JPS63151655A - Sintering aid for ceramics - Google Patents
Sintering aid for ceramicsInfo
- Publication number
- JPS63151655A JPS63151655A JP61300247A JP30024786A JPS63151655A JP S63151655 A JPS63151655 A JP S63151655A JP 61300247 A JP61300247 A JP 61300247A JP 30024786 A JP30024786 A JP 30024786A JP S63151655 A JPS63151655 A JP S63151655A
- Authority
- JP
- Japan
- Prior art keywords
- sintering aid
- temperature
- added
- dielectric
- weight
- 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.)
- Granted
Links
- 238000005245 sintering Methods 0.000 title claims description 42
- 239000000919 ceramic Substances 0.000 title claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 description 21
- 239000003989 dielectric material Substances 0.000 description 17
- 239000003990 capacitor Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 210000003754 fetus Anatomy 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 229910002113 barium titanate 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
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明はセラミクス用焼結助剤に関し、特に誘電体材
料の主成分に添加混合されるセラミクス用焼結助剤に関
する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a sintering aid for ceramics, and particularly to a sintering aid for ceramics that is added and mixed with the main component of a dielectric material.
（従来技術）
たとえば、チタン酸バリウム（ＢａＴｉＯａ） 、チタ
ン酸ストロンチウム（ＳｒＴｉＯｓ） 、酸化チタン、
（ＴｉＯｚ）などを主体とする誘電体磁器は、通常１゜
３００℃以上の温度で焼成される。(Prior art) For example, barium titanate (BaTiOa), strontium titanate (SrTiOs), titanium oxide,
Dielectric ceramics mainly made of (TiOz) are usually fired at temperatures of 1° to 300° C. or higher.
（発明が解決しようとする問題点）
このような磁器組成物を用いてたとえば積層コンデンサ
を製造する場合には、各セラミック層の間に内部電極が
介在されるが、誘電体組成物は上述したように１．３０
０℃以上の温度で焼成されるため、未焼成のセラミック
積層体には、内部電極として高融点の白金、パラジウム
などの貴金属のペーストが用いられる。しかしながら、
これらの貴金属は高価なため、積層コンデンサに占める
内部電極の材料費が３０〜５０％にものぼり、積層コン
デンサのコストダウンに対応できないことになる。(Problems to be Solved by the Invention) When manufacturing, for example, a multilayer capacitor using such a ceramic composition, internal electrodes are interposed between each ceramic layer. Like 1.30
Since the ceramic laminate is fired at a temperature of 0° C. or higher, a paste of a noble metal such as platinum or palladium with a high melting point is used as an internal electrode in the unfired ceramic laminate. however,
Since these precious metals are expensive, the material cost of the internal electrodes in a multilayer capacitor accounts for as much as 30 to 50%, making it impossible to reduce the cost of multilayer capacitors.
また、焼成温度が１．３００℃以上になれば、使用され
る焼成炉の損傷が激しいので、焼成炉の保守、管理コス
トが使用時間の経緯とともに高（なり、しかも、焼成温
度が高いため、磁器化に要するエネルギコストも膨大な
ものとなる。In addition, if the firing temperature exceeds 1.300℃, the firing furnace used will be severely damaged, so the maintenance and management costs of the firing furnace will increase as the usage time increases.Moreover, since the firing temperature is high, The energy cost required for porcelain production is also enormous.
このため、最近では、低温焼結用の材料として鉛系のコ
ンデンサ材料、内部電極に安価なニッケルを用いた非還
元性のコンデンサ材料、さらには、内部電極として鉛、
鉛−錫合金を用い、あらかじめ積層体に内部電極が形成
される領域に空隙層を形成しておき、この空隙層に溶融
した鉛、鉛−錫合金を注入し、冷却、固化することによ
り、積層コンデンサとしたものがある。For this reason, recently lead-based capacitor materials have been developed as materials for low-temperature sintering, non-reducible capacitor materials that use inexpensive nickel for internal electrodes, and even lead-based capacitor materials for internal electrodes.
By using a lead-tin alloy, a void layer is formed in advance in the area where the internal electrodes will be formed in the laminate, and molten lead and lead-tin alloy are injected into this void layer and cooled and solidified. There are also multilayer capacitors.
しかしながら、従来よりすでに存在する誘電体材料につ
いて、そのものが有する特性が使用要求レベルに十分に
応えられるものである以上、この特性を損なわずに低温
で焼成できれば、それに越したことはない。However, since the properties of existing dielectric materials are sufficient to meet the usage requirements, it would be better if they could be fired at low temperatures without impairing these properties.
それゆえに、この発明の主たる目的は、たとえばコンデ
ンサ材料などの誘電体材料の焼成温度を下げることがで
きる、セラミクス用焼結助剤を提供することである。Therefore, the main object of the present invention is to provide a sintering aid for ceramics that is capable of lowering the firing temperature of dielectric materials, such as capacitor materials.
（問題点を解決するための手段）
この発明は、ＭｎＯが２〜４０モル％、ＲＯ（ただし、
ＲはＢａ、 Ｓｒ、 ＣａおよびＭｇのうち少なくとも
１種）が５〜４０モル％、および（Ｔｉ、 Ｓｉ） Ｏ
ｘが３０〜７０モル％（ただし、（７ｉ、 Ｓｔ） Ｏ
ｌのうちＳｉＯ３成分が１５モル％以上）からなる主成
分に、１００重量部の主成分に対して、Ａｌｔ’ｓ 、
Ｂｔｕｓ 。(Means for Solving the Problems) This invention is characterized in that MnO is 2 to 40 mol% and RO (however,
R is 5 to 40 mol% of at least one of Ba, Sr, Ca and Mg), and (Ti, Si)O
x is 30 to 70 mol% (however, (7i, St) O
100 parts by weight of the main component, Alt's,
Btus.
ＣｕＯ＋ Ｎｂｔ０５ 、 Ｔａ２０１ 、 Ｇａｚｅ
ｓ ＋ Ｇｅ０ｚ ｌ ＭＯＯｓ ＋ＺｒＱｔ ｌ ｗ
ｏ３１ ’ＡＯＯｓ ＋ Ｆｅｔ０３ ＋ Ｃｏｏ ｌ
ＮＩＯ＋ ＰｂＯ９およびＢｉ、０３のうち少なくと
も１種を０〜２０重量部（ただし、ＭＯＯｓ ＋ Ｚｒ
（ｈ ＋ Ｉ’１０３ ＋ Ｍｏ５ｓ ＋ Ｆｅｇｇ３
＋ ＣｏＯ＋ ＮｔＯ＋ ＰｂＯおよびＢｉ、０２につ
いては１０重量部以下）添加した、セラミクス用焼結助
剤である。CuO+ Nbt05, Ta201, Gaze
s + Ge0z l MOOs + ZrQt l w
o31 'AOOs + Fet03 + Cool
NIO + 0 to 20 parts by weight of at least one of PbO9 and Bi, 03 (however, MOOs + Zr
(h + I'103 + Mo5s + Fegg3
+ CoO + NtO + PbO and Bi (10 parts by weight or less for 02) are added as a sintering aid for ceramics.
この発明のセラミクス用焼結助剤を上述のような組成範
囲に限定したのは次の理由による。The reason why the composition range of the ceramic sintering aid of the present invention is limited to the above-mentioned range is as follows.
つまり、ＭｎＯが２モル％未満では焼成温度が１３００
℃を超えてしまい、この発明の目的が達成できなくなる
からである。一方、ＭｎＯが４０モル％を超える場合も
焼成温度が１，３００℃を超えてしまうからである。In other words, when MnO is less than 2 mol%, the firing temperature is 1300.
This is because the object of the present invention cannot be achieved if the temperature exceeds . On the other hand, when MnO exceeds 40 mol%, the firing temperature also exceeds 1,300°C.
また、ＲＯが５モル％未満あるいは４０モル％を超える
と、焼成温度が１．３００℃を超えてしまうからである
。Further, if RO is less than 5 mol% or exceeds 40 mol%, the firing temperature will exceed 1.300°C.
さらに、（Ｔｉｔ Ｓｉ） Ｏｘが３０モル％未満ある
いは７０モル％を超えると、焼成温度が１．３００℃を
超えてしまい、この発明の目的が達成できなくなってし
まうからであるａ （Ｔｔ、 Ｓｔ） ０１のうち、
５ｉＯ１が１５モル％未満あるいはＴｉ（ｈが含有され
ない場合にも、焼成温度の低減化が実現されないからで
ある。Furthermore, if (Tit Si) Ox is less than 30 mol% or exceeds 70 mol%, the firing temperature will exceed 1.300°C, making it impossible to achieve the object of the present invention.a (Tt, St ) out of 01,
This is because, even when 5iO1 is less than 15 mol% or Ti(h) is not contained, the firing temperature cannot be lowered.
また、ＭｎＯ、ＲＯおよび（Ｔｉｔ Ｓｔ） Ｏｔから
なる主成分に、１００重量部の主成分に対して、Ａｌ１
ｔＯｓ ＋ Ｂｔｕｓ ＋ ＣｕＯ＋ Ｎｂ
ｔＱｓ ＋ Ｔａｇ’ｓ ＋ ＧａｚＯ＝
、 ＧｅＯｌ ｌ ＹｚＯｓ ＋ Ｚｒ０ｔ ｌ Ｗ
Ｏｓ ＋ ＭＯＯｓ ＋ Ｆｅｔｕｓ Ｉ Ｃｏｏ ＋
ＮｉＯ、ＰｂＯおよびＢｉ露０３のうち少なくとも１種
を２０重量部（ＹｚＯｓ 、 Ｚｒ０ｔ ｌ Ｔｉｔ３
、 Ｍｏｂ、 、 Ｆｅｔｕｓ＋ Ｃｏｏ ＋ ＩＯ
＋ ＰｂＯおよびＢｉｔ’ｓについては１０重量部）を
超えた範囲で添加した場合にも、焼成温度の低減化が実
現されないからである。In addition, Al1 was added to the main component consisting of MnO, RO and (Tit St) Ot to 100 parts by weight of the main component.
tOs + Btus + CuO+ Nb
tQs + Tag's + GazO=
, GeOl l YzOs + Zr0t l W
Os + MOOs + Fetus I Coo +
20 parts by weight of at least one of NiO, PbO and Bi Tit3 (YzOs, Zr0tl Tit3
, Mob, , Fetus + Coo + IO
This is because even if PbO and Bit's are added in an amount exceeding 10 parts by weight), the firing temperature cannot be reduced.
（発明の効果）
この発明によれば、誘電体材料の焼成温度を下げること
ができる。しかも、この場合、焼結された誘電体磁器は
その誘電損失に悪影響が与えられない。(Effects of the Invention) According to the present invention, the firing temperature of dielectric material can be lowered. Moreover, in this case, the dielectric loss of the sintered dielectric ceramic is not adversely affected.
この発明の上述の目的、その他の目的、特徴および利点
は、以下の実施例の詳細な説明から一層明らかとなろう
。The above objects, other objects, features and advantages of the present invention will become more apparent from the detailed description of the following embodiments.
（実施例）
この発明のセラミクス用焼結助剤は、主体となる誘電体
材料を焼結する際に、あらかじめ所定の割合で誘電体材
料の主成分に添加混合された後成形体とされ、その後焼
成プロセスにもたらされる。(Example) The sintering aid for ceramics of the present invention is added to the main component of the dielectric material in advance at a predetermined ratio when sintering the main dielectric material, and then formed into a molded body. Then brought to the firing process.
この場合、セラミクス用焼結助剤は誘電体材料の主成分
に対して、個々に添加してもよいが、あらかじめセラミ
クス用焼結助剤を配合しておき、これを熱処理して溶融
し、その後ガラス化して粉砕したものを、誘電体材料の
主成分に添加混合してもよい。In this case, the sintering aid for ceramics may be added individually to the main components of the dielectric material, but the sintering aid for ceramics is blended in advance, and this is heat-treated and melted. Thereafter, the vitrified and pulverized material may be added to and mixed with the main component of the dielectric material.
なお、この発明のセラミクス用焼結助剤を誘電体材料の
主成分に添加する割合は、誘電体材料の主成分によって
異なるが、全体の０．０５〜２５．０重量％の範囲であ
る。これは、セラミクス用焼結助剤の添加する割合が０
．０５重重量未満では焼成温度の低減化が実現されず、
一方、２５゜０重量％を超えると誘電体特性が著しく損
なわれるからである。The proportion of the ceramic sintering aid of the present invention added to the main component of the dielectric material varies depending on the main component of the dielectric material, but is in the range of 0.05 to 25.0% by weight of the total. This means that the proportion of ceramic sintering aid added is 0.
．． If the weight is less than 0.05 weight, the firing temperature cannot be reduced,
On the other hand, if it exceeds 25.0% by weight, the dielectric properties will be significantly impaired.
次ＪＬＩｆｉ上
まず、別表１に示した組成の焼結助剤が得られるように
、各成分の酸化物、炭酸塩あるいは水酸化物を調合した
。これらをアルミナボールを玉石としてポリボットミル
で１６時時間式混合、粉砕した後蒸発乾燥して、粉末を
得た。得られた粉末をジルコニア質の匣に入れて８００
℃の温度で２時間焼成した後、２００メツシユの篩を通
過するように粗粉砕して、焼結助剤を準備した。NextJLIfi First, oxides, carbonates, or hydroxides of each component were prepared so as to obtain a sintering aid having the composition shown in Attached Table 1. These were mixed for 16 hours using a polybot mill using alumina balls as cobblestones, pulverized, and then evaporated to dryness to obtain a powder. The obtained powder was placed in a zirconia box and heated to 800
After firing at a temperature of 200° C. for 2 hours, the mixture was coarsely ground to pass through a 200-mesh sieve to prepare a sintering aid.
一方、セラミック原料として、８４ＢａＴｉＯｓ １
０ＣａＳｎ０３−６ ＣａＺｒＯｓ （モル比）の主成
分にＭｎＯが１重量％添加された組成物が得られるよう
に、各原料の酸化物または炭酸塩を調合した。これらを
アルミナボールを玉石としてポリボットミルで１６時時
間式混合、粉砕した後蒸発乾燥して、粉末を得た。得ら
れた粉末をジルコニア質の匣にいれて１．１００℃の温
度で２時間焼成した後、２００メツシユの篩を通過する
ように粗粉砕して、誘電体粉末を準備した。On the other hand, as a ceramic raw material, 84BaTiOs 1
0CaSn03-6 The oxide or carbonate of each raw material was prepared so as to obtain a composition in which 1% by weight of MnO was added to the main component of CaZrOs (molar ratio). These were mixed for 16 hours using a polybot mill using alumina balls as cobblestones, pulverized, and then evaporated to dryness to obtain a powder. The obtained powder was placed in a zirconia box and fired at a temperature of 1.100° C. for 2 hours, and then coarsely ground to pass through a 200 mesh sieve to prepare a dielectric powder.
次に、準備した誘電体粉末に焼結助剤を別表１に示す割
合で添加し、これにポリビニルアルコール系のバインダ
を加えてポリボットミルで１６時時間式混合した。これ
を蒸発乾燥し、造粒した後、１．０００ｋｇ／−の圧力
で加圧して直径１０ｍ。Next, a sintering aid was added to the prepared dielectric powder in the proportion shown in Attached Table 1, a polyvinyl alcohol binder was added thereto, and the mixture was mixed in a polybot mill for 16 hours. This was evaporated to dryness, granulated, and then pressurized at a pressure of 1.000 kg/- to form particles with a diameter of 10 m.
厚み１ｆｉの円板に成形して成形体を得た。この成形体
を自然雰囲気中で１．０００℃〜１，３５０℃の温度で
２時間焼成して、焼結体を得た。A molded body was obtained by molding into a disk having a thickness of 1fi. This molded body was fired in a natural atmosphere at a temperature of 1.000°C to 1,350°C for 2 hours to obtain a sintered body.
得られた焼結体について、ふくしん液に漬けて焼結度の
試験を行い、最適焼成温度を決定した。The obtained sintered body was immersed in a sintering solution to test the degree of sintering, and the optimum firing temperature was determined.
また、得られた焼結体の両面に電極となる銀ペーストを
印刷塗布し、銀ペーストを空気中で８００℃の温度で３
０分分間−て、電極を形成して、コンデンサ（試料）を
得た。得られたコンデンサ（試料）について２５℃の温
度におけるｌＫＨ２゜Ｉ Ｖｒ、ｍ、ｓでの誘電率（ε
）、誘電損失（Ｔａｎ δ）および＋２０℃を基準にし
た一２５〜＋８５℃の温度範囲で誘電率の温度特性を測
定した。この測定結果を別表２に示した。In addition, silver paste to serve as electrodes was applied by printing on both sides of the obtained sintered body, and the silver paste was applied in air at a temperature of 800°C for 30 minutes.
After 0 minutes, electrodes were formed and a capacitor (sample) was obtained. For the obtained capacitor (sample), the dielectric constant (ε
), dielectric loss (Tan δ), and temperature characteristics of dielectric constant in a temperature range of -25 to +85°C based on +20°C were measured. The measurement results are shown in Attached Table 2.
なお、別表１および別表２中、＊印のものはこの発明範
囲外のものである。In addition, in Attached Table 1 and Attached Table 2, those marked with * are outside the scope of this invention.
また、別表２において、温度特性について、Ｂ、 Ｃ
，Ｄ、 ＥおよびＦの各特性はＪＩＳ規格による温度特
性を意味し、各特性について詳細に説明すれば次のとお
りである。In addition, in Attached Table 2, regarding temperature characteristics, B, C
, D, E, and F mean temperature characteristics according to JIS standards, and each characteristic will be explained in detail as follows.
Ｂ特性＝２０℃における静電容量を基準として、−２５
℃〜＋８５℃における容量変化
率が一１０〜＋１０％を超えない。B characteristic = -25 based on capacitance at 20°C
The rate of change in capacity at temperatures between 110 and +85°C does not exceed 110 to +10%.
Ｃ特性：２０℃における静電容量を基準として、−２５
℃〜＋８５℃における容量変化
率が一２０〜＋２０％を超えない。C characteristic: -25 based on capacitance at 20°C
The rate of change in capacity at temperatures between 120 and +85°C does not exceed 120 to +20%.
Ｂ特性：２０℃における静電容量を基準として、′−２
５℃〜＋８５℃における容量変化
率が一３０〜＋２０％を超えない。B characteristic: Based on the capacitance at 20℃, '-2
The rate of change in capacity at 5°C to +85°C does not exceed 130% to +20%.
Ｂ特性：２０℃における静電容量を基準として、−２５
℃〜＋８５℃における容量変化
率が一５５〜＋２０％を超えない。B characteristic: -25 based on capacitance at 20°C
The rate of change in capacity between 155 and 20% at temperatures between 155 and 85 degrees Celsius does not exceed 155 to 20%.
Ｂ特性：２０℃における静電容量を基準として、−２５
℃〜＋８５℃における容量変化
率が一８０〜＋３０！４を超えない。B characteristic: -25 based on capacitance at 20°C
The rate of change in capacity at temperatures between 180 and +85°C does not exceed 180 to +30!4.
この実施例１においては、この発明の焼結助剤を誘電体
材料に添加して焼成することによって、焼結助剤を未添
加のものに比べて、焼結温度を低減できることがわかる
。また、焼結助剤の添加量を増加していくと、室温にお
ける誘電率は低下するが、一方では、誘電率の温度特性
がＢ特性−Ｂ特性−り特性−Ｃ特性−Ｂ特性のように変
化し、その変化率を徐々に少なくでき、温度特性の改善
に効果がみられることがわかる。さらに、１００重量％
の誘電体材料に対して０．０５重量％の焼結助剤が添加
されているときには、誘電率の低下現象はみられないこ
とがわかる。また、室温における誘電損失は焼結助剤の
添加量にほとんど影響されないことがわかる。In this Example 1, it can be seen that by adding the sintering aid of the present invention to the dielectric material and firing it, the sintering temperature can be lowered compared to the case where the sintering aid is not added. In addition, as the amount of sintering aid added increases, the dielectric constant at room temperature decreases, but on the other hand, the temperature characteristic of the dielectric constant becomes B characteristic - B characteristic - C characteristic - C characteristic - B characteristic. It can be seen that the rate of change can be gradually reduced, which is effective in improving temperature characteristics. Furthermore, 100% by weight
It can be seen that when 0.05% by weight of the sintering aid is added to the dielectric material, no decrease in dielectric constant is observed. Furthermore, it can be seen that the dielectric loss at room temperature is hardly affected by the amount of the sintering aid added.
叉立五ｌ
セラミック原料として、３５ＳｒＴｉＯｉ １５Ｐｂ
ＴｉＯｓ−１７ＣａＴｉＯａ ７Ｂｉｚ０３ ２６Ｔ
ｉＯｇ （モル比）にＭｎＯが０．１重量％添加された
組成の誘電体粉末を実施例１と同様に準備し、別表３に
示した組成の焼結助剤を添加して、実施例１と同様に評
価した。得られた結果を別表４に示した。なお、別表３
および別表４中、＊印のものはこの発明範囲外のもので
ある。35SrTiOi 15Pb as a ceramic raw material
TiOs-17CaTiOa 7Biz03 26T
A dielectric powder having a composition in which 0.1% by weight of MnO was added to iOg (molar ratio) was prepared in the same manner as in Example 1, and a sintering aid having the composition shown in Attached Table 3 was added to prepare Example 1. It was evaluated in the same way. The results obtained are shown in Attached Table 4. In addition, attached table 3
In Table 4, those marked with * are outside the scope of this invention.
この実施例２においても、実施例１と同様に、この発明
の焼結助剤を誘電体材料に添加して焼成することによっ
て、焼結助剤を未添加のものに比べて、焼結温度を低減
できることがわかる。また、焼結助剤の添加量を増加し
ていくと、室温における誘電率は低下するが、一方では
、誘電率の温度特性がＣ特性−Ｂ特性のように変化し、
その変化率を徐々に少なくでき、温度特性の改善に効果
がみられることがわかる。さらに、焼結助剤が０゜０５
重量％添加されているときには、誘電率の低下現象はみ
られないことがわかる。また、室温における誘電損失は
焼結助剤の添加量にほとんど影響されないことがわかる
。In this Example 2, as in Example 1, by adding the sintering aid of the present invention to the dielectric material and firing it, the sintering temperature is lower than that of the dielectric material without the addition of the sintering aid. It can be seen that it is possible to reduce the In addition, as the amount of sintering aid added increases, the dielectric constant at room temperature decreases, but on the other hand, the temperature characteristic of the dielectric constant changes as shown in C characteristic - B characteristic,
It can be seen that the rate of change can be gradually reduced, which is effective in improving temperature characteristics. Furthermore, the sintering aid is 0°05
It can be seen that when % by weight is added, no decrease in dielectric constant is observed. Furthermore, it can be seen that the dielectric loss at room temperature is hardly affected by the amount of the sintering aid added.
大血医主
セラミック原料として、８１．５ＢａＴｉＯｓ −８Ｂ
ａＺｒ０゜−１０ＣａＺｒＯｓ ０．５Ｍｇ０ （モ
ル比）にＭｎＯが０．３重量％添加された組成の誘電体
粉末を実施例１と同様に準備し、別表５に示した組成の
焼結助剤を添加して実施例１と同様に評価した。ただし
、この実施例３ではその焼成雰囲気として還元性雰囲気
（Ｈｚを１％含むＮ２雰囲気）を用いて焼成した。得ら
れた結果を別表６に示した。なお、別表５および別表６
中、＊印のものはこの発明範囲外のものである。As a major ceramic raw material, 81.5BaTiOs-8B
A dielectric powder having a composition of aZr0゜-10CaZrOs 0.5Mg0 (molar ratio) and 0.3% by weight of MnO was prepared in the same manner as in Example 1, and a sintering aid having the composition shown in Attached Table 5 was added. and evaluated in the same manner as in Example 1. However, in this Example 3, a reducing atmosphere (N2 atmosphere containing 1% Hz) was used as the firing atmosphere. The results obtained are shown in Attached Table 6. In addition, Attached Table 5 and Attached Table 6
Items marked * are outside the scope of this invention.
この実施例３のように、還元性雰囲気で焼成した場合で
も、他の実施例と同様に、この発明の焼結助剤を誘電体
材料に添加して焼成することによって、焼結助剤を未添
加のものに比べて、焼結温度を低減できることがわかる
。また、焼結助剤の添加量を増加していくと、室温にお
ける誘電率は低下するが、一方では、誘電率の温度特性
がＢ特性−Ｂ特性−り特性のように変化し、その変化率
を徐々に少なくでき、温度特性の改善に効果がみられる
ことがわかる。さらに、焼結助剤が０． １重量％のと
きには、誘電率の低下現象は認められないことがわかる
。また、室温における誘電損失は焼結助剤の添加量にほ
とんど影響されないこともわかる。Even in the case of firing in a reducing atmosphere as in Example 3, the sintering aid can be removed by adding the sintering aid of this invention to the dielectric material and firing, as in the other examples. It can be seen that the sintering temperature can be lowered compared to that without additives. In addition, as the amount of sintering aid added increases, the dielectric constant at room temperature decreases, but on the other hand, the temperature characteristics of the dielectric constant change as shown in B characteristic-B characteristic, and the change It can be seen that the ratio can be gradually reduced, which is effective in improving temperature characteristics. Furthermore, the sintering aid is 0. It can be seen that when the amount is 1% by weight, no decrease in dielectric constant is observed. It can also be seen that the dielectric loss at room temperature is hardly affected by the amount of sintering aid added.
上述の各実施例から明らかなように、この発明の焼結助
剤を、Ｔｉ１ｔを主たる成分として含有する誘電体材料
に添加することによって、誘電体損失に悪影響を与えず
焼結温度の低減化を図ることができる。これは、焼結助
剤にも、ＴｉＯ意が含まれ、それと誘電体材料中のＴｉ
０１との焼結温度域における濡れ性がよくなり、緻密な
誘電体セラミクス焼結体が得られるように働くことによ
るものである。As is clear from the above examples, by adding the sintering aid of the present invention to a dielectric material containing Ti1t as a main component, the sintering temperature can be reduced without adversely affecting dielectric loss. can be achieved. This is because the sintering aid also contains TiO, and the dielectric material contains TiO.
This is because the wettability in the sintering temperature range with 01 is improved and a dense dielectric ceramic sintered body can be obtained.
特許出願人 株式会社 村田製作所 代理人 弁理士 岡 １） 全 啓 （ほか１名）Patent applicant: Murata Manufacturing Co., Ltd. Agent: Patent Attorney Oka 1) Zenkei (1 other person)
Claims (1)
少なくとも１種）が５〜４０モル％、および （Ｔｉ、Ｓｉ）Ｏ＿２が３０〜７０モル％（ただし、（
Ｔｉ、Ｓｉ）Ｏ＿２のうちＳｉＯ＿２成分が１５モル％
以上）からなる主成分に、 １００重量部の前記主成分に対して、Ａｌ＿２Ｏ＿３、
Ｂ＿２Ｏ＿３、ＣｕＯ、Ｎｂ＿２Ｏ＿５、Ｔａ＿２Ｏ＿
５、Ｇａ＿２Ｏ＿３、ＧｅＯ＿２、Ｙ＿２Ｏ＿３、Ｚｒ
Ｏ＿２、ＷＯ＿３、ＭｏＯ＿３、Ｆｅ＿２Ｏ＿３、Ｃｏ
Ｏ、ＮｉＯ、ＰｂＯおよびＢｉ＿２Ｏ＿３のうち少なく
とも１種を０〜２０重量部（ただし、Ｙ＿２Ｏ＿３、Ｚ
ｒＯ＿２、ＷＯ＿３、ＭｏＯ＿３、Ｆｅ＿２Ｏ＿３、Ｃ
ｏＯ、ＮｉＯ、ＰｂＯおよびＢｉ＿２Ｏ＿３については
１０重量部以下）添加した、セラミクス用焼結助剤。[Claims] 2 to 40 mol% of MnO, 5 to 40 mol% of RO (R is at least one of Ba, Sr, Ca, and Mg), and 30 to 40 mol% of (Ti, Si)O_2 70 mol% (however, (
Ti, Si) SiO_2 component is 15 mol% of O_2
above), based on 100 parts by weight of the main component, Al_2O_3,
B_2O_3, CuO, Nb_2O_5, Ta_2O_
5, Ga_2O_3, GeO_2, Y_2O_3, Zr
O_2, WO_3, MoO_3, Fe_2O_3, Co
0 to 20 parts by weight of at least one of O, NiO, PbO and Bi_2O_3 (however, Y_2O_3, Z
rO_2, WO_3, MoO_3, Fe_2O_3, C
10 parts by weight or less of oO, NiO, PbO and Bi_2O_3) are added as sintering aids for ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61300247A JP2666262B2 (en) | 1986-12-16 | 1986-12-16 | Sintering aid used in dielectric ceramics containing TiO2 as a main component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61300247A JP2666262B2 (en) | 1986-12-16 | 1986-12-16 | Sintering aid used in dielectric ceramics containing TiO2 as a main component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63151655A true JPS63151655A (en) | 1988-06-24 |
| JP2666262B2 JP2666262B2 (en) | 1997-10-22 |
Family
ID=17882481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61300247A Expired - Lifetime JP2666262B2 (en) | 1986-12-16 | 1986-12-16 | Sintering aid used in dielectric ceramics containing TiO2 as a main component |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2666262B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996008019A1 (en) * | 1994-09-07 | 1996-03-14 | Sumitomo Metal Industries, Ltd. | Dielectric procelain composition and its manufacture |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI461383B (en) * | 2011-08-30 | 2014-11-21 | Sintering aid composition, dielectric ceramic composition, and multilayer ceramic capacitor comprising the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5436598A (en) * | 1977-08-26 | 1979-03-17 | Takagi Kogyo Kk | Ceramic dielecyric composite for temperature compensation |
| JPS5556066A (en) * | 1978-10-18 | 1980-04-24 | Thomson Csf | Ceramic material for low sintering temperature dielectric body |
| JPS57183365A (en) * | 1981-05-01 | 1982-11-11 | Tam Ceramics Inc | Low temperature bake dielectric ceramic composition and manufacture |
-
1986
- 1986-12-16 JP JP61300247A patent/JP2666262B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5436598A (en) * | 1977-08-26 | 1979-03-17 | Takagi Kogyo Kk | Ceramic dielecyric composite for temperature compensation |
| JPS5556066A (en) * | 1978-10-18 | 1980-04-24 | Thomson Csf | Ceramic material for low sintering temperature dielectric body |
| JPS57183365A (en) * | 1981-05-01 | 1982-11-11 | Tam Ceramics Inc | Low temperature bake dielectric ceramic composition and manufacture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996008019A1 (en) * | 1994-09-07 | 1996-03-14 | Sumitomo Metal Industries, Ltd. | Dielectric procelain composition and its manufacture |
| US5846892A (en) * | 1994-09-07 | 1998-12-08 | Sumitomo Metal Industries Ltd. | Ceramic dielectrics and methods for forming the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2666262B2 (en) | 1997-10-22 |
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