JPS63160108A - Powder for low temperature sintering capacitor material - Google Patents
Powder for low temperature sintering capacitor materialInfo
- Publication number
- JPS63160108A JPS63160108A JP61305223A JP30522386A JPS63160108A JP S63160108 A JPS63160108 A JP S63160108A JP 61305223 A JP61305223 A JP 61305223A JP 30522386 A JP30522386 A JP 30522386A JP S63160108 A JPS63160108 A JP S63160108A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- dielectric
- particle size
- temperature
- dielectric constant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims description 20
- 239000003990 capacitor Substances 0.000 title claims description 8
- 239000000463 material Substances 0.000 title claims description 6
- 238000009766 low-temperature sintering Methods 0.000 title description 3
- 239000002245 particle Substances 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 etc. Chemical compound 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は誘電体セラミックス粉末に関するものである。[Detailed description of the invention] (Industrial application field) The present invention relates to dielectric ceramic powder.
近年、各種電気回路の小型化に伴い、小型で大容量かつ
温度変化率の小さいコンデンサーが要求され積層セラミ
ックコンデンサーが数多く使われてきている。In recent years, with the miniaturization of various electrical circuits, there has been a demand for capacitors that are compact, have large capacity, and have a low rate of temperature change, and many multilayer ceramic capacitors have been used.
（従来の技術およびその問題点）
従来、前述のコンデンサーに用いられる誘電体材料とし
てはチタン酸バリウムを主体に各種添加物を加えた材料
が知られている。しかしながら従来使われているチタン
酸バリウム系粉末は粒径が１μｍ以上と比較的大きいた
め磁器化する場合、焼成温度を１３００°Ｃ以上の高温
にする必要があった。したがって積層セラミックコンデ
ンサーを製造する際には内部電極として高価なパラジウ
ム、白金を主体とした材料を用いなければならず、積層
コンデンサーのコストダウンに大きな障害になっていた
またコンデンサーの小型、大容量化に対処するには誘電
率の高い材料を用いることの他に誘電体素材の肉厚を薄
くし、多層に積重ねることが必要であるが、そのために
は誘電体セラミックスの抗折力強度が大きくなければな
らない。周知のように抗折力強度はセラミックスのダレ
インサイズに関係し、大きい抗折力強度を得るには、ダ
レインサイズを小さくし高密度化する必要があるが、粒
径が１μｍ以上の大きな粒子を出発物質として成型、磁
器化した場合ダレインサイズは１０μｍ前後の大きなも
のになり抗折力強度の大きいセラミックスが得られない
。(Prior Art and its Problems) Conventionally, as a dielectric material used in the above-mentioned capacitor, a material made mainly of barium titanate and various additives is known. However, since the barium titanate powder used in the past has a relatively large particle size of 1 μm or more, it was necessary to increase the firing temperature to 1300° C. or higher when making it into porcelain. Therefore, when manufacturing multilayer ceramic capacitors, expensive materials mainly containing palladium or platinum must be used for the internal electrodes, which is a major obstacle to reducing the cost of multilayer capacitors. In order to deal with this, in addition to using materials with high dielectric constants, it is necessary to reduce the thickness of dielectric materials and stack them in multiple layers. There must be. As is well known, the transverse rupture strength is related to the particle size of ceramics, and in order to obtain a large transverse rupture strength, it is necessary to reduce the particle size and increase the density. When the particles are molded and made into porcelain as a starting material, the dalein size becomes large, around 10 μm, and ceramics with high transverse rupture strength cannot be obtained.
（発明の目的）
本発明は従来使われているチタン酸バリウム系粉末のか
かる問題点を解消し、サブミクロンの微粒子で焼結温度
が低く、磁器化した場合、抗折力強度が大きく、さらに
誘電率が大きく、誘電損失が小さく、容量温度変化率が
小さいというコンデンサーとしての望ましい特性を有す
るチタン酸バリウム系粉末を提供するものである。(Objective of the invention) The present invention solves the problems of conventionally used barium titanate powders, has submicron fine particles, has a low sintering temperature, and has high transverse rupture strength when made into porcelain. The present invention provides a barium titanate-based powder that has desirable characteristics as a capacitor, such as a high dielectric constant, low dielectric loss, and low rate of change in capacitance with temperature.
（間即点を解決するための技術的手段）本発明は、一般
式
％式％
くただし、Ｘ１ｉＺｒ、Ｃｅ、Ｓｎがら選ばれる一種以
上の金属を示し、ａ、 ｂ、 ｃ、 ｄ、 ｅ、 ｆ、
ｘは、Ｂａを１とした時の原子比を表し、ａ＝０．９
〜１，３、ｂ＝０．００１〜０．１ ＝ ｃ ＝０．０
０１〜０．１−ｄ＝０．００５〜０．１、ｅ ＝ ０．
００１〜０．０５、 ｆ＝０．００３〜０，０３、Ｘ−
複合酸化物としての原子価を満足する値である。）で示
され、かつ粒径が０．０１〜１μｍであることを特徴と
する低温焼結性の高強度コンデンサー材料用粉末に関す
る。(Technical means for solving the problem) The present invention has the general formula %, where X1i represents one or more metals selected from Zr, Ce, Sn, a, b, c, d, e, f,
x represents the atomic ratio when Ba is 1, a=0.9
~1,3, b = 0.001 ~ 0.1 = c = 0.0
01~0.1-d=0.005~0.1, e=0.
001~0.05, f=0.003~0.03, X-
This value satisfies the valence as a composite oxide. ) and having a particle size of 0.01 to 1 μm.
本発明において、前記一般式の組成は、Ｂａを１とした
時の原子比がそれぞれ、ａ＝０．９〜１．３、ｂ＝ｏ、
００１〜０．１、Ｃ−０，００１〜０．１、ｄ＝０．０
０５〜０．１、ｅ＝０．００１〜０２０５、 ｔ−０，
００３−０，０３の範囲である。すなわち、Ｂ１、Ｗは
低温焼結化をもたらし、また絶縁抵抗を大きくし、誘電
損失を小さくする作用がある。Ｗはさらに抗折強度を上
げる。Ｂｉ、Ｗがこれらの効果を発現するにはＢａに対
して原子比で０．００１以上含まれていることが必要で
あるが、０．１を越えると誘電率が低下する。またＮｂ
は誘電率の温度変化率の平坦化、焼結性の向上をもなら
ずため、０．００５以上含まれることが必要であるが、
０．１を越えると誘電率の低下が著しくなる。Ｃｏは低
温焼結化に寄与するなめ０．００１以上含まれることが
必要であるが、０．０５より多くなると誘電率が低下す
る。Ｃｅ、Ｚｒ、Ｓｎは誘電率の改善効果があるが、多
ずぎると誘電率が低下する。またＴＩはＢａに対して原
子比で０．９〜１．３の範囲をはずれると誘電率が低下
し、誘電損失も大きくなる。In the present invention, the composition of the general formula has an atomic ratio of a=0.9 to 1.3, b=o, and Ba=1, respectively.
001~0.1, C-0,001~0.1, d=0.0
05~0.1, e=0.001~0205, t-0,
The range is 003-0,03. That is, B1 and W have the effect of bringing about low-temperature sintering, increasing insulation resistance, and reducing dielectric loss. W further increases the bending strength. In order for Bi and W to exhibit these effects, it is necessary that they be contained in an atomic ratio of 0.001 or more to Ba, but if it exceeds 0.1, the dielectric constant decreases. Also Nb
Since it does not flatten the temperature change rate of dielectric constant or improve sinterability, it is necessary to contain 0.005 or more.
If it exceeds 0.1, the dielectric constant will drop significantly. It is necessary that the Co content be 0.001 or more to contribute to low-temperature sintering, but if it is more than 0.05, the dielectric constant will decrease. Ce, Zr, and Sn have the effect of improving the dielectric constant, but if they are present too much, the dielectric constant decreases. Further, when the atomic ratio of TI to Ba is out of the range of 0.9 to 1.3, the dielectric constant decreases and the dielectric loss increases.
本発明の誘電セラミックス粉末は以下に示す湿式法で合
成される。湿式法を用いることにより、粒径が０．０１
〜１μｍの微粒子のものが得られる。The dielectric ceramic powder of the present invention is synthesized by the wet method described below. By using the wet method, the particle size is 0.01
Fine particles of ~1 μm are obtained.
従来の乾式法では、組成的には同等のものが得られるが
、粒径が１ノ１ｍ以上と大きくなるため、磁器化した場
合のダレインサイズも１０μｍ前後の大きなものになっ
てしまうので好ましくない。In the conventional dry method, although the same composition can be obtained, the particle size becomes larger than 1 m or more, and the dalein size when made into porcelain is also large, around 10 μm, so it is preferable. do not have.
本発明の誘電セラミックス粉末を湿式法で合成するには
、まず構成成分のそれぞれの金属の化合物を水に溶解し
た後、溶液中の金属イオンを沈澱剤により、沈澱させる
。In order to synthesize the dielectric ceramic powder of the present invention by a wet method, first, each constituent metal compound is dissolved in water, and then the metal ions in the solution are precipitated using a precipitant.
構成成分のそれぞれの金属の化合物としては、水溶性の
化合物、水酸化物あるいは微粒子の酸化物が用いられる
。例えばバリウム源としては硝酸バリウム、塩化バリウ
ム等が、チタン源としてはチタンアルコキシド、塩化チ
タン、水酸化チタン、酸化チタン、ビスマス源としては
硝酸ビスマス、水酸化ビスマス、タングステン源として
はパラタングステン酸アンモニウム、タングステン酸、
ニオブ源としてはハロゲン化ニオブ、酸化ニオブ、コバ
ルト源としては硝酸コバルト、塩化コバル１〜、セリウ
ム源としては硝酸セリウム、塩化セリウム、ジルコニウ
ム源としては硝酸ジルコニル、塩化ジルコニル、酸化ジ
ルコニウム、スズ源としてはハロケン化スズ、酸化スズ
等を用いることができる。As the metal compound of each constituent component, a water-soluble compound, hydroxide, or fine particle oxide is used. For example, barium sources include barium nitrate, barium chloride, etc., titanium sources include titanium alkoxide, titanium chloride, titanium hydroxide, and titanium oxide, bismuth sources include bismuth nitrate and bismuth hydroxide, and tungsten sources include ammonium paratungstate, etc. tungstic acid,
Niobium sources include niobium halides and niobium oxides; cobalt sources include cobalt nitrate and cobalt chloride; cerium sources include cerium nitrate and cerium chloride; zirconium sources include zirconyl nitrate, zirconyl chloride, and zirconium oxide; and tin sources include cerium nitrate and cerium chloride; Tin halide, tin oxide, etc. can be used.
これらは−最に水溶液として使用されるが水に可溶でな
い場合には酸を添加して可溶させればよく、不溶原料に
ついては懸濁液として使用してもよい。These are primarily used as an aqueous solution, but if they are not soluble in water, an acid may be added to make them soluble, and insoluble raw materials may be used as a suspension.
また沈澱剤としては、アンモニア、アミン類、シュウ酸
、炭酸ア〉・モニウム等を用いることができる。沈澱形
成は逐次的でも共沈でもよい。Further, as a precipitant, ammonia, amines, oxalic acid, ammonium carbonate, etc. can be used. Precipitate formation may be sequential or co-precipitation.
次いで得られた沈澱物を水洗し、沢別、乾燥した後、仮
焼することにより、誘電体セラミックス粉末が得られる
。仮焼温度は５００〜１０００°Ｃの範囲が好適である
。温度が低すぎると沈澱物の脱水、分解が不十分であり
、また温度が高すぎると粉末が租大化する。Next, the obtained precipitate is washed with water, separated, dried, and calcined to obtain a dielectric ceramic powder. The calcination temperature is preferably in the range of 500 to 1000°C. If the temperature is too low, dehydration and decomposition of the precipitate will be insufficient, and if the temperature is too high, the powder will become coarse.
（実施例）
次に実施例により本発明を具体的に明らかにするが、本
発明は実施例のみよって制限されるものではない。実施
例および比較例において粉体の粒径は透過型電子顕微鏡
により求めた。電気特性を測定するに際しては、まず粉
体をＩｔ／ｃ＋（の圧力で直径２０ｍｍ、厚さ１．０
ｍｍの円板に成型した後、１０００〜１２００℃で焼成
し、次いで円板の両面に銀電極を６００℃で焼付けて、
誘電率および誘電正接をＬＣＲメーターを用いて、室温
でｌＫ１１ｚで測定した。また温度特性は、誘電率の温
度変化を２０℃を基準として一２５℃および＋８０℃で
測定した。また焼結体のダレインサイズは破断面の走査
型電子顕微鏡写真より求めた。抗折力強度は長さ１５ｍ
×巾５ ｍｍ Ｘ厚さ１ｍの焼結体試料を１０ｍｍのス
パンで測定した。(Examples) Next, the present invention will be specifically clarified by Examples, but the present invention is not limited only by the Examples. In Examples and Comparative Examples, the particle size of the powder was determined using a transmission electron microscope. When measuring the electrical properties, first the powder was heated to a diameter of 20 mm and a thickness of 1.0 mm at a pressure of It/c+ (
After molding into a mm disc, it is fired at 1000-1200°C, and then silver electrodes are baked on both sides of the disc at 600°C.
The dielectric constant and dielectric loss tangent were measured using an LCR meter at room temperature and lK11z. Regarding temperature characteristics, temperature changes in dielectric constant were measured at -25°C and +80°C with 20°C as a reference. In addition, the dalein size of the sintered body was determined from a scanning electron micrograph of the fracture surface. Transverse rupture strength is 15m long
A sintered sample measuring 5 mm wide and 1 m thick was measured over a span of 10 mm.
実施例１
誘電体組成が原子比でＢａ ：Ｔｉ ：Ｂｉ ：Ｗ
：Ｎｂ ：Ｃｏ ：Ｃｅ＝１：１：０．０５：０．０５
：０．０５： ０．０１ ： ｃｉ、ｏｌとなるように
硝酸バリウム［Ｂａ（Ｎｏ３）２］、チタンイソプロポ
キシド［Ｔ ｉ（ＯＣＨ（ＣＨ３）２）４］、硝酸ビス
マス［Ｂｉ（Ｎｏ３）３ ・５Ｈ２０］、パラタングス
テン酸アンモニウム［（Ｎ Ｈ４）１０Ｗ１２０４１
・５ Ｈ２０］、五酸化ニオブ（Ｎ ｂ ２０ ｓ ）
、硝酸コバルト［Ｃｏ（ＮＯ３）２ ・６Ｈ２０］、硝
酸セリウム［′Ｃｏ（Ｎｏ３）３・６Ｈ２０］を秤量し
た。Example 1 Dielectric composition is Ba:Ti:Bi:W in atomic ratio
:Nb :Co :Ce=1:1:0.05:0.05
:0.05: 0.01: ci, ol barium nitrate [Ba(No3)2], titanium isopropoxide [Ti(OCH(CH3)2)4], bismuth nitrate [Bi(No3)] 3 ・5H20], ammonium paratungstate [(NH4)10W12041
・5 H20], niobium pentoxide (N b 20 s )
, cobalt nitrate [Co(NO3)2 .6H20], and cerium nitrate ['Co(No3)3.6H20] were weighed.
次いで３規定アンモニア水にパラタングステン酸アンモ
ニウムを溶解させ、硝酸ビスマスの希硝酸溶液を滴下し
な。この中にシュウ酸を加えた後、硝酸バリウム、硝酸
セリウムの水溶液を撹拌しながら滴下した。さらにチタ
ンイソプロポキシド、五酸化ニオブのエタノール溶液を
滴下した。Next, dissolve ammonium paratungstate in 3N ammonia water, and dropwise add a dilute nitric acid solution of bismuth nitrate. After adding oxalic acid to this, an aqueous solution of barium nitrate and cerium nitrate was added dropwise with stirring. Further, an ethanol solution of titanium isopropoxide and niobium pentoxide was added dropwise.
次に得られた沈澱生成物を水でデカンテーションを５回
繰返し洗浄した。さらにＮａＯＨ水溶液を加えｐＨを１
２とし、硝酸コバルトの水溶液を加えた。再度水洗し、
ボールミルを行った後、沢過して沈澱物を回収し、１０
０℃で乾燥後、９００℃で空気中仮焼した。The resulting precipitated product was then washed with water by repeated decantation five times. Furthermore, add NaOH aqueous solution to adjust the pH to 1.
2 and an aqueous solution of cobalt nitrate was added. Wash again with water,
After ball milling, the precipitate was collected by filtration, and 10
After drying at 0°C, it was calcined in air at 900°C.
得られた誘電体粉末の粒径は約０．１μｍであった。The particle size of the obtained dielectric powder was about 0.1 μm.
この粉末を成型し、１０５０℃で焼成し１６ｍφＸ１．
Ｏｍｍｔの円板にしな。走査型電子顕微鏡写真よりダレ
インサイズは約１μｍであった。電気特性は表３に示す
。This powder was molded and fired at 1050°C to form a 16mφ×1.
Make it a disk of Ommt. A scanning electron micrograph showed that the size of the dalein was about 1 μm. The electrical properties are shown in Table 3.
実施例２〜１０
実施例１に準じて表１に示す組成比の誘電体粉末を調製
した。得られた粉末の電気特性値は表３に示しているが
、いずれもコンデンサー材料として好ましい値を与えた
。Examples 2 to 10 According to Example 1, dielectric powders having the composition ratios shown in Table 1 were prepared. The electrical property values of the obtained powders are shown in Table 3, and all of them gave values preferable as a capacitor material.
比較例１〜６ 本発明の範囲外の組成物を実施例１に準じて調製した。Comparative examples 1 to 6 A composition outside the scope of the invention was prepared according to Example 1.
得られた粉末の組成比および電気特性値をそれぞれ表２
、表４に示すが、誘電率が低かったり、誘電正接が大き
かったり、また温度特性が悪かったりして好ましいもの
ではなかった。Table 2 shows the composition ratio and electrical property values of the obtained powder.
, as shown in Table 4, were not preferable because they had a low dielectric constant, a large dielectric loss tangent, and poor temperature characteristics.
比較例７
実施例Ｊの組成比になるように、酸化チタン（Ｔ ｉ
Ｏ２）、炭酸バリウム（ＢａＣｏ３）、酸化ビスマス（
Ｂｉ Ｏ）、酸化タングステン（ＷＯ３）、五酸化ニオ
ブ（Ｎ ｂ２０ ’ｓ ）、酸化コバルト（ＣＯ２０３
）酸化セリウム（ＣｅＯ２）、酸化ジルコニウム（Ｚｒ
Ｏ２）を秤量し、水を加えボールミルを行い、沢過、乾
燥後、８００℃で仮焼した。以下実施例１と同様な処理
を行い、電気特性値を測定した。Comparative Example 7 Titanium oxide (Ti
O2), barium carbonate (BaCo3), bismuth oxide (
BiO), tungsten oxide (WO3), niobium pentoxide (Nb20's), cobalt oxide (CO203)
) Cerium oxide (CeO2), zirconium oxide (Zr
O2) was weighed, water was added thereto, ball milled, filtered, dried, and calcined at 800°C. Thereafter, the same treatment as in Example 1 was performed, and the electrical characteristic values were measured.
結果は表４に示しているが、仮焼粉末の粒径は２゜５μ
ｍと大きく、また、成型体焼結物のダレインサイズも９
．５μｍとかなり大きく、コンデンサーに要求される電
気特性も１Ｏ５０′Ｃ焼成では著しく悪いものであった
。The results are shown in Table 4, and the particle size of the calcined powder was 2°5μ.
m, and the diameter size of the sintered molded product is 9.
．． It was quite large at 5 μm, and the electrical properties required for a capacitor were extremely poor when fired at 1O50'C.
（発明の効果）
本発明によれば、一般式
％式％
（ただし、ＸはＺ ｒ、 Ｃｅ、 Ｓ ｎから選ばれる
一種以上の金属を示し、ａ、 ｂ、 ｃ、 ’ｄ、 ｅ
、 ｆ、 ｘは、Ｂａを１とした時の原子比を表し、ａ
＝０．９〜１．３、ｂ＝ｏ、ｏｏ１〜０．１ 、ｃ ＝
Ｏ，ＯＯ１〜０．１−２ｄ−〇、００５〜Ｏ１１、ｅ
＝ ０．００ ］、 〜０．０５、 ｆ−０，００３
〜０．０３、Ｘ−複合酸化物としての原子価を満足する
値である。）で示され、かつ粒径が０．０１〜１μｍで
ある誘電体セラミックス粉末が得られる。(Effect of the invention) According to the present invention, the general formula % (where X represents one or more metals selected from Zr, Ce, Sn, a, b, c, 'd, e
, f, x represent the atomic ratio when Ba is 1, and a
=0.9~1.3, b=o, oo1~0.1, c=
O, OO1~0.1-2d-〇, 005~O11, e
= 0.00], ~0.05, f-0,003
~0.03, a value that satisfies the valence as an X-complex oxide. ) and a particle size of 0.01 to 1 μm is obtained.
この誘電体セラミックス粉末は、粒径が微細で、焼結温
度が低く、また磁器化した場合、抗折力強度が大きく、
さらに誘電率が大きく、誘電損失が小さく、かつ広い温
度範囲にねたって小さな誘電率温度変化を与えるもので
ある。すなわち、本発明の誘電体セラミックス粉末は、
加圧成型後、１０００〜１２００℃という低い温度で焼
結でき、焼結体のダレインサイズは１〜３μｍと小さな
ものになる。また抗折力強度は８００ｋｇ／ｃｉ以上と
大きな値を示し、誘電率は２０００以上、誘電正接は２
％以下となる。This dielectric ceramic powder has a fine particle size, a low sintering temperature, and a high transverse rupture strength when made into porcelain.
Furthermore, it has a large dielectric constant, a small dielectric loss, and a small temperature change in the dielectric constant over a wide temperature range. That is, the dielectric ceramic powder of the present invention is
After pressure molding, it can be sintered at a low temperature of 1000 to 1200°C, and the sintered body has a small dale size of 1 to 3 μm. In addition, the transverse rupture strength shows a large value of over 800 kg/ci, the dielectric constant is over 2000, and the dielectric loss tangent is 2.
% or less.
Claims (1)
ｆＯ＿ｘ（ただし、ＸはＺｒ、Ｃｅ、Ｓｎから選ばれる
一種以上の金属を示し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｘは
、Ｂａを１とした時の原子比を表し、ａ＝０．９〜１．
３、ｂ＝０．００１〜０．１、ｃ＝０．００１〜０．１
ｄ＝０．００５〜０．１、ｅ＝０．００１〜０．０５、
ｆ＝０．００３〜０．０３、ｘ＝複合酸化物としての原
子価を満足する値である、）で示され、かつ粒径が０．
０１〜１μｍであることを特徴とする低温焼結性の高強
度コンデンサー材料用粉末。[Claims] General formula Ba_1Ti_aBi_bW_cNb_dCo_eX_
fO_x (where, X represents one or more metals selected from Zr, Ce, and Sn; a, b, c, d, e, f, and x represent the atomic ratio when Ba is 1; a= 0.9-1.
3, b=0.001~0.1, c=0.001~0.1
d=0.005~0.1, e=0.001~0.05,
f = 0.003 to 0.03, x = a value that satisfies the valence as a composite oxide), and the particle size is 0.
A low-temperature sinterable, high-strength capacitor material powder characterized by a particle size of 0.01 to 1 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61305223A JPS63160108A (en) | 1986-12-23 | 1986-12-23 | Powder for low temperature sintering capacitor material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61305223A JPS63160108A (en) | 1986-12-23 | 1986-12-23 | Powder for low temperature sintering capacitor material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63160108A true JPS63160108A (en) | 1988-07-02 |
Family
ID=17942521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61305223A Pending JPS63160108A (en) | 1986-12-23 | 1986-12-23 | Powder for low temperature sintering capacitor material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63160108A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012043208A1 (en) * | 2010-09-30 | 2012-04-05 | 株式会社村田製作所 | Dielectric ceramic, multilayer ceramic electronic component, and methods for producing same |
-
1986
- 1986-12-23 JP JP61305223A patent/JPS63160108A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012043208A1 (en) * | 2010-09-30 | 2012-04-05 | 株式会社村田製作所 | Dielectric ceramic, multilayer ceramic electronic component, and methods for producing same |
| US9064638B2 (en) | 2010-09-30 | 2015-06-23 | Murata Manufacturing Co., Ltd. | Dielectric ceramic, stack ceramic electronic component, and method of manufacturing these |
| JP5838968B2 (en) * | 2010-09-30 | 2016-01-06 | 株式会社村田製作所 | Dielectric ceramic, multilayer ceramic electronic component, and manufacturing method thereof |
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