JP2694209B2 - High dielectric constant porcelain composition - Google Patents
High dielectric constant porcelain compositionInfo
- Publication number
- JP2694209B2 JP2694209B2 JP63159251A JP15925188A JP2694209B2 JP 2694209 B2 JP2694209 B2 JP 2694209B2 JP 63159251 A JP63159251 A JP 63159251A JP 15925188 A JP15925188 A JP 15925188A JP 2694209 B2 JP2694209 B2 JP 2694209B2
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- mol
- composition
- batio
- 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 - Lifetime
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、磁器コンデンサ等に使用されるBaTiO3−Nb
2O5−Y2O3系高誘電率磁器組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is directed to BaTiO 3 —Nb used in porcelain capacitors and the like.
The present invention relates to a 2 O 5 —Y 2 O 3 -based high dielectric constant porcelain composition.
従来の誘電体磁器組成物として、例えばBaTiO3−BaZr
O3−BaSnO3−CaTiO3系の組成物がJIS・Ｆ特性用として
実用化されている。As a conventional dielectric ceramic composition, for example, BaTiO 3 --BaZr
O 3 -BaSnO 3 -CaTiO 3 based compositions have been practically used for the JIS · F characteristics.
上記組成物は誘電率が高く、温度特性も良好であると
いう長所を有しているものの、結晶粒径が10〜20μｍと
大きく、積層コンデンサを作成した場合にデラミネーシ
ョンを起こすためその歩留りが悪く、また破壊電圧も低
いため薄層化が困難であるという欠点があった。Although the above composition has the advantages that it has a high dielectric constant and good temperature characteristics, its crystal grain size is as large as 10 to 20 μm, and its yield is poor because delamination occurs when a multilayer capacitor is created. Also, there is a drawback that it is difficult to reduce the thickness because the breakdown voltage is low.
本発明者らは、上記欠点のない誘電体磁器組成物を得
るため鋭意研究を行った結果、BaTiO3−Nb2O5−Y2O3の
混合組成物に酸化セリウム（CeO2）及び酸化マンガン
（MnO）を添加することによって誘電率が高く、温度特
性も良好であり、しかも結晶粒径が５μｍ以下と微細化
した組成物が得られることを見い出し、本発明に到達し
たものである。The inventors of the present invention have conducted extensive studies to obtain a dielectric ceramic composition without the above-mentioned defects. As a result, a mixed composition of BaTiO 3 —Nb 2 O 5 —Y 2 O 3 has cerium oxide (CeO 2 ) and an oxide. The present invention has been completed by discovering that the addition of manganese (MnO) makes it possible to obtain a composition having a high dielectric constant, good temperature characteristics, and a fine crystal grain size of 5 μm or less.
〔課題を解決するための手段〕 本発明は、チタン酸バリウムBaTiO397.0〜98.25モル
％、五酸化ニオブNb2O50.75〜1.50モル％及び酸化イッ
トリウムY2O30.50〜2.00モル％を主成分としてなる組成
物100モル％に対して副成分として酸化セリウムCeO20.2
〜0.8重量％及び酸化マンガンMnO0.01〜0.3重量％を添
加含有したことを特徴とするBaTiO3−Nb2O5−Y2O3系高
誘電率磁器組成物である。[Means for Solving the Problems] The present invention mainly comprises barium titanate BaTiO 3 97.0 to 98.25 mol%, niobium pentoxide Nb 2 O 5 0.75 to 1.50 mol% and yttrium oxide Y 2 O 3 0.50 to 2.00 mol%. Cerium oxide CeO 2 0.2 as an auxiliary component to 100 mol% of the composition
The present invention is a BaTiO 3 —Nb 2 O 5 —Y 2 O 3 -based high-dielectric-constant porcelain composition characterized by containing 0.8 to 0.8% by weight and 0.01 to 0.3% by weight of manganese oxide MnO.
出発原料として炭酸バリウム（BaCO3）、酸化チタン
（TiO2）、五酸化ニオブ（Nb2O5）、酸化イットリウム
（Y2O3）、酸化セリウム（CeO2）及び炭酸マンガン（Mn
CO3）を用い、まず等モル比のBaCO3とTiO2にMnCO3を添
加して混合し、これを仮プレス後1100℃〜1200℃で２時
間安定で仮焼してBaTiO3を作成した。Barium carbonate (BaCO 3 ), titanium oxide (TiO 2 ), niobium pentoxide (Nb 2 O 5 ), yttrium oxide (Y 2 O 3 ), cerium oxide (CeO 2 ) and manganese carbonate (Mn) are used as starting materials.
(CO 3 ), first, MnCO 3 was added to and mixed with BaCO 3 and TiO 2 in an equimolar ratio, and this was calcined stably at 1100 to 1200 ° C for 2 hours to prepare BaTiO 3 . .
次いで、このBaTiO3を粉砕して微粉末とし第１表に示
す組成比で秤量後、ポットミル中で湿式混合し、脱水・
乾燥したのちポリビニルアルコール（PVA）をバインダ
ーとして加えて顆粒にし、これを約3ton/cm2の成形圧力
で直径16.5φmm、厚さ0.6mmの円板状成形物を作成し
た。さらに、この成形物を空気中で1280℃〜1360℃で２
時間安定して焼成した。Next, this BaTiO 3 was pulverized into a fine powder, weighed at the composition ratio shown in Table 1, wet-mixed in a pot mill, and dehydrated.
After drying, polyvinyl alcohol (PVA) was added as a binder to form granules, which were molded under a molding pressure of about 3 ton / cm 2 to prepare a disk-shaped molded product having a diameter of 16.5 mm and a thickness of 0.6 mm. Furthermore, this molded product is heated in air at 1280 ° C to 1360 ° C for 2
Sintered for a stable time.
このようにして得られた磁器素体に銀電極を焼付けて
試料とし、この試料について電気特性を測定した。結果
は第１表に示したとおりである。A silver electrode was baked on the thus obtained porcelain body to prepare a sample, and the electrical characteristics of this sample were measured. The results are as shown in Table 1.
ここで誘電率εｓおよび誘電体損失tanδ（％）は室
温20℃、周波数1kHzで測定した。また、温度特性すなわ
ち温度変化率（T.C）は＋20℃を基準とし、−25℃〜＋8
5℃の誘電率温度変化率（％）として求めた。Here, the dielectric constant ε s and the dielectric loss tan δ (%) were measured at room temperature of 20 ° C. and a frequency of 1 kHz. In addition, the temperature characteristics, that is, the temperature change rate (TC) is -25 ℃ to +8 with reference to + 20 ℃.
It was determined as the temperature change rate (%) of the dielectric constant at 5 ° C.
第１表において○印を付した試料番号は本発明の範囲
内のものであり、試料番号1,2,5,8,10,13,14,15,19,20,
21及び24は本発明の範囲外である。 The sample numbers marked with a circle in Table 1 are within the scope of the present invention, and sample numbers 1, 2, 5, 8, 10, 13, 14, 14, 15, 19, 20,
21 and 24 are outside the scope of the invention.
次に、本発明の高誘電率磁器組成物における各成分の
モル％または重量％の限定理由を説明する。Next, the reasons for limiting the mol% or weight% of each component in the high dielectric constant porcelain composition of the present invention will be described.
BaTiO3が97.0モル％未満では誘電率εｓが小さくなり
（試料番号13）、98.25モル％を超えると焼結性が悪く
（×印）なる（試料番号１）。If BaTiO 3 is less than 97.0 mol%, the dielectric constant ε s will be small (Sample No. 13), and if it exceeds 98.25 mol%, the sinterability will be poor (mark X) (Sample No. 1).
Nb2O5が0.75モル％未満では焼結性が悪く（試料番号
5,10）、1.5モル％を超えると誘電率εｓが小さくなる
（試料番号８）。If Nb 2 O 5 is less than 0.75 mol%, the sinterability is poor (Sample No.
5, 10), and if it exceeds 1.5 mol%, the dielectric constant ε s becomes small (Sample No. 8).
Y2O3が0.5モル％未満では誘電率εｓが小さく、誘電
体損失tanδが大きくなり、焼結性も悪く、絶縁抵抗も
低くなり（試料番号２）、2.0モル％を超えると誘電率
εｓが小さくなり、温度85℃における誘電率の温度変化
率T.Cが大きくなる（試料番号10）。When Y 2 O 3 is less than 0.5 mol%, the dielectric constant ε s is small, the dielectric loss tan δ is large, the sinterability is poor, and the insulation resistance is low (Sample No. 2). ε s decreases, and the temperature change rate TC of the dielectric constant at a temperature of 85 ° C increases (Sample No. 10).
CeO2はキュリーポイントC.Pをマイナス側へ移動させ
る働き、すなわちシフターの役割を果しており、0.2重
量％未満ではキュリーポイントC.Pが常温以上となり、
誘電体損失tanδが大きく、誘電率εｓも小さい（試料
番号14,15）。0.8重量％を超えるとキュリーポイントC.
Pが常温以下となり、誘電率が低くなり、誘電率の温度
変化率T.Cが温度85℃でJISのＦ特性規格から外れ、実用
的でない（試料番号19）。CeO 2 has a function of moving the Curie point CP to the negative side, that is, plays a role of a shifter. When the Curie point CP is less than 0.2% by weight, the Curie point CP becomes room temperature or more,
The dielectric loss tan δ is large and the dielectric constant ε s is also small (sample numbers 14 and 15). Curie point C when exceeding 0.8% by weight.
P is below room temperature, the permittivity is low, and the temperature change rate TC of the permittivity is out of the JIS F characteristic standard at a temperature of 85 ° C, which is not practical (Sample No. 19).
MnOが0.01重量％未満では焼成温度が高くなるうえ焼
結性が悪く、誘電率が小、tanδが大となり、絶縁抵抗
も低くなり（試料番号20,21）、0.3重量％を超えると誘
電率が小さくなり、焼結性も悪く実用的でない（試料番
号24）。If MnO is less than 0.01% by weight, the firing temperature will be high and the sinterability will be poor, the dielectric constant will be small, tan δ will be large, and the insulation resistance will be low (Sample Nos. 20 and 21). Is small and the sinterability is poor and it is not practical (Sample No. 24).
更に、本発明組成物にSiO2,Al2O3と少なくとも一方を
微量添加することにより、当該組成物の焼結性を更に向
上させることができる。Furthermore, by adding a trace amount of at least one of SiO 2 and Al 2 O 3 to the composition of the present invention, the sinterability of the composition can be further improved.
なお、前記焼成により得られた焼結体試料のうち本発
明組成物の自由表面の顕微鏡写真を第２図に示す。ま
た、比較のため従来のBaTiO3−BaZrO3− BaSnO3−CaTi
O3系の自由表面の顕微鏡写真を第３図に示す。これらの
写真を比較して明らかなように本発明に係る焼結体で
は、従来のものに比べ結晶粒径が著しく小さくなってい
ることが判る。In addition, a micrograph of the free surface of the composition of the present invention among the sintered body samples obtained by the firing is shown in FIG. Further, the conventional BaTiO 3 -BaZrO 3 for comparison - BaSnO 3 -CaTi
A micrograph of the free surface of the O 3 system is shown in FIG. As is clear from comparing these photographs, it is understood that the crystal grain size of the sintered body according to the present invention is significantly smaller than that of the conventional one.
第１表から明らかなように、本発明の高誘電率磁器組
成物は誘電率が約8000〜13000で、温度特性すなわち誘
電率の温度変化率T.CはJIS・Ｆ特性規格−25℃〜＋85℃
の温度範囲内で20℃を基準温度として＋30％〜−80％以
内であり、また第２図から明らかなように結晶粒径の平
均値は５μｍ以下と小さく、優れた性質を有するもので
ある。As is clear from Table 1, the high dielectric constant porcelain composition of the present invention has a dielectric constant of about 8000 to 13000, and the temperature characteristic, that is, the temperature change rate TC of the dielectric constant is JIS-F characteristic standard −25 ° C. to + 85 ° C.
Within the temperature range of, the temperature is within the range of + 30% to -80% with 20 ° C as the reference temperature, and as is clear from Fig. 2, the average grain size is as small as 5 µm or less and has excellent properties. .
なお、本発明のBaTiO3−Nb2O5−Y2O3系組成物に係る
主成分の組成範囲を三元図で示すと第１図のとおりであ
る。この図において、六角形内及びこの六角形を形成す
る各線分上にある組成物（黒点は実施例の組成物を、又
（ ）内の数字は試料番号を示す）が本発明の範囲内に
あるものである。The composition range of the main components of the BaTiO 3 —Nb 2 O 5 —Y 2 O 3 system composition of the present invention is shown in a ternary diagram as shown in FIG. In this figure, compositions within the hexagon and on each line segment forming the hexagon (black dots indicate compositions of Examples, and numbers in parentheses indicate sample numbers) fall within the scope of the present invention. There is something.
以上述べたように、本発明の高誘電率磁器組成物は、
チタン酸バリウムBaTiO397.0〜98.25モル％、五酸化ニ
オブNb2O50.75〜1.50モル％及び酸化イットリウムY2O
30.50〜2.00モル％を主成分としてなる組成物100モル％
に対して副成分として酸化セリウムCeO20.2〜0.8重量％
及び酸化マンガンMnO0.01〜0.3重量％を添加含有せしめ
たことにより、誘電率εｓが高く、誘電率の温度変化率
T.CがJIS・Ｆ特性を満足しているうえ、結晶粒径が従来
のものに比べ著しく微細化しているものであり、したが
って本発明組成物を積層チップコンデンサに応用した場
合、デラミネーションを起こさず、また破壊電圧の向
上、薄層上による容量取得範囲の拡大等、従来のBaTiO3
−BaZrO3−BaSnO3−CaTiO3系組成物では得られなかった
利点を有するものであり、実用的価値が大きいものであ
る。As described above, the high dielectric constant porcelain composition of the present invention is
Barium titanate BaTiO 3 97.0 to 98.25 mol%, niobium pentoxide Nb 2 O 5 0.75 to 1.50 mol% and yttrium oxide Y 2 O
3 0.50-2.00 mol% as a main component composition 100 mol%
Cerium oxide CeO 2 0.2 to 0.8 wt% as an accessory component
And 0.01% to 0.3% by weight of manganese oxide MnO are added, the dielectric constant ε s is high, and the temperature change rate of the dielectric constant is high.
TC satisfies JIS / F characteristics, and the crystal grain size is significantly finer than conventional ones. Therefore, when the composition of the present invention is applied to a multilayer chip capacitor, delamination does not occur. and improvement of the breakdown voltage, expansion of capacity acquisition range by the upper thin layer, conventional BaTiO 3
-BaZrO 3 -BaSnO 3 are those having the advantages which can not be obtained by -CaTiO 3 based compositions are those large practical value.
第１図は本発明組成物に係る主成分の組成範囲を示す三
元図、第２図は本発明の実施例組成物の結晶構造を示す
顕微鏡写真（倍率3500）、第３図は従来の誘電体磁器組
成物の結晶構造を示す顕微鏡写真（倍率3500）である。FIG. 1 is a ternary diagram showing the composition range of the main components of the composition of the present invention, FIG. 2 is a micrograph showing the crystal structure of the example composition of the present invention (magnification 3500), and FIG. 3 is a micrograph (magnification: 3500) showing a crystal structure of a dielectric ceramic composition.
Claims (1)
％、五酸化ニオブNb2O50.75〜1.50モル％及び酸化イッ
トリウムY2O30.50〜2.00モル％を主成分としてなる組成
物100モル％に対して副成分として酸化セリウムCeO20.2
〜0.8重量％及び酸化マンガンMnO0.01〜0.3重量％を添
加含有したことを特徴とするBaTiO3−Nb2O5−Y2O3系高
誘電率磁器組成物。1. A composition comprising barium titanate BaTiO 3 97.0 to 98.25 mol%, niobium pentoxide Nb 2 O 5 0.75 to 1.50 mol% and yttrium oxide Y 2 O 3 0.50 to 2.00 mol% as main components 100 mol% As an accessory component to cerium oxide CeO 2 0.2
0.8 wt% and BaTiO 3 -Nb 2 O 5 -Y 2 O 3 based high dielectric constant ceramic composition characterized by containing added manganese oxide MnO0.01~0.3 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63159251A JP2694209B2 (en) | 1988-06-29 | 1988-06-29 | High dielectric constant porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63159251A JP2694209B2 (en) | 1988-06-29 | 1988-06-29 | High dielectric constant porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0210711A JPH0210711A (en) | 1990-01-16 |
| JP2694209B2 true JP2694209B2 (en) | 1997-12-24 |
Family
ID=15689664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63159251A Expired - Lifetime JP2694209B2 (en) | 1988-06-29 | 1988-06-29 | High dielectric constant porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2694209B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640679B (en) * | 2018-07-24 | 2022-02-11 | 江苏科技大学 | Barium zirconate titanate-based capacitor ceramic material and preparation method thereof |
-
1988
- 1988-06-29 JP JP63159251A patent/JP2694209B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0210711A (en) | 1990-01-16 |
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