JPH0610100B2 - Porcelain composition - Google Patents
Porcelain compositionInfo
- Publication number
- JPH0610100B2 JPH0610100B2 JP2014797A JP1479790A JPH0610100B2 JP H0610100 B2 JPH0610100 B2 JP H0610100B2 JP 2014797 A JP2014797 A JP 2014797A JP 1479790 A JP1479790 A JP 1479790A JP H0610100 B2 JPH0610100 B2 JP H0610100B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- points
- component
- lead
- silver
- 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 - Fee Related
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- 239000000203 mixture Substances 0.000 title claims description 53
- 229910052573 porcelain Inorganic materials 0.000 title claims description 21
- 239000011777 magnesium Substances 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 7
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 6
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 claims description 5
- FKSZLDCMQZJMFN-UHFFFAOYSA-N [Mg].[Pb] Chemical compound [Mg].[Pb] FKSZLDCMQZJMFN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010586 diagram Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 101000939676 Androctonus crassicauda Toxin a Proteins 0.000 claims 1
- 239000000463 material Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003985 ceramic capacitor Substances 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 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 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 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
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は磁器組成物に関し、特に誘電率および絶縁抵抗
が高く、誘電損失が小さく、かつ1050℃以下の温度で焼
結可能な磁器組成物に関するものである。Description: TECHNICAL FIELD The present invention relates to a porcelain composition, and particularly to a porcelain composition having a high dielectric constant and insulation resistance, a small dielectric loss, and sinterable at a temperature of 1050 ° C. or lower. It is about.
［従来の技術］ 従来、高誘電率系磁器組成物としてチタン酸バリウム
（ＢａＴｉＯ３）系がよく知られており、チタン酸カル
シウム［ＣａＴｉＯ３］、チタン酸鉛［ＰｂＴｉＯ３］
などを添加、置換することにより温度特性の改善を図っ
ている。[Prior Art] Conventionally, barium titanate (BaTiO 3 ) series is well known as a high dielectric constant porcelain composition, and calcium titanate [CaTiO 3 ] and lead titanate [PbTiO 3 ] are known.
The temperature characteristics are improved by adding and replacing the above.
［発明が解決しようとする課題］ 従来の材料で温度変化率の小さい材料を実現した場合、
得られる誘電率はせいぜい2000程度にすぎず、コンデン
サ用の材料としては小さすぎる。近年、低温で焼結し、
かつ誘電率が高く温度変化率の小さい材料として鉛系複
合ペロブスカイト化合物が報告されている。マグネシウ
ム・ニオブ酸鉛［Ｐｂ（Ｍｇ1/3Ｎｂ2/3）Ｏ３］、ニッ
ケル・ニオブ酸鉛［Ｐｂ（Ｎｉ1/3Ｎｂ2/3）Ｏ３］およ
びチタン酸鉛［ＰｂＴｉＯ３］からなる３成分組成物
は、誘電率が20000以上もあり、温度変化率も比較的小
さいが、1100℃以上の高温でなければ焼結できないとう
欠点がある。また、上記の３成分組成物にマンガン・ニ
オブ酸鉛［Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ３］を添加した組
成物は誘電率が12000以上もあるが、1150℃以上の高温
でなければ焼結できないという欠点がある。[Problems to be Solved by the Invention] When a material having a small temperature change rate is realized by a conventional material,
The dielectric constant obtained is only about 2000 at most, which is too small as a material for capacitors. In recent years, sintering at low temperature,
A lead-based composite perovskite compound has been reported as a material having a high dielectric constant and a small temperature change rate. From magnesium lead niobate [Pb (Mg 1/3 Nb 2/3 ) O 3 ], nickel lead niobate [Pb (Ni 1/3 Nb 2/3 ) O 3 ], and lead titanate [PbTiO 3 ]. The three-component composition has a dielectric constant of 20,000 or more and a relatively small temperature change rate, but has the drawback that it cannot be sintered unless it is at a high temperature of 1100 ° C. or more. Further, a composition obtained by adding manganese / lead niobate [Pb (Mn 1/3 Nb 2/3 ) O 3 ] to the above three-component composition has a dielectric constant of 12000 or more, but at a high temperature of 1150 ° C. or more. The disadvantage is that it cannot be sintered unless it is done.
以上のことから、コンデンサを製造するときに内部電極
として安価な銀・パラジウム合金は使用できない。From the above, inexpensive silver-palladium alloy cannot be used as an internal electrode when manufacturing a capacitor.
本発明は以上述べたような従来の課題を解決するために
なされたもので、上記の３成分組成物の優れた特性を満
足し、かつ1050℃以下で焼結可能な磁器組成物を提供す
ることにある。The present invention has been made to solve the conventional problems as described above, and provides a porcelain composition which satisfies the excellent characteristics of the above three-component composition and can be sintered at 1050 ° C or lower. Especially.
［課題を解決するための手段］ 本発明は、マグネシウム・ニオブ酸鉛［Ｐｂ（Ｍｇ1/3
Ｎｂ2/3）Ｏ３］、ニッケル・ニオブ酸鉛［Ｐｂ（Ｎｉ
1/3Ｎｂ2/3）Ｏ３］およびチタン酸鉛［ＰｂＴｉＯ３］
からなる３成分組成物を［Ｐｂ（Ｍｇ1/3Ｎｂ2/3）
Ｏ３］ｘ［Ｐｂ（Ｎｉ1/3Ｎｂ2/3）Ｏ３］ｙ［ＰｂＴｉ
Ｏ３］ｚ（ただしｘ＋ｙ＋ｚ＝1.0）と表現したとき、
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）…(a) （ｘ＝0.15，ｙ＝0.60，ｚ＝0.25）…(b) （ｘ＝0.15，ｙ＝0.70，ｚ＝0.15）…(c) （ｘ＝0.40，ｙ＝0.35，ｚ＝0.25）…(d) （ｘ＝0.60，ｙ＝0.20，ｚ＝0.20）…(e) （ｘ＝0.70，ｙ＝0.20，ｚ＝0.10）…(f) （ｘ＝0.50，ｙ＝0.40，ｚ＝0.10）…(g) の各点を結ぶ線上、およびこの７点に囲まれる組成範囲
内にある主成分組成物に、副成分として銀［Ａｇ］を0.
01〜2.0重量％添加したことを特徴とする磁器組成物、
および上記の主成分組成物に、第１副成分としてマンガ
ン・ニオブ酸鉛［Ｐｂ（Ｍｇ1/3Ｎｂ2/3）Ｏ３］を0.01
〜10mol％、第２副成分として銀［Ａｇ］を0.01〜2.0重
量％添加したことを特徴とする磁器組成物、および上記
の主成分組成物に、第１副成分としてマンガン［Ｍｎ］
および／またはニオブ［Ｎｂ］を主成分に対して0.01〜
３mol％、第２副成分として銀［Ａｇ］を0.01〜2.0重量
％添加したことを特徴とする磁器組成物である。[Means for Solving the Problems] The present invention is directed to lead magnesium niobate [Pb (Mg 1/3
Nb 2/3 ) O 3 ], nickel lead niobate [Pb (Ni
1/3 Nb 2/3 ) O 3 ] and lead titanate [PbTiO 3 ]
A three-component composition consisting of [Pb (Mg 1/3 Nb 2/3 )
O 3] x [Pb (Ni 1/3 Nb 2/3) O 3] y [PbTi
When expressed as O 3 ] z (where x + y + z = 1.0),
In this three-component composition diagram, the following composition points (x = 0.10, y = 0.70, z = 0.20) (a) (x = 0.15, y = 0.60, z = 0.25) (b) (x = 0.15) , Y = 0.70, z = 0.15) ... (c) (x = 0.40, y = 0.35, z = 0.25) ... (d) (x = 0.60, y = 0.20, z = 0.20) ... (e) (x = 0.70, y = 0.20, z = 0.10)… (f) (x = 0.50, y = 0.40, z = 0.10)… (g) on the line connecting the points and within the composition range surrounded by these 7 points Silver [Ag] as an auxiliary component is added to the main component composition in an amount of 0.
Porcelain composition characterized by adding 01 to 2.0% by weight,
And 0.01% lead manganese / niobate [Pb (Mg 1/3 Nb 2/3 ) O 3 ] as the first subcomponent to the above main component composition.
.About.10 mol%, and 0.01 to 2.0% by weight of silver [Ag] as a second subcomponent, and the above main component composition, manganese [Mn] as the first subcomponent.
And / or niobium [Nb] is 0.01 to
It is a porcelain composition characterized by adding 3 mol% and 0.01 to 2.0% by weight of silver [Ag] as a second subcomponent.
本発明における主成分組成範囲を表す３成分組成物は第
１図で示される。図中、(a)〜(g)は各組成点を表し、本
発明に含まれる組成範囲は図の斜線で示す範囲およびそ
の境界線上である。A three-component composition representing the main component composition range in the present invention is shown in FIG. In the figure, (a) to (g) represent each composition point, and the composition range included in the present invention is the range indicated by the diagonal lines in the figure and the boundary line thereof.
［実施例］ 以下、本発明の実施例について詳細に説明する。実施例
１〜35、比較例１〜19 出発原料として酸化鉛（ＰｂＯ）、酸化マグネシウム
（ＭｇＯ）、酸化ニオブ（Ｎｂ２Ｏ５）、酸化ニッケル
（ＮｉＯ）、酸化チタン（ＴｉＯ２）および銀（Ａｇ）
を使用し、第１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
たのち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、有機バインダを入れて整粒後
プレスし、直径約16mm、厚さ約２mmの円板２枚と、直径
約16mm、厚さ約10mmの円柱を作製した。次にこれらの組
成範囲の試料を950〜1100℃の温度で１時間焼成を行っ
た。[Examples] Examples of the present invention will be described in detail below. Examples 1 to 35, Comparative Examples 1 to 19 Lead oxide (PbO), magnesium oxide (MgO), niobium oxide (Nb 2 O 5 ), nickel oxide (NiO), titanium oxide (TiO 2 ) and silver (as starting materials). Ag)
Are weighed so that the blending ratios shown in Table 1 are obtained. Next, each of the weighed materials is wet mixed in a ball mill and then calcined at 750 to 800 ° C., the powder is crushed by a ball mill, filtered, dried, and then an organic binder is added to the powder, which is then pressed to obtain a diameter of about Two discs having a diameter of 16 mm and a thickness of about 2 mm and a cylinder having a diameter of about 16 mm and a thickness of about 10 mm were prepared. Next, the samples having these composition ranges were fired at a temperature of 950-1100 ° C. for 1 hour.
焼成した円柱でアルキメデス法を用いて密度を求めた。
次に、円板の上下面に600℃で銀電極を焼き付け、デジ
タルＬＣＲメータで周波数１kHz、電圧１Vr.m.s、室温
で容量と誘電損失を測定し、誘電率を求めた。The density was determined using the Archimedes method on the fired cylinder.
Next, silver electrodes were baked on the upper and lower surfaces of the disk at 600 ° C., the capacitance and the dielectric loss were measured with a digital LCR meter at a frequency of 1 kHz, a voltage of 1 Vr.ms and room temperature to obtain the dielectric constant.
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（Ｎｉ1/3Ｎｂ2/3）Ｏ３］ｙ［ＰｂＴｉＯ３］
ｚの配合比ｘ、ｙ、ｚおよび副成分添加量と、密度、誘
電率、誘電損失および比抵抗の関係を第１表に示す。Next, a voltage of 50 V was applied for 1 minute with an insulation resistance meter, the insulation resistance was measured, and the specific resistance was calculated. The main component of porcelain thus obtained [Pb (Mg 1/3 Nb 2/3 ) O 3 ]
x [Pb (Ni 1/3 Nb 2/3 ) O 3 ] y [PbTiO 3 ]
a mixing ratio x, y, z and subcomponents amount of z, the density shows the dielectric constant, the relationship between dielectric loss and specific resistance in Table 1.
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
分系組成物に副成分である銀（Ａｇ）を主成分に対して
0.01〜2.0重量％添加した本発明の磁器組成物は、高い
誘電率、比抵抗を保持し、1000゜℃以下の低い温度で焼
結し、積層セラミック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。 As is clear from Table 1, Pb (Mg 1/3 Nb 2/3 )
O 3 -Pb (Ni 1/3 Nb 2/3 ) O 3 -PbTiO 3 Three-component composition with silver (Ag) as a sub-component relative to the main component
The porcelain composition of the present invention added with 0.01 to 2.0% by weight retains a high dielectric constant and a specific resistance and is sintered at a low temperature of 1000 ° C. or less to provide an excellent material as a porcelain composition for a laminated ceramic capacitor. To do.
実施例36〜60、比較例20〜49 出発原料として酸化鉛（ＰｂＯ）、酸化マグネシウム
（ＭｇＯ）、酸化ニオブ（Ｎｂ２Ｏ５）、酸化ニッケル
（ＮｉＯ）、酸化チタン（ＴｉＯ２）、炭酸マンガン
（ＭｎＣＯ３）および銀（Ａｇ）を使用し、第２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のち800〜850℃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、有機バインダを入れて整粒後プレスし、直径約16m
m、厚さ約２mmの円板２枚と、直径約16mm、厚さ約10mm
の円柱を作製した。次にこれらの組成範囲の試料を1050
〜1200℃の温度で１時間焼成を行った。Example 36 to 60, lead oxide Comparative Example 20 to 49 The starting material (PbO), magnesium oxide (MgO), niobium oxide (Nb 2 O 5), nickel oxide (NiO), titanium oxide (TiO 2), manganese carbonate (MnCO 3 ) and silver (Ag) are used and weighed so that the compounding ratios shown in Table 2 are obtained. Next, the weighed materials are wet-mixed in a ball mill and then calcined at 800 to 850 ° C. The powder is crushed in a ball mill, filtered, dried, and then an organic binder is added to the powder, which is then pressed to obtain a diameter of approx. 16m
m, 2 discs with a thickness of about 2 mm, diameter of about 16 mm, thickness of about 10 mm
The cylinder of was produced. Samples in these composition ranges are then
Baking was performed at a temperature of ~ 1200 ° C for 1 hour.
焼成した円柱でアルキメデス法を用いて密度を求めた。
次に、円板の上下面に600℃で銀電極を焼き付け、デジ
タルＬＣＲメータで周波数１kHz、電圧１Vr.m.s、室温
で容量と誘電損失を測定し、誘電率およびその変化率を
求めた。The density was determined using the Archimedes method on the fired cylinder.
Next, silver electrodes were baked on the upper and lower surfaces of the disk at 600 ° C., the capacitance and the dielectric loss were measured with a digital LCR meter at a frequency of 1 kHz, a voltage of 1 Vr.ms and room temperature to obtain the dielectric constant and its change rate.
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（Ｎｉ1/3Ｎｂ2/3）Ｏ３］ｙ［ＰｂＴｉＯ３］
ｚの配合比ｘ、ｙ、ｚおよび副成分添加量と密度、誘電
率、誘電損失および比抵抗の関係を第２表に示す。Next, a voltage of 50 V was applied for 1 minute with an insulation resistance meter, the insulation resistance was measured, and the specific resistance was calculated. The main component of porcelain thus obtained [Pb (Mg 1/3 Nb 2/3 ) O 3 ]
x [Pb (Ni 1/3 Nb 2/3 ) O 3 ] y [PbTiO 3 ]
z compounding ratio of x, y, z and subcomponent amount and density, dielectric constant, the relationship between dielectric loss and specific resistance shown in Table 2.
第２表からも明らかなように、Ｐｂ（Ｍｇ1/3Ｎｂ2/3）
Ｏ３−Ｐｂ（Ｎｉ1/3Ｎｂ2/3）Ｏ３−ＰｂＴｉＯ３３成
分系組成物に第１副成分であるマンガン・ニオブ酸鉛
［Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ３］を0.01〜10mol％、第
２副成分である銀（Ａｇ）を主成分に対して0.01〜2.0
重量％添加した本発明の磁器組成物は、高い誘電率、比
抵抗を保持し、かつ1050℃以下の低い温度で焼結し、積
層セラミック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。 As is clear from Table 2, Pb (Mg 1/3 Nb 2/3 )
O 3 -Pb (Ni 1/3 Nb 2/3 ) O 3 -PbTiO 3 three-component composition has the first subcomponent, manganese / lead niobate [Pb (Mn 1/3 Nb 2/3 ) O 3 ] 0.01 to 10 mol%, and silver (Ag) as the second subcomponent is 0.01 to 2.0 with respect to the main component.
The porcelain composition of the present invention added by weight% retains a high dielectric constant and a specific resistance and is sintered at a low temperature of 1050 ° C. or less, and provides an excellent material as a porcelain composition for a laminated ceramic capacitor. is there.
実施例61〜97、比較例50〜104 出発原料として酸化鉛（ＰｂＯ）、酸化マグネシウム
（ＭｇＯ）、酸化ニオブ（Ｎｂ２Ｏ５）、酸化ニッケル
（ＮｉＯ）、酸化チタン（ＴｉＯ２）、炭酸マンガン
（ＭｎＣＯ３）および銀（Ａｇ）を使用し、第３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のち800〜850℃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、有機バインダを入れて整粒後プレスし、直径約16m
m、厚さ約２mmの円板２枚と、直径約16mm、厚さ約10mm
の円柱を作製した。次にこれらの組成範囲の試料を1050
〜1200℃の温度で１時間焼成を行った。Examples 61 to 97, Comparative Examples 50 to 104 Lead oxide (PbO), magnesium oxide (MgO), niobium oxide (Nb 2 O 5 ), nickel oxide (NiO), titanium oxide (TiO 2 ) and manganese carbonate as starting materials. (MnCO 3 ) and silver (Ag) are used and weighed so that the compounding ratios shown in Table 3 are obtained. Next, the weighed materials are wet-mixed in a ball mill and then calcined at 800 to 850 ° C. The powder is crushed in a ball mill, filtered, dried, and then an organic binder is added to the powder, which is then pressed to obtain a diameter of approx. 16m
m, 2 discs with a thickness of about 2 mm, diameter of about 16 mm, thickness of about 10 mm
The cylinder of was produced. Samples in these composition ranges are then
Baking was performed at a temperature of ~ 1200 ° C for 1 hour.
焼成した円柱でアルキメデス法を用いて密度を求めた。
次に、円板の上下面に600℃で銀電極を焼き付け、デジ
タルＬＣＲメータで周波数１kHz、電圧１Vr.m.s、室温
で容量と誘電損失を測定し、誘電率を求めた。The density was determined using the Archimedes method on the fired cylinder.
Next, silver electrodes were baked on the upper and lower surfaces of the disk at 600 ° C., the capacitance and the dielectric loss were measured with a digital LCR meter at a frequency of 1 kHz, a voltage of 1 Vr.ms and room temperature to obtain the dielectric constant.
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（Ｎｉ1/3Ｎｂ2/3）Ｏ３］ｙ［ＰｂＴｉＯ３］
ｚの配合比ｘ、ｙ、ｚおよび副成分添加量と、密度、誘
電率、誘電損失および比抵抗の関係を第３表に示す。Next, a voltage of 50 V was applied for 1 minute with an insulation resistance meter, the insulation resistance was measured, and the specific resistance was calculated. The main component of porcelain thus obtained [Pb (Mg 1/3 Nb 2/3 ) O 3 ]
x [Pb (Ni 1/3 Nb 2/3 ) O 3 ] y [PbTiO 3 ]
a mixing ratio x, y, z and subcomponents amount of z, the density shows the dielectric constant, the relationship between dielectric loss and specific resistance in Table 3.
第２表からも明らかなように、Ｐｂ（Ｍｇ1/3Ｎｂ2/3）
Ｏ３−Ｐｂ（Ｎｉ1/3Ｎｂ2/3）Ｏ３−ＰｂＴｉＯ３３成
分系組成物に第１副成分としてマンガン（Ｍｎ）、ニオ
ブ（Ｎｂ）の中から少なくとも一種以上の元素を主成分
に対して0.02〜３mol％、第２副成分として銀（Ａｇ）
を主成分に対して0.01〜2.0重量％添加した本発明の磁
器組成物は、高い誘電率、比抵抗を保持し、かつ1050℃
以下の低い温度で焼結し、積層セラミックコンデンサ用
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、実施例では、第１副成分としてマンガンまたはニオ
ブを用いたが、この両成分をともに用いても同様の効果
が得られた。 As is clear from Table 2, Pb (Mg 1/3 Nb 2/3 )
O 3 -Pb (Ni 1/3 Nb 2/3 ) O 3 -PbTiO 3 3 manganese (Mn) as a first subcomponent component composition, the main component at least one element from among niobium (Nb) 0.02 to 3 mol% with respect to silver (Ag) as the second subcomponent
The porcelain composition of the present invention in which 0.01 to 2.0% by weight is added to the main component retains a high dielectric constant and a specific resistance and is 1050 ° C.
The present invention provides an excellent material as a porcelain composition for laminated ceramic capacitors by sintering at the following low temperatures. Although manganese or niobium was used as the first subcomponent in the examples, the same effect was obtained by using both of these components together.
なお、本発明の主成分の範囲以外および副成分添加量以
外では焼結温度が高くなったり、誘電率、比抵抗が低下
し、実用的でないため、前述のように限定される。In addition, since it is not practical since the sintering temperature becomes high, the dielectric constant and the specific resistance decrease except for the range of the main component of the present invention and the amount of the sub-components added, it is limited as described above.
［発明の効果］ 以上説明したように、本発明の磁器組成物は誘電率、比
抵抗の値が高く、良好な誘電損失の値を持ち、かつ低い
温度で焼結が可能である。このため、本発明の磁器組成
物を用いれば積層セラミックコンデンサの内部電極に安
価な銀−パラジウムを用いることができる等の効果を有
する。[Effects of the Invention] As described above, the porcelain composition of the present invention has a high dielectric constant and a high specific resistance, a good dielectric loss, and can be sintered at a low temperature. Therefore, if the porcelain composition of the present invention is used, there is an effect that inexpensive silver-palladium can be used for the internal electrodes of the laminated ceramic capacitor.
第１図は本発明の主成分組成範囲を示す３成分組成物で
ある。FIG. 1 is a three-component composition showing the main component composition range of the present invention.
Claims (3)
1/3Ｎｂ2/3）Ｏ３］、ニッケル・ニオブ酸鉛［Ｐｂ（Ｎ
ｉ1/3Ｎｂ2/3）Ｏ３］およびチタン酸鉛［ＰｂＴｉ
Ｏ３］からなる３成分組成物を［Ｐｂ（Ｍｇ1/3Ｎ
ｂ2/3）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、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） の各点を結ぶ線上、およびこの７点に囲まれる組成範囲
内にある主成分組成物に、副成分として銀［Ａｇ］を0.
01〜2.0重量％添加したことを特徴とする磁器組成物。1. Magnesium lead niobate [Pb (Mg
1/3 Nb 2/3 ) O 3 ], nickel lead niobate [Pb (N
i 1/3 Nb 2/3 ) O 3 ] and lead titanate [PbTi
O 3] 3-component composition consisting of [Pb (Mg 1/3 N
b 2/3 ) O 3 ] x [Pb (Ni 1/3 Nb 2/3 ) O 3 ]
When expressed as y [PbTiO 3 ] z (where x + y + z = 1.0), the following composition points are shown 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) on the line connecting the points and within the composition range surrounded by these seven points, the silver component [ Ag] to 0.
A porcelain composition characterized by being added in an amount of 01 to 2.0% by weight.
1/3Ｎｂ2/3）Ｏ３］、ニッケル・ニオブ酸鉛［Ｐｂ（Ｎ
ｉ1/3Ｎｂ2/3）Ｏ３］およびチタン酸鉛［ＰｂＴｉ
Ｏ３］からなる３成分組成物を［Ｐｂ（Ｍｇ1/3Ｎ
ｂ2/3）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、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） の各点を結ぶ線上、およびこの７点に囲まれる組成範囲
内にある主成分組成物に、第１副成分としてマンガン・
ニオブ酸鉛［Ｐｂ（Ｍｎ1/3Ｎｂ2/3）Ｏ３］を0.01〜10
mol％、第２副成分として銀［Ａｇ］を0.01〜2.0重量％
添加したことを特徴とする磁器組成物。2. Magnesium lead niobate [Pb (Mg
1/3 Nb 2/3 ) O 3 ], nickel lead niobate [Pb (N
i 1/3 Nb 2/3 ) O 3 ] and lead titanate [PbTi
O 3] 3-component composition consisting of [Pb (Mg 1/3 N
b 2/3 ) O 3 ] x [Pb (Ni 1/3 Nb 2/3 ) O 3 ]
When expressed as y [PbTiO 3 ] z (where x + y + z = 1.0), the following composition points are shown 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) on the line connecting the points and within the composition range surrounded by these 7 points, as the first subcomponent manganese·
Lead niobate [Pb (Mn 1/3 Nb 2/3 ) O 3 ] 0.01 to 10
mol%, 0.01-2.0% by weight of silver [Ag] as the second subcomponent
A porcelain composition characterized by being added.
1/3Ｎｂ2/3）Ｏ３］、ニッケル・ニオブ酸鉛［Ｐｂ（Ｎ
ｉ1/3Ｎｂ2/3）Ｏ３］およびチタン酸鉛［ＰｂＴｉ
Ｏ３］からなる３成分組成物を［Ｐｂ（Ｍｇ1/3Ｎ
ｂ2/3）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、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） の各点を結ぶ線上、およびこの７点に囲まれる組成範囲
内にある主成分組成物に、第１副成分としてマンガン
［Ｍｎ］および／またはニオブ［Ｎｂ］を主成分に対し
て0.01〜３mol％、第２副成分として銀［Ａｇ］を0.01
〜2.0重量％添加したことを特徴とする磁器組成物。3. Magnesium lead niobate [Pb (Mg
1/3 Nb 2/3 ) O 3 ], nickel lead niobate [Pb (N
i 1/3 Nb 2/3 ) O 3 ] and lead titanate [PbTi
O 3] 3-component composition consisting of [Pb (Mg 1/3 N
b 2/3 ) O 3 ] x [Pb (Ni 1/3 Nb 2/3 ) O 3 ]
When expressed as y [PbTiO 3 ] z (where x + y + z = 1.0), the following composition points are shown 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) on the line connecting the points and within the composition range surrounded by these 7 points, as the first subcomponent 0.01 to 3 mol% of manganese [Mn] and / or niobium [Nb] with respect to the main component, and 0.01 [silver [Ag] as the second sub-component.
A porcelain composition characterized by being added in an amount of up to 2.0% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014797A JPH0610100B2 (en) | 1990-01-26 | 1990-01-26 | Porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014797A JPH0610100B2 (en) | 1990-01-26 | 1990-01-26 | Porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03223149A JPH03223149A (en) | 1991-10-02 |
| JPH0610100B2 true JPH0610100B2 (en) | 1994-02-09 |
Family
ID=11871043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014797A Expired - Fee Related JPH0610100B2 (en) | 1990-01-26 | 1990-01-26 | Porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610100B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5935485A (en) * | 1996-10-31 | 1999-08-10 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Piezoelectric material and piezoelectric element |
| CN100449813C (en) * | 2006-10-24 | 2009-01-07 | 北京科技大学 | A functionally graded piezoelectric drive device and its preparation method |
| CN114804872A (en) * | 2022-04-29 | 2022-07-29 | 杭州瑞声海洋仪器有限公司 | Lead meta-niobate based piezoelectric ceramic material with high Curie temperature and high stability and preparation method thereof |
-
1990
- 1990-01-26 JP JP2014797A patent/JPH0610100B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03223149A (en) | 1991-10-02 |
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