JPH07192530A - Dielectric ceramic composition - Google Patents
Dielectric ceramic compositionInfo
- Publication number
- JPH07192530A JPH07192530A JP5330468A JP33046893A JPH07192530A JP H07192530 A JPH07192530 A JP H07192530A JP 5330468 A JP5330468 A JP 5330468A JP 33046893 A JP33046893 A JP 33046893A JP H07192530 A JPH07192530 A JP H07192530A
- Authority
- JP
- Japan
- Prior art keywords
- dielectric
- dielectric ceramic
- ceramic composition
- mol
- 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.)
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は結晶粒径が微細で、しか
も温度特性が良好でしかも誘電体損失が小さい誘電体磁
器組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic composition having a fine crystal grain size, good temperature characteristics and a small dielectric loss.
【０００２】[0002]
【従来の技術】従来コンデンサ等に使用する高誘電率の
誘電体組成物として、チタン酸バリウムにシフターとし
てＬａ2 Ｏ3 やＣｅＯ2 等の希土類を添加し、そのキュ
ーリー点Ｔｃを室温付近にシフトして、誘電率が高く、
かつ微細な結晶を持つものが使用されている。2. Description of the Related Art As a high dielectric constant dielectric composition used in conventional capacitors, barium titanate is added with rare earth elements such as La 2 O 3 and CeO 2 as shifters, and the Curie point Tc thereof is shifted to around room temperature. And has a high dielectric constant,
And those with fine crystals are used.
【０００３】しかしながらこのような誘電体では、誘電
率の温度特性が大きく、実用上製品の品種が限定される
等の欠点があった。チタン酸バリウム等にＣｅＯ2 等を
含有させた誘電体磁器組成物として特開昭５８−２２３
６６９号公報や特開昭５８−１０６７０２号公報等に記
載されたものがあるが、これらに記載のものより誘電体
損失の小さいものが要求されている。However, such a dielectric material has drawbacks that the temperature characteristic of the dielectric constant is large and that the product types are practically limited. As a dielectric ceramic composition containing CeO 2 or the like in barium titanate or the like, JP-A-58-223.
There are those described in Japanese Patent No. 669, Japanese Patent Laid-Open No. 58-106702, etc., but those having a dielectric loss smaller than those described therein are required.
【０００４】[0004]
【発明が解決しようとする課題】本発明は前記の如き結
晶粒径が微細な高誘電率の誘電体組成物において、誘電
率の温度特性が大きいという問題点を改善した、温度特
性の良好な、しかも誘電体損失が小さい新規の誘電体磁
器組成物を提供することである。DISCLOSURE OF THE INVENTION The present invention has improved the temperature characteristic of the dielectric constant in the above-described dielectric composition having a fine crystal grain size and a high dielectric constant. Moreover, it is to provide a novel dielectric ceramic composition having a small dielectric loss.
【０００５】[0005]
【課題を解決するための手段】前記の問題点を改善する
ために、本発明では、 ＢａＯ ４７．４〜４９．０ ｍｏｌ％ ＴｉＯ2 ４５．１〜５１．６ ｍｏｌ％ ＺｒＯ2 ０．５〜 ５．０ ｍｏｌ％ からなる組成物１００重量部に、添加物として、 ＣｅＯ2 ２．７〜 ３．７ ｗｔ％ ＭｎＯ ０．１〜 ０．５ ｗｔ％ ＳｉＯ2 ０．０５〜０．５０ ｗｔ％ ＳｒＯ ０．０５〜０．１５ ｗｔ％ を含有させてなる誘電体磁器組成物を提供する。In order to solve the above problems, in the present invention, BaO 47.4 to 49.0 mol% TiO 2 45.1 to 51.6 mol% ZrO 2 0.5 to CeO 2 2.7 to 3.7 wt% MnO 0.1 to 0.5 wt% SiO 2 0.05 to 0.50 wt% as an additive to 100 parts by weight of a composition consisting of 5.0 mol% Provided is a dielectric ceramic composition containing 0.05 to 0.15 wt% of SrO.
【０００６】[0006]
【作用】これにより結晶粒径が１．８μｍ以下と小さく
した、しかも誘電率の温度特性変化Ｔｃが小さく、誘電
体損失もこれまた小さい誘電体磁器組成物を得ることが
できる。This makes it possible to obtain a dielectric ceramic composition having a crystal grain size as small as 1.8 μm or less, a small change Tc in the dielectric constant with temperature characteristics, and a small dielectric loss.
【０００７】[0007]
【実施例】本発明を実施例に基づき詳細に説明する。原
料としてＢａＣＯ3 、ＴｉＯ2 、ＣｅＯ2 、ＺｒＯ2 、
ＭｎＣＯ3 を焼成後にそれぞれＢａＯ４７．４〜４９．
０モル％、ＴｉＯ2 ４５．１〜５１．６モル％、ＺｒＯ
2 ０．５〜５．０モル％、ＣｅＯ2 １．０〜３．７ｗｔ
％、ＭｎＯ０．１〜０．５ｗｔ％、ＳｉＯ2 ０．０５〜
０．５０ｗｔ％、ＳｒＯ０．０５〜０．１５ｗｔ％とな
るように秤量、配合し、これをボールミルにて湿式混合
し、脱水、乾燥後、仮焼成を行った。そしてこの仮焼成
したものを粉砕し、成形圧力３ｔｏｎ／ｃｍ2 で直径１
６ｍｍ、厚さ０．６ｍｍに加圧成形し、この成形物を１
３４０℃の温度で２時間焼成した。EXAMPLES The present invention will be described in detail based on examples. As raw materials, BaCO 3 , TiO 2 , CeO 2 , ZrO 2 ,
After firing MnCO 3 , BaO 47.4 to 49.
0 mol%, TiO 2 45.1-51.6 mol%, ZrO
2 0.5-5.0 mol%, CeO 2 1.0-3.7 wt
%, MnO 0.1-0.5 wt%, SiO 2 0.05-
0.50 wt% and SrO 0.05 to 0.15 wt% were weighed and mixed, wet-mixed with a ball mill, dehydrated, dried, and calcined. Then, this calcined product is crushed and the diameter is 1 at a molding pressure of 3 ton / cm 2.
6mm and 0.6mm thick, press-molded
It was baked at a temperature of 340 ° C. for 2 hours.
【０００８】このようにして得られた誘電体磁器の両面
に銀電極をメッキしてコンデンサを形成した後、その誘
電率、ｔａｎδを１ＫＨｚの周波数でＹＨＰ（横河・ヒ
ューレット・パッカード株式会社）製のＬＣＲメータを
使用して測定した。又、結晶粒径は走査形電子顕微鏡に
て２０００倍で観察した。温度特性は恒温槽を使用し、
前記ＹＨＰのＬＣＲメータを使用してこれまた１ＫＨｚ
の周波数にて測定した。The dielectric ceramic thus obtained was plated with silver electrodes on both sides to form a capacitor, and its dielectric constant, tan δ, was made by YHP (Yokogawa / Hewlett-Packard Co., Ltd.) at a frequency of 1 KHz. It measured using the LCR meter. The crystal grain size was observed with a scanning electron microscope at 2000 times. Temperature characteristics use a constant temperature bath,
This is also 1 KHz using the YHP LCR meter
Was measured at the frequency of.
【０００９】温度特性Ｔｃ−６０はキューリー点での誘
電率εｃとキューリー点より６０℃高温側での誘電率ε
60から次式によって算出した。The temperature characteristic Tc-60 is the dielectric constant εc at the Curie point and the dielectric constant ε at a temperature of 60 ° C. higher than the Curie point.
It was calculated from 60 by the following formula.
【００１０】[0010]
【数１】 [Equation 1]
【００１１】このようにして得られた各試料の試験条件
及び測定結果を表１に示す。Table 1 shows the test conditions and measurement results of each sample thus obtained.
【００１２】[0012]
【表１】 [Table 1]
【００１３】表１で試料番号１６−２〜１６−４、１６
−７〜１６−９が本発明の範囲内のものであり、それ以
外のものは本発明の範囲外のものである。この表１から
ＢａＯが４７．４モル％以下の場合や４９．０モル％以
上の場合では、誘電率εｓが低く、実用性に乏しいこと
がわかる。In Table 1, sample numbers 16-2 to 16-4 and 16
-7 to 16-9 are within the scope of the present invention, and others are outside the scope of the present invention. From Table 1, it can be seen that when BaO is 47.4 mol% or less or when it is 49.0 mol% or more, the dielectric constant εs is low and the practicality is poor.
【００１４】又、ＺｒＯ2 を０．５モル％以上添加する
と温度特性が改善されるが、５モル％を越えると誘電率
εｓが低下し過ぎてしまう。ＴｉＯ2 が５１．６モル％
を越えるとキューリー点が一側にいき過ぎ温度特性の変
化が大となり実用的でない。４５．１モル％以下では誘
電体損失が悪化する。If ZrO 2 is added in an amount of 0.5 mol% or more, the temperature characteristics are improved, but if it exceeds 5 mol%, the dielectric constant εs is excessively lowered. 51.6 mol% of TiO 2
If it exceeds, the Curie point goes too far to one side and the temperature characteristic changes greatly, which is not practical. If it is 45.1 mol% or less, the dielectric loss becomes worse.
【００１５】ＺｒＯ2 はＣｅＯ2 と同様にシフターとし
ての働きもあるが、必要なＴｃ−６０と誘電率が得られ
るＺｒＯ2 の量だけではキューリー点が高温に行き過ぎ
ている。従ってキューリー点を室温付近へ移動させるた
めにＣｅＯ2 で補正することが必要であり、ＣｅＯ
2 ２．７〜３．７ｗｔ％が適当である。これにもとづ
き、温度特性Ｔｃ−６０が−５５〜−７９％と小さくＹ
５Ｕ及びＹ５Ｖ特性を満たすものとなり、誘電率εが
５，０００〜１０，０００と比較的高いものとすること
が可能となり、誘電体損失ｔａｎδがと比較的良好であ
る。[0015] ZrO 2 is also serves as the shifter in the same manner as CeO 2, only the amount of ZrO 2 which required Tc-60 and the dielectric constant can be obtained Curie point is too far to high temperatures. Therefore, it is necessary to correct with CeO 2 in order to move the Curie point to near room temperature.
2 2.7-3.7 wt% is suitable. Based on this, the temperature characteristic Tc-60 is as small as -55 to -79% and Y
The 5U and Y5V characteristics are satisfied, the permittivity ε can be made relatively high as 5,000 to 10,000, and the dielectric loss tan δ is relatively good.
【００１６】ＭｎＯは磁器の焼結性向上のために添加す
るものであるが、０．５ｗｔ％以上の添加量では誘電率
が低下し、絶縁抵抗も低下し実用的でない。ＳｉＯ2 は
結晶粒径を１．８μｍ以下に小さくするために添加する
ものであるが、０．０５ｗｔ％未満では粒径は２μｍと
大きく、また０．５ｗｔ％を越えると誘電率が低下す
る。しかもＳｉＯ2 を０．０５〜０．１５ｗｔ％添加す
ることにより誘電体損失を０．４〜０．６％と小さくす
ることができる。MnO is added to improve the sinterability of porcelain, but if it is added in an amount of 0.5 wt% or more, the dielectric constant decreases and the insulation resistance also decreases, which is not practical. SiO 2 is added in order to reduce the crystal grain size to 1.8 μm or less, but if it is less than 0.05 wt%, the grain size is as large as 2 μm, and if it exceeds 0.5 wt%, the dielectric constant decreases. Moreover, the dielectric loss can be reduced to 0.4 to 0.6% by adding 0.05 to 0.15 wt% of SiO 2 .
【００１７】ＳｒＯは０．０５ｗｔ％未満では粒径が大
きくなる。また０．１５ｗｔ％を越えるとキューリー点
の移動が生じ、温度特性Ｔｃ−６０を大きくする。If SrO is less than 0.05 wt%, the particle size becomes large. If it exceeds 0.15 wt%, the Curie point moves, and the temperature characteristic Tc-60 is increased.
【００１８】[0018]
【発明の効果】本発明による誘電体磁器は誘電率が高
く、温度特性が良好で、しかも結晶粒径が１．０〜１．
８μｍという非常に細かく、しかも誘電体損失が０．４
〜０．６％と小さいものが得られるので、例えば積層コ
ンデンサ等の材料として好適である。The dielectric ceramic according to the present invention has a high dielectric constant, good temperature characteristics, and a crystal grain size of 1.0 to 1.
Very fine, 8 μm, with a dielectric loss of 0.4
Since it is possible to obtain a small value of up to 0.6%, it is suitable as a material for, for example, a multilayer capacitor.
Claims (1)
ｌ％ ＴｉＯ2 ４５．１〜５１．６ ｍｏｌ％ ＺｒＯ2 ０．５〜 ５．０ ｍｏｌ％ からなる組成物１００重量部に、添加物として、 ＣｅＯ2 ２．７〜 ３．７ ｗｔ％ ＭｎＯ ０．１〜 ０．５ ｗｔ％ ＳｉＯ2 ０．０５〜０．５０ ｗｔ％ ＳｒＯ ０．０５〜０．１５ ｗｔ％ を含有させてなる誘電体磁器組成物。1. BaO 47.4 to 49.0 mo
100% by weight of a composition consisting of 1% TiO 2 45.1 to 51.6 mol% ZrO 2 0.5 to 5.0 mol% and CeO 2 2.7 to 3.7 wt% MnO 0 as an additive. 1 to 0.5 wt% SiO 2 0.05 to 0.50 wt% SrO 0.05 to 0.15 wt% Dielectric ceramic composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5330468A JPH07192530A (en) | 1993-12-27 | 1993-12-27 | Dielectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5330468A JPH07192530A (en) | 1993-12-27 | 1993-12-27 | Dielectric ceramic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07192530A true JPH07192530A (en) | 1995-07-28 |
Family
ID=18232968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5330468A Withdrawn JPH07192530A (en) | 1993-12-27 | 1993-12-27 | Dielectric ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07192530A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262227A (en) * | 2021-11-26 | 2022-04-01 | 西安交通大学 | Method for improving dielectric nonlinear dielectricity of barium titanate ceramic by equivalent-acceptor doping |
-
1993
- 1993-12-27 JP JP5330468A patent/JPH07192530A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262227A (en) * | 2021-11-26 | 2022-04-01 | 西安交通大学 | Method for improving dielectric nonlinear dielectricity of barium titanate ceramic by equivalent-acceptor doping |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20010306 |