, the Q value can be increased as the mixing ratio of the Y-type hexagonal ferrite material is lower. However, when the mixing ratio is less than 40% by volume, the permeability μ ′ of the sintered body decreases. There is a possibility that it is not suitable as a magnetic material for electronic parts such as inductance elements. Further, if the mixing ratio of the Y-type hexagonal ferrite material exceeds 95% by volume, the Q-value becomes low as it approaches the Q-value of the sintered body of the Y-type hexagonal ferrite material alone, such being undesirable.
また、Ｃｏの一部をＣｕで置換した上記組成のＹ型六方晶フェライト材料は、１０００℃以下の温度で合成することができ、このＹ型六方晶フェライト材料と非磁性体材料とを上記混合比率で含む本発明のセラミック磁器組成物は、１０００℃以下の温度で焼成することができ、相対密度が９０％以上で、機械的強度の優れたセラミック焼結体を得ることができる。また、本発明のセラミック磁器組成物は、１０００℃以下の温度で焼成することができるため、電子部品の内部導体としてＡｇやＡｇ−Ｐｄ合金等の導体損失の少ない導電性金属を使用することができる。Ｃｕの置換量を示すｙ値が０．２５未満になると焼結温度が１０００℃以上になり、またｙ値が０．７５を超えるとＣｕＯ等の異相が発生して数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値が１００未満になって好ましくない。尚、相対密度とは、アルキメデス法で実測した焼結体の密度を、Ｘ線回折法で得られた格子定数から算出された理論密度で除した値である。 Further, the Y-type hexagonal ferrite material having the above composition in which a part of Co is substituted with Cu can be synthesized at a temperature of 1000 ° C. or less, and the Y-type hexagonal ferrite material and the nonmagnetic material are mixed together. The ceramic porcelain composition of the present invention contained in a ratio can be fired at a temperature of 1000 ° C. or less, and a ceramic sintered body having a relative density of 90% or more and excellent mechanical strength can be obtained. In addition, since the ceramic porcelain composition of the present invention can be fired at a temperature of 1000 ° C. or lower, it is possible to use a conductive metal with low conductor loss such as Ag or Ag—Pd alloy as an internal conductor of an electronic component. it can. When the y value indicating the amount of substitution of Cu is less than 0.25, the sintering temperature is 1000 ° C. or more, and when the y value exceeds 0.75, a heterogeneous phase such as CuO is generated, and several hundred MHz to several GHz band region. The Q value at is less than 100, which is not preferable. The relative density is a value obtained by dividing the density of the sintered body actually measured by the Archimedes method by the theoretical density calculated from the lattice constant obtained by the X-ray diffraction method.
また、本発明に用いられる非磁性体材料は、Ｙ型六方晶フェライトの結晶構造と同様に六方晶系の結晶構造を有するものが好ましい。中でも、Ｙ型六方晶フェライトの結晶構造に近い結晶構造を有する、組成式（Ｂａ１−ｚＳｒｚ）Ｏ・ｃＦｅ２Ｏ３（但し、０≦ｚ≦１．０及び０．７５≦ｃ≦１．２５）で表される非磁性体材料が好ましい。このような非磁性体材料を用いることによって、焼成時にＹ型六方晶フェライト材料と非磁性体材料の結晶間に歪が少なく、焼成時における割れ等の不具合を生じる虞がない。この非磁性体材料の組成式におけるｚ値及びｃ値が上記範囲を外れた場合には、Ｙ型六方晶フェライト材料と混合しても数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値が１００以上のセラミック焼結体を得られない虞がある。 The nonmagnetic material used in the present invention preferably has a hexagonal crystal structure similar to the crystal structure of Y-type hexagonal ferrite. Among them, the composition formula (Ba 1−z Sr z ) O · cFe 2 O 3 (where 0 ≦ z ≦ 1.0 and 0.75 ≦ c ≦) has a crystal structure close to that of Y-type hexagonal ferrite. The nonmagnetic material represented by 1.25) is preferable. By using such a non-magnetic material, there is little distortion between the crystals of the Y-type hexagonal ferrite material and the non-magnetic material at the time of firing, and there is no possibility of causing problems such as cracks at the time of firing. When the z value and c value in the composition formula of this non-magnetic material are out of the above ranges, the Q value in the region of several hundred MHz to several GHz is 100 or more even when mixed with the Y-type hexagonal ferrite material. There is a possibility that a ceramic sintered body cannot be obtained.
また、非磁性体材料としては、少なくともＳｉＯ２、Ｂ２Ｏ３、ＣａＯを含むガラス材料であっても良い。このガラス材料は誘電率が６程度と低いため、本発明のセラミック磁器組成物として用いることによって、インダクタ材料やアンテナ材料として適用する場合に、インダクタの共振周波数を高める材料として有効である。非磁性体材料としては、例えばＳｉＯ２が６０〜８５モル％の範囲で含まれていることが好ましい。また、ＳｉＯ２、Ｂ２Ｏ３、ＣａＯ以外にＡｌ２Ｏ３やＴｉＯ２等の酸化物を含むものであっても良い。 Further, as the non-magnetic material, it may be a glass material containing at least SiO 2, B 2 O 3, CaO. Since this glass material has a low dielectric constant of about 6, it is effective as a material for increasing the resonance frequency of an inductor when used as a ceramic porcelain composition of the present invention when applied as an inductor material or an antenna material. The non-magnetic material, for example, it is preferable that SiO 2 is contained in the range of 60 to 85 mol%. Moreover, oxides such as Al 2 O 3 and TiO 2 may be included in addition to SiO 2 , B 2 O 3 , and CaO.
本発明のセラミック磁器組成物を製造する場合には、予め上記組成式で表されるＹ型六方晶フェライト材料及び非磁性体材料をそれぞれ得た後、これら両材料を上述の混合比率で混合することによって得ることができる。また、本発明のセラミック焼結体を製造する場合には、Ｙ型六方晶フェライト材料と非磁性体材料を上述の混合比率で混合した後、この混合物を、Ｙ型六方晶フェライト材料の合成温度よりも低い温度で焼成することによって得ることができる。Ｙ型六方晶フェライト材料及び非磁性体材料としては、それぞれ上述した組成を有するものが好ましい。 When producing the ceramic porcelain composition of the present invention, after obtaining the Y-type hexagonal ferrite material and the nonmagnetic material represented by the above composition formula in advance, these two materials are mixed in the above-mentioned mixing ratio. Can be obtained. When the ceramic sintered body of the present invention is manufactured, after mixing the Y-type hexagonal ferrite material and the non-magnetic material at the mixing ratio described above, this mixture is mixed with the synthesis temperature of the Y-type hexagonal ferrite material. Can be obtained by firing at a lower temperature. As the Y-type hexagonal ferrite material and the nonmagnetic material, those having the above-described compositions are preferable.
つまり、上記組成の六方晶フェライト材料は１０００℃以下でも焼成可能であるが、敢えて１０００℃以上の高温で仮焼し、本発明のセラミック磁器組成物として焼成する時には１０００℃以下の温度で焼成する。このように焼成温度を制御することによってＹ型六方晶フェライト材料相と非磁性体材料相との２相に分離したセラミック焼結体を得ることができ、Ｙ型六方晶フェライト材料単相の場合よりもセラミック焼結体の数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値を高めることができる。 In other words, the hexagonal ferrite material having the above composition can be fired at 1000 ° C. or lower, but it is preliminarily fired at a high temperature of 1000 ° C. or higher, and is fired at a temperature of 1000 ° C. or lower when fired as the ceramic porcelain composition of the present invention. . By controlling the firing temperature in this way, a ceramic sintered body separated into two phases of a Y-type hexagonal ferrite material phase and a non-magnetic material phase can be obtained. It is possible to increase the Q value of the ceramic sintered body in the several hundred MHz to several GHz band region.
本発明のセラミック磁器組成物の焼成温度が上記組成の六方晶フェライト材料の合成温度に近づくと、焼成時にＹ型六方晶フェライト材料と非磁性体材料との間で相互拡散が起こり、Ｙ型六方晶フェライト材料相と非磁性体材料相の２相に分離できない虞があるため好ましくない。 When the firing temperature of the ceramic porcelain composition of the present invention approaches the synthesis temperature of the hexagonal ferrite material having the above composition, mutual diffusion occurs between the Y-type hexagonal ferrite material and the non-magnetic material during firing, and the Y-type hexagonal This is not preferable because there is a possibility that it cannot be separated into two phases of a crystal ferrite material phase and a non-magnetic material phase.
本発明によれば、数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値が１００以上の磁性体材料を得ることができるセラミック磁器組成物及びその製造方法を提供することができる。 According to the onset bright, can Q value of the number 100MHz~ several GHz region to provide a ceramic porcelain composition and the manufacturing how it is possible to obtain 100 or more magnetic materials.
本実施形態では、組成式（１−ａ−ｂ）（Ｂａ１−ｘＳｒｘ）・ａ（Ｃｏ１−ｙＣｕｙ）Ｏ・ｂＦｅ２Ｏ３（但し、０．２０５≦ａ≦０．２５、０．５５≦ｂ≦０．５９５、０≦ｘ≦０．５０、及び０．２５≦ｙ≦０．７５）で表されるＹ型六方晶フェライト材料と、組成式（Ｂａ１−ｚＳｒｚ）Ｏ・ｃＦｅ２Ｏ３（但し、０≦ｚ≦１．０及び０．７５≦ｃ≦１．２５）で表される非磁性体材料とからなるセラミック磁器組成物、及びＹ型六方晶フェライト材料と、ＳｉＯ２、Ｂ２Ｏ３、ＣａＯを含むガラス材料からなるセラミック磁器組成物を用いて評価用のセラミック焼結体を作製し、それぞれの相対密度、透磁率μ’及びＱ値を測定した。 In this embodiment, the composition formula (1-a-b) ( Ba 1-x Sr x) · a (Co 1-y Cu y) O · bFe 2 O 3 ( where, 0.205 ≦ a ≦ 0.25 , 0.55 ≦ b ≦ 0.595, 0 ≦ x ≦ 0.50, and 0.25 ≦ y ≦ 0.75), and a composition formula (Ba 1-z Sr) z ) a ceramic porcelain composition comprising a nonmagnetic material represented by O.cFe 2 O 3 (where 0 ≦ z ≦ 1.0 and 0.75 ≦ c ≦ 1.25), and Y-type hexagonal crystal A ceramic sintered body for evaluation is produced using a ceramic porcelain composition made of a ferrite material and a glass material containing SiO 2 , B 2 O 3 , and CaO, and the relative density, permeability μ ′, and Q value of each are determined. It was measured.
本実施例では、非磁性体材料の組成を（Ｂａ０．２５Ｓｒ０．７５）Ｏ・Ｆｅ２Ｏ３の組成に固定し、Ｙ型六方晶フェライト材料の組成式中のａ、ｂ、ｘ及びｙそれぞれを表１に示すように本発明の範囲から本発明の範囲外まで振って、各組成の影響を観る評価用試料を作製した。尚、表１において＊印を付した試料は本発明の範囲外の試料である。 In this example, the composition of the non-magnetic material is fixed to the composition of (Ba 0.25 Sr 0.75 ) O · Fe 2 O 3 , and a, b, x in the composition formula of the Y-type hexagonal ferrite material are used. As shown in Table 1, each of y and y was shaken from the scope of the present invention to outside the scope of the present invention, and a sample for evaluation was prepared to observe the influence of each composition. In Table 1, samples marked with * are out of the scope of the present invention.
（１）評価用試料の作製
まず、出発原料として、炭酸バリウム（ＢａＣＯ３）、炭酸ストロンチウム（ＳｒＣＯ３）、酸化コバルト（Ｃｏ３Ｏ４）、酸化鉄（Ｆｅ２Ｏ３）及び酸化銅（ＣｕＯ）を用意し、これらを表１に示す組成式（１−ａ−ｂ）（Ｂａ１−ｘＳｒｘ）・ａ（Ｃｏ１−ｙＣｕｙ）Ｏ・ｂＦｅ２Ｏ３となるように調合した。次いで、調合した原料粉をボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中で１０００〜１１５０℃で仮焼し、Ｙ型六方晶フェライト材料の仮焼粉を得た。一方、非磁性体材料は、出発原料として、ＢａＣＯ３、ＳｒＣＯ３及びＦｅ２Ｏ３を用意し、（Ｂａ０．２５Ｓｒ０．７５）Ｏ・Ｆｅ２Ｏ３となるように調合し、これをボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中１０００〜１１５０℃で仮焼して非磁性体材料粉を得た。
(1) Preparation of evaluation sample First, as starting materials, barium carbonate (BaCO 3 ), strontium carbonate (SrCO 3 ), cobalt oxide (Co 3 O 4 ), iron oxide (Fe 2 O 3 ), and copper oxide (CuO) ) was prepared and formulated them so as to have the composition formula shown in Table 1 (1-a-b) (Ba 1-x Sr x) · a (Co 1-y Cu y) O · bFe 2 O 3 . Next, the prepared raw material powder was wet-mixed with a ball mill, the mixture was dried, and then calcined at 1000 to 1150 ° C. in an air atmosphere to obtain a calcined powder of Y-type hexagonal ferrite material. On the other hand, the non-magnetic material is prepared by preparing BaCO 3 , SrCO 3 and Fe 2 O 3 as starting materials and (Ba 0.25 Sr 0.75 ) O · Fe 2 O 3. Was mixed with a ball mill and dried, and then calcined at 1000 to 1150 ° C. in an air atmosphere to obtain non-magnetic material powder.
次いで、上述の方法によって得られたＹ型六方晶フェライト材料の仮焼粉及び非磁性体材料粉をそれぞれ秤量し、Ｙ型六方晶フェライト材料の仮焼粉が９５体積％、非磁性体材料粉が５体積％となるように調合し、この調合物をボールミルで湿式粉砕し、比表面積が５ｍ２/ｇ以上の仮焼混合粉を得た。この仮焼混合粉に酢酸ビニル系バインダを加えて十分に混練、乾燥し、その仮焼混合粉をトロイダルコア状にプレス成形し、表１に示す温度で空気中において焼成して、試料Ｎｏ.１〜３６を評価用のセラミック焼結体として得た。 Next, the Y-type hexagonal ferrite material calcined powder and non-magnetic material powder obtained by the above-mentioned method are weighed, and the Y-type hexagonal ferrite material calcined powder is 95% by volume. Of 5% by volume, and this mixture was wet pulverized by a ball mill to obtain a calcined mixed powder having a specific surface area of 5 m 2 / g or more. A vinyl acetate binder was added to the calcined mixed powder and sufficiently kneaded and dried. The calcined mixed powder was press-molded into a toroidal core and fired in air at the temperature shown in Table 1. 1 to 36 were obtained as ceramic sintered bodies for evaluation.
（２）評価用試料の評価方法
試料Ｎｏ.１〜３６の評価用のセラミック焼結体（２相が混合したセラミック焼結体）の透磁率μ’、Ｑ値（＝μ’／μ”）及び相対密度を測定し、その測定結果を表１に示した。μ’、Ｑ値は、それぞれμ’、Ｑ値をインピーダンスアナライザ（ヒューレットパッカード社製）を用いて周波数１ＧＨｚの条件で測定した。また、これらのセラミック焼結体の相対密度は、アルキメデス法で実測した焼結密度とＸ線回折による理論密度に基づいて計算し、その結果を表１に示した。
(2) Evaluation method of sample for evaluation Magnetic permeability μ ′ and Q value (= μ ′ / μ ″) of ceramic sintered bodies for evaluation (ceramic sintered bodies mixed with two phases) of sample Nos. 1 to 36 The relative density was measured, and the measurement results are shown in Table 1. The μ ′ and Q values were measured using a impedance analyzer (manufactured by Hewlett-Packard) at a frequency of 1 GHz, respectively. The relative densities of these ceramic sintered bodies were calculated based on the sintered density measured by Archimedes method and the theoretical density by X-ray diffraction, and the results are shown in Table 1.
表１に示す結果によれば、本発明の範囲内の試料Ｎｏ.４〜６、試料Ｎｏ.９〜１２、試料Ｎｏ.２１〜２３及び試料Ｎｏ.２６〜２８のセラミック焼結体は、いずれも１ＧＨｚでのＱ値が１００以上を示し、しかも１０００℃以下で焼成することができるセラミック焼結体であることが判った。これに対して、本発明の範囲外でＣｕの置換量を示すｙ値が０．２５未満の試料Ｎｏ.３、８、２０、２５、３０のセラミック焼結体は、いずれも焼成温度が１０００℃以上の高温であり、また、ｙ値が０．７５を超える試料Ｎｏ.７、１３、１８、２４、２９、及び３４は、いずれも１０００℃以下で焼成することができるが、いずれもＣｕＯ等の異相が発生して１ＧＨｚでのＱ値が１００未満に減少することが判った。 According to the results shown in Table 1, the ceramic sintered bodies of sample Nos. 4 to 6, sample Nos. 9 to 12, sample Nos. 21 to 23 and sample Nos. 26 to 28 within the scope of the present invention are Was found to be a ceramic sintered body that exhibited a Q value of 100 or more at 1 GHz and that could be fired at 1000 ° C. or less. On the other hand, the ceramic sintered bodies of sample Nos. 3, 8, 20, 25, and 30 having y values less than 0.25 indicating the amount of substitution of Cu outside the scope of the present invention all have a firing temperature of 1000. Sample Nos. 7, 13, 18, 24, 29, and 34 having a high temperature of not lower than ℃ and y value exceeding 0.75 can all be fired at 1000 ℃ or lower. It has been found that the Q value at 1 GHz decreases to less than 100 due to the occurrence of a different phase.
本実施例では、Ｙ型六方晶フェライト材料を０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３の組成に固定し、組成式（Ｂａ１−ｚＳｒｚ）Ｏ・ｃＦｅ２Ｏ３で表される非磁性体材料のｃ値及びｚ値それぞれを表２に示すように本発明の範囲から本発明の範囲外まで振って、各組成の影響を観る評価用試料を作製した。尚、表２において＊印を付した試料は本発明の範囲外の試料である。 In this example, the Y-type hexagonal ferrite material is made into a composition of 0.20 (Ba 0.50 Sr 0.50 ) · 0.24 (Co 0.50 Cu 0.50 ) O · 0.56Fe 2 O 3 . The c value and the z value of the nonmagnetic material represented by the composition formula (Ba 1-z Sr z ) O · cFe 2 O 3 are fixed and the range of the present invention is as shown in Table 2. The sample for evaluation was prepared by shaking to the outside and observing the influence of each composition. In Table 2, samples marked with * are samples outside the scope of the present invention.
（１）評価用試料の作製
まず、出発原料として、ＢａＣＯ３、ＳｒＣＯ３、Ｃｏ３Ｏ４、Ｆｅ２Ｏ３及びＣｕＯを用意し、これらを０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３となるように調合した。次いで、調合した原料粉をボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中１０００〜１１５０℃で仮焼し、Ｙ型六方晶フェライト材料の仮焼粉を得た。一方、非磁性体材料は、出発原料として、ＢａＣＯ３、ＳｒＣＯ３及びＦｅ２Ｏ３を用意し、表１に示す組成式（Ｂａ１−ｚＳｒｚ）Ｏ・ｃＦｅ２Ｏ３となるように調合し、これをボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中１０００〜１１５０℃で仮焼して表１に示す非磁性体材料粉を得た。
(1) Preparation of Evaluation Sample First, BaCO 3 , SrCO 3 , Co 3 O 4 , Fe 2 O 3 and CuO are prepared as starting materials, and these are 0.20 (Ba 0.50 Sr 0.50 ). · 0.24 (Co 0.50 Cu 0.50) is prepared to have a O · 0.56Fe 2 O 3. Next, the prepared raw material powder was wet-mixed with a ball mill, the mixture was dried, and then calcined at 1000 to 1150 ° C. in an air atmosphere to obtain a calcined powder of Y-type hexagonal ferrite material. On the other hand, for the non-magnetic material, BaCO 3 , SrCO 3, and Fe 2 O 3 are prepared as starting materials so that the composition formula (Ba 1-z Sr z ) O · cFe 2 O 3 shown in Table 1 is obtained. After mixing and wet-mixing with a ball mill, and drying this mixture, it was calcined at 1000 to 1150 ° C. in an air atmosphere to obtain nonmagnetic material powders shown in Table 1.
次いで、上述の方法によって得られたＹ型六方晶フェライト材料の仮焼粉及び非磁性体材料粉をそれぞれ秤量し、Ｙ型六方晶フェライト材料の仮焼粉が９５体積％、非磁性体材料粉が５体積％となるように調合し、この調合物をボールミルで湿式粉砕し、比表面積が５ｍ２/ｇ以上の仮焼混合粉を得た。この仮焼混合粉に酢酸ビニル系バインダを加えて十分に混練、乾燥し、その仮焼混合粉をトロイダルコア状にプレス成形し、表２に示す温度で空気中において焼成して、試料Ｎｏ.３７〜５１を評価用のセラミック焼結体として得た。 Next, the Y-type hexagonal ferrite material calcined powder and non-magnetic material powder obtained by the above-mentioned method are weighed, and the Y-type hexagonal ferrite material calcined powder is 95% by volume. Of 5% by volume, and this mixture was wet pulverized by a ball mill to obtain a calcined mixed powder having a specific surface area of 5 m 2 / g or more. A vinyl acetate binder was added to the calcined mixed powder and sufficiently kneaded and dried. The calcined mixed powder was press-molded into a toroidal core and fired in air at the temperatures shown in Table 2. 37 to 51 were obtained as ceramic sintered bodies for evaluation.
（２）評価用試料の評価方法
試料Ｎｏ.３７〜５１の評価用のセラミック焼結体について実施例１と同様の評価を行い、その結果を表１に示した。
(2) Evaluation Method of Evaluation Sample Evaluation of the ceramic sintered bodies for evaluation of sample Nos. 37 to 51 was performed in the same manner as in Example 1, and the results are shown in Table 1.
表２に示す結果によれば、本発明の範囲内の試料Ｎｏ.４２〜４７のセラミック焼結体は、いずれも数１００ＭＨｚ〜数ＧＨｚ帯領域でのＱ値が１００以上を示し、しかも１０００℃以下で焼成することができるセラミック焼結体であることが判った。これに対して、本発明の範囲外の試料Ｎｏ.３７〜４１及び試料Ｎｏ.４８〜５１のセラミック焼結体は、いずれも１ＧＨｚでのＱ値が１００未満に減少することが判った。 According to the results shown in Table 2, all of the ceramic sintered bodies of sample Nos. 42 to 47 within the scope of the present invention have a Q value of 100 or more in the region of several hundred MHz to several GHz, and 1000 ° C. It was found to be a ceramic sintered body that can be fired below. On the other hand, it was found that the Q values at 1 GHz decreased to less than 100 for the ceramic sintered bodies of Sample Nos. 37 to 41 and Sample Nos. 48 to 51 outside the scope of the present invention.
本実施例では、Ｙ型六方晶フェライト材料を０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３の組成に固定すると共に非磁性体材料を（Ｂａ０．２５Ｓｒ０．７５）Ｏ・Ｆｅ２Ｏ３の組成に固定し、これら両者の混合比率を表３に示すように本発明の範囲から本発明の範囲外まで振って、混合比率の影響を観る評価用試料を作製した。尚、表３において＊印を付した試料は本発明の範囲外の試料である。 In this example, the Y-type hexagonal ferrite material is made into a composition of 0.20 (Ba 0.50 Sr 0.50 ) · 0.24 (Co 0.50 Cu 0.50 ) O · 0.56Fe 2 O 3 . While fixing, the nonmagnetic material was fixed to the composition of (Ba 0.25 Sr 0.75 ) O.Fe 2 O 3 , and the mixing ratio of these two is shown in Table 3 from the scope of the present invention. A sample for evaluation was prepared by shaking outside the range and observing the influence of the mixing ratio. In Table 3, samples marked with * are samples outside the scope of the present invention.
（１）評価用試料の作製
まず、出発原料として、ＢａＣＯ３、ＳｒＣＯ３、Ｃｏ３Ｏ４、Ｆｅ２Ｏ３及びＣｕＯを用意し、これらを０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３となるように調合した。次いで、調合した原料粉をボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中１０００〜１１５０℃で仮焼し、Ｙ型六方晶フェライト材料の仮焼粉を得た。一方、非磁性体材料は、出発原料として、ＢａＣＯ３、ＳｒＣＯ３及びＦｅ２Ｏ３を用意し、（Ｂａ０．２５Ｓｒ０．７５）Ｏ・Ｆｅ２Ｏ３となるように調合し、これをボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中１０００〜１１５０℃で仮焼して表１に示す非磁性体材料粉を得た。
(1) Preparation of Evaluation Sample First, BaCO 3 , SrCO 3 , Co 3 O 4 , Fe 2 O 3 and CuO are prepared as starting materials, and these are 0.20 (Ba 0.50 Sr 0.50 ). · 0.24 (Co 0.50 Cu 0.50) is prepared to have a O · 0.56Fe 2 O 3. Next, the prepared raw material powder was wet-mixed with a ball mill, the mixture was dried, and then calcined at 1000 to 1150 ° C. in an air atmosphere to obtain a calcined powder of Y-type hexagonal ferrite material. On the other hand, the non-magnetic material is prepared by preparing BaCO 3 , SrCO 3 and Fe 2 O 3 as starting materials and (Ba 0.25 Sr 0.75 ) O · Fe 2 O 3. Were mixed with a ball mill and dried, and then calcined at 1000 to 1150 ° C. in an air atmosphere to obtain non-magnetic material powders shown in Table 1.
次いで、上述の方法によって得られたＹ型六方晶フェライト材料の仮焼粉及び非磁性体材料粉を表３に示す混合比率になるようにそれぞれ秤量して調合し、この調合物をボールミルで湿式粉砕し、比表面積が５ｍ２/ｇ以上の仮焼混合粉を得た。この仮焼混合粉に酢酸ビニル系バインダを加えて十分に混練、乾燥し、その仮焼混合粉をトロイダルコア状にプレス成形し、表３に示す温度で空気中において焼成して、試料Ｎｏ.５３〜５７を評価用のセラミック焼結体として得た。 Next, the Y-type hexagonal ferrite material calcined powder and non-magnetic material powder obtained by the above method are weighed and mixed so as to have the mixing ratio shown in Table 3, and this mixture is wet-treated with a ball mill. The mixture was pulverized to obtain a calcined mixed powder having a specific surface area of 5 m 2 / g or more. A vinyl acetate binder was added to the calcined mixed powder and sufficiently kneaded and dried. The calcined mixed powder was press-molded into a toroidal core and fired in air at the temperatures shown in Table 3. 53 to 57 were obtained as ceramic sintered bodies for evaluation.
（２）評価用試料の評価方法
試料Ｎｏ. ５３〜５７の評価用のセラミック焼結体について実施例１と同様の評価を行い、その結果を表３に示した。
(2) Evaluation Method of Evaluation Sample Evaluation of the ceramic sintered bodies for evaluation of sample Nos. 53 to 57 was performed in the same manner as in Example 1, and the results are shown in Table 3.
表３に示す結果によれば、本発明の範囲内の試料Ｎｏ.５４〜５６のセラミック焼結体は、いずれも１ＧＨｚでのＱ値が１００以上を示し、しかも１０００℃以下で焼成することができるセラミック焼結体であることが判った。また、Ｙ型六方晶フェライト材料の混合比率が減少するほどＱ値が高くなることが判った。これに対して、非磁性体材料の混合比率が６０体積％を超える試料Ｎｏ.５３のセラミック焼結体は、１ＧＨｚでのＱ値が１００以上であるが、透磁率μ’が１．１まで減少し、実用的でないことが判った。また、非磁性体材料の混合比率が５体積％未満の試料Ｎｏ.５７のセラミック焼結体は、１ＧＨｚでのＱ値が１００以下に減少することが判った。 According to the results shown in Table 3, all of the ceramic sintered bodies of sample Nos. 54 to 56 within the scope of the present invention have a Q value of 1 or more at 100 GHz and are fired at 1000 ° C. or less. It was found to be a ceramic sintered body that can be obtained. It was also found that the Q value increased as the mixing ratio of the Y-type hexagonal ferrite material decreased. In contrast, the ceramic sintered body of sample No. 53 in which the mixing ratio of the nonmagnetic material exceeds 60% by volume has a Q value at 1 GHz of 100 or more, but the magnetic permeability μ ′ is up to 1.1. Decreased and found impractical. Moreover, it turned out that the Q value in 1 GHz reduces to 100 or less in the ceramic sintered compact of sample No. 57 whose mixing ratio of nonmagnetic material is less than 5 volume%.
本実施例では、Ｙ型六方晶フェライト材料を０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３の組成に固定し、非磁性体材料としてＳｉＯ２、Ｂ２Ｏ３、ＣａＯを含むガラス材料を用い、ガラス材料の各組成を振って、ガラス材料の各組成の影響を観る評価用試料を作製した。 In this example, the Y-type hexagonal ferrite material is made into a composition of 0.20 (Ba 0.50 Sr 0.50 ) · 0.24 (Co 0.50 Cu 0.50 ) O · 0.56Fe 2 O 3 . A glass sample containing SiO 2 , B 2 O 3 , and CaO as a nonmagnetic material was fixed, and each composition of the glass material was shaken to produce a sample for evaluation to observe the influence of each composition of the glass material.
（１）評価用試料の作製
まず、出発原料として、ＢａＣＯ３、ＳｒＣＯ３、Ｃｏ３Ｏ４、Ｆｅ２Ｏ３及びＣｕＯを用意し、これらを０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３となるように調合した。次いで、調合した原料粉をボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中１０００〜１１５０℃で仮焼し、Ｙ型六方晶フェライト材料の仮焼粉を得た。一方、非磁性体材料は、出発原料として、ＳｉＯ２、Ｂ２Ｏ３及びＣａＯの各酸化物を用意し、ＳｉＯ２を６０〜８５モル％、Ｂ２Ｏ３を１〜３５モル％、ＣａＯを１〜１４モル％の範囲でそれぞれを振って表４に示すように調合し、これをアルミナ坩堝に入れて、約１５００℃まで加熱した後、室温まで急冷した。得られたガラス材料を粗粉砕してボールミルで微粉砕して表４に示す非磁性体材料を得た。
(1) Preparation of Evaluation Sample First, BaCO 3 , SrCO 3 , Co 3 O 4 , Fe 2 O 3 and CuO are prepared as starting materials, and these are 0.20 (Ba 0.50 Sr 0.50 ). · 0.24 (Co 0.50 Cu 0.50) is prepared to have a O · 0.56Fe 2 O 3. Next, the prepared raw material powder was wet-mixed with a ball mill, the mixture was dried, and then calcined at 1000 to 1150 ° C. in an air atmosphere to obtain a calcined powder of Y-type hexagonal ferrite material. On the other hand, the non-magnetic material is prepared by using SiO 2 , B 2 O 3 and CaO oxides as starting materials, SiO 2 being 60 to 85 mol%, B 2 O 3 being 1 to 35 mol%, and CaO. In the range of 1-14 mol%, each was shaken and prepared as shown in Table 4. The mixture was put in an alumina crucible and heated to about 1500 ° C., and then rapidly cooled to room temperature. The resulting glass material was coarsely crushed and finely pulverized by a ball mill to obtain a non-magnetic material shown in Table 4.
次いで、上述の方法によって得られたＹ型六方晶フェライト材料の仮焼粉及び非磁性体材料粉をそれぞれ秤量し、Ｙ型六方晶フェライト材料の仮焼粉が９５体積％、非磁性体材料粉が５体積％となるように調合し、この調合物をボールミルで湿式粉砕し、比表面積が５ｍ２/ｇ以上の仮焼混合粉を得た。この仮焼混合粉に酢酸ビニル系バインダを加えて十分に混練、乾燥し、その仮焼混合粉をトロイダルコア状にプレス成形し、表４に示す温度で空気中において焼成して、試料Ｎｏ.５８〜６４の評価用のセラミック焼結体を得た。 Next, the Y-type hexagonal ferrite material calcined powder and non-magnetic material powder obtained by the above-mentioned method are weighed, and the Y-type hexagonal ferrite material calcined powder is 95% by volume. Of 5% by volume, and this mixture was wet pulverized by a ball mill to obtain a calcined mixed powder having a specific surface area of 5 m 2 / g or more. A vinyl acetate binder was added to the calcined mixed powder and sufficiently kneaded and dried. The calcined mixed powder was press-molded into a toroidal core, fired in the air at the temperatures shown in Table 4, and sample No. Ceramic sintered bodies for evaluation of 58 to 64 were obtained.
（２）評価用試料の評価方法
試料Ｎｏ. ５８〜６４の評価用のセラミック焼結体について実施例１と同様の評価を行い、その結果を表４に示した。
(2) Evaluation method of evaluation sample Evaluations similar to Example 1 were performed on the evaluation ceramic sintered bodies of sample Nos. 58 to 64, and the results are shown in Table 4.
表４に示す結果によれば、６０〜８５モル％のＳｉＯ２を含む試料Ｎｏ.５９〜６３のセラミック焼結体は、いずれも１ＧＨｚでのＱ値が１００以上を示し、しかも１０００℃以下で焼成することができるセラミック焼結体であることが判った。ＳｉＯ２の含有量が上記範囲より低い試料Ｎｏ.６４のセラミック焼結体は、１０００℃以下の温度で焼成することができるが、１ＧＨｚでのＱ値が１００以下であることが判った。ＳｉＯ２の含有量が上記範囲より低い試料Ｎｏ.５８のセラミック焼結体は、焼成温度が１０００℃以上で、１ＧＨｚでのＱ値が１００以下であることが判った。 According to the results shown in Table 4, each of the ceramic sintered bodies of sample Nos. 59 to 63 containing 60 to 85 mol% of SiO 2 has a Q value at 1 GHz of 100 or more and 1000 ° C. or less. It was found to be a ceramic sintered body that can be fired. The ceramic sintered body of sample No. 64 having a SiO 2 content lower than the above range can be fired at a temperature of 1000 ° C. or lower, but it was found that the Q value at 1 GHz is 100 or lower. The ceramic sintered body of Sample No. 58 having a SiO 2 content lower than the above range was found to have a firing temperature of 1000 ° C. or higher and a Q value at 1 GHz of 100 or lower.
本実施例では、Ｙ型六方晶フェライト材料を０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３の組成に固定すると共に非磁性体材料のガラス成分のＳｉＯ２、Ｂ２Ｏ３及びＣａＯを一定のモル比率の組成に固定し、これら両者の混合比率を表５に示すように本発明の範囲から本発明の範囲外まで振って、混合比率の影響を観る評価用試料を作製した。尚、表５において＊印を付した試料は本発明の範囲外の試料である。 In this example, the Y-type hexagonal ferrite material is made into a composition of 0.20 (Ba 0.50 Sr 0.50 ) · 0.24 (Co 0.50 Cu 0.50 ) O · 0.56Fe 2 O 3 . In addition to fixing, SiO 2 , B 2 O 3 and CaO as glass components of the non-magnetic material are fixed to a composition having a constant molar ratio, and the mixing ratio of these two is shown in Table 5 from the scope of the present invention. The sample for evaluation which shakes outside the range and observes the influence of a mixing ratio was produced. In Table 5, samples marked with * are out of the scope of the present invention.
（１）評価用試料の作製
まず、出発原料として、ＢａＣＯ３、ＳｒＣＯ３、Ｃｏ３Ｏ４、Ｆｅ２Ｏ３及びＣｕＯを用意し、これらを０．２０（Ｂａ０．５０Ｓｒ０．５０）・０．２４（Ｃｏ０．５０Ｃｕ０．５０）Ｏ・０．５６Ｆｅ２Ｏ３となるように調合した。次いで、調合した原料粉をボールミルで湿式混合し、この混合物を乾燥させた後、大気雰囲気中１０００〜１１５０℃で仮焼し、Ｙ型六方晶フェライト材料の仮焼粉を得た。一方、非磁性体材料は、出発原料として、ＳｉＯ２、Ｂ２Ｏ３及びＣａＯの各酸化物を用意し、ＳｉＯ２７５モル％、Ｂ２Ｏ３２５モル％、ＣａＯ５モル％になるように調合し、これをアルミナ坩堝に入れて、約１５００℃まで加熱した後、室温まで急冷した。得られたガラス材料を粗粉砕してモールミルで微粉砕して所望の非磁性体材料を得た。
(1) Preparation of Evaluation Sample First, BaCO 3 , SrCO 3 , Co 3 O 4 , Fe 2 O 3 and CuO are prepared as starting materials, and these are 0.20 (Ba 0.50 Sr 0.50 ). · 0.24 (Co 0.50 Cu 0.50) is prepared to have a O · 0.56Fe 2 O 3. Next, the prepared raw material powder was wet-mixed with a ball mill, the mixture was dried, and then calcined at 1000 to 1150 ° C. in an air atmosphere to obtain a calcined powder of Y-type hexagonal ferrite material. On the other hand, the non-magnetic material is prepared by using SiO 2 , B 2 O 3 and CaO oxides as starting materials so that SiO 2 is 75 mol%, B 2 O 3 25 mol%, and CaO 5 mol%. This was prepared, put in an alumina crucible, heated to about 1500 ° C., and then rapidly cooled to room temperature. The obtained glass material was coarsely pulverized and finely pulverized with a molding mill to obtain a desired nonmagnetic material.
次いで、上述の方法によって得られたＹ型六方晶フェライト材料の仮焼粉及び非磁性体材料粉を表５に示す混合比率になるようにそれぞれ秤量して調合し、この調合物をボールミルで湿式粉砕し、比表面積が５ｍ２/ｇ以上の仮焼混合粉を得た。この仮焼混合粉に酢酸ビニル系バインダを加えて十分に混練、乾燥し、その仮焼混合粉をトロイダルコア状にプレス成形し、表５に示す温度で空気中において焼成して、試料Ｎｏ.６５〜６９を評価用のセラミック焼結体として得た。 Next, the Y-type hexagonal ferrite material calcined powder and non-magnetic material powder obtained by the above-mentioned method are weighed and mixed so as to have the mixing ratios shown in Table 5, and this mixture is wet-treated with a ball mill. The mixture was pulverized to obtain a calcined mixed powder having a specific surface area of 5 m 2 / g or more. A vinyl acetate binder was added to the calcined mixed powder and sufficiently kneaded and dried. The calcined mixed powder was press-molded into a toroidal core and fired in the air at the temperatures shown in Table 5 to obtain a sample No. 65 to 69 were obtained as ceramic sintered bodies for evaluation.
（２）評価用試料の評価方法
試料Ｎｏ. ６５〜６９の評価用のセラミック焼結体について実施例１と同様の評価を行い、その結果を表５に示した。
(2) Evaluation method of evaluation sample The evaluation similar to Example 1 was performed about the ceramic sintered body for evaluation of sample No. 65-69, and the result was shown in Table 5.
表５に示す結果によれば、実施例３の場合と同一傾向を示す結果が得られた。即ち、本発明の範囲内の試料Ｎｏ.６６〜６８のセラミック焼結体は、いずれも１ＧＨｚでのＱ値が１００以上を示し、しかも１０００℃以下で焼成することができるセラミック焼結体であることが判った。また、Ｙ型六方晶フェライト材料の混合比率が減少するほどＱ値が高くなることが判った。これに対して、非磁性体材料の混合比率が６０体積％を超える試料Ｎｏ.６５のセラミック焼結体は、１ＧＨｚでのＱ値が１００以上であるが、透磁率μ’が１．０まで減少することが判った。また、非磁性体材料の混合比率が５体積％未満の試料Ｎｏ.６９のセラミック焼結体は、１ＧＨｚでのＱ値が１００以下に減少することが判った。 According to the result shown in Table 5, the result which shows the same tendency as the case of Example 3 was obtained. That is, all of the ceramic sintered bodies of sample Nos. 66 to 68 within the scope of the present invention are ceramic sintered bodies that exhibit a Q value of 100 or more at 1 GHz and can be fired at 1000 ° C. or less. I found out. It was also found that the Q value increased as the mixing ratio of the Y-type hexagonal ferrite material decreased. In contrast, the ceramic sintered body of sample No. 65 in which the mixing ratio of the non-magnetic material exceeds 60% by volume has a Q value at 1 GHz of 100 or more, but the magnetic permeability μ ′ is up to 1.0. It turned out to decrease. Moreover, it turned out that the Q value in 1 GHz decreases to 100 or less in the ceramic sintered body of sample No. 69 in which the mixing ratio of the nonmagnetic material is less than 5% by volume.
尚、本発明は上記各実施例に何等制限されるものではなく、本発明の範囲内において各構成元素量を適宜設定することができる。 In addition, this invention is not restrict | limited at all to said each Example, Each component element amount can be suitably set within the scope of the present invention.
本発明は、例えば数１００ＭＨｚ〜数ＧＨｚの高周波領域に用いられるインダクタンス素子やアンテナ素子等の電子部品を製造する場合に適用することができる。 The present invention can be applied when manufacturing electronic components such as an inductance element and an antenna element used in a high frequency region of several hundred MHz to several GHz, for example.
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