JPH0510764B2 - - Google Patents
Info
- Publication number
- JPH0510764B2 JPH0510764B2 JP14362684A JP14362684A JPH0510764B2 JP H0510764 B2 JPH0510764 B2 JP H0510764B2 JP 14362684 A JP14362684 A JP 14362684A JP 14362684 A JP14362684 A JP 14362684A JP H0510764 B2 JPH0510764 B2 JP H0510764B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- oxide
- dielectric constant
- less
- exceeds
- 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.)
- Expired - Lifetime
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 8
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- 229910002367 SrTiO Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims 1
- 238000010304 firing Methods 0.000 description 9
- 230000005684 electric field Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
Description
（産業上の利用分野）
この発明は高誘電率系の誘電体磁器組成物に関
するものである。
（従来の技術）
誘電率が2000以上の磁器組成物としては、
BaTiO3またはBaTiO3を変性したものが実用化
されてきた。しかしながら、このような組成から
なるセラミツクコンデンサは、その静電容量値が
バイアス電界に強く影響されて大きく減少し、１
mm当り2KVの高圧直流電圧を印加すると、静電
容量値が−30〜−50％も変化するという欠点が見
られた。そしてこの欠点についての改良はほとん
ど行われていない。
また、SrTiO3−PbTiO3−Bi2O3−TiO2などを
主成分とする磁器組成物が近年実用化されてい
る。この系の磁器組成物は室温で500〜2000の誘
電率を有し、かつそのバイアス電界に対する静電
容量値の変化がBaTiO3系にくらべて小さいとい
う特徴を有している。しかしながら、最適な誘電
特性を得るための焼成温度が1220〜1320℃と高い
ため、蒸発しやすいPbO，Bi2O3を含んでいるこ
とから、かかる焼成温度での鉛やビスマスの焼成
雰囲気をコントロールしなければ均一な焼結体を
得ることができず、工業生産上の量産性、品質の
上で解決すべき種々の問題を含んでいる。
さらに、セラミツクコンデンサの小型化、薄板
化の傾向の中で、さらに誘電率が高く、バイアス
電界に対する静電容量値の変化の小さい誘電体磁
器組成物の出現が要求されている。
（発明の目的）
したがつて、この発明は誘電率が2000以上で、
バイアス電界に対する静電容量値の変化の小さい
誘電体磁器組成物を提供することを目的とする。
（発明の概要）
この発明にかかる誘電体磁器組成物を要約すれ
ば、チタン酸ストロンチウム、チタン酸鉛、チタ
ン酸カルシウム、酸化ビスマス、酸化錫、酸化チ
タンを主成分とし、これに酸化亜鉛、酸化ニオ
ブ、酸化セリウム、酸化アルミニウムからなる副
成分が添加含有されたものである。
（実施例）
素原料として、Pb2O3，SrCO3，CaCO3，TiO2
SnO2，Bi2O3，ZnO，Nb2O5，CeO2およびAl2O3
準備した。各素原料を第１表に示す組成比率の磁
器が得られるように秤量した。各秤量原料をポツ
トミルに入れ、アルミナボールを用いて16時間湿
式混合粉砕したのち脱水乾燥した。乾燥した混合
原料をジルコニア質の匣に入れ、1000℃の温度で
２時間仮焼し、その後粉砕した。粉砕した粉末に
バインダーを加えて造粒し、造粒粉末を1000Kg／
cm2の圧力で加圧成形し、直径17mm、厚み1.2mmの
成形物を得た。この成形物を1060〜1290℃の温度
で２時間焼成して磁器素体を得た。得られた磁器
素体の両面に銀ペーストを塗布し、空気中800℃
で焼付けして電極を形成し、これを試料とした。
得られた試料について、周波数1KHzで誘電率
（ε）、誘電損失正接（tanδ）を測定した。また、
試料に2KV／mmの直流電圧を重畳したときの誘
電率の変化（バイアス特性）を測定した。さら
に、−25℃における誘電率＋85℃における誘電率
を測定し、常温（＋25℃）に対する変化率（温度
特性）を示した。
第２表は各測定結果を示したものである。
なお、第１表、第２表中※印はこの発明範囲外
であり、それ以外はこの発明範囲内のものであ
る。また、第２表には各試料の最適焼成温度を示
した。
(Industrial Application Field) This invention relates to a high dielectric constant dielectric ceramic composition. (Prior art) As a porcelain composition with a dielectric constant of 2000 or more,
BaTiO 3 or modified BaTiO 3 has been put into practical use. However, the capacitance value of a ceramic capacitor with such a composition is strongly influenced by the bias electric field and decreases significantly.
When a high DC voltage of 2 KV per mm was applied, a drawback was observed that the capacitance value changed by -30 to -50%. And little improvement has been made to address this drawback. Furthermore, ceramic compositions containing SrTiO 3 --PbTiO 3 --Bi 2 O 3 --TiO 2 as main components have been put into practical use in recent years. This type of ceramic composition has a dielectric constant of 500 to 2000 at room temperature, and is characterized in that the change in capacitance value with respect to the bias electric field is smaller than that of the BaTiO 3 type. However, since the firing temperature to obtain optimal dielectric properties is high at 1220-1320℃, it is necessary to control the firing atmosphere for lead and bismuth at such firing temperatures, as they contain PbO and Bi 2 O 3 that easily evaporate. Otherwise, a uniform sintered body cannot be obtained, and there are various problems that need to be solved in terms of mass productivity and quality in industrial production. Furthermore, with the trend towards smaller and thinner ceramic capacitors, there is a demand for dielectric ceramic compositions that have higher dielectric constants and smaller changes in capacitance with respect to bias electric fields. (Object of the invention) Therefore, this invention has a dielectric constant of 2000 or more,
It is an object of the present invention to provide a dielectric ceramic composition whose capacitance value changes little with respect to a bias electric field. (Summary of the Invention) To summarize the dielectric ceramic composition according to the present invention, the main components are strontium titanate, lead titanate, calcium titanate, bismuth oxide, tin oxide, and titanium oxide, and zinc oxide and titanium oxide. It contains additional subcomponents consisting of niobium, cerium oxide, and aluminum oxide. (Example) Raw materials include Pb 2 O 3 , SrCO 3 , CaCO 3 , TiO 2
SnO 2 , Bi 2 O 3 , ZnO, Nb 2 O 5 , CeO 2 and Al 2 O 3
Got ready. Each raw material was weighed so as to obtain porcelain having the composition ratio shown in Table 1. Each weighed raw material was placed in a pot mill, wet mixed and ground using an alumina ball for 16 hours, and then dehydrated and dried. The dried mixed raw materials were placed in a zirconia box, calcined at a temperature of 1000°C for 2 hours, and then pulverized. Add a binder to the pulverized powder and granulate it to produce 1000 kg/1000 kg of granulated powder.
Pressure molding was performed at a pressure of cm 2 to obtain a molded product with a diameter of 17 mm and a thickness of 1.2 mm. This molded product was fired at a temperature of 1060 to 1290°C for 2 hours to obtain a porcelain element. Silver paste was applied to both sides of the obtained porcelain body and heated at 800℃ in air.
An electrode was formed by baking the electrode, and this was used as a sample. The dielectric constant (ε) and dielectric loss tangent (tan δ) of the obtained sample were measured at a frequency of 1 KHz. Also,
Changes in dielectric constant (bias characteristics) were measured when a DC voltage of 2 KV/mm was applied to the sample. Furthermore, the dielectric constant at -25°C + the dielectric constant at 85°C was measured, and the rate of change (temperature characteristics) with respect to room temperature (+25°C) was shown. Table 2 shows the results of each measurement. In Tables 1 and 2, the items marked * are outside the scope of this invention, and the others are within the scope of this invention. Table 2 also shows the optimum firing temperature for each sample.
【表】【table】
【表】【table】
【表】【table】
【表】
第１表、第２表から明らかなように、この発明
範囲内のものによれば、誘電率は2000〜6500の値
を示し、tanδは１％以下とすぐれた値を示してい
る。またバイアス特性は−25％以内であり、バイ
アス電界に対する誘電率の変化が小さいという特
徴を有している。さらに最適焼成温度が1060〜
1180℃と従来のそれにくらべ100〜200℃と低温で
の焼成が可能となつている。
ここで、組成範囲を限定した理由は以下の通り
である。
SrTiO3が30重量％未満になると、tanδが１％
以上になるとともにバイアス特性が−30％以上と
なり、一方46重量％を越えると、誘電率が2000未
満になる。
PbTiO3が31.5重量％未満になると、誘電率が
2000未満となり、一方44重量％を越えると、tanδ
が１％以上になるとともにバイアス特性が−30％
以上となる。
CaTiO3が２重量％未満になると、tanδが１％
以上になるとともにバイアス特性が−30％以上と
なり、一方17重量％を超えると、誘電率が2000未
満となる。
Bi2O3が５重量％未満になると、誘電率が2000
に達せず、一方15重量％を超えると、tanδが１％
以上になるとともにバイアス特性が悪くなる。
SnO2が0.5重量％未満になると、tanδが１％以
上となり、温度特性が悪くなる。一方10重量％を
超えると、誘電率が2000に達しない。
TiO2が１重量％未満になると、誘電率が2000
未満となり、一方10重量％を超えると、tanδが１
％以上となり、バイアス特性が悪くなる。
ZnOが0.1重量％未満になると、焼成温度が高
くなり、一方４重量％を超えると、誘電率が2000
未満となる。
Nb2O5が0.1重量％未満になると、焼成温度が
高くなり、一方４重量％を超えると、誘電率が
2000未満となる。
CeO2が0.1重量％未満になると、焼成温度が高
くなり、一方４重量％を超えると、誘電率が2000
未満となる。
Al2O3が0.1重量％未満になると、焼成温度が高
くなり、一方２重量％を超えると、誘電率が2000
未満となる。
（発明の効果）
以上の実施例から明らかならようにこの発明に
よれば、誘電率が2000〜6500と高い値を示し、
tanδが１％以下とすぐれた値を示す。またバイア
ス特性も−25％以内に抑えることができ、さらに
焼成温度も1060〜1180℃と比較的低い温度での焼
成が可能な誘電体磁器組成物を提供することがで
きる。[Table] As is clear from Tables 1 and 2, according to the products within the scope of this invention, the dielectric constant shows a value of 2000 to 6500, and the tan δ shows an excellent value of 1% or less. . Moreover, the bias characteristic is within -25%, and the change in dielectric constant with respect to the bias electric field is small. Furthermore, the optimum firing temperature is 1060~
It is now possible to fire at a lower temperature of 100 to 200 degrees Celsius, compared to 1180 degrees Celsius. Here, the reason for limiting the composition range is as follows. When SrTiO 3 is less than 30% by weight, tanδ is 1%
When the content exceeds 46% by weight, the bias property becomes -30% or more, and when the content exceeds 46% by weight, the dielectric constant becomes less than 2000. When PbTiO 3 is less than 31.5% by weight, the dielectric constant
If it becomes less than 2000, while if it exceeds 44% by weight, tanδ
When becomes 1% or more, the bias characteristic decreases by -30%
That's all. When CaTiO 3 is less than 2% by weight, tanδ is 1%
When the content exceeds 17% by weight, the bias property becomes -30% or more, and when the content exceeds 17% by weight, the dielectric constant becomes less than 2000. When Bi 2 O 3 is less than 5% by weight, the dielectric constant is 2000.
However, if it exceeds 15% by weight, tanδ decreases to 1%
As the value increases, the bias characteristics deteriorate. When SnO 2 is less than 0.5% by weight, tan δ becomes 1% or more, and the temperature characteristics deteriorate. On the other hand, if it exceeds 10% by weight, the dielectric constant will not reach 2000. When TiO 2 is less than 1% by weight, the dielectric constant is 2000.
On the other hand, when it exceeds 10% by weight, tanδ becomes 1
% or more, the bias characteristics deteriorate. When ZnO is less than 0.1% by weight, the firing temperature becomes high, while when it exceeds 4% by weight, the dielectric constant increases to 2000.
less than When Nb 2 O 5 is less than 0.1% by weight, the firing temperature increases, while when it exceeds 4% by weight, the dielectric constant decreases.
It will be less than 2000. When CeO 2 is less than 0.1% by weight, the calcination temperature increases, while when it exceeds 4% by weight, the dielectric constant increases to 2000.
less than When Al 2 O 3 is less than 0.1% by weight, the firing temperature becomes high, while when it exceeds 2% by weight, the dielectric constant increases to 2000.
less than (Effects of the Invention) As is clear from the above examples, according to the present invention, the dielectric constant exhibits a high value of 2000 to 6500,
It shows an excellent value of tan δ of 1% or less. Further, it is possible to provide a dielectric ceramic composition that can suppress bias characteristics to within -25% and can be fired at a relatively low firing temperature of 1060 to 1180°C.
Claims (1)
ン酸カルシウム、酸化ビスマス、酸化錫酸化チタ
ン、酸化亜鉛、酸化ニオブ、酸化セリウムおよび
酸化アルミニウムからなり、 これら各成分をSrTiO3，PbTiO3，CaTiO3，
Bi2O3，SnO2，TiO2，ZnO，Nb2O5，CeO2およ
びAl2O3と表わしたとき、 SrTiO3 30〜46重量％ PbTiO3 31.5〜44重量％ CaTiO3 ２〜17重量％ Bi2O3 ５〜15重量％ SnO2 0.5〜10重量％ TiO2 １〜10重量％ からなる主成分に対し、 ZnO 0.1〜４重量％ Nb2O5 0.1〜４重量％ CeO2 0.1〜４重量％ Al2O3 0.1〜２重量％ からなる副成分が添加含有されてなることを特徴
とする誘電体磁器組成物。[Scope of Claims] 1 Consists of strontium titanate, lead titanate, calcium titanate, bismuth oxide, tin oxide, titanium oxide, zinc oxide, niobium oxide, cerium oxide, and aluminum oxide, each of which is combined with SrTiO 3 , PbTiO 3 , CaTiO 3 ,
When expressed as Bi 2 O 3 , SnO 2 , TiO 2 , ZnO, Nb 2 O 5 , CeO 2 and Al 2 O 3 , SrTiO 3 30-46% by weight PbTiO 3 31.5-44% by weight CaTiO 3 2-17% by weight % Bi 2 O 3 5-15% by weight SnO 2 0.5-10% by weight TiO 2 1-10% by weight, ZnO 0.1-4% by weight Nb 2 O 5 0.1-4% by weight CeO 2 0.1- A dielectric ceramic composition characterized in that it further contains a subcomponent consisting of 4% by weight Al 2 O 3 and 0.1 to 2% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14362684A JPS6122507A (en) | 1984-07-10 | 1984-07-10 | Dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14362684A JPS6122507A (en) | 1984-07-10 | 1984-07-10 | Dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6122507A JPS6122507A (en) | 1986-01-31 |
| JPH0510764B2 true JPH0510764B2 (en) | 1993-02-10 |
Family
ID=15343124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14362684A Granted JPS6122507A (en) | 1984-07-10 | 1984-07-10 | Dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6122507A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2521055B2 (en) * | 1986-08-21 | 1996-07-31 | 日本ビクター株式会社 | Horizontal deflection circuit |
| JP3294983B2 (en) * | 1996-01-08 | 2002-06-24 | 富士通株式会社 | Dot line printer |
-
1984
- 1984-07-10 JP JP14362684A patent/JPS6122507A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6122507A (en) | 1986-01-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |