JPH0321488B2 - - Google Patents
Info
- Publication number
- JPH0321488B2 JPH0321488B2 JP60249941A JP24994185A JPH0321488B2 JP H0321488 B2 JPH0321488 B2 JP H0321488B2 JP 60249941 A JP60249941 A JP 60249941A JP 24994185 A JP24994185 A JP 24994185A JP H0321488 B2 JPH0321488 B2 JP H0321488B2
- Authority
- JP
- Japan
- Prior art keywords
- alkoxide
- perovskite compound
- compound
- precipitate
- composite
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 19
- 150000004703 alkoxides Chemical class 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000010304 firing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Inorganic Insulating Materials (AREA)
Description
〔産業上の利用分野〕
本発明は、圧電セラミツクス材料、誘電体セラ
ミツクス材料に適する金属酸化物の複合ペロブス
カイト化合物の製造方法に関するものである。
〔従来技術とその問題点〕
従来、Ｗ、Fe、Nb、Pbの酸化物を含む複合ペ
ロブスカイト化合物は、それぞれの金属の酸化物
を混合後、仮焼、粉砕、焼成して製造していた。
しかしながら、このように従来の方法では、固溶
状態が均一になりにくく、その上、製造された化
合物粉末の粒径分布が広くかつ粒子形状が不均一
である。従つて、こうして得られた複合ペロブス
カイト化合物は高い誘電率を示さないという欠点
がある。更に、焼成のために、1000℃以上の高温
が必要であり、エネルギー消費の点からも不利で
あるばかりでなく、例えば、コンデンサに用いる
場合使用する内部電極に高価なパラジウムを多く
含むAg−Pd合金を使用しなければならないとい
う欠点もある。
〔問題点を解決するための手段〕
上記問題点に鑑み、本発明は、固溶状態が均一
で、かつ粒子の粒度がほぼ一定でかつ粒子形状も
均一で、エネルギー消費がな少く、かつ例えばコ
ンデンサに用いた場合内部電極に高価なパラジウ
ムの使用を少なくできる複合プロブスカイト化合
物の製造方法を提供することを目的とするもので
ある。
本発明の製造方法は、Pbアルコキシド、Feア
ルコキシド、およびNbアルコキシドを化学論比
に混合し、これに水を加えて加水分解を行ない、
析出物を乾燥して第一のペロブスカイト化合物を
得、一方Pbアルコキシド、Feアルコキシド、お
よびＷアルコキシドを、同様に混合および加水分
解して、析出物を乾燥して第二のペロブスカイト
化合物を得、該第一および第二のペロブスカイト
化合物を混合し、焼成してxPb（Fe1/2・Nb1/2）
O3−１−xPb（Fe2/3・W1/3）O3系（０ｘ１）
の複合ペロブスカイト化合物を得ることを特徴と
するものである。
以下、本発明の実施例について述べる。
〔実施例〕
Pbアルコキシド（Pb（OR）2）、Feアルコキシ
ド（Fe（OR）3）、Nbアルコキシド（Nb（OR）5）
（但しＲはアルキル基）を、モル比で、２：１：
１の割合となるように、例えばそれぞれ12.00ｇ、
4.28ｇ、7.16ｇを、混合する。この混合は、N2気
流中のベンゼン液（あるいは、メチルやブタノー
ル等の有機溶媒も用いられる）の例えば200ml中
へ溶かしながら温度40〜50℃で、４時間ないし５
時間、例えば、50℃で５時間行なう。その後この
溶液に過剰の蒸留水を加えて加水分解を行ない10
時間放置する。その結果生じた沈澱物を過、洗
浄、乾燥してＡ微粉末を得る。
一方、Pbアルコキシド（Pb（OR）2）、Feアル
コキシド（Fe（OR）3）、Ｗアルコキシド（Ｗ
（OR）6）を、モル比で、３：２：１の割合となる
ように、例えばそれぞれ、12.00ｇ、5.73ｇｒ、
6.61ｇを、混合する。この混合も上記と同様の条
件で行いその後上記と同様に水を加えて、沈澱物
を過、洗浄、乾燥してＢ微粉末を得る。
ＡおよびＢ微粉末を混合後、空気中にて約900
℃で焼成することによつて、複合ペロブスカイト
化合物の粉末が得られる。
得られた微粉末の粒径は電子顕微鏡観察により
約0.1μｍであることが確認された。これは従来法
による場合の0.4μｍよりはるかに小さくなつてい
る。また、Ｘ線回折によつて、結晶質の粉体化合
物となつていることが確認された。
このようにして得た複合プロブスカイト化合物
の微粉末の特性を測定した。即ち得られた化合物
微粉末を整粒後単板に成形し、900℃大気中で焼
成したものについて密度を測定し、更にこれに銀
電極を焼付けそして誘電率、誘電損失、比抵抗を
測定した。得られた特性を、従来法によつたもの
の特性と一緒に表１に示した。
[Industrial Application Field] The present invention relates to a method for manufacturing a metal oxide composite perovskite compound suitable for piezoelectric ceramic materials and dielectric ceramic materials. [Prior art and its problems] Conventionally, composite perovskite compounds containing oxides of W, Fe, Nb, and Pb have been produced by mixing oxides of the respective metals, followed by calcining, crushing, and firing.
However, in such conventional methods, it is difficult to obtain a uniform solid solution state, and furthermore, the particle size distribution of the produced compound powder is wide and the particle shape is non-uniform. Therefore, the composite perovskite compound thus obtained has the disadvantage that it does not exhibit a high dielectric constant. Furthermore, high temperatures of 1000℃ or higher are required for firing, which is not only disadvantageous in terms of energy consumption, but also, for example, when used in capacitors, the internal electrodes used are Ag-Pd, which contains a large amount of expensive palladium. Another disadvantage is that alloys must be used. [Means for Solving the Problems] In view of the above-mentioned problems, the present invention provides a method in which the solid solution state is uniform, the particle size is almost constant, the particle shape is uniform, and energy consumption is low, and, for example, The object of the present invention is to provide a method for producing a composite probskite compound that can reduce the use of expensive palladium in internal electrodes when used in a capacitor. The production method of the present invention involves mixing Pb alkoxide, Fe alkoxide, and Nb alkoxide in a stoichiometric ratio, adding water to the mixture, and performing hydrolysis.
The precipitate is dried to obtain a first perovskite compound, while the Pb alkoxide, Fe alkoxide, and W alkoxide are similarly mixed and hydrolyzed to dry the precipitate to obtain a second perovskite compound. Mix the first and second perovskite compounds and sinter to form xPb(Fe 1/2・Nb 1/2 )
O 3 −1−xPb (Fe 2/3・W 1/3 ) O 3 system (0x1)
The present invention is characterized in that a composite perovskite compound is obtained. Examples of the present invention will be described below. [Example] Pb alkoxide (Pb(OR) 2 ), Fe alkoxide (Fe(OR) 3 ), Nb alkoxide (Nb(OR) 5 )
(where R is an alkyl group) in a molar ratio of 2:1:
For example, 12.00g each, so that the ratio is 1.
Mix 4.28g and 7.16g. This mixing is carried out at a temperature of 40 to 50°C for 4 to 5 hours while dissolving it in, for example, 200 ml of a benzene solution (or an organic solvent such as methyl or butanol can also be used) in a N2 stream.
For example, at 50° C. for 5 hours. Then add excess distilled water to this solution to perform hydrolysis10
Leave it for a while. The resulting precipitate is filtered, washed and dried to obtain fine powder A. On the other hand, Pb alkoxide (Pb(OR) 2 ), Fe alkoxide (Fe(OR) 3 ), W alkoxide (W
(OR) 6 ) in a molar ratio of 3:2:1, for example, 12.00g, 5.73g,
Mix 6.61 g. This mixing is also carried out under the same conditions as above, and then water is added in the same manner as above, and the precipitate is filtered, washed and dried to obtain fine powder B. After mixing A and B fine powders, about 900
By firing at ℃, a powder of the composite perovskite compound is obtained. The particle size of the obtained fine powder was confirmed to be about 0.1 μm by electron microscopic observation. This is much smaller than 0.4 μm in the case of the conventional method. Furthermore, it was confirmed by X-ray diffraction that it was a crystalline powder compound. The properties of the fine powder of the composite provskite compound thus obtained were measured. That is, the obtained compound fine powder was sized, formed into a single plate, and fired in the atmosphere at 900°C.The density was then measured.A silver electrode was then baked on this, and the dielectric constant, dielectric loss, and specific resistance were measured. . The properties obtained are shown in Table 1 together with the properties of those obtained by the conventional method.
以上述べたごとく、本発明によれば、
Pb（Fe1/2・Nb1/2）O3−Pb（Fe2/3・W1/3）O3の複
合ペロブスカイト化合物を低温焼成温度で、分布
中の小さい極めて微細な粒子として、しかも均一
組成をもつて容易に製造することができる。また
焼成温度が低いので、コンデンサ等への適用の
際、内部電極金属として高価なパラジウムを使用
することを不用とする利点をも有する。
As described above, according to the present invention, a composite perovskite compound of Pb(Fe 1/2・Nb 1/2 )O 3 −Pb(Fe 2/3・W 1/3 )O 3 is produced at a low firing temperature It can be easily produced as small, extremely fine particles in a distribution and with a uniform composition. Furthermore, since the firing temperature is low, it also has the advantage of eliminating the need to use expensive palladium as an internal electrode metal when applied to capacitors and the like.
Claims (1)
アルコキシドを化学量論比に混合し、これに水を
加えて加水分解を行ない、析出物を乾燥して第一
のペロブスカイト化合物を得、一方Pbアルコキ
シド、Feアルコキシド、およびＷアルコキシド
を同様に混合し、加水分解して、その析出物を乾
燥して第二のペロブスカイト化合物を得、該第一
および第二のペロブスカイト化合物を焼成して
xPb（Fe1/2・Nb1/2）O3−１−xPb（Fe2/3・W1/3）
O3系（但し０ｘ１）の複合ペロブスカイト
化合物を得ることを特徴とする複合ペロブスカイ
ト化合物の製造方法。1 Pb alkoxide, Fe alkoxide and Nb
The alkoxides are mixed in stoichiometric proportions and water is added to carry out hydrolysis, and the precipitate is dried to obtain the first perovskite compound, while Pb alkoxide, Fe alkoxide and W alkoxide are similarly mixed. , hydrolyze, dry the precipitate to obtain a second perovskite compound, and sinter the first and second perovskite compounds.
xPb(Fe 1/2・Nb 1/2 )O 3 −1−xPb(Fe 2/3・W 1/3 )
A method for producing a composite perovskite compound, which comprises obtaining an O 3 -based (0x1) composite perovskite compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60249941A JPS62113722A (en) | 1985-11-09 | 1985-11-09 | Production of complex perovskite compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60249941A JPS62113722A (en) | 1985-11-09 | 1985-11-09 | Production of complex perovskite compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62113722A JPS62113722A (en) | 1987-05-25 |
| JPH0321488B2 true JPH0321488B2 (en) | 1991-03-22 |
Family
ID=17200448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60249941A Granted JPS62113722A (en) | 1985-11-09 | 1985-11-09 | Production of complex perovskite compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62113722A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304533A (en) * | 1987-08-24 | 1994-04-19 | Mitsubishi Denki Kabushiki Kaisha | Process for producing an oxide superconductor from alkoxides |
-
1985
- 1985-11-09 JP JP60249941A patent/JPS62113722A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62113722A (en) | 1987-05-25 |
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