JPH0769634A - Production of composition - Google Patents
Production of compositionInfo
- Publication number
- JPH0769634A JPH0769634A JP5212879A JP21287993A JPH0769634A JP H0769634 A JPH0769634 A JP H0769634A JP 5212879 A JP5212879 A JP 5212879A JP 21287993 A JP21287993 A JP 21287993A JP H0769634 A JPH0769634 A JP H0769634A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- hydrothermal
- powder
- group element
- alkaline
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はペロブスカイト型化合物
を含有する組成物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a composition containing a perovskite type compound.
【０００２】[0002]
【従来の技術】近年電子デバイスは著しく小型高性能化
している。これに対応して、電子デバイスを構成するセ
ラミック電子部品も同様であり、小型高性能を目的とし
て、セラミックの製造工程の改良が種々検討されてきた
が、ほとんどその限界に達してきている。したがって、
現状よりさらに優れたセラミックスを得るためには、そ
の素材を改善する必要性がある。2. Description of the Related Art In recent years, electronic devices have become significantly smaller and have higher performance. Correspondingly, the same applies to the ceramic electronic parts constituting the electronic device, and various improvements in the manufacturing process of the ceramic have been studied for the purpose of miniaturization and high performance, but the limit has almost been reached. Therefore,
In order to obtain ceramics that are even better than the current situation, it is necessary to improve the material.
【０００３】例えば、誘電体セラミックスとしては、１
μｍ以下好ましくは０．５μｍ以下の均一で球形状のペ
ロブスカイト型化合物（以下、ＡＢＯ3型化合物とい
う）が研究されている。このような粒径のＡＢＯ3型化
合物は、粒径が小さければ表面エネルギ−が高くなり、
粒径分布が均一で球状であれば、成形時のパッキングが
よくなるため、焼結性は著しく改善され、より低い温度
で緻密強固なセラミックスが得られる。さらに、積層セ
ラミックコンデンサの薄層化・多積層化を実現させるた
めに、厚み１０μｍ以下のセラミックグリ−ンシ−トが
要求されているが、その場合も、１μｍ以下好ましくは
０．５μｍ以下の均一で球形状のＡＢＯ3型化合物が必
要になる。For example, as the dielectric ceramics, 1
A uniform and spherical perovskite-type compound (hereinafter referred to as ABO 3 type compound) having a size of μm or less, preferably 0.5 μm or less has been studied. The ABO 3 type compound having such a particle size has a high surface energy when the particle size is small,
If the particle size distribution is uniform and spherical, packing at the time of molding is improved, so the sinterability is remarkably improved, and dense and strong ceramics can be obtained at a lower temperature. Further, a ceramic green sheet having a thickness of 10 μm or less is required in order to realize thinning and multi-layering of a monolithic ceramic capacitor, and in that case as well, 1 μm or less, preferably 0.5 μm or less of uniform thickness. Therefore, a spherical ABO 3 type compound is required.
【０００４】従来より、ＡＢＯ3型化合物、例えばチタ
ン酸バリウムの製造方法としては、炭酸バリウムと酸化
チタンを１０００℃以上の高温で反応（仮焼）させてチ
タン酸バリウムを合成し、機械的に粉砕、分級する方法
（固相合成法）が知られている。また、これに対して、
湿式合成法として、金属アルコキシド法、水酸化物法、
水熱合成法等が知られている。Conventionally, as a method for producing an ABO 3 type compound such as barium titanate, barium carbonate and titanium oxide are reacted (calcined) at a high temperature of 1000 ° C. or more to synthesize barium titanate and mechanically A method of pulverizing and classifying (solid phase synthesis method) is known. Against this,
As a wet synthesis method, a metal alkoxide method, a hydroxide method,
Hydrothermal synthesis method and the like are known.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、固相合
成法の場合、仮焼後のチタン酸バリウムが固結している
ため、機械的粉砕、分級を行っても１μｍ以下の微細な
状態にするのは困難である。またその粒子形状は破砕物
状になっているため、これを任意の形状に成形して焼結
した場合、焼結性に欠けていた。さらに、前述したよう
に、積層セラミックコンデンサの薄層化・多積層化を実
現させるためには、厚み１０μｍ以下のセラミックグリ
−ンシ−トを問題なく成形することが必要であるが、固
相合成法で得られたチタン酸バリウム粉末を用いた場
合、グリ−ンシ−トの生密度が低下したり、あるいは、
グリ−ンシ−トの厚みばらつきが大きくなったりという
不具合が生じていた。However, in the case of the solid phase synthesis method, since barium titanate after calcination is solidified, even if it is mechanically pulverized and classified, it becomes a fine state of 1 μm or less. Is difficult. Further, since the particle shape thereof is a crushed product, when this was molded into an arbitrary shape and sintered, it lacked in sinterability. Further, as described above, in order to realize the thinning and multi-layering of the monolithic ceramic capacitor, it is necessary to form a ceramic green sheet having a thickness of 10 μm or less without any problem. When using barium titanate powder obtained by the method, the green density of the green sheet is reduced, or,
There was a problem that the thickness variation of the green sheet became large.
【０００６】また、湿式合成法に関して言えば、金属ア
ルコキシド法の場合、原料が高価で工業化には問題があ
る。一方、水酸化物法については、原料も比較的安価で
あり、得られる粉末も焼結性が高いという点で注目され
ている。Further, regarding the wet synthesis method, in the case of the metal alkoxide method, the raw materials are expensive and there is a problem in industrialization. On the other hand, the hydroxide method has been attracting attention because the raw material is relatively inexpensive and the obtained powder has high sinterability.
【０００７】たとえば、特開昭６０−９０８２５号公報
において、チタン酸と水酸化バリウムを多量の水の存在
化で、沸点以下の温度で加熱する方法がとられている
が、この場合、チタン酸をあらかじめ調整しなければな
らない。例えば、チタン酸をチタン化合物の水溶液の中
和によって沈澱させた場合には、コロイドであるため、
洗浄および濾過が工業的に困難であるという問題があ
る。For example, in JP-A-60-90825, a method of heating titanic acid and barium hydroxide at a temperature below the boiling point in the presence of a large amount of water is used. In this case, titanic acid is used. Must be adjusted in advance. For example, when titanic acid is precipitated by neutralizing an aqueous solution of a titanium compound, it is a colloid,
There is a problem that washing and filtration are industrially difficult.
【０００８】また、特開昭５９−３９７２６号公報にお
いて、チタン塩の水溶液に塩化バリウム、硝酸バリウム
等水溶性バリウム塩を溶解させ、アルカリを加えてｐＨ
を１３以上に調整して、沸点以下で加熱する方法が提案
されている。しかしながら、この方法で得られるチタン
酸バリウム粉末は、粒子径が０．０２〜０．０３μｍと
微細すぎるため、成形加工した場合の密度が低く、焼結
時の収縮が大きいという問題があり、用途によっては好
ましくない場合がある。Further, in JP-A-59-39726, a water-soluble barium salt such as barium chloride or barium nitrate is dissolved in an aqueous solution of titanium salt, and alkali is added to adjust the pH.
Is adjusted to 13 or more and heating at a boiling point or lower is proposed. However, since the barium titanate powder obtained by this method has a particle size of 0.02 to 0.03 μm, which is too fine, it has a problem that the density when molded is low and the shrinkage during sintering is large. Depending on the case, it may not be preferable.
【０００９】水熱合成法に関しては、積層セラミックコ
ンデンサの薄層化・多積層化に耐え得るのに最適なチタ
ン酸バリウム粉末を得ることができるとして、近年特に
注目されている。With respect to the hydrothermal synthesis method, attention has recently been paid particularly to the fact that it is possible to obtain the barium titanate powder most suitable for withstanding the thinning and multi-layering of a monolithic ceramic capacitor.
【００１０】たとえば、特開昭６１−３１３４５号公報
では、Ｂａ、Ｓｒ等のＡ群元素及びＴｉ、Ｚｒ等のＢ群
元素の水酸化物の所望のＡ／Ｂ比の混合物を水性媒体中
で水熱反応させた後、水性媒体中に溶存するＡ群元素を
水不溶性の形にして濾過、水洗、乾燥させる方法が提案
されている。ところが、この場合、Ａ群元素を水不溶性
の形にするいわゆる不溶化剤の添加量を、製造ロット毎
に決めなければならない煩雑さが生じてくる。つまり、
水熱反応において、製造ロット毎に反応率にばらつきが
あるため、そのたびごとに、濾液に溶存しているＡ群元
素イオン濃度を分析し、その値に応じて不溶化剤の添加
量を決定する必要がある。For example, in JP-A-61-31345, a mixture of a group A element such as Ba and Sr and a group B element hydroxide such as Ti and Zr in a desired A / B ratio is prepared in an aqueous medium. A method has been proposed in which, after hydrothermal reaction, a group A element dissolved in an aqueous medium is made into a water-insoluble form, followed by filtration, washing with water and drying. However, in this case, the amount of the so-called insolubilizing agent that makes the group A element insoluble in water has to be determined for each production lot, which is complicated. That is,
In the hydrothermal reaction, the reaction rate varies depending on the production lot. Therefore, the concentration of group A element ions dissolved in the filtrate is analyzed each time, and the amount of the insolubilizer added is determined according to the value. There is a need.
【００１１】また、特開昭６２−７２５２５号公報で
は、四塩化チタンの水溶液に、バリウム等の炭酸塩、塩
化物、硝酸塩のうち、いずれか１種類の化合物を溶解さ
せ、水酸化ナトリウムまたは水酸化カリウムを加えて、
オ−トクレ−ブ中で加熱する方法が提案されている。し
かしながら、詳細に検討した結果、ＮａやＫ等のアルカ
リ金属不純物をどうしても除去することができず、例え
ば、合成されたチタン酸バリウム粉末中に８００〜１０
００ppm程度残存することが明らかとなった。Further, in JP-A-62-72525, any one of carbonate, chloride and nitrate compounds such as barium is dissolved in an aqueous solution of titanium tetrachloride to prepare sodium hydroxide or water. Add potassium oxide,
A method of heating in an autoclave has been proposed. However, as a result of detailed examination, alkali metal impurities such as Na and K could not be removed by any means. For example, in the synthesized barium titanate powder, 800-10
It became clear that about 00 ppm remained.
【００１２】本発明の目的は、１μｍ以下好ましくは
０．５μｍ以下の均一で球形状の粒子であり、かつ、Ａ
サイト元素とＢサイト元素のモル比が１．０００±０．
００２の範囲にあり、さらに、結晶性が良く、アルカリ
金属等の不純物が極めて少ないＡＢＯ3型化合物が得ら
れる製造方法を提供することである。The object of the present invention is to provide uniform spherical particles of 1 μm or less, preferably 0.5 μm or less, and A
The molar ratio of the site element and the B site element is 1.000 ± 0.
It is an object of the present invention to provide a method for producing an ABO 3 type compound having a crystallinity of 002, good crystallinity, and very few impurities such as alkali metals.
【００１３】[0013]
【課題を解決するための手段】すなわち、本発明にかか
る組成物の製造方法の要旨とするところは、（ａ）Ｍ
ｇ、Ｃａ、Ｓｒ、Ｂａ、及びＰｂよりなるＡ群元素から
選ばれる少なくとも１種の塩と、Ｔｉ、Ｚｒ、Ｈｆ及び
ＳｎよりなるＢ群元素から選ばれる少なくとも１種の塩
と、水またはアルカリ性水溶液との混合物スラリ−を得
る第１工程、（ｂ）前記混合物スラリ−を水熱反応させ
て水熱合成粉末を得る第２工程、（ｃ）第２工程で得ら
れた水熱合成粉末とアルカリ性水溶液との混合物を水熱
反応させる第３工程、とからなることを特徴とする。That is, the gist of the method for producing a composition according to the present invention is (a) M
g, Ca, Sr, Ba, and Pb, at least one salt selected from the group A elements, at least one salt selected from group B elements consisting of Ti, Zr, Hf, and Sn, water or alkaline A first step of obtaining a mixture slurry with an aqueous solution, (b) a second step of hydrothermally reacting the mixture slurry to obtain a hydrothermal synthetic powder, (c) a hydrothermal synthetic powder obtained in the second step, And a third step of hydrothermally reacting the mixture with the alkaline aqueous solution.
【００１４】また、第３工程において、アルカリ性水溶
液としては、例えば、ｐＨが７〜１０の間に調整された
水酸化バリウム水溶液を用いる。In the third step, as the alkaline aqueous solution, for example, a barium hydroxide aqueous solution having a pH adjusted to 7 to 10 is used.
【００１５】第１工程で混合物スラリーを調整したの
ち、次の第２工程で混合物スラリーを水熱処理すること
により合成粉末が得られることになる。この合成粉末に
Ｌｉ、Ｎａなどのアルカリ金属が含まれている場合に
は、洗浄することが好ましい。洗浄回数はアルカリ金属
量が一定量まで低減できるまで任意繰り返せばよい。こ
ののち濾過、乾燥して乾燥粉末とする。この乾燥粉末は
次の第３工程にもちこまれ、アルカリ性水溶液と混合
し、この混合物を水熱反応させる。ここで、ＡＢＯ3型
化合物が含まれるアルカリ金属不純物をさらに低減させ
ることができる。After the mixture slurry is prepared in the first step, the mixture slurry is hydrothermally treated in the next second step to obtain a synthetic powder. If the synthetic powder contains an alkali metal such as Li or Na, it is preferably washed. The number of times of washing may be arbitrarily repeated until the amount of alkali metal can be reduced to a certain amount. Then, it is filtered and dried to obtain a dry powder. This dry powder is brought to the next third step, mixed with an alkaline aqueous solution and the mixture hydrothermally reacted. Here, the alkali metal impurities including the ABO 3 type compound can be further reduced.
【００１６】[0016]
【作用】本発明によれば、水熱合成して得られた粉末を
さらにアルカリ性水溶液と混合し、この混合物を水熱反
応させる工程を有しており、ここでＡＢＯ3型化合物に
含まれるアルカリ金属不純物量を低減することができ
る。このようにして得られたＡＢＯ3型化合物は粒子径
が小さく、粒度が均一で、球形状であるため、反応性が
よく、焼結温度を低下させることができる。また、粉砕
工程が省けるため、粉砕による不純物の混入を防げる。According to the present invention, there is a step of further mixing the powder obtained by hydrothermal synthesis with an alkaline aqueous solution, and subjecting this mixture to a hydrothermal reaction, in which the alkali contained in the ABO 3 type compound is used. The amount of metal impurities can be reduced. The ABO 3 type compound thus obtained has a small particle size, a uniform particle size, and a spherical shape, so that it has good reactivity and can lower the sintering temperature. Further, since the crushing step can be omitted, it is possible to prevent impurities from being mixed by crushing.
【００１７】[0017]
【実施例】 （実施例１）０．１molのＴｉ（Ｏ−ｉＣ3Ｈ7）4と、イ
ソプロピルアルコ−ル（以下、ＩＰＡという）３０ml
を、ポリフッ化エチレン系樹脂製ビ−カ−に入れる。次
に、この溶液をウルトラディスパ−サ−にて攪拌しなが
ら、０．６molのＮａＯＨ水溶液を含有する１３５mlで
加水分解を行う。そして、０．１molのＢａＣｌ2・２Ｈ
2Ｏを投入する（第１工程）。EXAMPLES Example 1 0.1 mol of Ti (O—iC 3 H 7 ) 4 and 30 ml of isopropyl alcohol (hereinafter referred to as IPA)
Is placed in a beaker made of polyfluorinated ethylene resin. Next, this solution is hydrolyzed with 135 ml containing 0.6 mol of an aqueous NaOH solution while being stirred with an ultra disperser. And 0.1 mol of BaCl 2 · 2H
2 O is charged (first step).
【００１８】この混合物スラリ−をポリフッ化エチレン
系樹脂製ビ−カ−に入れて、オ−トクレ−ブ装置に装着
し、温度：１７０℃、圧力：１６kg/cm2の条件で４時
間、ポリフッ化エチレン系樹脂製の攪拌棒を用いて、１
５０rpmで攪拌させながら水熱合成を行った。得られた
沈殿物を取り出し、水洗及び濾過を数回繰り返した後、
乾燥及び解砕をへて原料粉末を得た（第２工程）。この
粉末の粒子径は０．２〜０．３μｍであり、Ｂａ／Ｔｉ
比：１．００１、Ｎａ量：１０００ppm、Ｃｌ量：２０p
pmであった。This mixture slurry was placed in a beaker made of polyfluoroethylene resin and mounted in an autoclave apparatus, and the polyfluoride was kept for 4 hours under the conditions of temperature: 170 ° C. and pressure: 16 kg / cm 2. Using a stir bar made of ethylene oxide resin, 1
Hydrothermal synthesis was performed while stirring at 50 rpm. The precipitate obtained is taken out, washed with water and filtered several times,
A raw material powder was obtained by drying and crushing (second step). The particle diameter of this powder is 0.2 to 0.3 μm, and Ba / Ti
Ratio: 1.001, Na amount: 1000 ppm, Cl amount: 20 p
It was pm.
【００１９】次に、その粉末２０gとｐＨ＝１０に調整
された水酸化バリウム水溶液２００mlとを、上記同様ポ
リフッ化エチレン系樹脂製ビ−カ−に入れ、そのビ−カ
−をオ−トクレ−ブ装置に装着し、温度：２００℃、圧
力：１５kg/cm2の条件で４時間、ポリフッ化エチレン系
樹脂製の攪拌棒を用いて、１５０rpmで攪拌させながら
水熱処理を行った。処理終了後、濾過、乾燥及び解砕を
へて原料粉末を得た（第３工程）。この粉末の粒子径は
０．２〜０．３μｍであり、Ｂａ／Ｔｉ比：０．９９
９、Ｎａ量：１００ppm、Ｃｌ量：２０ppmであった。図
１はこの方法で得られた組成物のＸ線回折パタ−ンであ
り、（１１０）の鋭いピークから立方晶のペロブスカイ
ト構造を有していることを示している。Next, 20 g of the powder and 200 ml of an aqueous barium hydroxide solution adjusted to pH = 10 were placed in a polyfluorinated ethylene resin beaker as above, and the beaker was autoclaved. It was attached to a heating device and subjected to hydrothermal treatment under the conditions of temperature: 200 ° C. and pressure: 15 kg / cm 2 for 4 hours while stirring at 150 rpm using a stirring rod made of polyfluoroethylene resin. After completion of the treatment, filtration, drying and crushing were performed to obtain a raw material powder (third step). The powder has a particle size of 0.2 to 0.3 μm and a Ba / Ti ratio of 0.99.
9, Na amount: 100 ppm, Cl amount: 20 ppm. FIG. 1 is an X-ray diffraction pattern of the composition obtained by this method and shows that it has a cubic perovskite structure from the sharp peak of (110).
【００２０】各工程について若干説明を付け加えると、
第１工程においてＢａとＴｉを等モルの割合で仕込んで
いるが、第２工程水熱合成後モル比ずれが起きる。これ
を防ぐにはＢａおよびＴｉの仕込み濃度の少なくとも４
倍、好ましくは６倍以上のＯＨ濃度が必要である。A brief description of each step is as follows:
Although Ba and Ti are charged in an equimolar ratio in the first step, a molar ratio shift occurs after the second step hydrothermal synthesis. To prevent this, at least 4 of the concentrations of Ba and Ti should be added.
The OH concentration is required to be twice, preferably 6 times or more.
【００２１】次に、第２工程後、洗浄を行うが、Ｂａ抜
けを防ぐためアルカリ性の水溶液で数回洗浄する。アル
カリ性のｐＨとしては少なくとも９以上である。なお、
洗浄回数は、Ｎａ、Ｋ、Ｃｌ等の不純物低減に影響して
いる。Ｃｌに関しては２〜３回の洗浄でほぼ完全に除去
できるが、ＮａやＫ等のアルカリ金属不純物は、ある濃
度に達すると、その後何回洗浄しても低減せず一定であ
る。本実施例においては残存Ｎａ量は３回目以降の洗浄
で１０００ppmのままであった。これは、Ｎａ等のアル
カリ金属不純物がチタン酸バリウムの結晶格子の中に取
り込まれているものと推察される。Next, after the second step, washing is carried out, but washing is carried out several times with an alkaline aqueous solution in order to prevent Ba escape. The alkaline pH is at least 9 or higher. In addition,
The number of times of cleaning affects the reduction of impurities such as Na, K and Cl. Although Cl can be almost completely removed by washing 2-3 times, when an alkali metal impurity such as Na or K reaches a certain concentration, it does not decrease and is constant no matter how many times it is washed thereafter. In this example, the amount of residual Na remained at 1000 ppm after the third and subsequent washings. It is presumed that this is because alkali metal impurities such as Na are incorporated in the crystal lattice of barium titanate.
【００２２】この残存Ｎａの低減は第３工程の再水熱処
理を行うことで解決することがわかった。このことは、
今までの公知例からは、全く予想し得なかった極めて新
しい事実である。再水熱処理条件としては温度は高いほ
どよいが、ポリフッ化エチレン系樹脂製ビ−カ−を使用
する場合は、２００℃以下が望ましい。また反応時間は
４時間で充分である。It was found that this reduction of residual Na can be solved by performing the re-hydrothermal treatment in the third step. This is
This is a very new fact that could not have been predicted from the known examples up to now. As the re-hydrothermal treatment condition, the higher the temperature, the better. However, when a polyfluorinated ethylene resin beaker is used, it is preferably 200 ° C or lower. A reaction time of 4 hours is sufficient.
【００２３】加えて、再水熱処理時の溶液については、
Ｂａ抜けを防ぐためにアルカリ性にしておく必要があ
る。アルカリ性を付与するものとして、アンモニア水、
水酸化ナトリウム溶液や水酸化カリウム溶液などのアル
カリ金属を含む水溶液、水酸化バリウム溶液などのアル
カリ土類金属を含む水溶液が考えられる。In addition, regarding the solution at the time of rehydrothermal treatment,
It is necessary to make it alkaline so as to prevent Ba escape. Ammonia water, which gives alkalinity,
An aqueous solution containing an alkali metal such as a sodium hydroxide solution or a potassium hydroxide solution and an aqueous solution containing an alkaline earth metal such as a barium hydroxide solution are considered.
【００２４】この中で、アンモニア水は水熱処理条件下
ではアンモニアが揮発し、ｐＨの低下によるＢａ抜けが
生じることと、揮発したアンモニアがポリフッ化エチレ
ン系樹脂製ビーカーなどと反応するなど好ましくない。
また、水酸化ナトリウム溶液などアルカリ金属を含む水
溶液は、この発明で得られる組成物からアルカリ金属を
除去することも目的の一つであるから使用できない。Among these, ammonia water is not preferable because under the condition of hydrothermal treatment, the ammonia volatilizes to cause Ba loss due to a decrease in pH, and the volatilized ammonia reacts with a beaker made of a polyfluoroethylene resin.
Further, an aqueous solution containing an alkali metal such as a sodium hydroxide solution cannot be used because it is one of the purposes to remove the alkali metal from the composition obtained by the present invention.
【００２５】従って、水酸化バリウム溶液などのアルカ
リ土類金属を含む水溶液がよい。特に、水酸化バリウム
溶液がよく、その際のｐＨは７〜１０好ましくは９〜１
０の間に設定するのがよい。ｐＨが１０を越えると、最
終的に得られる粉末のＢａ／Ｔｉの比がＢａが多い側に
ずれるし、ｐＨが９以下であれば水熱処理条件化におい
て、Ｂａ抜けを起こすことになる。Therefore, an aqueous solution containing an alkaline earth metal such as a barium hydroxide solution is preferable. Particularly, a barium hydroxide solution is preferable, and the pH at that time is 7 to 10 and preferably 9 to 1
It is better to set it between 0. If the pH exceeds 10, the Ba / Ti ratio of the finally obtained powder will shift to the side with a large amount of Ba, and if the pH is 9 or less, Ba will be lost under hydrothermal treatment conditions.
【００２６】（実施例２）０．１molのＴｉ（Ｏ−ｉＣ3
Ｈ7）4と、ＩＰＡ３０mlとを、ポリフッ化エチレン系樹
脂製ビ−カ−に入れて、ウルトラディスパ−サ−にて攪
拌しながら、０．６molのＮａＯＨを含有する水溶液１
３５mlにて加水分解を行う。そして、０．１molのＳｒ
Ｃｌ2を入れる（第１工程）。[0026] (Example 2) 0.1 mol of Ti (O-iC 3
H 7 ) 4 and 30 ml of IPA were put into a polyfluorinated ethylene resin beaker and stirred with an ultra disperser, and an aqueous solution containing 0.6 mol of NaOH 1
The hydrolysis is carried out with 35 ml. And 0.1 mol of Sr
Add Cl 2 (first step).
【００２７】この混合物スラリ−を中に含むポリフッ化
エチレン系樹脂製ビ−カ−をオ−トクレ−ブ装置に装着
し、温度：１７０℃、圧力１６kg/cm2の条件で４時間、
ポリフッ化エチレン系樹脂製の攪拌棒を用いて、１５０
rpmで攪拌させながら水熱処理を行った。得られた沈殿
物を取り出し、水洗及び濾過を数回繰り返した後、乾燥
及び解砕をへて原料粉末を得た（第２工程）。この粉末
の粒子径は０．１〜０．２μｍであり、Ｓｒ／Ｔｉ比：
１．００２、Ｎａ量：９００ppm、Ｃｌ量：１０ppmであ
った。A beaker made of a polyfluoroethylene resin containing the mixture slurry was mounted in an autoclave apparatus, and the temperature was 170 ° C. and the pressure was 16 kg / cm 2 for 4 hours.
Use a stirring rod made of polyfluorinated ethylene resin to
Hydrothermal treatment was performed while stirring at rpm. The resulting precipitate was taken out, washed with water and filtered several times, then dried and crushed to obtain a raw material powder (second step). The particle diameter of this powder is 0.1 to 0.2 μm, and the Sr / Ti ratio is:
The amount was 1.002, the amount of Na was 900 ppm, and the amount of Cl was 10 ppm.
【００２８】次に、上記粉末２０gとｐＨ＝１０に調整
された水酸化バリウム水溶液２００mlとをポリフッ化エ
チレン系樹脂製ビ−カ−に入れ、このビ−カ−をオ−ト
クレ−ブ装置に装着し、温度：２００℃、圧力：１５kg
/cm2の条件で４時間、ポリフッ化エチレン系樹脂製の攪
拌棒を用いて、１５０rpmで攪拌させながら水熱処理を
行った。処理終了後、濾過、乾燥及び解砕をへて原料粉
末を得た（第３工程）。Next, 20 g of the above powder and 200 ml of a barium hydroxide aqueous solution adjusted to pH = 10 were placed in a polyfluorinated ethylene resin beaker, and this beaker was placed in an autoclave apparatus. Attached, temperature: 200 ℃, pressure: 15kg
The hydrothermal treatment was performed for 4 hours under the condition of / cm 2 using a stirring rod made of polyfluoroethylene resin while stirring at 150 rpm. After completion of the treatment, filtration, drying and crushing were performed to obtain a raw material powder (third step).
【００２９】この粉末の粒子径及び粒子形状は、電子顕
微鏡による観察の結果、０．１〜０．２μｍで球形状で
あり、Ｓｒ／Ｔｉ比：０．９９８、Ｎａ量：８０ppm、
Ｃｌ量：１０ppmであった。またＸ線回折の結果より、
立方晶のペロブスカイト構造を有するチタン酸ストロン
チウムが生成していた。As a result of observation with an electron microscope, the particle diameter and particle shape of this powder were 0.1 to 0.2 μm and spherical, Sr / Ti ratio: 0.998, Na amount: 80 ppm,
Cl amount: 10 ppm. Moreover, from the result of X-ray diffraction,
Strontium titanate having a cubic perovskite structure was formed.
【００３０】上述のように実施例に関しては、チタン酸
バリウム（ＢａＴｉＯ3）粉末及びチタン酸ストロンチ
ウム（ＳｒＴｉＯ3）粉末に関して述べたが、例えば、
ＣａＴｉＯ3、（Ｂａ，Ｃａ）ＴｉＯ3、Ｂａ（Ｔｉ，Ｚ
ｒ）Ｏ3、（Ｂａ，Ｃａ）（Ｔｉ，Ｚｒ）Ｏ3等の粉末に
ついても、もちろん同様な方法で製造できる。As described above, the examples have been described with reference to barium titanate (BaTiO 3 ) powder and strontium titanate (SrTiO 3 ) powder.
CaTiO 3 , (Ba, Ca) TiO 3 , Ba (Ti, Z
Powders such as r) O 3 and (Ba, Ca) (Ti, Zr) O 3 can of course be manufactured by the same method.
【００３１】[0031]
【発明の効果】本発明により製造されたＡＢＯ3型粉末
は、粒子径が０．１〜０．３μｍで球形状であり、か
つ、Ａ／Ｂ比が１．０００±０．００２の範囲にある。
また、結晶性が良く、アルカリ金属の不純物が極めて少
ない。これらの特徴を有するＡＢＯ3型粉末は、積層セ
ラミックコンデンサの薄層化・多積層化に加え、高機能
化・高信頼性化に対応できる。The ABO 3 type powder produced according to the present invention has a spherical shape with a particle size of 0.1 to 0.3 μm and an A / B ratio within the range of 1.000 ± 0.002. is there.
Also, the crystallinity is good, and the impurities of alkali metal are extremely small. The ABO 3 type powder having these characteristics can support not only thinning and multi-layering of a monolithic ceramic capacitor, but also high functionality and high reliability.
【図１】実施例１により生成されたチタン酸バリウムの
Ｘ線回折パタ−ンである。FIG. 1 is an X-ray diffraction pattern of barium titanate produced in Example 1.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｂ 3/00 Ｈ 9059−5Ｇ Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location H01B 3/00 H 9059-5G
Claims (2)
ｂよりなるＡ群元素から選ばれる少なくとも１種の塩
と、Ｔｉ、Ｚｒ、Ｈｆ及びＳｎよりなるＢ群元素から選
ばれる少なくとも１種の塩と、水またはアルカリ性水溶
液との混合物スラリ−を得る第１工程、（ｂ）前記混合
物スラリ−を水熱反応させて水熱合成粉末を得る第２工
程、（ｃ）第２工程で得られた水熱合成粉末とアルカリ
性水溶液との混合物を水熱反応させる第３工程、とから
なることを特徴とするペロブスカイト型化合物を含有す
る組成物の製造方法。1. (a) Mg, Ca, Sr, Ba, and P
to obtain a mixture slurry of at least one salt selected from the group A element consisting of b, at least one salt selected from the group B element consisting of Ti, Zr, Hf and Sn, and water or an alkaline aqueous solution. 1 step, (b) a second step of hydrothermally reacting the mixture slurry to obtain a hydrothermal synthetic powder, (c) a hydrothermal reaction of a mixture of the hydrothermal synthetic powder obtained in the second step and an alkaline aqueous solution And a third step of allowing the perovskite-type compound to be contained in the composition.
液として、ｐＨが７〜１０の間に調整された水酸化バリ
ウム水溶液を用いることを特徴とする請求項１記載の組
成物の製造方法。2. The method for producing a composition according to claim 1, wherein in the third step, a barium hydroxide aqueous solution having a pH adjusted to 7 to 10 is used as the alkaline aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21287993A JP3838523B2 (en) | 1993-08-27 | 1993-08-27 | Method for producing the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21287993A JP3838523B2 (en) | 1993-08-27 | 1993-08-27 | Method for producing the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0769634A true JPH0769634A (en) | 1995-03-14 |
| JP3838523B2 JP3838523B2 (en) | 2006-10-25 |
Family
ID=16629779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21287993A Expired - Lifetime JP3838523B2 (en) | 1993-08-27 | 1993-08-27 | Method for producing the composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3838523B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002234771A (en) * | 2001-02-05 | 2002-08-23 | Murata Mfg Co Ltd | Oxide powder having tetragonal perovskite structure, method for producing the same, dielectric ceramic and multilayer ceramic capacitor |
| KR100451827B1 (en) * | 2001-10-15 | 2004-10-08 | (주)디오 | Method for preparing barium titanates |
| KR100489403B1 (en) * | 2002-05-30 | 2005-05-12 | 주식회사 나노 | METHOD OF PREPARING BaTiO3 POWDER |
| JP2006298677A (en) * | 2005-04-18 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | Method for synthesizing ceramic powder |
| JP2008105870A (en) * | 2006-10-23 | 2008-05-08 | Tdk Corp | Barium titanate powder, dielectric porcelain composition and electronic component |
| KR20120013981A (en) * | 2009-04-10 | 2012-02-15 | 에스톨, 인코포레이티드 | Hydrothermal processing in the wet-chemical preparation of mixed metal oxide ceramic powders |
| JP2020034654A (en) * | 2018-08-28 | 2020-03-05 | キヤノン株式会社 | Image forming device |
-
1993
- 1993-08-27 JP JP21287993A patent/JP3838523B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002234771A (en) * | 2001-02-05 | 2002-08-23 | Murata Mfg Co Ltd | Oxide powder having tetragonal perovskite structure, method for producing the same, dielectric ceramic and multilayer ceramic capacitor |
| JP4660935B2 (en) * | 2001-02-05 | 2011-03-30 | 株式会社村田製作所 | Method for producing barium titanate-based ceramic powder having tetragonal perovskite structure |
| KR100451827B1 (en) * | 2001-10-15 | 2004-10-08 | (주)디오 | Method for preparing barium titanates |
| KR100489403B1 (en) * | 2002-05-30 | 2005-05-12 | 주식회사 나노 | METHOD OF PREPARING BaTiO3 POWDER |
| JP2006298677A (en) * | 2005-04-18 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | Method for synthesizing ceramic powder |
| JP2008105870A (en) * | 2006-10-23 | 2008-05-08 | Tdk Corp | Barium titanate powder, dielectric porcelain composition and electronic component |
| KR20120013981A (en) * | 2009-04-10 | 2012-02-15 | 에스톨, 인코포레이티드 | Hydrothermal processing in the wet-chemical preparation of mixed metal oxide ceramic powders |
| JP2012523369A (en) * | 2009-04-10 | 2012-10-04 | イーストー，インコーポレイティド | Hydrothermal process for wet chemical preparation of mixed metal oxide ceramic powders |
| JP2020034654A (en) * | 2018-08-28 | 2020-03-05 | キヤノン株式会社 | Image forming device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3838523B2 (en) | 2006-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0641740B1 (en) | Process for the synthesis of crystalline ceramic powders of perovskite compounds | |
| US5445806A (en) | Process for preparing fine powder of perovskite-type compound | |
| US4520004A (en) | Method of manufacturing metal titanate fine powder | |
| JPH0459261B2 (en) | ||
| KR100497938B1 (en) | Method for producing complex oxide powder and complex oxide powder | |
| US4670243A (en) | Method of precipitating metal titanate powders | |
| JP2726439B2 (en) | Method for producing ceramic powder having perovskite structure | |
| US7001585B2 (en) | Method of making barium titanate | |
| EP1860069B1 (en) | Method for producing composition | |
| JP4556398B2 (en) | Method for producing the composition | |
| JPH0339018B2 (en) | ||
| EP0439620B1 (en) | Method of producing pulverized perovskite compound | |
| JP3838523B2 (en) | Method for producing the composition | |
| JP3319807B2 (en) | Perovskite-type compound fine particle powder and method for producing the same | |
| JP2010120850A (en) | Method for producing composition | |
| JP3772354B2 (en) | Manufacturing method of ceramic powder | |
| JP3668985B2 (en) | Manufacturing method of ceramic powder | |
| JPH0339014B2 (en) | ||
| JPH0246531B2 (en) | ||
| JPS61111957A (en) | Composition for ceramic dielectric | |
| KR100596519B1 (en) | Method for manufacturing ceramic composition | |
| JPH07277710A (en) | Production of perovskite-type multiple oxide powder | |
| JPH0769645A (en) | Production of lead-containing multiple oxide | |
| CN113307305B (en) | Preparation method and application of barium titanate powder | |
| KR100647247B1 (en) | Method for Synthesizing Barium Titanate Powder by solvothermal technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060531 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060728 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090811 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100811 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100811 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110811 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120811 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120811 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130811 Year of fee payment: 7 |
|
| EXPY | Cancellation because of completion of term |