JPH0449504B2 - - Google Patents
Info
- Publication number
- JPH0449504B2 JPH0449504B2 JP61257335A JP25733586A JPH0449504B2 JP H0449504 B2 JPH0449504 B2 JP H0449504B2 JP 61257335 A JP61257335 A JP 61257335A JP 25733586 A JP25733586 A JP 25733586A JP H0449504 B2 JPH0449504 B2 JP H0449504B2
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- composition
- pbtio
- present
- temperature
- 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
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 9
- 229910019653 Mg1/3Nb2/3 Inorganic materials 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese 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 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 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 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 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、磁器組成物、特に誘電率が著しく大
きく、誘電率、絶縁抵抗の温度特性および誘電損
失の良好な、磁器組成物に関するものである。
（従来技術と発明が解決しようとする問題点）
従来、高誘電率磁器組成物として、チタン酸バ
リウム（BaTiO3）が、またチタン酸バリウム
（BaTiO3）とチタン酸カルシウム（CaTiO3）、
チタン酸鉛（PbTiO3）などの固溶体組成物が広
く実用化されているのは周知のとおりである。し
かしながらこれら公知の誘導体磁器組成物で得ら
れる誘電率は高々8000程度にすぎず、特性改善の
ために常温での誘電率を大きくすると誘電率の温
度変化が大きくなり、一方誘電率の温度変化を小
さくすれば誘電率の最大値が減少するなど実用上
種々の問題点があつた。
また磁器組成物の電気的特性として、誘電損失
が小さく、絶縁抵抗が高いことが要求される。さ
らに絶縁抵抗の値に関しては、高信頼性の部品を
要求する米国防総省の規格であるミリタリースペ
シフイケイシヨン（Military Specification）の
MIL−Ｃ−55681Bにおいて、室温における値の
みならず、125℃における値も定められているよ
うに、信頼性の高い磁器コンデンサを得るために
は、室温における値のみならず、最高使用温度に
おける絶縁抵抗も高い値をとることが必要であ
る。
従来、これらの条件を備えた磁器誘導体は少な
く、その実現が望まれていた。
（問題点を解決するための手段）
本発明は、上述の要請に鑑み、誘電率が高く、
誘電損失が小さく、室温および高温における絶縁
抵抗の値が高く、さらに誘電率の温度特性の良好
な優れた電気特性を有した磁器組成物を提供しよ
うとするものであり、その要旨は、マグネシウ
ム・ニオブ酸鉛［Pb（Mg1/3Nb2/3）O3］、チタ
ン酸鉛［PbTiO3］およびニツケル・ニオブ酸鉛
［Pb（Ni1/3Nb2/3）O3］からなる３成分系組成
物を、［Pb（Mg1/3Nb2/3）O3］ｘ［Pb（Ni1/3Nb
２／３）O3］ｙ［PbTiO3］ｚと表わしたときに（た
だしｘ＋ｙ＋ｚ＝1.00）この３成分組成図におい
て以下の組成点
（ｘ＝0.10， ｙ＝0.70， ｚ＝0.20）
（ｘ＝0.15， ｙ＝0.60， ｚ＝0.25）
（ｘ＝0.15， ｙ＝0.70， ｚ＝0.15）
（ｘ＝0.40， ｙ＝0.35， ｚ＝0.25）
（ｘ＝0.60， ｙ＝0.20， ｚ＝0.20）
（ｘ＝0.70， ｙ＝0.20， ｚ＝0.10）
（ｘ＝0.50， ｙ＝0.40， ｚ＝0.10）
を結ぶ線上、および７点に囲まれる組成範囲にあ
る主成分組成物に、副成分として、マンガン
（Mn）を主成分に対して0.01〜３原子％添加含有
せしめてなることを特徴とするものである。
すなわち、本願発明者達は既にPb（Mg1/3Nb
２／３）O3−Pb（Ni1/3Nb2/3）O3−（PbTiO3）か
らなる３成分系に新たに検討した範囲を加え、誘
電率と比抵抗の温度安定性改善を目的とし、副成
分として、マンガン（Mn）を添加含有せしめる
もので、誘電率と絶縁抵抗の温度安定性が良好
で、さらに誘電損失の小さい優れた電気的特性を
有する磁器組成物を提供しようとするものであ
る。
（実施例）
以下、本発明を実施例により詳細に説明する。
出発原料として純度99.9％以上の酸化鉛（PbO）、
酸化マグネシウム（MgO）、酸化ニオブ（Nb2
O5）、酸化ニツケル（NiO）、酸化チタン（TiO2）
および炭酸マンガン（MnCO3）を使用し、表に
示した配合比となるように各々秤量する。次に秤
量した各材料をボールミル中で湿式混合した後
750〜800℃で仮焼を行い、この粉末をボールミル
で粉砕し、濾過、乾燥後、誘起バインダーを入れ
て整粒後プレスし、直径16mm、厚さ２mmの円板４
枚と、直径16mm、厚さ約10mmの円柱を作成した。
次に本発明の組成範囲の試料は空気中1000〜1080
℃の温度で１時間焼結した。焼結した円板４枚の
上下面に600℃で銀電極を焼付け、デジタルLCR
メーターで周波数1KHz、電圧1Vr.m.s.温度→−
30℃→20℃→85℃の順次で容量と誘電損失を測
定、誘電率と誘電率を求めた。
次に絶縁抵抗計で50Vの電圧を１分間印加し
て、絶縁抵抗を温度20℃と125℃で測定し、比抵
抗を算出した。このようにして得られた磁器の主
成分［Pb（Mg1/3Nb2/3）O3］ｘ［Pb（Ni1/3Nb
２／３）O3］ｙ［PbTiO3］ｚの配合比ｘ，ｙ，ｚお
よび副成分添加量と誘電率、誘電損失、85℃にお
ける誘電率の変化率、および20℃と125℃におけ
る比抵抗の関係を第１表に示す。
(Field of Industrial Application) The present invention relates to a ceramic composition, particularly a ceramic composition having a significantly large dielectric constant and good temperature characteristics of dielectric constant, insulation resistance, and dielectric loss. (Prior art and problems to be solved by the invention) Conventionally, barium titanate (BaTiO 3 ), barium titanate (BaTiO 3 ) and calcium titanate (CaTiO 3 ) have been used as high dielectric constant ceramic compositions.
It is well known that solid solution compositions such as lead titanate (PbTiO 3 ) are widely put into practical use. However, the dielectric constant obtained with these known dielectric ceramic compositions is only about 8000 at most, and increasing the dielectric constant at room temperature in order to improve properties will result in large temperature changes in the dielectric constant; If it is made smaller, there are various problems in practical use, such as a decrease in the maximum value of the dielectric constant. Furthermore, the electrical properties of the ceramic composition are required to be low dielectric loss and high insulation resistance. Furthermore, the value of insulation resistance is based on the Military Specification, a US Department of Defense standard that requires highly reliable components.
In MIL-C-55681B, not only the value at room temperature but also the value at 125℃ is specified. It is also necessary that the resistance be of a high value. Conventionally, there have been few ceramic derivatives that meet these conditions, and their realization has been desired. (Means for solving the problems) In view of the above-mentioned requirements, the present invention has a high dielectric constant,
The aim is to provide a porcelain composition that has excellent electrical properties such as low dielectric loss, high insulation resistance at room temperature and high temperature, and good temperature characteristics of dielectric constant. A three-component composition consisting of lead niobate [Pb(Mg1/3Nb2/3)O 3 ], lead titanate [PbTiO 3 ] and lead nickel niobate [Pb(Ni1/3Nb2/3)O 3 ], [Pb(Mg1/3Nb2/3)O 3 ] x [Pb(Ni1/3Nb
2/3) When expressed as O 3 ]y[PbTiO 3 ]z (x+y+z=1.00), the following composition points in this three-component composition diagram (x=0.10, y=0.70, z=0.20) (x= 0.15, y=0.60, z=0.25) (x=0.15, y=0.70, z=0.15) (x=0.40, y=0.35, z=0.25) (x=0.60, y=0.20, z=0.20) ( x = 0.70, y = 0.20, z = 0.10) (x = 0.50, y = 0.40, z = 0.10) and in the composition range surrounded by 7 points, manganese is added as a subcomponent. (Mn) is added in an amount of 0.01 to 3 atomic % based on the main component. In other words, the inventors of the present application have already developed Pb (Mg1/3Nb
2/3) Adding a newly studied range to the three-component system consisting of O 3 - Pb (Ni1/3Nb2/3) O 3 - (PbTiO 3 ), with the aim of improving the temperature stability of dielectric constant and resistivity. By adding manganese (Mn) as a subcomponent, the purpose is to provide a ceramic composition that has good temperature stability in terms of dielectric constant and insulation resistance, and also has excellent electrical properties with low dielectric loss. be. (Example) Hereinafter, the present invention will be explained in detail with reference to Examples.
Lead oxide (PbO) with a purity of over 99.9% as a starting material,
Magnesium oxide (MgO), niobium oxide ( Nb2)
O 5 ), nickel oxide (NiO), titanium oxide (TiO 2 )
and manganese carbonate (MnCO 3 ), and each is weighed so as to achieve the mixing ratio shown in the table. Next, after wet-mixing each weighed material in a ball mill,
Calcinate at 750-800℃, crush this powder with a ball mill, filter it, dry it, add an induction binder, size it and press it to form a disk 4 with a diameter of 16 mm and a thickness of 2 mm.
A cylinder with a diameter of 16 mm and a thickness of approximately 10 mm was created.
Next, the sample with the composition range of the present invention is 1000 to 1080 in air.
It was sintered for 1 hour at a temperature of . Digital LCR is performed by baking silver electrodes at 600℃ on the top and bottom surfaces of four sintered disks.
Meter shows frequency 1KHz, voltage 1Vr.ms temperature →-
The capacitance and dielectric loss were measured at 30°C → 20°C → 85°C, and the permittivity and permittivity were determined. Next, a voltage of 50V was applied for 1 minute using an insulation resistance meter, the insulation resistance was measured at temperatures of 20°C and 125°C, and the specific resistance was calculated. The main component of the porcelain thus obtained is [Pb(Mg1/3Nb2/3)O 3 ] x [Pb(Ni1/3Nb
2/3) Mixing ratio x, y, z of O 3 ] y [PbTiO 3 ] z and additive amount of subcomponents, dielectric constant, dielectric loss, rate of change in dielectric constant at 85°C, and ratio at 20°C and 125°C Table 1 shows the resistance relationship.
【表】【table】
【表】【table】
【表】
＊印のついているものは本発明の範囲以外
のものである。
第１表からも明らかなようにPb（Mg1/3Nb2/3）
O3−Pb（Ni1/3Nb2/3）O3−PbTiO3３成分組成
物に副成分であるマンガン（Mn）を主成分に対
して0.01〜３原子％添加含有せしめた本発明は高
い誘電率を保持しながら、誘電損失や誘電率及び
比抵抗の温度特性を良好かつ実用的なレベルまで
高めており、積層コンデンサ用磁器組成物として
優れた材料を提供するものである。
なお、本発明の主成分組成範囲外および、副成
分添加量範囲外では焼結温度が高くなつたり、誘
電率が低下し実用的でないため、前述のように限
定される。
なお、第１図に本発明の主成分組成範囲を示
す。図に示した番号は、表に示した主成分配合比
の番号に対応する。[Table] Items marked with * are outside the scope of the present invention.
As is clear from Table 1, Pb (Mg1/3Nb2/3)
O 3 -Pb (Ni1/3Nb2/3) O 3 -PbTiO 3 The present invention has a high dielectric constant by adding manganese (Mn) as a subcomponent to the main component in an amount of 0.01 to 3 at%. While maintaining this, the temperature characteristics of dielectric loss, dielectric constant, and specific resistance are improved to a good and practical level, and the material is excellent as a ceramic composition for multilayer capacitors. It should be noted that outside the main component composition range and the subcomponent addition amount range of the present invention, the sintering temperature becomes high and the dielectric constant decreases, making it impractical, and therefore, it is limited as described above. Incidentally, FIG. 1 shows the composition range of the main components of the present invention. The numbers shown in the figure correspond to the numbers of the main component blending ratios shown in the table.
第１図は、本発明の主成分組成範囲と実施例に
示した組成点を示す図である。
FIG. 1 is a diagram showing the main component composition range of the present invention and the composition points shown in Examples.
Claims (1)
O3−PbTiO3の３成分系磁器組成物を［Pb（Mg1/
３Nb2/3）O3］ｘ［Pb（Ni1/3Nb2/3）O3］ｙ
［PbTiO3］ｚ（ただしｘ＋ｙ＋ｚ＝1.0）と表現し
たとき （ｘ＝0.10， ｙ＝0.70， ｚ＝0.20） （ｘ＝0.15， ｙ＝0.60， ｚ＝0.25） （ｘ＝0.15， ｙ＝0.70， ｚ＝0.15） （ｘ＝0.40， ｙ＝0.35， ｚ＝0.25） （ｘ＝0.60， ｙ＝0.20， ｚ＝0.20） （ｘ＝0.70， ｙ＝0.20， ｚ＝0.10） （ｘ＝0.50， ｙ＝0.40， ｚ＝0.10） を結ぶ線上およびこの７点に囲まれる組成範囲に
ある主成分組成物に副成分としてマンガン
（Mn）を0.1〜３原子％添加含有せしめてなるこ
とを特徴とする磁器組成物。[Claims] 1 Pb(Mg1/3Nb2/3)O 3 −Pb(Ni1/3Nb2/3)
A three-component ceramic composition of O 3 −PbTiO 3 [Pb(Mg1/
3Nb2/3)O 3 ]x[Pb(Ni1/3Nb2/3)O 3 ]y
When expressed as [PbTiO 3 ]z (x+y+z=1.0) (x=0.10, y=0.70, z=0.20) (x=0.15, y=0.60, z=0.25) (x=0.15, y=0.70, z=0.15) (x=0.40, y=0.35, z=0.25) (x=0.60, y=0.20, z=0.20) (x=0.70, y=0.20, z=0.10) (x=0.50, y= 0.40, z=0.10) and in the composition range surrounded by these seven points, a porcelain composition characterized by adding 0.1 to 3 at. thing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61257335A JPS63112451A (en) | 1986-10-28 | 1986-10-28 | Ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61257335A JPS63112451A (en) | 1986-10-28 | 1986-10-28 | Ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63112451A JPS63112451A (en) | 1988-05-17 |
| JPH0449504B2 true JPH0449504B2 (en) | 1992-08-11 |
Family
ID=17304931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61257335A Granted JPS63112451A (en) | 1986-10-28 | 1986-10-28 | Ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63112451A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0354144A (en) * | 1989-07-20 | 1991-03-08 | Nec Corp | Dielectric ceramic composition |
-
1986
- 1986-10-28 JP JP61257335A patent/JPS63112451A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63112451A (en) | 1988-05-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |