JPS6117085B2 - - Google Patents
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- Publication number
- JPS6117085B2 JPS6117085B2 JP59004440A JP444084A JPS6117085B2 JP S6117085 B2 JPS6117085 B2 JP S6117085B2 JP 59004440 A JP59004440 A JP 59004440A JP 444084 A JP444084 A JP 444084A JP S6117085 B2 JPS6117085 B2 JP S6117085B2
- Authority
- JP
- Japan
- Prior art keywords
- samples
- temperature
- series resistance
- sample
- equivalent series
- 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
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- 239000000203 mixture Substances 0.000 claims description 22
- 239000000919 ceramic Substances 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000003985 ceramic capacitor Substances 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004014 plasticizer Substances 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
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
Description
〔発明の分野〕
この発明は、温度補償用磁器コンデンサの誘電
材料として使用される誘電磁器組成物に関するも
のである。
〔発明の背景及び従来技術〕
電子チユーナ等の電子機器に使用されるチツプ
形磁器コンデンサは、等価直列抵抗ESRができ
る限り小さいことが望まれている。
ところが、例えばLa2O3−CaO−TiO2系，ZnO
−TiO2系，MgO2−TiO2系等、従来の磁器組成物
を誘電体とするチツプ形円筒磁器コンデンサで、
外径1.6mm、内径1.3mm、長さ3.2mmのものでは、上
記等価直列抵抗ESRが約110ｍΩと高かつた。こ
うしたことから、上記ESRが110ｍΩより低い素
子を得ることのできる磁器組成物の開発が要請さ
れている。
〔発明の目的〕
この発明は、上記の要請を満たすべくなされた
ものであつて、従来のものに比べて等価直列抵抗
ESRの低い素子を得ることができる誘電体磁器
組成物を提供するものである。
〔発明の概要〕
第一の発明の誘電体磁器組成物は、xZrO2・
（１−ｘ）CeO2・TiO2（但し、0.8≦ｘ≦0.99）
からなるものである。また第二の発明の誘電体磁
器組成物は、xZrO2・（１−ｘ）CeO2・TiO2（但
し、0.8≦ｘ≦0.99）からなる成分100重量部と、
MnO2，Cr2O3，La2O3，Al2O3の何れか一種以上
のからなる成分が0.05〜1.0重量部からなるもの
である。
磁器組成物の成分及びその組成比をそれぞれ上
記のように選択した理由は、前掲の円筒チツプ形
磁器コンデンサにおいて、等価直列抵抗ESRが
100ｍΩ以下、静電容量の温度特性TCが±０（Ｃ
特性）〜−80（Ｌ特性）ppm／℃でその許容差
が±60（Ｈ特性）ppm／℃以内の特性を得るた
めである。換言すると各成分が上記の範囲外にあ
ると、これら目標値を得ることができないことに
よる。なお、上記温度TCは、JIS C6423で規定
されたHH，LH，CHの特性を満足するものであ
る。
〔実施例〕
次ぎに、この発明の実施例を説明する。
（実施例 １）
この実施例では、第一の発明による磁器組成
物を使用して試料を作製した。先ずこの作製方
法について説明すると、最初に純度99％の
TiO2粉末を38.59ｇ（50mol％相当）、純度99％
のZrO2粉末を54.75ｇ（46mol％相当）、純度99
％のCeO2粉末を6.65ｇ（4mol％相当）宛秤量
し、これらをボールミルでアルコールと共に約
20時間混合撹拌した。
次いでこの混合物を乾燥した後、大気中にお
いて1100℃の温度で仮焼きし、再度混合粉砕し
た。この粉末にバンイダーとしてポリビニルア
ルコール8wt％、水及び可塑材を加えて混練
し、これから押出法により外径2.0mm、内径
1.63mmのチユーブを成形した。さらにこれを長
さ4.0mm毎に切断し、円筒体を得た。
次ぎに、この円筒体をアルミナ製の匣の中に
入れ、1380℃の温度で約２時間焼成し、焼結さ
せた。以上の工程によりxZrO2・（１−ｘ）
CeO2・TiO2からなる組成式において、ｘ＝
0.96の磁器組成物が得られた。焼結後の円筒体
は、外径1.6mm、内径1.3mm、長さ3.2mmであつ
た。この円筒体の内周、外周及び端面に硼珪酸
鉛を１重量部含む銀ペーストを塗布し、これを
800℃の温度で10分間加熱して焼付け、上記円
筒体を挾んで互いに対向する一対の銀電極を設
けた。
こうして得られた円筒チツプ形磁器コンデン
サ20個を試料３とし、これについて比誘電率
ε，等価直列抵抗ESR（ｍΩ）及び静電容量
の温度特性TC（ppm／℃）を測定し、この結
果を表１に示した。なお、上記温度特性TCに
ついては、JIS C6423に規定された特性CH，
HH，LHの内、どれを満足するかを示した。
上記誘電率εについては、20℃、1MHzにお
ける静電容量を横河ヒユーレツトパツカード社
製4192A型インピーダンスアナライザにより、
測定し、この結果から計算により求め、平均値
を示した。等価直列抵抗ESRについては、共
振時約470MHzにおける値を横河ヒユーレツト
パツカード製4191A型インピーダンスアナライ
ザにより測定し、やはり平均値を示した。また
静電容量の温度特性TCにいては、JIS C5102
に基づき、横河ヒユーレツトパツカード社製
4192A型インピーダンスアナライザにより測定
した静電容量をもとに計算で求めた。
この他の試料についてもそれぞれ表１に示す
ような組成の磁器組成物を使用して上記と同じ
方法及び条件で同形の試料を作製し、こられに
ついて試験を行い、その結果を同表に示した。
但し、焼結温度は、各試料毎にそれぞれ異なり
るが、何れも1400℃前後の温度であつた。
この結果から明らかな通り、第一の発明によ
る実施例では、等価直列抵抗ESRが80〜98ｍ
Ωと何れも100ｍΩより低い値であつた。また
比誘電率εも38.2〜43.0と高く、静電容量の温
度係数TCも全ての試料が上記CH，HH，LHの
特性を満足するものであつた。
これに対してｘが0.8未満の磁器組成物を使
用して同様に作製した上記と同形の試料では、
等価直列抵抗ESRが100ｍΩ以上であり、また
ｘが0.9を越えるものを用いて作製した試料も
やはり同ESRが100ｍΩを越えた。
（実施例 ２）
次に第二の発明による実施例について説明す
ると、この実施例では、それぞれ表２で示す組
成を有する磁器組成物を用いて上記実施例１と
同様の方法及び条件で同形の試料を作製し、こ
れらについて同実施例１と同じ方法、条件によ
り特性試験を行い、この結果を表２に示した。
この結果から明らかな通り、この実施例で
は、等価直列抵抗ESRが69〜95ｍΩであつ
た。特に試料１と試料５〜11、試料２と試料12
〜20、試料４と試料21〜26といつたように、上
記実施例１の対応する試料と比較すると、この
実施例における試料は、実施例１における試料
より等価直列抵抗ESRが低く、この点の改良
が見られる。
また、この実施例では、比誘電率εが38.2〜
42.9の範囲にあり、また静電容量の温度特性
TCも、全ての試料がCH，HH，LHの特性を満
足している。
これに対してMnO2，Cr2O3，La2O3，Al2O3
の何れか一種以上のものからなる成分が
xZrO2・（１−ｘ）CeO2・TiO2からなる成分
100重量部に対して0.05重量部末満である磁器
組成物を用いて作製した上記と同形の試料で
は、上記成分の含有効果が充分得られなかつ
た。また逆に上記成分が0.5重量部を越えるも
のを用いて作製した試料では、静電容量の温度
特性TCが何れも上記特性を満足しなかつた。
なお、前掲の各実施例では、便宜上磁器組成物
をこれから作製した円筒チツプ形磁器コンデンサ
の特性により評価したが、この発明は、これ以外
の素子、例えば円板形磁器コンデンサ、積層磁器
コンデンサ等にも適用することができる。
〔発明の効果〕
以上のようにこの発明による磁器組成物から
は、前掲の円筒チツプ形磁器コンデンサにおい
て、比誘電率εが38.2〜43.0、静電容量の温度係
数TCがJIS C6423で規定されたHH，LH，CHの
特性を満足する誘電体が得られた。また特に等価
直列抵抗ESRについては、69〜98ｍΩと従来の
磁器組成物から作製されたものに比べて低く、優
れた特性が得られた。
[Field of the Invention] This invention relates to a dielectric ceramic composition used as a dielectric material for a temperature-compensating ceramic capacitor. [Background of the Invention and Prior Art] Chip-type ceramic capacitors used in electronic devices such as electronic tuners are desired to have an equivalent series resistance ESR as small as possible. However, for example, La 2 O 3 −CaO−TiO 2 system, ZnO
A chip-shaped cylindrical ceramic capacitor whose dielectric is a conventional ceramic composition such as −TiO 2 system, MgO 2 −TiO 2 system, etc.
For the one with an outer diameter of 1.6 mm, an inner diameter of 1.3 mm, and a length of 3.2 mm, the equivalent series resistance ESR was as high as about 110 mΩ. For these reasons, there is a demand for the development of a ceramic composition that can provide an element with an ESR lower than 110 mΩ. [Object of the Invention] The present invention has been made to meet the above requirements, and has a lower equivalent series resistance than conventional ones.
The object of the present invention is to provide a dielectric ceramic composition capable of obtaining an element with low ESR. [Summary of the invention] The dielectric ceramic composition of the first invention comprises xZrO 2 .
(1-x) CeO2・TiO2 (however, 0.8≦x≦0.99)
It consists of Further, the dielectric ceramic composition of the second invention contains 100 parts by weight of a component consisting of xZrO 2 .(1-x)CeO 2 .TiO 2 (0.8≦x≦0.99);
The component consisting of one or more of MnO 2 , Cr 2 O 3 , La 2 O 3 , and Al 2 O 3 is 0.05 to 1.0 parts by weight. The reason why the components of the ceramic composition and their composition ratios were selected as described above is that the equivalent series resistance ESR is
100 mΩ or less, temperature characteristic of capacitance TC is ±0 (C
This is to obtain characteristics whose tolerance is within ±60 (H characteristics) ppm/° C. from −80 (L characteristics) ppm/° C. In other words, if each component is outside the above range, these target values cannot be obtained. Note that the above temperature TC satisfies the characteristics of HH, LH, and CH specified in JIS C6423. [Example] Next, an example of the present invention will be described. (Example 1) In this example, a sample was prepared using the porcelain composition according to the first invention. First of all, to explain this production method, first, we will start with a 99% pure
38.59g TiO 2 powder (equivalent to 50mol%), purity 99%
54.75g (equivalent to 46mol%) of ZrO 2 powder, purity 99
% CeO 2 powder was weighed to 6.65 g (equivalent to 4 mol%) and mixed with alcohol in a ball mill.
The mixture was mixed and stirred for 20 hours. Next, this mixture was dried, calcined in the air at a temperature of 1100°C, and mixed and ground again. To this powder, 8wt% polyvinyl alcohol as a binder, water and a plasticizer were added and kneaded, and then extruded to create a powder with an outer diameter of 2.0 mm and an inner diameter of 2.0 mm.
A 1.63mm tube was molded. Further, this was cut into lengths of 4.0 mm to obtain cylindrical bodies. Next, this cylindrical body was placed in an alumina box and fired at a temperature of 1380°C for about 2 hours to sinter it. Through the above steps, xZrO 2・(1−x)
In the composition formula consisting of CeO 2 and TiO 2 , x=
A porcelain composition of 0.96 was obtained. The cylindrical body after sintering had an outer diameter of 1.6 mm, an inner diameter of 1.3 mm, and a length of 3.2 mm. A silver paste containing 1 part by weight of lead borosilicate is applied to the inner periphery, outer periphery, and end face of this cylindrical body.
The cylindrical body was baked by heating for 10 minutes at a temperature of 800°C, and a pair of silver electrodes were provided sandwiching the cylindrical body and facing each other. Twenty cylindrical chip-shaped ceramic capacitors thus obtained were used as sample 3, and the relative dielectric constant ε, equivalent series resistance ESR (mΩ), and temperature characteristic of capacitance TC (ppm/℃) were measured, and the results were It is shown in Table 1. The above temperature characteristics TC are based on the characteristics CH and CH specified in JIS C6423.
We have shown which of HH and LH is satisfied. Regarding the above dielectric constant ε, the capacitance at 20°C and 1MHz was measured using an impedance analyzer model 4192A manufactured by Yokogawa Heuretsu Pat Card Co., Ltd.
It was measured and calculated from the results, and the average value is shown. Regarding the equivalent series resistance ESR, the value at approximately 470 MHz during resonance was measured using an impedance analyzer model 4191A manufactured by Yokogawa Huretsu Pack Card, and the average value was also shown. In addition, regarding temperature characteristics TC of capacitance, JIS C5102
Manufactured by Yokogawa Heuretsu Pats Card Co., Ltd. based on
It was calculated based on the capacitance measured with a 4192A impedance analyzer. For other samples, samples of the same shape were prepared using the same method and conditions as above using the porcelain compositions shown in Table 1, and tests were conducted on these samples, and the results are shown in the same table. Ta.
However, although the sintering temperature differed for each sample, it was around 1400°C in all cases. As is clear from this result, in the embodiment according to the first invention, the equivalent series resistance ESR is 80 to 98 m.
Ω and both values were lower than 100 mΩ. In addition, the relative dielectric constant ε was high at 38.2 to 43.0, and the temperature coefficient TC of capacitance was such that all samples satisfied the above-mentioned characteristics of CH, HH, and LH. On the other hand, in a sample of the same shape as above, prepared in the same way using a porcelain composition with x less than 0.8,
The equivalent series resistance ESR was 100 mΩ or more, and the sample prepared using a material with x exceeding 0.9 also had an ESR of over 100 mΩ. (Example 2) Next, an example according to the second invention will be described. In this example, porcelain compositions having the compositions shown in Table 2 were used, and the same shape was prepared in the same manner and under the same conditions as in Example 1. Samples were prepared and characteristic tests were conducted on them using the same method and conditions as in Example 1, and the results are shown in Table 2. As is clear from the results, in this example, the equivalent series resistance ESR was 69 to 95 mΩ. Especially sample 1, samples 5 to 11, sample 2 and sample 12
~20, Sample 4 and Samples 21 to 26, when compared with the corresponding samples of Example 1 above, the samples in this Example have lower equivalent series resistance ESR than the samples in Example 1, and this point is Improvements can be seen. In addition, in this example, the relative dielectric constant ε is 38.2~
42.9, and the temperature characteristics of capacitance
Regarding TC, all samples satisfied the characteristics of CH, HH, and LH. On the other hand, MnO 2 , Cr 2 O 3 , La 2 O 3 , Al 2 O 3
A component consisting of one or more of
Component consisting of xZrO 2・(1-x)CeO 2・TiO 2
In a sample of the same type as above prepared using a ceramic composition containing less than 0.05 parts by weight per 100 parts by weight, the effect of containing the above components could not be sufficiently obtained. On the other hand, in the samples prepared using more than 0.5 parts by weight of the above components, none of the capacitance temperature characteristics TC satisfied the above characteristics. In each of the above-mentioned examples, for convenience, the ceramic composition was evaluated based on the characteristics of a cylindrical chip-shaped ceramic capacitor manufactured from it, but the present invention can be applied to other elements such as a disk-shaped ceramic capacitor, a laminated ceramic capacitor, etc. can also be applied. [Effects of the Invention] As described above, the ceramic composition according to the present invention has a relative dielectric constant ε of 38.2 to 43.0 and a capacitance temperature coefficient TC specified by JIS C6423 in the above-mentioned cylindrical chip type ceramic capacitor. A dielectric material satisfying the characteristics of HH, LH, and CH was obtained. In particular, the equivalent series resistance ESR was 69 to 98 mΩ, which was lower than those made from conventional ceramic compositions, and excellent characteristics were obtained.
【表】【table】
【表】【table】
Claims (1)
≦ｘ≦0.99）からなることを特徴とする誘電体磁
器組成物。 ２ xZrO2・（１−ｘ）CeO2・TiO2（但し、0.8
≦ｘ≦0.99）かからなる成分100重量部と、
MnO2，Cr2O3，La2O3，Al2O3の何れか一種以上
のものからなる成分が0.05〜1.0重量部からなる
ことを特徴とする誘電体磁器組成物。[Claims] 1 xZrO 2・(1−x)CeO 2・TiO 2 (however, 0.8
≦x≦0.99). 2 xZrO 2・(1−x)CeO 2・TiO 2 (However, 0.8
≦x≦0.99) and 100 parts by weight of the component,
A dielectric ceramic composition comprising 0.05 to 1.0 parts by weight of one or more of MnO 2 , Cr 2 O 3 , La 2 O 3 , and Al 2 O 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59004440A JPS60148006A (en) | 1984-01-13 | 1984-01-13 | Dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59004440A JPS60148006A (en) | 1984-01-13 | 1984-01-13 | Dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60148006A JPS60148006A (en) | 1985-08-05 |
| JPS6117085B2 true JPS6117085B2 (en) | 1986-05-06 |
Family
ID=11584272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59004440A Granted JPS60148006A (en) | 1984-01-13 | 1984-01-13 | Dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60148006A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04274107A (en) * | 1991-02-28 | 1992-09-30 | Taiyo Yuden Co Ltd | Manufacture of dielectric porcelain |
-
1984
- 1984-01-13 JP JP59004440A patent/JPS60148006A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60148006A (en) | 1985-08-05 |
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