JPH0132182B2 - - Google Patents
Info
- Publication number
- JPH0132182B2 JPH0132182B2 JP58239227A JP23922783A JPH0132182B2 JP H0132182 B2 JPH0132182 B2 JP H0132182B2 JP 58239227 A JP58239227 A JP 58239227A JP 23922783 A JP23922783 A JP 23922783A JP H0132182 B2 JPH0132182 B2 JP H0132182B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- composition
- class
- dielectric constant
- present
- 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
Links
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000010586 diagram Methods 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims 2
- 239000000463 material Substances 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- -1 WO 3 Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Description
産業上の利用分野
本発明は焼成温度が低く、温度特性に優れたセ
ラミツクコンデンサ用材料に関するものである。
従来例の構成とその問題点
セラミツクコンデンサ用の高誘電率材料として
は、チタン酸バリウム系の材料が広く用いられて
いる。この系の材料が有している比誘電率は、そ
の温度特性と密接な関係にあり、JIS規格に定め
られたＹ級Ｆ特性（誘電率の温度変化が−25〜85
℃の温度範囲で20℃の値を基準として＋30％、−
80％以内）を満たす材料としては比誘電率が
10000程度、Ｙ級Ｄ特性（前述の条件で＋20％、−
30％以内）を満たす材料では比誘電率が4000程
度、さらにＹ級Ｂ特性（前述の条件で±10％以
内）を満たす材料では2000〜3000程度である。こ
のチタン酸バリウム系の材料は誘電体損失tanδも
低く、その他の諸特性も優れているが、その焼成
には1300〜1400℃という相当高い温度を必要とす
る。そのため、この系の材料を積層セラミツクコ
ンデンサに用いるときには、内部電極として高価
な白金系の電極が必要となる。一方、900℃前後
の低温で焼成が可能な材料としてPb（Fe1/2Nb1/2）
O3―Pb（Fe2/3W1/3）O3系等の誘電体材料が知ら
れている。これらは室温の比誘電率が10000〜
20000と大きい値を有するが、その温度変化の大
きいものが多い。
民生用電子機器で使用されているコンデンサの
大半は、温度変化の小さいＹ級Ｄ特性、Ｙ級Ｂ特
性に相当するものであるため、900℃前後の温度
で焼成が可能であり、温度特性に優れたコンデン
サ材料が得られるならば、その工業的価値は大で
ある。
発明の目的
本発明は、焼成温度が850〜900℃と低く、かつ
−25〜85℃の温度範囲でＹ級Ｂ特性、もしくはＹ
級Ｄ特性を満たす誘電体磁器組成物を提供するこ
とを目的とする。
発明の構成
本発明の誘電体磁器組成物は、Pb（Zn1/3Nb2/3）
ｘ（Fe1/2Nb1/2）ｙ（Mg1/2W1/2）zO3の組成物にお
いて、ｘ、ｙ、ｚが図に示す多角形Ａ、Ｂ、Ｃ、
Ｄの範囲内の組成にあることを特徴とする。さら
に前記組成物を主成分とし、副成分としてMnO2
を0.05〜１重量％含むことを特徴する。
実施例の説明
原料として化学的に高純度のPbO、ZnO、
Nb2O5、Fe2O3、MgO、WO3、MnO2を下表の組
成に従つて秤量し、めのう玉石と純水を加えてポ
リエチレンポツトで15時間混合し、乾燥した後、
750℃で２時間仮焼し、さらに前述のポツトで15
時間粉砕して乾燥させた。その後、ポリビニルア
ルコール水溶液をバインダとして加え、直径13
mm、高さ10mmの円柱状に加圧成形し、バインダを
焼却した後、マグネシア磁器容器に入れ、850〜
900℃の範囲内の温度で２時間焼成した。得られ
た磁器焼成物を厚さ１mmに切断し、両面にCr―
Auを蒸着して電極を形成し、20℃の温度下での
比誘電率と誘電正接tanδおよびその温度変化を
1KHz、1V／mmの電界で測定した。キユリー点は
誘電率が最大となる温度とした。これらの結果を
下表に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a material for ceramic capacitors that has a low firing temperature and excellent temperature characteristics. Conventional Structure and Problems Barium titanate-based materials are widely used as high dielectric constant materials for ceramic capacitors. The relative permittivity of this type of material is closely related to its temperature characteristics.
+30%, - based on the value of 20℃ in the temperature range of ℃
Materials that satisfy the dielectric constant (within 80%) have a relative dielectric constant of
Approximately 10000, Y class D characteristics (+20%, - under the above conditions)
Materials that satisfy Y class B characteristics (within 30%) have a relative dielectric constant of about 4000, and materials that satisfy Y class B characteristics (within ±10% under the above conditions) have a relative dielectric constant of about 2000 to 3000. Although this barium titanate-based material has a low dielectric loss tan δ and other excellent properties, it requires a considerably high temperature of 1300 to 1400°C for firing. Therefore, when this type of material is used in a multilayer ceramic capacitor, expensive platinum-based electrodes are required as internal electrodes. On the other hand, Pb (Fe 1/2 Nb 1/2 ) is a material that can be fired at a low temperature of around 900℃.
Dielectric materials such as O 3 -Pb (Fe 2/3 W 1/3 ) O 3 are known. These have relative dielectric constants of 10,000 to 10,000 at room temperature.
It has a large value of 20,000, but many have large temperature changes. Most of the capacitors used in consumer electronic devices have Y-class D characteristics and Y-class B characteristics, which have small temperature changes, so they can be fired at temperatures around 900°C, and their temperature characteristics do not change. If a superior capacitor material can be obtained, it would have great industrial value. Purpose of the Invention The present invention has a low firing temperature of 850 to 900°C, and a temperature range of -25 to 85°C that produces Y class B characteristics or
The object of the present invention is to provide a dielectric ceramic composition that satisfies class D characteristics. Structure of the Invention The dielectric ceramic composition of the present invention includes Pb (Zn 1/3 Nb 2/3 )
In the composition of x(Fe 1/2 Nb 1/2 ) y (Mg 1/2 W 1/2 ) zO 3 , x, y, and z are polygons A, B, C,
It is characterized by having a composition within the range of D. Furthermore, the above composition is used as a main component, and MnO 2 is used as a subcomponent.
It is characterized by containing 0.05 to 1% by weight. Description of Examples Chemically high-purity PbO, ZnO,
Weigh Nb 2 O 5 , Fe 2 O 3 , MgO, WO 3 , and MnO 2 according to the composition in the table below, add agate cobblestone and pure water, mix in a polyethylene pot for 15 hours, and dry.
Calcinate at 750℃ for 2 hours, then heat in the pot mentioned above for 15 minutes.
Grind and dry for hours. Then, add polyvinyl alcohol aqueous solution as a binder and
Pressure molded into a cylindrical shape with a height of 10mm and incinerated the binder, then placed in a magnesia porcelain container and sold for 850~
It was fired for 2 hours at a temperature in the range of 900°C. The obtained fired porcelain was cut into 1 mm thick pieces, and both sides were coated with Cr-
We deposited Au to form electrodes, and measured the relative dielectric constant, dielectric loss tangent tanδ, and their temperature changes at a temperature of 20°C.
Measured at 1KHz and 1V/mm electric field. The Curie point was defined as the temperature at which the dielectric constant was maximum. These results are shown in the table below.
【表】【table】
【表】
＊は、本発明範囲外の比較例
表において＊印を付した試料は本発明の範囲外
の試料である。本発明の範囲内の試料は、JIS規
格に定められたＹ級Ｂ特性、あるいはＹ級Ｄ特性
に定められた温度変化率を満足し、20℃の比誘電
率が1000以上を示す。組成式Pb（Zn1/3Nb2/3）ｘ
（Fe1/2Nb1/2）ｙ（Mg1/2W1/2）zO3（ただしｘ＋ｙ
＋ｚ＝１）のｘ、ｙ、ｚが図に示すＡ、Ｂ、Ｃ、
Ｄの四点を頂点とする四角形の領域外では、比誘
電率が1000以下と小さいが、温度変化がＹ級Ｄ特
性で定められた変化率より大きいか、あるいはキ
ユリー点が室温より高温側または低温側に大きく
はずれており、コンデンサ材料として不適当であ
るかの各れかであるため、本発明の範囲から除か
れる。またMnO2を0.05重量％以上、1.0重量％以
下含有させたものは、tanδが添加しない試料に比
べ大きく改善される。MnO2が1.0重量％より多く
含有させた試料は、tanδが大きくなる。
発明の効果
以上述べてきたように、本発明による誘電体磁
器組成物によれば、比誘電率の温度変化が小さ
く、また焼成温度が低いため、安価な内部電極材
料を使用した積層型セラミツクコンデンサを作成
することができるので、本発明の工業的価値は大
きい。[Table] * indicates a comparative example outside the scope of the present invention Samples marked with an asterisk (*) in the table are samples outside the scope of the present invention. A sample within the scope of the present invention satisfies the temperature change rate defined for Y class B characteristics or Y class D characteristics specified in the JIS standard, and exhibits a dielectric constant of 1000 or more at 20°C. Composition formula Pb (Zn 1/3 Nb 2/3 ) x
(Fe 1/2 Nb 1/2 ) y (Mg 1/2 W 1/2 ) zO 3 (x+y
+z=1) x, y, z are A, B, C shown in the figure,
Outside the rectangular area with the four points of D as vertices, the dielectric constant is small at 1000 or less, but the temperature change is greater than the rate of change determined by the Y-class D characteristic, or the Curie point is on the higher temperature side than room temperature. It is excluded from the scope of the present invention because it deviates significantly to the low temperature side and is unsuitable as a capacitor material. Furthermore, in the case where MnO 2 is contained in an amount of 0.05% by weight or more and not more than 1.0% by weight, tan δ is significantly improved compared to a sample not added. A sample containing more than 1.0% by weight of MnO 2 has a large tan δ. Effects of the Invention As described above, according to the dielectric ceramic composition according to the present invention, the temperature change in the dielectric constant is small and the firing temperature is low, so that multilayer ceramic capacitors using inexpensive internal electrode materials can be manufactured. The present invention has great industrial value.
図はPb（Zn1/3Nb2/3）O3―Pb（Fe1/2Nb1/2）O3―
Pb（Mg1/2W1/2）O3三元系の組成図である。
The figure shows Pb (Zn 1/3 Nb 2/3 ) O 3 - Pb (Fe 1/2 Nb 1/2 ) O 3 -
FIG. 2 is a composition diagram of a Pb(Mg 1/2 W 1/2 )O 3 ternary system.
Claims (1)
W1/2）zO3系固溶体（ただし、ｘ＋ｙ＋ｚ＝１）
の三元系の組成図において、ｘ、ｙ、ｚの値が、
下記点Ａ、Ｂ、Ｃ、Ｄを頂点とする四角形の領域
内にあることを特徴とする誘電体磁器組成物。 【表】 ２ Pb（Zn1/3Nb2/3）ｘ（Fe1/2Nb1/2）ｙ（Mg1/2
W1/2）zO3系固溶体（ただし、ｘ＋ｙ＋ｚ＝１）
の三元系の組成図において、ｘ、ｙ、ｚの値が、
下記点Ａ、Ｂ、Ｃ、Ｄを頂点とする四角形の領域
内にある組成物を主成分とし、さらに副成分とし
てMnO2を0.05〜１重量％添加含有させたことを
特徴とする誘電体磁器組成物。 【表】[Claims] 1 Pb (Zn 1/3 Nb 2/3 ) x (Fe 1/2 Nb 1/2 ) y (Mg 1/2
W 1/2 ) zO 3 solid solution (x+y+z=1)
In the composition diagram of the ternary system, the values of x, y, and z are
A dielectric ceramic composition characterized by being located within a rectangular region having the following points A, B, C, and D as vertices. [Table] 2 Pb (Zn 1/3 Nb 2/3 ) x (Fe 1/2 Nb 1/2 ) y (Mg 1/2
W 1/2 ) zO 3 solid solution (x+y+z=1)
In the composition diagram of the ternary system, the values of x, y, and z are
A dielectric porcelain whose main component is a composition located within a rectangular region with the following points A, B, C, and D as vertices, and further contains 0.05 to 1% by weight of MnO 2 as a subcomponent. Composition. 【table】
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58239227A JPS60131856A (en) | 1983-12-19 | 1983-12-19 | Dielectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58239227A JPS60131856A (en) | 1983-12-19 | 1983-12-19 | Dielectric ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60131856A JPS60131856A (en) | 1985-07-13 |
| JPH0132182B2 true JPH0132182B2 (en) | 1989-06-29 |
Family
ID=17041634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58239227A Granted JPS60131856A (en) | 1983-12-19 | 1983-12-19 | Dielectric ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60131856A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2186278A (en) * | 1986-02-08 | 1987-08-12 | Stc Plc | Ceramic capacitors and dielectric compositions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767209A (en) * | 1980-10-15 | 1982-04-23 | Nippon Electric Co | Porcelain composition |
-
1983
- 1983-12-19 JP JP58239227A patent/JPS60131856A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767209A (en) * | 1980-10-15 | 1982-04-23 | Nippon Electric Co | Porcelain composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60131856A (en) | 1985-07-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |