JPS6238316B2 - - Google Patents
Info
- Publication number
- JPS6238316B2 JPS6238316B2 JP57071789A JP7178982A JPS6238316B2 JP S6238316 B2 JPS6238316 B2 JP S6238316B2 JP 57071789 A JP57071789 A JP 57071789A JP 7178982 A JP7178982 A JP 7178982A JP S6238316 B2 JPS6238316 B2 JP S6238316B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- dielectric constant
- tio
- high dielectric
- capacitance
- 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 31
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Description
本発明は高誘電率磁器組成物に関する。
高誘電率磁器組成物としては、チタン酸バリウ
ムを主体とし、これにスズ酸塩、ジルコン酸塩あ
るいは他のチタン酸塩等を固溶させたものが広く
実用に供されている。しかしながら、この系の磁
器材料は、誘電率が高い組成にすると容量温度特
性が悪化するばかりでなく、容量の電圧依存性が
著しく大きくなる傾向があり、これらのことがコ
ンデンサ材料として用いる場合の大きな問題とな
つていた。しかも、この系の磁器はその焼成に
1300〜1400℃という高い温度を必要とするため焼
成コストが高く、さらに積層コンデンサに適用す
る場合には内部電極材料として高価なパラジウム
や白金を用いざるを得ず、コンデンサのコストダ
ウンを計ることができないという問題があつた。
このような問題を解決するため、Pb（Ni〓Nb
〓）O3―PbTiO3―Pb（Co〓Ｗ〓）O3からなる
高誘電率磁器組成物が提案されている。この三成
分系磁器組成物はチタン酸バリウム系のものに比
して、焼結性、誘電率、容量温度依存性および電
圧依存性において格段に優れてはいるが、未だ容
量温度特性等の点で十分満足しうるものとは言い
難いのが現状である。
本発明は、このような問題に鑑みてなされたも
のであつた、容量温度特性および絶縁抵抗を向上
させた高誘電率磁器組成物を提供することを目的
とし、その要旨は、一般式：
xPb（Ni〓Nb〓）O3―yPbTiO3
―zPb（Co〓Ｗ〓）O3
（但し、式中ｘ、ｙ、ｚは各成分のモル分率を表
わし、ｘ＋ｙ＋ｚ＝1.00）で表わされ、かつ第１
図に示される下記組成の点Ａ，Ｂ，Ｃ，Ｄを頂点
とする多角形ABCDで囲まれた範囲内の組成（但
し、AD線上の組成を除く）を有する三成分系組
成物を主成分とし、副成分としてBi2O30.50〜
5.0wt％とTiO20.05〜2.5wt％を含み、かつTiO2
とBi2O3のモル比（TiO2／Bi2O3）が0.5〜３である
ことを特徴とする高誘電率磁器組成物、にある。
前記多角形ABCDの各頂点における各成分のモル
分率は次の通りである。
ｘ ｙ ｚ
Ａ 0.77 0.23 0.00
Ｂ 0.37 0.35 0.28
Ｃ 0.33 0.43 0.24
Ｄ 0.67 0.33 0.00
本発明に係る高誘電率磁器組成物の組成を前記
のように限定したのは次の理由による。主成分の
組成範囲を多角形ABCDの範囲内に限定したの
は、組成がAB線より外側では、キユリー点が低
温側に下がりすぎて、容量温度変化率が悪化し、
BC線より外側では、常温での誘電率が下がりす
ぎて実用上好ましくなく、CD線より外側では、
キユリー点が高温側に上がりすぎて、容量変化率
が悪化するからである。副成分のBi2O3が0.50wt
％未満では、誘電率は高くなるものの容量温度特
性の平坦化および比抵抗を向上させる効果が充分
に得られず、5.0wt％を超えると誘電率の低下お
よび誘電正接の上昇が著しいことからBi2O3は
0.50〜5.0wt％とした。TiO2を0.05〜2.5wt％とし
たのは、0.05wt％より少ないと誘電率の低下およ
び誘電正接の上昇が著しく、また、2.5wt％より
多いと誘電率の低下および誘電正接の上昇の他、
−25℃における容量温度変化率が大きくなるから
である。また、TiO2とBi2O3のモル比TiO2／
Bi2O3を0.5〜３としたのは、0.5より小さいと誘
電率の低下および誘電正接の上昇が著しく、３よ
り大きいとそれらに加えて−25℃における容量温
度変化率も大きくなるからである。
本発明に係る前記組成の高誘電率磁器組成物
は、誘電率が高いにもかかわらず、容量温度特性
において従来のチタン酸バリウム系のものに比べ
て著しく優れ、JISに規定されるＤ特性を満足
し、また高い比抵抗値を示す。しかも、本発明に
係る高誘電率磁器組成物は約900〜1100℃と従来
のものに比べて低い温度で焼結させることができ
るので、焼成コストを低下させることができるだ
けでなく、積層コンデンサを製造する場合に内部
電極材料として従来のPbやPtに比べてはるかに
安価な銀系合金、例えば、Ag―Pd合金、Ag―Pt
合金などを使用でき、コンデンサのコストダウン
を計ることができるなど、優れた効果を奏する。
次に、本発明の実施例について説明する。
原料としてPbO、NiO、Nb2O5、TiO2、
CoCO3、WO3およびBi2O3を用い、これらを第１
表に示す組成割合になるように秤量し、メノウ石
を用いたボールミルにて５〜20時間湿式混合し
た。得られた各混合物を脱水、乾燥後、650〜800
℃で２時間保持して仮焼し、再びボールミルにて
粉砕した。得られた粉末をバインダとしてのポリ
ビニルアルコール３重量％（wt％）と混練し、
造粒した後、2000Kg／cm2の圧力で直径15mm、厚さ
１mmの円板に成形した。この円板を電気炉にて鉛
範囲気中900〜1100℃で２時間焼成して磁器を得
た。
得られた磁器円板の両面に銀電極を焼付けてコ
ンデンサとなし、その誘電率（ε）、誘電正接
（tan δ）、容量温度特性および比抵抗（ρ）を
測定した。その結果を第２表に示す。
なお、εおよびtan δは温度20℃、周波数
1KHzで測定し、容量温度特性については、20℃
での容量を基準とし、−25℃および＋85℃での容
量の変化率を求めた。また、比抵抗は20℃で試料
に500V／mmの直流電圧を印加し、１分後の電流
値から計算により求めた。
表中、〓は本発明の範囲外の組成の磁器を示
す。
The present invention relates to high dielectric constant ceramic compositions. As high dielectric constant ceramic compositions, compositions containing barium titanate as a main ingredient, in which stannate, zirconate, or other titanate, etc. are dissolved, are widely used in practical use. However, when this type of ceramic material has a composition with a high dielectric constant, not only does the capacitance temperature characteristic deteriorate, but also the voltage dependence of the capacitance tends to become significantly large. It was becoming a problem. Moreover, this type of porcelain is fired
Because it requires a high temperature of 1300 to 1400℃, the firing cost is high, and when applied to multilayer capacitors, expensive palladium or platinum must be used as internal electrode materials, making it difficult to reduce the cost of capacitors. The problem was that I couldn't do it.
To solve this problem, Pb(Ni〓Nb
A high dielectric constant ceramic composition consisting of 〓)O 3 --PbTiO 3 --Pb(Co〓W〓)O 3 has been proposed. Although this ternary ceramic composition is significantly superior to barium titanate-based compositions in terms of sinterability, dielectric constant, capacitance temperature dependence, and voltage dependence, it still has problems such as capacitance temperature characteristics. At present, it is difficult to say that this is completely satisfactory. The present invention was made in view of such problems, and aims to provide a high dielectric constant ceramic composition with improved capacitance-temperature characteristics and insulation resistance. (Ni〓Nb〓)O 3 -yPbTiO 3 -zPb(Co〓W〓)O 3 (where x, y, z represent the mole fraction of each component, x+y+z=1.00), and the first
The main component is a ternary composition having a composition within the range surrounded by the polygon ABCD whose vertices are points A, B, C, and D of the following composition shown in the figure (excluding the composition on the AD line). and Bi 2 O 3 as a subcomponent from 0.50 to
5.0wt% and TiO2 0.05~2.5wt%, and TiO2
and Bi 2 O 3 molar ratio (TiO 2 /Bi 2 O 3 ) of 0.5 to 3.
The mole fraction of each component at each vertex of the polygon ABCD is as follows. x y z A 0.77 0.23 0.00 B 0.37 0.35 0.28 C 0.33 0.43 0.24 D 0.67 0.33 0.00 The reason why the composition of the high dielectric constant ceramic composition according to the present invention is limited as described above is as follows. The reason why the composition range of the main components is limited to the range of polygon ABCD is that if the composition is outside the line AB, the Curie point will drop too much to the low temperature side, and the rate of change in capacity with temperature will deteriorate.
Outside the BC line, the dielectric constant at room temperature decreases too much, which is not practical, and outside the CD line,
This is because the Curie point rises too high to the high temperature side and the rate of change in capacity deteriorates. Sub-component Bi 2 O 3 is 0.50wt
Bi 2 O 3 is
The content was set at 0.50-5.0wt%. The reason for setting TiO 2 to 0.05 to 2.5wt% is that if it is less than 0.05wt%, the dielectric constant will decrease significantly and the dielectric loss tangent will increase, and if it is more than 2.5wt%, the dielectric constant will decrease and the dielectric loss tangent will increase. ,
This is because the capacitance temperature change rate at −25° C. increases. Also, the molar ratio of TiO 2 and Bi 2 O 3 is TiO 2 /
The reason why Bi 2 O 3 is set to 0.5 to 3 is because if it is smaller than 0.5, the dielectric constant will drop significantly and the dielectric loss tangent will rise, and if it is larger than 3, the capacitance temperature change rate at -25℃ will also increase. be. Although the high dielectric constant ceramic composition of the present invention has a high dielectric constant, it has significantly superior capacitance-temperature characteristics compared to conventional barium titanate-based materials, and has the D characteristic specified by JIS. Satisfied, and also shows a high specific resistance value. Moreover, the high dielectric constant ceramic composition according to the present invention can be sintered at a temperature of approximately 900 to 1100°C, which is lower than that of conventional compositions. When manufacturing, silver-based alloys, which are much cheaper than conventional Pb and Pt, are used as internal electrode materials, such as Ag-Pd alloys and Ag-Pt.
It has excellent effects such as being able to use alloys and reducing the cost of capacitors. Next, examples of the present invention will be described. PbO, NiO, Nb 2 O 5 , TiO 2 as raw materials,
Using CoCO 3 , WO 3 and Bi 2 O 3 , these were
The compositions were weighed so as to have the composition ratios shown in the table, and wet mixed in a ball mill using agate for 5 to 20 hours. After dehydrating and drying each mixture obtained, 650-800
The mixture was kept at ℃ for 2 hours to be calcined, and then ground again using a ball mill. The obtained powder was kneaded with 3% by weight (wt%) of polyvinyl alcohol as a binder,
After granulation, it was molded into a disk with a diameter of 15 mm and a thickness of 1 mm under a pressure of 2000 Kg/cm 2 . This disk was fired in an electric furnace at 900 to 1100° C. for 2 hours in a lead atmosphere to obtain porcelain. A capacitor was prepared by baking silver electrodes on both sides of the resulting porcelain disk, and its dielectric constant (ε), dielectric loss tangent (tan δ), capacitance-temperature characteristics, and specific resistance (ρ) were measured. The results are shown in Table 2. Note that ε and tan δ are at a temperature of 20℃ and a frequency of
Measured at 1KHz, 20℃ for capacitance temperature characteristics
Based on the capacity at -25°C and +85°C, the rate of change in capacity was determined. Further, the specific resistance was determined by applying a DC voltage of 500 V/mm to the sample at 20° C. and calculating from the current value after 1 minute. In the table, 〓 indicates porcelain whose composition is outside the scope of the present invention.
【表】【table】
【表】【table】
【表】【table】
【表】
第２表に示す結果から明らかなように、本発明
に係る磁気は誘電率が約6800以上と著しく高いに
もかかわらず、静電容量変化率は−30％以下で
JISに規定するＤ特性を満足し、また比抵抗も
1013Ωcm以上の高い値を示す他、1100℃以下の温
度で焼結させることができる。[Table] As is clear from the results shown in Table 2, although the magnet according to the present invention has a significantly high dielectric constant of about 6800 or more, the capacitance change rate is -30% or less.
It satisfies the D characteristics stipulated by JIS and also has specific resistance.
In addition to exhibiting a high value of over 10 13 Ωcm, it can be sintered at temperatures below 1100°C.
図は本発明に係る高誘電率磁器組成物の主成分
の組成範囲を示す三角図である。
The figure is a triangular diagram showing the composition range of the main components of the high dielectric constant ceramic composition according to the present invention.
Claims (1)
わし、ｘ＋ｙ＋ｚ＝1.00）で表わされ、かつ第１
図に示される下記組成の点Ａ，Ｂ，Ｃ，Ｄを頂点
とする多角形ABCDで囲まれた範囲内の組成（但
し、AD線上の組成を除く）を有する三成分系組
成物を主成分とし、副成分としてBi2O30.50〜
5.0wt％と、TiO20.05〜2.5wt％を含み、かつ
TiO2とBi2O3のモル比（TiO2／Bi2O3）が0.5〜３
であることを特徴とする高誘電率磁器組成物。 ｘ ｙ ｚ Ａ 0.77 0.23 0.00 Ｂ 0.37 0.35 0.28 Ｃ 0.33 0.43 0.24 Ｄ 0.67 0.33 0.00[Claims] 1 General formula: xPb(Ni〓Nb〓)O 3 -yPbTiO 3 -zPb(Co〓W〓)O 3 (wherein x, y, and z represent the mole fraction of each component. x + y + z = 1.00), and the first
The main component is a ternary composition having a composition within the range surrounded by the polygon ABCD whose vertices are points A, B, C, and D of the following composition shown in the figure (excluding the composition on the AD line). and Bi 2 O 3 0.50 ~ as a subcomponent
5.0wt% and TiO 2 0.05-2.5wt%, and
The molar ratio of TiO 2 and Bi 2 O 3 (TiO 2 /Bi 2 O 3 ) is 0.5 to 3
A high dielectric constant ceramic composition characterized by: x y z A 0.77 0.23 0.00 B 0.37 0.35 0.28 C 0.33 0.43 0.24 D 0.67 0.33 0.00
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57071789A JPS58190870A (en) | 1982-04-27 | 1982-04-27 | High dielectric constant ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57071789A JPS58190870A (en) | 1982-04-27 | 1982-04-27 | High dielectric constant ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58190870A JPS58190870A (en) | 1983-11-07 |
| JPS6238316B2 true JPS6238316B2 (en) | 1987-08-17 |
Family
ID=13470688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57071789A Granted JPS58190870A (en) | 1982-04-27 | 1982-04-27 | High dielectric constant ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58190870A (en) |
-
1982
- 1982-04-27 JP JP57071789A patent/JPS58190870A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58190870A (en) | 1983-11-07 |
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